CN118085323A - High-strength degradable polyester composite material and preparation method thereof - Google Patents

High-strength degradable polyester composite material and preparation method thereof Download PDF

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CN118085323A
CN118085323A CN202410528085.4A CN202410528085A CN118085323A CN 118085323 A CN118085323 A CN 118085323A CN 202410528085 A CN202410528085 A CN 202410528085A CN 118085323 A CN118085323 A CN 118085323A
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composite material
modified
acid
polyester
strength degradable
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王小威
宁恒斌
杨家淑
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Taizhou Huangyan Zeyu New Material Technology Co ltd
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Taizhou Huangyan Zeyu New Material Technology Co ltd
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Abstract

The invention relates to a high-strength degradable polyester composite material and a preparation method thereof, which belong to the technical field of high polymer materials and are prepared by the following steps: modifying cellulose micro-nano material by using a silane coupling agent, grafting the modified cellulose micro-nano material onto N, N' -carbonyl diimidazole activated camphorcarboxylic acid, and then combining the modified cellulose micro-nano material with tartaric acid to obtain a composite material; polycondensing the composite material with dimethyl terephthalate and diol monomer to obtain modified polyester material; mixing a modified polyester material, a lubricant and an antioxidant, and carrying out melt blending extrusion by a double-screw extruder to obtain a high-strength degradable polyester composite material; according to the technical scheme, the thermal stability of the composite material and the interfacial compatibility with polyester are improved by combining the modified camphorcarboxylic acid with the tartaric acid, the composite material is polycondensed with the dimethyl terephthalate and the glycol, the strength, the heat resistance and the degradability of the polyester material are enhanced, and the comprehensive performance of the polyester composite material is generally improved.

Description

High-strength degradable polyester composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-strength degradable polyester composite material and a preparation method thereof.
Background
In recent years, general plastics have been widely used because of their excellent combination of properties and low production cost, but they have also brought about great environmental pollution problems while satisfying people's convenience lives. The raw materials are not renewable, which is the most important disadvantage of all petrochemical products, and most importantly, the degradability is poor, the conventional plastic can be degraded under natural conditions for a long time, and the large-scale use of the plastic has caused serious 'white pollution' to the earth ecological system, thus threatening the survival of a plurality of animals, plants and even our human beings. Therefore, from the viewpoint of protecting ecological balance, the main attack direction of development has been shifted to biodegradable plastics that are friendly to the environment.
At present, polyester polymers such as polycaprolactone, poly (trimethylene carbonate), polyhydroxybutyrate, poly (succinic acid) glycol ester and the like have good biocompatibility and biodegradability and certain strength, but the materials have poor heat resistance and processability, and the strength is still different from that of the traditional hard plastics; the nano material is filled into the polyester material, and although the mechanical property of the polyester material can be enhanced, the problems of poor interfacial compatibility, low strength, poor thermal stability and the like are also commonly existed, so that the polyester composite material with better heat resistance, higher strength and biodegradability needs to be prepared.
Disclosure of Invention
The invention aims to provide a high-strength degradable polyester composite material and a preparation method thereof, wherein a silane coupling agent is used for modifying cellulose micro-nano materials, and then the cellulose micro-nano materials are grafted onto N, N '-carbonyldiimidazole activated camphorcarboxylic acid to obtain modified camphorcarboxylic acid, so that the dispersibility of the nano materials is improved by silane, the reactivity of silane and camphorcarboxylic acid is improved by using N, N' -carbonyldiimidazole as an activating agent, and the interfacial compatibility of the modified camphorcarboxylic acid in the polyester material is improved; the modified camphorcarboxylic acid is combined with tartaric acid, and the rigid spiro and bridged bicyclo structure improves the thermal stability of the composite material; the composite material is polycondensed with the dimethyl terephthalate and the diol monomer, so that the strength, the heat resistance and the degradability of the modified polyester material are enhanced, the comprehensive performance of the polyester composite material is generally improved, the pollution to the environment is reduced, and the environment is more environment-friendly.
