CN107163240A - 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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 are grafted with the transistion metal compound of chain-transferring agent；Wherein, transistion metal compound includes transition metal chalcogen and/or chalcogenide；The mol ratio of ionic liquid and transistion metal compound is (1~8):1.In the preparation process that the immobilized ionic-liquid catalyst is used for makrolon：Using dihydroxy compounds and carbonic diester as raw material, using melt transesterification process polycarbonate synthesis；Wherein, the mol ratio of carbonic diester and dihydroxy compounds is (1.01~1.2)：1, the consumption 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 has dramatically speeded up the process of makrolon industrial applications.
Description
Technical field
The present invention relates to the synthesis technical field of makrolon, and in particular to a kind of melt transesterification process polycarbonate synthesis
Immobilized ionic-liquid catalyst.
Background technology
Makrolon is total as the high molecular polymer for containing repeat unit carbonate group (- OROCO-) in strand
Claim, be a kind of engineering thermoplastic's material of high comprehensive performance, be also in global five large-engineering plastics a unique class possess well
The product of translucency, thus it is widely used in the fields such as electronic/electrical device product, building and automobile making.
The industrial process of makrolon 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, from carbonic diester and dihydroxyaromatic compound conduct
Raw material carries out ester exchange reaction；However, the method in kinetics as reversible reaction, exist equilibrium conversion it is low, reaction
The shortcomings of cycle is long.
In order to realize the continuous production of makrolon, the performance and yield of makrolon are improved, it is necessary in course of reaction
Middle addition catalyst.However, in the prior art, the type of selected catalyst not only influences reaction during melt transesterification
Speed, and certain side reaction (such as branched and crosslinking) can be caused, and then influence the performance of polymer；For example：Alkali metal, alkali
Oxide or hydroxide of earth metal etc. are used as conventional ester exchange catalyst, although can improve ester friendship to a certain extent
Reaction rate is changed, but still suffers from some conflicting and unsatisfactory situations；Lanthanide metal compound can make polymer
Heat endurance be improved, but such catalyst can introduce each heavy metal species in the polymer, so as to limit making for polymer
With；The catalyst of heterocycle structure such as triazine structure, metalloporphyrin complex structure have preferable ester exchange catalytic effect, but its activity
Shorter, cost of holding time is higher.
In recent years, ionic liquid is more and more paid close attention to based on its excellent physical and chemical performance by people, but
Directly applied in the building-up process of makrolon and still there are problems.Based on this, a kind of new catalysis is studied
Agent system, makes it to reduce side reaction again while catalytic fusion polymerization obtains polyphosphazene polymer carbonic ester, and improve product
Performance is particularly important.
The content of the invention
For defect of the prior art, the present invention is intended to provide a kind of melt transesterification process polycarbonate synthesis is consolidated
Loadization ionic-liquid catalyst.The immobilized ionic-liquid catalyst provided using the present invention, with dihydroxy compounds and carbonic acid
Diester is that raw material prepares makrolon：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, the catalyst thus prepared can not only realize immobilized ionic-liquid catalyst
In the slow releasing function of the building-up process of makrolon, and the catalyst have long lifespan, pollute less, reusable edible and energy
The drawbacks of enough significantly reducing the advantage of reaction cost, and then effectively overcome in traditional makrolon building-up process.
Therefore, the present invention provides 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 the further embodiment of the present invention, transistion metal compound is specifically included：It is grafted with the mistake of chain-transferring agent
Cross metallic compound nano ball.
In the further embodiment of the present invention, chain-transferring agent includes one kind in alkyl aluminum, alkyl magnesium and zinc alkyl
Or it is a variety of；Transistion metal compound includes the one or more in molybdenum oxide, molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide.
In the further embodiment of the present invention, the mol ratio of ionic liquid and transistion metal compound is (1~8):
1。
In the further embodiment of the present invention, ionic liquid selects acidic ion liquid, and acidic ion liquid bag
Include [Cn1MIM]Hn2XO4；Wherein, n1=3,4,5,6；n2=1,2；X=P, S.
