CN105381819A - Supported biquaternary ammonium salt catalyst, preparation method, and preparation method of cyclic carbonate - Google Patents
Supported biquaternary ammonium salt catalyst, preparation method, and preparation method of cyclic carbonate Download PDFInfo
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- CN105381819A CN105381819A CN201510916235.XA CN201510916235A CN105381819A CN 105381819 A CN105381819 A CN 105381819A CN 201510916235 A CN201510916235 A CN 201510916235A CN 105381819 A CN105381819 A CN 105381819A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
The invention relates to a supported biquaternary ammonium salt catalyst. The supporter of the supported biquaternary ammonium salt catalyst is bonded with a biquaternary ammonium salt represented by formula (1). The invention also provides a preparation method of the supported biquaternary ammonium salt catalyst, and the supported biquaternary ammonium salt catalyst prepared through the preparation method. The invention further provides a preparation method of cyclic carbonate by adopting the supported biquaternary ammonium salt catalyst as a catalyst. The cyclic carbonate is represented by formula (2). The catalyst has the advantages of simple preparation method, high yield, solving of the problems of difficult separation and addition of cocatalyst as needed of common catalysts, good stability and long circulation service life; and the cyclic carbonate is prepared in a high-yield and high-selectivity manner by adopting the catalyst provided by the invention as a catalyst for a coupling reaction of carbon dioxide and epoxide.
Description
Technical field
The present invention relates to support type bi-quaternary ammonium salt Catalysts and its preparation method, and adopt this support type bi-quaternary ammonium salt catalyst as the method for catalyst preparing cyclic carbonate.
Background technology
Carbon dioxide is current topmost greenhouse gases, but it is also a kind of very important C1 resource simultaneously, and it absorbs and utilization becomes one of the hugest challenging problem in this century.Cyclic carbonate is the important organic synthesis intermediate of a class, has a wide range of applications in medicine, fine chemistry industry synthetic intermediate, lithium battery, resins synthesis etc.Carbon dioxide is coupled with epoxides and prepares the reaction of cyclic carbonate, and its atom utilization is high, meets the direction of the development of Green Chemistry, and while realizing carbon dioxide utilization, additionally reduces the discharge of greenhouse gases.
Catalyst at present for the coupled reaction of carbon dioxide and epoxides is mainly divided into two classes, i.e. homogeneous catalyst and heterogeneous catalysis.Wherein, homogeneous catalyst mainly comprises: the catalyst such as alkali metal, organic phosphine, organic base, ionic liquid, metal complex; This type of catalyst often has such as catalyst synthesis condition harshness, poor stability, catalytic performance is not high, recovery is difficult and recycle the not high defect of number of times.At present, more focus has been placed in the research of heterogeneous catalysis by people, and heterogeneous catalysis mainly comprises: metal oxide, as MgO, Al
2o
3; Molecular sieve and clay class catalyst; Loaded catalyst, as support type organic base, load type gold metal complex, load-type ion liquid catalyst etc.Wherein, loaded catalyst, owing to can effectively solve catalyst recovery problem, decreases the cost of catalyst thus obtains more concern.Catalyst is divided into physical load and chemical load according to its mode of loading, and physical load is realized by the physisorption between functional group and carrier, and the stability of this kind of mode of loading is relatively not high, easily causes the loss of catalyst; And chemical load is realized by the effect of chemical bonding, there is higher stability, effectively reduce the loss of functional group.Chemical load common at present comprises: load quaternary amines, pyridines and imidazoles etc.But the heterogeneous catalysis of existing this kind of chemical load type still has the defects such as catalyst activity is not high, severe reaction conditions, poor stability.
Summary of the invention
The catalyst activity that the object of the invention is to overcome the existing coupled reaction for participating in carbon dioxide and epoxides is not high, recycle the not high defect of number of times, there is provided a kind of and there is higher catalytic activity, and still can the support type bi-quaternary ammonium salt Catalysts and its preparation method of highly selective, with high yield catalysis carbon dioxide and epoxides synthesizing annular carbonate and the preparation method of cyclic carbonate after circulation repeatedly.
To achieve these goals, the invention provides a kind of support type bi-quaternary ammonium salt catalyst, the carrier of this support type bi-quaternary ammonium salt catalyst be bonded with the bi-quaternary ammonium salt that formula (1) represents:
Wherein, in formula (1), the X of 2 molecules
-identical or different, be selected from F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-; N is the integer of 1-6; R
1for H, OH, NH
2or COOH; Relative to the support type bi-quaternary ammonium salt catalyst described in 1g, the molar content of the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol; One or more in described carriers selected from silica, mesopore molecular sieve and fluoropolymer resin; Described mesopore molecular sieve is MCM-41 or SBA-15; Described fluoropolymer resin is the styrene resin of chloromethylation, shitosan or Field resin.
Present invention also offers the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst, the method comprises:
(1) carrier and triethylene diamine are carried out the first haptoreaction, make triethylene diamine and support chemistry bonding obtain being connected with the intermediate product of triethylene diamine; Described carrier and the usage ratio 1g:1-15mmol of triethylene diamine; Described carrier is one in silica, mesopore molecular sieve, fluoropolymer resin and combination thereof; Described reaction temperature is 10-50 DEG C, and the reaction time is 1-24h;
(2) by step (1) gained intermediate product and formula X'-(CH
2)
n-R
1carry out the support type bi-quaternary ammonium salt catalyst that the second haptoreaction obtains having triethylene diamine structure, triethylene diamine structure is the active component of support type bi-quaternary ammonium salt catalyst; X' is F
-, Cl
-, Br
-or I
-, n is the integer of 1-6, R
1for H, OH, NH
2or COOH; Described triethylene diamine and formula X'-(CH
2)
n-R
1mole dosage than for 1:1-3; Described reaction temperature is 60-90 DEG C, and the reaction time is 1-48h.
The method also comprises, the support type bi-quaternary ammonium salt catalyst that step (2) is obtained with containing CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more anion salt solution contact, obtain anion X
-for CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more described support type bi-quaternary ammonium salt catalyst.
