CN116284698A - Production process for simultaneously preparing various molecular weight gradient degradable materials - Google Patents
Production process for simultaneously preparing various molecular weight gradient degradable materials Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 56
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000007790 solid phase Substances 0.000 claims abstract description 32
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims description 82
- 238000005336 cracking Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000007670 refining Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- 229920000180 alkyd Polymers 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 6
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000954 Polyglycolide Polymers 0.000 description 31
- 239000004633 polyglycolic acid Substances 0.000 description 31
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic 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
- C08G63/78—Preparation processes
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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
- C08G63/78—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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a production process for simultaneously preparing various molecular weight gradient degradable materials. The process of the invention comprises the following steps: (1) prepolymerization; (2) polycondensation-tackifying, or cleavage-refining-polymerization; (3) granulating; (4) solid phase polymerization; the invention can obtain products with different molecular weight gradients through different preparation processes of the process step (2), namely, the invention adopts a direct polycondensation method to prepare degradable materials with medium and low molecular weight and adopts a ring-opening polymerization method to prepare degradable materials with high molecular weight. The invention has the beneficial effects that the production process capable of simultaneously obtaining various molecular weight gradient degradable materials is provided, the investment of fixed cost in the preparation process of products is greatly reduced, in addition, the self-enhanced production of the high molecular weight PGA on the middle and low molecular weight PGA is realized through the double screw extruder, and the production of glycolide, the middle and low molecular weight PGA, the high molecular weight PGA and the self-enhanced PGA are realized.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a production process for simultaneously preparing degradable materials with various molecular weight gradients.
Background
The degradable material occupies a considerable share of plastic market with reliable biological safety and good biological degradability, and the research and application of the degradable material greatly reduce the difficulty of plastic garbage centralized treatment. The polyglycolic acid (PGA) as a fully biodegradable material has the advantages of mild degradation condition, high degradation speed, no need of special degradation condition and the like, can realize rapid degradation in natural environment, is finally degraded into carbon dioxide and water, and is widely applied to agricultural films and biological medicine polymer industries.
But PGA polymers of different molecular weights have significantly different uses.
Generally, PGA having a molecular weight of 1 ten thousand or more can be used as a medical absorbable suture, but is not strong enough for fracture or other internal fixation; when the average molecular weight of the PGA reaches 2 to 14.5 ten thousand, the polymer can be pulled into a fiber shape, the molecular arrangement of the polymer can have directionality, the strength of the PGA is enhanced, and the PGA can be made into films or other different shapes; in addition, the mechanical strength of the self-reinforced PGA is greatly improved, generally 1 to 3 times or more of that of a PGA matrix, and the self-reinforced PGA is more widely applied.
Therefore, the production process for preparing the PGA products with various molecular weight gradients simultaneously is developed, the investment cost of the PGA is reduced, and the method has important significance for popularization and application of degradable plastics.
Disclosure of Invention
In order to solve the technical problems, the invention provides a production process for simultaneously preparing various molecular weight gradient degradable materials.
The invention provides a production process capable of preparing various molecular weight gradient degradable materials simultaneously, which comprises the following steps: (1) prepolymerization; (2) polycondensation-tackifying, or cleavage-refining-polymerization; (3) granulating; (4) solid phase polymerization.
The simultaneous preparation process of the various molecular weight gradient degradable materials is realized through different polymerization processes in the step (2); specifically, the two processes are respectively a polycondensation-tackifying process and a cracking-refining-polymerization process.
Namely, a polycondensation-tackifying process is adopted to prepare the degradable material with medium and low molecular weight; preparing a degradable material with high molecular weight by adopting a cracking-refining-polymerization process;
wherein, the polycondensation in the preparation process of the degradable material with medium and low molecular weight is direct polycondensation;
the polymerization in the preparation process of the degradable material with high molecular weight is ring-opening polymerization.
The degradable material prepared by the invention is specifically an alkyd high molecular polymer.
The granulation in the step (3) is realized by a double-screw extruder.
