CN111423570A - Process method and device for continuously producing degradable polyester - Google Patents
Process method and device for continuously producing degradable polyester Download PDFInfo
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- CN111423570A CN111423570A CN202010428503.4A CN202010428503A CN111423570A CN 111423570 A CN111423570 A CN 111423570A CN 202010428503 A CN202010428503 A CN 202010428503A CN 111423570 A CN111423570 A CN 111423570A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention aims to provide a process method and a device for continuously producing degradable polyester, aiming at the defects of the continuous polymerization production process and reactors of aliphatic/aromatic copolyester in the prior industry, the invention is characterized in that the addition amount of a catalyst in the esterification reaction is small, the total retention time of materials in each reactor is shorter than the normal reaction time of the prior art, and the color and the quality of the product are ensured; in order to achieve the above object, the present invention provides an apparatus for continuously producing a degradable polyester, comprising: an esterification reactor, a pre-polycondensation reactor, a final polycondensation reactor, a separation tower and an esterification heater.
Description
Technical Field
The invention belongs to the field of polymer chemical industry, and particularly relates to a process method and a device for continuously producing degradable polyester.
Background
The biodegradable polyester, in particular to biodegradable aliphatic/aromatic copolyester, takes dibasic acid and dihydric alcohol as raw materials, the dibasic acid consists of aliphatic dibasic acid and aromatic dibasic acid, the aromatic dibasic acid is phenyl dibasic acid, and the aliphatic dibasic acid is aliphatic dibasic acid of C3-C10; the dihydric alcohol is aliphatic dihydric alcohol of C2-C6.
The catalyst used in the polyester reaction process is a composite catalyst consisting of a main catalyst and a synergistic catalyst, wherein the main catalyst is a titanium catalyst, and the synergistic catalyst is any one of acetate, carbonate, oxalate, oxide or alkoxy compound of magnesium, calcium, antimony, cobalt, manganese, zinc, barium or aluminum metal ions.
The technological process of preparing copolyester includes esterification and polycondensation, the esterification reaction needs to be carried out in the presence of catalyst, the produced reactant is pre-polycondensed, and then final polycondensation is carried out to obtain biodegradable copolyester with high molecular weight.
In the conventional aliphatic/aromatic copolyester production process at present:
CN 105524258A discloses a continuous production process of biodegradable aliphatic/aromatic copolyester, which comprises continuously feeding aromatic dibasic acid, aliphatic dibasic acid and dihydric alcohol, performing esterification reaction in an esterification kettle in the presence of a catalyst to generate oligomers, then feeding the oligomers into a prepolymerization tower for prepolymerization, finally feeding the oligomers into a polycondensation kettle for polycondensation, and continuously discharging to obtain the biodegradable polyester with high molecular weight. By adopting the continuous production process, the residence time in the process is controllable, the operation cost can be effectively reduced, the high-energy-efficiency flexible production requirement is met, and the high-quality biodegradable polyester finished product is obtained. The invention relates to a method for producing copolyester by adopting three reactors, and the weight-average molecular weight of the obtained product can reach 10.37 ten thousand.
CN 102558515B discloses a method for continuously preparing biodegradable plastics, which mainly comprises the following steps: and continuously adding slurry prepared from one or more dibasic acids and one or more dihydric alcohols into a first esterification kettle for esterification reaction to obtain homopolyester or copolyester oligomer, further carrying out esterification reaction on the obtained esterified substance by a second esterification kettle to obtain an esterified substance, continuously feeding the obtained esterified substance into a first polycondensation kettle for polycondensation reaction, removing small molecules under the condition of low vacuum to obtain a prepolymer, continuously feeding the prepolymer into a high-vacuum second polycondensation kettle for condensation polymerization, removing the small molecules, and continuously tackifying and polymerizing the obtained polymer in a final polycondensation kettle with tackifying effect to obtain the biodegradable plastic slice with high molecular weight and the melt index less than 5. The process for continuously preparing the biodegradable plastic slices is simple and convenient to operate, the automation degree of the process is high, and the obtained biodegradable plastic slices have uniform product quality and no batch difference. The invention is a method for producing copolyester by using 5 reactors, and the intrinsic viscosity of the obtained product can reach 1.62 dl/g.
The TW 201422663A patent discloses a method for producing copolyester by using 5 reactors, the weight average molecular weight of the obtained product can reach 12.0-17.0 ten thousand, the intrinsic viscosity can reach 1.4-1.9 dl/g, and the melt index is 2.0-4.0g/10 min.
Due to the requirements of post-processability, tensile strength, film forming and blending with other polymers of degradable polyester products, only polymers with higher molecular weights (weight average molecular weight above 15 ten thousand, melt index below 4.0, intrinsic viscosity above 1.6 dg/l) have been marketed, whereas high molecular weight copolyesters can only be synthesized in continuous processes and horizontal polycondensation reactors.