The support type bi-quaternary ammonium salt catalyst that the present invention also provides said method obtained.
Present invention also offers a kind of method of above-mentioned support type bi-quaternary ammonium salt catalyst preparing cyclic carbonate, described cyclic carbonate is the compound shown in formula (2), wherein, the method comprises: under support type bi-quaternary ammonium salt catalyst exists, compound shown in formula (3) and carbon dioxide are carried out coupled reaction and obtains the cyclic carbonate shown in formula (2), described coupled reaction temperature is 80-160 DEG C, and the time is 0.5-24h, and pressure is 0.3-10MPa; Wherein, described catalyst is one or more in the support type quaternary ammonium salt catalyst that obtains of the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst or above-mentioned support type bi-quaternary ammonium salt catalyst; Relative to the compound shown in 1mol formula (3), in described support type bi-quaternary ammonium salt catalyst, the amount of active component is 3-50mmol;
Wherein, R
2and R
3be hydrogen independently of one another, the alkyl of C1-C6, by the alkyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, the alkoxyl of C1-C6, by the alkoxyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, phenyl, by the phenyl that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace, phenoxy group, by the phenoxy group that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace;
Or, R
2and R
3bonding forms 3-6 unit cycloaliphatic ring together, and one or more substituting groups that this cycloaliphatic ring is optionally selected from halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replaced.
By adopting support type bi-quaternary ammonium salt catalyst provided by the invention as the catalyst of coupled reaction between carbon dioxide and epoxides (i.e. compound shown in formula (3)), higher yields ground, comparatively highly selective can prepare cyclic carbonate (i.e. compound shown in formula (2)), particularly by catalyst after repeatedly recycling, still can higher yields ground, comparatively highly selective prepare cyclic carbonate.Especially one of the present invention preferred embodiment in, when adopting support type bi-quaternary ammonium salt catalyst of the present invention as catalyst, can not adopt any solvent in the coupled reaction of carbon dioxide and epoxides thus greatly reduce the cost of this reaction, and also reducing the probability that side reaction produces.
Beneficial effect of the present invention is: catalyst preparation process is simple, productive rate is high, overcome common catalyst to be difficult to be separated and need to add the problems such as co-catalyst, without the need under adding any organic solvent condition, to epoxides and carbon dioxide reaction, there is higher catalytic activity, and catalyst have good stability and service life cycle.This catalyst is as the catalyst of coupled reaction between carbon dioxide and epoxides, higher yields ground, comparatively highly selective can prepare cyclic carbonate, particularly by catalyst after repeatedly recycling, still can higher yields ground, comparatively highly selective prepare cyclic carbonate.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of support type bi-quaternary ammonium salt catalyst, this support type bi-quaternary ammonium salt catalyst adopts fluoropolymer resin and molecular sieve to do carrier, carrier is bonded with the bi-quaternary ammonium salt that formula (1) represents:
Wherein, in formula (1), the X of 2 molecules
-identical or different, be selected from F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-; N is the integer of 1-6; R
1for H, OH, NH
2or COOH; One or more in described carriers selected from silica, mesopore molecular sieve and fluoropolymer resin, described mesopore molecular sieve is MCM-41 or SBA-15; Described fluoropolymer resin is preferably selected from the one in the styrene resin of chloromethylation, shitosan and Field resin, is more preferably the styrene resin of chloromethylation.
According to the present invention, support type bi-quaternary ammonium salt catalyst of the present invention be a class by ionic liquid chemical bonding to the material on carrier, it has two molecule N cations, subsidiary anion X
-can be the reactant that adds when preparing such structure with, also can be got by ion-exchange, also can be the anion that carrier takes off, therefore, the X of 2 molecules
-identical or different separately.Such as can by as shown in the formula represented by (a):
carrier in this formula (a), X, n and R
1as herein to formula (1) define.
Consider for improving in the stability of described support type bi-quaternary ammonium salt catalyst as the catalyst of the coupled reaction between carbon dioxide and epoxides, catalytic activity, preferably, in formula (1), X
-be selected from Cl
-, Br
-, I
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-[BF
4]
-.Preferably, n is the integer of 1-4.More preferably, the X of 2 molecules
-identical, X
-for Cl
-, Br
-, I
-or [BF
4]
-; N is 1,2 or 3.
According to the present invention, because described support type bi-quaternary ammonium salt catalyst is actually the form of chemical bonding between bi-quaternary ammonium salt that carrier and formula (1) represent, therefore to a kind of carrier be selected from dioxide/silica gel, mesopore molecular sieve and fluoropolymer resin, there is no particular limitation in the present invention, as long as can be real above-mentioned purpose.
One of the present invention preferred embodiment in, in formula (1), the X of 2 molecules
-identical, X
-for Cl
-, Br
-, I
-or [BF
4]
-; N is 1,2 or 3; Described carrier is the one in the styrene resin of chloromethylation, silica supports, MCM-41 and SBA-15.
In another preferred embodiment of the present invention, in formula (1), the X of 2 molecules
-identical, X
-for Cl
-, Br
-or I
-; R
1for OH, NH
2or COOH; N is 1,2 or 3; Described carrier is the one in the styrene resin of chloromethylation, silica supports, MCM-41 and SBA-15.
According to the present invention, although adopt described support type bi-quaternary ammonium salt catalyst just can have higher activity, stability and circulation ability as the catalyst of the coupled reaction between carbon dioxide and epoxides, but in order to higher performance can be obtained, preferably, in described support type bi-quaternary ammonium salt catalyst, relative to support type bi-quaternary ammonium salt catalyst described in 1g, the molar content of the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol, be more preferably 1-3mmol, be further preferably 1.4-2.5mmol.Shown in formula (1)
part, this part grafting, on carrier, also can be thought to have carried out functionalization to carrier, and therefore support type bi-quaternary ammonium salt catalyst of the present invention also can be recognized as the two quaternary ammonium functionalized carrier mass of a kind of support type." bi-quaternary ammonium salt that formula (1) represents " in the present invention also can represent with english abbreviation " DABCO ".
