CN117645712A - Production process for transferring production PBT, PBS, PBST, PBSA of PBAT device - Google Patents
Production process for transferring production PBT, PBS, PBST, PBSA of PBAT device Download PDFInfo
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- CN117645712A CN117645712A CN202311672740.5A CN202311672740A CN117645712A CN 117645712 A CN117645712 A CN 117645712A CN 202311672740 A CN202311672740 A CN 202311672740A CN 117645712 A CN117645712 A CN 117645712A
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- 229920001896 polybutyrate Polymers 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 title claims abstract description 20
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920009537 polybutylene succinate adipate Polymers 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 238000005886 esterification reaction Methods 0.000 claims abstract description 74
- 230000032050 esterification Effects 0.000 claims abstract description 56
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 52
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000012546 transfer Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000001361 adipic acid Substances 0.000 claims description 14
- 235000011037 adipic acid Nutrition 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 4
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000011552 falling film Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 polybutylene terephthalate adipate Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a production process for flexible transfer PBT, PBS, PBST, PBSA of a PBAT device, which comprises the following steps: slurry preparation, esterification 1, esterification 2, pre-polycondensation, final polycondensation, liquid phase tackifying, chain extension, slicing, drying and the like, wherein the polybasic polyester takes PBAT as an example, PTA and AA are subjected to esterification step by step under the same conditions, then co-esterification is carried out, the polyester is transferred into a pre-shrinking tower for pre-shrinking after the esterification is finished, the polyester is transferred into a final shrinking reactor for further reaction after the pre-shrinking is finished, and the tackifying or chain extension is selected according to the final shrinking condition after the final shrinking is finished to obtain a PBAT polyester product; the binary polyester takes PBT as an example, PTA is esterified in two ester 1 reactors, then the esterification is carried out in an ester 2 reactor under controlled conditions, the esterification is carried out in a preshrinking tower for preshrinking, the preshrinking is carried out in a final polycondensation reactor after the preshrinking is finished, the further reaction is carried out in the final polycondensation reactor, the thickening or discharging is selected according to the final polycondensation condition after the final polycondensation is finished, and the PBT polyester product is obtained, and polyester products such as PBT, PBS, PBST, PBSA and the like can be flexibly produced by controlling and adjusting related process formulas on the device.
Description
Technical Field
The invention relates to the technical field of polyester product production processes, in particular to a device capable of realizing flexible switching production of polyester products such as PBAT, PBT, PBS, PBST, PBSA through process and auxiliary agent formula adjustment.
Background
The polymer material has certain advantages compared with the traditional inorganic materials (steel, ceramics and the like) due to the characteristics of light weight, easy processing and forming, corrosion resistance and the like, and is widely applied to various polymer products in various industries and markets, thereby bringing convenience to people and improving the life of people. The aging, discarding and continuously updating of the products lead to a large amount of undegradable polymer materials and further form a large amount of wastes, so that the problems of increasingly severe white pollution and other environmental pollution are caused, and the sustainable development of ecology is seriously hindered. In order to solve the environmental problems caused by non-degradable plastics, various methods have been tried to treat, including physical recycling, chemical recycling, etc. methods in order to realize recycling of plastics. However, the above method requires a lot of manpower, material resources and financial resources, and may cause further pollution in the treatment process. In order to fundamentally solve a series of ecological problems brought by high polymer materials, fully biodegradable high polymer materials are developed, waste and aged polymers are fully decomposed in the nature, the waste and aged polymers are naturally obtained, and are continuously demonstrated by universities, research institutions and enterprises, polyester products such as PBAT, PBS, PBST, PBSA all meet the characteristic of fully biodegradation, and the fully biodegradable high polymer materials are fully biodegradable engineering plastics, and PBT is particularly favored by the market as high-viscosity PBT, so that the polyester products can be flexibly produced by using a set of production devices through adjusting a process auxiliary agent formula system, the investment of resources can be greatly reduced, and the damage to the environment in the production process is reduced.
