CN112831017A - Method for preparing PLA-PPC-PU copolymer alloy by using PLA reclaimed materials, product and application thereof - Google Patents
Method for preparing PLA-PPC-PU copolymer alloy by using PLA reclaimed materials, product and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a PLA-PPC-PU copolymer alloy by using a PLA reclaimed material, and a product and application thereof. The method comprises the following steps: mixing the PLA reclaimed materials with chloroform, heating to dissolve, adding dihydric alcohol and a catalyst to carry out alcoholysis reaction, condensing and refluxing the chloroform in the reaction process, and removing the solvent after the reaction is finished to obtain hydroxyl-terminated low-molecular-weight PLA liquid, wherein the molecular weight of the PLA liquid is 3000-15000g/mol, and the hydroxyl value of the PLA liquid is 7.5-37.5 mgKOH/g; mixing PPC and polyhydric alcohol according to the mass ratio of 6-10:1, heating to 100-120 ℃ for dehydration, then cooling to 70-90 ℃, adding diisocyanate for reaction to obtain PPC-PU liquid; and (2) pouring the hydroxyl-terminated low-molecular-weight PLA liquid into a double-screw extruder, vacuumizing and devolatilizing, adding the NCO-terminated PPC-PU liquid into a second exhaust port of the double-screw extruder, performing subsequent screw copolymerization reaction, extruding, and performing underwater grain cutting to obtain the PLA-PPC-PU copolymerized alloy.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing a PLA-PPC-PU copolymer alloy by using a PLA reclaimed material, and a product and application thereof.
Background
With the enhancement of environmental awareness, the green consumer market is gradually expanded, the development and application of biodegradable plastics which are resource-saving, easy to recover and easy to degrade are gradually paid attention by people, and polylactic acid (PLA) and polypropylene carbonate (PPC) are the biodegradable plastics which are researched and used more at present.
With the increasing use of PLA in the market, compost and natural microbial degradation alone cannot meet the requirements, and degradation of PLA into carbon dioxide and water with little use is a waste from the point of recycling, so recycling of PLA waste products needs to be considered.
At present, a thermal depolymerization method is generally adopted for recycling PLA, but the thermal depolymerization process needs higher reaction temperature and pressure, side reactions such as racemization, dehydration and the like are easily caused, and finally a certain amount of lactide monomer is recycled, and the lactide monomer is further polymerized for recycling.
Further, although PLA has good mechanical properties, transparency, heat resistance, and chemical stability, it generally needs to be modified for use because of its high crystallinity, excessively high hardness, poor elasticity, and slow biodegradation rate.
The PPC material is a novel aliphatic polycarbonate, has good biocompatibility and barrier property, can be used as degradable plastics, and is an environment-friendly material with development prospect, but because the PPC material is of an amorphous structure, the molecular chain flexibility is large, the intermolecular acting force is small, the glass transition temperature of the PPC material is lower than that of aromatic polycarbonate, the PPC material has poor mechanical property and high cost, the application of the PPC material is greatly limited, and the PPC material is generally required to be modified.
The existing PPC material is generally prepared by the addition reaction of carbon dioxide and propylene oxide under a metal catalyst, and has the problems of complex process, residual metal catalyst, residual by-product cyclic carbonate and the like, so that the performance and the application of the PPC material are influenced.
For modification researches on PLA and PPC materials, researchers have adopted the PLA and the PPC materials for blending modification, but the PLA and the PPC cannot be completely compatible, and the PLA and the PPC have thermal degradation or unzipping degradation in the extrusion blending process to generate annular monomers, so that the blend has general performance and does not remarkably improve the toughness of the PLA and the resilience of the PPC. Currently, Polyurethane (PU) materials and PLA and PPC plastics are less studied. The patent specification with the publication number of CN 107603168A discloses a polylactic acid-based film and a preparation method thereof, the patent technology still adopts fresh high molecular weight polylactic acid instead of oligomer of PLA reclaimed material after alcoholysis, the final product is also a physical blend of PLA, PBAT, PPC-based TPU, the preparation process has no chemical reaction, degradation of PLA, PPC chain segments is difficult to avoid in the extrusion blending process, and PPC in the methyl ethylene carbonate (i.e. PPC) -polyurethane copolymer adopted by the patent technology is still obtained by copolymerization of carbon dioxide and propylene oxide, the problems of complex process, metal catalyst residue, byproduct cyclic carbonate residue and the like exist, which affect the performance and subsequent application of block copolymerization with polyurethane and the like.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a method for preparing PLA-PPC-PU copolymer alloy by using PLA reclaimed materials, the PLA reclaimed materials are subjected to alcoholysis by using dihydric alcohol to obtain hydroxyl-terminated PLA with low molecular weight, and then the hydroxyl-terminated PLA is subjected to copolymerization reaction with PPC and a prepolymer PPC-PU of polyester/polyether glycol and diisocyanate and extruded to prepare the PLA-PPC-PU copolymer alloy, so that the problem of the recovery and utilization of the PLA materials and the problem of the annular monomer generated by the unzipping degradation of the PPC in the screw extrusion process are solved, and the obtained product improves the brittleness of the PLA and the rebound resilience of the PPC, has biodegradability and is a copolymer with excellent comprehensive performance.
