CN103992470A - Preparation method of epoxy propane-carbon dioxide copolymer - Google Patents
Preparation method of epoxy propane-carbon dioxide copolymer Download PDFInfo
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- CN103992470A CN103992470A CN201410110619.8A CN201410110619A CN103992470A CN 103992470 A CN103992470 A CN 103992470A CN 201410110619 A CN201410110619 A CN 201410110619A CN 103992470 A CN103992470 A CN 103992470A
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Abstract
The invention discloses an epoxy propane carbon dioxide copolymer preparation method, characteristic includes the following steps: (1) sequentially adding epoxy propane and a multi-element catalyst to a polymerization reaction kettle, then introducing high purity carbon dioxide into the reaction kettle, controlling the pressure at 3.0-3.5 MPag and the temperature at 70-80 DEG C, reacting for 3-5 h until the viscosity reaches 7*105 CP, controlling the temperature at 65-70 DEG C, reacting for 4-5 h until the viscosity reaches 7*106 CP, cooling the material to 45-55 DEG C to obtain a crude copolymer product; and (2) starting a blender of a condensed washing kettle, reducing the pressure in the polymerization reaction kettle to 0.5 MPag, sending the crude product and a condensation detergent to the copolymerization washing kettle for even mixing, and conducting liquid-solid separation on the condensed washing mixed liquid to obtain the product. The invention has the advantages of high polymerization efficiency, a small amount of reaction by-products and low catalyst consumption.
Description
Technical field
The present invention relates to a kind of preparation method of propylene oxide-carbon dioxide copolymer.
Background technology
One of main raw material of synthetic carbon dioxide-epoxy propane copolymer-carbonic acid gas is the CO that many field of industrial productions produce
2waste gas, is discharged into and in atmosphere, has not only caused environmental pollution, and be the waste of carbon resource.Under catalyst action, while being activated higher degree, can there is copolyreaction with epoxide etc. in carbonic acid gas, generate carbonic acid gas-epoxide co-polymer, through aftertreatment, just obtains carbonic acid gas degradation material.Can be by CO by the synthetic of carbon dioxide-epoxy propane copolymer
2resource immobilization, this has not only opened up new carbon resource, alleviates the shortage of petrochemical materials, and can alleviate the environmental destruction causing because of Carbon emission.On the other hand, the complete biodegradable characteristic of carbon dioxide-epoxy propane copolymer, with the nonbiodegradable common plastics of replacement, can be widely used in the aspects such as packaging, table ware, daily use Sundry goods, disposable medical material, operation stitching, there is revolutionary meaning for solving " white pollution ".
Existing carbon dioxide-epoxypropane copolymer is by by carbonic acid gas (CO
2) be placed in synthesis reaction vessel with propylene oxide (PO), control the temperature and pressure in kettle, under the effect of catalyzer, directly react synthetic, this process chemistry reaction formula is as follows:
nCO
2?+?n(CH
2)
3O=-[O-(CO)-O(CH
2)
3-]
n
But, the stage up till now, in the documents and materials of having reported, all point out this reaction process complexity, process is difficult to control, and polymerization process thermal discharge is large, and heat is difficult to remove in time, thereby causes polymerization to be difficult to realize scale operation.Meanwhile, polymerization post polymerization cyclosiloxane monomer Ethylene Oxide is also the huge difficult problem that suitability for industrialized production faces with separating of polymkeric substance.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method that a kind of reaction efficiency is high, can realize the propylene oxide-carbon dioxide copolymer of large-scale industrial production.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of propylene oxide-carbon dioxide copolymer, comprises the following steps:
(1) crude product preparation
Water content is joined in polymerization reaction kettle lower than the propylene oxide of 50ppm, then add quantitative multicomponent catalyst, the stirring velocity of controlling polymerization reaction kettle is 10～70 revs/min, again purity is passed in polymerization reaction kettle higher than 99.95% carbon dioxide, controlling polymerization reaction kettle internal pressure is 3.0～3.5MPag, then be 70～80 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 3-5 hour, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be then 65-70 DEG C by polymeric reaction temperature control, continue reaction 4～5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 45-55 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product;
(2) reaction product separation and purification
The pressure of polymerization reaction kettle is dropped to after 0.5MPag, start the agitator of cohesion washing kettle, propylene oxide-carbon dioxide copolymer crude product is delivered to cohesion washing kettle, cohesion washing composition is delivered to cohesion washing kettle simultaneously, the cohesion washing composition adding makes catalyst deactivation, stop polyreaction, unreacted polymerization single polymerization monomer-propylene oxide is dissolved in cohesion washing composition simultaneously, propylene oxide-carbon dioxide copolymer is dispersed in cohesion washing composition with solid particulate form, after cohesion has been washed, cohesion cleaning mixture is through liquid-solid separation, obtain solids epoxy propane-carbon dioxide copolymer.
The addition of described propylene oxide is 1/4～1/2 of described polymerization reaction kettle volume, and the addition of described multicomponent catalyst is 1～2 wt % of described propylene oxide quality.
Described multicomponent catalyst is the Rare Earth complexing multicomponent catalyst of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine composition, and in described Rare Earth complexing multicomponent catalyst, the mass ratio of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine is (3～5): 1:(1～1.5).This matching polybasic catalyst best results.
Described cohesion washing composition is one or more the mixed solution in methyl alcohol, ethanol, Virahol, water, and the addition of described cohesion washing composition is 1.5 times of described propylene oxide add-on.
The kettle periphery wall of described polymerization reaction kettle is provided with chuck, in the still of described polymerization reaction kettle, is provided with spiral coil cooling tube.Chuck and coil pipe can be realized the temperature of charge in accurate control polymerization reaction kettle.
Described cohesion washing kettle, comprise round shape kettle, described kettle uprightly arranges, in kettle, be vertically arranged with the central rotating shaft being connected with external motor, described central rotating shaft lower end is longitudinally arranged side by side the elliposoidal agitator of some layers of hollow, described elliposoidal agitator stirs frame leaf by the ellipse of several hollows on described central rotating shaft that are crisscross arranged and surrounds, the internal side wall of described kettle is provided with filtration unit, and described kettle outer wall and the described corresponding position of filtration unit are provided with washings delivery pipe.Under this elliposoidal agitator effect, polymkeric substance is subject to the effect of centrifugal force in stirring, make solid polymer surface not complete reaction material fully washed, washings is discharged outside kettle by filtration unit and washings delivery pipe, thus make to stick to solid polymer surface not complete reaction material separate completely with solid polymer.
The angular interval that described adjacent ellipse stirs frame leaf is identical, and it is different that described ellipse stirs the horizontal diameter of frame leaf, and the height that described ellipse stirs frame leaf is 1/8～1/6 of described central rotating shaft length.The angular interval that stirs frame leaf due to each adjacent ellipse is identical, makes mixed with polymers liquid be distributed in each oval stirring between frame leaf of elliposoidal agitator, stir stressed evenly, thereby make washing more abundant, improve washing effect; The horizontal diameter that stirs frame leaf due to ellipse is different, makes mixed with polymers liquid all be subject to the effect of the oval stirring shearing force that stirs frame leaf and outside centrifugal force at different positions radially, improves cohesion washing effect; Due to ellipse stir rotating shaft centered by the height of frame leaf length 1/8～1/6, can better discharge polymkeric substance from discharge port, discharge solvent from washings delivery pipe.
Described elliposoidal agitator is 2 layers, elliposoidal agitator described in every layer stirs frame leaf by the ellipse of 5 hollows and surrounds, described ellipse stirs frame leaf and is respectively the first oval frame leaf that stirs, the second oval frame leaf that stirs, the 3rd oval frame leaf that stirs, the 4th oval frame leaf and the 5th oval frame leaf that stirs of stirring, the first described oval frame leaf that stirs, the second described oval frame leaf that stirs, the 3rd described oval frame leaf that stirs, 15/16 of kettle diameter described in the 4th described oval stirring frame leaf and the 5th described oval horizontal diameter that stirs frame leaf are respectively, 3/4, 9/16, 3/8 and 3/16.Each oval horizontal diameter that stirs frame leaf arranges according to the above ratio, can make to stir shear effect and centrifugation performance maximum effectiveness.
Described washings delivery pipe is distributed on the sidewall of described kettle and is positioned at described ellipse the side top of stirring frame leaf, described washings delivery pipe be inclined upwardly and and horizontal plane between angle be 20～30 °.Make washings be subject to centrifugal force upwards and throw away smoothly outside kettle.
On described central rotating shaft, be positioned at the top that described ellipse stirs frame leaf and be provided with oblique leaf formula stirring arm device, the length of described oblique leaf paddle agitator is 5/8 of described kettle diameter.The mixed with polymers liquid that makes to be positioned at oval agitator top is subject to stirring action, mixes more even, thereby make to wash more abundant, polymeric articles quality is improved.
Compared with prior art, the invention has the advantages that: the preparation method of a kind of propylene oxide-carbon dioxide copolymer of the present invention, comprise propylene oxide, carbonic acid gas is under the effect of certain temperature and pressure and catalyzer, reaction certain hour prepares propylene oxide-carbon dioxide copolymer crude product, propylene oxide-carbon dioxide copolymer crude product is delivered to cohesion washing kettle, cohesion washing composition is delivered to cohesion washing kettle simultaneously, after reaction certain hour, make catalyst deactivation stop polyreaction, make cyclosiloxane monomer Ethylene Oxide be dissolved in cohesion washing composition simultaneously, propylene oxide-carbon dioxide copolymer is dispersed in cohesion washing composition with solid particulate form, after cohesion has been washed, cohesion cleaning mixture is through liquid-solid separation, obtain solids epoxy propane-carbon dioxide copolymer.In this reaction process, initial reaction stage is because level of response is low, and material viscosity is less, temperature control is higher is conducive to add fast response, and more than reaction later stage viscosity reaches 700000CP, speed of response is fast, temperature control is lower is conducive to reduce speed of response, thereby better controls reaction process; Polymerization crude product, by cohesion detergent washing, is removed catalyzer through solid-liquid separation, and is reclaimed propylene oxide, and final resulting polymers purity is high, and propylene oxide consumes low.
In sum, the preparation method of a kind of propylene oxide-carbon dioxide copolymer of the present invention, by controlling different temperature and pressure in polymerization process, reaches that polyreaction efficiency is high, byproduct of reaction is few, catalyst consumption is low; The cohesion washing process of optimum combination has been realized the coupling of polymkeric substance purification and MONOMER RECOVERY, has significantly reduced production cost, and has obtained high-quality polymeric articles.
Brief description of the drawings
Fig. 1 is the structural representation of cohesion washing kettle of the present invention;
Fig. 2 is the structural representation of elliposoidal agitator of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment mono-
The preparation method of a kind of propylene oxide-carbon dioxide copolymer of the present invention, comprises the following steps:
(1) crude product preparation
Water content is joined in polymerization reaction kettle lower than the propylene oxide of 50ppm, then add quantitative multicomponent catalyst, controlling stirring velocity in polymerization reaction kettle is 10 revs/min, again purity is passed in polymerization reaction kettle higher than 99.95% carbon dioxide, controlling polymerization reaction kettle internal pressure is 3.0MPag, then be 70 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be 65 DEG C by polymeric reaction temperature control, sustained reaction 5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 45 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product;
(2) reaction product separation and purification
The pressure of polymerization reaction kettle is dropped to after 0.5MPag, start the agitator of cohesion washing kettle, propylene oxide-carbon dioxide copolymer crude product is delivered to cohesion washing kettle, cohesion washing composition is delivered to cohesion washing kettle stirs simultaneously, make catalyst deactivation stop polyreaction, make cyclosiloxane monomer Ethylene Oxide be dissolved in cohesion washing composition simultaneously, propylene oxide-carbon dioxide copolymer is dispersed in cohesion washing composition with solid particulate form, after cohesion has been washed, cohesion cleaning mixture, through liquid-solid separation, obtains solids epoxy propane-carbon dioxide copolymer.
In this specific embodiment, the addition of propylene oxide is 1/4 of described polymerization reaction kettle volume, and the addition of multicomponent catalyst is 1% of propylene oxide quality; Multicomponent catalyst mainly comprises zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine, and the mass ratio of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine is 3:1:1.
In this specific embodiment, cohesion washing composition is at least one in methyl alcohol, ethanol, isopropyl alcohol and water, and the addition of cohesion washing composition is 1.5 times of quality of described propylene oxide; The kettle periphery wall of polymerization reaction kettle is provided with heating jacket, and the inwall of the kettle of described polymerization reaction kettle is provided with spiral coil cooling tube.
In this specific embodiment, as shown in Figure 1, this cohesion washing kettle comprises round shape kettle 1, kettle 1 uprightly arranges, in kettle 1, be vertically arranged with the central rotating shaft 3 being connected with external motor 2, central rotating shaft 3 lower ends are longitudinally arranged side by side the elliposoidal agitator 4 of some layers of hollow, elliposoidal agitator 4 stirs frame leaf 5 by the ellipse of several hollows on central rotating shaft 3 that are crisscross arranged and surrounds, the internal side wall of kettle 1 is provided with filtration unit 6, and kettle 1 outer wall and the corresponding position of filtration unit 6 are provided with washings delivery pipe 7.
In this specific embodiment, the angular interval that each adjacent ellipse stirs frame leaf 5 is identical, and the horizontal diameter of oval stirring frame leaf 5 is different, the 1/8-1/6 of the length of rotating shaft 3 centered by the oval height that stirs frame leaf 5.Washings delivery pipe 7 is distributed on the sidewall of kettle 1 and is positioned at oval side top of stirring frame leaf 5, washings delivery pipe 7 be inclined upwardly and and horizontal plane between angle be 20-30 °, kettle 1 bottom is provided with polymer masses outlet 10.
In this specific embodiment, on central rotating shaft 3, be positioned at oval top of stirring frame leaf 5 and be provided with oblique leaf paddle agitator 8, tiltedly the length of leaf paddle agitator 8 is 5/8 of kettle 1 diameter.The position of stirring between frame leaf 5 and oblique leaf paddle agitator 8 at ellipse on central rotating shaft 3 is provided with the spiral conveying blade 9 for carrying mixed reaction solution downwards, the lower end of spiral conveying blade 9 is near oval upper end of stirring frame leaf 5, the direction of rotation of spiral direction and the central rotating shaft 3 of spiral conveying blade 9 and spiral conveying blade 9 one-body molded with central rotating shaft 3, centered by the distance between two ends up and down of spiral conveying blade 9 1/8～1/6 of rotating shaft 3 length.