However, since the reaction of the aromatic dibasic acid and the aliphatic diol is carried out under the condition of adding the catalyst in the esterification process of the continuous production of the aliphatic/aromatic copolyester, water, which is a byproduct of the esterification reaction, easily hydrolyzes the catalyst to lose activity, so that excessive catalyst is added in the esterification process, and the excessive catalyst is extremely unfavorable for the subsequent polycondensation reaction, so that the polymer is easily thermally degraded and the color is deteriorated.
In the polycondensation process of the aliphatic/aromatic copolyester continuous production, reactants have high molecular weight, poor fluidity and small devolatilization area of melt, so that the long retention time is easily required at a higher reaction temperature, and the color of a reaction product is influenced.
In summary, the continuous polymerization production of aliphatic/aromatic copolyesters requires esterification and polycondensation processes and reactors similar to those used in the industry today for aromatic copolyesters, such as: poly (terephthalic acid) (PET), all have great differences.
Therefore, it is a technical problem to be solved to provide a continuous polymerization production process of aliphatic/aromatic copolyester, which adds a catalyst as little as possible in the esterification reaction and reduces the residence time of the reaction as much as possible in the polycondensation reaction, in a targeted manner in the field of polymer chemical industry.
Disclosure of Invention
The invention aims to provide a process method and a device for continuously producing degradable polyester, aiming at the defects of the continuous polymerization production process and reactors of aliphatic/aromatic copolyester in the prior industry.
In order to achieve the above object, the present invention provides an apparatus for continuously producing a degradable polyester, comprising: an esterification reactor, a pre-polycondensation reactor, a final polycondensation reactor, a separation tower and an esterification heater;
the esterification heater and the separation tower are respectively connected with the esterification reactor, the esterification heater heats raw materials and then conveys the raw materials to the esterification reactor, and the separation tower separates gas-phase compounds generated by the esterification reactor;
the esterification reactor, the pre-polycondensation reactor and the final polycondensation reactor are sequentially connected, and the raw materials are processed step by step.
Further, the esterification reaction tower comprises: the reaction device comprises a first kettle type reaction section positioned at the bottom, a first tower type reaction section positioned at the upper part of the first kettle type reaction section, and a first heating section positioned in the tower type reaction section, wherein the upper part of the first kettle type reaction section is connected with the lower part of the first tower type reaction section;
the first kettle type reaction section is internally provided with a nested first reaction chamber, which comprises a first annular guide cylinder and a first inner chamber cover, wherein the first annular guide cylinder is positioned at the center of the bottom of the first kettle type reaction section and is surrounded by the wall of the reaction inner chamber; the reaction materials can flow in each chamber in a baffling mode, and a first discharge hole is formed in the bottom of the first annular guide cylinder; the first tower reaction section comprises a plurality of layers of circulation trays arranged in the radial direction of a central shaft and a first degassing pipe positioned on the central shaft; a plurality of air holes are formed in the tube body of the first degassing tube, adjacent circulation trays are fixed on the inner wall of the first tower type reaction section on one layer, the outer wall of the first degassing tube on the other layer, and a first feeding hole is formed in the side wall of the head of the first tower type reaction section; the top of the first tower type reaction section is provided with a first exhaust port, the first degassing pipe is connected with the first exhaust port, the top of the first reaction outer chamber wall is provided with a first exhaust pipe which is vertically upward, a row of vertically downward heating pipes is arranged in the first heating section, and the first heating section is heated by an organic heat carrier; .
Furthermore, a supplementary feeding hole is also formed in the side wall of the first tower type reaction section below the first heating section.
Further, the polycondensation reaction tower includes: the second kettle type reaction section is positioned at the bottom, the second tower type reaction section is positioned at the upper part of the second kettle type reaction section, and the second heating section is positioned in the second reaction section, wherein the upper part of the second kettle type reaction section is connected with the lower part of the second tower type reaction section;
a nested second reaction chamber is arranged in the second kettle type reaction section and comprises a second annular guide cylinder and a second inner chamber cover, wherein the second annular guide cylinder is positioned at the center of the bottom of the second kettle type reaction section and is surrounded by the wall of the reaction inner chamber, and the second inner chamber cover is covered on the upper part of the second annular guide cylinder and is surrounded by the wall of the second reaction outer chamber; the inner spaces of the second annular guide cylinder, the second inner chamber cover and the second kettle type reaction section are in a communicated state, reaction materials can flow in each chamber in a baffling mode, and a second discharge hole is formed in the bottom of the second annular guide cylinder; the second tower reaction section comprises a plurality of layers of circulation trays arranged in the radial direction of a central shaft and a second degassing pipe positioned on the central shaft; a plurality of air holes are formed in the tube body of the second degassing tube, adjacent circulation trays are fixed on the inner wall of the second tower type reaction section on one layer, the outer wall of the second degassing tube on the other layer, and a second feeding hole is formed in the side wall of the head of the first tower type reaction section; a second exhaust port is formed in the side wall of the shell of the second kettle type reaction section, a bent second exhaust pipe is arranged at the top of the wall of the second reaction outer chamber, rows of vertically downward heating pipes are arranged in the second heating section, and the second heating section is heated by an organic heat carrier;
furthermore, a third feeding port, a third discharging port and a third exhaust port are arranged on the final polycondensation reaction kettle.
