CN109438689A - A kind of propylene oxide-carbon dioxide copolymer and preparation method thereof - Google Patents
A kind of propylene oxide-carbon dioxide copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN109438689A CN109438689A CN201811222321.0A CN201811222321A CN109438689A CN 109438689 A CN109438689 A CN 109438689A CN 201811222321 A CN201811222321 A CN 201811222321A CN 109438689 A CN109438689 A CN 109438689A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- propylene oxide
- kettle
- prepolymerization
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 45
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- QEYNXBRMPSQXIG-UHFFFAOYSA-N carbon dioxide;2-methyloxirane Chemical compound O=C=O.CC1CO1 QEYNXBRMPSQXIG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 230000008901 benefit Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 20
- 238000003756 stirring Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 11
- 229960004424 carbon dioxide Drugs 0.000 description 39
- 239000000047 product Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 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
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
Abstract
The present invention discloses a kind of propylene oxide-carbon dioxide copolymer and preparation method thereof, and the preparation method of the propylene oxide-carbon dioxide copolymer includes: S1: propylene oxide and catalyst being added into prepolymerization kettle, are stirred；It is passed through carbon dioxide gas in S2: Xiang Suoshu prepolymerization kettle, carries out prepolymerization, obtains propylene oxide-carbon dioxide prepolymer；S3: the propylene oxide-carbon dioxide prepolymer being added in polymeric kettle, is stirred, and carbon dioxide gas is passed through in Xiang Suoshu polymeric kettle, is carried out polymerization reaction, is obtained propylene oxide-carbon dioxide copolymer.The preparation method of propylene oxide-carbon dioxide copolymer provided by the invention, by the way that the preparation of propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization and polymerization reaction, so that the viscosity of product is closer in same reaction kettle, stirring structure is easy to select, and stirring is more uniform, is conducive to the stability for improving product.
Description
Technical field
The present invention relates to technical field of macromolecules, and in particular to a kind of propylene oxide-carbon dioxide copolymer and its preparation
Method.
Background technique
Carbon dioxide is to influence maximum greenhouse gases to global warming, and synthesizing epoxypropane-carbon dioxide copolymer
One of primary raw material be carbon dioxide, propylene oxide-carbon dioxide copolymer can consume a large amount of two in the synthesis process
Carbonoxide；Meanwhile propylene oxide-carbon dioxide copolymer is a kind of Full degradation type polymer, propylene oxide-carbon dioxide copolymerization
Object has many advantages, such as that production cost is low, transparent and gas good barrier property, processing performance are excellent, alternative nondegradable plastics
Product is widely used in film and packaging material field, has revolutionary significance for solution " white pollution ".
But existing propylene oxide-carbon dioxide copolymer is mainly by being placed in synthesis for carbon dioxide and propylene oxide
In reaction kettle, the temperature and pressure in synthesis reaction vessel is controlled, directly carries out reaction synthesis under the action of catalyst；Epoxy at present
Propane-carbon dioxide copolymer synthesis technology reaction process is complicated, and process is difficult to control.
In view of the above drawbacks, creator of the present invention obtains the present invention by prolonged research and practice finally.
Summary of the invention
To solve above-mentioned technological deficiency, the technical solution adopted by the present invention is, provides a kind of propylene oxide-carbon dioxide
The preparation method of copolymer, includes the following steps:
S1: propylene oxide and catalyst are added into prepolymerization kettle, are stirred；
It is passed through carbon dioxide gas in S2: Xiang Suoshu prepolymerization kettle, controlling the temperature in the prepolymerization kettle is 60-90 DEG C, into
Row prepolymerization obtains propylene oxide-carbon dioxide prepolymer；
S3: the propylene oxide-carbon dioxide prepolymer is added in polymeric kettle, is stirred, in Xiang Suoshu polymeric kettle
It is passed through carbon dioxide gas, controlling the temperature in the polymeric kettle is 60-90 DEG C, carries out polymerization reaction, obtains propylene oxide-two
Carbon oxide copolymer.
Optionally, the pressure in prepolymerization kettle described in step S2 is 4.0-7.0Mpag.
Optionally, the pressure in polymeric kettle described in step S3 is 4.0-7.0Mpag.
