CN113292530B - Method for preparing cyclic carbonate from quaternary phosphonium salt - Google Patents
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- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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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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- C07D317/10—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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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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Abstract
In order to overcome the problems of insufficient catalyst activity and low yield of target products in the existing process for preparing cyclic carbonate by using a quaternary phosphonium salt catalyst, the invention provides a method for preparing cyclic carbonate by using carbon dioxide and an epoxy compound as reactants, and the method is characterized in that under the condition that the quaternary phosphonium salt shown in a structural formula 1 is used as a catalyst and no solvent exists, the carbon dioxide and the epoxy compound react to generate the cyclic carbonate;
Description
Technical Field
The invention belongs to the technical field of preparation of cyclic carbonates, and particularly relates to a method for preparing cyclic carbonates from quaternary phosphonium salts.
Background
In the chemical fields of medicine synthesis, coating, fiber treatment, lubricating oil synthesis and the like, the cyclic carbonate is an important chemical product, especially in the field of lithium ion batteries, is one of the most commonly used solvents and additives in the existing electrolyte, and can effectively improve the cycle performance of the lithium ion batteries.
Cyclic carbonates have different preparation methods, and in the early days, cyclic carbonates for chemical use were mainly prepared by reacting ethylene glycol with phosgene, however, phosgene has a certain environmental pollution and is forbidden by some countries. The subsequent cyclic carbonate preparation methods include an ester exchange method and a cycloaddition method, wherein the cycloaddition method is used for preparing the cyclic carbonate mainly by catalyzing the reaction between the epoxy compound and the carbon dioxide through a catalyst, and the selection of a proper catalyst is a key point of whether the reaction can be smoothly performed.
The existing quaternary phosphonium salt ionic liquid is widely applied to cycloaddition synthesis of cyclic carbonate because of simple preparation and various types, however, the existing quaternary phosphonium salt ionic liquid has low activity, and can show better catalytic activity and stability only by being added with metal oxide or being matched with transition metal halide, metal oxide and organic halide or being assisted by solvent, thereby improving the complexity of the preparation process and being unfavorable for separation of reaction products; on the other hand, the existing quaternary phosphonium salt ionic liquid catalyst has poor selectivity on reaction products, and increases the separation difficulty of target products. Therefore, how to develop a quaternary phosphonium salt catalyst with high catalytic activity and high product selectivity is a key to solve the above problems.
Disclosure of Invention
Aiming at the problems of insufficient catalyst activity and low yield of target products in the existing process for preparing cyclic carbonate by using a quaternary phosphonium salt catalyst, the invention provides a preparation method for preparing cyclic carbonate by using quaternary phosphonium salt.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a method for preparing cyclic carbonate by using quaternary phosphonium salt, which adopts carbon dioxide and epoxy compound as reactants, and enables the carbon dioxide and the epoxy compound to react to generate the cyclic carbonate under the condition of taking the quaternary phosphonium salt shown in a structural formula 1 as a catalyst and no solvent;
wherein R is 1 、R 2 、R 3 Each independently selected from a hydrocarbon group having 1 to 15 carbon atoms, a halogenated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic aromatic hydrocarbon group, or a group in which at least one hydrogen atom of the above groups is substituted with a hydroxyl group; r is R 4 Selected from single bond or saturated or unsaturated hydrocarbon group with 1-15 carbon atoms, carbonyl, carboxylate group or carbonate group; r is R 5 Selected from saturated or unsaturated hydrocarbon groups having 1 to 8 carbon atoms, aromatic hydrocarbon groups, heterocyclic aromatic hydrocarbon groups, or at least one hydrogen atom of the above groups is halogenatedA plain or hydroxy substituted group; x is X - Selected from F – 、Cl – 、Br – 、I – 、BF 4 – 、BF 6 – 、ClO 4 – 、BH 4 – 、SbF 6 – 、ZnCl 3 – 、SnCl 3 – 、CF 3 SO 3 – 、NO 2 – 、NO 3 – 、N(FSO 2 ) 2 – 、N(CF 3 SO 2 ) 2 – 、C(CF 3 SO 2 ) 3 – 、CF 3 COO – 、CF 3 SO 3 – Or CH (CH) 3 SO 3 – 。
Alternatively, R 1 、R 2 、R 3 Each independently selected from a hydrocarbon group having 1 to 15 carbon atoms, a halogenated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic aromatic hydrocarbon group or a hydroxy-substituted aromatic hydrocarbon group, and R 1 、R 2 、R 3 At least one of which is selected from heterocyclic aromatic hydrocarbon groups; r is R 4 Selected from single bond or saturated or unsaturated hydrocarbon group with 1-15 carbon atoms, carbonyl, carboxylate group or carbonate group; r is R 5 Is selected from unsaturated hydrocarbon groups with 1-8 carbon atoms, aromatic hydrocarbon groups or heterocyclic aromatic hydrocarbon groups.