Further, the esterification reactor is also connected with a separation tower, and the separation tower is used for introducing the byproducts generated in the esterification reactor and the diol which is not completely reacted into the separation tower from the top of the esterification reactor for separation, and returning the diol into a polyol supply system or directly introducing the diol into the raw material blending system for recycling.
Preferably, according to the molecular weight distribution of the separated components, the upper part of the separation tower is connected with a vacuum system through a vacuum gas phase pipeline, and water is recovered to a water collection system after water vapor is pumped out from the top of the separation tower and condensed through the vacuum system; the middle part of the separation tower is connected with the size mixing system and/or the polyol supply system through a pipeline, and the recovered polyol is recycled; the lower part of the separation tower is connected with a system collecting tank through a pipeline, and the by-product of the heavy component is discharged and collected.
Further, the esterification heater is connected with the first feed inlet or the supplementary feed inlet through a pipeline, the first discharge outlet is connected with the second feed inlet through a pipeline with a first conveying pump, the second discharge outlet is connected with the third feed inlet through a pipeline with a second conveying pump, and a third conveying pump is arranged at the third discharge outlet.
Further, the third conveying pump is also connected with a melt valve, and the melt valve is connected with the screw mixing system and/or the liquid phase tackifying system through a pipeline.
Further, the screw mixing system comprises a melt cooler, a screw mixer and a fourth conveying pump which are sequentially connected through pipelines, materials enter the granulating, drying and packaging processes after passing through the fourth conveying pump, and the screw mixer is further connected with an additive feeder.
Further, the liquid phase tackifying system comprises a tackifying kettle, a screw discharging pump and a fifth conveying pump which are sequentially connected through pipelines, and materials enter the procedures of granulating, drying and packaging after passing through the fifth conveying pump.
The system is characterized by further comprising a spray cooling system, wherein the spray cooling system comprises a pre-condensation spray system, a final condensation spray system and an adhesion increasing kettle spray system which are connected with one another, the pre-condensation spray system, the final condensation spray system and the adhesion increasing kettle spray system have the same structure, and all comprise a spray condenser, a receiving tank, a delivery pump, a filter and a condenser which are sequentially connected end to end through pipelines.
Further, the pre-polycondensation spraying system is connected with the pre-polycondensation reactor through a vacuum gas pipeline, the final polycondensation spraying system is connected with the final polycondensation reaction kettle through a vacuum gas pipeline, the tackifying kettle spraying system is connected with the tackifying kettle through a vacuum gas pipeline, the final polycondensation spraying system and the tackifying kettle spraying system flow materials to the pre-polycondensation spraying system through pipelines, the pre-polycondensation spraying system flows materials to the separation tower through pipelines, and the pre-polycondensation spraying system, the final polycondensation spraying system and the tackifying kettle spraying system are all connected with the vacuum system through vacuum gas pipelines.
The invention also provides a process method for continuously producing the degradable polyester by adopting the device, which comprises the following steps:
I. esterification reaction:
taking dihydric alcohol and dibasic acid as raw materials, mixing the slurry according to the alcohol-acid ratio of 1: 1.1-1: 4.0, wherein the temperature of the mixed slurry material is 80-120 ℃, then heating the mixed slurry material to 160-200 ℃, and then sending the mixed slurry material to an esterification reactor for esterification reaction; the esterification separation of the obtained esterification product positioned at the bottom of the esterification reactor is more than or equal to 98.0 percent, and the acid value is less than or equal to 20.0mg KOH/g;
II. Pre-polycondensation reaction:
introducing the esterification product from the bottom of the esterification reactor into the pre-polycondensation reactor through a pipeline, wherein a branch pipe for adding the catalyst is arranged on the pipeline in the case that the catalyst is added optionally; before the materials enter the pre-polycondensation reactor, the materials are heated and then enter the pre-polycondensation reactor to ensure that the reaction temperature in the pre-polycondensation reactor is 250 ℃ plus 220 ℃, the absolute pressure is 1.0-10.0KPa, the residence time is 1.5-2.5h, the pre-polycondensation reaction is carried out, the acid value of a pre-polycondensation product obtained at the bottom of the pre-polycondensation reactor is less than or equal to 8mg KOH/g, and the weight-average molecular weight is 8000-plus 12000;
III, final polycondensation reaction:
the product from the pre-polycondensation reaction is conveyed to a final polycondensation reaction kettle, the final polycondensation reaction is carried out under the conditions of the temperature of 240-260 ℃, the absolute pressure of 60.0-200.0Pa and the residence time of 1.0-2.0h, and the product at the bottom of the final polycondensation kettle after the final polycondensation reaction is polyester with the acid value of less than or equal to 4mg KOH/g and the weight-average molecular weight of 50000-80000;
IV, liquid-phase tackifying reaction:
the copolyester obtained in the final polycondensation enters a tackifying kettle, and under the conditions of temperature 240-260 ℃, absolute pressure of 60.0-200.0Pa and residence time of 0.5-1.0h, the weight average molecular weight of the reaction product is 120000-170000, and the melt index is 2.0-4.0g/10min (190 ℃).