Optionally, the additive amount of propylene oxide described in step S1 is the 1/4-2/3 of the prepolymerization kettle volume.
Optionally, the additive amount of catalyst described in step S1 is the 0.5%-2.5% that the propylene oxide adds quality.
Optionally, the addition quality of carbon dioxide described in step S2 is the charging quality of propylene oxide described in step S1
40%-80%.
Optionally, in step S3 carbon dioxide addition quality be step S1 described in propylene oxide feed quality 2%-
10%.
Optionally, the adding manner of carbon dioxide gas described in step S2 is to be added from the bottom of the prepolymerization kettle.
Optionally, the adding manner of carbon dioxide gas described in step S3 is to be added from the bottom of the polymeric kettle.
A kind of propylene oxide-carbon dioxide copolymer, the propylene oxide-carbon dioxide copolymer is by above-mentioned epoxy third
Alkane-carbon dioxide copolymer preparation method is made.
Compared with the prior art the beneficial effects of the present invention are:
1, the preparation method of propylene oxide-carbon dioxide copolymer provided by the invention polymerize by using multi-floating bodies
The preparation of propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization and polymerization reaction by technique, so that same
The viscosity of product is closer in reaction kettle, simultaneously because the molecular weight of product is closer in same reaction kettle, in reaction kettle
Range of temperature is smaller, and the reaction process in each reaction kettle is relatively simple, and therefore, the stirring structure in reaction kettle is easy
In selection, and stirring is more uniform, so that reaction is more abundant, is conducive to the stability for improving product；
2, propylene oxide-carbon dioxide is total to by the preparation method of propylene oxide-carbon dioxide copolymer provided by the invention
After the preparation of polymers is divided into two processes of prepolymerization and polymerization reaction, on the one hand, due to product in prepolymerization kettle viscosity compared with
It is small, it is easy to stir, therefore, the power of stirring motor is lower, so as to reduce being produced into for propylene oxide-carbon dioxide copolymer
This；On the other hand, due in polymeric kettle propylene oxide-carbon dioxide copolymer viscosity differ smaller, even molecular weight distribution,
It stirs evenly, therefore polymerization reaction progress is more abundant, is conducive to the increasing of propylene oxide-carbon dioxide molecular weight of copolymer
It is long, so that the molecular weight of propylene oxide-carbon dioxide copolymer is higher, be conducive to enhance product performance.
Detailed description of the invention
It, below will be to required in embodiment description in order to illustrate more clearly of the technical solution in various embodiments of the present invention
The attached drawing used is briefly described.
Fig. 1 is the flow chart of propylene oxide-carbon dioxide copolymer preparation method of the present invention；
Fig. 2 is the gel permeation chromatogram of propylene oxide-carbon dioxide copolymer of the present invention；
Fig. 3 is the thermogravimetric analysis spectrogram of propylene oxide-carbon dioxide copolymer of the present invention.
Specific embodiment
Below in conjunction with attached drawing, the forgoing and additional technical features and advantages are described in more detail.
The present invention provides a kind of preparation method of propylene oxide-carbon dioxide copolymer, shown in Figure 1, the preparation side
The preparation of propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization and polymerization reaction, wherein prepolymerization by method
Reaction carries out in prepolymerization kettle, and polymerization reaction carries out in polymeric kettle, i.e., propylene oxide-carbon dioxide copolymerization provided by the invention
The preparation method of object is using multi-floating bodies polymerization technique.
Specific preparation process is that propylene oxide and catalyst are added into prepolymerization kettle according to a certain percentage first, into
Row stirring, then is passed through carbon dioxide gas into prepolymerization kettle, and wherein the additional amount of carbon dioxide is according to the additional amount of propylene oxide
It determines；Pressure in control prepolymerization kettle is maintained within the scope of 4.0-7.0Mpag, and keeps the temperature in prepolymerization kettle at 60-90 DEG C
Prepolymerization is carried out in range, under the conditions of so that propylene oxide and carbon dioxide are existing for the catalyst；Due to polymer
Viscosity increases with the increase of molecular weight, therefore, prepolymerization process again by detect prepolymerization product viscosity come
The molecular weight of prepolymerization product is monitored, and then controls the end time of prepolymerization according to the viscosity of prepolymerization product, i.e.,
When the viscosity of prepolymerization product reaches preset viscosity number, terminate prepolymerization, obtains that average molecular weight is smaller, average mark
The shorter prepolymerization product of subchain；Detailed process is to detect prepolymerization product by the in-line viscometer in prepolymerization kettle
Viscosity, when the viscosity of prepolymerization product reaches 200-700cP, terminate prepolymerization, obtain propylene oxide-carbon dioxide
Prepolymer.