The PBAT chinese name is: polybutylene terephthalate adipate PBAT. Adipic Acid (AA), terephthalic acid (PTA) and Butanediol (BDO) are taken as monomers, and poly (adipic acid-butylene terephthalate) is synthesized under the action of a catalyst according to a certain proportion by controlling the technological conditions of each stage, so that the poly (adipic acid-butylene terephthalate) is a multi-element biodegradable material (PBST, PBSA are similar). The specific synthesis process comprises a batching beating kettle, an esterification reaction kettle, a di-esterification reaction kettle, a pre-polycondensation reactor, a final polycondensation reaction kettle, a tackifying reaction kettle/dynamic mixer and a granulating and packaging system, wherein the esterification reaction comprises three modes of esterification, namely esterification, co-esterification and esterification, the esterification reaction of dibasic acid is carried out by adopting esterification on the device, and PTA and AA esterified substances are co-esterified until the esterification is finished.
The Chinese name of PBT is: polybutylene terephthalate, a high molecular polyester product produced by dehydrating and Polycondensing Terephthalic Acid (PTA) and 1, 4-Butanediol (BDO), is an important thermoplastic polyester. The production method of PBT is mainly transesterification, and along with the continuous improvement of PTA purity, a direct esterification polycondensation method becomes the main stream gradually. The specific synthetic process of the PBT comprises a batching and pulping kettle, a PTA esterification reaction kettle, a di-esterification reaction kettle, a pre-polycondensation reactor, a final polycondensation reaction kettle and a granulating and packaging system.
Defects and deficiencies of the prior art: the traditional polyester process can not finish flexible production transfer of PBAT, PBT, PBS, PBST, PBSA and other polyesters in the same production line due to different equipment, process routes and formula systems, namely, various polyester products can only realize production of a single product on the production line, products outside the production design category can not be realized, and when the market fluctuates on the requirements of various resins, the device can not flexibly transfer the production according to the market requirements, so that the market is missed.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a production process for flexibly transferring PBT, PBS, PBST, PBSA of a PBAT device, so that various polyester products can be produced in the same production line, and the aim of flexible production can be achieved.
In order to achieve the above purpose, the invention provides a production process for flexible transfer PBT, PBS, PBST, PBSA of a PBAT device, which comprises the following steps: (1) slurry preparation: preparing phthalic acid, adipic acid and 1,4 butanediol into slurry for producing PBAT according to a certain molar ratio or preparing terephthalic acid and 1,4 butanediol into slurry for producing PBT according to a certain molar ratio; (2) esterification 1: pumping the slurry obtained in the step 1 to an esterification 1 reaction kettle for esterification to obtain an esterified substance I; (3) esterification 2: pumping the esterified substance obtained in the step (2) into an esterification 2 reaction kettle for esterification to obtain an esterified substance II; (4) precondensation: pumping the esterified substance II obtained in the step (3) into a pre-shrinking tower reactor to perform pre-shrinking polymerization reaction to obtain a prepolymer III; (5) final polycondensation: pumping the prepolymer in the step (4) into a final polycondensation reaction kettle for final polycondensation reaction to obtain a final polymer IV; (6) tackifying/chain extending: carrying out further polycondensation reaction in a tackifying reaction kettle or a dynamic mixer pumped by the final polymer in the step (5) to obtain a final polymer V; (7) pelleting/drying: carrying out underwater die cutting on the final polymer IV in the step (5) or the polyester melt in the step (6) by using a granulator to form particles, and then drying, weighing and packaging to finally obtain a polyester finished product; (8) switching: when producing polybasic polyester such as PBAT, PTA, AA slurry tank and esterification kettle are simultaneously put into reaction by adopting esterification separation process to respectively obtain target PTA esterified substance and AA esterified substance, and then two esterification kettles which are pumped by the esterification kettle are further subjected to esterification reaction; when producing the binary polyester such as PBT, whether to use an AA slurry tank, an esterification kettle and a di-esterification kettle is selected according to the requirement, namely, when the set of PBAT equipment flexibly produces the multi-polyester and the binary polyester, the equipment is selected according to the specific production requirement, and meanwhile, the process is adjusted to obtain the di-esterified substance and the prepolymer with corresponding indexes, and then the final polycondensation and the subsequent reaction are carried out.
Preferably, the external molar ratio of PTA slurry is between 1.1 and 1.5, the internal molar ratio of PTA slurry is between 2.5 and 3.0, the external molar ratio of AA slurry is between 1.1 and 1.5, and the internal molar ratio of PTA slurry is between 2.5 and 2.8; the external molar ratio of the slurry is between 1.2 and 1.8 and the internal molar ratio is between 3.0 and 3.8 when the PBT is produced. More preferably, the external molar ratio of PTA slurry is controlled between 1.25 and 1.35, the internal molar ratio is controlled between 2.6 and 2.8, the external molar ratio of AA slurry is controlled between 1.25 and 1.35, and the internal molar ratio is controlled between 2.6 and 2.7 when PBAT is produced; the external molar ratio of the slurry is between 1.4 and 1.6 and the internal molar ratio is between 3.4 and 3.6 when the PBT is produced.
