CN116333278A - Polymerization process and device of carbon dioxide-based polycarbonate copolymer - Google Patents
Polymerization process and device of carbon dioxide-based polycarbonate copolymer Download PDFInfo
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- CN116333278A CN116333278A CN202310484358.5A CN202310484358A CN116333278A CN 116333278 A CN116333278 A CN 116333278A CN 202310484358 A CN202310484358 A CN 202310484358A CN 116333278 A CN116333278 A CN 116333278A
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 238
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 121
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 121
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 95
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 45
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011344 liquid material Substances 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 62
- 239000003054 catalyst Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 18
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 18
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims description 11
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 11
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- PLFLRQISROSEIJ-UHFFFAOYSA-N methylborane Chemical compound CB PLFLRQISROSEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 2
- YUPAWYWJNZDARM-UHFFFAOYSA-N tri(butan-2-yl)borane Chemical compound CCC(C)B(C(C)CC)C(C)CC YUPAWYWJNZDARM-UHFFFAOYSA-N 0.000 claims description 2
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- -1 triethylboron-bis (triphenylphosphine) ammonium chloride Chemical group 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 230000005501 phase interface Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 125000005587 carbonate group Chemical group 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003046 tetrablock copolymer Polymers 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/087—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polymerization process and a polymerization device of a carbon dioxide-based polycarbonate copolymer. The polymerization process and the device of the carbon dioxide-based polycarbonate copolymer can be operated intermittently or continuously, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase in an upper space in the reaction kettle through the distributor, and then enter the external heat exchanger again for circulation through a lower liquid phase in the reaction kettle so as to provide a sufficient reaction phase interface, the chain quantity of the carbonic ester can not be reduced after amplification, and the risk of temperature runaway is avoided. In addition, in the whole reaction process, the carbon dioxide does not transfer mass with the outside, so that the carbon dioxide does not need to be recovered, the energy consumption is reduced, and the safety risk caused by compression recovery of the carbon dioxide containing propylene oxide is avoided.
Description
Technical Field
The invention relates to the field of high molecular polymer synthesis, in particular to a polymerization process and a polymerization device of a carbon dioxide-based polycarbonate copolymer.
Background
The massive use of fossil energy has prompted the development of the global industry, and also has led to serious greenhouse effects due to increased carbon dioxide emissions. The development and application of the carbon dioxide-based polycarbonate synthesized by taking carbon dioxide as a raw material greatly relieves the environmental pollution problem and the greenhouse effect caused by the existence of a large amount of carbon dioxide.
The carbon dioxide-based polycarbonate is polymerized from carbon dioxide and a comonomer comprising one or more of an epoxy compound (e.g., propylene oxide, cyclohexane oxide, epichlorohydrin), phthalic anhydride, and the like.
CN113929890a and CN111333825A disclose the preparation of carbon dioxide based polycarbonate tetrablock copolymers, both using one pot process, however, at commercial scale up this process results in lower quality of carbon dioxide embedded in the polymer segments, meaning lower amounts of carbonate segments and more significant changes as the degree of scale up is greater.
CN100516115C discloses a process for producing polycarbonate, which uses carbon dioxide and epoxy compound as main raw materials, and makes polymerization reaction under the action of catalyst, wherein the reaction is performed by using a loop reactor, and the main equipment comprises the loop reactor, a condenser, a gas-liquid separator, a high-pressure carbon dioxide buffer tank, a carbon dioxide compressor, a mixing kettle and a high-pressure metering pump. The process avoids the problem that the chain link amount of the carbonic ester becomes low during the amplification to a certain extent, but the energy consumption is increased because a large amount of unreacted carbon dioxide and propylene oxide mixed gas needs to flow out of the upper part of the loop reactor and be condensed and recovered by a condenser; in addition, since propylene oxide in the mixture is not completely separated, it is unavoidable that propylene oxide is still present in the recovered carbon dioxide, and when the recovered carbon dioxide is compressed again by a compressor, safety risks are increased.
CN111804218A discloses a process and equipment for producing carbon dioxide-based polycarbonate, in which a straight tube reactor is adopted as a main reactor, and a recovered carbon dioxide adding device and a primary mixture adding device are connected to the bottom of the straight tube reactor, and because carbon dioxide needs to be recovered through a condensation system, the energy consumption is increased, the recovered carbon dioxide is still mixed with propylene oxide, and the safety risk is increased when the recovered carbon dioxide is pumped back again.
