CN118562111A - Continuous preparation method and production equipment of polyoxalate - Google Patents
Continuous preparation method and production equipment of polyoxalate Download PDFInfo
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- CN118562111A CN118562111A CN202410548072.3A CN202410548072A CN118562111A CN 118562111 A CN118562111 A CN 118562111A CN 202410548072 A CN202410548072 A CN 202410548072A CN 118562111 A CN118562111 A CN 118562111A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 53
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 34
- 238000005886 esterification reaction Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 23
- 230000032050 esterification Effects 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000011268 mixed slurry Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 238000010924 continuous production Methods 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001463 antimony compounds Chemical class 0.000 claims description 4
- 150000002291 germanium compounds Chemical class 0.000 claims description 4
- 210000001503 joint Anatomy 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 150000002697 manganese compounds Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 3
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000000155 melt Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 49
- 229920000728 polyester Polymers 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- -1 oxalic acid diester Chemical class 0.000 description 6
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000007655 standard test method Methods 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000035618 desquamation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JTICYANOTVKIFT-UHFFFAOYSA-N 2-ethenoxy-2-oxoacetic acid Chemical compound OC(=O)C(=O)OC=C JTICYANOTVKIFT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- PEJVLWCOQVHCAF-UHFFFAOYSA-N dioctyl oxalate Chemical compound CCCCCCCCOC(=O)C(=O)OCCCCCCCC PEJVLWCOQVHCAF-UHFFFAOYSA-N 0.000 description 1
- ULOZDEVJRTYKFE-UHFFFAOYSA-N diphenyl oxalate Chemical compound C=1C=CC=CC=1OC(=O)C(=O)OC1=CC=CC=C1 ULOZDEVJRTYKFE-UHFFFAOYSA-N 0.000 description 1
- HZHMMLIMOUNKCK-UHFFFAOYSA-N dipropyl oxalate Chemical compound CCCOC(=O)C(=O)OCCC HZHMMLIMOUNKCK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a continuous preparation method of polyoxalate, which comprises the following steps of uniformly mixing aliphatic raw materials, dihydric alcohol and a first additive; step two, carrying out esterification or transesterification on the uniformly mixed slurry obtained in the step one; step three, carrying out a single removal reaction on the esterification or transesterification product obtained in the step two under the conditions that the reaction temperature is 150-170 ℃ and the pressure is 50-70 kPa; step four, uniformly mixing the monomer removing product obtained in the step three with a second additive, and carrying out continuous polycondensation reaction; continuously feeding the pre-polycondensate obtained in the step four into a final polycondensation reaction kettle for continuous polycondensation reaction; and step six, feeding the polycondensate melt obtained in the step five into a granulating system to obtain a polymer product. The method has continuous flow and high automation degree, and can continuously prepare polyoxalate with the melt index lower than the traditional 3.8, and the obtained granulated product has uniform quality and no batch difference.
Description
Technical Field
The invention belongs to the technical field of polyester production processes, and particularly relates to a continuous preparation method and production equipment of polyoxalate.
Background
In the current life, 70% of plastic products are derived from petrochemical resources, the petrochemical resources are non-renewable resources, the problem of resource shortage can be brought to people in the future, and white pollution caused in the use process can be completely degraded within tens of hundreds of years.
The bio-based polyester is used as the most potential class for replacing the traditional fossil energy, has the advantages of degradability, environmental friendliness, friendly use and the like, and meanwhile, partial raw materials are widely available. Oxalic acid polyester is used as a polyester material with a melting point exceeding 100 ℃ in a few aliphatic polyesters, and has better thermodynamic property. Meanwhile, oxalic acid is the simplest dicarboxylic acid which can be extracted from plants, and has wide sources and low cost.
At present, aliphatic polyoxalates have not been particularly studied for Guan Caosuan-group aliphatic polyesters due to various limitations in application properties. The aliphatic polyoxalate can be synthesized by adopting oxalic acid diester and dihydric alcohol through transesterification and polycondensation, and has the advantages of biocompatibility, biodegradability and the like. However, the existing synthesis of polyoxalate is mainly batch production, the batch difference is large, and the product quality is unstable.