Preferably, the reaction pressure of the PTA esterification kettle is 50-65 Kpa (A) when the esterification 1 reaction kettle is used for producing PBAT in the step (2); the reaction temperature is 225-235 ℃, the temperature of the heating medium is 240-260 ℃, the liquid level is 35-45%, and the residence time is 1-3 h; the reaction pressure of the AA esterification kettle is normal pressure/micro negative pressure; the reaction temperature is 180-200 ℃, the temperature of the heating medium is 200-220 ℃, the liquid level is 20-30%, and the residence time is 1-3 h; the reaction pressure of the PTA esterification kettle is 50Kpa (A) when the PBT is produced; the reaction temperature is 240 ℃, the temperature of the heating medium is 260-280 ℃, the liquid level is 60-70%, and the residence time is 3-4 h. More preferably, the reaction pressure of the PTA esterifier in the production of PBAT is 55Kpa (A); the reaction temperature is 230 ℃, the temperature of the heating medium is 245 ℃, the liquid level is 38%, and the residence time is 2h; the reaction pressure of the AA esterification kettle is normal pressure/micro negative pressure; the reaction temperature is 190 ℃, the temperature of the heating medium is 210 ℃, the liquid level is 20-30%, and the residence time is 2h; the reaction pressure of the PTA esterification kettle is 50Kpa (A) when the PBT is produced; the reaction temperature is 240 ℃, the temperature of the heating medium is 260-280 ℃, the liquid level is 60-70%, and the residence time is 3.5h.
Preferably, the reaction pressure is 60-70 Kpa (A), the reaction temperature is 220-240 ℃, the temperature of the heating medium is 240-260 ℃, the liquid level is 20-30% and the residence time is 45-90 minutes when the PBAT is produced by the esterification 2 reaction kettle in the step (3). More preferably, the reaction pressure at the time of producing PBAT is 65Kpa (A), the reaction temperature is 230 ℃, the heat medium temperature is 249 ℃, the liquid level is 25%, and the residence time is 75 minutes.
Preferably, the reaction pressure in the step (3) for producing the PBT by the esterification 2 reaction kettle is 50Kpa (A), the reaction temperature is 240 ℃, the temperature of the heating medium is 260-280 ℃, the liquid level is 20-30%, and the residence time is 2.5-3 h. More preferably, the temperature of the heating medium is 280 ℃, the liquid level is 25%, and the residence time is 2.7h.
Preferably, the precondensation reactor in the step (4) adopts a falling film tray type reactor. When producing PBAT, the pressure at the top of the tower is 1-5 Kpa (A), the temperature at the top of the tower is 220-230 ℃, the pressure at the bottom of the tower is 4-8 Kpa (A), the temperature at the bottom of the tower is 225-235 ℃, and the liquid level at the bottom of the tower is 10-15%. More preferably, the PBAT is produced at a column top pressure of 1 to 3Kpa (A), a column top temperature of 228℃and a column bottom pressure of 4.8Kpa (A), a column bottom temperature of 231℃and a column bottom liquid level of 13%.
Preferably, when the pre-polycondensation reactor in the step (4) produces PBT, the pressure at the top of the column is 3-8 Kpa (A), the temperature at the top of the column is 230-240 ℃, the pressure at the bottom of the column is 1-5 Kpa (A), the temperature at the bottom of the column is 230-240 ℃, and the liquid level at the bottom of the column is 10-20%. More preferably, when PBT is produced, the top pressure is 4.5Kpa (A), the top temperature is 237 ℃, the bottom pressure is 3.26Kpa (A), the bottom temperature is 237 ℃, and the bottom liquid level is 16%.
Preferably, when the final polycondensation reaction vessel in the step (5) produces PBAT, the reaction pressure is 100 to 300Pa (A), the inlet temperature is 230 to 240 ℃, and the outlet temperature is 225 to 230 ℃; when the PBT is produced, the reaction pressure is 100-300Pa (A), the inlet temperature is 240-250 ℃, and the outlet temperature is 240-250 ℃. More preferably, in the production of PBAT, the reaction pressure is 100Pa (A), the inlet temperature is 235 ℃, and the outlet temperature is 228.5 ℃; in the production of PBT, the reaction pressure was 180Pa (A), the inlet temperature was 242.5℃and the outlet temperature was 242.5 ℃.