CN100569830C discloses a method and apparatus for preparing aliphatic polycarbonate, wherein the polymerization reaction apparatus adopts a jacketed reaction kettle, and after the amplification of the process apparatus, the reaction temperature time required for the former stage to rise is prolonged, the product quality is reduced, the temperature in the later stage polymerization reaction process is not easy to control, and the temperature is easy to fly.
Disclosure of Invention
In order to solve the defects and problems in the prior art, the invention provides a polymerization process and a polymerization device of a carbon dioxide-based polycarbonate copolymer, which can be operated intermittently or continuously, and the carbon dioxide-based polycarbonate copolymer is produced by taking carbon dioxide and a comonomer as main raw materials and carrying out polymerization under the action of a catalyst.
In a first aspect of the present invention, there is provided a polymerization process for a carbon dioxide-based polycarbonate copolymer comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle, and introducing carbon dioxide under stirring to maintain the pressure in the reaction kettle at 0.12-7.5MPa;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase of an upper space in the reaction kettle through a distributor, and then enter the external heat exchanger again for circulation through a lower liquid phase in the reaction kettle; the external heat exchanger maintains the temperature of the materials in the reaction kettle to be 45-140 ℃, and the materials are discharged after the materials react for 4-70 hours;
c) And separating unreacted comonomer from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer.
In some embodiments, the polymerization process is a batch operation comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle at one time, and introducing carbon dioxide under stirring to maintain the pressure in the reaction kettle at 0.12-7.5MPa;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase in the upper space in the reaction kettle through the distributor, then enter the external heat exchanger again for circulation through a liquid phase in the lower part of the reaction kettle, and are discharged after the liquid materials are subjected to circulation reaction for 4-70 hours; the external heat exchanger maintains the temperature of materials in the reaction kettle to be 45-140 ℃;
c) And separating unreacted comonomer from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer.
In some embodiments, the polymerization process is a continuous operation comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle respectively at a certain flow rate, introducing carbon dioxide to maintain the pressure in the reaction kettle at 0.12-7.5MPa, and stirring;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase of an upper space in the reaction kettle through a distributor, and then enter the external heat exchanger again for circulation through a lower liquid phase in the reaction kettle; the external heat exchanger maintains the temperature of materials in the reaction kettle to be 45-140 ℃; the liquid material is discharged after the average residence time of the liquid material in the reaction kettle is 4-70 hours, and the liquid level in the reaction kettle is kept constant by controlling the continuous discharge flow rate;
c) And separating unreacted comonomer from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer.
In a specific embodiment, in step a), the comonomer comprises one or more of an epoxy compound, phthalic anhydride; the epoxy compound includes propylene oxide, cyclohexane oxide and epichlorohydrin.
In a specific embodiment, in step a), the comonomer comprises an epoxy compound and phthalic anhydride, wherein the molar ratio of epoxy compound to phthalic anhydride is greater than 1.
In a specific embodiment, in step a), the comonomer is propylene oxide, phthalic anhydride, epoxycyclohexane, wherein the molar ratio of the sum of propylene oxide and epoxycyclohexane to phthalic anhydride is 2-9:1, preferably 2-5:1, more preferably 2.5-4:1; in particular embodiments, the molar ratio of cyclohexane oxide to propylene oxide is from 0.001 to 0.2:1, preferably from 0.05 to 0.15:1, and more preferably from 0.08 to 0.1:1.
In a specific embodiment, in step a), the catalyst is a lewis acid base complex catalyst; wherein the Lewis acid is an organoboron compound such as triethylboron, triphenylboron, tributylboron, tri-sec-butylboron, and methylboron; the Lewis base is an organic amine (salt) such as bis (triphenylphosphine) ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium chloride, 1, 8-diazabicyclo [5.4.0] undec-7-ene.
In a specific embodiment, in the step a), the catalyst is a triethylboron-bis (triphenyl-n-phosphate) ammonium chloride composite catalyst, wherein the molar ratio of triethylboron to bis (triphenyl-n-phosphate) ammonium chloride is 2-10:1, preferably 3-8:1.