Chinese patent application No. CN201811638244.7 discloses a method for preparing polyoxalate-polyester copolymer, which comprises esterifying oxalic acid and succinic acid under nitrogen atmosphere, and then performing reduced pressure polycondensation reaction to obtain polyoxalate-polyester copolymer, but the product obtained by the method is dark yellow and has uncontrollable viscosity, and is not easy to obtain the target performance product.
The Chinese patent with the application number of CN202110533601.9 discloses a method for preparing oxalic acid glycol ester by solid phase polymerization of oxalic acid and glycol obtained after oxalic acid is extracted from plants, and the method is complicated in esterification polycondensation stage and is not suitable for economic production.
In view of the defects of unstable product quality, low product molecular weight, limited application range and less product types in the existing polyoxalate production process, a process method with high molecular weight and wide product application range, which can realize batch production, has uniform product quality and has no batch difference, is needed at present.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a continuous process for producing polyoxalates, which can be used for producing polyoxalates.
The invention provides a continuous preparation method of polyoxalate, which is characterized by comprising the following steps:
step one, uniformly mixing aliphatic raw materials, dihydric alcohol and a first additive;
Wherein the aliphatic raw material is one or more of oxalic acid and derivatives thereof;
step two, carrying out esterification or transesterification on the uniformly mixed slurry obtained in the step one;
step three, carrying out a single removal reaction on the esterification or transesterification product obtained in the step two under the conditions that the reaction temperature is 150-170 ℃ and the pressure is 50-70 kPa;
Step four, uniformly mixing the monomer removing product obtained in the step three with a second additive, and carrying out continuous polycondensation reaction;
continuously feeding the pre-polycondensate obtained in the step four into a final polycondensation reaction kettle for continuous polycondensation reaction;
And step six, feeding the polycondensate melt obtained in the step five into a granulating system to obtain a polymer product.
Further, the continuous preparation method of the polyoxalate provided by the invention is further characterized by comprising the following steps of:
The esterification reaction temperature is 120-150 ℃ and the reaction is carried out at normal pressure, and the reaction time is 3-15h;
The temperature of the deallocation reaction is 150-170 ℃, the pressure is 50-70kPa, and the reaction time is 0.5-2h;
the reaction temperature of the pre-polycondensation kettle is 170-190 ℃, the pressure is 0.2-10kPa, and the reaction time is 2-8 hours;
The reaction temperature of the final polycondensation kettle is 190-220 ℃, the pressure is 5-100Pa, and the reaction time is 3-8h.
Further, the continuous preparation method of the polyoxalate provided by the invention is further characterized by comprising the following steps of:
After the esterification is completed, the polymerization degree n of the esterification product is 2 to 5, preferably 2.5 to 3.5.
Further, the continuous preparation method of the polyoxalate provided by the invention is further characterized by comprising the following steps of:
The dihydric alcohol is selected from any one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and diethylene glycol.
Further, the continuous preparation method of the polyoxalate provided by the invention is further characterized by comprising the following steps of:
the first additive and the second additive are the same or different and comprise at least one of a catalyst and a stabilizer;
the catalyst is selected from any one or a mixture of more than one of acetate compounds, magnesium compounds, manganese compounds, titanium compounds, antimony compounds and germanium compounds;
The stabilizer is selected from one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite, phosphorous acid or phosphoric acid.
Further, the continuous preparation method of the polyoxalate provided by the invention is further characterized by comprising the following steps of:
the amount of the first additive is 0.001-1% of the mass ratio of the polymer product;
The second additive is used in an amount of 0.01 to 10% of the mass ratio of the polymer product;
The mole ratio of the aliphatic raw material to the dihydric alcohol is 1 (1.0-2.0).
The above-mentioned parts by weight of additives are added according to different comparison objects, generally calculated on the basis of the theoretical yield of the polymer product.
In addition, the invention also provides production equipment applied to the preparation method, which is characterized in that:
comprises a size mixing tank, an esterification kettle, a single removing kettle, a pre-polycondensation kettle, a final polycondensation kettle and a granulating system which are sequentially arranged along the material flow direction;
the single removing kettle, the pre-polycondensation kettle and the final polycondensation kettle are all provided with channels communicated with a vacuum system.
The single removing kettle is a vacuum single removing kettle.