Preferably, the viscosity increasing kettle is a horizontal double-shaft stirring reaction kettle, reaction materials are tangent and mixed by a radial scraper on a double shaft in the liquid phase viscosity increasing reaction process, and meanwhile, an axial scraper on the double shaft can form a self-cleaning effect on the inner wall of the reactor.
Further, the product obtained by liquid phase tackifying is further processed into particles and dried for storage and transportation.
In another embodiment of the present invention, there is also provided a process for continuously producing a degradable polyester by using the apparatus, including:
I. esterification reaction:
taking dihydric alcohol and dibasic acid as raw materials, mixing the slurry according to the alcohol-acid ratio of 1: 1.1-1: 4.0, wherein the temperature of the mixed slurry material is 80-120 ℃, then heating the mixed slurry material to 160-200 ℃, and then sending the mixed slurry material to an esterification reactor for esterification reaction; the esterification separation of the obtained esterification product positioned at the bottom of the esterification reactor is more than or equal to 98.0 percent, and the acid value is less than or equal to 20.0mg KOH/g;
II. Pre-polycondensation reaction:
introducing the esterification product from the bottom of the esterification reactor into the pre-polycondensation reactor through a pipeline, wherein a branch pipe for adding the catalyst is arranged on the pipeline in the case that the catalyst is added optionally; before the materials enter the pre-polycondensation reactor, the materials are heated and then enter the pre-polycondensation reactor to ensure that the reaction temperature in the pre-polycondensation reactor is 250 ℃ plus 220 ℃, the absolute pressure is 1.0-10.0KPa, the residence time is 1.5-2.5h, the pre-polycondensation reaction is carried out, the acid value of a pre-polycondensation product obtained at the bottom of the pre-polycondensation reactor is less than or equal to 8mg KOH/g, and the weight-average molecular weight is 8000-plus 12000;
III, final polycondensation reaction:
conveying a product from the pre-polycondensation reaction to a final polycondensation reaction kettle, and carrying out the final polycondensation reaction under the conditions that the temperature is 220-260 ℃, the absolute pressure is 60.0-200.0Pa and the residence time is 1.0-2.0h, wherein the final polycondensation reaction kettle adopts a cage-frame type stirrer, reactants are brought up by a stainless steel braided net disc to form a large devolatilization surface, so that diol molecules can be conveniently removed, and the product at the bottom of the final polycondensation kettle after the final polycondensation reaction is copolyester with the acid value of less than or equal to 4mg KOH/g and the weight-average molecular weight of 50000-80000;
IV, chain extension reaction:
cooling the copolyester melt obtained by the final polycondensation reaction by a melt cooler, adding a chain extender, and then entering a double-screw reactor together for chain extension reaction, optionally adding polylactic acid (P L A), calcium carbonate or starch for modifying degradable polyester in the chain extension reaction to obtain a reaction product with the weight-average molecular weight of 120000-170000 and the melt index of 2.0-4.0g/10min (190 ℃), and directly entering the subsequent granulating process.
Further, in the esterification reaction, the reaction temperature in the first tower reactor of the esterification reactor is 180-220 ℃, and the reaction pressure is-30 to-60 KPa (relative pressure); the residence time in the first kettle reactor of the esterification reactor is 2.0-4.0 h. More preferably, a heater is provided in the middle of the esterification reactor for maintaining the reaction temperature at a set value.
In a preferred embodiment, the copolyester obtained in the step III is led out through two branch pipes, and is respectively connected with the double-screw reactor and the tackifying kettle, and meanwhile, a polyester product required by the subsequent process is produced.
The invention has the beneficial effects that:
1. the esterification reactor and the pre-polycondensation reactor of the invention, through the combination of the tower reaction section and the kettle reaction section which are specially designed, the byproducts are removed quickly, the reaction efficiency is high, the addition of the catalyst can be greatly reduced, and the color and quality of the product are improved. The material retention time is short, the side reaction and the by-product are less, and the product quality is improved.