By in prepolymerization kettle reactant and product be added polymeric kettle in, and into polymeric kettle supplement be passed through a certain amount of two
The amount of carbon oxide gas, the carbon dioxide gas which is passed through is determined according to the amount for the propylene oxide being added into prepolymerization kettle；
Pressure in control polymeric kettle is maintained within the scope of 4.0-7.0Mpag, and keeps the temperature in polymeric kettle in 60-90 DEG C of range
It is interior so that average molecular weight is smaller, the shorter propylene oxide-carbon dioxide prepolymer of average mark subchain residual catalyst catalysis
Effect is lower, and the reaction was continued, and the strand of product continues growing, i.e. propylene oxide-carbon dioxide prepolymer is gathered in polymeric kettle
Close reaction；The viscosity that polymerizate is detected by the in-line viscometer in polymeric kettle, when the viscosity of polymerizate reaches 1000-
When 15000cP, terminate polymerization reaction, propylene oxide-carbon dioxide copolymer is made.
The preparation of propylene oxide-carbon dioxide copolymer is divided into prepolymerization by using multi-floating bodies polymerization technique
With two processes of polymerization reaction, so that the viscosity of product is within the scope of 200-700cP in prepolymerization kettle, the viscosity of product in polymeric kettle
The viscosity of product is closer within the scope of 1000-15000cP, that is, in same reaction kettle, simultaneously because same reaction kettle
The molecular weight of interior product is closer to, and reactor temperature variation range is smaller, and the reaction process in each reaction kettle is more
Simply, therefore, the stirring structure in prepolymerization kettle and polymeric kettle is easy to select, and stir it is more uniform so that reaction
More sufficiently, be conducive to improve the stability of product.
After the preparation of propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization and polymerization reaction, one
Aspect is easy to stir since the viscosity of product in prepolymerization kettle is smaller, and therefore, the power of stirring motor is lower, so as to reduce ring
Ethylene Oxide-carbon dioxide copolymer production cost；On the other hand, due to propylene oxide-carbon dioxide copolymer in polymeric kettle
Viscosity difference it is smaller, even molecular weight distribution stirs evenly, thus polymerization reaction carry out more sufficiently, be conducive to epoxy
The growth of propane-carbon dioxide copolymer molecular weight, so that the molecular weight of propylene oxide-carbon dioxide copolymer is higher,
Be conducive to enhance product performance.
During prepolymerization, to react propylene oxide sufficiently with carbon dioxide, propylene oxide and dioxy are improved
Change charcoal percent conversion, the additive amount of propylene oxide can be depending on the volume of prepolymerization kettle, the addition of the preferred propylene oxide of the present invention
Amount is the 1/4-2/3 of prepolymerization kettle volume, that is, the volume for being added to the propylene oxide in prepolymerization kettle is the 1/4-2/ of prepolymerization kettle volume
3；The quality of the catalyst added in prepolymerization is the 0.5%-2.5% that propylene oxide adds quality；In prepolymerization
The addition quality of carbon dioxide is the 40%-80% that propylene oxide adds quality；Mixing speed during prepolymerization is
10-70 revs/min.The catalyst that the present invention mentions is common propylene oxide-carbon dioxide copolyreaction catalyst, for the benefit of originally
Prepolymerization and the progress of polymerization reaction in invention, preferred catalyst of the present invention are zinc based catalyst.