In a specific embodiment, in step a), the molar ratio of catalyst to comonomer is from 1:510 to 1000, preferably from 1:700 to 900, more preferably from 1:800 to 900. In a specific embodiment, the catalyst is added to the reaction vessel in the form of a solution, and the solvent in which the catalyst is dissolved is selected from one or a combination of dibutyl ether and propylene oxide, preferably dibutyl ether.
In a specific embodiment, the reactor pressure is preferably maintained at 0.8 to 1.5MPa, for example 1MPa, 1.2MPa, as the polymerization reaction occurs.
In a specific embodiment, in step b), the temperature of the contents of the reaction vessel is maintained preferably between 70 and 90 ℃, for example 75 ℃, 80 ℃, by means of an external heat exchanger.
In a specific embodiment, in step b), the cyclic reaction time of the liquid material in the reaction vessel is preferably 4-10 hours, for example 4 hours, 7 hours. In particular, in a continuous operation polymerization process, the liquid level in the reaction kettle is constant by controlling the continuous feeding flow rate of the comonomer and the catalyst and the continuous discharging flow rate of the polymerization liquid, so that the circulating reaction time of the liquid material in the reaction kettle reaches the time.
In a second aspect of the present invention, there is provided a polymerization apparatus for a carbon dioxide-based polycarbonate copolymer, comprising:
the reaction kettle comprises a comonomer feeding inlet, a catalyst feeding inlet, a carbon dioxide feeding inlet and a polymerization liquid outlet, and a distributor and a stirring device are arranged in the reaction kettle; the distributor is connected with the comonomer feed inlet, and the comonomer feed inlet, the catalyst feed inlet and the carbon dioxide feed inlet are respectively connected with the comonomer feed flow path, the catalyst feed flow path and the carbon dioxide feed flow path; the reaction kettle is used for carrying out polymerization reaction on the polymerization solution, and the distributor is used for distributing the polymerization solution in a carbon dioxide gas phase in the reaction kettle;
the circulating pump is used for providing driving force for the circulation of the polymerization solution inside and outside the reaction kettle;
the external heat exchanger is used for exchanging heat to the polymerization liquid circulating outside the reaction kettle so as to control the required polymerization temperature;
an external circulation flow path of the polymerization liquid, which is connected with a polymerization liquid outlet of the reaction kettle, a circulating pump, a heat exchanger and a comonomer feeding flow path;
discharge flow path: the device is arranged in the external circulation path of the polymerization liquid and is used for discharging the reacted polymerization liquid.
In a specific embodiment, a jacket is arranged outside the reaction kettle.
In particular embodiments, the distributor may take the form of any means for distributing the liquid material in the vapor space, such as orifice plates, tubes, etc., and may be one or more.
In a specific embodiment, the comonomer feed inlet, the catalyst feed inlet, and the carbon dioxide feed inlet are disposed at the top or side of the reaction vessel, and the polymerization liquid outlet is disposed at the bottom or side of the reaction vessel, so as to facilitate the entry and exit of the materials and the distribution of the liquid materials in the carbon dioxide gas phase.
In a specific embodiment, the comonomer feed flow passage, the catalyst feed flow passage, and the carbon dioxide feed flow passage may each have a pressurizing device therein.
In a specific embodiment, the comonomer feeding flow path, the catalyst feeding flow path, the carbon dioxide feeding flow path, the polymerization liquid external circulation flow path and the discharging flow path are all provided with valves for controlling flow path opening and closing or material flow.
Advantageous effects
The polymerization process and apparatus of the carbon dioxide-based polycarbonate copolymer of the present invention may be operated either batchwise or continuously. Since a sufficient reaction phase interface is provided, the carbonate chain amount does not become low after the enlargement; because the carbon dioxide does not transfer mass with the outside in the whole reaction process, the carbon dioxide does not need to be recovered, the energy consumption is reduced, and the safety risk caused by compression recovery of the carbon dioxide containing propylene oxide is avoided; in addition, an external heat exchanger is adopted, so that the temperature in the polymerization process is easy to control, and the risk of temperature runaway is avoided.
Drawings
FIG. 1 is a system diagram of a polymerization apparatus for carbon dioxide-based polycarbonate copolymer of the present invention.