The invention discloses a production process for simultaneously preparing various molecular weight gradient degradable materials, which comprises the following four steps:
(1) Prepolymerization: weighing alkyd, a water removing agent and a prepolymerized catalyst, adding the alkyd, the water removing agent and the prepolymerized catalyst into a reaction kettle, heating and stirring, and preserving heat for 1-3 h when the temperature in the kettle is increased to 120-140 ℃;
wherein the prepolymerized catalyst accounts for 0.5 wt% of the raw material;
when the water content to be collected reaches 80% of the theoretical amount, the temperature in the kettle is raised to 150-170 ℃ and kept for 1-2 h;
when the collected moisture content reaches 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2-4 hours to obtain a prepolymerization product;
(2) Polymerization: directly polycondensing and tackifying or ring-opening polymerizing to obtain a polymer product;
(3) And (3) granulating: extruding and granulating the polymer intermediate prepared in the step (2) by adopting a double-screw extruder to obtain granules, setting the rotating speed of the screw to be 10-40 rpm and the extruding temperature to be 200-250 ℃;
(4) Solid phase polymerization: carrying out solid-phase polymerization on the granules obtained in the step (3), wherein the pressure is kept above-99 KPa, and the temperature is respectively 170 ℃ for 2-8 hours; and (3) at 195 ℃ for 3-12 hours, and finally obtaining alkyd polymer products with various molecular weight gradients.
In the step (2) of the preparation process of the medium-low molecular weight degradable material, the direct polycondensation process is adopted, and the method specifically comprises the following steps:
s1, polycondensation: transferring the pre-polymerized product obtained in the step (1) to a polycondensation kettle, adjusting the temperature to be 180-200 ℃ and the pressure to be more than-90 KPa, adding a condensation chain extender, and reacting for 1-2h to obtain a polycondensation product;
s2, tackifying: transferring the polycondensation product prepared in the step S1 to a tackifying kettle, maintaining the temperature at 180-200 ℃ and the pressure above-95 KPa, and carrying out tackifying reaction to obtain a polymer product.
In addition, the step (2) of the preparation process of the high molecular weight degradable material is carried out by adopting a ring-opening polymerization process, and specifically comprises the following steps:
s1, cracking: transferring the prepolymerized product obtained in the step (1) to a cracking kettle, adding a cracking catalyst and a cracking solution, setting the temperature to be 200-250 ℃, maintaining the pressure to be more than-95 KPa, further reacting for 6-12h, and collecting distillate to a collecting tank;
s2, refining: refining and purifying the crude polymer in the collecting tank in the step S1 to obtain a refined polymer product;
s3, polymerization: and (2) transferring the refined polymer product obtained in the step (S2) into a polymerization device, adding a polymerization catalyst, setting the temperature to be 130-210 ℃, and preserving the heat for 2-5 h to obtain the polymer product.
Preferably, the water scavenger in the step (1) is xylene, and the prepolymerized catalyst is nano zinc oxide.
Preferably, in the step (2), the condensation chain extender of the direct polycondensation process is any one of 1, 3-dicyclohexylcarbodiimide and ADR-4370S;
the cracking catalyst of the ring-opening polymerization process is any one of antimony trioxide, stannous octoate and zinc acetylacetonate;
the cracking solution is any one of dioctyl terephthalate and polyethylene glycol 1000 mixed solution, dioctyl terephthalate and polyethylene glycol monomethyl ether mixed solution and butyl benzyl phthalate and polyethylene glycol 1000 mixed solution;
the polymerization catalyst is a mixed solution of stannous octoate and dodecanol.
In addition, the invention also realizes the self-reinforced production of the high molecular weight PGA and the middle and low molecular weight PGA by a double screw extruder, and realizes the production of four types of products of glycolide, the middle and low molecular weight PGA, the high molecular weight PGA and the self-reinforced PGA.
The invention has the beneficial effects that:
(1) The invention provides a mould test production device compatible with two process routes and a process thereof, which can prepare PGA products with various molecular weight gradients simultaneously according to the actual production requirements;
(2) In the simultaneous preparation process of various molecular weight gradients, a feeding control system, a high-low temperature control system, a prepolymerization reaction device, a production granulating device, a solid-phase polymerization device and the like are all common equipment of all processes, so that the investment cost of process equipment is greatly reduced, and the production cost of PGA is further reduced;
(3) The invention also realizes the self-enhancement production of the high molecular weight PGA and the middle and low molecular weight PGA by extrusion granulation of a double screw extruder, and realizes the production of four types of products of glycolide, the middle and low molecular weight PGA, the high molecular weight PGA and the self-enhancement PGA.