Second aspect, the present invention provides a kind of preparation method of immobilized ionic-liquid catalyst, comprises the following steps：
S101：By ionic liquid, it is grafted with after the transistion metal compound nanosphere of chain-transferring agent is mixed with water and carries out mechanical agitation, it
Salt acid for adjusting pH value to 5 or so rear continuation are added afterwards to stir, and will continue the product stewing process after stirring；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 obtains immobilized ionic-liquid catalyst.It should be noted that drying time is according to this
Criterion in the usual drying processes of field is controlled；The addition of S101 reclaimed waters is not particularly limited.
In the further embodiment of the present invention, in S101, the churned mechanically time is 10~30min, continues to stir
Time be 30min~180min, time of stewing process is 12~24h, and stewing process is carried out in high-temperature kettle, high-temperature kettle
Temperature be 150~220 DEG C；In S102, centrifuge and carry out for several times, and in centrifugal separation processes, washed；In S103,
Vacuum drying temperature is 60~80 DEG C.
The third aspect, application of the immobilized ionic-liquid catalyst that the present invention is provided in makrolon is prepared, including
Following steps：Using dihydroxy compounds and carbonic diester as raw material, in the presence of immobilized ionic-liquid catalyst, using molten
Melt ester-interchange method polycarbonate synthesis；Wherein, the mol ratio of carbonic diester and dihydroxy compounds is (1.01~1.2)：1, Gu
The consumption of loadization ionic-liquid catalyst is the 0.5%~5% of dihydroxy compounds quality.
In the further embodiment of the present invention, the building-up process of makrolon includes Exchange Ester Process and polycondensation
Journey；Wherein, Exchange Ester Process is specially：Reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, and the reaction time is
1.5~2.5h, obtains prepolymer afterwards；Polycondensation process is specially：By prepolymer temperature be 260~300 DEG C, pressure be 27~
0.5~1h is reacted under conditions of 100Pa, makrolon is finally prepared.
In the further embodiment of the present invention, dihydroxy compounds is selected from aromatic dihydroxy compound, carbonic acid two
Ester is selected from diphenyl carbonate.It should be noted that the dihydroxy compounds of the present invention specifically selects bisphenol-A, scientific name：2,2- bis-
(4- hydroxy phenyls) propane, abbreviation diphenol propane；Certainly, it is also possible from other dihydroxy compounds.
The above-mentioned technical proposal that the present invention is provided has advantages below：
(1) applicant has found by numerous studies：The immobilized ionic-liquid catalyst provided using the present invention, with dihydroxy
Based compound and carbonic diester are that raw material prepares makrolon：It is by the physicochemical property that ionic liquid is excellent, its is immobilized in mistake
On the meso-porous nano ball for crossing metal chalcogen and/or chalcogenide, the catalyst thus prepared can not only be realized immobilized
Change ionic-liquid catalyst the building-up process of makrolon slow releasing function, and the catalyst have long lifespan, pollute less,
Reusable edible and the advantage that reaction cost can be significantly reduced, and then effectively overcome in traditional makrolon building-up process
Drawback.
(2) the immobilized ionic-liquid catalyst for providing the present invention is used in the building-up process of makrolon, and technique is steady
Fixed, yield is high, quality is good, energy consumption is low；And production can be completed using existing equipment, equipment requirement is reduced, so that significantly
Reduce production cost.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention one in immobilized ionic-liquid catalyst scanning electron microscope (SEM) photograph.
Embodiment
The embodiment to technical solution of the present invention is described in detail below.Following examples are only used for clearer
Explanation technical scheme, therefore be only used as example, and can not be limited the scope of the invention with this.
Experimental method in following embodiments, is conventional method unless otherwise specified.
Test material used, is to be commercially available from conventional reagent shop unless otherwise specified in following embodiments.
Quantitative test in following examples, is respectively provided with three repetition experiments, and data are the average value of three repetition 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 is from 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 mol ratio of sub- liquid and transistion metal compound is (1~8):1.
Preferably, transistion metal compound is specifically included：It is grafted with the transistion metal compound nanosphere of chain-transferring agent.Its
In, chain-transferring agent includes the one or more in alkyl aluminum, alkyl magnesium and zinc alkyl；Transistion metal compound include molybdenum oxide,
One or more in molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide.
