CN100516115C - Continuous production of fatty poly-ester carbonate polyhydric alcohol - Google Patents
Continuous production of fatty poly-ester carbonate polyhydric alcohol Download PDFInfo
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- CN100516115C CN100516115C CNB2007100203114A CN200710020311A CN100516115C CN 100516115 C CN100516115 C CN 100516115C CN B2007100203114 A CNB2007100203114 A CN B2007100203114A CN 200710020311 A CN200710020311 A CN 200710020311A CN 100516115 C CN100516115 C CN 100516115C
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Abstract
Continuous production of fatty polycarbonate polyol is carried out by taking carbon dioxide/epoxide as raw materials and reacting under action of catalyst to obtain the final product in cyclic reactor. The main apparatus consists of cyclic reactor, condenser, vapor-liquid separator, high-pressure carbon dioxide buffer tank, carbon dioxide compressor, mixing kettle and high-pressure metering pump. It costs low is efficient.
Description
Technical field
The present invention relates to a kind of production technique of polyvalent alcohol, more specifically to a kind of continuous production technology of aliphatic polycarbonate polybasic alcohol.
Background technology
Aliphatic polycarbonate polybasic alcohol is the novel polyol resin of a class, its molecular backbone chain contains aliphatics alkylidene group and carbonate group repeating unit, differ bigger with traditional polycarbonate material, and it is close with the how pure and mild polyether polyol of aliphatic polyester, and between polyester and polyether glycol, as has a lower second-order transition temperature (glass transition), room temperature kindliness etc. preferably, with this polyvalent alcohol is that the polyurethane material of feedstock production has many special performances, has possessed the good hydrolytic resistance of polyether(poly)urethane elastomerics simultaneously as such polyurethane elastomer, the elastomeric high mechanical strength of low temperature kindliness and PAUR, good wear resistance and oil-proofness; Such polyurethane coating, tackiness agent etc. not only have good solvent resistance, heat-resisting fadedness, scratch resistance, weathering resistance, and some also has excellent biological compatibility; Utilize the polyurethane foam of polymerized thylene carbonate ethyl ester preparation owing to have good biodegradation type, can be used as the packing of product, heat insulation etc., can effectively alleviate white pollution, have vast market prospect.
Carbon dioxide/epoxide can be by regulating the copolymerization aliphatic polycarbonate polybasic alcohol in the presence of catalyzer, and this method has the explicit costs advantage owing to use a large amount of cheap carbonic acid gas, and relevant research is subjected to paying close attention to widely.
Existing carbon dioxide/epoxide copolymerization is to adopt tank reactor, drops into catalyzer, epoxide, carbonic acid gas, molecular weight regulator 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 the 1/2-2/3 of reactor useful volume generally.Above-mentioned reason causes the production cost height of aliphatic polycarbonate polybasic alcohol, and 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 continuous production technology of aliphatic polycarbonate polybasic alcohol is provided.This technology has characteristics such as facility investment is little, utilization ratio is high, product weight is stable, energy consumption is low, catalyst utilization height.
The present invention is achieved by the following technical solutions:
The continuous production technology of aliphatic polycarbonate polybasic alcohol of the present invention, be to be main raw material with the carbon dioxide/epoxide, under the effect of catalyzer, react the production aliphatic polycarbonate polybasic alcohol, its reaction is the continuous operation that utilizes the circulation reaction unit to carry out, and major equipment comprises circulation reaction unit, condenser, gas-liquid separator, high-pressure carbon dioxide surge tank, carbon dioxide compressor, mixing kettle and high-pressure metering pump; Described circulation reaction unit is the inner single guide shell of heat exchange jacket or the loop reactor of multiple draft tubes of being provided with, elder generation is with catalyzer during production, epoxide and molecular weight regulator input, open whipping appts, thorough mixing stirs, then will with drop into mixing kettle in the identical catalyzer of proportioning, epoxide and molecular weight regulator add in the loop reactor, feed carbonic acid gas again to system pressure to 0.1～8Mpa, be warming up to 40～150 ℃, open carbon dioxide compressor, make in the system 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, gas-liquid separator enters carbon dioxide storage tank and enters the loop reactor reaction through carbon dioxide compressor again, the system solid content for the treatment of reaches at 20%～80% o'clock, open high-pressure metering pump, carry mixture from hybrid reactor toward polymerization system, open the loop reactor discharge port simultaneously, with with reinforced identical speed discharging, isolate unreacted epoxide and can obtain aliphatic polycarbonate polybasic alcohol.