A method for preparing PLA-PPC-PU copolymer alloy by using PLA reclaimed materials comprises the following steps:
(1) and (3) carrying out alcoholysis on PLA to obtain a reclaimed material: mixing the PLA reclaimed materials with chloroform, heating to dissolve, adding dihydric alcohol and a catalyst to carry out alcoholysis reaction, condensing and refluxing the chloroform in the reaction process, and removing the solvent after the reaction is finished to obtain hydroxyl-terminated low-molecular-weight PLA liquid, wherein the molecular weight of the PLA liquid is 3000-15000g/mol, and the hydroxyl value of the PLA liquid is 7.5-37.5 mgKOH/g;
the dihydric alcohol is at least one of ethylene glycol and 1, 2-propylene glycol, the catalyst is 4-dialkylaminopyridine or phosphazene base catalyst, and the temperature of the alcoholysis reaction is 40-60 ℃;
(2) preparation of NCO-terminated PPC-PU liquids: mixing PPC and polyhydric alcohol according to the mass ratio of 6-10:1, heating to 100-120 ℃ for dehydration, then cooling to 70-90 ℃, and adding diisocyanate for reaction to obtain the PPC-PU liquid;
the ratio of the amount of the diisocyanate to the sum of the amounts of the PPC and the polyol is 1.8-2.2:1, and the polyol is polyester polyol and/or polyether polyol;
(3) preparing a PLA-PPC-PU copolymer alloy: pouring the hydroxyl-terminated low molecular weight PLA liquid into a double-screw extruder, vacuumizing and devolatilizing, then adding the NCO-terminated PPC-PU liquid into a second exhaust port of the double-screw extruder, extruding through subsequent screw copolymerization reaction, and underwater pelletizing to obtain the PLA-PPC-PU copolymer alloy;
the temperature of each zone of the double-screw extruder is 150-200 ℃.
The alcoholysis PLA reclaimed material process in the step (1) aims to obtain the target low molecular weight hydroxyl-terminated PLA oligomeric polyol, namely the hydroxyl-terminated low molecular weight PLA liquid, so that the PLA-PPC-PU copolymer alloy with high molecular weight can be obtained by the chemical reaction with the NCO group of the subsequent PPC-PU. Dissolving PLA by using chloroform, and then carrying out alcoholysis at a low temperature of 40-60 ℃, wherein the aim is to replace solid-liquid alcoholysis by using liquid-liquid alcoholysis so as to increase the alcoholysis reaction rate, and the alcoholysis is carried out by using ethylene glycol and/or 1, 2-propylene glycol with stronger nucleophilic reaction activity under the action of a catalyst, so that the problem of difficult alcoholysis of an ester group in the PLA due to the steric hindrance of a side methyl group is solved; in addition, the alcoholysis of PLA is carried out at low temperature, compared with the thermal depolymerization reaction of PLA, the alcoholysis is mild, the thermal oxidative degradation of PLA cannot occur, the controllability is good, the molecular weight of hydroxyl-terminated low-molecular-weight PLA after alcoholysis can be controlled according to the proportion of dihydric alcohol and PLA, no lactide monomer is generated in the process, the hydroxyl-terminated low-molecular-weight PLA can be used as PLA polyol to continue the subsequent copolymerization reaction, and compared with the direct use of PLA polyol, the problems of high cost and high acid value (the PLA polyol is usually prepared by lactic acid polymerization and has more carboxyl-terminated ends) are solved.