Drawings
FIG. 1 is a diagram of a process for producing various molecular weight gradient degradable materials of the present invention.
In the figure, a preheating tank 11, a prepolymerization tank 12, a solvent reflux tank 13, a polycondensation tank 21, a tackifying tank 22, a cleavage tank 31, a crude product collecting tank 32, a refining device 33, an open-loop polymerization device 34, a twin-screw granulator 41, a granulator 42, a stock bin 43, a solid-phase polymerization device 44, a heat exchanger 51, a condensate storage tank 52, a cyclone 53, a buffer tank 54, a vacuum pump 55, and a three-way on-off valve 6.
Detailed Description
The present invention will now be further described in connection with specific embodiments in order to enable those skilled in the art to better understand the invention.
Example 1
(1) Prepolymerization: weighing alkyd and a water scavenger, adding the alkyd and the water scavenger into a prepolymerization reactor, setting the temperature of heat conduction oil to be 130-140 ℃ and the rotating speed to be 10-20 Hz, adding a catalyst (the water scavenger is used for preparing a solution state according to 0.5% by weight of the raw materials), starting heating and stirring, and keeping for 2 hours after the temperature in a kettle is increased to 130 ℃;
setting the temperature of the heat conducting oil to 165 ℃ when the content of the collected water reaches 80% of the theoretical amount, and keeping for 1-2h after the temperature in the kettle is raised to 160 ℃;
when the collected moisture content reaches 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2-4 hours to obtain a prepolymerization product;
(2) Transferring the pre-polymerized product obtained in the step (1) to a polycondensation kettle, adjusting the temperature to 180-200 ℃, maintaining the pressure above-90 KPa, adding a condensing agent, and further reacting for 1-2h to obtain a product;
tackifying: transferring the prepared product to a tackifying kettle, wherein the temperature is 180-200 ℃, and the pressure is maintained to be more than-95 KPa to obtain a product 1;
(3) Transferring the product 1 to a double-screw extruder, setting the rotating speed of the screw to be 10-40 rpm and the temperature to be 200-250 ℃, extruding and granulating by using the double-screw extruder;
(4) Transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is higher than-99 KPa, and the temperature is 170 ℃ for 2-8 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 3-12 h to finally obtain a product 11.
In the production process diagram of various mass gradient degradable materials shown in the attached figure 1, the system structure used in the production process is as follows:
comprises a prepolymerization device, a polycondensation device, a cracking device, a refining device, a ring-opening polymerization device, a production granulation device, a solid-phase polymerization device, a feeding control system, a high-low temperature control system, a heat exchanger, a condensate storage tank and a vacuum device.
The system structure used in the production process is as follows:
the device comprises a prepolymerization device, wherein an outlet d of the prepolymerization device is respectively communicated with an inlet a of the polycondensation device and an inlet a of the cracking device, and an outlet c of the prepolymerization device is communicated with an inlet a of the heat exchanger 51; the outlet of the cracking device is communicated with the inlet of the refining device 33, the outlet of the refining device 33 is communicated with the inlet of the ring-opening polymerization device 34, and the outlet of the ring-opening polymerization device 34 and the outlet of the polycondensation device are communicated with the inlet of the production granulating device; the outlet of the production granulating device is communicated with the inlet of the solid-phase polymerization device 44; the outlet b of the heat exchanger 51 is communicated with the inlet of the vacuum device, and the outlet c of the heat exchanger 51 is communicated with the condensate storage tank 52.
The outlet d channel of the prepolymerization device, which leads to the polycondensation device and the cracking device, is provided with a three-way switch valve 6 which is respectively communicated with the inlet of the polycondensation device and the inlet of the cracking device.
The prepolymerization device comprises a preheating tank 11, a prepolymerization kettle 12 and a solvent reflux tank 13; inlet a of preheating tank 11 is connected with feed control system; the inlet b of the preheating tank 11 is communicated with the inlet a of the prepolymerization reactor, and the inlet a and the outlet b of the solvent reflux tank 13 are respectively communicated with the outlet b and the inlet c of the prepolymerization reactor 12 to form a reflux mode.