The invention aims to solve the technical problems: the polyester polymers such as polycaprolactone, poly trimethylene carbonate, polyhydroxy butyric acid, poly succinic acid glycol ester and the like have good biocompatibility and biodegradability and certain strength, but the materials have poor heat resistance and processability, and the strength is still different from that of the traditional hard plastics; the nano material is filled into the polyester material, and the mechanical property of the polyester material can be enhanced, but the problems of poor interfacial compatibility, low strength, poor thermal stability and the like are also common, so that the nano material is limited in practical application.
The aim of the invention can be achieved by the following technical scheme:
A preparation method of a high-strength degradable polyester composite material comprises the following steps:
S1, modifying a cellulose micro-nano material by using a silane coupling agent, and then grafting the modified cellulose micro-nano material onto N, N' -carbonyl diimidazole activated camphorcarboxylic acid to obtain modified camphorcarboxylic acid;
S2, combining modified camphorcarboxylic acid with tartaric acid to obtain a composite material;
S3, polycondensing the composite material with dimethyl terephthalate and diol monomers to obtain a modified polyester material;
And S4, putting the modified polyester material into a mixer, adding a lubricant and an antioxidant, uniformly stirring, adding into a double-screw extruder, and extruding and granulating after melt blending to obtain the high-strength degradable polyester composite material.
Further, in step S1, the modified camphorcarboxylic acid is prepared by the steps of:
Adding a silane coupling agent into a mixture of ethanol and deionized water, uniformly stirring at 55-65 ℃, adding cellulose micro-nano material powder, stirring at 115-125 ℃ for 2 hours, centrifuging at 8000r/min for 10 minutes, washing with absolute ethanol for 3-5 times to remove unreacted silane coupling agent, fractionating at 80 ℃ to remove ethanol, and freeze-drying to obtain the modified cellulose micro-nano material, wherein the dosage ratio of the silane coupling agent to the ethanol to the deionized water to the cellulose micro-nano material powder is 1.8-2.2g:80-100mL:5-15mL:0.8-1.2g;
A2, uniformly mixing toluene, camphorcarboxylic acid and N, N '-carbonyldiimidazole, heating to 100 ℃ and refluxing for 4 hours, adding modified cellulose micro-nano materials, continuously stirring for 1 hour, filtering, extracting with toluene for 18 hours, and finally vacuum drying at 110 ℃ for 4 hours to obtain modified camphorcarboxylic acid, wherein the dosage ratio of toluene, camphorcarboxylic acid, N' -carbonyldiimidazole and modified cellulose micro-nano materials is 40-60mL:0.08-0.12g:0.04-0.08g:1.9-2.1g.
In the reaction process, the cellulose micro-nano material is provided with hydroxyl groups, and the silane coupling agent generates silicon hydroxyl groups after hydrolysis and can be combined with the hydroxyl groups on the cellulose micro-nano material, so that the silane coupling agent is grafted to the surface of the cellulose micro-nano material to obtain the modified cellulose micro-nano material; the camphorcarboxylic acid has carboxyl group, carbonyl group on N, N' -carbonyl diimidazole can be combined with carboxyl group on camphorcarboxylic acid, the generated carbonyl imidazole can react with amino group on silane coupling agent, and the modified cellulose micro-nano material is grafted on camphorcarboxylic acid to obtain the modified camphorcarboxylic acid.
Further, the silane coupling agent is KH550.
Further, the cellulose micro-nano material comprises one of nanocrystalline cellulose, cellulose nanowhiskers, cellulose microcrystals or cellulose microfibers.