The recovered polylactic acid in the prior art usually adopts methanol for alcoholysis to form methyl lactate, which is not suitable for the technical route of the invention, while the ethylene glycol and the 1, 2-propylene glycol adopted in the alcoholysis in the step (1) of the invention are two types of dihydric alcohol which are carefully screened by the inventor aiming at the integral technical route of PLA-PPC-PU copolymer alloy and the alcoholysis process of the recovered PLA material, and other dihydric alcohol (such as 1, 4-butanediol) is difficult to alcoholyze PLA in the method of the invention and is basically not suitable for use.
Preferably, in the step (1), the PLA reclaimed materials and chloroform are mixed and heated to 50 ℃ for dissolution, and the solid content of the mixture obtained by mixing the PLA reclaimed materials and chloroform is 50%.
Preferably, in the step (1), the molecular weight of the PLA reclaimed material is 6-15 ten thousand g/mol, the mass ratio of the dihydric alcohol to the PLA reclaimed material is 0.01-0.2:1, the mass of the catalyst is 50-100ppm of that of the PLA reclaimed material, and the alcoholysis reaction time is 2-4 h.
Preferably, in the step (1), the temperature of the desolventizing agent is 60-80 ℃, and the vacuum degree is-0.09 to-0.1 MPa. Chloroform obtained by removing the solvent can be collected for recycling.
In the process of preparing the NCO-terminated PPC-PU liquid in the step (2), a prepolymerization process is adopted, and the amount of diisocyanate, PPC and polyalcohol is regulated to prepare the NCO-terminated PPC, so that on one hand, the problem of poor reactivity of the hydroxyl activity of the PPC can be solved, and on the other hand, zipper-releasing degradation that adjacent groups of a carbonate group and an ether oxygen group in a chain segment are bitten back can not occur in the subsequent high-temperature copolymerization extrusion process after the PPC is terminated by NCO, and therefore cyclic carbonate can not be formed. The polyol used in the step (2) of the invention is polyester polyol and/or polyether polyol, which is different from small molecular polyol which is usually used as a chain extender, and the polyol used in the invention plays a role of TU chain segment in the step (2) and is used for adjusting the properties of the PLA-PPC-PU copolymer alloy, such as elasticity, toughness and the like.
Preferably, in the step (2), the PPC is prepared by performing ring opening reaction on propylene carbonate and micromolecular dihydric alcohol for 6-8h at normal temperature under the action of a ring opening catalyst, then heating to 90-100 ℃, vacuumizing and removing low-boiling-point substances, wherein the molecular weight is 1000-10000 g/mol; the micromolecular dihydric alcohol is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol and 2-methyl-1, 3-propylene glycol; the addition proportion of the ring-opening catalyst is 50-200ppm of the mass of the propylene carbonate; the ring-opening catalyst is at least one of an organic phosphazene catalyst and ionic liquid; the molar ratio of the micromolecule dihydric alcohol to the propylene carbonate is 1: 8.5-97.5; compared with the traditional PPC prepared by carbon dioxide and propylene oxide addition polymerization, the PPC prepared by the ring-opening reaction does not contain metal catalyst residues and cyclic carbonate byproducts, has small influence on the subsequent reaction activity, and is simpler and more controllable in the ring-opening method compared with the carbon dioxide copolymerization process.
Preferably, in step (2), the molecular weight of the PPC is 1000-10000 g/mol.
Preferably, in step (2), the polyol is at least one of poly (butylene adipate-glycol) glycol, poly (ethylene adipate-glycol) glycol, poly (propylene adipate-glycol) glycol and poly (tetrahydrofuran ether glycol), and the molecular weight is 600-4000 g/mol. The introduction of the polyester or polyether polyols described above further improves the elasticity and toughness of the copolymers after subsequent reaction with the hydroxyl terminated low molecular weight PLA.
Preferably, in the step (2), the dehydration time is 2 hours.
Preferably, in the step (2), the diisocyanate is at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, in the step (2), the time for adding the diisocyanate to carry out the reaction is 1.5 to 3 hours.
