CN109438689B - Propylene oxide-carbon dioxide copolymer and preparation method thereof - Google Patents
Propylene oxide-carbon dioxide copolymer and preparation method thereof Download PDFInfo
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- CN109438689B CN109438689B CN201811222321.0A CN201811222321A CN109438689B CN 109438689 B CN109438689 B CN 109438689B CN 201811222321 A CN201811222321 A CN 201811222321A CN 109438689 B CN109438689 B CN 109438689B
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 47
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- QEYNXBRMPSQXIG-UHFFFAOYSA-N carbon dioxide;2-methyloxirane Chemical compound O=C=O.CC1CO1 QEYNXBRMPSQXIG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 16
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 2
- HFRNYBAXHBSKIG-UHFFFAOYSA-N C1CC1.O=C=O Chemical compound C1CC1.O=C=O HFRNYBAXHBSKIG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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 Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a propylene oxide-carbon dioxide copolymer and a preparation method thereof, wherein the preparation method of the propylene oxide-carbon dioxide copolymer comprises the following steps: s1: adding propylene oxide and a catalyst into a prepolymerization reactor, and stirring; s2: introducing carbon dioxide gas into the prepolymerization reactor to perform prepolymerization reaction to obtain propylene oxide-carbon dioxide prepolymer; s3: and adding the propylene oxide-carbon dioxide prepolymer into a polymerization kettle, stirring, introducing carbon dioxide gas into the polymerization kettle, and carrying out polymerization reaction to obtain the propylene oxide-carbon dioxide copolymer. According to the preparation method of the propylene oxide-carbon dioxide copolymer, the preparation of the propylene oxide-carbon dioxide copolymer is divided into the two processes of the prepolymerization reaction and the polymerization reaction, so that the viscosity of the product in the same reaction kettle is relatively close, the stirring structure is easy to select, the stirring is relatively uniform, and the stability of the product is improved.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a propylene oxide-carbon dioxide copolymer and a preparation method thereof.
Background
Carbon dioxide is a greenhouse gas with the greatest influence on global warming, one of the main raw materials for synthesizing the propylene oxide-carbon dioxide copolymer is carbon dioxide, and the propylene oxide-carbon dioxide copolymer can consume a large amount of carbon dioxide in the synthesis process; meanwhile, the propylene oxide-carbon dioxide copolymer is a fully degradable polymer, has the advantages of low production cost, good transparency, good gas barrier property, excellent processability and the like, can replace nondegradable plastic products to be widely applied to the fields of films and packaging materials, and has revolutionary significance for solving the problem of white pollution.
However, the existing epoxypropane-carbon dioxide copolymer is synthesized by directly reacting carbon dioxide and epoxypropane in a synthesis reaction kettle under the action of a catalyst by controlling the temperature and pressure in the synthesis reaction kettle; the existing synthetic process of the propylene oxide-carbon dioxide copolymer has complex reaction process and difficult control of the process.
In view of the above drawbacks, the present inventors have finally achieved the present invention through long-time studies and practices.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is that the preparation method of the propylene oxide-carbon dioxide copolymer comprises the following steps:
s1: adding propylene oxide and a catalyst into a prepolymerization reactor, and stirring;
s2: introducing carbon dioxide gas into the prepolymerization reactor, controlling the temperature in the prepolymerization reactor to be 60-90 ℃ and carrying out prepolymerization reaction to obtain propylene oxide-carbon dioxide prepolymer;
s3: adding the propylene oxide-carbon dioxide prepolymer into a polymerization kettle, stirring, introducing carbon dioxide gas into the polymerization kettle, controlling the temperature in the polymerization kettle to be 60-90 ℃ and carrying out polymerization reaction to obtain the propylene oxide-carbon dioxide copolymer.
Optionally, the pressure in the prepolymerization reactor in step S2 is 4.0-7.0Mpa g.
Optionally, the pressure in the polymerization vessel in step S3 is 4.0-7.0 Mpa.
Optionally, the addition amount of the propylene oxide in the step S1 is 1/4-2/3 of the volume of the prepolymerization reactor.