Wherein, the reactor comprises a 1-reaction kettle, a 11-comonomer feeding inlet, a 12-catalyst feeding inlet, a 13-carbon dioxide feeding inlet, a 14-polymerization liquid outlet, a 2-circulating pump, a 3-external heat exchanger, a 4 a-distributor, a 4 b-distributor, a 5-stirring device, a 6-comonomer feeding flow path, a 7-catalyst feeding flow path, a 8-carbon dioxide feeding flow path, a 9-polymerization liquid external circulation flow path, a 10-polymerization liquid external circulation flow path, a 15-discharging flow path, a 16 a-valve, a 16 b-valve, a 16 c-valve, a 16 d-valve and a 16 e-valve.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings according to examples, but the embodiments of the present invention are not limited to the following examples.
The process for producing a carbon dioxide-based polycarbonate copolymer of the present invention comprises polymerizing carbon dioxide and a comonomer as main raw materials in the presence of a catalyst to produce a carbon dioxide-based polycarbonate copolymer, and FIG. 1 is a system diagram of an embodiment of an apparatus for carrying out the above process, the apparatus comprising:
a reaction kettle 1, which comprises a comonomer feeding inlet 11, a catalyst feeding inlet 12, a carbon dioxide feeding inlet 13 and a polymerization liquid outlet 14, wherein the reaction kettle is internally provided with distributors 4a and 4b and a stirring device 5, and a jacket is arranged outside the reaction kettle; wherein the distributors 4a, 4b are connected with a comonomer feed inlet 11, and the comonomer feed inlet 11, a catalyst feed inlet 12 and a carbon dioxide feed inlet 13 are respectively connected with a comonomer feed flow path 6, a catalyst feed flow path 7 and a carbon dioxide feed flow path 8; the reaction kettle 1 is used for carrying out polymerization reaction on the polymerization solution, and the distributors 4a and 4b are used for distributing the polymerization solution in a carbon dioxide gas phase in the reaction kettle 1;
a circulation pump 2 for providing driving force for circulation of the polymerization solution inside and outside the reaction kettle;
an external heat exchanger 3 for exchanging heat with the polymerization liquid circulated outside the reaction kettle so as to control the required polymerization temperature;
the polymerization liquid external circulation flow paths 9 and 10 are connected with a polymerization liquid outlet 14 of the reaction kettle, the circulation pump 2, the external heat exchanger 3 and the comonomer feeding flow path 6;
discharge flow path 15: the device is arranged in the polymerization liquid external circulation flow path 9 and is used for discharging the reacted polymerization liquid;
The specific process steps of the production process of the carbon dioxide-based polycarbonate copolymer are as follows:
batch operation:
the comonomer and the catalyst are respectively put into the reaction kettle 1 through a comonomer feeding flow path 6 and a catalyst feeding flow path 7 respectively through a comonomer feeding inlet 11 and a catalyst feeding inlet 12 at one time, so that the liquid level in the kettle is not more than 2/3 of the highest liquid level, and a valve 16a of the comonomer feeding flow path 6 and a valve 16b of the catalyst feeding flow path 7 are closed; starting the stirring device 5 to fully mix, then opening a valve 16c of the carbon dioxide feeding flow path 8, and adding carbon dioxide gas through the carbon dioxide feeding flow path 8 to maintain the pressure in the kettle at 0.12-7.5MPa; the valve 16d of the external circulation flow path 9 of the polymerization liquid is in an open state, the circulation pump 2 is started to enable materials to pass through the external heat exchanger 3, the distributors 4a and 4b return into the reaction kettle 1, and the temperature of the polymerization liquid in the kettle is maintained at 45-140 ℃; after 4-70 hours of reaction, the valve 16d is closed, the valve 16e of the discharging flow path 15 is opened, discharging is carried out through the discharging flow path 15, one period of intermittent operation is completed, and then unreacted epoxy compound is separated, so that the carbon dioxide-based polycarbonate copolymer product can be obtained.