In polymerization process, the addition quality of carbon dioxide is the 2%- of prepolymerization oxypropylene charging quality
10%；Mixing speed in polymerization process is 10-70 revs/min.Carbon dioxide is added in supplement in polymerization process, increases
The amount of reactant is conducive to the conversion ratio for improving polymerization reaction oxypropylene；Since cost is relatively low for carbon dioxide, and epoxy
The higher cost of propane improves the conversion ratio of propylene oxide by increasing the amount of carbon dioxide, is conducive to improve propylene oxide
Utilization rate, increase propylene oxide-carbon dioxide copolymer yield, reduce propylene oxide-carbon dioxide copolymer production
Cost.
For the contact area for increasing propylene oxide and carbon dioxide, reacted convenient for propylene oxide with carbon dioxide, this
The adding manner of carbon dioxide is to be added from the bottom of reaction kettle in invention prepolymerization and polymerization process；It is i.e. pre-
Carbon dioxide is passed through from the bottom of prepolymerization kettle in polymerization process, by carbon dioxide from the bottom of polymeric kettle in polymerization reaction
It is passed through；Since carbon dioxide is gas, and the motion mode of gas is to move from the bottom up, and the adding manner of carbon dioxide is selected
Be selected as being added from the bottom of reaction kettle, on the one hand convenient for carbon dioxide during moving from bottom to top sufficiently and propylene oxide
Contact, reacts propylene oxide sufficiently with carbon dioxide, improves the yield of propylene oxide-carbon dioxide；On the other hand, titanium dioxide
During carbon moves from bottom to top, hole is generated in propylene oxide, is conducive to stir evenly, so that reaction is sufficiently,
Improve the stability of product.
The preparation method using propylene oxide-carbon dioxide copolymer provided by the invention is detected by gel permeation chromatography
The molecular weight distribution of propylene oxide-carbon dioxide copolymer obtained, by atlas analysis it is found that obtained propylene oxide-
The number-average molecular weight of carbon dioxide copolymer reaches 300,000, and weight average molecular weight is more than 600,000；Obtained by being detected by thermogravimetric analysis
Propylene oxide-carbon dioxide copolymer thermal stability, by atlas analysis it is found that propylene oxide-carbon dioxide copolymer
At 275.32 DEG C, quality changes, and illustrates that the propylene oxide-carbon dioxide copolymer has good thermal stability.
Embodiment one
The present embodiment provides a kind of preparation method of propylene oxide-carbon dioxide copolymer, which includes as follows
Step:
S1: being the catalysis of propylene oxide addition quality 0.5% by propylene oxide and quality that volume is prepolymerization kettle volume 1/4
Agent is added into prepolymerization kettle, is stirred with 10 revs/min of mixing speed；
S2: the carbon dioxide gas that quality is propylene oxide charging quality 40% is passed through into prepolymerization kettle from the bottom of prepolymerization kettle
Body, controlling the pressure in prepolymerization kettle is 4.0Mpag, and controlling the temperature in the prepolymerization kettle is 60 DEG C, carries out prepolymerization extremely
The viscosity of product is 200cP in prepolymerization kettle, obtains propylene oxide-carbon dioxide prepolymer；
S3: propylene oxide-carbon dioxide prepolymer being added in polymeric kettle, is stirred with 10 revs/min of mixing speed,
The carbon dioxide gas that quality is propylene oxide charging quality 2%, control polymerization are passed through into polymeric kettle from the bottom of polymeric kettle
Pressure in kettle is 4.0Mpag, and controlling the temperature in polymeric kettle is 60 DEG C, carries out the viscosity of product in polymerization reaction to polymeric kettle
For 1000cP, propylene oxide-carbon dioxide copolymer is obtained.
By the method for vacuum volatilization, propylene oxide-carbon dioxide copolymer obtained is separated, and passes through gel
Permeation chromatography measures the molecular mass of propylene oxide-carbon dioxide copolymer obtained, is detected by thermogravimetric analysis obtained
Propylene oxide-carbon dioxide copolymer thermal stability.
Shown in Figure 2, the peak molecular weight of propylene oxide-carbon dioxide copolymer made from the present embodiment reaches 70
Ten thousand；It is reached by the number-average molecular weight that gel permeation chromatography measures propylene oxide-carbon dioxide copolymer prepared by the present embodiment
To 300,000, weight average molecular weight is more than 600,000；Shown in Figure 3, propylene oxide-carbon dioxide copolymer made from the present embodiment exists
Quality changes at 275.32 DEG C, illustrates that the propylene oxide-carbon dioxide copolymer has good thermal stability, is suitble to use
In thin-film material.