The cracking device comprises a cracking kettle 31 and a crude product collection 32; the polycondensation device comprises a polycondensation kettle 21 and a tackifying kettle 22; an outlet c of the solvent reflux tank 13 in the cracking device is communicated with an inlet of the heat exchanger 51; the outlet d of the prepolymerization tank 12 is respectively communicated with the inlet a of the polycondensation tank 21 and the inlet a of the cracking tank 31 through a three-way switch valve 6.
The system also comprises a high-low temperature control system which is respectively communicated with the prepolymerization device, the polycondensation device and the cracking device.
The outlet b of the cracking kettle 31 is communicated with the inlet of the heat exchanger 51, the outlet c of the cracking kettle 31 is communicated with the inlet of the crude product collecting tank 32, and the outlet of the crude product collecting tank 32 is communicated with the refining device 33.
An outlet b of the polycondensation kettle 21 is communicated with an inlet of the heat exchanger 51, an outlet c of the polycondensation kettle 21 is communicated with an inlet of the tackifying kettle 22, and an outlet of the tackifying kettle 22 is communicated with an inlet of the double-screw extruder 41; the twin screw extruder 41 is part of the production pelletiser.
The production granulating device comprises a double-screw extruder 41, a granulator 42 and a bin 43, wherein the inlet of the double-screw extruder 41 is respectively communicated with the outlet of the tackifying kettle 22 and the outlet of the ring-opening polymerization device 34, the outlet of the double-screw extruder 41 is communicated with the inlet of the granulator 42, the outlet of the granulator 42 is communicated with the inlet of the bin 43, and the outlet of the bin 43 is communicated with the inlet of the solid-phase polymerization device 44.
The vacuum device comprises a cyclone separating tank 53, a buffer tank 54 and a vacuum pump 55, wherein the inlet of the cyclone separating tank 53 is communicated with the outlet b of the heat exchanger 51, the outlet of the cyclone separating tank 53 is communicated with the inlet of the buffer tank 54, and the outlet of the buffer tank 54 is communicated with the inlet of the vacuum pump 55.
Example 2
(1) Weighing alkyd and a water scavenger, adding the alkyd and the water scavenger into a prepolymerization reactor, setting the temperature of heat conduction oil to be 130-140 ℃ and the rotating speed to be 10-20 Hz, adding a catalyst (the water scavenger is used for preparing a solution state according to 0.5% by weight of the raw materials), starting heating and stirring, and keeping for 2 hours after the temperature in a kettle is increased to 130 ℃;
setting the temperature of the heat conducting oil to 165 ℃ when the content of the collected water reaches 80% of the theoretical amount, and preserving the heat for 1-2 hours after the temperature in the kettle is raised to 160 ℃;
when the collected moisture content reaches 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2-4 hours to obtain a prepolymerization product;
(2) Cracking: transferring the prepolymerized product to a cracking kettle, adding a cracking catalyst and a cracking solution, setting the temperature to be 200-250 ℃, maintaining the pressure to be more than-95 KPa, further reacting for 6-12h, and collecting distillate to a collecting tank;
refining: refining and purifying the crude product in the collecting tank to obtain glycolide product 2;
polymerization: transferring the product 2 obtained in the step (2) into a polymerization device, adding a catalyst, setting the temperature to be 130-210 ℃, and preserving heat for 2-5 h to obtain a product 3;
(3) Transferring the obtained product 3 to a double-screw extruder, setting the rotating speed of the screw to be 10-40 rpm and the temperature to be 200-250 ℃, extruding and granulating by using the double-screw extruder;
(4) Transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is higher than-99 KPa, and the temperature is 170 ℃ for 2-8 hours respectively; solid-phase polymerization is carried out at 195 ℃ for 4-12 h, and finally the product 33 is obtained.
Example 3
The preparation process for preparing the degradable material and the intermediate selects the products 1 and 3 obtained in the examples 1 and 2 respectively, and the products are granulated according to a certain proportion to realize the production of self-reinforced products, and the specific steps are as follows:
(1) Simultaneously adding a product 1 obtained by polycondensation and tackifying and a product 3 obtained by ring-opening polymerization into a double-screw extruder according to a certain proportion, setting the rotating speed of the screw to be 10-40 rpm, extruding and granulating by using the double-screw extruder at the temperature of 200-250 ℃;
(2) Transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is higher than-99 KPa, and the temperature is 170 ℃ for 2-8 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 4-12 h to finally obtain a product 13.