Continuous operation
The comonomer and the catalyst are respectively and continuously added into the reaction kettle 1 through a comonomer feeding flow path 6 and a catalyst feeding flow path 7 respectively through a comonomer feeding inlet 11 and a catalyst feeding inlet 12 at a certain flow rate, and simultaneously a valve 16c of a carbon dioxide feeding flow path 8 is opened, and carbon dioxide gas is added through the carbon dioxide feeding flow path 8, so that the pressure in the kettle is maintained at 0.12-7.5MPa; starting a stirring device 5, opening a valve 16d of a polymerization liquid external circulation flow path 9, starting a circulation pump 2, enabling polymerization liquid to pass through an external heat exchanger 3, returning the distributors 4a and 4b into the reaction kettle 1, and maintaining the temperature of the polymerization liquid in the kettle at 45-140 ℃; the average residence time of the materials in the reaction kettle 1 is 4-70 hours, when the liquid level in the kettle reaches a certain value, the valve 16e is opened, the polymer liquid is continuously discharged through the discharge flow path 15 at a certain flow rate, the liquid level in the reaction kettle is maintained to be constant, and the continuous operation is stable; and then separating unreacted epoxy compound from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer product.
Example 1
This example is a batch operation, taking the apparatus shown in FIG. 1 as an example, a mixture of 50mol of propylene oxide, 20mol of phthalic anhydride, 5mol of cyclohexene oxide, and 10ml of dibutyl ether solution containing 0.07mol of triethylboron and 0.02mol of bis (triphenylphosphine) ammonium chloride were fed into a 12L reaction vessel 1 at one time through a comonomer feed passage 6 and a catalyst feed passage 7, respectively, and valves 16a and 16b were closed; starting the stirring device 5 to fully mix, then opening the valve 16c, and adding carbon dioxide gas through the carbon dioxide feeding flow path 7 to maintain the pressure in the kettle at 1MPa; the valve 16d of the external circulation flow path 9 of the polymerization liquid is in an open state, the circulation pump 2 is started to enable materials to return into the reaction kettle through the external heat exchanger 3 and the distributors 4a and 4b, and the temperature of the polymerization liquid in the kettle is maintained at 75 ℃; after 7 hours of reaction, valve 16d is closed and valve 16e is opened, the materials are discharged through discharge flow path 15, then unreacted epoxy compound is separated to obtain carbon dioxide based polycarbonate copolymer product, and the molecular weight of the copolymer and the content of carbonate chain links are measured: mn=37.1 kda, pdi=3.32, carbonate mer content 53.1%.
Example 2
This example is a batch operation, taking the apparatus shown in FIG. 1 as an example, a mixture of 500mol of propylene oxide, 200mol of phthalic anhydride, 50mol of cyclohexane oxide, and 100ml of dibutyl ether solution containing 0.7mol of triethylboron and 0.2mol of bis (triphenylphosphine) ammonium chloride were fed into 200L of reactor 1 at one time through comonomer feed passage 6 and catalyst feed passage 7, respectively, and valves 16a and 16b were closed; starting the stirring device 5 to fully mix, then opening the valve 16c, and adding carbon dioxide gas through the carbon dioxide feeding flow path 8 to maintain the pressure in the kettle at 1MPa; the valve 16d of the external circulation flow path 9 of the polymerization liquid is in an open state, the circulation pump 2 is started to enable materials to return into the reaction kettle through the external heat exchanger 3 and the distributors 4a and 4b, and the temperature of the polymerization liquid in the kettle is maintained at 75 ℃; after 7 hours of reaction, valve 16d is closed and valve 16e is opened, the materials are discharged through discharge flow path 15, then unreacted epoxy compound is separated to obtain carbon dioxide based polycarbonate copolymer product, and the molecular weight of the copolymer and the content of carbonate chain links are measured: mn=37.9 kda, pdi=3.33, carbonate mer content 52.7%.
Example 3
This example is a continuous operation, taking the apparatus shown in FIG. 1 as an example, a mixture of propylene oxide, phthalic anhydride, cyclohexane oxide=50:18:4 was continuously fed into a 50L reaction vessel 1 at a flow rate of 0.12kg/h with a dibutyl ether solution (60 wt% concentration) of triethylboron, bis (triphenylphosphine) ammonium chloride=7:1 at a flow rate of 7.2kg/h, and carbon dioxide gas was fed through a carbon dioxide feed flow path 8 to maintain the pressure in the vessel at 1MPa by opening a valve 16 c; starting a stirring device 5, opening a valve 16d of a polymerization liquid external circulation flow path 9, starting a circulation pump 2, enabling polymerization liquid to pass through an external heat exchanger 3, returning the distributors 4a and 4b into the reaction kettle, and maintaining the temperature of the polymerization liquid in the kettle at 80 ℃; the average residence time of the materials in the reaction kettle is 4 hours, after the materials reach a certain liquid level, a valve 16e is opened, the polymer liquid is continuously discharged through a discharge flow path 15 at a flow rate of 12.2kg/h, and the liquid level is kept stable by small-amplitude adjustment of the flow rate through a control valve; after continuous operation and stable running, separating unreacted epoxy compound from discharged material to obtain carbon dioxide based polycarbonate copolymer product, and measuring the molecular weight of the copolymer and the content of carbonate chain links: mn=39.1 kda, pdi=3.43, carbonate mer content 40.5%.