Further, in step S2, the composite material is prepared by the following steps:
Tartaric acid, methanol, trimethyl orthoformate and sulfuric acid solution are mixed and stirred for 2 hours, then modified camphorcarboxylic acid is added, after stirring for 48 hours under dry nitrogen, the mixture is dissolved in chloroform, neutralized with NaHCO 3 solution, washed with deionized water and dried with MgSO 4, then methanol, methyl formate and trimethyl orthoformate are removed from the solution by a rotary evaporator, and reduced pressure distillation is carried out, finally a composite material is obtained, wherein the dosage ratio of tartaric acid, methanol, trimethyl orthoformate, sulfuric acid solution and modified camphorcarboxylic acid is 59-61g:80-120mL:150-170mL:3-7mL:39-41g.
In the reaction process, two hydroxyl groups are arranged in tartaric acid, carbonyl groups are arranged in modified camphorcarboxylic acid, hydroxyl groups on the tartaric acid can be combined with carbonyl groups on the modified camphorcarboxylic acid to form a rigid spiro structure, and finally, the composite material is obtained, and the thermal stability of the composite material is improved.
Further, in step S3, the modified polyester material is prepared by the following steps:
Uniformly mixing a diol monomer, dimethyl terephthalate, a composite material and isopropyl titanate, preheating to 180 ℃ and maintaining for 10min, performing transesterification at 180 ℃ and nitrogen for 1.5h to inhibit sublimation of the diol, then raising the temperature to 240 ℃ and maintaining for 30min to prevent the diol from sublimating under reduced pressure to cause sudden temperature drop and possibly causing oligomer crystallization, performing polycondensation at 240 ℃ and a low pressure of 1.73-2.93mbar for 2-3.5h to effectively remove byproducts, then precipitating in methanol, drying and purifying to obtain a modified polyester material, wherein the dosage ratio of the diol monomer, the dimethyl terephthalate, the composite material and the isopropyl titanate is 21-23g:89-91g:9-11g:0.05-0.1g.
In the reaction process, the diol monomer has hydroxyl groups, the dimethyl terephthalate has ester groups, the composite material has carboxyl groups, and the diol monomer, the dimethyl terephthalate and the composite material are combined through polycondensation reaction, so that the modified polyester material is finally obtained, and the heat resistance and the degradability of the polyester material are improved.
Further, the diol monomer is one of ethylene glycol, 1, 4-butanediol or hexamethylene glycol.
Further, in step S4, the high-strength degradable polyester composite material is prepared by the following steps:
Adding the modified polyester material into a mixer, adding a lubricant and an antioxidant, stirring for 5-10min at 150-200 ℃, adding into a double screw extruder, carrying out melt blending, extruding and granulating, wherein the extrusion temperature is 150-180 ℃, and the screw speed is 85-100rpm, so as to obtain the high-strength degradable polyester composite material.
Further, the lubricant is one or more of zinc stearate, polyethylene wax, dioctadecyl phthalate and ethylene bis-stearamide.
Further, the antioxidant is one or more of triethyl phosphate, antioxidant 1010 and phosphite ester amine.
The invention has the beneficial effects that:
(1) According to the technical scheme, the cellulose micro-nano material is modified by the silane coupling agent and grafted to N, N ' -carbonyldiimidazole activated camphorcarboxylic acid to obtain modified camphorcarboxylic acid, the cellulose micro-nano material is modified by the silane coupling agent, the hydrophobic property of the nano material is improved, the dispersibility of the nano material in the polyester material is improved, N, N ' -carbonyldiimidazole can be combined with carboxyl on the camphorcarboxylic acid, the generated carbonylimidazole is combined with amino on the silane coupling agent in a reaction manner, the modified cellulose nano material is grafted to the camphorcarboxylic acid, the N, N ' -carbonyldiimidazole is used as an activating agent, the reactivity between the camphorcarboxylic acid and the silane coupling agent is improved, the combination of the camphorcarboxylic acid and the nano material is enhanced, meanwhile, the modified camphorcarboxylic acid and the polyester material have good interface compatibility, and the thermal stability and the mechanical property of the polyester material are improved.