The following procedure for the 5 experimental groups polymerized according to the above procedure using glycolic acid as the starting material was as follows:
experiment group 1
(1) Prepolymerization: 10kg of glycolic acid and 10L of xylene are weighed and added into a prepolymerization reactor; setting the temperature of the heat conduction oil at 138 ℃ and the rotating speed of 10Hz, adding the catalyst nano zinc oxide, heating and stirring, and keeping for 2 hours after the temperature in the kettle is increased to 130 ℃; setting the temperature of the heat conducting oil to 165 ℃ when the content of the collected water reaches 80% of the theoretical amount, and keeping for 1.5h after the temperature in the kettle is raised to 160 ℃; when the water content to be collected reaches 90% of the theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2.5h;
(2) Polycondensation: transferring the prepolymerization product to a polycondensation reactor, adjusting the temperature to 180-200 ℃, maintaining the pressure above-90 KPa, adding a condensation chain extender 1, 3-dicyclohexylcarbodiimide, and further reacting for 1h to obtain a product;
tackifying: transferring the prepared polycondensation product to a tackifying reactor, maintaining the temperature at 180-200 ℃ and the pressure above-95 KPa for 0.5h to obtain a product 1;
(3) And (3) granulating: transferring the product 1 to a double-screw extruder, setting the screw rotating speed to 20rpm, and extruding and granulating by using the double-screw extruder at the temperature of 210 ℃/235 ℃/240 ℃/245 ℃/235 ℃;
(4) Solid phase polymerization: transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is-99 KPa, and the temperature is 170 ℃ for 2 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 4 hours to finally obtain a product 11.
Experiment group 2
(1) Prepolymerization: 10kg of glycolic acid and 10L of xylene are weighed and added into a prepolymerization reactor; setting the temperature of the heat conduction oil at 138 ℃ and the rotating speed of 15Hz, adding the catalyst nano zinc oxide, starting heating and stirring, and keeping for 2 hours after the temperature in the kettle is increased to 130 ℃; setting the temperature of the heat conducting oil to 165 ℃ when the content of the collected water reaches 80% of the theoretical amount, and keeping for 2 hours after the temperature in the kettle is raised to 160 ℃; when the water content to be collected reaches more than 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 3h;
(2) Polycondensation: transferring the prepolymerization product to a polycondensation reactor, adjusting the temperature to 180-200 ℃, maintaining the pressure above-95 KPa, adding a condensation chain extender ADR-4370S, and further reacting for 1.5h to obtain a product;
(3) Tackifying: continuously transferring the product obtained in the step (2) to a tackifying reactor, maintaining the temperature at 180-200 ℃ and the pressure above-98 KPa for 1h to obtain a product 1;
(4) Granulating; transferring the product 1 to a double-screw extruder, setting the screw rotating speed to 20rpm, and extruding and granulating the product 1 by using the double-screw extruder at the temperature of 225 ℃/235 ℃/240 ℃/245 ℃/235 ℃;
(5) Solid phase polymerization: transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is-99 KPa, and the temperature is 170 ℃ for 3 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 5 hours to finally obtain a product 11.
Experiment group 3
(1) Prepolymerization: 10kg of glycolic acid and 10L of xylene are weighed and added into a prepolymerization reactor; setting the temperature of the heat conduction oil at 138 ℃ and the rotating speed of 15Hz, starting heating and stirring, and keeping for 2 hours after the temperature in the kettle is increased to 130 ℃; setting the temperature of the heat conducting oil to 165 ℃ when the content of the collected water reaches 80% of the theoretical amount, and keeping for 1h after the temperature in the kettle is raised to 160 ℃; when the water content to be collected reaches more than 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2 hours to obtain a prepolymerization product;
(2) Cracking: transferring the pre-polymerized product to a cracking device, adding a cracking catalyst of antimony trioxide, a mixed solution of a cracking solution of dioctyl terephthalate and polyethylene glycol 1000, setting the temperature to be 220-250 ℃, maintaining the pressure above-95 KPa, further reacting for 8 hours, and collecting distillate to a collecting tank;
refining: transferring the crude glycolide in the collecting tank to a refining device for refining and purifying to obtain a refined glycolide product 2;
polymerization: adding the refined product 2 into a polymerization device, adding a catalyst stannous octoate and dodecanol mixed solution, setting the temperature to be 130-210 ℃, and keeping the pressure above-95 KPa for 3 hours to obtain a product 3;
(3) Granulating; transferring the product 3 to a double-screw extruder, setting the screw rotation speed to 20rpm, and extruding and granulating by using the double-screw extruder at the temperature of 225 ℃/235 ℃/240 ℃/245 ℃/235 ℃;
(4) Solid phase polymerization: transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is-99 KPa, and the temperature is 170 ℃ for 6 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 10 hours to finally obtain a product 33.