Alternatively, the heterocyclic aromatic hydrocarbon group is selected from imidazolyl, pyrrolyl or thienyl.
Optionally, in the quaternary phosphonium salt shown in the structural formula 1, R 4 And R is 5 At least one of them is selected from unsaturated hydrocarbon groups.
Alternatively, R 1 、R 2 、R 3 Each independently selected from phenyl, tolyl, ethylphenyl, propylphenyl, hydroxyphenyl, imidazolyl, propyl, bromoethyl or bromopropyl, R 4 Selected from ethylene, 2-alkenyl-propylene,
R 5 Selected from methyl, ethyl, propyl, ethenyl, propenyl, bromoethyl, hydroxyethyl or 1, 1-tribromopropyl.
Optionally, the quaternary phosphonium salt represented by structural formula 1 is selected from one or more of the following compounds:
optionally, the molar ratio of the epoxy compound to the catalyst is 1: 1X 10 -3 ～5×10 -3 。
Optionally, the catalyst comprises at least two quaternary phosphonium salts shown in the structural formula 1, wherein the molar ratio of any one of the quaternary phosphonium salts is at least 1%.
Alternatively, when the quaternary phosphonium salt in the catalyst is two or more, the catalyst comprises R 4 And R is 5 At least one quaternary phosphonium salt selected from unsaturated hydrocarbon groups.
Alternatively, the epoxy compound is selected from the group consisting of compounds represented by structural formula 2:
wherein R is 6 And R is 7 Each independently selected from H or alkyl, alkenyl, haloalkyl, aryl or heterocyclic aryl groups containing 1 to 10 carbon atoms, R 6 And R is 7 Are connected with each other to form a ring or not.
Optionally, the reaction temperature of the reaction of the carbon dioxide and the epoxy compound is 100-200 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 0.5-2 h; preferably, the reaction temperature is 120-160 ℃, the reaction pressure is 1-3 MPa, and the reaction time is 0.5-1 h.