The process of preparing the PLA-PPC-PU copolymer alloy in the step (3) is a process of obtaining a high molecular weight copolymer by carrying out polymerization chain extension on the hydroxyl-terminated oligomeric PLA and the NCO-terminated PPC-PC, and is completely different from a common blending process. The problems of lactide monomer formation by thermal depolymerization of high molecular weight PLA, degradation of PPC unzipping and the like exist in the conventional blending process, and the problems of compatibility among materials and the like also exist, but the technical problems are completely absent in the copolymerization reaction extrusion process.
According to the invention, a double-screw extruder is adopted for vacuum devolatilization to further remove residual solvent in hydroxyl-terminated low-molecular-weight PLA, and then the hydroxyl-terminated low-molecular-weight PLA is continuously extruded to be copolymerized with isocyanate groups of PPC-PU at a specific temperature to form a high-molecular-weight copolymer, compared with PPC/PLA blending modification, the mechanical property is not influenced due to the compatibility problem, the problem that cyclic monomers are generated due to degradation to influence the copolymer property is avoided, in addition, the brittleness, hand feeling, elasticity, stiffness and heat resistance of the PPC are further improved by a PU chain segment, and the comprehensive performance is excellent.
Preferably, in step (3), the molar ratio of the hydroxyl-terminated low molecular weight PLA liquid to the PPC-PU liquid is 1:1 to 1.2.
The invention also provides the PLA-PPC-PU copolymer alloy prepared by the method for preparing the PLA-PPC-PU copolymer alloy by utilizing the PLA reclaimed material.
The PLA-PPC-PU copolymer alloy has the advantages that the elongation at break is more than or equal to 500 percent, the GB/T1843-2008 notch impact strength test result is nondestructive, and the PLA-PPC-PU copolymer alloy has biodegradability and excellent comprehensive properties such as toughness, elasticity and strength.
The invention also provides application of the PLA-PPC-PU copolymer alloy in films, packages, disposable products, medical instruments and 3D printing materials.
Compared with the prior art, the invention has the main advantages that:
1) by adopting the technical scheme of the invention, the PLA is recovered by alcoholysis at a low temperature, no thermal degradation is caused in the recovery process, byproducts such as carboxylic acid and aldehyde are not generated, the problem of low yield of lactide monomers in the recovered PLA by thermal depolymerization is solved, the crystallinity of the PLA can be changed by alcoholysis by a solution method, a PLA chain segment with low crystallinity is obtained, the toughness after subsequent copolymerization is good, the low molecular weight PLA with the required molecular weight and the hydroxyl-terminated end can be directly obtained by controlling the proportion of dihydric alcohol and the PLA, the subsequent PPC-PU can be directly reacted, the step of recovering and preparing the lactide and then polymerizing the lactide into PLA polyol is reduced, the process is simple, and the problems of high acid value and high cost of the PLA polyol carboxyl-terminated end are solved.
2) By adopting the PPC prepolymerization in the technical scheme of the invention to prepare PPC-PU, the PPC material without metal catalyst and cyclic carbonate residue is prepared by using an open-loop method, and the use amount of diisocyanate, PPC and polyhydric alcohol is regulated and controlled to ensure that the diisocyanate terminates the PPC, thereby solving the problems of poor PPC hydroxyl reaction activity and easy PPC unzipping degradation of the terminal hydroxyl end during subsequent extrusion processing, ensuring that the system does not contain cyclic carbonate micromolecules, having high tensile strength and high elongation in the aspect of mechanical property, and avoiding the negative influence of the small-molecule cyclic carbonate residue on the mechanical property.
3) According to the technical scheme, the PLA-PPC-PU copolymer alloy is prepared by copolymerization at a specific temperature, carbamate chemical bonding exists between PPC and PLA chain segments, the compatibility problem of blending modification is solved, the brittleness and hard hand feeling of a PLA material are improved by the PPC and PU chain segments, the biodegradation speed is increased, the rebound resilience, stiffness and glass transition temperature of the PPC are improved by the PLA and PU chain segments, and the PLA-PPC-PU copolymer is a copolymer with good mechanical property and biodegradability.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 8 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 3.59kg of 1, 2-propylene glycol and 6.5g of 4-dialkylaminopyridine, carrying out alcoholysis reaction for 3.5h, heating to 75 ℃, vacuumizing to-0.09 MPa, removing solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, and testing after removing the solvent in a vacuum oven to obtain hydroxyl-terminated PLA liquid with low molecular weight, wherein the hydroxyl value of the PLA liquid is 27.91mgKOH/g, the acid value is 0.38mgKOH/g, and the molecular weight is 4020 g/mol.