(2) According to the technical scheme, the composite material is obtained by combining the modified camphorcarboxylic acid and the tartaric acid, two hydroxyl groups on the tartaric acid can be combined with carbonyl groups on the modified camphorcarboxylic acid to form a rigid spiro structure, and the modified camphorcarboxylic acid is provided with a bridged bicyclic structure, so that the thermal stability of the composite material is enhanced by the rigid spiro structure and the bridged bicyclic structure, and meanwhile, the mechanical strength of the composite material is further improved; the composite material is polycondensed with the dimethyl terephthalate and the diol monomer to obtain the modified polyester material, and ketal groups generated by combining tartaric acid and camphorcarboxylic acid in the composite material can improve the reaction rate with the diol monomer and the dimethyl terephthalate, and further enhance the heat resistance, the degradability and the thermal stability of the polyester material.
(3) According to the technical scheme, the cellulose micro-nano material is modified by the silane coupling agent, then grafted to the N, N' -carbonyl diimidazole activated camphorcarboxylic acid, then combined with tartaric acid, and finally polycondensed with the diol monomer and the dimethyl terephthalate to obtain the modified polyester material, so that the mechanical strength and the thermal stability of the modified polyester material are improved, the heat resistance and the degradability of the modified polyester material are improved, the pollution of the polyester material to the environment is reduced, the environment is more environment-friendly, and the application range of the modified polyester material is widened.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The modified camphorcarboxylic acid is prepared by the following steps:
A1, adding 1.9g KH550 into a mixture of 80mL of ethanol and 5mL of deionized water, uniformly stirring at 55 ℃, adding 0.9g nanocrystalline cellulose powder, stirring at 115 ℃ for 2 hours, centrifuging at 8000r/min for 10 minutes, washing with absolute ethanol for 3 times to remove unreacted KH550, fractionating at 80 ℃ to remove ethanol, and freeze-drying to obtain a modified cellulose micro-nano material;
A2, uniformly mixing 40mL of toluene, 0.08g of (+) -camphorcarboxylic acid and 0.04g of N, N' -carbonyl diimidazole, heating to 100 ℃ and refluxing for 4 hours, adding 1.9g of modified cellulose micro-nano material, continuously stirring for 1 hour, filtering, extracting with toluene for 18 hours, and finally drying in vacuum at 110 ℃ for 4 hours to obtain the modified camphorcarboxylic acid.
Example 2
The modified camphorcarboxylic acid is prepared by the following steps:
A1, adding 2g KH550 into a mixture of 90mL of ethanol and 10mL of deionized water, uniformly stirring at 60 ℃, adding 1g of nanocrystalline cellulose powder, stirring at 120 ℃ for 2 hours, centrifuging at 8000r/min for 10 minutes, washing with absolute ethanol for 4 times to remove unreacted KH550, fractionating at 80 ℃ to remove ethanol, and freeze-drying to obtain a modified cellulose micro-nano material;
A2, uniformly mixing 50mL of toluene, 0.1g of (+) -camphorcarboxylic acid and 0.06g of N, N' -carbonyl diimidazole, heating to 100 ℃ and refluxing for 4 hours, adding 2g of modified cellulose micro-nano material, continuously stirring for 1 hour, filtering, extracting with toluene for 18 hours, and finally drying in vacuum at 110 ℃ for 4 hours to obtain the modified camphorcarboxylic acid.
Example 3
The modified camphorcarboxylic acid is prepared by the following steps:
A1, adding 2.1g KH550 into a mixture of 100mL of ethanol and 15mL of deionized water, uniformly stirring at 65 ℃, adding 1.1g nanocrystalline cellulose powder, stirring at 125 ℃ for 2 hours, centrifuging at 8000r/min for 10 minutes, washing with absolute ethanol for 5 times to remove unreacted KH550, fractionating at 80 ℃ to remove ethanol, and freeze-drying to obtain a modified cellulose micro-nano material;
A2, mixing 60mL of toluene, 0.12g of (+) -camphorcarboxylic acid and 0.08g of N, N' -carbonyl diimidazole uniformly, heating to 100 ℃ and refluxing for 4 hours, adding 2.1g of modified cellulose micro-nano material, continuously stirring for 1 hour, filtering, extracting with toluene for 18 hours, and finally drying in vacuum at 110 ℃ for 4 hours to obtain the modified camphorcarboxylic acid.