According to the method for preparing the cyclic carbonate by using the quaternary phosphonium salt, which is shown in the structural formula 1, the quaternary phosphonium salt shown in the structural formula 1 has better catalytic activity than the existing quaternary phosphonium salt when being used as a catalyst for preparing the cyclic carbonate by a cycloaddition method, and can have obviously excellent catalytic activity without the assistance of other solvents, transition metal halides, metal oxides, organic halides and the like, so that the reaction time of cycloaddition reaction is shortened, the reaction efficiency is improved, the selectivity of a target product is especially improved, the generation of byproducts is effectively reduced, the operation difficulty of a preparation process is further reduced, the material selection of the catalyst is reduced, and meanwhile, the separation difficulty of the target product is also reduced.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a method for preparing cyclic carbonate by using quaternary phosphonium salt, which adopts carbon dioxide and an epoxy compound as reactants, and enables the carbon dioxide and the epoxy compound to react to generate the cyclic carbonate under the condition that the quaternary phosphonium salt shown in a structural formula 1 is used as a catalyst and no solvent exists;
wherein R is 1 、R 2 、R 3 Each independently selected from a hydrocarbon group having 1 to 15 carbon atoms, a halogenated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic aromatic hydrocarbon group, or a group in which at least one hydrogen atom of the above groups is substituted with a hydroxyl group; r is R 4 Selected from single bond or saturated or unsaturated hydrocarbon group with 1-15 carbon atoms, carbonyl, carboxylate group or carbonate group; r is R 5 Selected from saturated or unsaturated hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic aromatic hydrocarbon groups, and C1-C8 hydrocarbon groups,Or a group in which at least one hydrogen atom of the above groups is substituted with halogen or hydroxy; x is X - Selected from F – 、Cl – 、Br – 、I – 、BF 4 – 、BF 6 – 、ClO 4 – 、BH 4 – 、SbF 6 – 、ZnCl 3 – 、SnCl 3 – 、CF 3 SO 3 – 、NO 2 – 、NO 3 – 、N(FSO 2 ) 2 – 、N(CF 3 SO 2 ) 2 – 、C(CF 3 SO 2 ) 3 – 、CF 3 COO – 、CF 3 SO 3 – Or CH (CH) 3 SO 3 – 。
When the quaternary phosphonium salt shown in the structural formula 1 is used as a catalyst for preparing cyclic carbonate by a cycloaddition method, the catalyst has better catalytic activity than the existing quaternary phosphonium salt, can have obviously excellent catalytic activity without the assistance of other solvents, transition metal halides, metal oxides, organic halides and the like, shortens the reaction time of cycloaddition reaction, improves the reaction efficiency, particularly improves the selectivity of target products, effectively reduces the generation of byproducts, is beneficial to reducing the operation difficulty of the preparation process, reduces the material selection of the catalyst, and simultaneously reduces the separation difficulty of the target products.
Examples of the saturated hydrocarbon group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 4-methylpentyl, hexyl, heptyl, 2-hexylhexyl, 1-dimethylpentyl, octyl, 3, 7-dimethyloctyl, nonyl and decyl.
Examples of the unsaturated hydrocarbon group include: vinyl, 1-methylvinyl, 1-ethylvinyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-methyl-1-butenyl, 1, 3-butadienyl, 1-pentenyl, 2-pentenyl, 4-methyl-1-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1, 5-hexadienyl, 2-heptenyl, 2-octenyl, 2-nonenyl, and 2-decenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-methyl-1-butynyl, 3-dimethyl-1-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 1-methyl-3-pentynyl, 1-methyl-3-hexynyl, 2-heptynyl, 2-octynyl, 2-nonynyl and 2-decynyl.
As the aromatic hydrocarbon group, phenyl group, 1-naphthyl group and 2-naphthyl group can be exemplified.
Examples of the heterocyclic aromatic hydrocarbon group include pyrimidine, furan, pyrrole, thiophene, imidazole, thiazole, pyridine, benzofuran, and indole.
Examples of the halogen include: F. cl, br and I.
In the description of the present invention, a carbonyl group having 1 to 15 carbon atoms refers to a group having a branched or straight aliphatic chain and having 1 to 15 total carbon atoms, and an ester group having 1 to 15 carbon atoms and a carbonate group having 1 to 15 carbon atoms may be defined and understood as modified.
In some embodiments, R 1 、R 2 、R 3 Each independently selected from a hydrocarbon group having 1 to 15 carbon atoms, a halogenated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic aromatic hydrocarbon group or a hydroxy-substituted aromatic hydrocarbon group, and R 1 、R 2 、R 3 At least one of which is selected from heterocyclic aromatic hydrocarbon groups; r is R 4 Selected from single bond or saturated or unsaturated hydrocarbon group with 1-15 carbon atoms, carbonyl, carboxylate group or carbonate group; r is R 5 Is selected from unsaturated hydrocarbon groups with 1-8 carbon atoms, aromatic hydrocarbon groups or heterocyclic aromatic hydrocarbon groups.