In addition, the immobilized ionic-liquid catalyst provided for the present invention, the present invention specially provides preparation method, bag
Include following steps：
S101：By ionic liquid, it is grafted with after the transistion metal compound nanosphere of chain-transferring agent is mixed with water and carries out machine
Tool is stirred, and is added afterwards after salt acid for adjusting pH value and is continued to stir, and will continue the product stewing process after stirring.Wherein, machinery is stirred
The time mixed is 10~30min, and the time for continuing to stir is 30min~180min, and the time of stewing process is 12~24h, and
Stewing process is carried out in high-temperature kettle, and the temperature of high-temperature kettle is 150~220 DEG C.
S102：The obtained products of S101 are centrifuged, the head product of immobilized ionic-liquid catalyst is obtained.Its
In, centrifuge and carry out for several times, and in centrifugal separation processes, washed.
S103：The head product of immobilized ionic-liquid catalyst is dried in vacuo, immobilized ionic liquid is obtained and urges
Agent.Wherein, vacuum drying temperature is 60~80 DEG C.
In addition, the immobilized ionic-liquid catalyst provided for the present invention, uses it for the preparation process of makrolon
In, comprise 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 mol ratio of carbonic diester and dihydroxy compounds for (1.01~
1.2)：1, the consumption 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 building-up process of makrolon includes Exchange Ester Process and polycondensation process；Wherein, Exchange Ester Process is specific
For：Reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, and the reaction time is 1.5~2.5h, and pre-polymerization is obtained afterwards
Thing；Polycondensation process is specially：By prepolymer temperature be 260~300 DEG C, pressure be 27~100Pa under conditions of reaction 0.5~
1h, finally prepares makrolon.The Exchange Ester Process and polycondensation process of makrolon are specific as follows shown：
The Exchange Ester Process of makrolon
Polycarbonate polycondensation process
Illustrated with reference to embodiment：
Embodiment one
(1) preparation of immobilized ionic-liquid catalyst
S101：By 1mol ionic liquids [C4MIM]HSO4With 1mol be grafted with the molybdenum disulfide nano ball of diethyl zinc with
And mechanical agitation 10min after the mixing of 25mL water, then continue to stir 30min by salt acid for adjusting pH value to 5, afterwards turn product
Move in pyroreaction kettle, the still aging 24h at 150 DEG C.
S102：The product that S101 is obtained carries out high speed centrifugation, removes supernatant, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst, its scanning electron microscope (SEM) photograph (SEM) is as shown in Figure 1.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 165 DEG C, pressure obtains the performed polymer of makrolon to react 2.5h under 30kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio is 1.015:1, the consumption of immobilized ionic-liquid catalyst is the 0.5% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 300 DEG C, is in reactor vacuum
Polycondensation 1h under the conditions of 27Pa, obtains makrolon.
Embodiment two
(1) preparation of immobilized ionic-liquid catalyst
S101：By 3mol ionic liquids [C4MIM]HSO4With 1mol be grafted with the molybdenum disulfide nano ball of zinc methide with
And mechanical agitation 10min after the mixing of 25mL water, then by continuing to stir 30min after salt acid for adjusting pH value to 5, afterwards by product
It is transferred in pyroreaction kettle, the still aging 24h at 150 DEG C.
S102：The product that S101 is obtained carries out high speed centrifugation, removes supernatant, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 165 DEG C, pressure obtains the performed polymer of makrolon to react 2h under 30kPa；Wherein, diphenyl carbonate and bisphenol-A rub
You are than being 1.015:1, the consumption of immobilized ionic-liquid catalyst is the 0.5% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 300 DEG C, is in reactor vacuum
Polycondensation 1h under the conditions of 27Pa, obtains makrolon.
Embodiment three
(1) preparation of immobilized ionic-liquid catalyst
S101：By 8mol ionic liquids [C6MIM]HSO4With the 1mol molybdenum oxide nanosphere for being grafted with dibutyl zinc and
Mechanical agitation 30min after the mixing of 50mL water, then by continuing to stir 30min after salt acid for adjusting pH value to 5, afterwards turns product
Move 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, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 210 DEG C, pressure obtains the performed polymer of makrolon to react 1.5h under 100kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio be 1.2:1, the consumption of immobilized ionic-liquid catalyst is the 1% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 260 DEG C, is in reactor vacuum
Polycondensation 0.5h under the conditions of 100Pa, obtains makrolon.