Experiment group 4
(1) Prepolymerization: as in experimental group 3;
(2) Cracking: transferring the prepolymerized product to a pyrolysis device, adding pyrolysis catalyst stannous octoate and pyrolysis liquid dioctyl terephthalate and polyethylene glycol monomethyl ether, setting the temperature to 220-250 ℃, maintaining the pressure above-96 KPa, further reacting for 10 hours, and collecting distillate to a collecting tank;
refining: transferring the crude glycolide in the collecting tank to a refining device for refining and purifying to obtain a refined glycolide product 2;
polymerization: and adding the product 2 into a polymerization device, adding a catalyst stannous octoate and dodecanol mixed solution, setting the temperature to be 130-210 ℃, and keeping the pressure above-95 KPa for 3.5 hours to obtain the product 3.
Pelletization and solid-phase polymerization in steps (4) and (5) as in experiment 3 finally gave product 33.
Experiment group 5
(1) Prepolymerization: as in experimental group 3;
(2) Transferring the pre-polymerized product to a cracking device, adding cracking catalyst zinc acetylacetonate, cracking solution butyl benzyl phthalate and polyethylene glycol 1000, setting the temperature to 220-250 ℃, maintaining the pressure above-98 KPa, further reacting for 10 hours, and collecting distillate to a collecting tank;
refining: transferring the crude glycolide in the collecting tank to a refining device for refining and purifying to obtain a refined glycolide product 2;
polymerization: and adding the product 2 into a polymerization device, adding a catalyst stannous octoate and dodecanol mixed solution, setting the temperature to be 130-210 ℃, and keeping the pressure above-95 KPa for 4 hours to obtain the product 3.
(3) Granulating and solid-phase polymerization: as in experimental group 3, product 33 was finally obtained.
(1) Direct polycondensation: product 1 was obtained as in experimental group 2;
(2) Ring-opening polymerization: product 3 was obtained as in experimental group 5;
(3) Granulating: simultaneously adding the product 1 and the product 3 into a double-screw extruder according to a certain proportion, setting the rotating speed of the screw to be 10-40 rpm and the temperature to be 200-250 ℃, extruding and granulating by using the double-screw extruder;
(4) Solid phase polymerization: transferring the granules to a solid-phase polymerization reaction device, wherein the pressure is higher than-99 KPa, and the temperature is 170 ℃ for 2-8 hours respectively; and (3) carrying out solid-phase polymerization at 195 ℃ for 4-12 h to finally obtain a product 13.
As can be seen from comparison of experimental groups 1-2 and 3-5, the production of products with different gradients of PGA relative molecular weight from low to high can be realized by using the process device of the invention;
it can also be seen from the table that the total yield of the direct polycondensation method of experimental groups 1-2 is far greater than that of experimental groups 3-5, i.e. if a single production process is adopted, the cost of obtaining the low molecular weight PGA by the ring-opening polymerization method is huge, but the advantages of the two PGA preparation methods can be realized on the device of the invention, the optimal production of the PGA cost can be realized under the condition of meeting different application requirements, and the market popularization and application of the degradable material PGA are facilitated.
In addition, by utilizing the process of the invention, the enhancement of the ring-opening polymerization PGA to the direct polycondensation PGA can be realized by a self-enhancement technology.
Claims (8)
1. A production process for simultaneously preparing a plurality of molecular weight gradient degradable materials, which is characterized by comprising the following four steps: (1) prepolymerization; (2) polycondensation-tackifying, or cleavage-refining-polymerization; (3) granulating; (4) solid phase polymerization.