Preferably, when the tackifying reaction kettle in the step (6) is used for producing PBAT, the reaction pressure is 50-100Pa (A), the inlet temperature is 230-240 ℃, and the outlet temperature is 225-230 ℃; when the PBT is produced, the reaction pressure is 50-100Pa (A), the inlet temperature is 240-250 ℃, and the outlet temperature is 240-250 ℃. More preferably, when the tackifying reaction kettle is used for producing PBAT, the reaction pressure is 80Pa (A), the inlet temperature is 230 ℃, and the outlet temperature is 228 ℃; in the production of PBT, the reaction pressure was 80Pa (A), the inlet temperature was 242℃and the outlet temperature was 242 ℃.
Preferably, in the step (6), when the dynamic mixer is used to produce the PBAT, the reaction pressure is 50-100Pa (A), the inlet temperature is 200-210 ℃, the outlet temperature is 160-180 ℃, and the addition amount of the chain extender is 3-4 per mill. More preferably, when the dynamic mixer is used for producing PBAT, the reaction pressure is 80Pa (A), the inlet temperature is 203 ℃, the outlet temperature is 170 ℃, and the addition amount of the chain extender is 3.5 per mill.
The invention has the advantages that: the flexible production of various polyester products can be realized by only using a single set of device, and the production products can be timely adjusted according to market demands.
Detailed Description
Preparing phthalic acid, adipic acid and 1,4 butanediol into slurry for producing PBAT according to a certain molar ratio or preparing phthalic acid and 1,4 butanediol into slurry for producing PBT according to a certain molar ratio, wherein the external molar ratio of the slurry for producing PBAT is 2.78; the external molar ratio of the slurry for producing PBT is 2.68; pumping the slurry to an esterification reaction kettle 1 for esterification to prepare an esterified substance, and controlling the esterification rate by controlling the reaction temperature, the pressure, the residence time and the catalyst addition amount; the reaction pressure of the PTA esterification kettle is 55Kpa (A) when the esterification 1 reaction kettle is used for producing PBAT; the reaction temperature is 230 ℃, the temperature of a heating medium is 245 ℃, the liquid level is 38%, the residence time is 2h, and the acid value of the esterified substance is 65+/-5 mg/Kg (KOH); the reaction pressure of the AA esterification kettle is normal pressure/micro negative pressure; the reaction temperature is 190 ℃, the temperature of the heating medium is 210 ℃, the liquid level is 20-30%, the residence time is 2h, and the carboxyl of the esterified substance is 300+/-30 mol/t; the reaction pressure of the PTA esterification kettle is 50Kpa (A) when the PBT is produced; the reaction temperature is 240 ℃, the temperature of a heating medium is 260-280 ℃, the liquid level is 60-70%, the retention time is 3.5h, the acid value of an esterified substance is 3-6 mg/Kg (KOH), after the esterification 1 is finished, the esterification 2 reaction kettle pumped by the esterified substance is subjected to co-esterification (di-esterification), the reaction pressure of the di-esterification kettle is 65Kpa (A) when PBAT is produced, the reaction temperature is 230 ℃, the liquid level is 25%, the retention time is 75 minutes, the acid value of the esterified substance is 80+/-10 mg/Kg (KOH), the reaction pressure of the di-esterification kettle is 50Kpa (A), the reaction temperature is 240 ℃, the temperature of the heating medium is 280 ℃, the liquid level is 25%, the retention time is 2.7h, and the acid value of the esterified substance is 2-4 mg/Kg (KOH); after the esterification 2 is finished, a pre-polycondensation reactor for pumping a diester is used for pre-polycondensation, the pre-polycondensation tower top pressure is 1-3 Kpa (A) when PBAT is produced, the tower top temperature is 228 ℃, the tower bottom pressure is 4.8Kpa (A), the tower bottom temperature is 231 ℃, the tower bottom liquid level is 13%, the residence time is 2h, the prepolymer viscosity is 0.32+/-0.02 dL/L, the carboxyl group is 10+/-5 mol/t, the tower top pressure is 4.5Kpa (A), the tower top temperature is 237 ℃, the tower bottom pressure is 3.26Kpa (A), the tower bottom temperature is 237 ℃, the tower bottom liquid level is 16%, the residence time is 1.8h, and the carboxyl group of the prepolymer is 15+/-3 mol/t; after the pre-polymerization is completed, a final polycondensation reaction kettle for pumping the prepolymer is carried out, when PBAT