Example IV
(1) preparation of immobilized ionic-liquid catalyst
S101：By 5mol ionic liquids [C4MIM]H2PO4With 1mol be grafted with the molybdenum oxide nanosphere of diethyl zinc with
And mechanical agitation 30min after the mixing of 50mL water, then by continuing to stir 30min after salt acid for adjusting pH value to 5, afterwards 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, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 200 DEG C, pressure obtains the performed polymer of makrolon to react 2h under 100kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio is 1.1:1, the consumption of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 270 DEG C, is in reactor vacuum
Polycondensation 0.5h under the conditions of 55Pa, obtains makrolon.
In addition, the advantage in order to further highlight immobilized ionic-liquid catalyst of the invention, carries out comparative testing below；
Formed it should be noted that following contrast experiment changes relevant parameter on the basis of example IV.
Comparative example one
(1) preparation of immobilized ionic-liquid catalyst
S101：By 5mol ionic liquids [C4MIM]H2PO4Mechanical agitation 30min, then passes through salt after being mixed with 50mL water
Acid for adjusting pH value is continuation stirring 30min after 5, and product is transferred in pyroreaction kettle afterwards, still aging at 190 DEG C
15h。
S102：The product that S101 is obtained carries out high speed centrifugation, removes supernatant, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 200 DEG C, pressure obtains the performed polymer of makrolon to react 2h under 100kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio is 1.1:1, the consumption of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 270 DEG C, is in reactor vacuum
Polycondensation 0.5h under the conditions of 55Pa, obtains makrolon.
Comparative example two
(1) preparation of immobilized ionic-liquid catalyst
S101：1mol is grafted with mechanical agitation 30min after the molybdenum oxide nanosphere of diethyl zinc is mixed with 50mL water,
Then by salt acid for adjusting pH value be 5 after continue stir 30min, product is transferred in pyroreaction kettle afterwards, at 190 DEG C
Still aging 15h.
S102：The product that S101 is obtained carries out high speed centrifugation, removes supernatant, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 200 DEG C, pressure obtains the performed polymer of makrolon to react 2h under 100kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio is 1.1:1, the consumption of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 270 DEG C, is in reactor vacuum
Polycondensation 0.5h under the conditions of 55Pa, obtains makrolon.
Comparative example three
(1) preparation of immobilized ionic-liquid catalyst
S101：By 5mol ionic liquids [C4MIM]H2PO4It is mechanical after being mixed with 1mol molybdenum oxides nanosphere and 50mL water
Stir 30min, then by salt acid for adjusting pH value be 5 after continue stir 30min, product is transferred to pyroreaction kettle afterwards
In, the still aging 15h at 190 DEG C.
S102：The product that S101 is obtained carries out high speed centrifugation, removes supernatant, add continue after the micro- ultrasound of ultra-pure water 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, mesoporous consolidate is obtained
Loadization ionic-liquid catalyst.
(2) synthesis of makrolon
Diphenyl carbonate, bisphenol-A and immobilized ionic-liquid catalyst are added in transesterification reactor, in reaction temperature
Spend for 200 DEG C, pressure obtains the performed polymer of makrolon to react 2h under 100kPa；Wherein, diphenyl carbonate and bisphenol-A
Mol ratio is 1.1:1, the consumption of immobilized ionic-liquid catalyst is the 3% of bisphenol-A quality.
Above-mentioned polycarbonate prepolymer body is entered after polycondensation reactor, temperature brings up to 270 DEG C, is in reactor vacuum
Polycondensation 0.5h under the conditions of 55Pa, obtains makrolon.
In addition, the advantage in order to preferably highlight the present invention, determines the aromatic polycarbonate receipts that each embodiment is prepared
Rate and performance etc., specifically as shown in Table 1 and Table 2.
The composition list of the immobilized ionic-liquid catalyst of each embodiment of table 1
| 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 makrolon of table 2
| Makrolon 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 the immobilized ionic-liquid catalyst provided using the present invention, what is prepared is poly-
Carbonic ester high income and performance is good.
Certainly, except the situation that embodiment one to example IV is enumerated, in the proportionings of other raw material components, preparation process
Each condition and parameter etc. are also possible.
The immobilized ionic-liquid catalyst provided using the present invention, using dihydroxy compounds and carbonic diester as raw material system
Standby makrolon：It is by the physicochemical property that ionic liquid is excellent, its is immobilized in transition metal chalcogen and/or chalcogenide
On meso-porous nano ball, the catalyst thus prepared can not only realize immobilized ionic-liquid catalyst in makrolon
The slow releasing function of building-up process, and the catalyst has long lifespan, pollutes less, reusable edible and can significantly reduce anti-
The drawbacks of answering the advantage of cost, and then effectively overcome in traditional makrolon building-up process.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implies relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".In the description of the invention,
" multiple " are meant that 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 to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of immobilized ionic-liquid catalyst, it is characterised 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.