The preparation method of propylene oxide-carbon dioxide copolymer provided in this embodiment, polymerize by using multi-floating bodies
The preparation of propylene oxide-carbon dioxide copolymer is divided into two processes of prepolymerization and polymerization reaction by technique, so that same
The viscosity of product and molecular weight are closer in reaction kettle, and reactor temperature variation range is smaller, in each reaction kettle
Reaction process is relatively simple, and therefore, the stirring structure in prepolymerization kettle and polymeric kettle is easy to select, and stirs more equal
It is even, so that reaction is more abundant, propylene oxide-carbon dioxide copolymer obtained molecular weight with higher and good
Thermal stability is suitable for thin-film material.
Embodiment two
What is different from the first embodiment is that the preparation method packet of propylene oxide-carbon dioxide copolymer provided in this embodiment
Include following steps:
S1: being successively propylene oxide addition quality 1.5% by propylene oxide and quality that volume is prepolymerization kettle volume 1/2
Catalyst is added into prepolymerization kettle, is stirred with 40 revs/min of mixing speed；
S2: the carbon dioxide gas that quality is propylene oxide charging quality 60% is passed through into prepolymerization kettle from the bottom of prepolymerization kettle
Body, controlling the pressure in prepolymerization kettle is 5.5Mpag, and controlling the temperature in the prepolymerization kettle is 75 DEG C, carries out prepolymerization extremely
The viscosity of product is 450cP in prepolymerization kettle, obtains propylene oxide-carbon dioxide prepolymer；
S3: propylene oxide-carbon dioxide prepolymer being added in polymeric kettle, is stirred with 40 revs/min of mixing speed,
The carbon dioxide gas that quality is propylene oxide charging quality 2%, control polymerization are passed through into polymeric kettle from the bottom of polymeric kettle
Pressure in kettle is 5.5Mpag, and controlling the temperature in polymeric kettle is 75 DEG C, carries out the viscosity of product in polymerization reaction to polymeric kettle
For 8000cP, propylene oxide-carbon dioxide copolymer is obtained.
By the method for vacuum volatilization, propylene oxide-carbon dioxide copolymer obtained is separated, and passes through gel
Permeation chromatography measures the molecular mass of propylene oxide-carbon dioxide copolymer obtained, is detected by thermogravimetric analysis obtained
Propylene oxide-carbon dioxide copolymer thermal stability.
The number-average molecular weight of propylene oxide-carbon dioxide copolymer made from the present embodiment reaches 300,000, weight average molecular weight
More than 600,000, while there is good thermal stability, is suitable for thin-film material.
Embodiment three
It is unlike the embodiments above, the preparation method of propylene oxide-carbon dioxide copolymer provided in this embodiment
Include the following steps:
S1: be successively propylene oxide addition quality by propylene oxide that volume is prepolymerization kettle volume 2/3 and quality being 2.5%
Catalyst be added into prepolymerization kettle, be stirred with 70 revs/min of mixing speed；
S2: the carbon dioxide gas that quality is propylene oxide charging quality 80% is passed through into prepolymerization kettle from the bottom of prepolymerization kettle
Body, controlling the pressure in prepolymerization kettle is 7.0Mpag, and controlling the temperature in the prepolymerization kettle is 90 DEG C, carries out prepolymerization extremely
The viscosity of product is 700cP in prepolymerization kettle, obtains propylene oxide-carbon dioxide prepolymer；
S3: propylene oxide-carbon dioxide prepolymer being added in polymeric kettle, is stirred with 70 revs/min of mixing speed,
The carbon dioxide gas that quality is propylene oxide charging quality 2%, control polymerization are passed through into polymeric kettle from the bottom of polymeric kettle
Pressure in kettle is 7.0Mpag, and controlling the temperature in polymeric kettle is 90 DEG C, carries out the viscosity of product in polymerization reaction to polymeric kettle
For 15000cP, propylene oxide-carbon dioxide copolymer is obtained.