Optionally, the addition amount of the catalyst in the step S1 is 0.5% -2.5% of the addition mass of the propylene oxide.
Optionally, the carbon dioxide in the step S2 is added in an amount of 40% -80% of the propylene oxide in the step S1.
Optionally, the carbon dioxide in the step S3 is added in an amount which is 2% -10% of the added mass of the propylene oxide in the step S1.
Optionally, the carbon dioxide gas is added in the step S2 from the bottom of the prepolymerization reactor.
Optionally, the carbon dioxide gas is added in the step S3 from the bottom of the polymerization kettle.
A propylene oxide-carbon dioxide copolymer produced by the above-mentioned propylene oxide-carbon dioxide copolymer production method.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the propylene oxide-carbon dioxide copolymer, the preparation of the propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization reaction and polymerization reaction by adopting a multi-kettle serial polymerization process, so that the viscosities of products in the same reaction kettle are relatively close, meanwhile, the molecular weights of the products in the same reaction kettle are relatively close, the temperature change range in the reaction kettle is relatively small, and the reaction process in each reaction kettle is relatively simple, so that the stirring structure in the reaction kettle is easy to select, and the stirring is relatively uniform, so that the reaction is relatively sufficient, and the stability of the products is improved;
according to the preparation method of the propylene oxide-carbon dioxide copolymer, the preparation of the propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization reaction and polymerization reaction, on one hand, the viscosity of a product in a prepolymerization kettle is smaller, and stirring is easy, so that the power of a stirring motor is lower, and the production cost of the propylene oxide-carbon dioxide copolymer can be reduced; on the other hand, because the viscosity difference of the cyclopropane-carbon dioxide copolymer in the polymerization kettle is smaller, the molecular weight distribution is even, and the stirring is even, the polymerization reaction is more fully carried out, thereby being beneficial to the increase of the molecular weight of the propylene oxide-carbon dioxide copolymer, further leading the molecular weight of the propylene oxide-carbon dioxide copolymer to be higher and being beneficial to improving the product performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are used in the description of the embodiments will be briefly described below.
FIG. 1 is a flow chart of a process for preparing propylene oxide-carbon dioxide copolymer of the present invention;
FIG. 2 is a gel permeation chromatogram of a propylene oxide-carbon dioxide copolymer of the present invention;
FIG. 3 is a thermogravimetric analysis of the propylene oxide-carbon dioxide copolymer of the present invention.
Detailed Description
The above and further technical features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The invention provides a preparation method of a propylene oxide-carbon dioxide copolymer, which is shown in a figure 1, and divides the preparation of the propylene oxide-carbon dioxide copolymer into two processes of prepolymerization and polymerization, wherein the prepolymerization is carried out in a prepolymerization kettle, and the polymerization is carried out in a polymerization kettle, namely, the preparation method of the propylene oxide-carbon dioxide copolymer provided by the invention adopts a multi-kettle serial polymerization process.
The preparation method comprises the steps of firstly adding propylene oxide and a catalyst into a prepolymerization reactor according to a certain proportion, stirring, and then introducing carbon dioxide gas into the prepolymerization reactor, wherein the addition of carbon dioxide is determined according to the addition of propylene oxide; controlling the pressure in the prepolymerization reactor to be kept in the range of 4.0-7.0Mpa, and keeping the temperature in the prepolymerization reactor to be in the range of 60-90 ℃ so as to carry out prepolymerization reaction on propylene oxide and carbon dioxide in the presence of a catalyst; since the viscosity of the polymer increases with the increase of the molecular weight, the molecular weight of the pre-polymerized product is monitored by detecting the viscosity of the pre-polymerized product during the pre-polymerization reaction, and the end time of the pre-polymerization reaction is controlled according to the viscosity of the pre-polymerized product, namely, when the viscosity of the pre-polymerized product reaches a preset viscosity value, the pre-polymerization reaction is ended, so that the pre-polymerized product with smaller average molecular weight and shorter average molecular chain is obtained; the specific process is that the viscosity of the pre-polymerized product is detected by an on-line viscometer in the pre-polymerization reaction kettle, and when the viscosity of the pre-polymerized product reaches 200-700cP, the pre-polymerization reaction is ended, and the propylene oxide-carbon dioxide prepolymer is obtained.