2. The esterification reactor in the invention is beneficial to feeding different alkyd raw materials in different reaction stages, reaction temperatures and different molar ratios, and is beneficial to accurately controlling esterification reaction.
3. The esterification reactor and the tower reactor part of the pre-polycondensation reactor are not mechanically stirred, so that the equipment operation and maintenance cost is reduced, and the industrial large-scale use of related technologies and equipment is facilitated.
Drawings
FIG. 1 is a schematic view of an apparatus for continuously producing a degradable polyester according to the present invention;
FIG. 2 is a schematic diagram of an esterification reactor provided by the present invention;
FIG. 3 is a schematic diagram of a prepolycondensation reactor provided by the present invention;
FIG. 4 is a pre-polycondensation spray system provided by the present invention;
FIG. 5 is a schematic view of a first embodiment of the present invention;
FIG. 6 is a schematic view of a second embodiment of the present invention;
10-esterification reactor, 101-first discharge port, 102-first feed port, 103-first degassing pipe, 104-first discharge pipe, 105-first discharge port, 106-supplementary feed port, 11-esterification heater, 12-separation column, 13-first transfer pump, 20-prepolycondensation reactor, 201-second feed port, 202-second degassing pipe, 203-second discharge pipe, 204-second discharge port, 205-second discharge port, 21-second transfer pump, 30-final polycondensation reactor, 31-third transfer pump, 32-melt valve, 40-screw mixer, 41-additive feeder, 42-melt cooler, 43-fourth transfer pump, 50-tackifying kettle, 51-screw discharge pump, 52-a fifth delivery pump, 60-a pre-polycondensation spray system, 61-a final polycondensation spray system, 62-a tackifying kettle spray system, 601-a spray condenser, 602-a receiving tank, 603-a delivery pump, 604-a filter and 605-a condenser.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Example 1
As shown in fig. 5, a process for continuously producing a degradable polyester comprises:
I. esterification reaction:
taking 1, 4-butanediol (BDO for short) and succinic acid (SA for short) as raw materials, mixing the raw materials according to the molar ratio of 1:1.2 to prepare the raw materials, wherein the temperature of the raw materials is 100 ℃, conveying the raw materials by a pump, heating the raw materials to 210 ℃ by an esterification heater 11, feeding the raw materials into an esterification reactor 10 from the upper part of a first tower reactor of the esterification reactor 10, and keeping the reaction pressure of-50 KPa (gauge pressure) and the retention time of 2.5 h;
setting the reaction temperature of a first kettle type reactor of an esterification reactor 10 to 235 ℃, the reaction pressure to be-50 KPa (gauge pressure), the residence time to be 1.5h, and the total residence time of the two sections to be 4.0h, adding a catalyst tetrabutyl titanate into the first kettle type reactor, wherein the adding amount is 80ppm of the weight content of tetrabutyl titanate in the finally obtained degradable polyester product, and the esterification rate is more than or equal to 98.0 percent, and the acid value of the material obtained by the reaction is 15.0mg KOH/g;
II. Pre-polycondensation reaction:
introducing the esterification product from the bottom of the esterification reactor 10 into the upper part of a second tower reactor of the pre-polycondensation reactor 20 through a pipeline, heating the materials before the materials enter the pre-polycondensation reactor 20, and then entering the pre-polycondensation reactor 20 to ensure that the reaction temperature in the pre-polycondensation reactor 20 is 240 ℃, the reaction pressure is 1000KPa (absolute pressure), the residence time is 1.5h, performing the pre-polycondensation reaction, wherein the reaction temperature in the pre-polycondensation reactor 20 is 245 ℃, the reaction pressure is 100KPa (absolute pressure), the residence time is 1.0h, the acid value of the obtained pre-polycondensation product is 6mg KOH/g, and the weight-average molecular weight is 8000-12000;
the reaction waste gas is discharged from the second exhaust port and then enters the pre-polycondensation spraying system 60, after the waste gas is cooled circularly, the gas phase is discharged through a vacuum system, and the liquid phase flows back to the separation tower 12 through a pipeline;
III, final polycondensation reaction:
the product from the pre-polycondensation reaction is conveyed to a final polycondensation reaction kettle 30, and the final polycondensation reaction is carried out under the conditions of 245 ℃ of temperature, 150.0Pa (absolute pressure) of reaction pressure and 1.5h of residence time, wherein the product of the final polycondensation reaction is a homopolyester melt with the acid value of 3.0mgKOH/g, the melting point of 110 ℃ and the weight-average molecular weight of 60000;
the reaction waste gas is discharged from a third exhaust port and then enters a final condensation spraying system 61, after the waste gas is cooled circularly, a gas phase is discharged through a vacuum system, and a liquid phase enters a pre-condensation spraying system 60 through a pipeline;
IV, liquid-phase tackifying reaction:
and (3) introducing the homopolyester melt obtained by the final polycondensation into a tackifying reaction kettle, wherein the reaction temperature is 250 ℃, the reaction pressure is 60Pa (absolute pressure), and the residence time is 1.0h, so as to obtain the binary degradable polyester product of which the weight-average molecular weight of the reaction product is 160000, the melting point is 114 ℃, and the melt index is 3.0g/10min (190 ℃).