By the method for vacuum volatilization, propylene oxide-carbon dioxide copolymer obtained is separated, and passes through gel
Permeation chromatography measures the molecular mass of propylene oxide-carbon dioxide copolymer obtained, is detected by thermogravimetric analysis obtained
Propylene oxide-carbon dioxide copolymer thermal stability.
The number-average molecular weight of propylene oxide-carbon dioxide copolymer made from the present embodiment reaches 300,000, weight average molecular weight
More than 600,000, while there is good thermal stability, is suitable for thin-film material.
Example IV
The present embodiment provides a kind of propylene oxide-carbon dioxide copolymers, and the propylene oxide-carbon dioxide copolymer is by upper
The preparation method stated in embodiment is made.
The number-average molecular weight of propylene oxide-carbon dioxide copolymer provided in this embodiment reaches 300,000, weight average molecular weight
More than 600,000, while there is good thermal stability, is suitable for thin-film material.
The foregoing is merely presently preferred embodiments of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive
's.Those skilled in the art understand that in the spirit and scope defined by the claims in the present invention many changes can be carried out to it,
It modifies or even equivalent, but falls in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of propylene oxide-carbon dioxide copolymer, which comprises the steps of:
S1: propylene oxide and catalyst are added into prepolymerization kettle, are stirred；
It is passed through carbon dioxide gas in S2: Xiang Suoshu prepolymerization kettle, controlling the temperature in the prepolymerization kettle is 60-90 DEG C, is carried out pre-
Polymerization reaction obtains propylene oxide-carbon dioxide prepolymer；
S3: the propylene oxide-carbon dioxide prepolymer is added in polymeric kettle, is stirred, is passed through in Xiang Suoshu polymeric kettle
Carbon dioxide gas, controlling the temperature in the polymeric kettle is 60-90 DEG C, carries out polymerization reaction, obtains propylene oxide-titanium dioxide
Carbon copolymer.
2. the preparation method of propylene oxide-carbon dioxide copolymer as described in claim 1, which is characterized in that in step S2
Pressure in the prepolymerization kettle is 4.0-7.0Mpag.
3. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 2, which is characterized in that in step S3
Pressure in the polymeric kettle is 4.0-7.0Mpag.
4. the preparation method of propylene oxide-carbon dioxide copolymer as described in any one of claims 1-3, which is characterized in that
The additive amount of propylene oxide described in step S1 is the 1/4-2/3 of the prepolymerization kettle volume.
5. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 4, which is characterized in that in step S1
The additive amount of the catalyst is the 0.5%-2.5% that the propylene oxide adds quality.
6. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 4, which is characterized in that in step S2
The addition quality of the carbon dioxide is the 40%-80% of the charging quality of propylene oxide described in step S1.
7. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 6, which is characterized in that in step S3
The addition quality of carbon dioxide is the 2%-10% of the charging quality of propylene oxide described in step S1.
8. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 4, which is characterized in that in step S2
The adding manner of the carbon dioxide gas is to be added from the bottom of the prepolymerization kettle.
9. the preparation method of propylene oxide-carbon dioxide copolymer as claimed in claim 4, which is characterized in that in step S3
The adding manner of the carbon dioxide gas is to be added from the bottom of the polymeric kettle.