Present invention also offers a kind of preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst, the method comprises:
(1) carrier and triethylene diamine are carried out the first haptoreaction, make triethylene diamine and support chemistry bonding obtain being connected with the intermediate product of triethylene diamine; One or more in described carriers selected from silica, mesopore molecular sieve and fluoropolymer resin;
(2) by step (1) gained intermediate product and formula X'-(CH
2)
n-R
1carry out the second haptoreaction, obtain the support type bi-quaternary ammonium salt catalyst with triethylene diamine structure, triethylene diamine structure is the active component of support type bi-quaternary ammonium salt catalyst;
X' is F
-, Cl
-, Br
-or I
-, n is the integer of 1-6, R
1for H, OH, NH
2or COOH.
According to the present invention, in order to obtain X
-the more support type bi-quaternary ammonium salt catalyst of the present invention of horn of plenty, the method can also comprise: by step (2) products therefrom and containing F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more anion salt solution contact, to obtain anion X
-for F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more described support type bi-quaternary ammonium salt catalyst.
According to the present invention, in step (1), triethylene diamine and support chemistry bonding can be made to obtain being connected with the carrier of triethylene diamine by described first haptoreaction, thus provide precursor for the preparation of support type bi-quaternary ammonium salt catalyst above.
Wherein, triethylene diamine has the structure shown in following formula (5): formula (5)
described carrier carries out selecting or preferably, not repeating them here as described above.
For the styrene resin that described carrier is chloromethylation, the functional group chloromethyl of the styrene resin of described chloromethylation can react with the N of triethylene diamine, obtains a part N cation and anion is the mono-quaternaries structure of chlorion.
According to the present invention, the consumption of triethylene diamine is not particularly limited, but in order to obtain above described support type bi-quaternary ammonium salt catalyst (wherein, relative to support type bi-quaternary ammonium salt catalyst described in 1g, the molar content of the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol), preferably, relative to 1g carrier, the mole dosage of triethylene diamine is 1-15mmol, is preferably 2-10mmol, can be such as 2.2-9.6mmol, 4-9.6mmol etc.
According to the present invention, described first catalytic condition is not particularly limited, can as the precursor of support type bi-quaternary ammonium salt catalyst of the present invention as long as can obtain, preferably, described first catalytic condition comprises: temperature is 10-50 DEG C, is preferably 30-50 DEG C; Time is 1-24h, is preferably 12-24h.
According to the present invention, described first haptoreaction can adopt solvent to be such as one or more in acetonitrile, toluene and dichloroethanes, to be not particularly limited the capacity of solvent, such as relative to 1g carrier, the consumption of solvent is 15-100mL, is preferably 18-50ml, is more preferably 18-30ml.
According to the present invention, reaction system after step (1) haptoreaction directly directly can be carried out the second haptoreaction without any process by step (2), certainly in order to more pure support type bi-quaternary ammonium salt catalyst can be obtained, preferably, first the precursor of step (1) gained is extracted the reaction for step (2), such extraction such as can comprise the mixture after filtering described first haptoreaction, by filter cake ethyl acetate washing 2-4 time, use washed with diethylether 2-4 time again, then vacuum drying.
According to the present invention, by step (1) products therefrom and formula X'-(CH in above-mentioned steps (2)
2)
n-R
1carry out the second haptoreaction, described support type bi-quaternary ammonium salt catalyst is had catalytic site-(CH is provided
2)
n-R
1structure.For this reason, the present invention is to formula X'-(CH
2)
n-R
1consumption be not particularly limited, as long as described support type bi-quaternary ammonium salt catalyst can be obtained, preferably, triethylene diamine and formula X'-(CH
2)
n-R
1mole dosage than for 1:1-3.
According to the present invention, to described second catalytic condition, also there is no particular limitation, as long as can obtain described support type bi-quaternary ammonium salt catalyst, preferably, described second catalytic condition comprises: temperature is 60-90 DEG C, is preferably 70-85 DEG C; Time is 1-48h, is preferably 12-24h.
As formula X'-(CH of the present invention
2)
n-R
1can select according to support type bi-quaternary ammonium salt catalyst provided by the present invention, such as, can be Br-(CH
2)
2-OH (2-bromoethanol), Br-CH
2-COOH (3-monobromo-acetic acid), Br-(CH
2)
2-NH
2(2-bromoethylamine), Br-(CH
2)
3-OH (3-bromo propyl alcohol), Br-CH
2-H (bromomethane), Br-CH
2-OH (bromo methyl alcohol), I-CH
2-OH (iodo methyl alcohol), Cl-CH
2-OH (chloro methyl alcohol).But one skilled in the art will appreciate that because X' is F
-, Cl
-, Br
-or I
-, the support type bi-quaternary ammonium salt catalyst of gained must have F
-, Cl
-, Br
-or I
-as anion, in order to the support type bi-quaternary ammonium salt catalyst of the anion with other kinds or single kind can be obtained, optionally, by step (2) products therefrom and containing F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more anion salt solution contact, to obtain anion X
-for F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more described support type bi-quaternary ammonium salt catalyst.That is, namely the product of step (2) gained can be used as described support type bi-quaternary ammonium salt catalyst, but also can by the mode of the product of step (2) gained by ion-exchange, anion exchange is become other kind, or by the multiple anion in the product of script step (2) gained by being exchanged into single anion.Such as, as needs preparation X
-for [BF
4]
-formula (1) shown in the support type bi-quaternary ammonium salt catalyst of structure time, can by the product of step (2) gained and NaBF
4water-soluble solution carry out contacting to carry out ion-exchange, can obtain.
According to the present invention, it is one or more in acetonitrile, toluene and dichloroethanes that described second haptoreaction can adopt solvent such as, the capacity of solvent is not particularly limited, such as relative to 1g step (1) products therefrom (referring to dry weight here), the consumption of solvent is 10-100mL, be preferably 10-50mL, be more preferably 13-25mL.