The final polymerization kettle adopts a horizontal type film drawing reactor.
The slurry mixing tank is provided with a first additive input end which is in butt joint with a storage tank of the first additive;
The underwater pelletizing system is selected as the pelletizing system.
A second additive input end is arranged on a fluid pipeline between the single removing kettle and the pre-condensation kettle, and a storage tank for the second additive is in butt joint;
A fluid delivery system, and/or a temperature regulating system, and/or a high shear homogenizing pump, and/or a homogenizer are mounted on the fluid conduit for feed liquid delivery between the containers.
The invention has the following functions and effects:
The continuous preparation method of the polyoxalate has continuous flow and high automation degree, and can continuously prepare the traditional polyoxalate with the melt index lower than 3.8g/10min (150 ℃ and 2.16 kg), and the obtained granulated product has uniform quality and no batch difference. Compared with the prior art, the method realizes industrial continuous production and greatly reduces the production cost.
The single kettle is used for preventing the problem of pipeline blockage in the polycondensation process, increasing the reaction convenience and stability, and being capable of carrying out large-scale industrial production.
The popularization and application of the process technology can further meet the demands of people on biodegradable materials, and the biodegradable material is used as an environment-friendly material, so that the pollution to the environment is further reduced, the contribution to protecting the environment on which the human beings depend to survive is made, and the sustainable development of the environment and the plastic industry is facilitated.
Drawings
FIG. 1, schematic diagram of a production facility for a continuous process for the preparation of polyoxalates.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement of the purposes and the effects of the present invention easy to understand, the following embodiments specifically describe the technical scheme of the present invention with reference to the accompanying drawings. The following examples are only specific examples of the present invention and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
As shown in fig. 1, the present embodiment provides an apparatus for continuously preparing polyoxalate, comprising a size mixing tank, an esterification tank, a single removal tank, a pre-polycondensation tank, a final polycondensation tank and a pelletizing system, which are sequentially arranged along the material flow direction;
The single removing kettle, the pre-polycondensation kettle and the final polycondensation kettle are all provided with channels communicated with a vacuum system.
The adding positions of the first additive are a storage tank and a size mixing tank;
The adding position of the second additive is arranged on a melt conveying pipeline between the single removing kettle and the polycondensation kettle.
The above-mentioned esterified substance conveying pipeline and melt conveying pipeline are equipped with injection system, temperature regulating system and high-shearing homogenizing pump and/or homogenizer.
Regarding the single removing kettle, a vacuum single removing kettle is selected, so that methanol generated in the reaction of better removing and a small amount of raw materials which are not reacted completely are adopted, the esterification efficiency is improved, the adjustment of the molecular configuration of an esterification product is facilitated, and the polycondensation efficiency is improved in the subsequent polycondensation process; meanwhile, in the polycondensation process, excessive methanol in the esterified slurry is prevented from entraining oligomer to block a pipeline in the volatilization process, so that the integral vacuum degree of polycondensation is reduced, and the polycondensation effect is not ideal. The single removing kettle is favorable for adjusting molecular configuration and distribution, synthesizing high molecular weight polymer, reducing byproduct yield, improving product yield, saving energy and reducing consumption.
The single removing kettle used in the embodiment belongs to multistage serial single removing kettles with different gradients, and the device is more suitable for actual industrial production. The problem of entrainment caused by instantaneous removal of a large amount of methanol and solvent contained in the melt after the transesterification reaction is finished and serious pipeline blockage caused by the entrainment problem can be avoided.
In addition, in the process of the invention, the scheme of high-temperature removal of small molecular impurities is different from the traditional process, and the small molecular impurities are removed in a low-temperature and high-pressure mode. Overcomes the problems of large number of side reactions caused by the traditional normal pressure and high temperature and reduces the quality of the final product.
Regarding the final polymerization kettle, a horizontal type film drawing reactor is adopted, so that the devolatilization area is effectively increased, the removal of small molecular substances is facilitated, and the synthesis of products with good quality and high molecular weight is facilitated.
Regarding the granulating system, the underwater granulating system is adopted, so that uniform and stable polyester chips can be obtained, and the system is green, efficient, safe and environment-friendly.