Example 4
This example is a continuous operation, taking the apparatus shown in FIG. 1 as an example, a mixture of propylene oxide, phthalic anhydride, cyclohexane oxide=50:18:4 was fed into a 500L reaction vessel 1 at a flow rate of 72kg/h while a dibutyl ether solution (60 wt% concentration) of triethylboron, bis (triphenylphosphine) ammonium chloride=7:1 was fed into the vessel at a flow rate of 1.2kg/h through a comonomer feed flow path 6 and a catalyst feed flow path 7, respectively, while a valve 16c was opened and carbon dioxide gas was fed into the vessel through a carbon dioxide feed flow path 8 to maintain the pressure in the vessel at 1MPa; starting a stirring device 5, opening a valve 16d of a polymerization liquid external circulation flow path 9, starting a circulation pump 2, enabling polymerization liquid to pass through an external heat exchanger 3, returning the distributors 4a and 4b into the reaction kettle, and maintaining the temperature of the polymerization liquid in the kettle at 80 ℃; the average retention time of the materials in the reaction kettle is 4 hours, after the materials reach a certain liquid level, the valve 16e is opened, the polymer liquid is continuously discharged through the discharging flow path 15 at the flow rate of 122kg/h, and the liquid level is kept stable by small-amplitude adjustment of the flow rate through the control valve; after continuous operation and stable running, separating unreacted epoxy compound from discharged material to obtain carbon dioxide based polycarbonate copolymer product, and measuring the molecular weight of the copolymer and the content of carbonate chain links: mn=39.3 kda, pdi=3.41, carbonate mer content 40.2%.
Comparative example 1
This example is a batch operation, taking the apparatus shown in FIG. 1 as an example, a mixture of 25mol of propylene oxide, 32mol of phthalic anhydride, 2mol of cyclohexene oxide, and 10ml of dibutyl ether solution containing 0.07mol of triethylboron and 0.02mol of bis (triphenylphosphine) ammonium chloride were fed into a 12L reaction vessel 1 at one time through a comonomer feed passage 6 and a catalyst feed passage 7, respectively, and valves 16a and 16b were closed; starting the stirring device 5 to fully mix, then opening the valve 16c, and adding carbon dioxide gas through the carbon dioxide feeding flow path 8 to maintain the pressure in the kettle at 1MPa; the valve 16d of the external circulation flow path 9 of the polymerization liquid and the circulating pump 2 are in a closed state, and the temperature of the internal polymerization liquid is maintained at 150 ℃ through a jacket of the reaction kettle; after 3 hours of reaction, opening a valve 16e, starting a circulating pump 2, discharging through a discharging flow path 15, separating unreacted epoxy compounds to obtain a carbon dioxide-based polycarbonate copolymer product, and measuring the molecular weight of the copolymer and the content of carbonate chain links: mn=11.1 kda, pdi=3.92, carbonate mer content 9.1%.
Comparative example 2
This example is a batch operation, taking the apparatus shown in FIG. 1 as an example, a mixture of 50mol of propylene oxide, 20mol of phthalic anhydride, 5mol of cyclohexene oxide, and 20ml of dibutyl ether solution containing 0.07mol of triethylboron and 0.02mol of bis (triphenylphosphine) ammonium chloride were fed into a 12L reaction vessel 1 at one time through a comonomer feed passage 6 and a catalyst feed passage 7, respectively, and valves 16a and 16b were closed; starting the stirring device 5 to fully mix, then opening the valve 16c, and adding carbon dioxide gas through the carbon dioxide feeding flow path 8 to maintain the pressure in the kettle at 1MPa; the valve 16d of the external circulation flow path 9 of the polymerization liquid and the circulating pump 2 are in a closed state, and the temperature of the internal polymerization liquid is maintained at 75 ℃ through a jacket of the reaction kettle; after 7 hours of reaction, opening a valve 16e, starting a circulating pump 2, discharging through a discharging flow path 15, separating unreacted epoxy compounds to obtain a carbon dioxide-based polycarbonate copolymer product, and measuring the molecular weight of the copolymer and the content of carbonate chain links: mn=31.1 kda, pdi=3.02, carbonate mer content 43.1%.
Comparative example 3
This example is a batch operation, taking the apparatus shown in FIG. 1 as an example, a mixture of 500mol of propylene oxide, 200mol of phthalic anhydride, 50mol of cyclohexane oxide, and 200ml of a dibutyl ether solution containing 0.7mol of triethylboron and 0.2mol of bis (triphenylphosphine) ammonium chloride were fed into 200L of reactor 1 at one time through comonomer feed passage 6 and catalyst feed passage 7, respectively, and valves 16a and 16b were closed; starting the stirring device 5 to fully mix, then opening the valve 16c, and adding carbon dioxide gas through the carbon dioxide feeding flow path 8 to maintain the pressure in the kettle at 1MPa; the valve 16d and the circulating pump 2 are in a closed state, and the temperature of the internal polymerization liquid is maintained at 75 ℃ through the jacket of the reaction kettle; after 7 hours of reaction, opening a valve 16e, starting a circulating pump 2, discharging through a discharging flow path 15, separating unreacted epoxy compounds to obtain a carbon dioxide-based polycarbonate copolymer product, and measuring the molecular weight of the copolymer and the content of carbonate chain links: mn=28.1 kda, pdi=3.22, carbonate mer content 31.1%.
Claims (10)
1. A process for polymerizing a carbon dioxide-based polycarbonate copolymer, comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle, and introducing carbon dioxide under stirring to maintain the pressure in the reaction kettle at 0.12-7.5MPa;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase of an upper space in the reaction kettle through a distributor, and then enter the external heat exchanger again for circulation through a lower liquid phase in the reaction kettle; the external heat exchanger maintains the temperature of the materials in the reaction kettle to be 45-140 ℃, and the materials are discharged after the liquid materials react for 4-70 hours;
c) And separating unreacted comonomer from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer.
2. The polymerization process of carbon dioxide-based polycarbonate copolymer of claim 1, wherein,
the polymerization process is a batch operation comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle at one time, and introducing carbon dioxide under stirring to maintain the pressure in the reaction kettle at 0.12-7.5MPa;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase in the upper space in the reaction kettle through the distributor, then enter the external heat exchanger again for circulation through a liquid phase in the lower part of the reaction kettle, and are discharged after the liquid materials are subjected to circulation reaction for 4-70 hours; the external heat exchanger maintains the temperature of materials in the reaction kettle to be 45-140 ℃;
c) Separating unreacted comonomer from the discharged material to obtain a carbon dioxide-based polycarbonate copolymer;
or alternatively
The polymerization process is a continuous operation comprising the steps of:
a) Adding a comonomer and a catalyst into a reaction kettle respectively at a certain flow rate, introducing carbon dioxide to maintain the pressure in the reaction kettle at 0.12-7.5MPa, and stirring;
b) Under the operation of a circulating pump, liquid materials in the reaction kettle return to the reaction kettle after passing through the external heat exchanger, are distributed in a carbon dioxide gas phase of an upper space in the reaction kettle through a distributor, and then enter the external heat exchanger again for circulation through a lower liquid phase in the reaction kettle; the external heat exchanger maintains the temperature of materials in the reaction kettle to be 45-140 ℃; the average residence time of the liquid material in the reaction kettle is 4-70 hours, and the liquid level in the reaction kettle is kept constant by controlling the continuous discharging flow rate;
c) And separating unreacted comonomer from the discharged material to obtain the carbon dioxide-based polycarbonate copolymer.
3. The polymerization process of carbon dioxide-based polycarbonate copolymer according to claim 1 or 2, wherein in step a), the comonomer comprises one or more of an epoxy compound, phthalic anhydride; the epoxy compound includes propylene oxide, cyclohexane oxide and epichlorohydrin;
preferably, the comonomer comprises an epoxy compound and phthalic anhydride, wherein the molar ratio of epoxy compound to phthalic anhydride is greater than 1;
more preferably, the comonomer is propylene oxide, phthalic anhydride, or cyclohexane oxide, wherein the molar ratio of the sum of propylene oxide and cyclohexane oxide to phthalic anhydride is 2-9:1, preferably 2-5:1, and more preferably 2.5-4:1;
preferably, the molar ratio of cyclohexane oxide to propylene oxide is from 0.001 to 0.2:1, preferably from 0.05 to 0.15:1, more preferably from 0.08 to 0.1:1.
4. The polymerization process of a carbon dioxide-based polycarbonate copolymer according to claim 1 or 2, wherein in step a), the catalyst is a lewis acid-base complex catalyst;
preferably, the Lewis acid is an organic boron compound, and is selected from one or a combination of a plurality of triethylboron, triphenylboron, tributylboron, tri-sec-butylboron and methyl boron;
preferably, the Lewis base is organic amine (salt) selected from one or more of tri-bis (triphenyl-n-phosphorus) ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium chloride and 1, 8-diazabicyclo [5.4.0] undec-7-ene;
more preferably, the catalyst is a triethylboron-bis (triphenylphosphine) ammonium chloride composite catalyst, wherein the molar ratio of triethylboron to bis (triphenylphosphine) ammonium chloride is 2-10:1, preferably 3-8:1.
5. The polymerization process of a carbon dioxide based polycarbonate copolymer according to claim 1 or 2, wherein in step a) the molar ratio of catalyst to comonomer is from 1:510 to 1000, preferably from 1:700 to 900, more preferably from 1:800 to 900; and/or
The catalyst is added into the reaction kettle in the form of a solution, and the solvent for dissolving the catalyst is selected from one or a combination of dibutyl ether and propylene oxide, preferably dibutyl ether.
6. The polymerization process of a carbon dioxide-based polycarbonate copolymer according to claim 1 or 2, wherein the reactor pressure is maintained at 0.8 to 1.5MPa when the polymerization reaction occurs: and/or
In the step b), an external heat exchanger is utilized to maintain the temperature of the materials in the reaction kettle to be preferably 70-90; and/or
In step b), the cycle reaction time of the liquid material in the reaction vessel is preferably from 4 to 10 hours.
7. A polymerization apparatus for a carbon dioxide-based polycarbonate copolymer, the polymerization apparatus comprising:
the reaction kettle comprises a comonomer feeding inlet, a catalyst feeding inlet, a carbon dioxide feeding inlet and a polymerization liquid outlet, and a distributor and a stirring device are arranged in the reaction kettle; the distributor is connected with the comonomer feed inlet, and the comonomer feed inlet, the catalyst feed inlet and the carbon dioxide feed inlet are respectively connected with the comonomer feed flow path, the catalyst feed flow path and the carbon dioxide feed flow path; the reaction kettle is used for carrying out polymerization reaction on the polymerization solution, and the distributor is used for distributing the polymerization solution in a carbon dioxide gas phase in the reaction kettle;
the circulating pump is used for providing driving force for the circulation of the polymerization solution inside and outside the reaction kettle;
the external heat exchanger is used for exchanging heat to the polymerization liquid circulating outside the reaction kettle so as to control the required polymerization temperature;
an external circulation flow path of the polymerization liquid, which is connected with a polymerization liquid outlet of the reaction kettle, a circulating pump, a heat exchanger and a comonomer feeding flow path;
discharge flow path: the device is arranged in the external circulation path of the polymerization liquid and is used for discharging the reacted polymerization liquid.
8. The polymerization apparatus for carbon dioxide-based polycarbonate copolymer according to claim 7, wherein a jacket is provided outside the reaction vessel; and/or
The distributor is one or more hole plate type or tubular type distributors; and/or
The comonomer feeding inlet, the catalyst feeding inlet and the carbon dioxide feeding inlet are arranged at the top or the side surface of the reaction kettle, and the polymerization liquid outlet is arranged at the bottom or the side surface of the reaction kettle.
9. The apparatus for polymerizing a carbon dioxide-based polycarbonate copolymer according to claim 7, wherein the comonomer feed passage, the catalyst feed passage, and the carbon dioxide feed passage may each have a pressurizing means.
10. The apparatus for polymerizing a carbon dioxide-based polycarbonate copolymer according to claim 7, wherein the comonomer feed passage, the catalyst feed passage, the carbon dioxide feed passage, the polymerization liquid external circulation passage, and the discharge passage are each provided with a valve.
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