Comparative example 1
This comparative example is a modified camphorcarboxylic acid not activated by N, N' -carbonyldiimidazole.
Comparative example 2
The comparative example is a modified camphorcarboxylic acid without modified cellulose micro-nano material.
Example 4
The composite material is prepared by the following steps:
59g of tartaric acid, 80mL of methanol, 150mL of trimethyl orthoformate and 3mL of sulfuric acid solution with a concentration of 18.4mol/L were mixed and stirred for 2 hours, then 39g of the modified camphorcarboxylic acid prepared in example 1 was added, and after stirring under dry nitrogen for 48 hours, the mixture was dissolved in 1L of chloroform, neutralized with NaHCO 3 solution, washed with deionized water and dried with MgSO 4, methanol, methyl formate and trimethyl orthoformate were removed from the solution by a rotary evaporator and distilled under reduced pressure, and finally a composite material was obtained.
Example 5
The composite material is prepared by the following steps:
60g of tartaric acid, 100mL of methanol, 160mL of trimethyl orthoformate and 5mL of sulfuric acid solution with a concentration of 18.4mol/L were mixed and stirred for 2 hours, then 40g of the modified camphorcarboxylic acid prepared in example 2 was added, and after stirring under dry nitrogen for 48 hours, the mixture was dissolved in 1L of chloroform, neutralized with NaHCO 3 solution, washed with deionized water and dried with MgSO 4, methanol, methyl formate and trimethyl orthoformate were removed from the solution by a rotary evaporator and distilled under reduced pressure, and finally a composite material was obtained.
Example 6
The composite material is prepared by the following steps:
61g of tartaric acid, 120mL of methanol, 170mL of trimethyl orthoformate and 7mL of sulfuric acid solution with a concentration of 18.4mol/L were mixed and stirred for 2 hours, then 41g of the modified camphorcarboxylic acid prepared in example 3 was added, and after stirring under dry nitrogen for 48 hours, the mixture was dissolved in 1L of chloroform, neutralized with NaHCO 3 solution, washed with deionized water and dried with MgSO 4, methanol, methyl formate and trimethyl orthoformate were removed from the solution by a rotary evaporator and distilled under reduced pressure, and finally a composite material was obtained.
Comparative example 3
This comparative example differs from example 5 in that the modified camphorcarboxylic acid prepared in example 2 was replaced with the material prepared in comparative example 1, and the rest of the procedure and the raw materials were synchronized with example 5.
Comparative example 4
This comparative example differs from example 5 in that the modified camphorcarboxylic acid prepared in example 2 was replaced with the material prepared in comparative example 2, and the rest of the procedure and the raw materials were synchronized with example 5.
Comparative example 5
This comparative example differs from example 5 in that this example is a composite material with unmodified camphorcarboxylic acid.
Comparative example 6
This comparative example differs from example 5 in that this example is a composite material without tartaric acid.
Example 7
The modified polyester material is prepared by the following steps:
21g of ethylene glycol monomer, 89g of dimethyl terephthalate, 9g of the composite material prepared in example 4 and 0.05g of isopropyl titanate are uniformly mixed, then preheated to 180 ℃ and kept for 10min, transesterification is performed for 1.5h under nitrogen at 180 ℃ to inhibit sublimation of glycol, then the temperature is raised to 240 ℃ and kept for 30min to prevent the glycol from sublimating under reduced pressure to cause sudden drop of temperature and possibly cause crystallization of oligomer, and in order to effectively remove byproducts, polycondensation is performed for 2h at 240 ℃ and a low pressure of 1.73mbar, then the mixture is precipitated in methanol, dried and purified to obtain the modified polyester material.