Compared with the common aromatic hydrocarbon, the heterocyclic aromatic hydrocarbon is more beneficial to the improvement of the catalytic activity of the quaternary phosphonium salt shown in the structural formula 1, and R is 4 And R is 5 On the premise that the groups of (3) are consistent,if R is 1 、R 2 、R 3 When part or all of the quaternary phosphonium salt is selected from heterocyclic aromatic hydrocarbon groups, the quaternary phosphonium salt has better catalytic activity compared with the aromatic hydrocarbon groups, halogenated hydrocarbon groups, aromatic hydrocarbon groups or hydroxyl substituted aromatic hydrocarbon groups.
In a preferred embodiment, the heterocyclic aromatic hydrocarbon group is selected from imidazolyl, pyrrolyl or thienyl.
In some embodiments, R in the quaternary phosphonium salt of formula 1 4 And R is 5 At least one of them is selected from unsaturated hydrocarbon groups.
The presence of unsaturated hydrocarbon groups can coordinate in the quaternary phosphorus structure, due to R 4 And R is 5 The existence of the m-O strengthens the action, so that the binding force between the quaternary phosphonium salt structure and an intermediate product is weakened in the catalysis process, the quaternary phosphonium salt structure and the intermediate product are easier to separate (the step is a step of fast speed), the balance is shifted to the right, and the yield of a target product is improved.
In some embodiments, R 1 、R 2 、R 3 Each independently having 1 to 15 carbon atoms, R 4 Has 1 to 15 carbon atoms, R 5 The number of carbon atoms of (2) is 1 to 8.
If said R 1 、R 2 、R 3 、R 4 、R 5 If the number of carbon atoms is too large, the quaternary phosphonium salt tends to be unstable in structure, and is further decomposed during the reaction to be deactivated, or by-products which are difficult to separate are left in the reaction product.
In some embodiments, R 1 、R 2 、R 3 Each independently selected from phenyl, tolyl, ethylphenyl, propylphenyl, hydroxyphenyl, imidazolyl, propyl, bromoethyl or bromopropyl, R 4 Selected from ethylene, 2-alkenyl-propylene,
R 5 Selected from methyl, ethyl, propyl, ethenyl, propenyl, bromoethyl, hydroxyethyl or 1, 1-tribromopropyl. .
In some embodiments, the quaternary phosphonium salt of formula 1 is selected from one or more of the following compounds:
the above is a part of the compounds claimed in the present invention, but is not limited thereto, and should not be construed as limiting the present invention.
In some embodiments, in the method for preparing cyclic carbonate from the quaternary phosphonium salt, the molar ratio of the epoxy compound and the quaternary phosphonium salt represented by structural formula 1 is 1: 1X 10 -3 ～5×10 -3 I.e. 1mol of epoxide is added corresponding to 1X 10 -3 ～5×10 -3 And mol quaternary phosphonium salt shown in a structural formula 1.
In a more preferred embodiment, the molar ratio of the epoxide to the catalyst is 1: 2X 10 -3 ～3.5×10 -3 。
The cycloaddition reaction of the epoxy compound can be realized by adding the quaternary phosphonium salt shown in the structural formula 1 in a very small amount, and excessive quaternary phosphonium salt cannot have a more remarkable lifting effect on the reaction, so that the production cost is increased, and particularly, excessive addition of the quaternary phosphonium salt shown in the structural formula 1 easily causes impurities to be mixed in the generated product, so that the purity of the target product is not improved.
In some embodiments, the quaternary phosphonium salt of formula 1 comprises at least two quaternary phosphonium salts of formula 1, wherein the molar ratio of any one of the quaternary phosphonium salts is at least 1%.
The inventor finds that compared with the single quaternary phosphonium salt shown in the structural formula 1 for catalytic reaction by carrying out combination experiments on the quaternary phosphonium salt shown in the structural formula 1, the combination of the two quaternary phosphonium salts shown in the structural formula 1 greatly prolongs the retention time of the catalytic activity of the quaternary phosphonium salt on the premise of keeping excellent catalytic activity, and presumably has certain interaction between functional groups between the two quaternary phosphonium salts so as to be beneficial to keeping the structural stability between the two quaternary phosphonium salts and further avoid the inactivation caused by the change of chemical structures in the long-term circulation process.