Reaction waste gas is discharged from the tackifying reaction kettle and then enters a tackifying kettle spraying system 62, after the waste gas is cooled circularly, a gas phase is discharged through a vacuum system, and a liquid phase enters a pre-polycondensation spraying system 60 through a pipeline;
and (4) further granulating a product obtained after liquid-phase tackifying, and drying the product to facilitate storage and transportation.
Example 2
As shown in fig. 6, a process for continuously producing a degradable polyester comprises:
the method is characterized in that adipic acid, terephthalic acid and 1, 4-butanediol are used as raw materials to produce degradable copolyester, and Adipic Acid (AA) and 1, 4-Butanediol (BDO) are mixed according to an alcohol acid molar ratio of 1:1.2 preparing raw materials, wherein the preparation temperature of the raw materials is 100 ℃, the raw materials are heated to 210 ℃ by a heater and enter the upper part of an esterification reactor 10;
setting the reaction temperature of a tower reaction section of an esterification reactor 10 to be 230 ℃, the reaction temperature of a kettle reaction section to be 235 ℃ and the reaction pressure to be-50 KPa, wherein the total residence time in the esterification reactor 10 is 3.5 hours in total, the esterification rate is more than or equal to 98.0 percent, and the acid value of the material obtained by reaction is 15.0mg KOH/g;
II. Pre-polycondensation reaction:
introducing the esterification product from the bottom of the esterification reactor 10 into the upper part of the tower-type reaction section of the pre-polycondensation reactor 20 through a pipeline, heating the materials before the materials enter the pre-polycondensation reactor 20, and then entering the pre-polycondensation reactor 20 to ensure that the reaction temperature in the pre-polycondensation reactor 20 is 240 ℃, the reaction pressure is 1000KPa (absolute pressure), the residence time is 1.5h, carrying out the pre-polycondensation reaction, wherein the acid value of the pre-polycondensation product obtained at the bottom of the pre-polycondensation reactor 20 is 6mg KOH/g, and the weight-average molecular weight is 12000;
the reaction waste gas is discharged from the second exhaust port and then enters the pre-polycondensation spraying system 60, after the waste gas is cooled circularly, the gas phase is discharged through a vacuum system, and the liquid phase flows back to the separation tower 12 through a pipeline;
III, final polycondensation reaction:
the product from the pre-polycondensation reaction is conveyed to a final polycondensation reaction kettle 30, and the final polycondensation reaction is carried out under the conditions of the temperature of 245 ℃, the reaction pressure of 150.0Pa (absolute pressure) and the residence time of 1.5h, wherein the acid value of the final polycondensation product is 3.0mgKOH/g, the weight-average molecular weight of the copolyester is 60000, and the melting point of the copolyester is 110 ℃;
the reaction waste gas is discharged from a third exhaust port and then enters a final condensation spraying system 61, after the waste gas is cooled circularly, a gas phase is discharged through a vacuum system, and a liquid phase enters a pre-condensation spraying system 60 through a pipeline;
IV, liquid-phase tackifying reaction:
the copolyester melt obtained by the final polycondensation enters a tackifying kettle 50, the reaction temperature is 250 ℃, the reaction pressure is 60Pa (absolute pressure), the residence time is 1.0h, and the weight average molecular weight of reactants is 160000, the melting point is 114 ℃, and the melt index is 3.0g/10min (190 ℃).
Reaction waste gas is discharged from the tackifying reaction kettle and then enters a tackifying kettle spraying system 62, after the waste gas is cooled circularly, a gas phase is discharged through a vacuum system, and a liquid phase enters a pre-polycondensation spraying system 60 through a pipeline;
and (4) further granulating the product obtained after liquid-phase tackifying, and drying the product to facilitate storage and transportation. .
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Claims (15)
1. An apparatus for continuously producing degradable polyester, comprising: an esterification reactor (10), a pre-polycondensation reactor (20), a final polycondensation reactor (30), a separation tower (12), an esterification heater (11) and a spray cooling system;
the esterification heater (11) and the separation tower (12) are respectively connected with the esterification reactor (10), the esterification heater (11) heats raw materials and then conveys the raw materials to the esterification reactor (10), and the separation tower (12) separates gas-phase compounds generated by the esterification reactor (10);
the esterification reactor (10), the pre-polycondensation reactor (20) and the final polycondensation reactor (30) are connected in sequence, and raw materials are processed into monomers to synthesize polymers.
