CN107163240B - The immobilized ionic-liquid catalyst of melt transesterification process polycarbonate synthesis - Google Patents
The immobilized ionic-liquid catalyst of melt transesterification process polycarbonate synthesis Download PDFInfo
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Abstract
The present invention relates to a kind of immobilized ionic-liquid catalyst of melt transesterification process polycarbonate synthesis, the raw material components of immobilized ionic-liquid catalyst include ionic liquid and the transistion metal compound for being grafted with chain-transferring agent；Wherein, transistion metal compound includes transition metal chalcogen and/or chalcogenide；The molar ratio of ionic liquid and transistion metal compound is (1~8): 1.The immobilized ionic-liquid catalyst is used in the preparation process of polycarbonate: using dihydroxy compounds and carbonic diester as raw material, using melt transesterification process polycarbonate synthesis；Wherein, the molar ratio of carbonic diester and dihydroxy compounds is (1.01~1.2): 1, the dosage of immobilized ionic-liquid catalyst is the 0.5%~5% of dihydroxy compounds quality.Process for synthetic catalyst of the present invention is simple, and catalyst choice and activity are high, and then have dramatically speeded up the process of polycarbonate industrial applications.
Description
Technical field
The present invention relates to the synthesis technical fields of polycarbonate, and in particular to a kind of melt transesterification process polycarbonate synthesis
Immobilized ionic-liquid catalyst.
Background technique
Polycarbonate is total as the high molecular polymer for containing repetitive unit carbonate group (- OROCO-) in strand
Claim, be a kind of engineering thermoplastic material of high comprehensive performance, and unique one kind possesses well in global five large-engineering plastics
The product of translucency, thus it is widely used in the fields such as electronic/electrical device product, building and automobile manufacture.
The industrial process of polycarbonate has phosgenation interface polycondensation and melt transesterification condensation methods, melt transesterification
Condensation methods are divided into conventional melt ester exchange polycondensation method and non-phosgene melt transesterification condensation methods again.Wherein, non-phosgene melting ester is handed over
The proper method that condensation methods are considered as current polycarbonate synthesis is changed, carbonic diester and dihydroxyaromatic compound conduct are selected
Raw material carries out ester exchange reaction；However, the method is used as reversible reaction in kinetics, low, reaction that there are equilibrium conversions
The disadvantages of period is long.
In order to realize the continuous production of polycarbonate, the performance and yield of polycarbonate are improved, is needed in reaction process
Middle addition catalyst.However, in the prior art, the type of selected catalyst not only influences to react during melt transesterification
Rate, and certain side reaction (such as branching and crosslinking) can be caused, and then influence the performance of polymer；Such as: alkali metal, alkali
Oxide or hydroxide of earth metal etc. are used as common ester exchange catalyst, although ester friendship can be improved to a certain extent
Reaction rate is changed, but there are still some conflicting and unsatisfactory situations；Lanthanide metal compound can make polymer
Thermal stability be improved, but such catalyst can introduce each heavy metal species in the polymer, to limit making for polymer
With；The catalyst of heterocycle structure such as triazine structure, metalloporphyrin complex structure have preferable transesterification catalytic effect, but its activity
It holds time shorter, higher cost.
In recent years, ionic liquid is more and more paid close attention to based on its excellent physical and chemical performance by people, however
Directly applied in the synthesis process of polycarbonate still that there are problems.Based on this, a kind of novel catalysis is studied
Agent system makes it can be reduced side reaction again while catalytic fusion polymerize and obtains polyphosphazene polymer carbonic ester, and improves product
Performance is particularly important.
Summary of the invention
For the defects in the prior art, the present invention is intended to provide a kind of melt transesterification process polycarbonate synthesis is consolidated
Loadization ionic-liquid catalyst.Using immobilized ionic-liquid catalyst provided by the invention, with dihydroxy compounds and carbonic acid
Diester is that raw material prepares polycarbonate: by the physicochemical property that ionic liquid is excellent, by its it is immobilized in transition metal chalcogen and/or
On the meso-porous nano ball of chalcogenide, immobilized ionic-liquid catalyst is not only may be implemented in the catalyst being thus prepared
In the slow releasing function of the synthesis process of polycarbonate, and the catalyst has service life length, pollutes less, can be recycled and energy
The advantage of reaction cost is enough significantly reduced, and then effectively overcomes the drawback in traditional polycarbonate synthesis process.
