CN100509913C - Production technique of aliphatic polycarbonate resin - Google Patents
Production technique of aliphatic polycarbonate resin Download PDFInfo
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- CN100509913C CN100509913C CNB2007100203148A CN200710020314A CN100509913C CN 100509913 C CN100509913 C CN 100509913C CN B2007100203148 A CNB2007100203148 A CN B2007100203148A CN 200710020314 A CN200710020314 A CN 200710020314A CN 100509913 C CN100509913 C CN 100509913C
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- aliphatic polycarbonate
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- polycarbonate resin
- epoxide
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Abstract
The invention discloses a manufacturing technique of aliphatic polycarbonate resin, which comprises the following steps: choosing carbon dioxide/epoxide as principal raw material; copolymerizing under function of activator; preparing the product; utilizing ring current sensing device to proceed intermittent operation; setting the main device as ring current sensing device, high pressure CO2 container, high pressure CO2 buffer tank, CO2 compressor, condenser and vapor-liquid separation device.
Description
Technical field
The present invention relates to a kind of production technique of resin, more specifically to a kind of production technique of aliphatic polycarbonate resin.
Background technology
Carbonic acid gas and epoxide can be by the synthetic aliphatic polycarbonate resins of copolymerization, resultant resin can be used as uses such as engineering plastics, biodegradable plastic master batch, oil resisting rubber starting material, this reaction is not owing to experience the reduction reaction of carbon, energy consumption is lower, resulting product performance uniqueness, Application Areas is very extensive, has good market outlook.
Existing carbon dioxide/epoxide copolymerization is to adopt tank reactor, drops into catalyst for copolymerization, epoxide, carbonic acid gas etc. in reactor, at 5-8Mpa, carries out under 40-120 ℃ of conditions.This technology is vapour, liquid, solid phase reaction, owing to 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 relatively poor.In addition, because carbon dioxide/epoxide copolyreaction pressure is bigger, when carrying out the industry amplification, increase with reactor volume, mechanical stirring energy consumption and cost of investment will sharply increase, and cause production cost to increase.Simultaneously, for reaction under high pressure, the tank reactor utilization ratio is lower, and its charging capacity only is 1/2-2/3 of a reactor useful volume generally.Finally cause the production cost height of aliphatic polycarbonate resin, product market competitiveness is lower, has influenced this resin large-scale industrial and has produced and use.
Summary of the invention
The objective of the invention is to solve above-mentioned the deficiencies in the prior art and problem, a kind of technological process of utilizing loop reactor to produce aliphatic polycarbonate resin is provided.This technology has characteristics such as facility investment is little, plant factor is high, product weight is stable, energy consumption is low, catalyst utilization height.
The present invention is achieved by the following technical solutions:
The production technique of aliphatic polycarbonate resin of the present invention, be to be main raw material with the carbon dioxide/epoxide, under the effect of catalyzer, pass through the copolymerization aliphatic polycarbonate resin, its copolyreaction is the batch operation that utilizes the circulation reaction unit to carry out, and major equipment comprises circulation reaction unit, high pressure CO
2Storage tank, high pressure CO
2Surge tank, CO
2Compressor, condenser and vapour liquid separator, described circulation reaction unit is the single guide shell of band heat exchange jacket or the loop reactor of multiple draft tubes, in loop reactor, drop into catalyzer and epoxide during production earlier, the weight ratio of catalyzer and epoxide is 1:50～200, feeding carbonic acid gas then reacts, the working pressure of loop reactor is 1.5～8Mpa, temperature of reaction is 40～150 ℃, the hybrid reaction material in guide shell from bottom to top and outside guide shell from top to down circulate reaction, unreacted carbonic acid gas is flowed out by loop reactor top, through condensation, vapour liquid separator enters carbon dioxide storage tank and enters the loop reactor reaction through carbon dioxide compressor again; The reaction times of periodical operation is 1～48 hour.
Further, the production technique of aliphatic polycarbonate resin of the present invention, also add in its described reaction can dissolved fat adoption carbonate resin polarity or non-polar solvent, the preferred acetone of solvent, pimelinketone, tetrahydrofuran (THF), N, N-dimethyl formamide, 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 or the tetracol phenixin, the add-on of solvent are 0～200% of epoxide weight, preferred 0～50%.
In the production technique of aliphatic polycarbonate resin of the present invention, described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene or the cyclopentene oxide; Described catalyzer is one or several the mixture in bimetal complex catalyst, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer or the zinc polycarboxylate catalyst.