According to the present invention, can be extracted in the product of support type bi-quaternary ammonium salt catalyst Step (2) gained of gained by the extracting method of this area routine, such as filter the mixture after described second haptoreaction or filter optional product mixtures after ion-exchange, by filter cake ethyl acetate washing 2-4 time, use washed with diethylether 2-4 time again, then vacuum drying.
The support type bi-quaternary ammonium salt catalyst that the preparation method that present invention also offers above-mentioned support type bi-quaternary ammonium salt catalyst obtains.Preparation method due to above-mentioned support type bi-quaternary ammonium salt catalyst can adopt variety carrier and/or multiple formula X'-(CH
2)
n-R
1compound, therefore, the support type bi-quaternary ammonium salt catalyst of gained can be the mixture with the multiple support type bi-quaternary ammonium salt catalyst of various structures presented hereinabove.
Present invention also offers a kind of preparation method of cyclic carbonate, described cyclic carbonate is the compound shown in formula (2), wherein, the method comprises: in the presence of a catalyst, compound shown in formula (3) and carbon dioxide are carried out coupled reaction and obtains the cyclic carbonate shown in formula (2), wherein, described catalyst is one or more in the support type bi-quaternary ammonium salt catalyst that obtains of the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst or above-mentioned support type bi-quaternary ammonium salt catalyst;
Wherein, R
2and R
3be hydrogen independently of one another, the alkyl of C1-C6, by the alkyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, the alkoxyl of C1-C6, by the alkoxyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, phenyl, by the phenyl that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace, phenoxy group, by the phenoxy group that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace;
Or, R
2and R
3bonding forms 3-6 unit cycloaliphatic ring together, and this cycloaliphatic ring one or more substituting groups be optionally selected from halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace (this optionally refers to be substituted and also can not be replaced by these substituting groups).
According to the present invention, when adopting one or more of support type bi-quaternary ammonium salt catalyst provided by the invention as described catalyst, just can the coupled reaction that carries out with carbon dioxide of compound (i.e. epoxides) effectively shown in catalysis type (3), thus obtained cyclic carbonate shown in formula (2), this coupled reaction of repeatedly catalysis and described support type bi-quaternary ammonium salt catalyst can circulate, and still can reach higher catalytic efficiency, with high yield, highly selective obtains the cyclic carbonate shown in formula (2).As described catalyst support type bi-quaternary ammonium salt catalyst as described in above or preparation method above carries out obtaining, do not repeat them here.
According to the present invention, the compound shown in formula (3) is a kind of epoxides, from the viewpoint of can better with described catalyst complex, preferably, in above-mentioned formula (3), and R
2and R
3be hydrogen independently of one another, the alkyl of C1-C4, by the alkyl of the C1-C4 that one or more in halogen, C=C-and phenyl replace, phenyl, by the phenyl that one or more in the alkyl of C1-C4 and halogen replace, phenoxy group, by the phenoxy group that one or more in the alkyl of C1-C4 and halogen replace; Or, R
2and R
3bonding forms 3-6 unit cycloaliphatic ring together, and one or more substituting groups that this cycloaliphatic ring is optionally selected from halogen, C=C-and phenyl replaced.
More preferably, R
2and R
3be hydrogen, methyl, ethyl, propyl group, isopropyl, chloromethyl, pi-allyl, phenyl, benzyl, p-methylphenyl and phenoxy group independently of one another; Or, R
2and R
3bonding forms 5-6 unit cycloaliphatic ring together, and one or more substituting groups that this cycloaliphatic ring is optionally selected from halogen, C=C-and phenyl replaced.
Still more preferably, R
2and R
3be all hydrogen; Or R
2and R
3in one of them be hydrogen, another is selected from methyl, ethyl, propyl group, chloromethyl, pi-allyl, phenyl, benzyl and phenoxy group; Or, R
2and R
3bonding forms 6 yuan of cycloaliphatic rings together.
Compound shown in formula (3) is such as selected from the one in structure shown in following formula:
According to the present invention, below by way of concrete preparating mechanism the process that the compound shown in catalyst formula (3) provided by the present invention and carbon dioxide carry out coupled reaction carried out to the explanation in mechanism:
According to the present invention, to the consumption of described catalyst, there is no particular limitation, as long as above-mentioned catalytic process can be completed, preferably, relative to the compound shown in 1mol formula (3), the consumption of described catalyst makes the amount of the bi-quaternary ammonium salt (the bi-quaternary ammonium salt part that formula (1) represents) with triethylene diamine structure be 3-50mmol, is more preferably 5-45mmol, further be preferably 6-20mmol, most preferably be 9-16mmol.Meeting under above-mentioned condition, usually, when adopting support type bi-quaternary ammonium salt catalyst of the present invention as catalyst, relative to the compound shown in 1mol formula (3), the consumption of described catalyst can be 1-25g, is preferably 5-20g, is more preferably 10-20g.
According to the present invention, to the consumption of carbon dioxide, there is no particular limitation, can be the conventional amount used of this area.Usual carbon dioxide is except as except reactant, an effect is also had to be the pressure keeping reaction system, for this reason, the consumption of carbon dioxide can be determined according to the pressure of reaction system, such as, adopt the carbon dioxide of 0.3-10MPa (being preferably 0.3-5MPa).The partial pressure of carbon dioxide of reaction environment when the pressure (referring to absolute pressure) of carbon dioxide here refers to initial, those skilled in the art should be clear, when the compound shown in common formula (3) and carbon dioxide carry out the cyclic carbonate that coupled reaction obtains shown in formula (2), carbon dioxide keeps such dividing potential drop to be the amount being enough to provide the carbon dioxide that makes the compound complete reaction shown in formula (3), therefore, the effect that carbon dioxide is larger is to provide the pressure needed for reaction, certainly because the amount of the carbon dioxide reacted away in course of reaction also can not be lost too large by build-up of pressure.