For this purpose, the invention provides the following technical scheme:
In a first aspect, the present invention provides a kind of immobilized ionic-liquid catalyst, the raw material components of catalyst include ion
Liquid and transistion metal compound；Wherein, transistion metal compound includes transition metal chalcogen and/or chalcogenide.
In further embodiment of the invention, transistion metal compound is specifically included: being grafted with the mistake of chain-transferring agent
Cross metallic compound nano ball.
In further embodiment of the invention, chain-transferring agent includes one of alkyl aluminum, alkyl magnesium and zinc alkyl
Or it is a variety of；Transistion metal compound includes one of molybdenum oxide, molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide or a variety of.
In further embodiment of the invention, the molar ratio of ionic liquid and transistion metal compound is (1~8):
1。
In further embodiment of the invention, ionic liquid selects acidic ion liquid, and acidic ion liquid packet
Include [Cn1MIM]Hn2XO4；Wherein, n1=3,4,5,6；n2=1,2；X=P, S.
Second aspect, the present invention provide a kind of preparation method of immobilized ionic-liquid catalyst, comprising the following steps:
S101: by ionic liquid, be grafted with chain-transferring agent transistion metal compound nanosphere mixed with water after carry out mechanical stirring, it
Salt acid for adjusting pH value is added afterwards to continuing to stir after 5 or so, the product stewing process after stirring will be continued；S102: S101 is obtained
To product be centrifuged, obtain the head product of immobilized ionic-liquid catalyst；S103: immobilized ionic liquid is urged
The head product of agent is dried in vacuo, and immobilized ionic-liquid catalyst is obtained.It should be noted that drying time is according to this
Judgment criteria in the usual drying processes of field controls；The additional amount of water is not particularly limited in S101.
In further embodiment of the invention, in S101, the churned mechanically time is 10~30min, continues to stir
Time be 30min~180min, time of stewing process is 12~for 24 hours, and stewing process carries out in high-temperature kettle, high-temperature kettle
Temperature be 150~220 DEG C；In S102, centrifuge separation is carried out for several times, and in centrifugal separation processes, is washed；In S103,
Vacuum drying temperature is 60~80 DEG C.
The third aspect, immobilized ionic-liquid catalyst provided by the invention are preparing the application in polycarbonate, including
Following steps: using dihydroxy compounds and carbonic diester as raw material, under the action of immobilized ionic-liquid catalyst, using molten
Melt ester-interchange method polycarbonate synthesis；Wherein, the molar ratio of carbonic diester and dihydroxy compounds is (1.01~1.2): 1, Gu
The dosage of loadization ionic-liquid catalyst is the 0.5%~5% of dihydroxy compounds quality.
In further embodiment of the invention, the synthesis process of polycarbonate includes Exchange Ester Process and polycondensation
Journey；Wherein, Exchange Ester Process specifically: reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, and the reaction time is
1.5~2.5h obtains prepolymer later；Polycondensation process specifically: by prepolymer temperature be 260~300 DEG C, pressure be 27~
0.5~1h is reacted under conditions of 100Pa, and polycarbonate is finally prepared.
In further embodiment of the invention, dihydroxy compounds is selected from aromatic dihydroxy compound, carbonic acid two
Ester is selected from diphenyl carbonate.It should be noted that dihydroxy compounds of the invention specifically selects bisphenol-A, scientific name: 2,2- bis-
(4- hydroxy phenyl) propane, abbreviation diphenol propane；Certainly, select other dihydroxy compounds also possible.