Further, the continuous production technology of above-mentioned aliphatic polycarbonate polybasic alcohol, also add in its described reaction can dissolved fat adoption carbonate resin polarity or non-polar solvent, the preferred acetone of solvent, Virahol, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1, the 1-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, toluene, benzene, the mixture of one or more in the tetracol phenixin, the add-on of solvent are 0～200% of epoxide weight, preferred 0～50%.
In the continuous production technology of aliphatic polycarbonate polybasic alcohol of the present invention, its 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 molecular weight regulator is the material that contains 1～10 reactive hydrogen atom in the molecule, the polymkeric substance of preferably water, small molecule alcohol, phenols, thio-alcohol, carboxylic-acid, hydroxyl or oligopolymer, the polymkeric substance that contains thiol or oligopolymer or carboxylic polymkeric substance or oligopolymer, or the mixture of these materials, its add-on is 0.01～20% of an epoxide weight, preferred 1～5%; Described carbon dioxide/epoxide catalyst for copolymerization is one or several the mixture in bimetal complex catalyst, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer or the zinc polycarboxylate catalyst, its consumption is 0.01～20% of an epoxide weight, preferred 0.1～10%.
The carbon dioxide/epoxide catalyst for copolymerization 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, the method that JP 9128227 or US 4789727 are 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.
Material's proportion can be identical with material ratio in the loop reactor in the reaction process involved in the present invention, mixing kettle, also can be different.
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.Because the present invention adopts continuous production technology, quality product is comparatively stable.
Description of drawings
Fig. 1 is a continuous production process synoptic 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, gas-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; 9, discharging valve; 10, valve; 11, high-pressure metering pump; 12, mixing kettle.
Embodiment
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 loop 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.Mixing kettle is the 10L reactor that has whipping appts.
The solvent-free system polymerization is adopted in reaction, with 8L according to 1.6: 3.4: 100 catalyzer according to CN 1044663A preparation, through thorough drying, molecular weight is 300, average functionality is 3 polyether glycol (moisture content 300ppm), propylene oxide etc. adds and drops into mixing kettle, open whipping appts, carry out thorough mixing.
Same catalyzer, molecular weight regulator and propylene oxide with the same ratio of 40kg adds in the loop reactor then, 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 reaction mass temperature remain on 60 ℃.When the system solid content reaches 35%, open high-pressure metering pump, beginning is opened discharge port simultaneously with the charging of 5l/min speed, with the discharging of phase same rate, keeps the system pressure carbon dioxide constant simultaneously.After material has advanced in the mixing kettle, add the material of same ratio.
Sampling survey molecular weight is 4580 behind the polyreaction 24h, intramolecularly carbonate group mass contg is 37% (molar percentage), and the 48h sampling records molecular weight basically identical 4520, and intramolecularly carbonate group mass contg is 37%, molecular weight 4560 is surveyed in the 72h sampling, and intramolecularly carbonate group mass contg is 37%.
Adopt embodiment 1 described poly-unit, with 8L according to 1.6: 4.8: 30: 100 catalyzer according to CN 1044663A preparation, through thorough drying, molecular weight is 300, average functionality is 3 polyether glycol (moisture content 300ppm), toluene, propylene oxide etc. add and drop into mixing kettle, open whipping appts, carry out thorough mixing.
Catalyzer, molecular weight regulator and propylene oxide with the same ratio of 40kg adds in the loop reactor then, 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 reaction mass temperature remain on 60 ℃.When the system solid content reaches 35%, open high-pressure metering pump, beginning is opened discharge port simultaneously with the charging of 5l/min speed, with the discharging of phase same rate, keeps the system pressure carbon dioxide constant simultaneously.After material has advanced in the mixing kettle, add the material of same ratio.
Sampling survey molecular weight is 3940 behind the polyreaction 24h, intramolecularly carbonate group mass contg 35%, and the 48h sampling records molecular weight basically identical 3950, intramolecularly carbonate group mass contg 35%, molecular weight 3900, intramolecularly carbonate group mass contg 35% are surveyed in the 72h sampling.