According to the present invention, to the condition of described coupled reaction, also there is no particular limitation, the condition of this area routine can be adopted, but consider that being more suitable for catalyst of the present invention plays better catalytic activity, preferably, the condition of described coupled reaction comprises: temperature is 80-160 DEG C (being preferably 90-130 DEG C), and the time is 0.5-24h (being preferably 4-12h), and pressure is 0.3-10MPa.
According to the present invention, because catalyst of the present invention has the performance of good reusable edible, preferably, the method also comprises the reactant mixture after by described coupled reaction and filters and obtain solid phase and be catalyst, using the catalyst filtering gained as the coupled reaction of a new round part or whole described catalyst use.
According to the present invention, because catalyst of the present invention has higher catalytic activity, the preparation method of the cyclic carbonate shown in above-mentioned formula (2) can not adopt solvent, thus reduces cost to a greater extent, and it also avoid the side reaction that solvent causes.
According to the present invention, adopt support type bi-quaternary ammonium salt catalyst of the present invention as the catalyst in the preparation method of the cyclic carbonate shown in above-mentioned formula (2), higher yields ground, comparatively highly selective can obtain cyclic carbonate, such as yield can reach more than 85%, preferably reaches more than 95%.Selection rate can reach more than 90%, preferably can reach more than 99%.Especially catalyst circulation is being used more than 10 times, the yield of more than 95% and the selection rate of more than 99% can also reached.
Below will be described the present invention by embodiment.In following examples and comparative example: yield refers to weight × 100% of the weight/raw material of product.Selection rate is weight × 100% of weight/whole product of target compound.
In the support type bi-quaternary ammonium salt catalyst of gained (namely shown in formula (1)
part, also refers to DABCO) content be detected by the mode of elementary analysis to obtain.
H
1-NMR and C
13-NMR is measured by the nuclear magnetic resonance spectrometer of AVANCEIII500MHz model.
Embodiment 1
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
(1) by the styrene resin of the chloromethylation of 2g (purchased from the chlorine ball of company of Chemical Plant of Nankai Univ., there is 7%DVB be cross-linked, chlorinity is 17 % by weight, as follows) and the triethylene diamine of 19.2mmol join in the acetonitrile of 50mL, stir and react 24h at 35 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 3g.
(2) solid of step (1) gained is joined in the acetonitrile of 50mL, the 2-bromoethanol of 19.2mmol is added under stirring, and 24h is reacted at 75 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 4.1g, by the 1mol/L kbr aqueous solution mixing 12h of this solid and 100mL to carry out anion exchange, filter solid drying, thus obtain formula (1) middle n=2, R
1=OH and X
-=Br
-support type bi-quaternary ammonium salt catalyst 4.2g of the present invention, wherein the content of DABCO is 2.3mmol/g after measured.
Embodiment 2
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
(1) styrene resin of the chloromethylation of 1g and the triethylene diamine of 4.8mmol are joined in the acetonitrile of 30mL, stir and react 12h at 35 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 1.3g.
(2) solid of step (1) gained is joined in the acetonitrile of 30mL, the 2-monobromo-acetic acid of 4.8mol is added under stirring, and 20h is reacted at 80 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 1.9g, by the 1mol/L kbr aqueous solution mixing 12h of this solid and 50mL to carry out anion exchange, filter solid drying, thus obtain formula (1) middle n=1, R
1=COOH and X
-=Br
-support type bi-quaternary ammonium salt catalyst 2g of the present invention, wherein the content of DABCO is 2mmol/g after measured.
Embodiment 3
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
(1) styrene resin of the chloromethylation of 4g and the triethylene diamine of 9.6mol are joined in the dichloroethanes of 75mL, stir and react 20h at 40 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 5.0g.
(2) solid of step (1) gained is joined in the dichloroethanes of 75mL, the 2-bromoethylamine of 19.2mmol is added under stirring, and 12h is reacted at 75 DEG C, filter, filter cake is respectively washed 3 times with ethyl acetate and ether respectively, and vacuum drying obtains solid 6.1g, by the 1mol/L kbr aqueous solution mixing 12h of this solid and 100mL to carry out anion exchange, filter solid drying, thus obtain formula (1) middle n=2, R
1=NH
2and X
-=Br
-support type bi-quaternary ammonium salt catalyst 6.2g of the present invention, wherein the content of DABCO is 1.4mmol/g after measured.
Embodiment 4
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
Method according to embodiment 1, difference is, adopts 3-bromo propyl alcohol to replace 2-bromoethanol, thus obtains formula (1) middle n=3, R
1=OH and X
-=Br
-support type bi-quaternary ammonium salt catalyst 4.3g of the present invention, wherein the content of DABCO is 2.2mmol/g after measured.
Embodiment 5
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
Method according to embodiment 1, difference is, adopts bromomethane to replace 2-bromoethanol, thus obtains formula (1) middle n=1, R
1=H and X
-=Br
-support type bi-quaternary ammonium salt catalyst 4.1g of the present invention, wherein the content of DABCO is 2.4mmol/g after measured.
Embodiment 6
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
Method according to embodiment 1, difference is, adopts chloro methyl alcohol to replace 2-bromoethanol, does not need through ion-exchange step, thus obtains formula (1) middle n=1, R
1=OH and X
-=Cl
-support type bi-quaternary ammonium salt catalyst 4.1g of the present invention, wherein the content of DABCO is 2.35mmol/g after measured.
Embodiment 7
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
By the NaI aqueous solution 12h of the support type bi-quaternary ammonium salt catalyst of embodiment 6 gained and the 1mol/L of 100mL to carry out anion exchange, filter solid drying, thus n=1, R in obtaining formula (1)
1=OH and X
-=I
-support type bi-quaternary ammonium salt catalyst 5.7g of the present invention, wherein the content of DABCO is 2mmol/g after measured.
Embodiment 8
The present embodiment is for illustration of support type bi-quaternary ammonium salt Catalysts and its preparation method of the present invention.
