CN112694733A - Biomass antibacterial plastic material and preparation method thereof - Google Patents
Biomass antibacterial plastic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a biomass antibacterial plastic material, which is characterized by comprising the following steps: step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate; step S2, preparing a 2-vinylfuran/5-allyl-3-methoxysalicylic acid methyl ester/probenazole/vinyltriethoxysilane copolymer; and step S3, material molding. The invention also provides the biomass antibacterial plastic material prepared by the preparation method of the biomass antibacterial plastic material. The biomass antibacterial plastic material disclosed by the invention is good in comprehensive performance and performance stability, remarkable in antibacterial effect, excellent in mechanical property, durability and aging resistance, safe to use and environment-friendly.
Description
Technical Field
The invention relates to the technical field of plastic materials, in particular to a biomass antibacterial plastic material and a preparation method thereof.
Background
The biomass material is a novel material which is prepared by using renewable biomass resources such as woody, gramineous and liana, forest product wastes and the like as raw materials and processing and manufacturing the raw materials by high-tech means such as physics, chemistry and bioengineering, has excellent performance, is environment-friendly, has various varieties, high added value and wide application, can replace petrochemical and mineral resource products, and has the characteristics of modern science and technology. The material has diversified raw materials; preparation and plastification; the product is environment-friendly; the advantages of economical application and low carbonization regeneration are widely applied to the fields of buildings, decoration, furniture, traffic, logistics, packaging and the like.
Biomass plastic is one of common biomass materials, and has a very important position in the fields of food preservation and packaging. In addition to excellent mechanical properties including strength, toughness, elasticity, etc., the ideal biomass plastic also needs to have better barrier property, water resistance, flame retardance, antibacterial property, etc. to provide better protection for the inner package. However, the existing biomass plastics have low impact strength and insufficient antibacterial performance, and the aging resistance is to be further improved.
In order to improve the antibacterial property of the biomass plastic, some antibacterial agents are added. At present, the common plastic antibacterial agents comprise an organic antibacterial agent and an inorganic antibacterial agent. The organic antibacterial agent mainly comprises quaternary ammonium salt, ether, phenol, thiazole, diphenyl ether compounds and the like, and is characterized by high sterilization speed and wide antibacterial spectrum, but the antibacterial function has poor heat resistance and short antibacterial effective period. The inorganic antibacterial agent is mainly silver, zinc and other ions and compounds or complexes thereof, and is characterized by good heat resistance, broad antibacterial spectrum, high safety and the like, but the inorganic antibacterial agent has poor compatibility with plastic base materials, is easy to seep out of plastics in the long-term use process, and has poor performance stability and short service life.
For example, chinese patent application No. 201710235486.0 discloses a method for preparing an environment-friendly biomass plastic material and its application, wherein the method comprises the steps of performing powdering and activation treatment reactions on a specific biomass material, polymerizing raw materials such as polypropylene, high-density polyethylene, acrylonitrile, kaolin, maleic anhydride polyolefin, etc., heating and calcining in a muffle furnace, adding coupling agent, defoaming agent, curing agent, toughening agent, etc. to improve the performance of the composite material, and then performing a series of operations such as casting a mold, surface activation treatment, demolding and drying to obtain the composite plastic material. The prepared environment-friendly biomass plastic material is high in strength, environment-friendly, harmless, recyclable and good in application prospect. Simultaneously discloses the application of the environment-friendly biomass plastic material prepared by the preparation method in plastic films, disposable medical materials and latex gloves. However, the material has no antibacterial function, and the added additive has high content, so that the processing flowability, comprehensive performance and performance stability of the material are influenced.
Therefore, the biomass antibacterial plastic material which has good comprehensive performance and performance stability, obvious antibacterial effect, excellent mechanical property, durability and aging resistance and safe and environment-friendly use is developed, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the field of biomass materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a biomass antibacterial plastic material, which is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the double-end hydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst to obtain a mixed material, then adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and esterifying for 1-3 hours at the temperature of 180-200 ℃ and the pressure of 50-100KPa, then increasing the temperature to 240 ℃ and the reaction pressure to 20-40kPa, and reacting for 1-2 hours; then, the reaction is carried out for 8-12h under the reaction pressure of 50-80Pa and the temperature of 230-240 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and then the precipitated condensation polymer is dried to constant weight in a vacuum drying oven at the temperature of 85-95 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid condensation polymer;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 4-6 hours at 60-70 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
Preferably, the molar ratio of the double-end hydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst in the step S1 is 1:1 (0.8-1.2).
Preferably, the catalyst is at least one of zinc acetate, zinc chloride and ethylene glycol antimony.