2) Adding 100kg of propylene carbonate and 2kg of 1, 6-hexanediol into a reaction kettle, stirring uniformly at normal temperature, adding 10.2g of an organic phosphazene catalyst, reacting for 6h, heating to 90 ℃, vacuumizing for 2h to remove low-boiling-point substances, obtaining PPC prepared by a propylene carbonate ring opening method, testing the molecular weight of 6000g/mol, taking 90kg of the PPC material and 10kg of poly adipic acid-butanediol glycol ester glycol, heating to 100 ℃ after mixing in the reaction kettle, vacuumizing and dehydrating for 2h, cooling to 80 ℃, adding 16.64kg of diphenylmethane diisocyanate, and reacting for 2h to obtain the NCO-terminated PPC-PU liquid.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC-PU liquid obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the two to be 1:1.1, setting the temperature of each area of the double-screw extruder to be 150-plus-material 190 ℃, reacting and tackifying the terminal hydroxyl of the PLA chain segment and the terminal NCO group of the PPC-PU after copolymerization and extrusion, and obtaining the PLA-PPC-PU copolymer alloy after underwater grain cutting.
Example 2
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 10 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 1.12kg of ethylene glycol and 8.5g of 4-dialkylaminopyridine, carrying out alcoholysis reaction for 3h, heating to 75 ℃, vacuumizing to-0.09 MPa, removing the solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, removing the solvent in a vacuum oven, and testing to obtain hydroxyl-terminated low-molecular-weight PLA liquid with the hydroxyl value of 11.2mgKOH/g, the acid value of 0.32mgKOH/g and the molecular weight of 10017 g/mol.
2) Adding 100kg of propylene carbonate and 1.575kg of ethylene glycol into a reaction kettle, stirring uniformly at normal temperature, adding 12.5g of an organic phosphazene catalyst, reacting for 7h, heating to 90 ℃, vacuumizing for 2h to remove low-boiling-point substances, obtaining PPC prepared by a propylene carbonate ring opening method, testing the molecular weight to 4000g/mol, taking 85kg of the PPC material and 10kg of poly adipic acid-ethylene glycol, mixing the PPC material and the poly adipic acid-ethylene glycol, heating to 105 ℃, vacuumizing, dehydrating for 2h, cooling to 80 ℃, adding 16.04kg of diphenylmethane diisocyanate, and reacting for 2h to obtain an NCO-terminated PPC-PU liquid.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC-PU liquid obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the two to be 1:1.2, setting the temperature of each area of the double-screw extruder to be 150-plus-material 190 ℃, reacting and tackifying the terminal hydroxyl of the PLA chain segment and the terminal NCO group of the PPC-PU after copolymerization and extrusion, and obtaining the PLA-PPC-PU copolymer alloy after underwater grain cutting.
Example 3
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 11.5 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 1.14kg of glycol and 9.7g of 4-dialkylaminopyridine, carrying out alcoholysis reaction for 2.5h, then heating to 75 ℃, vacuumizing to-0.09 MPa, removing the solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, and testing after removing the solvent in a vacuum oven to obtain hydroxyl-terminated PLA liquid with low molecular weight, wherein the hydroxyl value of the PLA liquid with low molecular weight is 9.32mgKOH/g, the acid value of the PLA liquid with low molecular weight is 0.3mgKOH/g, and the molecular weight of the PLA liquid.
2) Adding 120kg of propylene carbonate and 1.685kg of 1, 4-butanediol into a reaction kettle, uniformly stirring at normal temperature, adding 11.4g of an organic phosphazene catalyst, reacting for 6h, heating to 90 ℃, vacuumizing for 2h to remove low-boiling-point substances, obtaining the PPC prepared by adopting a propylene carbonate ring opening method, testing the molecular weight of 6500g/mol, taking 100kg of the PPC material and 10kg of poly adipic acid-butanediol glycol, the molecular weight of 3000g/mol, mixing in the reaction kettle, heating to 105 ℃, vacuumizing and dehydrating for 2h, cooling to 80 ℃, adding 9.6kg of diphenylmethane diisocyanate, and reacting for 2h to obtain the PPC-PU liquid with end capped by NCO.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC-PU liquid obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the two to be 1:1.05, setting the temperature of each area of the double-screw extruder to be 150-.