The catalyzer that the present invention simultaneously uses is present known carbon dioxide copolymerization catalyzer, its preparation method is as follows: the preparation method of bimetal complex catalyst such as CN 1044663A, disclosed methods such as US 4500704 or US 1747983A, disclosed (Macromol.Chem. such as zinc ethyl-aqueous systems Preparation of catalysts method such as Inoue S., 1969, method 130-210), disclosed methods such as rare earth class Preparation of catalysts method such as CN 1257753 or CN 00136189, the preparation method of zinc polycarboxylate catalyst such as US 478344,, EP 358326, US 4943677, US 4960862, JP 9128227 or the method that US4789727 announced; Catalyzer also can be other type known or unknown can the polymerizing catalyst of catalysis carbon dioxide/epoxide copolymerization in one or several mixture.
Beneficial effect of the present invention and advantage are that the loop reactor that is adopted has running simple in structure, no and sealing element, is easy to sealing, invests advantages such as little; In process of production, the peculiar flow direction of loop reactor is determined, flow losses are little, circulate characteristics such as rule, good mixing makes reaction system can realize good gas-to-liquid contact, can produce higher phase contact area and mass transfer velocity with lower energy consumption, make used carbonic acid gas polymerizing catalyst effectively evenly to suspend simultaneously, catalyzer reaches fully with material and contacts, thereby improves the content of carbonate group in the product significantly.
Description of drawings
Fig. 1 is a 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, vapour liquid separator; 6, condenser; 7, the single guide shell of strap clamp cover heat exchange or the loop reactor of multiple draft tubes; 8, band adds the guide shell of the loop reactor that overlaps heat exchange.
Embodiment
Embodiment 1
The existing loop reactor with single guide shell of embodiment is an example, further specifies technological process of the present invention: 0.2 meter of the reactor urceolus diameter of employing, and reactor is high 2 meters, 0.14 meter of inner draft tube diameter, guide shell is high 1.4 meters.
The solvent system polymerization is adopted in reaction, in said apparatus, feed intake, the quality of bimetallic catalyst (according to the CN-1044663A preparation), toluene, propylene oxide is respectively 1kg, 10kg, 32kg, feeding carbonic acid gas makes the interior pressure carbon dioxide of system rise to 4Mpa, start carbon dioxide compressor, material circulated in system, by add cover and in heat transfer tube make the inside reactor temperature remain on 60 ℃.The inner loop flow path is: carbonic acid gas autoreactor bottom enters back and mixing of materials, and material upwards flows in that guide shell is inner, flow to the guide shell top after, along between guide shell and reactor outer wall, flow downward.Unreacted carbonic acid gas flows out from reactor top, after condensation, enter Wu Mo and catch a section device, isolated propylene oxide is back in the reactor, carbonic acid gas enters the carbon dioxide buffer pipe through pipeline, is delivered to by carbon dioxide compressor with the carbonic acid gas that is imported by the high-pressure carbon dioxide storage tank and continues to participate in reaction in the reactor.
Reaction times is 24 hours, isolates unreacted after the discharging completely behind propylene oxide and the toluene, 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.
Adopt embodiment 1 described poly-unit, the non-solvent polymerization is adopted in reaction, in this device, feed intake, the quality of bimetallic catalyst (according to CNCN 1044663A preparation), propylene oxide is respectively 1kg, 40kg, feeding carbonic acid gas makes the interior pressure carbon dioxide of system rise to 3.5Mpa, start carbon dioxide compressor, material circulated in system, by add cover and in heat transfer tube make the inside reactor temperature remain on 60 ℃.The inner loop flow path is: carbonic acid gas autoreactor bottom enters back and mixing of materials, and material upwards flows in that guide shell is inner, flow to the guide shell top after, along between guide shell and reactor outer wall, flow downward.Unreacted carbonic acid gas flows out from reactor top, after condensation, enter Wu Mo and catch a section device, isolated propylene oxide is back in the reactor, carbonic acid gas enters the carbon dioxide buffer pipe through pipeline, is delivered to by carbon dioxide compressor with the carbonic acid gas that is imported by the high-pressure carbon dioxide storage tank and continues to participate in reaction in the reactor.
Reaction times is 24 hours, isolates unreacted after the discharging completely behind the propylene oxide, 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.
Embodiment 3
Adopt embodiment 1 described poly-unit, the non-solvent polymerization is adopted in reaction, in this device, feed intake, the quality of bimetallic catalyst (according to CNCN 1044663A preparation), oxyethane is respectively 1kg, 40kg, feeding carbonic acid gas makes the interior pressure carbon dioxide of system rise to 3.5Mpa, start carbon dioxide compressor, material circulated in system, by add cover and in heat transfer tube make the inside reactor temperature remain on 60 ℃.The inner loop flow path is: carbonic acid gas autoreactor bottom enters back and mixing of materials, and material upwards flows in that guide shell is inner, flow to the guide shell top after, along between guide shell and reactor outer wall, flow downward.Unreacted carbonic acid gas flows out from reactor top, after condensation, enter Wu Mo and catch a section device, isolated oxyethane is back in the reactor, carbonic acid gas enters the carbon dioxide buffer pipe through pipeline, is delivered to by carbon dioxide compressor with the carbonic acid gas that is imported by the high-pressure carbon dioxide storage tank and continues to participate in reaction in the reactor.