Preferably, the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the mass ratio of the 2-vinyl furan, the 5-allyl-3-methoxy methyl salicylate, the probenazole, the vinyltriethoxysilane, the initiator and the high-boiling-point solvent in the step S2 is 1 (1-2): 0.8-1.2): 0.2-0.4): 0.03-0.05): 14-20.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate, the copolymer, the lecithin, the epoxy vegetable oil, the citric acid and the bamboo charcoal fiber in the step S3 is (2-3) 1 (0.1-0.2) 0.1:0.3 (0.1-0.3).
Preferably, the epoxidized vegetable oil is at least one of epoxidized soybean oil, epoxidized sunflower oil and epoxidized corn oil; the preparation method of the epoxy vegetable oil is as follows: preparation of epoxidized vegetable oil, from the Chachen chapter, Wuyumin, applied chemistry 1994(011)004, 85-87.
Preferably, the epoxy value of the epoxidized soybean oil and the epoxidized sunflower oil is 6.2 to 6.6 percent, and the epoxy value of the epoxidized corn oil is 6.0 to 6.4 percent.
Preferably, the diameter of the bamboo charcoal fiber is 3-9 μm, and the length-diameter ratio is (10-15): 1.
Preferably, the temperature of the extrusion molding is 190-230 ℃.
The invention also aims to provide the biomass antibacterial plastic material prepared by the preparation method of the biomass antibacterial plastic material.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the biomass antibacterial plastic material provided by the invention has the advantages of simple process, less equipment investment, low energy consumption, high preparation efficiency and high qualified rate of finished products, and is suitable for continuous large-scale production.
(2) The biomass antibacterial plastic material provided by the invention overcomes the defects that the existing biomass plastic is low in impact strength, insufficient in antibacterial performance and low in aging resistance, and also overcomes the defects that the antibacterial function of the antibacterial biomass plastic on the market is poor in heat resistance and short in antibacterial effective period; poor compatibility with plastic base materials, and easy exudation from plastics in the long-term use process, which leads to the disadvantages of poor performance stability and short service life. Through the synergistic effect of the components, the prepared biomass antibacterial plastic has the advantages of good comprehensive performance and performance stability, obvious antibacterial effect, excellent mechanical property, durability and aging resistance, and safe and environment-friendly use.
(3) The biomass antibacterial plastic material provided by the invention is prepared from biomass, is non-toxic and harmless, is safe and environment-friendly to use, can be biodegraded after being discarded, and cannot cause white pollution.
(4) According to the biomass antibacterial plastic material provided by the invention, the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate and the copolymer are used as matrix materials, and the excellent performances of the two are combined, so that the prepared plastic material is good in comprehensive performance and excellent in performance stability, and the salicylic acid ester structure and the benzothiazole structure on the molecular chain of the copolymer and the bamboo charcoal fiber are in synergistic action, so that the material can be endowed with excellent antibacterial performance; the ethoxy silicon-based structure on the molecular chain of the copolymer can be connected with the bamboo charcoal fiber through a bridging effect, so that the compatibility of the bamboo charcoal fiber and the base material is improved, the furan structure contained on the molecular chain of the copolymer is similar to that in the condensation polymer, the compatibility of the furan structure and the condensation polymer is improved, the structure is more compact, and the performance stability is better.
(5) According to the biomass antibacterial plastic material provided by the invention, the acid groups on citric acid can catalyze the furan structures on the polycondensate and the copolymer to be crosslinked to form a three-dimensional network structure, so that the comprehensive performance and the performance stability are effectively improved, the material has stronger aging resistance, the oxidation resistance of the material can be improved by adding lecithin, and the amphoteric ion salt structure on the material can play a role in assisting in antibiosis and enhancing the connection effect among the components; the epoxy vegetable oil not only can play a role in plasticization, but also can react with active groups such as carboxyl, hydroxyl, furan and the like in other components, so that the crosslinking density is higher, and the comprehensive performance and the durability are further improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The preparation method of the epoxy vegetable oil in the embodiment of the invention is as follows: preparation of epoxidized vegetable oil, from the Chachen chapter, Wuyumin, applied chemistry 1994(011)004, 85-87. The double-end hydroxyl polylactic acid is prepared by the method of patent example 1 of Chinese invention with the application number of 201410665269.1.