The specific process steps are as follows:
Step one, preparing aliphatic raw materials, dihydric alcohol and a first additive into slurry, and uniformly mixing, wherein the aliphatic raw materials are one or more of oxalic acid and derivatives thereof, such as: any one or more of dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, vinyl oxalate, dioctyl oxalate and diphenyl oxalate;
The dihydric alcohol is selected from any one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and diethylene glycol;
the mol ratio of the aliphatic raw material to the dihydric alcohol is1 (1.0-2.0);
The first additive comprises at least one of a catalyst and a stabilizer; the catalyst is selected from one or more of acetate compound, magnesium compound, manganese compound, titanium compound, antimony compound, and germanium compound, preferably titanium compound. The stabilizer is selected from one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite, phosphorous acid or phosphoric acid. The first additive is used in an amount of 0.001-1% of the theoretical polymer product, and the stabilizer is used in an amount of 0.0001-1% of the theoretical polymer product.
Step two, the evenly mixed slurry obtained in the step one is sent into an esterification reaction kettle to carry out esterification or transesterification reaction;
step three, continuously feeding the esterification or transesterification product obtained in the step two into a single removing kettle for reaction;
Uniformly mixing the monomer removing product obtained in the step three with a second additive, and continuously feeding the mixture into a pre-polycondensation reaction kettle for continuous polycondensation reaction;
The second additive is any one or more of acetate compound, magnesium compound, manganese compound, titanium compound, antimony compound and germanium compound, preferably titanium compound. The second additive may be a catalyst+a stabilizer+another additive, and the second additive and the first additive may be the same kind of compound or different kinds of compound. The dosage of the second additive is 0.01-10% of the mass ratio;
continuously feeding the pre-polycondensate obtained in the step four into a final polycondensation reaction kettle for continuous polycondensation reaction;
And step six, feeding the polycondensate melt obtained in the step five into a granulating system to obtain a polymer product.
The reaction temperature of the esterification kettle is 120-150 ℃, the reaction is carried out at normal pressure, and the reaction time is 3-15h;
The reaction temperature of the single removing kettle is 150-170 ℃, the pressure is 50-70kPa absolute pressure, and the reaction time is 0.5-2h;
the reaction temperature of the pre-polycondensation kettle is 170-190 ℃, the pressure is 0.2-10kPa, and the reaction time is 2-8 hours;
The reaction temperature of the final polycondensation kettle is 190-220 ℃, the pressure is 5-100Pa, and the reaction time is 3-8h;
After the completion of the esterification, the polymerization degree (n) of the esterified product is 2 to 5, preferably 2.5 to 3.5.
The end point of the esterification reaction is that the byproduct distillation amount reaches 85% -98% of the theoretical distillation amount.
The reaction raw materials of oxalic acid diester and dihydric alcohol are industrial grade raw materials.
Preferred embodiment 1
Dimethyl oxalate and 1, 4-butanediol are put into a size mixing tank according to the proportion of 1:1.2, and a transesterification catalyst is added to prepare size. 0.22kg/h of mixed solution of zinc acetate, cobalt acetate, tetrabutyl titanate composite catalyst, triphenyl phosphate stabilizer and 1, 4-butanediol serving as a transesterification reaction catalyst is injected on a melt conveying pipeline between a storage tank and a size mixing tank, and uniform size is prepared in the size mixing tank. And then continuously feeding the uniformly mixed slurry into an esterification reaction kettle at a flow rate of 450kg/h, and staying at the temperature of 150 ℃ for 6 hours under normal pressure to obtain a transesterification product. Then, the transesterification product was continuously fed into a demonomerization kettle, and was allowed to stand at 50KPa at 170℃for 1 hour to obtain a demonomerized product. Then continuously feeding the product into a pre-polycondensation reaction kettle, simultaneously injecting 0.15kg/h tetrabutyl titanate into the pre-polycondensation reaction kettle together with the product, and stopping for 5 hours at 180 ℃ under the vacuum degree of 1KPa to remove byproducts. Then, the obtained prepolymer was fed into a final polycondensation reactor at 200℃under a vacuum of 50Pa for a residence time of 2 hours. Finally, cooling and granulating the obtained high polymer polybutylene oxalate (PBO) melt.