Reaction times is 24 hours, isolates unreacted after the discharging completely behind the oxyethane, 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.
Implement Comparative Examples 1
In the 1L autoclave, add the bimetallic catalyst of 10g according to CN 1044663A preparation, the 400g propylene oxide, be warming up to 60 ℃, feed carbonic acid gas and make system pressure remain on 3.5Mpa, open and stir, discharging behind the reaction 12h, after removing propylene oxide for reaction, obtain poly (propylene carbonate) resin 340g, the carbonate group mass contg is 42% in the resin, and the resin number-average molecular weight is 38000.
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 limiting the scope of the invention.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the claim scope of the present invention.
Claims (6)
1, a kind of production technique of aliphatic polycarbonate resin, with the carbon dioxide/epoxide is main raw material, under the effect of catalyzer, pass through the copolymerization aliphatic polycarbonate resin, it is characterized in that: copolyreaction is the batch operation that utilizes the circulation reaction unit to carry out, and major equipment comprises circulation reaction unit, high pressure CO
2Storage tank, high pressure CO
2Surge tank, CO
2Compressor, condenser and vapour liquid separator, described circulation reaction unit is the single guide shell of band heat exchange jacket or the loop reactor of multiple draft tubes, in loop reactor, drop into catalyzer and epoxide during production earlier, the weight ratio of catalyzer and epoxide is 1:50～200, feeding carbonic acid gas then reacts, the working pressure of loop reactor is 1.5～8Mpa, temperature of reaction is 40～150 ℃, the hybrid reaction material in guide shell from bottom to top and outside guide shell from top to down circulate reaction, unreacted carbonic acid gas is flowed out by loop reactor top, through condensation, vapour liquid separator enters carbon dioxide storage tank and enters the loop reactor reaction through carbon dioxide compressor again; The reaction times of periodical operation is 1～48 hour.
2, the production technique of aliphatic polycarbonate resin according to claim 1, it is characterized in that in the described reaction also adding can dissolved fat adoption carbonate resin polarity or non-polar solvent, the add-on of solvent is 0～200% of an epoxide weight.
3, the production technique of aliphatic polycarbonate resin according to claim 2, it is characterized in that described solvent is acetone, Virahol, pimelinketone, tetrahydrofuran (THF), N, N-dimethyl formamide, 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 or the tetracol phenixin.
4, according to the production technique of claim 2 or 3 described aliphatic polycarbonate resins, the add-on that it is characterized in that described solvent is 0～50% of an epoxide weight.
5, the production technique 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 or the cyclopentene oxide.
6, the production technique of aliphatic polycarbonate resin according to claim 1 is characterized in that described catalyzer is one or several the mixture in bimetal complex catalyst, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer or the zinc polycarboxylate catalyst.
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| CNB2007100203148A CN100509913C (en) | 2007-02-12 | 2007-02-12 | Production technique of aliphatic polycarbonate resin |
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| CNB2007100203148A CN100509913C (en) | 2007-02-12 | 2007-02-12 | Production technique of aliphatic polycarbonate resin |
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| CN103430242B (en) * | 2011-03-18 | 2018-09-07 | 住友精化株式会社 | Metal paste composition |
| 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 |
| CN103214666B (en) * | 2013-04-28 | 2015-06-10 | 北京旭阳化工技术研究院有限公司 | Method for preparing aliphatic polycarbonate through continuous solution polymerization method |
| EP2868684B1 (en) * | 2013-05-27 | 2019-04-24 | LG Chem, Ltd. | Method of manufacturing polyalkylene carbonate |
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Non-Patent Citations (4)
| Title |
|---|
| 二氧化碳与环氧化合物直接制备聚碳酸酯. 肖林飞，李福伟，夏春谷.化学进展，第17卷第04期. 2005 |
| 二氧化碳与环氧化合物直接制备聚碳酸酯. 肖林飞，李福伟，夏春谷.化学进展，第17卷第04期. 2005 * |
| 稀土络合催化二氧化碳和环氧化物的共聚反应. 郭锦棠，孙经武，张颖萍，高峰，王新英.高分子材料科学与工程，第15卷第03期. 1999 |
| 稀土络合催化二氧化碳和环氧化物的共聚反应. 郭锦棠，孙经武，张颖萍，高峰，王新英.高分子材料科学与工程，第15卷第03期. 1999 * |
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