2. The apparatus for continuously producing degradable polyester according to claim 1, wherein the esterification reaction tower (10) comprises: the reaction device comprises a first kettle type reaction section positioned at the bottom, a first tower type reaction section positioned at the upper part of the first kettle type reaction section, and a first heating section positioned in the tower type reaction section, wherein the upper part of the first kettle type reaction section is connected with the lower part of the first tower type reaction section;
the first kettle type reaction section is internally provided with a nested first reaction chamber, which comprises a first annular guide cylinder and a first inner chamber cover, wherein the first annular guide cylinder is positioned at the center of the bottom of the first kettle type reaction section and is surrounded by the wall of the reaction inner chamber; the inner spaces of the first annular guide cylinder, the first inner chamber cover and the first kettle type reaction section are in a communicated state, reaction materials can flow in each chamber in a baffling mode, and a first discharge hole (105) is formed in the bottom of the first annular guide cylinder; the first tower reaction section comprises a plurality of layers of circulation trays arranged in the radial direction of a central shaft and a first degassing pipe (103) positioned on the central shaft; a plurality of air holes are formed in the tube body of the first degassing tube (103), adjacent circulation trays are fixed on the inner wall of the first tower type reaction section on one layer, the outer wall of the first degassing tube (103) on the other layer, and a first feeding hole (102) is formed in the side wall of the head of the first tower type reaction section; first tower reaction section top is equipped with first gas vent (101), first degasification pipe (103) with first gas vent (101) are connected, the top of first reaction outer chamber wall is equipped with vertical ascending first exhaust pipe (104), be equipped with the vertical decurrent heating pipe in a row in the first heating section, first heating section is heated by organic heat carrier.
3. The apparatus for continuously producing degradable polyester according to claim 2, wherein the first tower reaction section is further provided with a supplementary feeding hole (106) on the side wall below the first heating section.
4. The apparatus for continuously producing degradable polyester according to claim 1, wherein the polycondensation reaction tower (20) comprises: the second kettle type reaction section is positioned at the bottom, the second tower type reaction section is positioned at the upper part of the second kettle type reaction section, and the second heating section is positioned in the second reaction section, wherein the upper part of the second kettle type reaction section is connected with the lower part of the second tower type reaction section;
a nested second reaction chamber is arranged in the second kettle type reaction section and comprises a second annular guide cylinder and a second inner chamber cover, wherein the second annular guide cylinder is positioned at the center of the bottom of the second kettle type reaction section and is surrounded by the wall of the reaction inner chamber, and the second inner chamber cover is covered on the upper part of the second annular guide cylinder and is surrounded by the wall of the second reaction outer chamber; the inner spaces of the second annular guide cylinder, the second inner chamber cover and the second kettle type reaction section are in a communicated state, reaction materials can flow in each chamber in a baffling mode, and a second discharge hole (205) is formed in the bottom of the second annular guide cylinder; the second tower reaction section comprises a plurality of layers of circulation trays which are arranged along the radial direction of a central shaft, and a second degassing pipe (202) which is positioned on the central shaft; a plurality of air holes are formed in the tube body of the second degassing tube (202), adjacent circulation trays are fixed on the inner wall of the second tower type reaction section on one layer, the outer wall of the second degassing tube (202) on the other layer, and a second feeding hole (201) is formed in the side wall of the head of the first tower type reaction section; be equipped with second gas vent (204) on the lateral wall of second cauldron formula reaction zone shell, the top of second reaction outer chamber wall is equipped with crooked second blast pipe (203), be equipped with the vertical decurrent heating pipe in row in the second heating section, the second heating section is heated by organic heat carrier.
5. The apparatus for continuously producing degradable polyester according to claim 1, wherein the final polycondensation reaction kettle (30) is provided with a third feeding port, a third discharging port and a third exhaust port.
6. The apparatus for continuously producing degradable polyester according to claim 2, wherein the esterification reactor (10) is further connected to a separation column (12), the separation column (12) is used for introducing the byproduct generated in the esterification reactor (10) and the diol which is not completely reacted into the separation column (12) from the top of the esterification reactor (10) for separation, and the diol in the separation column is returned to a diol supply system or directly introduced into the raw material blending system for recycling.
7. The apparatus for continuously producing degradable polyester according to any of the claims 1 to 6, wherein the esterification heater (11) is connected with the first feeding port (102) or the supplementary feeding port (106) through a pipeline, the first discharging port (105) is connected with the second feeding port (201) through a pipeline with a first conveying pump (13), the second discharging port (205) is connected with the third feeding port through a pipeline with a second conveying pump (21), and the third discharging port is provided with a third conveying pump (31).