The melt index was measured by the national standard test method for polyester at 3.3g/10min (150 ℃ C., 2.16 kg).
Preferred embodiment 2
Referring to FIG. 1, dimethyl oxalate and 1, 4-butanediol are put into a size mixing tank according to the proportion of 1:1.5, 0.25kg/h of mixed solution of a transesterification catalyst of manganese acetate, zinc acetate, tetrabutyl titanate, a stabilizer of triethyl phosphate and 1, 4-butanediol is injected into a melt conveying pipeline between the tank and the size mixing tank, and uniform sizing agent is prepared in the size mixing tank. Then, the evenly mixed slurry is continuously fed into an esterification reaction kettle according to the flow of 450kg/h, and stays for 8 hours at the temperature of 145 ℃ under normal pressure, thus obtaining the transesterification product. Then, the transesterification product is continuously fed into a single removing kettle, and stays for 1h at 60KPa and 165 ℃ to obtain the single removing product. Then continuously feeding the desquamation product into a pre-polycondensation reaction kettle, simultaneously injecting 0.15kg/h of ethylene glycol titanium into the pipeline, injecting the desquamation product into the pre-polycondensation reaction kettle together, and standing for 5 hours at the temperature of 180 ℃ and the vacuum degree of 800Pa to remove byproducts. Then, the obtained prepolymer was fed into a final polycondensation reactor at 200℃under a vacuum of 50Pa for a residence time of 2 hours. And finally, cooling and granulating the obtained PBO melt. Product performance data: the obtained PBO product is white solid particles and has good quality.
The melt index was measured by the national standard test method for polyester at 3.1g/10min (150 ℃ C., 2.16 kg).
Example 3
Referring to FIG. 1, dimethyl oxalate and 1, 4-butanediol are put into a size mixing tank according to the proportion of 1:2.0, 0.3kg/h of mixed solution of a transesterification catalyst of manganese acetate, zinc acetate, tetrabutyl titanate, stabilizer of trimethyl phosphate and 1, 4-butanediol is injected into a melt conveying pipeline between the tank and the size mixing tank, and uniform sizing agent is prepared in the size mixing tank. And then continuously feeding the uniformly mixed slurry into an esterification reaction kettle at a flow rate of 450kg/h, and staying for 4 hours at the temperature of 150 ℃ under normal pressure to obtain a transesterification product. Then, the transesterification product is continuously fed into a single removing kettle, and stays for 1h at 50KPa and 160 ℃ to obtain the single removing product. Then continuously feeding the product into a pre-polycondensation reaction kettle, simultaneously injecting 0.15kg/h tetrabutyl titanate into the pre-polycondensation reaction kettle together with the product, and standing for 5h at 180 ℃ under the vacuum degree of 500Pa to remove byproducts. Then, the obtained prepolymer was fed into a final polycondensation reactor at 200℃under a vacuum of 50Pa for a residence time of 1.5 hours.
And finally, cooling and granulating the obtained PBO melt. Product performance data: the obtained PBO product is white solid particles and has good quality.
The melt index was measured by the national standard test method for polyester at 3.5g/10min (150 ℃ C., 2.16 kg).
Comparative example 1
Dimethyl oxalate and 1, 4-butanediol are put into a size mixing tank according to the proportion of 1:2.0, 0.3kg/h of mixed solution of a transesterification catalyst of manganese acetate, zinc acetate, tetrabutyl titanate, stabilizer of trimethyl phosphate and 1, 4-butanediol is injected into a melt conveying pipeline between the tank and the size mixing tank, and uniform sizing agent is prepared in the size mixing tank. And then continuously feeding the uniformly mixed slurry into an esterification reaction kettle at a flow rate of 450kg/h, and staying for 4 hours at the temperature of 150 ℃ under normal pressure to obtain a transesterification product. Then, continuously feeding the transesterification product into a pre-polycondensation reaction kettle, simultaneously injecting 0.15kg/h tetrabutyl titanate into the pre-polycondensation reaction kettle through a pipeline, and standing for 5 hours at the temperature of 180 ℃ and the vacuum degree of 500Pa to remove byproducts. Then, the obtained prepolymer was fed into a final polycondensation reactor at 200℃under a vacuum of 50Pa for a residence time of 1.5 hours.