Above-mentioned technical proposal provided by the invention has the advantage that
(1) applicant has found by numerous studies: immobilized ionic-liquid catalyst provided by the invention is used, with dihydroxy
Based compound and carbonic diester are that raw material prepares polycarbonate: by the physicochemical property that ionic liquid is excellent, its is immobilized in mistake
It crosses on the meso-porous nano ball of metal chalcogen and/or chalcogenide, the catalyst being thus prepared not only may be implemented immobilized
Change ionic-liquid catalyst in the slow releasing function of the synthesis process of polycarbonate, and the catalyst has that the service life is long, pollution less,
Advantage Ke Xunhuanliyong and that reaction cost can be significantly reduced, and then effectively overcome in traditional polycarbonate synthesis process
Drawback.
(2) immobilized ionic-liquid catalyst provided by the invention is used in the synthesis process of polycarbonate, technique is steady
Determine, yield is high, high-quality, low energy consumption；And production can be completed using existing equipment, equipment requirement is reduced, thus significantly
Reduce production cost.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the immobilized ionic-liquid catalyst in the embodiment of the present invention one.
Specific embodiment
The embodiment of technical solution of the present invention will be described in detail below.Following embodiment is only used for clearer
Illustrate technical solution of the present invention, therefore be only used as example, and not intended to limit the protection scope of the present invention.
Experimental method in following embodiments is unless otherwise specified conventional method.
Test material as used in the following examples is unless otherwise specified to be commercially available from conventional reagent shop.
Quantitative test in following embodiment, is respectively provided with three repeated experiments, and data are the average value of three repeated experiments
Or mean+SD.
The present invention provides a kind of immobilized ionic-liquid catalyst, and the raw material components of catalyst include ionic liquid and transition
Metallic compound；Wherein, transistion metal compound includes transition metal chalcogen and/or chalcogenide.Ionic liquid selects acid
Property ionic liquid, and acidic ion liquid include [Cn1MIM]Hn2XO4；Wherein, n1=3,4,5,6；n2=1,2；X=P, S；From
The molar ratio of sub- liquid and transistion metal compound is (1~8): 1.
Preferably, transistion metal compound specifically includes: being grafted with the transistion metal compound nanosphere of chain-transferring agent.Its
In, chain-transferring agent includes one of alkyl aluminum, alkyl magnesium and zinc alkyl or a variety of；Transistion metal compound include molybdenum oxide,
One of molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide are a variety of.
In addition, being directed to immobilized ionic-liquid catalyst provided by the invention, the present invention specially provides preparation method, wraps
Include following steps:
S101: by ionic liquid, be grafted with chain-transferring agent transistion metal compound nanosphere mixed with water after carry out machine
Tool stirring, continues to stir after salt acid for adjusting pH value is added later, will continue the product stewing process after stirring.Wherein, machinery stirs
The time mixed is 10~30min, and the time for continuing stirring is 30min~180min, time of stewing process is 12~for 24 hours, and
Stewing process carries out in high-temperature kettle, and the temperature of high-temperature kettle is 150~220 DEG C.
S102: the product that S101 is obtained is centrifuged, and obtains the head product of immobilized ionic-liquid catalyst.Its
In, centrifuge separation carries out for several times, and in centrifugal separation processes, is washed.
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo, and is obtained immobilized ionic liquid and is urged
Agent.Wherein, vacuum drying temperature is 60~80 DEG C.
In addition, being directed to immobilized ionic-liquid catalyst provided by the invention, it is used for the preparation process of polycarbonate
In, comprising the following steps: using dihydroxy compounds and carbonic diester as raw material, in the effect of immobilized ionic-liquid catalyst
Under, using melt transesterification process polycarbonate synthesis；Wherein, the molar ratio of carbonic diester and dihydroxy compounds be (1.01~
1.2): 1, the dosage of immobilized ionic-liquid catalyst is the 0.5%~5% of dihydroxy compounds quality.Dihydroxy compounds
Selected from aromatic dihydroxy compound, carbonic diester is selected from diphenyl carbonate.