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 (10)
1, a kind of continuous production method of aliphatic polycarbonate polybasic alcohol, be to be main raw material with the carbon dioxide/epoxide, under the effect of catalyzer, react the production aliphatic polycarbonate polybasic alcohol, it is characterized in that: reaction is the continuous operation that utilizes the circulation reaction unit to carry out, and major equipment comprises circulation reaction unit, condenser, gas-liquid separator, high-pressure carbon dioxide surge tank, carbon dioxide compressor, mixing kettle and high-pressure metering pump; Described circulation reaction unit is the inner single guide shell of heat exchange jacket or the loop reactor of multiple draft tubes of being provided with, elder generation is with catalyzer during production, epoxide and molecular weight regulator drop in the mixing kettle, open whipping appts, thorough mixing stirs, and then with catalyzer, epoxide and molecular weight regulator add in the loop reactor, feed carbonic acid gas again to system pressure to 0.1～8Mpa, be warming up to 40～150 ℃, open carbon dioxide compressor, make in the system 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 condenser, enter carbon dioxide storage tank through gas-liquid separator again and enter the loop reactor reaction through carbon dioxide compressor again, the system solid content for the treatment of reaches at 20%～80% o'clock, open high-pressure metering pump, carry mixture from hybrid reactor toward polymerization system, open the loop reactor discharge port simultaneously, with with reinforced identical speed discharging, isolate unreacted epoxide and can obtain aliphatic polycarbonate polybasic alcohol.
2, the continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 1, it is characterized in that also can adding in the described reaction 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 continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 2, it is characterized in that described solvent is acetone, pimelinketone, tetrahydrofuran (THF), N, dinethylformamide, trichloromethane, monochloro methane, monochlorethane, 1,1-ethylene dichloride, 1,1, the mixture of one or more in 1-trichloroethane, vinyl trichloride, toluene, benzene, the tetracol phenixin.
4, according to the continuous production method of claim 2 or 3 described aliphatic polycarbonate polybasic alcohols, the add-on that it is characterized in that described solvent is 0～50% of an epoxide weight.
5, the continuous production method of aliphatic polycarbonate polybasic alcohol 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.
6, the continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 1 is characterized in that described molecular weight regulator is the material that contains 1～10 reactive hydrogen atom in the molecule, and its add-on is 0.01～20% of an epoxide weight.
7, the continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 6, it is characterized in that described molecular weight regulator is the polymkeric substance or the oligopolymer of water, small molecule alcohol, phenols, thio-alcohol, carboxylic-acid, hydroxyl, the polymkeric substance that contains thiol or oligopolymer or carboxylic polymkeric substance or oligopolymer, or the mixture of these materials.
8, according to the continuous production method of claim 6 or 7 described aliphatic polycarbonate polybasic alcohols, the add-on that it is characterized in that described molecular weight regulator is 1～5% of an epoxide weight.
9, the continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 1, it is characterized in that described carbon dioxide/epoxide catalyst for copolymerization is one or several the mixture in bimetal complex catalyst, zinc ethyl-aqueous systems catalyzer, rare earth class catalyzer or the zinc polycarboxylate catalyst, its consumption is 0.01～20% of an epoxide weight.
10, the continuous production method of aliphatic polycarbonate polybasic alcohol according to claim 9 is characterized in that described catalyst consumption is 0.1～10% of an epoxide weight.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100203114A CN100516115C (en) | 2007-02-12 | 2007-02-12 | Continuous production of fatty poly-ester carbonate polyhydric alcohol |
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| CNB2007100203114A CN100516115C (en) | 2007-02-12 | 2007-02-12 | Continuous production of fatty poly-ester carbonate polyhydric alcohol |
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| EP2307477A4 (en) * | 2008-07-30 | 2014-12-10 | Sk Innovation Co Ltd | Novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst |
| KR101308580B1 (en) * | 2009-09-03 | 2013-09-12 | 에스케이이노베이션 주식회사 | Continuous Process for Manufacturing Aliphatic Polycarbonates from Carbon Dioxide and Epoxides |
| GB201115565D0 (en) * | 2011-09-08 | 2011-10-26 | Imp Innovations Ltd | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
| CN107727805B (en) * | 2017-10-18 | 2021-06-08 | 中石化炼化工程（集团）股份有限公司 | High-temperature high-pressure gas-liquid phase balance testing device and method |
| CN111303379A (en) * | 2020-03-19 | 2020-06-19 | 江苏新视客光电科技有限公司 | PC lens without bisphenol A and preparation method thereof |
| CN111454179B (en) * | 2020-05-08 | 2023-10-20 | 河南金鹏化工有限公司 | Device and continuous process for producing methyl isocyanate from dimethyl sulfate |
| CN112939774A (en) * | 2021-03-05 | 2021-06-11 | 武汉海翎化学工业有限公司 | Production method of methacrylic acid hydroxy ester or acrylic acid hydroxy ester |
| 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 |
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