Adding reactants and products in the prepolymerization reactor into a polymerization reactor, and supplementing a certain amount of carbon dioxide gas into the polymerization reactor, wherein the amount of the carbon dioxide gas added into the polymerization reactor is determined according to the amount of propylene oxide added into the prepolymerization reactor; controlling the pressure in the polymerization kettle to be kept in the range of 4.0-7.0Mpa, and keeping the temperature in the polymerization kettle to be in the range of 60-90 ℃ so that the cyclopropane-carbon dioxide prepolymer with smaller average molecular weight and shorter average molecular chain continuously reacts under the catalysis of the residual catalyst, and the molecular chain of the product continuously increases, namely the propylene oxide-carbon dioxide prepolymer is polymerized in the polymerization kettle; the viscosity of the polymerization product was measured by an on-line viscometer in the polymerizer, and when the viscosity of the polymerization product reached 1000-15000cP, the polymerization reaction was ended to obtain a propylene oxide-carbon dioxide copolymer.
The preparation of the propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization reaction and polymerization reaction by adopting a multi-kettle serial polymerization process, so that the viscosity of a product in the prepolymerization kettle is in the range of 200-700cP, the viscosity of a product in the polymerization kettle is in the range of 1000-15000cP, namely, the viscosity of a product in the same reaction kettle is relatively close, meanwhile, the temperature change range in the reaction kettle is smaller because the molecular weight of the product in the same reaction kettle is relatively close, and the reaction process in each reaction kettle is relatively simple, therefore, the stirring structures in the prepolymerization kettle and the polymerization kettle are easy to select, and the stirring is relatively uniform, so that the reaction is relatively sufficient, and the stability of the product is improved.
After the preparation of the propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization reaction and polymerization reaction, on one hand, the product in the prepolymerization reactor has smaller viscosity and is easy to stir, so that the power of a stirring motor is lower, and the production cost of the propylene oxide-carbon dioxide copolymer can be reduced; on the other hand, because the viscosity difference of the cyclopropane-carbon dioxide copolymer in the polymerization kettle is smaller, the molecular weight distribution is even, and the stirring is even, the polymerization reaction is more fully carried out, thereby being beneficial to the increase of the molecular weight of the propylene oxide-carbon dioxide copolymer, further leading the molecular weight of the propylene oxide-carbon dioxide copolymer to be higher and being beneficial to improving the product performance.
In the prepolymerization reaction process, in order to fully react propylene oxide with carbon dioxide and improve the conversion rate of propylene oxide and carbon dioxide, the addition amount of propylene oxide can be determined according to the volume of the prepolymerization reactor, and the addition amount of propylene oxide is preferably 1/4-2/3 of the volume of the prepolymerization reactor, namely, the volume of propylene oxide added into the prepolymerization reactor is 1/4-2/3 of the volume of the prepolymerization reactor; the mass of the catalyst added in the prepolymerization reaction is 0.5-2.5% of the added mass of the propylene oxide; the addition mass of the carbon dioxide in the prepolymerization reaction is 40-80% of the addition mass of the propylene oxide; the stirring speed during the prepolymerization reaction is 10-70 rpm. The catalyst mentioned in the invention is a common propylene oxide-carbon dioxide copolymerization catalyst, and in order to facilitate the prepolymerization and the polymerization reaction in the invention, the catalyst is preferably a zinc-based catalyst.
In the polymerization reaction process, the addition mass of the carbon dioxide is 2-10% of the addition mass of the propylene oxide in the prepolymerization reaction; the stirring speed during the polymerization reaction is 10-70 rpm. Carbon dioxide is added in the polymerization process, so that the amount of reactants is increased, and the conversion rate of the epoxy propane in the polymerization reaction is improved; because the cost of the carbon dioxide is lower and the cost of the propylene oxide is higher, the conversion rate of the propylene oxide is improved by increasing the amount of the carbon dioxide, thereby being beneficial to improving the utilization rate of the propylene oxide, increasing the yield of the propylene oxide-carbon dioxide copolymer and reducing the production cost of the propylene oxide-carbon dioxide copolymer.