In a preferred embodiment, when the quaternary phosphonium salt in the catalyst is two or more, the catalyst comprises R 4 And R is 5 At least one quaternary phosphonium salt selected from unsaturated hydrocarbon groups.
As described above, the presence of the unsaturated hydrocarbon group can cause coordination in the quaternary phosphonium salt structure to enhance the selectivity of the target product, while the simultaneous presence of two quaternary phosphonium salts is advantageous for enhancing the stability of the catalyst in the long-term cycle process, and further, by the combination of the quaternary phosphonium salt containing the unsaturated hydrocarbon group and the quaternary phosphonium salt represented by other structural formula 1, a combination catalyst having high catalytic activity and strong component stability can be obtained.
In some embodiments, when two quaternary phosphonium salts are added as catalysts, the lower molar content of quaternary phosphonium salt is 1% to 50% of the total catalyst. Preferably, the quaternary phosphonium salt with a smaller molar content accounts for 5% -45% of the total catalyst, and more preferably, the quaternary phosphonium salt with a smaller molar content accounts for 10% -30% of the total catalyst.
If the amount of one of the two quaternary phosphonium salts is too small, the effect of the mutual combination is difficult to achieve.
In a preferred embodiment, the X - Selected from F – 、Cl – 、Br – 、I – 。
In a more preferred embodiment, the X - Selected from Cl – 、Br – 。
As the epoxy compound in the production method provided by the present invention, the choice of other substituent groups than the epoxy ring, that is, the compound having at least one epoxy ring (3-membered ring composed of 2 carbon atoms and one oxygen atom) in the structural formula can be all subjected to cycloaddition reaction by the present production method to produce a cyclic carbonate, for example, the epoxy compound may be selected from ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, vinyl ethylene oxide, trifluoromethyl ethylene oxide, cyclohexene oxide, styrene oxide, butadiene monooxide, butadiene dioxide, 2-methyl-3-phenylbutene oxide, pinene oxide, tetracyanoethylene oxide and the like.
In some embodiments, the epoxy compound is selected from the group consisting of compounds represented by structural formula 2:
wherein R is 6 And R is 7 Each independently selected from H or alkyl, alkenyl, haloalkyl, aryl or heterocyclic aryl groups containing 1 to 10 carbon atoms, R 6 And R is 7 Are connected with each other to form a ring or not.
In some embodiments, R 6 And R is 7 Each independently selected from H, -CH 3 、-C 2 H 3 、-CH 2 Cl、-C 2 H 5 、-C 4 H 9 、-C 6 H 5 、-C 4 H 9 O、-C 7 H 7 O or-C 8 H 7 O。
When the epoxy compound shown in the structural formula 2 is adopted for cycloaddition reaction to generate cyclic carbonate, the reaction equation is as follows:
in some embodiments, the reaction temperature of the reaction of the carbon dioxide and the epoxy compound is 100-200 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 0.5-2 h.
In a preferred embodiment, the reaction temperature of the reaction of the carbon dioxide and the epoxy compound is 120-160 ℃, the reaction pressure is 1-3 MPa, and the reaction time is 0.5-1 h.
The invention is further illustrated by the following examples.
Examples 1 to 29
This example is illustrative of the process of preparing cyclic carbonates from quaternary phosphonium salts disclosed herein, comprising the following operative steps:
(1) Into a 100mL stainless steel autoclave, an addition amount of a catalyst as shown in examples 1 to 29 in tables 1 to 3 was added.
(2) Epoxy compounds 1M as shown in examples 1 to 29 in tables 1 to 3 were introduced into a stainless steel autoclave;
(3) The reaction kettle is closed, carbon dioxide is flushed, and the pressure of the system is kept to be about 1.0MPa;
(4) Heating the reaction gas, and controlling the temperature to slowly rise by a temperature controller, wherein the final temperature is controlled at 130 ℃;
(5) Then controlling the pressure of the carbon dioxide to be 2.0Mpa;
(6) After 1h of reaction, cooling to room temperature, discharging the reaction kettle, absorbing excessive carbon dioxide by using saturated sodium carbonate solution, and distilling the obtained liquid under reduced pressure to obtain the product of the cyclic carbonate.