is produced, the reaction pressure is 100Pa (A), the inlet temperature is 235 ℃, the outlet temperature is 228.5 ℃, the residence time is 2 hours, the final polymer melt index is 60g/10min, when PBT is produced, the reaction pressure is 180Pa (A), the inlet temperature is 242.5 ℃, the outlet temperature is 242.5 ℃, the residence time is 2.6 hours, and the final polymer melt index is 28g/10min; after finishing the final polycondensation, a final polymer is pumped into a tackifying reaction kettle/dynamic mixer for further tackifying, when the tackifying reaction kettle produces PBAT, the reaction pressure is 80Pa (A), the inlet temperature is 230 ℃, the outlet temperature is 228 ℃, the residence time is 1h, when the dynamic mixer produces PBAT, the reaction pressure is 80Pa (A), the inlet temperature is 203 ℃, the outlet temperature is 170 ℃, the addition amount of a chain extender is 3.5 per mill, the residence time is 10min, and the melt index is 3-5 g/10min; when PBT is produced (optional application), the reaction pressure is 80Pa (A), the inlet temperature is 242 ℃, the outlet temperature is 242 ℃, the residence time is 0.5h, and the melting finger is 18+/-2 g/10min.
Detection result
The indexes of the PBAT product prepared in the embodiment are shown in Table 1:
the indexes of the PBT product prepared in the embodiment are shown in Table 2:
Claims (10)
1. the production process of the transfer production PBT, PBS, PBST, PBSA of the PBAT device is characterized by comprising the following steps of: (1) slurry preparation: preparing phthalic acid, adipic acid and 1,4 butanediol into slurry for producing PBAT according to a certain molar ratio or preparing terephthalic acid and 1,4 butanediol into slurry for producing PBT according to a certain molar ratio; (2) esterification 1: pumping the slurry obtained in the step 1 to an esterification 1 reaction kettle for esterification to obtain an esterified substance I; (3) esterification 2: pumping the esterified substance obtained in the step (2) into an esterification 2 reaction kettle for esterification to obtain an esterified substance II; (4) precondensation: pumping the esterified substance II obtained in the step (3) into a pre-shrinking tower reactor to perform pre-shrinking polymerization reaction to obtain a prepolymer III; (5) final polycondensation: pumping the prepolymer in the step (4) into a final polycondensation reaction kettle for final polycondensation reaction to obtain a final polymer IV; (6) tackifying/chain extending: carrying out further polycondensation reaction in a tackifying reaction kettle or a dynamic mixer pumped by the final polymer in the step (5) to obtain a final polymer V; (7) pelleting/drying: carrying out underwater die cutting on the final polymer IV in the step (5) or the polyester melt in the step (6) by using a granulator to form particles, and then drying, weighing and packaging to finally obtain a polyester finished product; (8) switching: when producing polybasic polyester such as PBAT, PTA, AA slurry tank and esterification kettle are simultaneously put into reaction by adopting esterification separation process to respectively obtain target PTA esterified substance and AA esterified substance, and then two esterification kettles which are pumped by the esterification kettle are further subjected to esterification reaction; when producing the binary polyester such as PBT, whether to use an AA slurry tank, an esterification kettle and a di-esterification kettle is selected according to the requirement, namely, when the set of PBAT equipment flexibly produces the multi-polyester and the binary polyester, the equipment is selected according to the specific production requirement, and meanwhile, the process is adjusted to obtain the di-esterified substance and the prepolymer with corresponding indexes, and then the final polycondensation and the subsequent reaction are carried out. .
2. The process for producing the set of PBAT device transfer products PBT, PBS, PBST, PBSA according to claim 1, wherein the process comprises the following steps of: the external molar ratio of PTA slurry is between 1.1 and 1.5, the internal molar ratio of PTA slurry is between 2.5 and 3.0, and the external molar ratio of AA slurry is between 1.1 and 1.5, and the internal molar ratio of PTA slurry is between 2.5 and 2.8 when PBAT is produced in the step (1); the external molar ratio of the slurry is between 1.2 and 1.8 and the internal molar ratio is between 3.0 and 3.8 when the PBT is produced.