By the NaBF of the support type bi-quaternary ammonium salt catalyst of embodiment 6 gained and the 1mol/L of 100mL
4aqueous solution 12h, to carry out anion exchange, filters solid drying, thus obtains formula (1) middle n=1, R
1=OH and X
-=[BF
4]
-support type bi-quaternary ammonium salt catalyst 4.25g of the present invention, wherein the content of DABCO is 2.25mmol/g after measured.
Product embodiments 1
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
In airtight autoclave, the support type bi-quaternary ammonium salt catalyst that the embodiment 1 adding 0.2g obtains and the epoxides (41.5mmol) shown in formula (3-2), and be filled with the carbon dioxide of 1.2MPa pressure, then at 120 DEG C, 2h is reacted,-10 DEG C are cooled to after reaction terminates, release excessive carbon dioxide, filter to isolate support type bi-quaternary ammonium salt catalyst, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, yield is 99%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=4.89 (m, 1H), 4.44 (m, 1H), 4.12 (m, 1H), 1.64 (d, 3H).
13cNMR (125MHz, CDCl
3) δ=157.13,74.74,72.07,17.30.
Product embodiments 2
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 2 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 99%.
Product embodiments 3
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 3 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 98%.
Product embodiments 4
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 4 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 99%.
Product embodiments 5
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 5 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 97%.
Product embodiments 6
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 6 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 93%.
Product embodiments 7
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 7 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 99%.
Product embodiments 8
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, employing be that support type bi-quaternary ammonium salt catalyst obtained by embodiment 8 replaces embodiment 1 to obtain, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 87%.
Product embodiments 9
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, passes into the CO of 0.3MPa
2, the pressure namely reacted is 0.3MPa, and the reaction time is 4h, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 99%.
Product embodiments 10
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, passes into the CO of 3MPa
2, the pressure namely reacted is 3MPa, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 99%.
Product embodiments 11
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, passes into the CO of 10MPa
2, the pressure namely reacted is 10MPa, and the reaction time is 4h, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 87%.
Product embodiments 12
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, the temperature of reaction is 90 DEG C, and the pressure of reaction is 2MPa, and the reaction time is 12h, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 98%.
Product embodiments 13
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, the temperature of reaction is 160 DEG C, and the reaction time is 0.5h, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 98%.
Product embodiments 14
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, adopt be the use of 10 times after catalyst (after employing 10 times by the support type bi-quaternary ammonium salt catalyst that embodiment 1 is obtained as catalyst), the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, and yield is 96%.
Product embodiments 15
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-1) product embodiments 1 of 30mmol, the liquid phase gas chromatographic analysis of gained, selection rate is 99.8%, yield is 99.2%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=4.40 (s, 4H).
13cNMR (125MHz, CDCl
3) δ=158.08,66.21.
Product embodiments 16
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-3) product embodiments 1 of 30mmol, reaction time is 4h, the liquid phase gas chromatographic analysis of gained, selection rate is 99%, and yield is 97%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=4.66 (m, 1H), 4.42 (m, 1H), 4.14 (m, 1H), 1.42 (m, 2H), 0.98 (t, 3H).
13cNMR (125MHz, CDCl
3) δ=156.71,78.41,71.52,24.08,9.65.
Product embodiments 17
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-4) product embodiments 1 of 25mmol, reaction time is 4h, the liquid phase gas chromatographic analysis of gained, selection rate is 99%, and yield is 96%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=5.11 (m, 1H), 4.49 (m, 1H), 4.24 (m, 1H), 3.95 (m, 1H), 3.64 (m, 1H).
13cNMR (125MHz, CDCl
3) δ=156.71,78.47,71.27,43.35.
Product embodiments 18
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-5) product embodiments 1 of 25mmol, reaction time is 8h, the liquid phase gas chromatographic analysis of gained, selection rate is 98%, and yield is 95%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=7.27-7.29 (m, 4H), 7.10 (m, 1H), 5.31 (t, 1H), 4.79 (m, 1H), 4.57 (m, 1H).
13cNMR (125MHz, CDCl
3) δ=158.25,137.61,128.74,128.21,126.77,80.90,73.04.
Product embodiments 19
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-6) product embodiments 1 of 30mmol, reaction pressure is 2MPa, reaction time is 8h, the liquid phase gas chromatographic analysis of gained, and selection rate is 95%, yield is 80%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=4.33 (m, 2H), 2.08 (m, 2H), 1.82 (m, 2H), 1.57-1.64 (m, 2H).
13cNMR (125MHz, CDCl
3) δ=154.94,77.82,26.80,24.51.
Product embodiments 20
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-7) product embodiments 1 of 35mmol, reaction pressure is 2MPa, reaction time is 8h, the liquid phase gas chromatographic analysis of gained, and selection rate is 98%, yield is 93%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=7.25 (t, 2H), 6.92-6.94 (m, 3H), 6.40 (t, 3H), 4.74 (m, 1H), 4.58 (m, 1H).
13cNMR (125MHz, CDCl
3) δ=156.55,154.15,129.76,122.70,118.73,100.55,70.63.
Product embodiments 21
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, what adopt is the epoxides shown in formula (3-2) adopted in the replacement of the epoxides shown in formula (3-8) product embodiments 1 of 30mmol, reaction pressure is 2MPa, reaction time is 8h, the liquid phase gas chromatographic analysis of gained, and selection rate is 98%, yield is 94%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=5.76 (m, 1H), 4.97-4.99 (m, 2H), 4.62 (m, 1H), 4.44 (m, 1H), 4.18 (m, 1H), 2.64 (m, 1H), 2.39 (m, 1H).
13cNMR (125MHz, CDCl
3) δ=156.71,135.21,117.03,78.56,71.49,34.39.
Product embodiments 23
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, reaction temperature is 80 DEG C, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 89%, nuclear-magnetism qualification result:
1hNMR (500MHz, CDCl
3) δ=4.89 (m, 1H), 4.44 (m, 1H), 4.12 (m, 1H), 1.64 (d, 3H).
13cNMR (125MHz, CDCl
3) δ=157.13,74.74,72.07,17.30.