2. The process according to claim 1, wherein step (2) employs a polycondensation-tackifying process to prepare a medium-low molecular weight degradable material; preparing a degradable material with high molecular weight by adopting a cracking-refining-polymerization process;
wherein, the polycondensation in the preparation process of the degradable material with medium and low molecular weight is direct polycondensation;
the polymerization in the preparation process of the degradable material with high molecular weight is ring-opening polymerization;
the degradable material is alkyd high molecular polymer.
3. The process according to claim 1, wherein the extrusion and pelletization in step (3) are carried out using a twin-screw extruder.
4. The production process according to claim 1, characterized by a process comprising the following four steps:
(1) Prepolymerization: weighing alkyd, a water removing agent and a prepolymerized catalyst, adding the alkyd, the water removing agent and the prepolymerized catalyst into a reaction kettle, heating and stirring, and preserving heat for 1-3 hours when the temperature in the kettle is increased to 120-140 ℃;
wherein the prepolymerized catalyst comprises the following raw materials in percentage by weight: 0.5% wt;
when the content of the collected water reaches 80% of the theoretical amount, the temperature in the kettle is raised to 150-170 ℃ and kept for 1-2 h;
when the collected moisture content reaches 90% of theoretical amount, starting vacuumizing operation, gradually increasing the pressure, maintaining the pressure at-20 to-90 KPa, adjusting the temperature to 160-180 ℃, and maintaining the temperature for 2-4 hours to obtain a prepolymerization product;
(2) Polymerization: directly polycondensing and tackifying or ring-opening polymerizing to obtain a polymer product;
(3) And (3) granulating: extruding and granulating the polymer product prepared in the step (2) by adopting a double-screw extruder to obtain granules, setting the rotating speed of the screw to be 10-40 rpm and the extruding temperature to be 200-250 ℃;
(4) Solid phase polymerization: carrying out solid-phase polymerization on the granules obtained in the step (3), wherein the pressure is kept above-99 KPa, and the temperature is respectively 170 ℃ for 2-8 hours; and (3) at 195 ℃ for 3-12 hours, and finally obtaining alkyd polymer products with various molecular weight gradients.
5. The production process according to claim 4, wherein the step (2) of the process for preparing the medium-low molecular weight degradable material is performed by a direct polycondensation process, and specifically comprises the following steps:
s1, polycondensation: transferring the pre-polymerized product obtained in the step (1) to a polycondensation kettle, adjusting the temperature to be 180-200 ℃, the pressure to be more than 90KPa, adding a condensation chain extender, and reacting 1-2h to obtain a polycondensation product;
s2, tackifying: and (3) transferring the polycondensation product prepared in the step (S1) to a tackifying kettle, maintaining the temperature at 180-200 ℃ and the pressure above-95 KPa, and carrying out tackifying reaction to obtain a polymer product.
6. The process according to claim 4, wherein the step (2) of the process for preparing a high molecular weight degradable material is performed by a ring-opening polymerization process, comprising the steps of:
s1, cracking: transferring the prepolymerized product obtained in the step (1) to a cracking kettle, adding a cracking catalyst and a cracking solution, setting the temperature to be 200-250 ℃, maintaining the pressure to be more than-95 KPa, further reacting for 6-12h, and collecting distillate to a collecting tank;
s2, refining: refining and purifying the crude product in the collecting tank in the step S1 to obtain refined glycolide;
s3, polymerization: and (2) transferring the refined glycolide product obtained in the step (S2) into a polymerization device, adding a polymerization catalyst, setting the temperature to be 130-210 ℃, and preserving heat for 2-5 h to obtain a polymer product.
7. The process of claims 4-6, wherein the water scavenger in step (1) is xylene and the prepolymerized catalyst is nano zinc oxide.
8. The production process according to claims 4 to 6, wherein in step (2), the condensation chain extender of the direct polycondensation process is any one of 1, 3-dicyclohexylcarbodiimide, ADR-4370S;
the cracking catalyst of the ring-opening polymerization process is any one of antimony trioxide, stannous octoate and zinc acetylacetonate;
the cracking solution is any one of dioctyl terephthalate and polyethylene glycol 1000 mixed solution, dioctyl terephthalate and polyethylene glycol monomethyl ether mixed solution and butyl benzyl phthalate and polyethylene glycol 1000 mixed solution;
the polymerization catalyst is a mixed solution of stannous octoate and dodecanol.
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