Example 1
A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing dihydroxyl polylactic acid, 2, 5-furandicarboxylic acid and a catalyst to obtain a mixed material, adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and carrying out esterification reaction for 1 hour at the temperature of 180 ℃ and the pressure of 50KPa, then raising the temperature to 220 ℃, adjusting the reaction pressure to 20kPa, and carrying out reaction for 1 hour; then, the reaction pressure is 50Pa, the reaction time is 8 hours at the temperature of 230 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, discharging is carried out, the obtained crude product is precipitated in water, and the precipitated polycondensate is dried to constant weight in a vacuum drying oven at the temperature of 85 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 4 hours at 60 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 3 times by using ethanol, and finally drying in a vacuum drying oven at 85 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
In the step S1, the molar ratio of the double-end hydroxyl polylactic acid to the 2, 5-furandicarboxylic acid to the catalyst is 1:1: 0.8; the catalyst is zinc acetate; the inert gas is nitrogen.
In the step S2, the mass ratio of the 2-vinyl furan to the 5-allyl-3-methoxy methyl salicylate to the probenazole to the vinyl triethoxysilane to the initiator to the high-boiling-point solvent is 1:1:0.8:0.2:0.03: 14; the initiator is azobisisobutyronitrile; the high boiling point solvent is dimethyl sulfoxide.
In the step S3, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate to the copolymer to the lecithin to the epoxy vegetable oil to the citric acid to the bamboo charcoal fiber is 2:1:0.1:0.1:0.3: 0.1; the epoxidized vegetable oil is epoxidized soybean oil; the epoxidized soybean oil had an epoxy value of 6.2%.
The diameter of the bamboo charcoal fiber is 3 mu m, and the length-diameter ratio is 10: 1; the temperature of the extrusion molding was 190 ℃.
The biomass antibacterial plastic material is prepared according to the preparation method of the biomass antibacterial plastic material.
Example 2
A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the dihydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst to obtain a mixed material, adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and carrying out esterification reaction for 1.5 hours at 185 ℃ and 60KPa, raising the temperature to 225 ℃, adjusting the reaction pressure to 23kPa, and carrying out reaction for 1.2 hours; then, the reaction pressure is 60Pa, the reaction time is 9 hours at the temperature of 233 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and the precipitated polycondensate is dried to constant weight in a vacuum drying oven at the temperature of 87 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 4.5 hours at 63 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 4 times by using ethanol, and finally drying in a vacuum drying oven at 87 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
In the step S1, the molar ratio of the double-end hydroxyl polylactic acid to the 2, 5-furandicarboxylic acid to the catalyst is 1:1: 0.9; the catalyst is zinc chloride; the inert gas is helium.
In the step S2, the mass ratio of the 2-vinyl furan to the 5-allyl-3-methoxy methyl salicylate to the probenazole to the vinyl triethoxysilane to the initiator to the high-boiling-point solvent is 1:1.3:0.9:0.25:0.035: 16; the initiator is azobisisoheptonitrile; the high boiling point solvent is N, N-dimethylformamide.
In the step S3, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate, the copolymer, the lecithin, the epoxy vegetable oil, the citric acid and the bamboo charcoal fiber is 2.3:1:0.13:0.1:0.3: 0.15; the epoxy vegetable oil is epoxy sunflower seed oil; the epoxy value of the epoxy sunflower seed oil is 6.4%.
The diameter of the bamboo charcoal fiber is 5 mu m, and the length-diameter ratio is 12: 1; the temperature of the extrusion molding was 200 ℃.
The biomass antibacterial plastic material is prepared according to the preparation method of the biomass antibacterial plastic material.
Example 3
A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the dihydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst to obtain a mixed material, adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring for esterification reaction for 2 hours at the temperature of 190 ℃ and the pressure of 75KPa, raising the temperature to 230 ℃, adjusting the reaction pressure to 30kPa, and reacting for 1.5 hours; then, the reaction pressure is 65Pa, the reaction time is 10 hours at the temperature of 235 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and the precipitated condensation polymer is dried to constant weight in a vacuum drying oven at the temperature of 90 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid condensation polymer;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 5 hours at 65 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying in a vacuum drying oven at 90 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
In the step S1, the molar ratio of the double-end hydroxyl polylactic acid to the 2, 5-furandicarboxylic acid to the catalyst is 1:1: 1; the catalyst is ethylene glycol antimony; the inert gas is neon.
In the step S2, the mass ratio of the 2-vinyl furan to the 5-allyl-3-methoxy methyl salicylate to the probenazole to the vinyl triethoxysilane to the initiator to the high-boiling-point solvent is 1:1.5:1:0.3:0.04: 17; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide.