8. The apparatus for continuously producing degradable polyester according to claim 7, wherein the third transfer pump (31) is further connected to a melt valve (32), and the melt valve (32) is connected to a screw mixing system and/or a liquid phase tackifying system through a pipeline.
9. The apparatus for continuously producing degradable polyester according to claim 8, wherein the screw mixing system comprises a melt cooler (42), a screw mixer (40) and a fourth delivery pump (43) which are connected in sequence through a pipeline, the material enters the pelletizing, drying and packaging processes after passing through the fourth delivery pump (43), and the screw mixer (40) is further connected with an additive feeder (41).
10. The apparatus for continuously producing degradable polyester according to claim 9, wherein the liquid phase viscosity increasing system comprises a viscosity increasing kettle (50), a screw discharge pump (51) and a fifth delivery pump (52) which are connected in sequence through pipelines, and the materials pass through the fifth delivery pump (52) and then enter the procedures of granulating, drying and packaging.
11. The device for continuously producing the degradable polyester according to claim 7, wherein a spray cooling system is further provided, the spray cooling system comprises a pre-condensation spray system (60), a final condensation spray system (61) and a tackifying kettle spray system (62) which are connected with each other, the pre-condensation spray system (60), the final condensation spray system (61) and the tackifying kettle spray system (62) have the same structure, and all comprise a spray condenser (601), a receiving tank (602), a delivery pump (603), a filter (604) and a condenser (605) which are connected end to end in sequence through pipelines.
12. The apparatus for continuously producing degradable polyester according to claim 7, the pre-polycondensation spraying system (60) is connected with the pre-polycondensation reactor (20) through a vacuum gas phase pipeline, the final polycondensation spray system (61) is connected with the final polycondensation reaction kettle (30) through a vacuum gas phase pipeline, the tackifying kettle spraying system (62) is connected with the tackifying kettle (50) through a vacuum gas phase pipeline, the final condensation spraying system (61) and the tackifying kettle spraying system (62) flow materials to the pre-condensation spraying system (60) through pipelines, the pre-polycondensation spray system (60) flows the material to the separation tower (12) through a pipeline, the pre-polycondensation spray system (60), the final polycondensation spray system (61) and the tackifying kettle spray system (62) are all connected with a vacuum system through vacuum gas phase pipelines.
13. A process for continuously manufacturing a device for degradable polyester according to any one of claims 1 to 12, comprising:
I. esterification reaction:
taking dihydric alcohol and dibasic acid as raw materials, mixing the slurry according to the alcohol-acid ratio of 1: 1.1-1: 4.0, wherein the temperature of the mixed slurry material is 80-120 ℃, then heating the mixed slurry material to 160-200 ℃, and then sending the mixed slurry material to an esterification reactor (10) for esterification reaction; the esterification separation of the obtained esterification product positioned at the bottom of the esterification reactor (10) is more than or equal to 98.0 percent, and the acid value is less than or equal to 20.0mg KOH/g;
II. Pre-polycondensation reaction:
introducing the esterification product from the bottom of the esterification reactor (10) into the prepolycondensation reactor (20) via a conduit, optionally with a catalyst addition manifold, where catalyst addition is desired; before the materials enter the pre-polycondensation reactor (20), the materials are heated and then enter the pre-polycondensation reactor (20) so as to ensure that the reaction temperature in the pre-polycondensation reactor (20) is 250 ℃ at 220-;
III, final polycondensation reaction:
the product from the pre-polycondensation reaction is conveyed to a final polycondensation reaction kettle (30) for carrying out the final polycondensation reaction under the conditions of the temperature of 240-260 ℃, the absolute pressure of 60.0-200.0Pa and the residence time of 1.0-2.0h, and the product at the bottom of the final polycondensation reaction is polyester with the acid value of less than or equal to 4mg KOH/g and the weight-average molecular weight of 50000-80000;
IV, liquid-phase tackifying reaction:
the copolyester obtained in the final polycondensation enters an adhesion-promoting kettle (50), and under the conditions of temperature 240-260 ℃, absolute pressure of 60.0-200.0Pa and residence time of 0.5-1.0h, the weight-average molecular weight of the reaction product is 120000-170000, and the melt index at 190 ℃ is 2.0-4.0g/10 min.
14. The method as claimed in claim 13, wherein the liquid phase tackified product is further processed into granules, dried and then stored and transported.
15. The process for continuous production of degradable polyester as claimed in claim 13, wherein in the esterification reaction, the reaction temperature inside the first tower reactor of the esterification reactor (10) is 180-220 ℃, the reaction pressure is-30 to-60 KPa; the residence time in the first kettle type reactor of the esterification reactor (10) is 2.0-4.0 h; more preferably, a heater is provided in the middle of the esterification reactor (10) for maintaining the reaction temperature thereof at a set value.
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