Example 8
The modified polyester material is prepared by the following steps:
22g of 1, 4-butanediol monomer, 90g of dimethyl terephthalate, 10g of the composite material prepared in example 5 and 0.07g of isopropyl titanate are uniformly mixed, then preheated to 180 ℃ and maintained for 10min, transesterified for 1.5h under nitrogen at 180 ℃ to inhibit sublimation of glycol, then the temperature is raised to 240 ℃ and maintained for 30min to prevent the glycol from sublimating under reduced pressure to cause sudden temperature drop which may cause oligomer crystallization, and for effective removal of byproducts, polycondensation is carried out at 240 ℃ and a low pressure of 2.33mbar for 2.8h, then precipitated in methanol, dried and purified to finally obtain the modified polyester material.
Example 9
The modified polyester material is prepared by the following steps:
23g of hexamethylene glycol monomer, 91g of dimethyl terephthalate, 11g of the composite material prepared in example 6 and 0.1g of isopropyl titanate are uniformly mixed, then preheated to 180 ℃ and maintained for 10min, transesterified for 1.5h under nitrogen at 180 ℃ to inhibit sublimation of glycol, then the temperature is raised to 240 ℃ and maintained for 30min to prevent the glycol from sublimating under reduced pressure to cause sudden temperature drop which may cause crystallization of oligomer, and for effective removal of byproducts, polycondensed for 3.5h at 240 ℃ and a low pressure of 2.93mbar, then precipitated in methanol, dried and purified to finally obtain the modified polyester material.
Comparative example 7
This comparative example differs from example 8 in that the composite material prepared in example 5 was replaced with the material prepared in comparative example 3, and the rest of the procedure and raw materials were synchronized with example 8.
Comparative example 8
This comparative example differs from example 8 in that the composite material prepared in example 5 was replaced with the material prepared in comparative example 4, and the rest of the procedure and raw materials were synchronized with example 8.
Comparative example 9
This comparative example differs from example 8 in that the composite material prepared in example 5 was replaced with the material prepared in comparative example 5, and the rest of the procedure and raw materials were synchronized with example 8.
Comparative example 10
This comparative example differs from example 8 in that the composite material prepared in example 5 was replaced with the material prepared in comparative example 6, and the rest of the procedure and raw materials were synchronized with example 8.
Comparative example 11
This comparative example differs from example 8 in that this example is a polyester material without a composite material.
Example 10
The high-strength degradable polyester composite material is prepared by the following steps:
the modified polyester material prepared in example 7 is put into a mixer, zinc stearate and triethyl phosphate are added, stirring is carried out for 5min at 150 ℃, then the mixture is put into a double-screw extruder, extrusion granulation is carried out after melt blending, the extrusion temperature is 150 ℃, and the screw rotation speed is 85rpm, so that the high-strength degradable polyester composite material is obtained.
Example 11
The high-strength degradable polyester composite material is prepared by the following steps:
The modified polyester material prepared in example 8 is put into a mixer, polyethylene wax and antioxidant 1010 are added, stirring is carried out for 8min at 180 ℃, then the mixture is put into a double-screw extruder, extrusion granulation is carried out after melt blending, the extrusion temperature is 170 ℃, and the screw rotation speed is 95rpm, so that the high-strength degradable polyester composite material is obtained.
Example 12
The high-strength degradable polyester composite material is prepared by the following steps:
The modified polyester material prepared in example 9 is put into a mixer, then ethylene bis stearamide and phosphite ester amine are added, stirring is carried out for 10min at 200 ℃, then the mixture is added into a double screw extruder, extrusion granulation is carried out after melt blending, the extrusion temperature is 180 ℃, and the screw rotation speed is 100rpm, so that the high-strength degradable polyester composite material is obtained.
Comparative example 12
This comparative example differs from example 11 in that the modified polyester material prepared in example 8 was replaced with the material prepared in comparative example 7, and the rest of the procedure and the raw materials were synchronized with example 11.