In the step S3, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate, the copolymer, the lecithin, the epoxy vegetable oil, the citric acid and the bamboo charcoal fiber is 2.5:1:0.15:0.1:0.3: 0.2; the epoxy vegetable oil is epoxy corn oil; the epoxy value of the epoxy corn oil is 6.0%.
The diameter of the bamboo charcoal fiber is 6 mu m, and the length-diameter ratio is 13: 1; the temperature of the extrusion molding was 210 ℃.
The biomass antibacterial plastic material is prepared according to the preparation method of the biomass antibacterial plastic material.
Example 4
A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the double-end hydroxyl polylactic acid, 2, 5-furandicarboxylic acid and a catalyst to obtain a mixed material, adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and carrying out esterification reaction for 2.5 hours at the temperature of 197 ℃ and the pressure of 90KPa, raising the temperature to 237 ℃, adjusting the reaction pressure to 38kPa, and carrying out reaction for 1.9 hours; then, the reaction pressure is 75Pa, the reaction time is 11 hours at the temperature of 238 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and the precipitated polycondensate is dried to constant weight in a vacuum drying oven at the temperature of 93 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 5.8 hours at 68 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 5 times by using ethanol, and finally drying in a vacuum drying oven at 93 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
In the step S1, the molar ratio of the double-end hydroxyl polylactic acid to the 2, 5-furandicarboxylic acid to the catalyst is 1:1: 1.1; the catalyst is formed by mixing zinc acetate, zinc chloride and ethylene glycol antimony in a mass ratio of 1:2: 4; the inert gas is argon.
In the step S2, the mass ratio of the 2-vinyl furan to the 5-allyl-3-methoxy methyl salicylate to the probenazole to the vinyl triethoxysilane to the initiator to the high-boiling-point solvent is 1:1.8:1.1:0.38:0.045: 18; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide according to a mass ratio of 1:2: 4.
In the step S3, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate, the copolymer, the lecithin, the epoxy vegetable oil, the citric acid and the bamboo charcoal fiber is 2.8:1:0.18:0.1:0.3: 0.28; the epoxy vegetable oil is prepared by mixing epoxy soybean oil, epoxy sunflower seed oil and epoxy corn oil according to the mass ratio of 1:1: 3; the epoxy values of the epoxidized soybean oil and the epoxidized sunflower oil are both 6.6 percent, and the epoxy value of the epoxidized corn oil is 6.4 percent.
The diameter of the bamboo charcoal fiber is 8 mu m, and the length-diameter ratio is 13; the temperature of the extrusion molding was 220 ℃.
The biomass antibacterial plastic material is prepared according to the preparation method of the biomass antibacterial plastic material.
Example 5
A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the double-end hydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst to obtain a mixed material, adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and carrying out esterification reaction for 3 hours at the temperature of 200 ℃ and the pressure of 100KPa, then raising the temperature to 240 ℃, adjusting the reaction pressure to 40kPa, and carrying out reaction for 2 hours; then, the reaction pressure is 80Pa, the reaction time is 12 hours at the temperature of 240 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and the precipitated polycondensate is dried to constant weight in a vacuum drying oven at the temperature of 95 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 6 hours at 70 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 6 times by using ethanol, and finally drying in a vacuum drying oven at 95 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
In the step S1, the molar ratio of the double-end hydroxyl polylactic acid to the 2, 5-furandicarboxylic acid to the catalyst is 1:1: 1.2; the catalyst is ethylene glycol antimony; the inert gas is nitrogen.
In the step S2, the mass ratio of the 2-vinyl furan to the 5-allyl-3-methoxy methyl salicylate to the probenazole to the vinyl triethoxysilane to the initiator to the high-boiling-point solvent is 1:2:1.2:0.4:0.05: 20; the initiator is azobisisobutyronitrile; the high boiling point solvent is N, N-dimethylacetamide.
In the step S3, the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate to the copolymer to the lecithin to the epoxy vegetable oil to the citric acid to the bamboo charcoal fiber is 3:1:0.2:0.1:0.3: 0.3; the epoxidized vegetable oil is epoxidized soybean oil; the epoxidized soybean oil had an epoxy value of 6.6%.
The diameter of the bamboo charcoal fiber is 9 mu m, and the length-diameter ratio is 15: 1; the temperature of the extrusion molding was 230 ℃.
The biomass antibacterial plastic material is prepared according to the preparation method of the biomass antibacterial plastic material.
Comparative example 1
This example provides a biomass antimicrobial plastic material of substantially the same formulation and method of manufacture as in example 1, except that no 2, 5-furandicarboxylic acid/double terminal hydroxy polylactic acid polycondensate was added.