Product embodiments 24
The present embodiment is for illustration of the preparation method of cyclic carbonate of the present invention.
Method according to product embodiments 1, difference is, catalyst amount is 0.1g, the liquid phase gas chromatographic analysis of gained, and selection rate is 99.5%, and yield is 90%, nuclear-magnetism qualification result:
1hNMR (500MHz, Chloroform) δ=δ=4.89 (m, 1H), 4.44 (m, 1H), 4.12 (m, 1H), 1.64 (d, 3H).
13cNMR (125MHz, CommonNMRSolvents) δ=157.13,74.74,72.07,17.30.
Comparative example 1
Method according to product embodiments 1, difference is, what adopt is the obtained support type bi-quaternary ammonium salt catalyst of embodiment 1 that the 1-methylimidazole salt (1-methylimidazole salt load capacity is 2.1mmol/g) of 0.2g styrene resin load replaces adopting in product embodiments 1, the liquid phase gas chromatographic analysis of gained, selection rate is 98%, and yield is 80%.
Comparative example 2
Method according to comparative example 1, difference is, the 1-methylimidazole salt (namely according to the 1-methylimidazole salt of the styrene resin load after the method catalysis 10 times of comparative example 1) being the use of the styrene resin load of 10 times adopted, the liquid phase gas chromatographic analysis of gained, selection rate is 98%, and yield is 70%.
Claims (10)
1. a support type bi-quaternary ammonium salt catalyst, is characterized in that, the carrier of this support type bi-quaternary ammonium salt catalyst is bonded with the bi-quaternary ammonium salt that formula (1) represents:
Wherein, X
-identical or different, X
-for F
-, Cl
-, Br
-, I
-, CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-or [NTf
2]
-; N is the integer of 1-6; R
1for H, OH, NH
2or COOH.
2. support type bi-quaternary ammonium salt catalyst according to claim 1, is characterized in that, when described support type bi-quaternary ammonium salt catalyst is 1g, the molar content of the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol.
3. a kind of support type bi-quaternary ammonium salt catalyst according to claim 1 and 2, is characterized in that, described carrier is one in silica, mesopore molecular sieve, fluoropolymer resin and combination thereof; Described mesopore molecular sieve is MCM-41 or SBA-15; Described fluoropolymer resin is the styrene resin of chloromethylation, shitosan or Field resin.
4. a preparation method for the support type bi-quaternary ammonium salt catalyst described in claim 1 or 2, is characterized in that, comprise the following steps:
(1) carrier and triethylene diamine are carried out the first haptoreaction, make triethylene diamine and support chemistry bonding obtain intermediate product; Described reaction temperature is 10-50 DEG C, and the reaction time is 1-24h; Described carrier and the usage ratio 1g:1-15mmol of triethylene diamine;
(2) by step (1) gained intermediate product and formula X'-(CH
2)
n-R
1carry out the support type bi-quaternary ammonium salt catalyst that the second haptoreaction obtains having triethylene diamine structure, triethylene diamine structure is the active component of support type bi-quaternary ammonium salt catalyst; Described X' is F
-, Cl
-, Br
-or I
-, n is the integer of 1-6, R
1for H, OH, NH
2or COOH; Described triethylene diamine and formula X'-(CH
2)
n-R
1mole dosage than for 1:1-3; Described reaction temperature is 60-90 DEG C, and the reaction time is 1-48h.
5. a preparation method for support type bi-quaternary ammonium salt catalyst according to claim 4, is characterized in that, comprise the following steps:
(1) carrier and triethylene diamine are carried out the first haptoreaction, make triethylene diamine and support chemistry bonding obtain intermediate product; Described reaction temperature is 10-50 DEG C, and the reaction time is 1-24h; Described carrier and the usage ratio 1g:1-15mmol of triethylene diamine;
(2) by step (1) gained intermediate product and formula X'-(CH
2)
n-R
1carry out the support type bi-quaternary ammonium salt catalyst that the second haptoreaction obtains having triethylene diamine structure, triethylene diamine structure is the active component of support type bi-quaternary ammonium salt catalyst; Described X' is F
-, Cl
-, Br
-or I
-, n is the integer of 1-6, R
1for H, OH, NH
2or COOH; Described triethylene diamine and formula X'-(CH
2)
n-R
1mole dosage than for 1:1-3; Described reaction temperature is 60-90 DEG C, and the reaction time is 1-48h.
6. the preparation method of support type bi-quaternary ammonium salt catalyst according to claim 4, it is characterized in that, the method also comprises, the support type bi-quaternary ammonium salt catalyst that step (2) is obtained with containing CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more anion salt solution contact, obtain anion X
-for CH
3cOO
-, NO
3 -, HSO
4 -, H
2pO
4 -, [OTf]
-, [BF
4]
-, [SbF
6]
-, [PF
6]
-[NTf
2]
-in one or more described support type bi-quaternary ammonium salt catalyst.
7. one kind utilizes the method for the support type bi-quaternary ammonium salt catalyst preparing cyclic carbonate described in claim 1 or 2, it is characterized in that, under support type bi-quaternary ammonium salt catalyst exists, compound shown in formula (3) and carbon dioxide are carried out coupled reaction and obtains the cyclic carbonate shown in formula (2), described coupled reaction temperature is 80-160 DEG C, time is 0.5-24h, and pressure is 0.3-10MPa;
Wherein, R
2and R
3be hydrogen independently of one another, the alkyl of C1-C6, by the alkyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, the alkoxyl of C1-C6, by the alkoxyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, phenyl, by the phenyl that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace, phenoxy group, by the phenoxy group that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace;
Or, R
2and R
3bonding forms 3-6 unit cycloaliphatic ring together, and one or more substituting groups that this cycloaliphatic ring is optionally selected from halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replaced.
8. one kind utilizes the method for the support type bi-quaternary ammonium salt catalyst preparing cyclic carbonate described in claim 3, it is characterized in that, under support type bi-quaternary ammonium salt catalyst exists, the compound shown in formula (3) and carbon dioxide are carried out coupled reaction and obtains the cyclic carbonate shown in formula (2);
Wherein, R
2and R
3be hydrogen independently of one another, the alkyl of C1-C6, by the alkyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, the alkoxyl of C1-C6, by the alkoxyl of the C1-C6 that one or more in halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replace, phenyl, by the phenyl that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace, phenoxy group, by the phenoxy group that one or more in the alkyl of C1-C4, halogen, hydroxyl, carboxyl and amino replace;
Or, R
2and R
3bonding forms 3-6 unit cycloaliphatic ring together, and one or more substituting groups that this cycloaliphatic ring is optionally selected from halogen, C=C-, phenyl, hydroxyl, carboxyl and amino replaced;
Described coupled reaction temperature is 80-160 DEG C, and the time is 0.5-24h, and pressure is 0.3-10MPa.
9. the method preparing cyclic carbonate according to claim 7, is characterized in that, during compound 1mol shown in formula (3), in described support type bi-quaternary ammonium salt catalyst, the amount of active component is 3-50mmol.
10. the method preparing cyclic carbonate according to claim 8, is characterized in that, during compound 1mol shown in formula (3), in described support type bi-quaternary ammonium salt catalyst, the amount of active component is 3-50mmol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715918A (en) * | 2016-08-10 | 2018-02-23 | 江苏苏博特新材料股份有限公司 | A kind of heterogeneous catalysis and the method for cyclic carbonate ester is prepared using it |
| CN111615510A (en) * | 2017-12-22 | 2020-09-01 | 新绿色世界有限公司 | Method for continuously preparing cyclic carbonate |
| CN111790438A (en) * | 2020-07-06 | 2020-10-20 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
| CN113996339A (en) * | 2021-10-12 | 2022-02-01 | 南京工业大学 | Catalyst for preparing cyclic carbonate and preparation method of cyclic carbonate |
| CN115475663A (en) * | 2022-09-05 | 2022-12-16 | 霖和气候科技(北京)有限公司 | DABCO type high-performance carbon dioxide adsorbent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336735A (en) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | Method for preparing cyclic carbonate by catalyzing with ionic liquid |
| CN102516220A (en) * | 2011-12-23 | 2012-06-27 | 中国科学院过程工程研究所 | Method for preparing annular carbonates through catalyzing by chemical supported polyhydroxy quaternary ammonium ionic liquid |
| CN102698799A (en) * | 2012-06-06 | 2012-10-03 | 湖南大学 | Polymer supported quaternary ammonium salt ion catalyst as well as preparation method and application thereof |
| CN102816182A (en) * | 2012-09-10 | 2012-12-12 | 南昌航空大学 | Phosphorus-containing dication ionic liquid as well as preparation method and application thereof |
| CN102838583A (en) * | 2012-09-10 | 2012-12-26 | 南昌航空大学 | Method for preparing cyclic carbonate by using functionalized quaternary phosphonium salt ionic liquid |
| CN103204840A (en) * | 2013-04-22 | 2013-07-17 | 南昌航空大学 | Method for preparing cyclic carbonate by using functional guanidinium ionic liquid |
-
2015
- 2015-12-09 CN CN201510916235.XA patent/CN105381819B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336735A (en) * | 2011-07-18 | 2012-02-01 | 中国科学院过程工程研究所 | Method for preparing cyclic carbonate by catalyzing with ionic liquid |
| CN102516220A (en) * | 2011-12-23 | 2012-06-27 | 中国科学院过程工程研究所 | Method for preparing annular carbonates through catalyzing by chemical supported polyhydroxy quaternary ammonium ionic liquid |
| CN102698799A (en) * | 2012-06-06 | 2012-10-03 | 湖南大学 | Polymer supported quaternary ammonium salt ion catalyst as well as preparation method and application thereof |
| CN102816182A (en) * | 2012-09-10 | 2012-12-12 | 南昌航空大学 | Phosphorus-containing dication ionic liquid as well as preparation method and application thereof |
| CN102838583A (en) * | 2012-09-10 | 2012-12-26 | 南昌航空大学 | Method for preparing cyclic carbonate by using functionalized quaternary phosphonium salt ionic liquid |
| CN103204840A (en) * | 2013-04-22 | 2013-07-17 | 南昌航空大学 | Method for preparing cyclic carbonate by using functional guanidinium ionic liquid |
Non-Patent Citations (2)
| Title |
|---|
| DAIWEI LI ET AL.: "Polymers anchored with carboxyl-functionalized di-cation ionic liqiuds as efficient catalysts for the fixation of CO2 into cyclic carbonates", 《CATALYSIS SCIENCE ＆ TECHNOLOGY》 * |
| 许燕等: "季铵盐与NHPI的协同催化氧化", 《济南大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715918A (en) * | 2016-08-10 | 2018-02-23 | 江苏苏博特新材料股份有限公司 | A kind of heterogeneous catalysis and the method for cyclic carbonate ester is prepared using it |
| CN107715918B (en) * | 2016-08-10 | 2020-08-07 | 江苏苏博特新材料股份有限公司 | Heterogeneous catalyst and method for preparing cyclic carbonate by using same |
| CN111615510A (en) * | 2017-12-22 | 2020-09-01 | 新绿色世界有限公司 | Method for continuously preparing cyclic carbonate |
| CN111615510B (en) * | 2017-12-22 | 2023-08-01 | 新绿色世界有限公司 | Process for the continuous preparation of cyclic carbonates |
| CN111790438A (en) * | 2020-07-06 | 2020-10-20 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
| CN111790438B (en) * | 2020-07-06 | 2021-12-03 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
| CN113996339A (en) * | 2021-10-12 | 2022-02-01 | 南京工业大学 | Catalyst for preparing cyclic carbonate and preparation method of cyclic carbonate |
| CN115475663A (en) * | 2022-09-05 | 2022-12-16 | 霖和气候科技(北京)有限公司 | DABCO type high-performance carbon dioxide adsorbent and preparation method thereof |
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