Comparative example 13
This comparative example differs from example 11 in that the modified polyester material prepared in example 8 was replaced with the material prepared in comparative example 8, and the rest of the procedure and raw materials were synchronized with example 11.
Comparative example 14
This comparative example differs from example 11 in that the modified polyester material prepared in example 8 was replaced with the material prepared in comparative example 9, and the rest of the procedure and the raw materials were synchronized with example 11.
Comparative example 15
This comparative example differs from example 11 in that the modified polyester material prepared in example 8 was replaced with the material prepared in comparative example 10, and the rest of the procedure and raw materials were synchronized with example 11.
Comparative example 16
This comparative example differs from example 11 in that the modified polyester material prepared in example 8 was replaced with the material prepared in comparative example 11, and the rest of the procedure and raw materials were synchronized with example 11.
Comparative example 17
The comparative example is polycaprolactone.
The high strength degradable polyester composites prepared in examples 10-12 and comparative examples 12-17 were tested for tensile strength, elongation at break, unnotched impact strength, TGA residual and biodegradability, wherein tensile strength and elongation at break were determined using ISO527 standard; the notched impact strength is determined using the ISO180 standard, the TGA residual is determined using the ISO11358 standard; the degree of biodegradation was determined using the ISO14855 standard. The test results are shown in the following table:
as can be seen from the data in table 1 above, as can be seen from the comparison of comparative examples 12 to 13 and example 11, the use of unmodified cellulose micro-nano material or modified camphorcarboxylic acid not activated by N, N '-carbonyldiimidazole for the preparation of polyester composite material resulted in poorer test results than that of example 11, which demonstrated that grafting of modified cellulose micro-nano material onto N, N' -carbonyldiimidazole activated camphorcarboxylic acid can better disperse cellulose micro-nano material, increase the compatibility with polyester, and further enhance the mechanical properties and thermal stability of polyester composite material;
from comparison of comparative examples 14 to 15 and example 11, it is shown that the polyester composite material is prepared by using a composite material without modified camphorcarboxylic acid or tartaric acid, and the combination of modified camphorcarboxylic acid and tartaric acid can form a structure with rigid spiro ring and bridged bi-ring, so that the heat resistance and mechanical property of the polyester material are further improved, and the strength and degradability of the polyester composite material are improved;
As can be seen from comparison of comparative example 16 and example 11, the preparation of the polyester composite material without adding the composite material, illustrates that the polycondensation of the composite material with dimethyl terephthalate and diol monomers can further improve the mechanical properties and the degradability of the polyester composite material;
As can be seen from the comparison of comparative example 17 and example 11, the use of polycaprolactone to prepare the high strength degradable polyester composite material has poorer mechanical strength and degradability than example 11, indicating that the polyester composite material prepared from the modified polyester material has better mechanical properties, degradability and thermal stability.
As can be seen from Table 1 above, the high-strength degradable polyester composite material prepared in examples 10-12 is modified by KH550 on cellulose micro-nano material, then grafted on N, N' -carbonyldiimidazole activated camphorcarboxylic acid, then combined with tartaric acid, finally polycondensed with diol monomer and dimethyl terephthalate, so that the thermal stability, mechanical properties and degradability of the polyester composite material are generally improved, and the requirement of test performance is met, while the high-strength degradable polyester composite material prepared in comparative examples 12-17 does not meet the standard of performance requirement, which indicates that the high-strength degradable polyester composite material prepared in the invention not only has better heat resistance and mechanical properties, but also has better degradability, greatly improves the comprehensive performance of the polyester material, and reduces environmental pollution.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (10)

1. The preparation method of the high-strength degradable polyester composite material is characterized by comprising the following steps of:
S1, modifying a cellulose micro-nano material by using a silane coupling agent, and then grafting the modified cellulose micro-nano material onto N, N' -carbonyl diimidazole activated camphorcarboxylic acid to obtain modified camphorcarboxylic acid;
S2, combining modified camphorcarboxylic acid with tartaric acid to obtain a composite material;
S3, polycondensing the composite material with dimethyl terephthalate and diol monomers to obtain a modified polyester material;
And S4, putting the modified polyester material into a mixer, adding a lubricant and an antioxidant, uniformly stirring, adding into a double-screw extruder, and extruding and granulating after melt blending to obtain the high-strength degradable polyester composite material.