2. immobilized ionic-liquid catalyst according to claim 1, it is characterised in that：
The transistion metal compound is specifically included：It is grafted with the transistion metal compound nanosphere of chain-transferring agent.
3. immobilized ionic-liquid catalyst according to claim 2, it is characterised in that：
The chain-transferring agent includes the one or more in alkyl aluminum, alkyl magnesium and zinc alkyl；
The transistion metal compound includes one kind or many in molybdenum oxide, molybdenum sulfide, zinc oxide, cobalt sulfide and titanium dioxide
Kind.
4. immobilized ionic-liquid catalyst according to claim 1, it is characterised in that：
The mol ratio of the ionic liquid and the transistion metal compound is (1~8):1.
5. the immobilized ionic-liquid catalyst according to any one of Claims 1 to 4, 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.
6. the preparation method of immobilized ionic-liquid catalyst according to claim 5, it is characterised in that including following step
Suddenly：
S101：By ionic liquid, be grafted with after the transistion metal compound nanosphere of chain-transferring agent is mixed with water carry out machinery stir
Mix, add afterwards after salt acid for adjusting pH value and continue to stir, the product stewing process after stirring is continued by described；
S102：The obtained products of the S101 are 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, the immobilized ionic liquid is obtained
Body catalyst.
7. the preparation method of immobilized ionic-liquid catalyst according to claim 6, it is characterised in that：
In the S101, the churned mechanically time is 10~30min, time of continuation stirring for 30min~
180min, time of the stewing process is 12~24h, and the stewing process is carried out in high-temperature kettle, the high-temperature kettle
Temperature is 150~220 DEG C；
In the S102, described centrifuge 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.
8. application of any one of Claims 1 to 5 immobilized ionic-liquid catalyst in makrolon is prepared, its feature
It is, comprises the following steps：
Using dihydroxy compounds and carbonic diester as raw material, in the presence of the immobilized ionic-liquid catalyst, using molten
Melt ester-interchange method polycarbonate synthesis；
Wherein, the mol ratio of the carbonic diester and the dihydroxy compounds is (1.01~1.2)：1, the immobilized ion
The consumption of liquid catalyst is the 0.5%~5% of the dihydroxy compounds quality.
9. application of the immobilized ionic-liquid catalyst in aromatic copolycarbonate is prepared according to claim 8, it is special
Levy and be：
The building-up process of the makrolon includes Exchange Ester Process and polycondensation process；
Wherein, the Exchange Ester Process is specially：Reaction temperature is 165~240 DEG C, and reaction pressure is 30~200kPa, reaction
Time is 1.5~2.5h, and prepolymer is obtained afterwards；
The polycondensation process is specially：By the prepolymer temperature be 260~300 DEG C, pressure be 27~100Pa under react
0.5~1h, finally prepares makrolon.
10. application of the immobilized ionic-liquid catalyst in aromatic copolycarbonate is prepared according to claim 8 or claim 9,
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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| CN101049575A (en) * | 2007-04-27 | 2007-10-10 | 陕西师范大学 | Solid carried multilaminar ion liquid, preparation method and application |
| KR20100052000A (en) * | 2008-11-10 | 2010-05-19 | 부산대학교 산학협력단 | Preparation of immobilized ionic liquid catalyst on porous amorphous silica and its use for the synthesis of five-membered cyclic carbonates |
| CN105642344A (en) * | 2015-12-24 | 2016-06-08 | 南京工业大学 | Immobilized ionic liquid catalyst and preparation method and application thereof |
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| KR20100052000A (en) * | 2008-11-10 | 2010-05-19 | 부산대학교 산학협력단 | Preparation of immobilized ionic liquid catalyst on porous amorphous silica and its use for the synthesis of five-membered cyclic carbonates |
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| CN110982054B (en) * | 2019-12-28 | 2021-03-12 | 中国科学院过程工程研究所 | Composite catalyst for catalytically synthesizing polycarbonate and method for catalytically synthesizing polycarbonate |
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