Comparative examples 1 to 8
This example is a comparative illustration of the process of preparing cyclic carbonates from the quaternary phosphonium salts disclosed herein, comprising the majority of the steps of example 1, except that:
in the step (1), the catalyst was added in the amounts shown in comparative examples 1 to 8 in tables 1 to 2.
In the step (2), the epoxy compounds 1M shown in comparative examples 1 to 8 in tables 1 to 2 were introduced into a stainless steel autoclave.
Performance testing
(1) The ethylene carbonates prepared in examples 1 to 12 and comparative examples 1 to 4 were quantitatively analyzed, the yield of the cyclic carbonate was calculated based on the ratio of the added raw materials, and the selectivity was calculated by the percentage of the objective product to the product, and is recorded in table 1:
TABLE 1
The data of comparative examples 1 to 12 and comparative examples 1 to 4 show that the use of the quaternary phosphonium salt represented by structural formula 1 of the present invention as a catalyst can more effectively increase the yield of cyclic carbonates and the selectivity of target products than the use of no catalyst or other types of additives, indicating that the quaternary phosphonium salt provided by the present invention has excellent catalytic activity, effectively reduces the production of by-products, and increases the duty ratio of the target products in the products.
As can be seen from the data of comparative examples 1 to 6, as the amount of the catalyst added increases, the selectivity and yield of the target product are improved and then reduced, and in particular, when the molar ratio of the epoxy compound to the quaternary phosphonium salt represented by structural formula 1 is 1: 3.2X10 -3 The catalyst has the highest catalytic effect.
As can be seen from the data of comparative examples 4, 9, 10 and examples 7, 8, 11, 12, in the quaternary phosphonium salt represented by structural formula 1, when R 4 And R is 5 At least one of the quaternary phosphonium salts is selected from unsaturated hydrocarbon groups, so that the selectivity of the obtained quaternary phosphonium salt to the cyclic carbonate in the cycloaddition reaction can be effectively improved, and the yield is improved.
(2) The ethylene carbonates prepared in examples 13 to 21 and comparative examples 5 to 8 were quantitatively analyzed, the yield of cyclic carbonate was calculated from the ratio of the added starting materials, the selectivity was calculated by the percentage of the target product to the product, and is reported in Table 2:
TABLE 2
The data of comparative examples 13 to 21 and comparative examples 5 to 8 show that when methyl ethylene oxide or 1, 3-diazadien pentacyclic ethylene oxide is used as the epoxy compound, the quaternary phosphonium salt represented by structural formula 1 provided by the present invention is used as the catalyst to more effectively improve the yield of cyclic carbonate and the selectivity of the target product, and the quaternary phosphonium salt represented by structural formula 1 has universality for the catalytic effect of cycloaddition reaction of different epoxy compounds.
As is clear from the comparison of examples 13 and 14, and examples 18 and 19, too large an addition amount of the quaternary phosphonium salt represented by the formula 1 adversely decreases the catalytic effect thereof, and also results in an increase in the material cost.
As can be seen from the data of comparative examples 13, 14, 16, 17, 20, 21 and examples 15, 18, 19, in the quaternary phosphonium salt represented by structural formula 1, R is as follows 1 、R 2 、R 3 When at least one of the quaternary phosphonium salts is selected from imidazolyl, the obtained quaternary phosphonium salt has better catalytic activity, and is beneficial to improving the selectivity and the yield of the target product.