10. a kind of propylene oxide-carbon dioxide copolymer, which is characterized in that the propylene oxide-carbon dioxide copolymer is by weighing
Benefit requires the preparation method of the described in any item propylene oxide-carbon dioxide copolymers of 1-9 to be made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811222321.0A CN109438689B (en) | 2018-10-19 | 2018-10-19 | Propylene oxide-carbon dioxide copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811222321.0A CN109438689B (en) | 2018-10-19 | 2018-10-19 | Propylene oxide-carbon dioxide copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109438689A true CN109438689A (en) | 2019-03-08 |
| CN109438689B CN109438689B (en) | 2024-01-12 |
Family
ID=65546931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811222321.0A Active CN109438689B (en) | 2018-10-19 | 2018-10-19 | Propylene oxide-carbon dioxide copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109438689B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143204A (en) * | 2020-10-21 | 2020-12-29 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN114031761A (en) * | 2021-10-14 | 2022-02-11 | 华峰集团上海工程有限公司 | PPC synthesis system and synthesis process thereof |
| CN116606428A (en) * | 2023-06-30 | 2023-08-18 | 中国科学院长春应用化学研究所 | Preparation method of carbon dioxide-epoxide copolymer by combining bulk and solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20160152651A1 (en) * | 2013-07-18 | 2016-06-02 | Sk Innovation Co.,Ltd. | Double Metal Cyanide Catalyst and Epoxide/Carbon Dioxide Copolymer Prepared Using the Same |
| 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 |
-
2018
- 2018-10-19 CN CN201811222321.0A patent/CN109438689B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160152651A1 (en) * | 2013-07-18 | 2016-06-02 | Sk Innovation Co.,Ltd. | Double Metal Cyanide Catalyst and Epoxide/Carbon Dioxide Copolymer Prepared Using the Same |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143204A (en) * | 2020-10-21 | 2020-12-29 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN112143204B (en) * | 2020-10-21 | 2021-07-23 | 中国科学院长春应用化学研究所 | Carbon dioxide-based copolymer foamed plastic and preparation method thereof |
| CN114031761A (en) * | 2021-10-14 | 2022-02-11 | 华峰集团上海工程有限公司 | PPC synthesis system and synthesis process thereof |
| CN114031761B (en) * | 2021-10-14 | 2023-09-08 | 华峰集团上海工程有限公司 | PPC synthesis system and synthesis process thereof |
| CN116606428A (en) * | 2023-06-30 | 2023-08-18 | 中国科学院长春应用化学研究所 | Preparation method of carbon dioxide-epoxide copolymer by combining bulk and solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109438689B (en) | 2024-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438689A (en) | A kind of propylene oxide-carbon dioxide copolymer and preparation method thereof | |
| KR101941732B1 (en) | Long chain branched polymers and methods of making same | |
| CN1131244C (en) | Method of catalyst transitions in olefin polymerizations | |
| CN103865047B (en) | Synthetic method of a kind of segmented copolymer of degradable and products thereof | |
| CN114524929B (en) | Preparation method of carbon dioxide-based tetrapolymer | |
| CN1032016A (en) | The method of olefinic polymerization | |
| CN102481556A (en) | Cyclic organosilicon compounds as electron donors for polyolefin catalysts | |
| CN108034051A (en) | A kind of vinyl polysiloxane and preparation method and application | |
| CN107602751A (en) | A kind of low molecule amount hydroxyl chlorinated polyether resin and preparation method thereof | |
| CN114395063B (en) | Cycloolefin copolymer with polar group and preparation method thereof | |
| CN104151754B (en) | High fluidity ethylene-tetrafluoroethylene copolymer composition and method of making the same | |
| US20100331514A1 (en) | Ph-sensitive polyethylene oxide co-polymer and synthetic method thereof | |
| CN1227572A (en) | Catalyst | |
| CN105859918B (en) | A kind of solution polymerization process for adjusting the distribution of butyl rubber molecules amount | |
| CN106336488A (en) | Method for synthesizing high solid content and low viscosity POP through composite initiator | |
| CN106543331A (en) | A kind of method for preparing EVA elastomers | |
| CN1265609A (en) | High activity catalyst prepared with alkoxysilanes | |
| CN106467588A (en) | A kind of catalytic component for vinyl polymerization, its preparation method and application | |
| CN101544713A (en) | Polyvinyl acetate macro molecules and synthetic method and hydrolytic method thereof | |
| CN114479045B (en) | Carbon dioxide-based elastomer and preparation method thereof | |
| CN105524203A (en) | Preparation method for ethylene-vinyl acetate copolymer (EVA) elastomer by using mixed solvent | |
| US20220251268A1 (en) | Resin composition for injection molding or compression molding | |
| US11142600B2 (en) | Ethylene/1-hexene copolymer | |
| CN104031267B (en) | A kind of preparation method of special ethylene base content polysiloxanes | |
| CN115894750B (en) | Hydroxyl-terminated silicone rubber supported alpha-diimine nickel heterogeneous catalyst and preparation method, application and application method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |