CN101062976A - Production method of aliphatic polycarbonate resin - Google Patents
Production method of aliphatic polycarbonate resin Download PDFInfo
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- CN101062976A CN101062976A CN 200710020312 CN200710020312A CN101062976A CN 101062976 A CN101062976 A CN 101062976A CN 200710020312 CN200710020312 CN 200710020312 CN 200710020312 A CN200710020312 A CN 200710020312A CN 101062976 A CN101062976 A CN 101062976A
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- loop reactor
- epoxide
- aliphatic polycarbonate
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Abstract
The invention discloses a preparing method of aliphatic polycarbonate resin, which comprises the following steps: choosing carbon dioxide and epoxide as raw material; using ring current reactor intermittent operation; proceeding copolymerization reaction under function of activator; setting the main reacting device as ring current reactor of single guide shell or multiple guide shell, high pressure CO2 container, high pressure CO2 buffer tank, CO2 compressor, condenser and entrainment catcher; putting polymerization catalyst and epoxide into ring current reactor; leading CO2 into the ring current reactor; proceeding copolymerization reaction; setting the operating pressure at 1. 5-8Mpa and reacting temperature at 40-150 deg. c; getting mixed reaction material; proceeding circulatory flow from down to up in the guild shell of the ring current reactor and from up to down out of the guild shell; circulated-utilizing the un-reacting CO2 with the total reacting time at 1-48hr. This invention possesses small investment, high equipment capacity factor and low energy consumption.
Description
Technical field
The present invention relates to the production of aliphatic polycarbonate, relate in particular to and utilize loop reactor to produce the method and the device of aliphatic polycarbonate resin, belong to the polycarbonate synthesis technical field.
Background technology
Carbonic acid gas and epoxide can generate aliphatic polycarbonate resin by copolyreaction, resulting high molecular weight polycarbonate resin can be used as uses such as engineering plastics, biodegradable plastic master batch, oil resisting rubber starting material, this reaction is without the reduction reaction of carbon, energy consumption is lower, the product performance uniqueness, Application Areas is very extensive, has good market outlook.
Tank reactor is adopted in existing carbon dioxide/epoxide copolymerization, drops into catalyst for copolymerization, epoxide, carbonic acid gas etc. in reactor, reacts under 5～8MPa, 40～120 ℃ of conditions.This technology is the gas, liquid, solid phase reaction; Adopt tank reactor, when carrying out the industry amplification, the system mixed effect is relatively poor, occurs the reaction dead angle easily, and constant product quality is poor.In addition, carbon dioxide/epoxide copolyreaction pressure is bigger, and when carrying out the industry amplification, along with the increase of reactor volume, mechanical stirring energy consumption and cost of investment will sharply increase; And the tank reactor utilization ratio is lower, and its charging capacity is 1/2～2/3 of a reactor useful volume only generally, causes the production cost height of aliphatic polycarbonate resin, and product market competitiveness is low, has a strong impact on the large-scale production and the application of this resin.
Summary of the invention
The purpose of this invention is to provide a kind of method and device that utilizes loop reactor to produce aliphatic polycarbonate resin, the loop reactor that is adopted is simple in structure, and the catalyst utilization height can significantly improve the content of carbonate group in the product.
Purpose of the present invention is achieved through the following technical solutions:
The production method of aliphatic polycarbonate resin, with carbonic acid gas and epoxide is raw material, carries out copolyreaction under the effect of catalyzer, generates aliphatic polycarbonate, it is characterized in that: reaction is to utilize the loop reactor batch operation, and the main reaction device comprises loop reactor, high pressure CO
2Storage tank, high pressure CO
2Surge tank, CO
2Compressor, condenser and mist trap; Inner chamber at loop reactor is provided with single guide shell or multiple draft tubes, drops into polymerizing catalyst and epoxide during production earlier in loop reactor, and the weight ratio of polymerizing catalyst and epoxide is 1: 50～200, feeds CO then in loop reactor
2React, the working pressure of loop reactor is that 1.5～8MPa, temperature of reaction are 40～150 ℃, the hybrid reaction material in the guide shell of reactor from bottom to top, outside guide shell, from top to bottom circulate unreacted CO
2Flow out from loop reactor top, through entering CO after condenser and the processing of mist trap
2Surge tank passes through CO again
2Compressor compresses and enter loop reactor; The reaction times of periodical operation is 1hr～48hr.
Further, the production method of above-mentioned aliphatic polycarbonate resin, wherein, also add in the reaction can dissolved fat adoption carbonate resin polarity or non-polar solvent, its add-on is 1～200% of an epoxide weight.
Again further, the production method of above-mentioned aliphatic polycarbonate resin, wherein, described polarity or non-polar solvent are toluene, benzene, tetracol phenixin, acetone, Virahol, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1,1, the mixture of one or more in the 2-trichloroethane.
Again further, the production method of above-mentioned aliphatic polycarbonate resin, wherein, described catalyzer is one or several the mixture in carbon dioxide copolymerization catalyzer, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer, the zinc polycarboxylate catalyst.
Further, the production method of above-mentioned aliphatic polycarbonate resin, wherein, described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention is mainly reflected in:
1. the loop reactor that is adopted running simple in structure, no and sealing element, be easy to sealing, cost is low;
2. in process of production, the distinctive definite flow direction of loop reactor, circulate characteristics such as rule, flow losses are little, good mixing and make reaction system can realize good gas-to-liquid contact, can produce higher phase contact area and mass transfer velocity with lower energy consumption, make the carbonic acid gas polymerizing catalyst effectively evenly to suspend simultaneously, catalyzer reaches fully with material and contacts, thereby significantly improves the content of carbonate group in the product;
3. the present invention invest little, plant factor is high, product weight is stable, energy consumption is low, catalyst utilization is high.
Description of drawings
Fig. 1: process flow diagram of the present invention.
Among the figure: 1-high pressure CO
2Storage tank; 2-valve; 3-high pressure CO
2Surge tank; 4-CO
2Compressor; 5-mist trap; 6-condenser; The loop reactor of single guide shell of 7-strap clamp cover heat exchange; The guide shell of 8-loop reactor.
Embodiment
The invention provides a kind of method of utilizing loop reactor to produce aliphatic polycarbonate resin.It is raw material with the carbon dioxide/epoxide, prepares aliphatic polycarbonate resin by copolyreaction under the effect of catalyzer.Below in conjunction with accompanying drawing technical solution of the present invention is described further.
As shown in Figure 1, main reaction device of the present invention comprises: loop reactor 7, the high pressure CO of single guide shell of strap clamp cover heat exchange
2Storage tank 1, high pressure CO
2Surge tank 3, CO
2Compressor 4, condenser 6, mist trap 5, the inner chamber of loop reactor 7 are provided with single guide shell 8.Its process using interrupter method operation drops into polymerizing catalyst and epoxide earlier in loop reactor 7, its weight ratio is 1: 50～200; The working pressure of loop reactor 7 is 1.5～8MPa, and temperature of reaction is 40～150 ℃, the hybrid reaction material in guide shell 8 from bottom to top, outside guide shell 8, circulate reaction from top to bottom; Unreacted CO in the process
2Reusable edible, unreacted CO
2Flow out, enter CO from the top of loop reactor 7 through condenser 6, mist trap 5
2 Surge tank 3 is again through CO
2Compressor 4 enters loop reactor 7 and continues circulating reaction; Reaction times is 1hr～48hr.
The epoxide that uses can be one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide.The carbon dioxide/epoxide catalyst for copolymerization that uses can be the carbon dioxide copolymerization catalyzer, as bimetal complex catalyst (preparation method such as CN1044663A, US4500704, US1747983A etc. announce), zinc ethyl-aqueous systems catalyzer (preparation method such as Inoue S. etc. announcement Macromol.Chem., 1969,130-210), rare earth class catalyzer (preparation method such as CN1257753, CN00136189 etc. announce), zinc polycarboxylate catalyst (preparation method such as US478344, EP358326, US4943677, US4960862, JP9128227, US4789727 announces) in one or several mixture; Also can be other type can the polymerizing catalyst of catalysis carbon dioxide/epoxide copolymerization in one or several mixture.
The present invention can adopt mass polymerization, also can carry out polymerization by adding a certain amount of polarity or non-polar solvent that can dissolved fat adoption carbonate resin, solvent types is selected from acetone, Virahol, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1,1-trichloroethane, 1,1, the mixture of one or more in 2-trichloroethane, toluene, benzene, the tetracol phenixin, solvent adding amount is 1～200% of an epoxide weight, preferred 1～50%.
Embodiment 1
Loop reactor with single guide shell is an example, and the urceolus diameter of loop reactor 7 is that 0.2 meter, height are 2 meters, and the diameter of guide shell 8 is that 0.14 meter, height are 1.4 meters.
The solvent system polymerization is adopted in reaction, feeds intake in reaction unit: bimetallic catalyst (according to the CN1044663A preparation), toluene and propylene oxide, its weight is respectively 1kg, 10kg, 32kg, feeds CO
2Make system pressure rise to 4MPa, start CO
2Compressor 4 circulates material in system, make reactor 7 internal temperatures remain on 60 ℃; The inner loop flow path is: CO
2Enter from the bottom of reactor 7 and and mixing of materials, upwards flow from the inside of guide shell 8, flow to the top of guide shell 8 after, flow downward along the zone between guide shell 8 and the reactor outer wall; Unreacted CO
2Flow out from the top of reactor 7, enter mist trap 5 through condenser 6, isolated propylene oxide circulation to reactor 7, CO
2Enter CO through pipeline
2Surge tank 3 is with high pressure CO
2The CO that storage tank 1 imports
2Together by CO
2Compressor 4 is delivered to and continues to participate in reaction in the reactor 7.
Reaction times is 12hr, isolates unreacted propylene oxide and toluene completely after the discharging, obtains poly (propylene carbonate) resin 30kg, and the carbonate group mass contg is 44% in the resin, and the resin number-average molecular weight is 34000.
Embodiment 2
Adopt embodiment 1 described device, the non-solvent polymerization is adopted in reaction, feeds intake in reaction unit: bimetallic catalyst (according to the CN1044663A preparation) and propylene oxide, its weight is respectively 1kg, 40kg, feeds CO
2Make system pressure rise to 3.5MPa, start CO
2Compressor 4 circulates material in system, make reactor 7 internal temperatures remain on 60 ℃; The inner loop flow path is: CO
2Enter from the bottom of reactor 7 and and mixing of materials, upwards flow from the inside of guide shell 8, flow to the top of guide shell 8 after, flow downward along the zone between guide shell 8 and the reactor outer wall.Unreacted CO
2Flow out from the top of reactor 7, enter mist trap 5 through condenser 6, isolated propylene oxide circulation to reactor, CO
2Enter CO through pipeline
2Surge tank 3 is with high pressure CO
2The CO that storage tank 1 imports
2Together by CO
2Compressor 4 is delivered to and continues to participate in reaction in the reactor 7.
Reaction times is 12hr, isolates unreacted propylene oxide completely after the discharging, obtains poly (propylene carbonate) resin 35.2kg, and the carbonate group mass contg is 45% in the resin, and the resin number-average molecular weight is 38000.
Adopt embodiment 1 described poly-unit, the non-solvent polymerization is adopted in reaction, feeds intake in reaction unit: bimetallic catalyst (according to the CN1044663A preparation) and oxyethane, its weight is respectively 1kg, 40kg, feeds CO
2Make system pressure rise to 3.5MPa, start CO
2Compressor 4 circulates material in system, make reactor 7 internal temperatures remain on 60 ℃; The inner loop flow path is: CO
2Enter from the bottom of reactor 7 and and mixing of materials, upwards flow from guide shell 8 is inner, flow to guide shell 8 tops after, flow downward along zone between guide shell 8 and the reactor outer wall.Unreacted CO
2Flow out from the top of reactor 7, enter mist trap 5 through condenser 6, isolated oxyethane circulation to reactor, CO
2Enter CO through pipeline
2Surge tank 3 is with high pressure CO
2The CO that storage tank 1 imports
2Together by CO
2Compressor 4 is delivered to and continues to participate in reaction in the reactor 7.
Reaction times is 12hr, isolates unreacted oxyethane completely after the discharging, obtains polymerized thylene carbonate ethyl ester resin 34.5kg, and the carbonate group mass contg is 39% in the resin, and the resin number-average molecular weight is 45000.
Comparative Examples 1
In the 1L autoclave, add 10g bimetallic catalyst (according to the CN1044663A preparation) and 400g propylene oxide, be warming up to 60 ℃, feed CO
2Make system pressure remain on 3.5MPa, open and stir, discharging behind the reaction 12hr removes unreacted propylene oxide, obtains poly (propylene carbonate) resin 340g, and the carbonate group mass contg is 42% in the resin, and the resin number-average molecular weight is 38000.
Loop reactor of the present invention running simple in structure, no and sealing element, be easy to the sealing, the investment little; The content that catalyst utilization height, product weight are stablized, energy consumption is low, significantly improve carbonate group in the product.
More than by specific embodiment technical solution of the present invention has been done to further specify, the example that provides only is an exemplary applications, can not be interpreted as a kind of restriction to claim protection domain of the present invention.
Claims (5)
1. the production method of aliphatic polycarbonate resin, with carbonic acid gas and epoxide is raw material, under the effect of catalyzer, carry out copolyreaction, generate aliphatic polycarbonate, it is characterized in that: reaction is to utilize the loop reactor batch operation, and the main reaction device comprises loop reactor, high pressure CO
2Storage tank, high pressure CO
2Surge tank, CO
2Compressor, condenser and mist trap; Inner chamber at loop reactor is provided with single guide shell or multiple draft tubes, drops into polymerizing catalyst and epoxide during production earlier in loop reactor, and the weight ratio of polymerizing catalyst and epoxide is 1: 50～200, feeds CO then in loop reactor
2React, the working pressure of loop reactor is that 1.5～8MPa, temperature of reaction are 40～150 ℃, the hybrid reaction material in the guide shell of reactor from bottom to top, outside guide shell, from top to bottom circulate unreacted CO
2Flow out from loop reactor top, through entering CO after condenser and the processing of mist trap
2Surge tank passes through CO again
2Compressor compresses and enter loop reactor; The reaction times of periodical operation is 1hr～48hr.
2. the production method of aliphatic polycarbonate resin according to claim 1 is characterized in that: also add in the reaction can dissolved fat adoption carbonate resin polarity or non-polar solvent, its add-on is 1～200% of an epoxide weight.
3. the production method of aliphatic polycarbonate resin according to claim 2, it is characterized in that: described polarity or non-polar solvent are, toluene, benzene, tetracol phenixin, acetone, Virahol, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1,1, the mixture of one or more in the 2-trichloroethane.
4. the production method of aliphatic polycarbonate resin according to claim 1 is characterized in that: described catalyzer is one or several the mixture in carbon dioxide copolymerization catalyzer, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer, the zinc polycarboxylate catalyst.
5. the production method of aliphatic polycarbonate resin according to claim 1 is characterized in that: described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide.
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| CNB2007100203129A CN100463932C (en) | 2007-02-12 | 2007-02-12 | Production method of aliphatic polycarbonate resin |
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| CNB2007100203129A CN100463932C (en) | 2007-02-12 | 2007-02-12 | Production method of aliphatic polycarbonate resin |
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| CN100463932C CN100463932C (en) | 2009-02-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690411A (en) * | 2012-06-11 | 2012-09-26 | 北京旭阳化工技术研究院有限公司 | Method for copolymerizing carbon dioxide and propylene oxide with circulation flow reactor |
| CN103923308A (en) * | 2014-03-24 | 2014-07-16 | 中国化学赛鼎宁波工程有限公司 | Preparation method of multielement catalyst for copolymerization of epoxypropane-carbon dioxide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100381480C (en) * | 1998-12-24 | 2008-04-16 | 中国科学院长春应用化学研究所 | Process for preparing high-molecular aliphatic polycarbonate |
| JP2005263991A (en) * | 2004-03-18 | 2005-09-29 | Chubu Electric Power Co Inc | Method for producing polycarbonate resin |
| KR100724550B1 (en) * | 2004-12-16 | 2007-06-04 | 주식회사 엘지화학 | Bimetallic zinc complexes and process of producing polycarbonate using the same as polymerization catalysts |
| CN100355804C (en) * | 2006-03-06 | 2007-12-19 | 浙江大学 | Method for preparing high-molecular-weight polycarbonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690411A (en) * | 2012-06-11 | 2012-09-26 | 北京旭阳化工技术研究院有限公司 | Method for copolymerizing carbon dioxide and propylene oxide with circulation flow reactor |
| CN102690411B (en) * | 2012-06-11 | 2014-07-23 | 北京旭阳化工技术研究院有限公司 | Method for copolymerizing carbon dioxide and propylene oxide with circulation flow reactor |
| CN103923308A (en) * | 2014-03-24 | 2014-07-16 | 中国化学赛鼎宁波工程有限公司 | Preparation method of multielement catalyst for copolymerization of epoxypropane-carbon dioxide |
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| CN100463932C (en) | 2009-02-25 |
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