(3) The ethylene carbonate prepared in examples 4, 7, 9 to 12, 22 to 29 was quantitatively analyzed, the yield of the cyclic carbonate was calculated according to the ratio of the added raw materials, the selectivity was calculated by the percentage of the target product to the product, the catalyst was recycled and repeatedly reacted to the 10 th batch of material, the yield of the cyclic carbonate at the 10 th cycle was calculated according to the ratio of the added raw materials, and recorded in table 3:
TABLE 3 Table 3
Compared with the single use of the quaternary phosphonium salt shown in the structural formula 1, the test results of the comparative examples 4, 7, 9-12 and 22-29 show that when any two compounds 1-15 provided by the invention are combined to serve as catalysts, the selectivity of target products and the yield of primary reaction are improved to a certain extent, and particularly, the material combination mode greatly improves the activity maintenance of the quaternary phosphonium salt catalysts in the long-term recycling process, which shows that the stability of the quaternary phosphonium salt catalysts in the catalytic reaction process can be effectively improved, the service life of the quaternary phosphonium salt catalysts can be prolonged, and the material combination mode has important significance for saving the production cost.
The test results of comparative examples 22 to 29 revealed that when two quaternary phosphonium salt catalysts were used in combination, the addition amount of one quaternary phosphonium salt catalyst having a smaller addition amount was 25% to 50% of the total addition amount, and better stability was obtained.
The data of comparative examples 23-26, 28 and examples 27, 29 demonstrate that when two quaternary phosphonium salt catalysts are used in combination, the combination of quaternary phosphonium salts comprising both unsaturated hydrocarbon groups and other quaternary phosphonium salts provides the best selectivity for the desired product and cyclic stability of catalytic activity.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. A method for preparing cyclic carbonate by using quaternary phosphonium salt is characterized in that carbon dioxide and an epoxy compound are used as reactants, and the carbon dioxide and the epoxy compound are reacted to generate the cyclic carbonate under the condition of taking the quaternary phosphonium salt shown in a structural formula 1 as a catalyst and no solvent;
wherein R is 1 、R 2 、R 3 Each independently selected from phenyl, tolyl, ethylphenyl, propylphenyl, hydroxyphenyl, imidazolyl, propyl, bromoethyl or bromopropyl, R 4 Selected from ethylene,
R 5 Selected from methyl, ethyl, propyl, ethenyl, propenyl, bromoethyl, hydroxyethyl or 1, 1-tribromopropyl; or, the compound shown in the structural formula 1 is selected from
X-is selected from F – 、Cl – 、Br – 、I – 、BF 4 – 、BF 6 – 、ClO 4 – 、BH 4 – 、SbF 6 – 、ZnCl 3 – 、SnCl 3 – 、CF 3 SO 3 – 、NO 2 – 、NO 3 – 、N(FSO 2 ) 2 – 、N(CF 3 SO 2 ) 2 – 、C(CF 3 SO 2 ) 3 – 、CF 3 COO – 、CF 3 SO 3 – Or CH (CH) 3 SO 3 – ；
The reaction equation for generating cyclic carbonate by cycloaddition reaction of epoxy compound is as follows:
wherein R is 6 And R is 7 Each independently selected from H or alkyl, alkenyl, haloalkyl, aryl or heterocyclic aryl groups containing 1 to 10 carbon atoms, R 6 And R is 7 Are connected with each other to form a ring or not;
the catalyst comprises at least two quaternary phosphonium salts shown in the structural formula 1, wherein the molar addition of one quaternary phosphonium salt catalyst with smaller addition accounts for 25% -50% of the total addition.
2. The method for preparing cyclic carbonate according to claim 1, wherein the quaternary phosphonium salt represented by structural formula 1 is selected from one or more of the following compounds:
3. the method for preparing cyclic carbonate according to claim 1, wherein the molar ratio of the epoxy compound to the catalyst is 1: 1X 10 -3 ～5×10 -3 。
4. The method for preparing cyclic carbonate according to claim 1, wherein the reaction temperature of the reaction of carbon dioxide and the epoxy compound is 100-200 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 0.5-2 h.
5. The method for preparing cyclic carbonate from quaternary phosphonium salt according to claim 4, wherein the reaction temperature is 120-160 ℃, the reaction pressure is 1-3 MPa, and the reaction time is 0.5-1 h.
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