Preferably, the synthesis process of polycarbonate includes Exchange Ester Process and polycondensation process；Wherein, Exchange Ester Process is specific
Are as follows: reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, and the reaction time is 1.5~2.5h, obtains pre-polymerization later
Object；Polycondensation process specifically: by prepolymer temperature be 260~300 DEG C, pressure be 27~100Pa under conditions of reaction 0.5~
Polycarbonate is finally prepared in 1h.Shown in the Exchange Ester Process and polycondensation process of polycarbonate are specific as follows:
The Exchange Ester Process of polycarbonate
Polycarbonate polycondensation process
It is illustrated With reference to embodiment:
Embodiment one
(1) preparation of immobilized ionic-liquid catalyst
S101: by 1mol ionic liquid [C4MIM]HSO4With the molybdenum disulfide nano ball for being grafted with diethyl zinc of 1mol with
And mechanical stirring 10min after the mixing of 25mL water, then continue to stir 30min by salt acid for adjusting pH value to 5, later turns product
Move in pyroreaction kettle, at 150 DEG C it is still aging for 24 hours.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 60 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst, scanning electron microscope (SEM) photograph (SEM) are as shown in Figure 1.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 165 DEG C, and pressure is to react 2.5h under 30kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio is 1.015:1, and the dosage of immobilized ionic-liquid catalyst is the 0.5% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 300 DEG C, is in reactor vacuum degree
Polycondensation 1h under the conditions of 27Pa, obtains polycarbonate.
Embodiment two
(1) preparation of immobilized ionic-liquid catalyst
S101: by 3mol ionic liquid [C4MIM]HSO4With the molybdenum disulfide nano ball for being grafted with zinc methide of 1mol with
And mechanical stirring 10min after the mixing of 25mL water, then by continuing to stir 30min after salt acid for adjusting pH value to 5, later by product
Be transferred in pyroreaction kettle, at 150 DEG C it is still aging for 24 hours.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 60 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 165 DEG C, and pressure is to react 2h under 30kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A rub
, than being 1.015:1, the dosage of immobilized ionic-liquid catalyst is the 0.5% of bisphenol-A quality for you.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 300 DEG C, is in reactor vacuum degree
Polycondensation 1h under the conditions of 27Pa, obtains polycarbonate.
Embodiment three
(1) preparation of immobilized ionic-liquid catalyst
S101: by 8mol ionic liquid [C6MIM]HSO4With the molybdenum oxide nanosphere for being grafted with dibutyl zinc of 1mol and
Mechanical stirring 30min after the mixing of 50mL water later turns product then by continuing to stir 30min after salt acid for adjusting pH value to 5
It moves in pyroreaction kettle, the still aging 12h at 220 DEG C.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 80 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 210 DEG C, and pressure is to react 1.5h under 100kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio be 1.2:1, the dosage of immobilized ionic-liquid catalyst is the 1% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 260 DEG C, is in reactor vacuum degree
Polycondensation 0.5h under the conditions of 100Pa, obtains polycarbonate.
Example IV
(1) preparation of immobilized ionic-liquid catalyst
S101: by 5mol ionic liquid [C4MIM]H2PO4With the molybdenum oxide nanosphere for being grafted with diethyl zinc of 1mol with
And mechanical stirring 30min after the mixing of 50mL water, then by continuing to stir 30min after salt acid for adjusting pH value to 5, later by product
It is transferred in pyroreaction kettle, the still aging 15h at 190 DEG C.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 70 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 200 DEG C, and pressure is to react 2h under 100kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio is 1.1:1, and the dosage of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 270 DEG C, is in reactor vacuum degree
Polycondensation 0.5h under the conditions of 55Pa, obtains polycarbonate.
In addition, the advantages of in order to further highlight immobilized ionic-liquid catalyst of the invention, carry out following comparative testing；
It is formed it should be noted that following comparative experiments changes relevant parameter on the basis of example IV.
Comparative example one
(1) preparation of immobilized ionic-liquid catalyst
S101: by 5mol ionic liquid [C4MIM]H2PO4Mechanical stirring 30min, then passes through salt after mixing with 50mL water
Acid for adjusting pH value continues to stir 30min after being 5, and product is transferred in pyroreaction kettle later, still aging at 190 DEG C
15h。
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 70 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 200 DEG C, and pressure is to react 2h under 100kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio is 1.1:1, and the dosage of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 270 DEG C, is in reactor vacuum degree
Polycondensation 0.5h under the conditions of 55Pa, obtains polycarbonate.