Example 4
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 15 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 1.22kg of 1, 2-propylene glycol and 10g of phosphazene base catalyst, carrying out alcoholysis reaction for 3.5h, heating to 75 ℃, vacuumizing to-0.09 MPa, removing the solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, removing the solvent in a vacuum oven, and testing to obtain hydroxyl-terminated PLA liquid with low molecular weight, wherein the hydroxyl value of the PLA liquid is 9.75mgKOH/g, the acid value of the PLA liquid is 0.28mgKOH/g, and the molecular weight of the PLA liquid is 12038 g/mol.
2) 100kg of propylene carbonate and 3.49kg of 1, 6-hexanediol are added into a reaction kettle and uniformly stirred at normal temperature, 14.5g of an organic phosphazene catalyst is added, after 6 hours of reaction, the temperature is raised to 90 ℃, vacuum pumping is carried out for 2 hours, low-boiling-point substances are removed, the PPC prepared by the propylene carbonate ring opening method is obtained, the molecular weight is tested to be 3500g/mol, 80kg of the PPC material and 10kg of polytetrahydrofuran ether glycol with the molecular weight of 1800g/mol are taken, after the mixture in the reaction kettle, the temperature is raised to 105 ℃, vacuum pumping is carried out for dehydration for 2 hours, then the temperature is lowered to 80 ℃, 14.93kg of diphenylmethane diisocyanate is added, and after 2 hours of reaction, the NCO-terminated PPC-PU liquid is obtained.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC-PU liquid obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the two to be 1:1.1, setting the temperature of each area of the double-screw extruder to be 150-plus-material 190 ℃, reacting and tackifying the terminal hydroxyl of the PLA chain segment and the terminal NCO group of the PPC-PU after copolymerization and extrusion, and obtaining the PLA-PPC-PU copolymer alloy after underwater grain cutting.
Example 5
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 7.5 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 1.8kg of ethylene glycol and 8g of phosphazene base catalyst, carrying out alcoholysis reaction for 4h, heating to 75 ℃, vacuumizing to-0.09 MPa, removing solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, removing the solvent in a vacuum oven, and testing to obtain hydroxyl-terminated low-molecular-weight PLA liquid with the hydroxyl value of 17.81mgKOH/g, the acid value of 0.29mgKOH/g and the molecular weight of 6300 g/mol.
2) Adding 80kg of propylene carbonate and 0.854kg of 1, 3-propylene glycol into a reaction kettle, stirring uniformly at normal temperature, adding 10.0g of an organic phosphazene catalyst, reacting for 7h, heating to 90 ℃, vacuumizing for 2h to remove low-boiling-point substances, obtaining the PPC prepared by the propylene carbonate ring opening method, testing the molecular weight to be 7200g/mol, taking 90kg of the PPC material and poly adipic acid-propylene glycol, 5kg of the poly adipic acid-propylene glycol, with the molecular weight of 1000g/mol, heating to 105 ℃, vacuumizing and dehydrating for 2h after mixing in the reaction kettle, cooling to 80 ℃, adding 4.16kg of hexamethylene diisocyanate, and reacting for 2h to obtain the PPC-PU liquid with NCO end capping.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC-PU liquid obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the two to be 1:1.15, setting the temperature of each area of the double-screw extruder to be 150-plus-material 190 ℃, reacting and tackifying the terminal hydroxyl of the PLA chain segment and the terminal NCO group of the PPC-PU after copolymerization and extrusion, and obtaining the PLA-PPC-PU copolymer alloy after underwater grain cutting.
Comparative example 1
1) Adopting waste PLA reclaimed materials, testing the molecular weight by GPC to be 7.5 ten thousand g/mol, adding 100kg of the PLA reclaimed materials into a reaction kettle with chloroform, heating to 50 ℃, stirring and dissolving, keeping the chloroform to be condensed and refluxed, adding 1.8kg of ethylene glycol and 8g of phosphazene base catalyst, carrying out alcoholysis reaction for 4h, heating to 75 ℃, vacuumizing to-0.09 MPa, removing solvent chloroform, condensing and collecting to a storage tank for later use, sampling in the kettle, removing the solvent in a vacuum oven, testing to obtain hydroxyl-terminated low-molecular-weight PLA liquid with the hydroxyl value of 17.81mgKOH/g and the acid value of 0.29mgKOH/g, and calculating the molecular weight to be 6300 g/mol.