And finally, cooling and granulating the obtained PBO melt. Product performance data: the obtained PBO product is dark yellow solid particles.
The melt index of the polyester is measured by a national standard test method of polyester to be 10-20 g/10min (150 ℃ C., 2.16 kg).
Claims (10)
1. A continuous process for the preparation of polyoxalates, comprising the steps of:
step one, uniformly mixing aliphatic raw materials, dihydric alcohol and a first additive;
Wherein the aliphatic raw material is one or more of oxalic acid and derivatives thereof;
step two, carrying out esterification or transesterification on the uniformly mixed slurry obtained in the step one;
step three, carrying out a single removal reaction on the esterification or transesterification product obtained in the step two under the conditions that the reaction temperature is 150-170 ℃ and the pressure is 50-70 kPa;
Step four, uniformly mixing the monomer removing product obtained in the step three with a second additive, and carrying out continuous polycondensation reaction;
continuously feeding the pre-polycondensate obtained in the step four into a final polycondensation reaction kettle for continuous polycondensation reaction;
And step six, feeding the polycondensate melt obtained in the step five into a granulating system to obtain a polymer product.
2. A continuous process for the preparation of polyoxalates as claimed in claim 1, wherein:
The esterification reaction temperature is 120-150 ℃ and the reaction is carried out at normal pressure, and the reaction time is 3-15h;
The temperature of the deallocation reaction is 150-170 ℃, the pressure is 50-70kPa, and the reaction time is 0.5-2h;
the reaction temperature of the pre-polycondensation kettle is 170-190 ℃, the pressure is 0.2-10kPa, and the reaction time is 2-8 hours;
The reaction temperature of the final polycondensation kettle is 190-220 ℃, the pressure is 5-100Pa, and the reaction time is 3-8h.
3. A continuous process for the preparation of polyoxalates as claimed in claim 1, wherein:
After the esterification is completed, the polymerization degree n of the esterification product is 2 to 5, preferably 2.5 to 3.5.
4. A continuous process for the preparation of polyoxalates as claimed in claim 1, wherein:
The dihydric alcohol is selected from any one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and diethylene glycol.
5. A continuous process for the preparation of polyoxalates as claimed in claim 1, wherein:
The first additive and the second additive are the same or different and comprise at least one of a catalyst and a stabilizer; the catalyst is selected from any one or a mixture of more of acetate compounds, magnesium compounds, manganese compounds, titanium compounds, antimony compounds and germanium compounds;
the stabilizer is selected from one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triphenyl phosphite, phosphorous acid or phosphoric acid.
6. A continuous process for the preparation of polyoxalates as claimed in claim 1, wherein:
The first additive is used in an amount of 0.001 to 1wt% based on the mass ratio of the polymer product;
the second additive is used in an amount of 0.01 to 10wt% based on the mass ratio of the polymer product;
the mol ratio of the aliphatic raw material to the dihydric alcohol is 1 (1.0-2.0).
7. Production equipment employing a continuous process for the preparation of polyoxalates according to any one of claims 1 to 6, characterized in that:
comprises a size mixing tank, an esterification kettle, a single removing kettle, a pre-polycondensation kettle, a final polycondensation kettle and a granulating system which are sequentially arranged along the material flow direction;
the single removing kettle, the pre-polycondensation kettle and the final polycondensation kettle are all provided with channels communicated with a vacuum system.
8. The production facility of claim 7, wherein:
The single removing kettle is a vacuum single removing kettle;
The final polymerization kettle adopts a horizontal type film drawing reactor.
9. The production facility of claim 7, wherein:
The underwater pelletizing system is selected as the pelletizing system.
10. The production facility of claim 7, wherein:
The slurry mixing tank is provided with a first additive input end which is in butt joint with a storage tank of the first additive;
a second additive input end is arranged on a fluid pipeline between the single removing kettle and the pre-condensation kettle, and a storage tank for the second additive is in butt joint;
A fluid delivery system, and/or a temperature regulating system, and/or a high shear homogenizing pump, and/or a homogenizer are mounted on the fluid conduit for feed liquid delivery between the containers.
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