2. The method for preparing a high-strength degradable polyester composite material according to claim 1, wherein the step S1 is specifically:
A1, adding a silane coupling agent into a mixture of ethanol and deionized water, uniformly stirring at 55-65 ℃, adding cellulose micro-nano material powder, stirring at 115-125 ℃ for 2 hours, centrifuging for 10 minutes, washing with absolute ethanol for 3-5 times, fractionating at 80 ℃, and freeze-drying to obtain a modified cellulose micro-nano material;
A2, uniformly mixing toluene, camphorcarboxylic acid and N, N' -carbonyl diimidazole, heating to 100 ℃ and refluxing for 4 hours, adding modified cellulose micro-nano materials, stirring for 1 hour, filtering, extracting with toluene for 18 hours, and vacuum drying at 110 ℃ for 4 hours to obtain the modified camphorcarboxylic acid.
3. The method for preparing the high-strength degradable polyester composite material according to claim 2, wherein the dosage ratio of the silane coupling agent, the ethanol, the deionized water and the cellulose micro-nano material powder is 1.9-2.1g:80-100mL:5-15mL:0.9-1.1g.
4. The method for preparing the high-strength degradable polyester composite material according to claim 2, wherein the dosage ratio of toluene, camphorcarboxylic acid, N' -carbonyldiimidazole and modified cellulose micro-nano material is 40-60mL:0.08-0.12g:0.04-0.08g:1.9-2.1g.
5. The method for preparing a high-strength degradable polyester composite material according to claim 1, wherein the step S2 is specifically:
And mixing tartaric acid, methanol, trimethyl orthoformate and sulfuric acid solution, stirring for 2 hours, adding modified camphorcarboxylic acid, continuously stirring for 48 hours under dry nitrogen, dissolving the mixture in chloroform, neutralizing with NaHCO 3 solution, washing with deionized water, drying with MgSO 4, and finally distilling under reduced pressure to obtain the composite material.
6. The method for preparing a high-strength degradable polyester composite according to claim 5, wherein the dosage ratio of tartaric acid, methanol, trimethyl orthoformate, sulfuric acid solution and modified camphorcarboxylic acid is 59-61g:80-120mL:150-170mL:3-7mL:39-41g.
7. The method for preparing a high-strength degradable polyester composite material according to claim 1, wherein the step S3 is specifically:
Mixing diol monomer, dimethyl terephthalate, composite material and isopropyl titanate, preheating to 180 deg.c and maintaining for 10min, transesterifying at 180 deg.c under nitrogen for 1.5 hr, raising the temperature to 240 deg.c and maintaining for 30min, polycondensing at 240 deg.c and low pressure of 1.73-2.93mbar for 2-3.5 hr, precipitating in methanol, drying and purifying to obtain modified polyester material.
8. The method for preparing a high strength degradable polyester composite according to claim 7, wherein the diol monomer is one of ethylene glycol, 1, 4-butanediol or hexamethylene glycol.
9. The method for preparing a high-strength degradable polyester composite material according to claim 1, wherein the step S4 is specifically:
Adding the modified polyester material into a mixer, adding a lubricant and an antioxidant, stirring for 5-10min at 150-200 ℃, adding into a double screw extruder, carrying out melt blending, extruding and granulating, wherein the extrusion temperature is 150-180 ℃, and the screw speed is 85-100rpm, so as to obtain the high-strength degradable polyester composite material.
10. A high strength degradable polyester composite material made by the method of any one of claims 1-9.
CN202410528085.4A 2024-04-29 2024-04-29 High-strength degradable polyester composite material and preparation method thereof Pending CN118085323A (en)

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