2) Adding 80kg of propylene carbonate and 0.854kg of 1, 3-propylene glycol into a reaction kettle, stirring uniformly at normal temperature, adding 10.0g of an organic phosphazene catalyst, reacting for 7h, heating to 90 ℃, vacuumizing for 2h, and removing low-boiling-point substances to obtain the PPC prepared by the propylene carbonate ring opening method, wherein the tested molecular weight is 7200g/mol, mixing 50kg of the PPC material in the reaction kettle, heating to 105 ℃, vacuumizing, dehydrating for 2h, cooling to 80 ℃, adding 2.57kg of hexamethylene diisocyanate, and reacting for 2h to obtain the NCO-terminated PPC-PU liquid.
3) Adding the hydroxyl-terminated low-molecular-weight PLA liquid obtained in the step 1) into a pouring gate of a double-screw extruder, vacuumizing and devolatilizing, adding the PPC and the isocyanate prepolymer obtained in the step 2) into a second exhaust port by adopting a liquid pump, controlling the adding molar ratio of the PPC and the isocyanate prepolymer to be 1:1.15, setting the temperature of each area of the double-screw extruder to be 150-plus-190 ℃, reacting and tackifying the terminal hydroxyl of the PLA chain segment and the terminal NCO group of the PPC prepolymer after copolymerization and extrusion, and obtaining the PLA-PPC copolymer alloy after underwater grain cutting.
Comparative example 2
PLA resin, PPC resin and polyester TPU material with the hardness of 90A are mixed according to the mass ratio of 5: 4: 1, uniformly mixing, adding the mixture into a double-screw extruder for blending modification, setting the temperature of each area of the extruder to be 170-210 ℃, and preparing the physical blending modified material by underwater cooling and grain extraction.
Comparative example 3
PPC (polypropylene random copolymer) polyol with the molecular weight of 2000g/mol is used as a soft segment, 1, 4-butanediol is used as a chain extender, diphenylmethane diisocyanate is used as a raw material, the hard segment content is 38%, the isocyanate index is 1.01, the reaction is carried out to prepare a PPC-based TPU material, then PLA resin and the PPC-based TPU material prepared by the method are mixed according to the mass ratio of 6/4, the mixture is extruded and blended by a double-screw extruder, the temperature of each zone of the extruder is set to be 170-plus-one 210 ℃, and the blending modified material of PLA and PPC-based TPU is prepared after underwater cooling and grain extraction.
The performance of the product prepared in the above examples and comparative examples was evaluated as follows:
as can be seen from the data in the above table, compared with PLA and PPC materials, the PLA-PPC-PU copolymer alloy prepared by the technical scheme of the invention has the characteristics closer to those of elastomers, the elongation at break and the impact strength are obviously improved, and the PLA (the typical value of the elongation at break of the PLA material is generally less than 10%, and the impact strength is generally less than 5kJ/m2) The brittleness problem of the PLA material is obviously improved, and the elongation and the impact strength of the obtained alloy material are improved more obviously compared with the PLA/PPC blend, so that the compatibility problem existing in the blending method is solved through chemical polymerization, and the performance of the copolymerized alloy is more excellent and stable. Compared with the comparative example data, the PLA-PPC copolymerization which is different from the technical scheme of the invention can be seen, and neither PLA/PPC/TPU blending nor PLA/PPC-based TPU blending can be comparable to the technical scheme of the invention in comprehensive performance. In addition, the copolymerized gold provided by the technical scheme of the invention greatly maintains the biodegradation performance of PLA and PPC materials, keeps higher biodegradation rate, and has biodegradation rate closer to unmodified PLA pure material (the biodegradation rate of the PLA pure material is about 88 percent in 90 days) compared with the mode of mixing TPU material.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing PLA-PPC-PU copolymer alloy by using PLA reclaimed materials is characterized by comprising the following steps:
(1) and (3) carrying out alcoholysis on PLA to obtain a reclaimed material: mixing the PLA reclaimed materials with chloroform, heating to dissolve, adding dihydric alcohol and a catalyst to carry out alcoholysis reaction, condensing and refluxing the chloroform in the reaction process, and removing the solvent after the reaction is finished to obtain hydroxyl-terminated low-molecular-weight PLA liquid, wherein the molecular weight of the PLA liquid is 3000-15000g/mol, and the hydroxyl value of the PLA liquid is 7.5-37.5 mgKOH/g;
the dihydric alcohol is at least one of ethylene glycol and 1, 2-propylene glycol, the catalyst is 4-dialkylaminopyridine or phosphazene base catalyst, and the temperature of the alcoholysis reaction is 40-60 ℃;
(2) preparation of NCO-terminated PPC-PU liquids: mixing PPC and polyhydric alcohol according to the mass ratio of 6-10:1, heating to 100-120 ℃ for dehydration, then cooling to 70-90 ℃, and adding diisocyanate for reaction to obtain the PPC-PU liquid;
the ratio of the amount of the diisocyanate to the sum of the amounts of the PPC and the polyol is 1.8-2.2:1, and the polyol is polyester polyol and/or polyether polyol;
(3) preparing a PLA-PPC-PU copolymer alloy: pouring the hydroxyl-terminated low molecular weight PLA liquid into a double-screw extruder, vacuumizing and devolatilizing, then adding the NCO-terminated PPC-PU liquid into a second exhaust port of the double-screw extruder, extruding through subsequent screw copolymerization reaction, and underwater pelletizing to obtain the PLA-PPC-PU copolymer alloy;
the temperature of each zone of the double-screw extruder is 150-200 ℃.
2. The method as claimed in claim 1, wherein in the step (1), the PLA reclaimed material is mixed with chloroform and heated to 50 ℃ for dissolution, and the solid content of the mixture obtained by mixing the PLA reclaimed material with chloroform is 50%.
3. The method according to claim 1, wherein in the step (1), the molecular weight of the PLA reclaimed material is 6-15 ten thousand g/mol, the mass ratio of the dihydric alcohol to the PLA reclaimed material is 0.01-0.2:1, the mass of the catalyst is 50-100ppm of that of the PLA reclaimed material, and the alcoholysis reaction time is 2-4 h.
4. The method according to claim 1, wherein in the step (1), the temperature of the solvent removal is 60-80 ℃, and the vacuum degree is-0.09 to-0.1 MPa.
5. The method as claimed in claim 1, wherein in step (2), the PPC is prepared by the ring-opening reaction of propylene carbonate and small molecular weight dihydric alcohol under the action of a ring-opening catalyst at normal temperature for 6-8h, then heating to 90-100 ℃, vacuumizing to remove low-boiling-point substances, and the molecular weight is 1000-10000 g/mol; the micromolecular dihydric alcohol is at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol and 2-methyl-1, 3-propylene glycol; the addition proportion of the ring-opening catalyst is 50-200ppm of the mass of the propylene carbonate; the ring-opening catalyst is at least one of an organic phosphazene catalyst and ionic liquid; the molar ratio of the micromolecule dihydric alcohol to the propylene carbonate is 1: 8.5-97.5;
the polyalcohol is at least one of poly (butylene adipate-glycol) glycol, poly (ethylene adipate-glycol) glycol, poly (propylene adipate-glycol) glycol and poly (tetrahydrofuran ether glycol), and the molecular weight is 600-4000 g/mol;
the dehydration time is 2 h.
6. The method according to claim 1, wherein in the step (2), the diisocyanate is at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate;
the time for adding diisocyanate to carry out reaction is 1.5-3 h.
7. The process of claim 1, wherein in step (3), the molar ratio of the hydroxyl terminated low molecular weight PLA liquid to the PPC-PU liquid is from 1:1 to 1.2.
8. The PLA-PPC-PU copolymer alloy prepared by the method of any one of claims 1 to 7.
9. The PLA-PPC-PU copolymer alloy of claim 8, wherein the elongation at break is 500% or more, and the GB/T1843-2008 notched impact strength test result is non-destructive and biodegradable.
10. Use of the PLA-PPC-PU copolymer alloy according to claim 8 or 9 in films, packaging, disposable articles, medical devices, 3D printed materials.
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| CN115616204A (en) * | 2022-12-21 | 2023-01-17 | 金发科技股份有限公司 | Method and system for identifying polyethylene terephthalate reclaimed materials |
| CN116284593A (en) * | 2023-02-23 | 2023-06-23 | 鑫双利(惠州)树脂有限公司 | Bio-based unsaturated polyester resin and preparation method thereof |
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