3. The production process of the set of PBAT device flexible transfer products PBT, PBS, PBST, PBSA as claimed in claim 2, wherein: the reaction pressure of the PTA esterification kettle is 50-65 Kpa (A) when the esterification reaction kettle 1 in the step (2) produces PBAT; the reaction temperature is 225-235 ℃, the temperature of the heating medium is 240-260 ℃, the liquid level is 35-45%, and the residence time is 2-4 h; the reaction pressure of the AA esterification kettle is normal pressure; the reaction temperature is 180-200 ℃, the temperature of the heating medium is 200-220 ℃, the liquid level is 20-30%, and the residence time is 2-4 h; the reaction pressure of the PTA esterification kettle is 50Kpa (A) when the PBT is produced; the reaction temperature is 240 ℃, the temperature of the heating medium is 260-280 ℃, the liquid level is 60-70%, and the residence time is 3-6 h.
4. The production process of the set of PBAT device flexible transfer PBT, PBS, PBST, PBSA according to claim 1: the reaction pressure is 60-70 Kpa (A) when the esterification 2 reaction kettle in the step (3) is used for producing PBAT, the reaction temperature is 220-240 ℃, the temperature of a heating medium is 240-260 ℃, the liquid level is 20-30%, and the residence time is 45-90 min.
5. The production process of the set of PBAT device flexible transfer PBT, PBS, PBST, PBSA according to claim 1: the reaction pressure in the step (3) when the esterification 2 reaction kettle is used for producing PBT is 50Kpa (A), the reaction temperature is 240 ℃, the temperature of a heating medium is 260-280 ℃, the liquid level is 20-30%, and the residence time is 2.5-3 h.
6. A process for producing a flexible transfer PBT, PBS, PBST, PBSA of a PBAT device according to any one of claims 1 to 5, wherein: the pre-polycondensation reactor in the step (4) adopts a falling film tray type reactor. When producing PBAT, the pressure at the top of the tower is 1-5 Kpa (A), the temperature at the top of the tower is 220-230 ℃, the pressure at the bottom of the tower is 4-8 Kpa (A), the temperature at the bottom of the tower is 225-235 ℃, and the liquid level at the bottom of the tower is 10-15%.
7. The process for producing the flexible transfer product PBT, PBS, PBST, PBSA of the PBAT device as claimed in claim 6, wherein: when the pre-polycondensation reactor in the step (4) is used for producing PBT, the pressure at the top of the column is 3-8 Kpa (A), the temperature at the top of the column is 230-240 ℃, the pressure at the bottom of the column is 1-5 Kpa (A), the temperature at the bottom of the column is 230-240 ℃, and the liquid level at the bottom of the column is 10-20%.
8. The production process of the flexible transfer PBT, PBS, PBST, PBSA of the PBAT device set according to claim 1: when the final polycondensation reaction kettle in the step (5) produces PBAT, the reaction pressure is 100-300Pa (A), the inlet temperature is 230-240 ℃, and the outlet temperature is 225-230 ℃; when the PBT is produced, the reaction pressure is 100-300Pa (A), the inlet temperature is 240-250 ℃, and the outlet temperature is 240-250 ℃.
9. The production process of the flexible transfer PBT, PBS, PBST, PBSA of the PBAT device set according to claim 1: when the tackifying reaction kettle in the step (6) is used for producing PBAT, the reaction pressure is 50-100Pa (A), the inlet temperature is 230-240 ℃, and the outlet temperature is 225-230 ℃; when the PBT is produced, the reaction pressure is 50-100Pa (A), the inlet temperature is 240-250 ℃, and the outlet temperature is 240-250 ℃.
10. The production process of the flexible transfer PBT, PBS, PBST, PBSA of the PBAT device set according to claim 1: when the dynamic mixer is used for producing the PBAT in the step (6), the reaction pressure is 50-100Pa (A), the inlet temperature is 200-210 ℃, the outlet temperature is 160-180 ℃, and the addition amount of the chain extender is 3-4 per mill.
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| CN202311672740.5A CN117645712A (en) | 2023-12-07 | 2023-12-07 | Production process for transferring production PBT, PBS, PBST, PBSA of PBAT device |
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