In order to increase the contact area of propylene oxide and carbon dioxide and facilitate the reaction of propylene oxide and carbon dioxide, the invention adopts the mode of adding carbon dioxide from the bottom of a reaction kettle in the prepolymerization reaction and the polymerization reaction process; introducing carbon dioxide from the bottom of a prepolymerization reactor in the prepolymerization reaction process, and introducing carbon dioxide from the bottom of the polymerization reactor in the polymerization reaction; because the carbon dioxide is gas, the movement mode of the gas is from bottom to top, and the addition mode of the carbon dioxide is selected to be added from the bottom of the reaction kettle, on one hand, the carbon dioxide is convenient to fully contact with the epoxypropane in the process of moving from bottom to top, the epoxypropane fully reacts with the carbon dioxide, and the yield of epoxypropane-carbon dioxide is improved; on the other hand, in the process of moving from bottom to top, pores are generated in the propylene oxide, so that uniform stirring is facilitated, the reaction is enabled to be full, and the stability of the product is improved.
The molecular weight distribution of the propylene oxide-carbon dioxide copolymer prepared by the preparation method of the propylene oxide-carbon dioxide copolymer provided by the invention is detected by gel permeation chromatography, and the number average molecular weight of the propylene oxide-carbon dioxide copolymer reaches 30 ten thousand and the weight average molecular weight exceeds 60 ten thousand; the thermal stability of the propylene oxide-carbon dioxide copolymer is detected by thermogravimetric analysis, and the mass of the propylene oxide-carbon dioxide copolymer is changed at 275.32 ℃ by spectrum analysis, so that the propylene oxide-carbon dioxide copolymer has good thermal stability.
Example 1
The present embodiment provides a method for producing a propylene oxide-carbon dioxide copolymer, comprising the steps of:
s1: adding propylene oxide with the volume of 1/4 of the volume of the prepolymerization reactor and a catalyst with the mass of 0.5 percent of the added mass of the propylene oxide into the prepolymerization reactor, and stirring at a stirring speed of 10 revolutions per minute;
s2: introducing carbon dioxide gas with the mass of 40% of the feeding mass of propylene oxide into the prepolymerization reactor from the bottom of the prepolymerization reactor, controlling the pressure in the prepolymerization reactor to be 4.0Mpa, controlling the temperature in the prepolymerization reactor to be 60 ℃, and performing prepolymerization reaction until the viscosity of a product in the prepolymerization reactor is 200cP, so as to obtain propylene oxide-carbon dioxide prepolymer;
s3: adding propylene oxide-carbon dioxide prepolymer into a polymerization kettle, stirring at a stirring speed of 10 revolutions per minute, introducing carbon dioxide gas with the mass of 2% of the feeding mass of propylene oxide into the polymerization kettle from the bottom of the polymerization kettle, controlling the pressure in the polymerization kettle to be 4.0Mpa, controlling the temperature in the polymerization kettle to be 60 ℃, and carrying out polymerization until the viscosity of a product in the polymerization kettle is 1000cP, thereby obtaining the propylene oxide-carbon dioxide copolymer.
The prepared propylene oxide-carbon dioxide copolymer was separated by a vacuum devolatilization method, and the molecular mass of the prepared propylene oxide-carbon dioxide copolymer was determined by gel permeation chromatography, and the thermal stability of the prepared propylene oxide-carbon dioxide copolymer was examined by thermogravimetric analysis.
Referring to FIG. 2, the peak molecular weight of the propylene oxide-carbon dioxide copolymer prepared in this example reached 70 ten thousand; the propylene oxide-carbon dioxide copolymer prepared in the example has a number average molecular weight of 30 ten thousand and a weight average molecular weight of more than 60 ten thousand as measured by gel permeation chromatography; referring to FIG. 3, the propylene oxide-carbon dioxide copolymer prepared in this example has a mass change at 275.32 ℃, which indicates that the propylene oxide-carbon dioxide copolymer has good thermal stability and is suitable for use in film materials.
According to the preparation method of the propylene oxide-carbon dioxide copolymer, the preparation of the propylene oxide-carbon dioxide copolymer is divided into the two processes of prepolymerization and polymerization by adopting a multi-kettle serial polymerization process, so that the viscosity and the molecular weight of the product in the same reaction kettle are relatively close, the temperature change range in the reaction kettle is relatively small, the reaction process in each reaction kettle is relatively simple, therefore, the stirring structures in the prepolymerization kettle and the polymerization kettle are easily selected, the stirring is relatively uniform, the reaction is relatively sufficient, and the prepared propylene oxide-carbon dioxide copolymer has relatively high molecular weight and good thermal stability and is suitable for film materials.
Example two
Unlike the first embodiment, the preparation method of the propylene oxide-carbon dioxide copolymer provided in this embodiment includes the following steps:
s1: sequentially adding propylene oxide with the volume of 1/2 of the volume of the prepolymerization reactor and a catalyst with the mass of 1.5% of the added mass of the propylene oxide into the prepolymerization reactor, and stirring at a stirring speed of 40 revolutions per minute;
s2: introducing carbon dioxide gas with the mass of 60% of the propylene oxide feeding mass into the prepolymerization reactor from the bottom of the prepolymerization reactor, controlling the pressure in the prepolymerization reactor to be 5.5Mpag, controlling the temperature in the prepolymerization reactor to be 75 ℃, and performing prepolymerization reaction until the viscosity of a product in the prepolymerization reactor is 450cP to obtain a propylene oxide-carbon dioxide prepolymer;
s3: adding propylene oxide-carbon dioxide prepolymer into a polymerization kettle, stirring at a stirring speed of 40 revolutions per minute, introducing carbon dioxide gas with the mass of 2% of the feeding mass of propylene oxide into the polymerization kettle from the bottom of the polymerization kettle, controlling the pressure in the polymerization kettle to be 5.5Mpa, controlling the temperature in the polymerization kettle to be 75 ℃, and carrying out polymerization until the viscosity of a product in the polymerization kettle is 8000cP, thereby obtaining the propylene oxide-carbon dioxide copolymer.
The prepared propylene oxide-carbon dioxide copolymer was separated by a vacuum devolatilization method, and the molecular mass of the prepared propylene oxide-carbon dioxide copolymer was determined by gel permeation chromatography, and the thermal stability of the prepared propylene oxide-carbon dioxide copolymer was examined by thermogravimetric analysis.
The propylene oxide-carbon dioxide copolymer prepared by the embodiment has the number average molecular weight of 30 ten thousand and the weight average molecular weight of more than 60 ten thousand, and simultaneously has good thermal stability, and is suitable for film materials.
Example III
Unlike the above examples, the preparation method of propylene oxide-carbon dioxide copolymer provided in this example includes the following steps:
s1: sequentially adding propylene oxide with the volume of 2/3 of the volume of the prepolymerization reactor and a catalyst with the mass of 2.5% of the added mass of the propylene oxide into the prepolymerization reactor, and stirring at a stirring speed of 70 rpm;
s2: introducing carbon dioxide gas with the mass of 80% of the propylene oxide feeding mass into the prepolymerization reactor from the bottom of the prepolymerization reactor, controlling the pressure in the prepolymerization reactor to be 7.0Mpa, controlling the temperature in the prepolymerization reactor to be 90 ℃, and performing prepolymerization reaction until the viscosity of a product in the prepolymerization reactor is 700cP, so as to obtain a propylene oxide-carbon dioxide prepolymer;
s3: adding propylene oxide-carbon dioxide prepolymer into a polymerization kettle, stirring at a stirring speed of 70 r/min, introducing carbon dioxide gas with the mass of 2% of the feeding mass of propylene oxide into the polymerization kettle from the bottom of the polymerization kettle, controlling the pressure in the polymerization kettle to be 7.0Mpa, controlling the temperature in the polymerization kettle to be 90 ℃, and carrying out polymerization until the viscosity of a product in the polymerization kettle is 15000cP, thus obtaining the propylene oxide-carbon dioxide copolymer.
The prepared propylene oxide-carbon dioxide copolymer was separated by a vacuum devolatilization method, and the molecular mass of the prepared propylene oxide-carbon dioxide copolymer was determined by gel permeation chromatography, and the thermal stability of the prepared propylene oxide-carbon dioxide copolymer was examined by thermogravimetric analysis.
The propylene oxide-carbon dioxide copolymer prepared by the embodiment has the number average molecular weight of 30 ten thousand and the weight average molecular weight of more than 60 ten thousand, and simultaneously has good thermal stability, and is suitable for film materials.
Example IV
This example provides a propylene oxide-carbon dioxide copolymer produced by the production method in the above example.
The propylene oxide-carbon dioxide copolymer provided by the embodiment has the number average molecular weight of 30 ten thousand and the weight average molecular weight of more than 60 ten thousand, and simultaneously has good thermal stability, and is suitable for film materials.
The foregoing description of the preferred embodiment of the invention is merely illustrative of the invention and is not intended to be limiting. It will be appreciated by persons skilled in the art that many variations, modifications, and even equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A method for preparing propylene oxide-carbon dioxide copolymer, which is characterized by comprising the following steps:
s1: adding propylene oxide and a catalyst into a prepolymerization reactor, and stirring; wherein the addition amount of the propylene oxide is 1/4-2/3 of the volume of the prepolymerization reactor, and the addition amount of the catalyst is 0.5% -2.5% of the addition mass of the propylene oxide;
s2: introducing carbon dioxide gas into the prepolymerization reactor, wherein the addition mass of the carbon dioxide is 40% -80% of the addition mass of the propylene oxide, controlling the temperature in the prepolymerization reactor to be 60-90 ℃ and the pressure to be 4.0-7.0MPaG, and performing prepolymerization reaction, and ending the prepolymerization reaction when the viscosity of a prepolymerization product reaches 200-700cP to obtain a propylene oxide-carbon dioxide prepolymer;
s3: adding reactants and products in the prepolymerization reactor into a polymerization reactor, stirring, adding carbon dioxide gas into the polymerization reactor, controlling the adding mass of the added carbon dioxide gas to be 2% -10% of the adding mass of the propylene oxide in the prepolymerization reaction, controlling the temperature in the polymerization reactor to be 60-90 ℃ and the pressure to be 4.0-7.0MPaG, carrying out polymerization reaction, and ending the polymerization reaction when the viscosity of the polymerization product reaches 1000-15000cP, thereby obtaining the propylene oxide-carbon dioxide copolymer.
2. The method for producing a propylene oxide-carbon dioxide copolymer according to claim 1, wherein the carbon dioxide gas is added in the step S2 from the bottom of the prepolymerization reactor.
3. The method for producing a propylene oxide-carbon dioxide copolymer according to claim 1, wherein the carbon dioxide gas is added in the step S3 from the bottom of the polymerizer.
4. A propylene oxide-carbon dioxide copolymer, characterized in that the propylene oxide-carbon dioxide copolymer is produced by the process for producing a propylene oxide-carbon dioxide copolymer as claimed in any one of claims 1 to 3.
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| CN103992470A (en) * | 2014-03-24 | 2014-08-20 | 中国化学赛鼎宁波工程有限公司 | Preparation method of epoxy propane-carbon dioxide copolymer |
| WO2015100517A1 (en) * | 2013-12-31 | 2015-07-09 | 内蒙古蒙西高新技术集团有限公司 | Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor |
| WO2018089568A1 (en) * | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Semi-batch process for making polycarbonate polyols via copolymerization of carbon dioxide and an oxirane |
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| WO2015100517A1 (en) * | 2013-12-31 | 2015-07-09 | 内蒙古蒙西高新技术集团有限公司 | Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor |
| CN103992470A (en) * | 2014-03-24 | 2014-08-20 | 中国化学赛鼎宁波工程有限公司 | Preparation method of epoxy propane-carbon dioxide copolymer |
| WO2018089568A1 (en) * | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Semi-batch process for making polycarbonate polyols via copolymerization of carbon dioxide and an oxirane |
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