Embodiment bis-
The preparation method of a kind of propylene oxide-carbon dioxide copolymer of the present invention, comprises the following steps:
(1) crude product preparation
Water content is joined in polymerization reaction kettle lower than the propylene oxide of 50ppm, then add quantitative multicomponent catalyst, controlling stirring velocity in polymerization reaction kettle is 30 revs/min, again purity is passed in polymerization reaction kettle higher than 99.95% carbon dioxide, controlling polymerization reaction kettle internal pressure is 3.2MPag, is then undertaken coolingly by chuck and coil pipe, is 74 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 4.5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be 667 DEG C by polymeric reaction temperature control, sustained reaction 4.8 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 48 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product;
(2) reaction product separation and purification
The pressure of polymerization reaction kettle drops to after 0.5 MPag, start the agitator of cohesion washing kettle, propylene oxide-carbon dioxide copolymer crude product is delivered to cohesion washing kettle, cohesion washing composition is delivered to cohesion washing kettle stirs simultaneously, make catalyst deactivation stop polyreaction, make cyclosiloxane monomer Ethylene Oxide be dissolved in cohesion washing composition simultaneously, propylene oxide-carbon dioxide copolymer is dispersed in cohesion washing composition with solid particulate form, after cohesion has been washed, cohesion cleaning mixture, through liquid-solid separation, obtains solids epoxy propane-carbon dioxide copolymer.
In this specific embodiment, the addition of propylene oxide is 1/3 of described polymerization reaction kettle volume, and the addition of multicomponent catalyst is 1.3% of propylene oxide quality; Multicomponent catalyst mainly comprises zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine, and the mass ratio of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine is 4:1:1.2.
In this specific embodiment, cohesion washing composition is at least one in methyl alcohol, ethanol, isopropyl alcohol and water, and the addition of cohesion washing composition is 1.5 times of quality of described propylene oxide; The kettle periphery wall of polymerization reaction kettle is provided with heating jacket, and the inwall of the kettle of this polymerization reaction kettle is provided with spiral coil cooling tube.
In this specific embodiment, as shown in Figure 1, this cohesion washing kettle, comprise round shape kettle 1, kettle 1 uprightly arranges, in kettle 1, be vertically arranged with the central rotating shaft 3 being connected with external motor 2, central rotating shaft 3 lower ends have longitudinally been arranged side by side some layers of elliposoidal agitator 4, elliposoidal agitator 4 stirs frame leaf 5 by the ellipse of several hollows on central rotating shaft 3 that are crisscross arranged and surrounds, the internal side wall of kettle 1 is provided with filtration unit 6, and kettle 1 outer wall and the corresponding position of filtration unit 6 are provided with washings delivery pipe 7.
In this specific embodiment, the angular interval that adjacent ellipse stirs frame leaf 5 is identical, and the oval horizontal diameter that stirs frame leaf 5 is different, centered by the oval height that stirs frame leaf 5 1/7 of the length of rotating shaft 3.
In this specific embodiment, elliposoidal agitator 4 is 2 layers, and every layer of elliposoidal agitator 4 stirs frame leaf 5 by the ellipse of 5 hollows and surround.5 oval frame leaves 5 that stir are respectively the first oval frame leaf 51, the second oval frame leaf 52, the 3rd oval frame leaf 53, the 4th oval frame leaf 54 and the 5th oval frame leaf 55 that stirs of stirring of stirring of stirring of stirring, the first oval stirring frame leaf 51, the second ellipse stir frame leaf 52, the 3rd oval frame leaf 53, the 4th ellipse stirring frame leaf 54 and the 5th oval horizontal diameter that stirs frame leaf 55 of stirring is respectively 15/16 of kettle 1 diameter, 3/4,9/16,3/8 and 3/16.
In this specific embodiment, washings delivery pipe 7 is distributed on the sidewall of kettle 1 and is positioned at oval side top of stirring frame leaf 5, washings delivery pipe 7 be inclined upwardly and and horizontal plane between angle be 25 °, kettle 1 bottom is provided with polymer masses outlet 10.On central rotating shaft 3, be positioned at oval top of stirring frame leaf 5 and be provided with oblique leaf paddle agitator 8, tiltedly the length of leaf paddle agitator 8 is 5/8 of kettle 1 diameter.The position of stirring between frame leaf 5 and oblique leaf paddle agitator 8 at ellipse on central rotating shaft 3 is provided with the spiral conveying blade 9 for carrying mixed reaction solution downwards, the lower end of spiral conveying blade 9 is near oval upper end of stirring frame leaf 5, the direction of rotation of spiral direction and the central rotating shaft 3 of spiral conveying blade 9 and spiral conveying blade 9 one-body molded with central rotating shaft 3, centered by the distance between two ends up and down of spiral conveying blade 9 1/7 of rotating shaft 3 length.
