CN116606428A - Preparation method of carbon dioxide-epoxide copolymer by combining bulk and solution - Google Patents
Preparation method of carbon dioxide-epoxide copolymer by combining bulk and solution Download PDFInfo
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- CN116606428A CN116606428A CN202310795841.5A CN202310795841A CN116606428A CN 116606428 A CN116606428 A CN 116606428A CN 202310795841 A CN202310795841 A CN 202310795841A CN 116606428 A CN116606428 A CN 116606428A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000008364 bulk solution Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 150000002118 epoxides Chemical class 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 230000001502 supplementing effect Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000006052 feed supplement Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 61
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 29
- 239000011541 reaction mixture Substances 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 125000005587 carbonate group Chemical group 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 5
- -1 polypropylene carbonate Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- SCRKTTJILRGIEY-UHFFFAOYSA-N pentanedioic acid;zinc Chemical compound [Zn].OC(=O)CCCC(O)=O SCRKTTJILRGIEY-UHFFFAOYSA-N 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229920000379 polypropylene carbonate Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 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 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- QEYNXBRMPSQXIG-UHFFFAOYSA-N carbon dioxide;2-methyloxirane Chemical compound O=C=O.CC1CO1 QEYNXBRMPSQXIG-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The application discloses a preparation method of a bulk-solution combination of a carbon dioxide-epoxide copolymer, which comprises the following steps: and (3) carrying out pressurizing and high-temperature treatment on the catalyst, carbon dioxide and epoxide, feeding after the pressurizing and high-temperature treatment is carried out in a carbon dioxide environment, and then cooling to obtain the carbon dioxide-epoxide copolymer. Compared with the prior scheme of adding all solvents at one time, the method needs shorter reaction time, reduces the system heat so as to lead the reaction to be more stable, and can realize the highest conversion rate of 99 percent.
Description
Technical Field
The application belongs to the technical field of high polymer materials, and particularly relates to a preparation method for bulk-solution combination of a carbon dioxide-epoxide copolymer.
Background
With the increasing white pollution caused by the traditional plastics, the degradable plastics are attracting more and more attention, and the comprehensive utilization of carbon dioxide as a main greenhouse gas is also an important subject along with the increase of environmental protection requirements, so that the polypropylene carbonate (PPC) capable of combining the two materials has high production value.
The PPC has higher carbon dioxide fixation amount and high melt strength, and has high application value in the fields of disposable packaging, agricultural films and the like. The traditional production process generally adopts a one-pot body method for production, the method has low monomer conversion rate, the monomer recovery process is complex, the reaction heat is difficult to remove due to the rising of viscosity in the later period of the reaction, the byproducts are increased, and the reaction is easy to run away. The main reason is that the solution polymerization method of bulk polymerization and one-time addition of propylene oxide puts a large amount of propylene oxide into a kettle at the initial stage of reaction, and if the heat is not removed timely, the reaction system can be raised to a very high temperature, so that a large risk is caused.
Current research progress in the art is referenced below: the Chinese patent with the application number of CN202111033408 discloses a solution polymerization method for continuously feeding monomer propylene oxide, which solves the problem of viscosity, improves the monomer conversion rate, and simultaneously, continuously feeding the monomer propylene oxide well avoids the risk of reaction heat release runaway caused by adding a large amount of propylene oxide at one time.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
It is therefore an object of the present application to overcome the deficiencies of the prior art and to provide a method for the preparation of a carbon dioxide-epoxide copolymer in bulk-solution combination.
In order to solve the technical problems, the application provides the following technical scheme: a method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer comprising the steps of:
preparation of carbon dioxide-epoxide copolymer: placing the catalyst in a carbon dioxide environment, adding epoxide, and pressurizing at high temperature;
supplementing carbon dioxide in a sealed environment, pressurizing and heating, adding a supplementing material, and stirring at a high temperature and a pressurizing state;
and cooling the sealed instrument, and waiting for cooling to obtain the carbon dioxide-epoxide copolymer.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: the feed supplement is one or more of dioxane, dichloromethane, dioxane and carbon dioxide.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: in preparing the carbon dioxide-epoxide copolymer, the pressurization is to be not less than 6MPa.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: the carbon dioxide-epoxide copolymer is prepared by adding epoxide and then supplementing carbon dioxide.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: after supplementing carbon dioxide, the pressure is increased to 7.5-9 MPa.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the high temperature is heated to 60-80 ℃.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the catalyst is one or more of a zinc dicarboxylic acid catalyst, a rare earth doped double metal cyanide catalyst and a ternary rare earth catalyst.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: cooling the sealing instrument to lower the temperature in the kettle to below 40 ℃, and vacuum drying at 30-60 ℃ for 48h after the temperature is reduced.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: and supplementing carbon dioxide in a sealed environment, wherein in the pressurizing and heating treatment, the pressurizing is to supplement the carbon dioxide to the pressure of 7.5-9 MPa and keep the pressure.
As a preferred embodiment of the method for preparing a bulk-solution combination of carbon dioxide-epoxide copolymer according to the present application, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the flow rate ratio of the introduced carbon dioxide to epoxide is 5-9:10
The application has the beneficial effects that:
the application provides a preparation method of a bulk-solution combination of a carbon dioxide-epoxide copolymer, which comprises the following steps: the preparation process is divided into a bulk polymerization prepolymerization process in which part of epoxy monomers are continuously added and a solution polymerization process in which inert solvents are continuously added. Compared with the prior art, the method has the advantages of fast reaction start, fast reaction rate and the like of bulk polymerization in the prepolymerization process, and the catalyst with high concentration in the initial stage enables the reaction to be easier to carry out. Part of epoxy monomers are continuously added, so that the once input amount of the epoxy monomers is reduced, the filling rate of an initial reaction kettle is reduced, and the safety coefficient is greatly increased compared with that of bulk polymerization; meanwhile, the continuously added low-temperature epoxy monomer and low-temperature liquid carbon dioxide consume more reaction heat, so that the reaction heat in the reaction kettle, which needs to be removed outside the system, is reduced, and the reaction is milder; the epoxy monomer added continuously also continuously dilutes the reaction mixture, thereby improving the problem of difficult removal of reaction heat caused by the continuous increase of viscosity along with the progress of the reaction. In the polymerization stage, the continuous addition of the inert solvent keeps the concentration of the epoxy monomer at a level as high as possible all the time, and the reaction can be carried out faster than the prior art in which all the solvent is added at one time; the continuously added low-temperature solvent consumes part of the reaction heat, so that the reaction heat required to be removed outside the system in the polymerization process is reduced, and the reaction is more stable; the added inert solvent counteracts the viscosity increase caused by the deepening of the reaction degree and is also more beneficial to the removal of the reaction heat. Experiments show that the conversion rate of the epoxy monomer is generally more than 90% and up to more than 99% compared with simple bulk polymerization, and the total reaction time can be obviously shortened when the same reaction degree is achieved compared with solution polymerization in which all solvents are added at one time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a carbon dioxide-propylene oxide copolymer prepared in example 1 of the present application;
FIG. 2 is a GPC chart of a carbon dioxide-propylene oxide copolymer obtained in example 1 of the present application;
FIG. 3 is a schematic view of a carbon dioxide-propylene oxide copolymer obtained in example 1 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
a) The preparation method of the embodiment refers to the preparation of a zinc dicarboxylic acid catalyst by the Chinese patent with the application number of 201510859248.8; 3g of zinc glutarate catalyst is added into a 1000mL autoclave which is dried, 110g of carbon dioxide gas is filled, 100mL of propylene oxide is added into the autoclave by a metering pump, the mixture is stirred and heated to 80 ℃, the pressure in the autoclave reaches 6MPa, 200mL of propylene oxide is added into the autoclave at a constant speed of 1.6mL/min, meanwhile, liquid carbon dioxide is added into the autoclave at a speed of 0.9mL/min, the addition of propylene oxide and carbon dioxide is stopped after 125min, and the mixture is stirred for 30min at 80 ℃ and 6MPa.
b) 50g of carbon dioxide is added into the kettle and heated, the temperature and the pressure in the kettle are changed to 85 ℃ and 7.5MPa, dioxane is added into the kettle at the rate of 2mL/min, simultaneously, about 120g of carbon dioxide is added into the kettle, the pressure in the kettle is always stable at 7.5MPa, after 2.5h, the addition of the dioxane and the carbon dioxide is stopped, 300mL of dioxane is added, and the kettle is kept at 85 ℃ and 7.5MPa for stirring for 1h.
c) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 50 ℃ for 48 hours to obtain 406.3g of carbon dioxide-propylene oxide copolymer to obtain 10.5g of propylene carbonate, and carrying out vacuum drying on the propylene carbonate 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 93.9% by H-NMR, the propylene oxide conversion was 97.7%, and the molecular weight of the product was determined by GPC and shown in Table 1.
The nuclear magnetic resonance hydrogen spectrum and GPC spectra of the obtained product are shown in FIGS. 1 and 2.
From figures 1 and 2, the product obtained in example 1 can be identified as carbon dioxide-propylene oxide.
Example 2
a) The preparation method of the embodiment refers to the Chinese patent with the application number of CN201510470795.7 for preparing the rare earth doped double metal cyanide catalyst; adding 0.1 rare earth doped double metal cyanide catalyst into a 1000mL autoclave which is subjected to drying treatment, charging 300g of carbon dioxide gas, adding 150mL of propylene oxide into the autoclave by using a metering pump, stirring and heating to 60 ℃, wherein the pressure in the autoclave reaches 9MPa, adding 150mL of propylene oxide into the autoclave at a constant speed of 2.5mL/min, simultaneously adding liquid carbon dioxide into the autoclave at a speed of 2mL/min, and stopping adding propylene oxide and carbon dioxide after 1h.
b) After the propylene oxide is added, maintaining the temperature and pressure of 60 ℃ and 9MPa in the kettle, adding methylene dichloride into the kettle at a rate of 2mL/min, simultaneously supplementing about 260g of carbon dioxide into the kettle to ensure that the pressure in the kettle is always stable at 9MPa, stopping adding the methylene dichloride and the carbon dioxide after 200min, adding 400mL of the methylene dichloride, and stirring for 1.5h at the temperature of 60 ℃ and 9MPa.
c) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 50 ℃ for 48h to obtain 409g of carbon dioxide-propylene oxide copolymer to obtain 9.5g of propylene carbonate, and carrying out vacuum drying on the propylene carbonate by using a vacuum oven 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 90.9% by H-NMR measurement, the propylene oxide conversion was 99.5%, and the molecular weight of the product was determined by GPC and shown in Table 1.
Example 3
a) The preparation method of the embodiment refers to the preparation of a zinc dicarboxylic acid catalyst by the Chinese patent with the application number of 201510859248.8; 3g of zinc glutarate catalyst is added into a 1000mL autoclave which is subjected to drying treatment, 130g of carbon dioxide gas is filled, 100mL of ethylene oxide is added into the autoclave by a metering pump, the mixture is stirred and heated to 80 ℃, the pressure in the autoclave reaches 7MPa, 200mL of ethylene oxide is added into the autoclave at a constant speed of 1mL/min, meanwhile, liquid carbon dioxide is added into the autoclave at a speed of 0.8mL/min, the addition of ethylene oxide and carbon dioxide is stopped after 200min, and the mixture is stirred for 1h at 80 ℃ and 7 MPa.
b) 50g of carbon dioxide is added into the kettle and heated, the temperature and the pressure in the kettle are changed to 90 ℃ and 7.5MPa, dioxane is added into the kettle at the rate of 1mL/min, simultaneously, about 120g of carbon dioxide is added into the kettle, the pressure in the kettle is always stable at 7.5MPa,200min later, the addition of dioxane and carbon dioxide is stopped, 200mL of dioxane is added, and the temperature is kept at 90 ℃ and 7.5MPa, and stirring is carried out for 2h.
c) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 30 ℃ for 48 hours to obtain 426g of carbon dioxide-ethylene oxide copolymer, obtaining 21.4g of ethylene carbonate, and carrying out vacuum drying on the reaction mixture 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 91.2% and the conversion of ethylene oxide was 90.5% as determined by H-NMR, and the molecular weight of the product was as shown in Table 1 by GPC.