Comparative example two
(1) preparation of immobilized ionic-liquid catalyst
S101: mechanical stirring 30min after the molybdenum oxide nanosphere for being grafted with diethyl zinc of 1mol is mixed with 50mL water,
Then pass through after salt acid for adjusting pH value is 5 and continue to stir 30min, product is transferred in pyroreaction kettle later, at 190 DEG C
Still aging 15h.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 70 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 200 DEG C, and pressure is to react 2h under 100kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio is 1.1:1, and the dosage of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 270 DEG C, is in reactor vacuum degree
Polycondensation 0.5h under the conditions of 55Pa, obtains polycarbonate.
Comparative example three
(1) preparation of immobilized ionic-liquid catalyst
S101: by 5mol ionic liquid [C4MIM]H2PO4It is mechanical after being mixed with 1mol molybdenum oxide nanosphere and 50mL water
30min is stirred, then passes through after salt acid for adjusting pH value is 5 and continues to stir 30min, product is transferred to pyroreaction kettle later
In, the still aging 15h at 190 DEG C.
S102: the product that S101 is obtained carries out high speed centrifugation, removes supernatant, be added after the micro- ultrasound of ultrapure water continue from
The heart removes supernatant, is repeated twice rear taking precipitate, obtains mesoporous immobilized ionic-liquid catalyst head product；
S103: the head product of immobilized ionic-liquid catalyst is dried in vacuo at 70 DEG C, obtains mesoporous consolidate
Loadization ionic-liquid catalyst.
(2) synthesis of polycarbonate
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Degree is 200 DEG C, and pressure is to react 2h under 100kPa, obtains the performed polymer of polycarbonate；Wherein, diphenyl carbonate and bisphenol-A
Molar ratio is 1.1:1, and the dosage of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
After above-mentioned polycarbonate prepolymer body is entered polycondensation reactor, temperature is increased to 270 DEG C, is in reactor vacuum degree
Polycondensation 0.5h under the conditions of 55Pa, obtains polycarbonate.
In addition, measuring the aromatic polycarbonate that each embodiment is prepared in order to preferably highlight advantage of the invention and receiving
Rate and performance etc., it is specific as shown in Table 1 and Table 2.
The composition list of the 1 immobilized ionic-liquid catalyst of each embodiment of table
| Ionic liquid | Chain-transferring agent | Transistion metal compound | |
| Embodiment one | [C4MIM]HSO4 | Zinc alkyl | Molybdenum disulfide |
| Embodiment two | C4MIM]HSO4 | Zinc alkyl | Molybdenum disulfide |
| Embodiment three | [C6MIM]HSO4 | Zinc alkyl | Molybdenum oxide |
| Example IV | [C4MIM]H2PO4 | Zinc alkyl | Molybdenum oxide |
| Comparative example one | [C4MIM]H2PO4 | -- | -- |
| Comparative example two | -- | Zinc alkyl | Molybdenum oxide |
| Comparative example three | [C4MIM]H2PO4 | -- | Molybdenum oxide |
The yield and capabilities list of each embodiment polycarbonate of table 2
| Polycarbonate yield/% | Mn | Mw/Mn | |
| Embodiment one | 95.6% | 2.7×104 | 1.15 |
| Embodiment two | 96.2% | 3.0×104 | 1.11 |
| Embodiment three | 96.8% | 4.2×104 | 1.05 |
| Example IV | 97.5% | 3.9×104 | 1.09 |
| Comparative example one | 77.8% | 1.3×104 | 1.37 |
| Comparative example two | 73.2% | 1.5×104 | 1.32 |
| Comparative example three | 71.5% | 1.5×104 | 1.42 |
From list data as can be seen that using immobilized ionic-liquid catalyst provided by the invention, what is be prepared is poly-
Carbonic ester high income and performance is good.
Certainly, the case where being enumerated in addition to embodiment one to example IV, in the proportions of other raw material components, preparation process
Each condition and parameter etc. are also possible.
Using immobilized ionic-liquid catalyst provided by the invention, using dihydroxy compounds and carbonic diester as raw material system
Standby polycarbonate: by the physicochemical property that ionic liquid is excellent, its is immobilized in transition metal chalcogen and/or chalcogenide
On meso-porous nano ball, immobilized ionic-liquid catalyst is not only may be implemented in polycarbonate in the catalyst being thus prepared
The slow releasing function of synthesis process, and the catalyst has service life length, pollutes less, can be recycled and can significantly reduce instead
The advantage of cost is answered, and then effectively overcomes the drawback in traditional polycarbonate synthesis process.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (8)
1. a kind of immobilized ionic-liquid catalyst, which is characterized in that the raw material components of the catalyst include ionic liquid and
Transistion metal compound；
Wherein, the transistion metal compound includes transition metal chalcogen and/or chalcogenide；
The transistion metal compound specifically includes: being grafted with the transistion metal compound nanosphere of chain-transferring agent；
The chain-transferring agent includes one of alkyl aluminum, alkyl magnesium and zinc alkyl or a variety of, and transistion metal compound includes oxygen
Change one of molybdenum, molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide or a variety of.
2. immobilized ionic-liquid catalyst according to claim 1, it is characterised in that:
The molar ratio of the ionic liquid and the transistion metal compound is (1~8): 1.
3. immobilized ionic-liquid catalyst according to claim 1 or 2, it is characterised in that:
The ionic liquid selects acidic ion liquid, and the acidic ion liquid includes [Cn1MIM]Hn2XO4；Wherein, n1=
3,4,5,6；n2=1,2；X=P, S.
4. the preparation method of immobilized ionic-liquid catalyst according to claim 3, which is characterized in that including following step
It is rapid:
S101: by ionic liquid, be grafted with chain-transferring agent transistion metal compound nanosphere mixed with water after carry out machinery stir
It mixes, continues to stir after salt acid for adjusting pH value is added later, continue the product stewing process after stirring for described；
S102: the obtained product of the S101 is centrifuged, the head product of immobilized ionic-liquid catalyst is obtained；
S103: the head product of the immobilized ionic-liquid catalyst is dried in vacuo, and obtains the immobilized ionic liquid
Body catalyst.
5. the preparation method of immobilized ionic-liquid catalyst according to claim 4, it is characterised in that:
In the S101, the churned mechanically time be 10~30min, it is described continue stirring time be 30min~
180min, time of the stewing process is 12~for 24 hours, and the stewing process carries out in high-temperature kettle, the high-temperature kettle
Temperature is 150~220 DEG C；
In the S102, the centrifuge separation is carried out for several times, and in centrifugal separation processes, is washed；
In the S103, the vacuum drying temperature is 60~80 DEG C.
6. any one of claims 1 to 3 immobilized ionic-liquid catalyst is preparing the application in polycarbonate, feature
It is, comprising the following steps:
Using dihydroxy compounds and carbonic diester as raw material, under the action of the immobilized ionic-liquid catalyst, using molten
Melt ester-interchange method polycarbonate synthesis；
Wherein, the molar ratio of the carbonic diester and the dihydroxy compounds is (1.01~1.2): 1, the immobilized ion
The dosage of liquid catalyst is the 0.5%~5% of the dihydroxy compounds quality.
7. immobilized ionic-liquid catalyst is preparing the application in aromatic copolycarbonate according to claim 6, special
Sign is:
The synthesis process of the polycarbonate includes Exchange Ester Process and polycondensation process；
Wherein, the Exchange Ester Process specifically: reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, reaction
Time is 1.5~2.5h, obtains prepolymer later；
The polycondensation process specifically: by the prepolymer temperature be 260~300 DEG C, pressure be 27~100Pa under react
Polycarbonate is finally prepared in 0.5~1h.
8. immobilized ionic-liquid catalyst described according to claim 6 or 7 is preparing the application in aromatic copolycarbonate,
It is characterized in that:
The dihydroxy compounds is selected from aromatic dihydroxy compound, and the carbonic diester is selected from diphenyl carbonate.
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