Embodiment tri-
With embodiment mono-, its difference is: in step (1), controlling stirring velocity in polymerization reaction kettle is 50 revs/min, controlling polymerization reaction kettle internal pressure is 3.4MPag, then it is 77 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 3.5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be 68.5 DEG C by polymeric reaction temperature control, sustained reaction 4.2 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 52 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product; The addition of propylene oxide is 1/2 of polymerization reaction kettle volume, and the addition of multicomponent catalyst is 1.8% of propylene oxide quality; The mass ratio of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine is 4.5:1:1.4.
Embodiment tetra-
With embodiment mono-, its difference is: in step (1), controlling stirring velocity in polymerization reaction kettle is 70 revs/min, controlling polymerization reaction kettle internal pressure is 3.5MPag, then it is 80 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 3 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be 70 DEG C by polymeric reaction temperature control, sustained reaction 4 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 55 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product; The addition of propylene oxide is 1/2 of polymerization reaction kettle volume, and the addition of multicomponent catalyst is 2% of propylene oxide quality; The mass ratio of zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine is 5:1:1.5.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned giving an example.Those skilled in the art are in essential scope of the present invention, and variation, remodeling, interpolation or the replacement made, also should belong to protection scope of the present invention.
Claims (10)
1. a preparation method for propylene oxide-carbon dioxide copolymer, is characterized in that comprising the following steps:
(1) crude product preparation
Water content is joined in polymerization reaction kettle lower than the propylene oxide of 50ppm, then add quantitative multicomponent catalyst, controlling stirring velocity in polymerization reaction kettle is 10～70 revs/min, again purity is passed in polymerization reaction kettle higher than 99.95% carbon dioxide, controlling polymerization reaction kettle internal pressure is 3.0～3.5MPag, be 70～80 DEG C by the control of polymerization reaction kettle interior reaction temperature, sustained reaction 3-5 hour, until material viscosity reaches 7 × 10 in polymerization reaction kettle
5after CP, be 65～70 DEG C by polymeric reaction temperature control, sustained reaction 4～5 hours, until material viscosity reaches 7 × 10 in polymerization reaction kettle
6after CP, make temperature of charge be down to 45～55 DEG C, obtain propylene oxide-carbon dioxide copolymer crude product;
(2) reaction product separating-purifying
The pressure of polymerization reaction kettle drops to after 0.5MPag, start the agitator of cohesion washing kettle, propylene oxide-carbon dioxide copolymer crude product is delivered to cohesion washing kettle, cohesion washing composition is delivered to cohesion washing kettle stirs simultaneously, make catalyst deactivation stop polyreaction, make cyclosiloxane monomer Ethylene Oxide be dissolved in cohesion washing composition simultaneously, propylene oxide-carbon dioxide copolymer is dispersed in cohesion washing composition with solid particulate form, after cohesion has been washed, cohesion cleaning mixture, through liquid-solid separation, obtains solids epoxy propane-carbon dioxide copolymer.
2. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 1, it is characterized in that: the addition of described propylene oxide is 1/4～1/2 of described polymerization reaction kettle volume, the addition of described multicomponent catalyst is 1.8% of described propylene oxide quality.
3. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 2, it is characterized in that: described multicomponent catalyst mainly comprises zinc ethyl, trichoroacetic acid(TCA) yttrium and glycerine, the mass ratio of described zinc ethyl, described trichoroacetic acid(TCA) yttrium and described glycerine is (3～5): 1:(1～1.5).
4. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 1, it is characterized in that: described cohesion washing composition is at least one in methyl alcohol, ethanol, isopropyl alcohol and water, the addition of described cohesion washing composition is 1.5 times of quality of described propylene oxide.
5. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 1, is characterized in that: the kettle periphery wall of described polymerization reaction kettle is provided with heating jacket, and the inwall of the kettle of described polymerization reaction kettle is provided with spiral coil cooling tube.
6. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 1, it is characterized in that: described cohesion washing kettle, comprise round shape kettle, described kettle uprightly arranges, in described kettle, be vertically arranged with the central rotating shaft being connected with external motor, described central rotating shaft lower end is longitudinally arranged side by side the elliposoidal agitator of some layers of hollow, described elliposoidal agitator stirs frame leaf by the ellipse of several hollows on described central rotating shaft that are crisscross arranged and surrounds, the internal side wall of described kettle is provided with filtration unit, described kettle outer wall and the described corresponding position of filtration unit are provided with washings delivery pipe.
7. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 6, it is characterized in that: the angular interval that each adjacent described ellipse stirs frame leaf is identical, it is different that described ellipse stirs the horizontal diameter of frame leaf, the height that described ellipse stirs frame leaf be described central rotating shaft length 1/8～1/6.
8. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 7, it is characterized in that: described elliposoidal agitator is 2 layers, elliposoidal agitator described in every layer stirs frame leaf by the ellipse of 5 hollows and surrounds, described ellipse stirs frame leaf and is respectively the first oval frame leaf that stirs, the second oval frame leaf that stirs, the 3rd oval frame leaf that stirs, the 4th oval frame leaf and the 5th oval frame leaf that stirs of stirring, the first described oval frame leaf that stirs, the second described oval frame leaf that stirs, the 3rd described oval frame leaf that stirs, 15/16 of kettle diameter described in the 4th described oval stirring frame leaf and the 5th described oval horizontal diameter that stirs frame leaf are respectively, 3/4, 9/16, 3/8 and 3/16.
9. the preparation method of a kind of propylene oxide-carbon dioxide copolymer according to claim 6, it is characterized in that: described washings delivery pipe is distributed on the sidewall of described kettle and is positioned at described ellipse the side top of stirring frame leaf, described washings delivery pipe be inclined upwardly and and horizontal plane between angle be 20～30 °.
10. according to the preparation method of a kind of propylene oxide-carbon dioxide copolymer described in any one in claim 1-6, it is characterized in that: on described central rotating shaft, be positioned at the top that described ellipse stirs frame leaf and be provided with oblique leaf formula stirring arm device, the length of described oblique leaf paddle agitator is 5/8 of described kettle diameter.
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| 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 |
| CN109485842A (en) * | 2017-09-11 | 2019-03-19 | 北京化工大学 | A kind of biological based elastomeric and preparation method using carbon dioxide preparation |
| CN111635517A (en) * | 2020-05-12 | 2020-09-08 | 中国化学赛鼎宁波工程有限公司 | Method for removing catalyst in carbon dioxide-propylene oxide copolymer |
| CN112898552A (en) * | 2021-03-11 | 2021-06-04 | 中山大学 | Condensation devolatilization device and method for semi-aromatic polyester-polycarbonate copolymer |
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| CN109438689B (en) * | 2018-10-19 | 2024-01-12 | 中国化学赛鼎宁波工程有限公司 | Propylene oxide-carbon dioxide copolymer and preparation method thereof |
| CN111635517A (en) * | 2020-05-12 | 2020-09-08 | 中国化学赛鼎宁波工程有限公司 | Method for removing catalyst in carbon dioxide-propylene oxide copolymer |
| CN112898552A (en) * | 2021-03-11 | 2021-06-04 | 中山大学 | Condensation devolatilization device and method for semi-aromatic polyester-polycarbonate copolymer |
| CN112898552B (en) * | 2021-03-11 | 2023-11-03 | 中山大学 | Apparatus and method for condensing and devolatilizing semi-aromatic polyester-polycarbonate copolymer |
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