Example 4
a) The preparation method of the embodiment refers to the preparation of a ternary rare earth catalyst by the Chinese patent with the application number ZL 03105023.9; 50mL of rare earth three-way catalyst (0.0015 mol Y (CCl-3 COO) +0.015mol glycerol+ 0.03mol ZnEt+45mL1,3-dioxypentacyclic) is added into a 1000mL autoclave which is subjected to drying treatment, 160g of carbon dioxide gas is filled, 100mL of propylene oxide is added into the autoclave by using a metering pump, stirring and heating are carried out until the temperature of the autoclave reaches 7MPa, 200mL of propylene oxide is added into the autoclave at a constant speed of 2mL/min, meanwhile liquid carbon dioxide is added into the autoclave at a speed of 1mL/min, the addition of propylene oxide and carbon dioxide is stopped after 100min, and stirring is carried out for 1h at 75 ℃ and 7 MPa.
b) The materials in the kettle are heated to 85 ℃ and the pressure is changed to 7.3MPa, the dioxygen pentacyclic is added into the kettle at the rate of 2mL/min, and simultaneously, 140g of carbon dioxide is added into the kettle to ensure that the pressure in the kettle is always stable at 7.5MPa, after 3h, the dioxygen pentacyclic and the carbon dioxide are stopped being added, 360mL of dioxygen pentacyclic is added, and the kettle is kept at 85 ℃ and stirred for 1h under 7.5 MPa.
c) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 50 ℃ for 48 hours to obtain 387.5g of carbon dioxide-propylene oxide copolymer to obtain 26.3g of propylene carbonate, and carrying out vacuum drying on the propylene carbonate by using a vacuum oven 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 97.7% as determined by H-NMR, the propylene oxide conversion was 95.4%, and the molecular weight of the product was determined by GPC and shown in Table 1.
Example 5
a) The preparation method of the embodiment refers to the preparation of a ternary rare earth catalyst by the Chinese patent with the application number ZL 03105023.9; 50mL of rare earth three-way catalyst (0.0015 mol Y (CCl-3 COO) +0.015mol glycerol+ 0.03mol ZnEt+45mL1,3-dioxypentacyclic) is added into a 1000mL autoclave after the drying treatment, 160g of carbon dioxide gas is filled, 100mL of propylene oxide is added into the autoclave by a metering pump, stirring and heating are carried out until the temperature of the autoclave reaches 7MPa, 200mL of cyclohexene oxide is added into the autoclave at a constant speed of 2mL/min, meanwhile, liquid carbon dioxide is added into the autoclave at a speed of 1mL/min, after 100min, the addition of propylene oxide and carbon dioxide is stopped, and stirring is carried out for 1h at 75 ℃ and 7 MPa.
b) The materials in the kettle are heated to 85 ℃ and the pressure is changed to 7.3MPa, the dioxygen pentacyclic is added into the kettle at the rate of 2mL/min, and simultaneously, 140g of carbon dioxide is added into the kettle to ensure that the pressure in the kettle is always stable at 7.5MPa, after 200min, the dioxygen pentacyclic and the carbon dioxide are stopped being added, 400mL of dioxygen pentacyclic is added, and the kettle is kept at 85 ℃ and stirred for 1h under 7.5 MPa.
c) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 60 ℃ for 48 hours to obtain 380g of carbon dioxide-propylene oxide-cyclohexane oxide copolymer to obtain 23.8g of propylene carbonate, and carrying out vacuum drying on the propylene carbonate by using a vacuum oven 1 The carbon dioxide-propylene oxide-cyclohexane oxide copolymer had a carbonate unit content of 98.6%, a propylene oxide conversion of 97.1% and a cyclohexane oxide conversion of 94.5% as determined by H-NMR, and the molecular weight of the product was found by GPC and shown in Table 1.
Comparative example 1
a) The same charge amount, reaction conditions and reaction time as in example 1 were the same, 3g of zinc glutarate catalyst, 300mL of propylene oxide and 300mL of dioxane were added to a 1000mL autoclave subjected to drying treatment, 300g of carbon dioxide gas was charged, heating and stirring were carried out, the temperature in the autoclave was increased to 85℃after reaching 80℃and 6MPa for 155min, 100g of carbon dioxide was supplemented to increase the pressure in the autoclave to 7.5MPa, and the reaction was continued for 3.5 hours.
b) Cooling water in the jacket of the fully opened reaction kettle to make the temperature in the kettle quickly lower than 40 ℃, discharging the reaction mixture, and placing the reaction mixture in a vacuum oven at 50 ℃ in vacuumDrying for 48h to obtain 357.7g of carbon dioxide-propylene oxide copolymer, 9.7g of propylene carbonate is obtained by 1 The carbon dioxide-propylene oxide copolymer had a carbonate unit content of 93.1% and a propylene oxide conversion of 86.4% as determined by H-NMR, and the molecular weight of the product was determined by GPC and shown in Table 2.
Comparative example 2
a) The same charge amount, reaction conditions and reaction time as in example 2 were the same, and 0.1 rare earth doped double metal cyanide catalyst, 300mL propylene oxide and 400mL methylene chloride were added to the dried 1000mL autoclave, 680g carbon dioxide gas was charged, heated and stirred to 60℃and 9MPa in the autoclave, and reacted for 6 hours.
b) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 50 ℃ for 48 hours to obtain 352.2g of carbon dioxide-propylene oxide copolymer to obtain 7.2g of propylene carbonate, and carrying out vacuum drying on the mixture 1 The carbon dioxide-propylene oxide copolymer had a carbonate unit content of 88.4% and a propylene oxide conversion of 86.3% as determined by H-NMR, and the molecular weight of the product was determined by GPC and shown in Table 2.
Comparative example 3
a) The same charge amount, reaction conditions and reaction time as in example 3 were the same, 3g of zinc glutarate catalyst, 300mL of ethylene oxide and 200mL of dioxane were added to a 1000mL autoclave subjected to drying treatment, 330g of carbon dioxide gas was charged, and the mixture was heated and stirred to 80℃and 7MPa for 260 minutes
80g of carbon dioxide is continuously filled and heated, so that the temperature in the kettle reaches 90 ℃, 7.5MPa and the reaction is carried out for 320min. b) Fully-opened cooling water for the jacket of the reaction kettle, so that the temperature in the kettle is quickly reduced to below 40 ℃ and the reaction mixture is discharged
The resultant was dried in a vacuum oven at 30℃for 48 hours to give 396.2g of a carbon dioxide-ethylene oxide copolymer, 16.3g of ethylene carbonate was obtained, and the resultant was subjected to vacuum drying 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 91.7% as determined by H-NMR, the conversion of ethylene oxide was 81.2%, and the molecular weight of the product was determined by GPC and shown in Table 2.
Comparative example 4
a) The same charge amount, reaction conditions and reaction time as in example 4 were the same, 50mL of rare earth three-way catalyst (0.0015 mol Y (CCl-3 COO) +0.015mol glycerol +0.03mol ZnEt+45mL1,3-dioxolane), 300mL of propylene oxide and 360mL of dioxolane were added to a 1000mL autoclave after drying treatment, 400g of carbon dioxide was charged, and the mixture was heated and stirred to 75℃and 7MPa in the autoclave, and after 160 minutes of reaction, the mixture was heated to 85℃and the reaction was continued for 4 hours.
b) Cooling water in the jacket of the fully-opened reaction kettle to quickly lower the temperature in the kettle to below 40 ℃, discharging a reaction mixture, placing the reaction mixture in a vacuum oven, and vacuum drying at 50 ℃ for 48 hours to obtain 325.96g of carbon dioxide-propylene oxide copolymer to obtain 21.1g of propylene carbonate, and carrying out vacuum drying on the propylene carbonate by using a vacuum oven 1 The content of carbonate units in the carbon dioxide-propylene oxide copolymer was 97.4% as determined by H-NMR, the propylene oxide conversion was 80.1%, and the molecular weight of the product was determined by GPC and shown in Table 2.
Comparative example 5
a) The same charge amount, reaction conditions and reaction time as in example 5 were the same, 50mL of rare earth three-way catalyst (0.0015 mol Y (CCl-3 COO) +0.015mol glycerol+ 0.03mol ZnEt+45mL1,3-dioxolane), 100mL of propylene oxide and 400mL of dioxolane were added to a 1000mL autoclave subjected to drying treatment, 300g of carbon dioxide gas was charged, heated and stirred to 75℃and 7MPa in the autoclave, 200mL of cyclohexene oxide was charged into the autoclave with a metering pump at a rate of 2mL/min while 100g of carbon dioxide was charged to maintain the reaction pressure at 7MPa, the charging took 100min, and the reaction was continued for 60min after the completion of the charging, the autoclave was heated to 85℃and the reaction was continued for 260min.
b) The reactor was cooled with jacket cooling water to rapidly lower the temperature in the reactor to below 40℃and the reaction mixture was discharged, and the reactor was placed in a vacuum oven and dried under vacuum at 60℃for 48 hours to give 348.3g of a carbon dioxide-propylene oxide-cyclohexane oxide copolymer, 21.2g of propylene carbonate was obtained, the content of carbonate units in the carbon dioxide-propylene oxide-cyclohexane oxide copolymer was 98.1% as determined by 1H-NMR, the conversion of propylene oxide was 82.3%, the conversion of cyclohexane oxide was 87.2%, and the molecular weight of the product was as shown in Table 2 by GPC.
Table 1 molecular weight of carbon dioxide-propylene oxide copolymer prepared in examples
Table 2 comparative molecular weight of carbon dioxide-propylene oxide copolymer
As shown in tables 1 and 2, the molecular weight distribution of the products prepared from the carbon dioxide-propylene oxide copolymer was more concentrated, the physical properties were better, and the average molecular weight was comparable.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (10)
1. A method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer, characterized by: the method comprises the following steps:
preparation of carbon dioxide-epoxide copolymer: placing the catalyst in a carbon dioxide environment, adding epoxide, and pressurizing at high temperature;
supplementing carbon dioxide in a sealed environment, pressurizing and heating, adding a supplementing material, and stirring at a high temperature and a pressurizing state;
and cooling the sealed instrument, and waiting for cooling to obtain the carbon dioxide-epoxide copolymer.
2. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: the feed supplement is one or more of dioxane, dichloromethane, dioxane and carbon dioxide.
3. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the pressurization is carried out to be not less than 6MPa.
4. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: the preparation of the carbon dioxide-epoxide copolymer further comprises the step of supplementing carbon dioxide after epoxide is added.
5. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1 or 4, wherein: after supplementing carbon dioxide, the pressure is increased to 7.5-9 MPa.
6. A method for the preparation of a bulk-solution combination of carbon dioxide-epoxide copolymer according to claim 1 or 3, characterized in that: in the preparation of the carbon dioxide-epoxide copolymer, the high temperature is heated to 60-80 ℃.
7. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the catalyst is one or more of a zinc dicarboxylic acid catalyst, a rare earth doped double metal cyanide catalyst and a ternary rare earth catalyst.
8. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: the sealing instrument is cooled to lower the temperature in the kettle to below 40 ℃, and the kettle is dried in vacuum for 48 hours at 30-60 ℃ after the temperature is lowered.
9. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: and in the pressurized heating treatment, the pressurization is to supplement the carbon dioxide to the pressure of 7.5-9 MPa and keep the pressure.
10. The method for preparing a bulk-solution combination of a carbon dioxide-epoxide copolymer according to claim 1, wherein: in the preparation of the carbon dioxide-epoxide copolymer, the flow rate ratio of the introduced carbon dioxide to the epoxide is 5-9:10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102482407A (en) * | 2009-09-03 | 2012-05-30 | Sk新技术株式会社 | Continuous process for manufacturing aliphatic polycarbonates from carbon dioxide and epoxides |
| CN109438689A (en) * | 2018-10-19 | 2019-03-08 | 中国化学赛鼎宁波工程有限公司 | A kind of propylene oxide-carbon dioxide copolymer and preparation method thereof |
| CN113683765A (en) * | 2021-09-03 | 2021-11-23 | 中国科学院长春应用化学研究所 | Carbon dioxide-epoxide copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482407A (en) * | 2009-09-03 | 2012-05-30 | Sk新技术株式会社 | Continuous process for manufacturing aliphatic polycarbonates from carbon dioxide and epoxides |
| CN109438689A (en) * | 2018-10-19 | 2019-03-08 | 中国化学赛鼎宁波工程有限公司 | A kind of propylene oxide-carbon dioxide copolymer and preparation method thereof |
| CN113683765A (en) * | 2021-09-03 | 2021-11-23 | 中国科学院长春应用化学研究所 | Carbon dioxide-epoxide copolymer and preparation method thereof |
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