Comparative example 2
This example provides a biomass antimicrobial plastic material having substantially the same formulation and preparation as in example 1, except that no copolymer was added.
Comparative example 3
This example provides a biomass antimicrobial plastic material having substantially the same formulation and preparation as in example 1, except that lecithin and epoxidized vegetable oil were not added.
Comparative example 4
This example provides a biomass antibacterial plastic material having substantially the same formulation and preparation as in example 1, except that no probenazole was added during the preparation of the copolymer.
The biomass antibacterial plastic materials described in examples 1-5 and comparative examples 1-4 are subjected to performance tests, the test results are shown in Table 1, and the test methods are shown in national standards GB/T1040.4-2006, GB/T1843-2008 and QB/T2591-2003 corresponding to the performances in China; wherein the aging resistance is measured by the retention of tensile strength after 100 hours of artificially accelerated aging at 90 ℃.
TABLE 1
As can be seen from table 1, the biomass antibacterial plastic material disclosed in the embodiment of the present invention has excellent mechanical properties, anti-aging properties and antibacterial properties, which are the result of the synergistic effect of the components, compared with the comparative product.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a biomass antibacterial plastic material is characterized by comprising the following steps:
step S1, preparation of 2, 5-furandicarboxylic acid/bishydroxy polylactic acid polycondensate: uniformly mixing the double-end hydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst to obtain a mixed material, then adding the mixed material into a high-pressure reaction kettle, replacing air in the kettle with inert gas, stirring and esterifying for 1-3 hours at the temperature of 180-200 ℃ and the pressure of 50-100KPa, then increasing the temperature to 240 ℃ and the reaction pressure to 20-40kPa, and reacting for 1-2 hours; then, the reaction is carried out for 8-12h under the reaction pressure of 50-80Pa and the temperature of 230-240 ℃, the reaction is cooled to room temperature after the reaction is finished, the pressure is adjusted to normal pressure, the materials are discharged, the obtained crude product is precipitated in water, and then the precipitated condensation polymer is dried to constant weight in a vacuum drying oven at the temperature of 85-95 ℃ to obtain the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid condensation polymer;
step S2, preparation of copolymer: adding 2-vinylfuran, 5-allyl-3-methoxy methyl salicylate, probenazole, vinyltriethoxysilane and an initiator into a high-boiling-point solvent, stirring and reacting for 4-6 hours at 60-70 ℃ in a nitrogen atmosphere, then precipitating in water, washing the precipitated polymer for 3-6 times by using ethanol, and finally drying in a vacuum drying oven at 85-95 ℃ to constant weight to obtain a copolymer;
step S3, material molding: and (2) uniformly mixing the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate prepared in the step (S1), the copolymer prepared in the step (S2), lecithin, epoxy vegetable oil, citric acid and bamboo charcoal fiber to obtain a mixture, and adding the mixture into a double-screw extruder for extrusion molding to obtain the biomass antibacterial plastic material.
2. The preparation method of the biomass antibacterial plastic material as claimed in claim 1, wherein the molar ratio of the double-terminal hydroxyl polylactic acid, the 2, 5-furandicarboxylic acid and the catalyst in step S1 is 1:1 (0.8-1.2).
3. The preparation method of the biomass antibacterial plastic material as claimed in claim 1, wherein the catalyst is at least one of zinc acetate, zinc chloride and ethylene glycol antimony.
4. The method for preparing the biomass antibacterial plastic material according to claim 1, wherein the inert gas is any one of nitrogen, helium, neon and argon.
5. The method for preparing a biomass antibacterial plastic material according to claim 1, wherein the mass ratio of the 2-vinylfuran, the 5-allyl-3-methoxysalicylic acid methyl ester, the allylbenzothiazole, the vinyltriethoxysilane, the initiator and the high boiling point solvent in step S2 is 1 (1-2): 0.8-1.2): 0.2-0.4): 0.03-0.05): 14-20.
6. The method for preparing the biomass antibacterial plastic material as claimed in claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
7. The method for preparing the biomass antibacterial plastic material according to claim 1, wherein the mass ratio of the 2, 5-furandicarboxylic acid/double-end hydroxyl polylactic acid polycondensate, the copolymer, the lecithin, the epoxy vegetable oil, the citric acid and the bamboo charcoal fiber in the step S3 is (2-3) to 1 (0.1-0.2) to 0.1:0.3 (0.1-0.3).
8. The method for preparing the biomass antibacterial plastic material according to claim 1, wherein the epoxy vegetable oil is at least one of epoxy soybean oil, epoxy sunflower oil and epoxy corn oil; the epoxy value of the epoxidized soybean oil and the epoxidized sunflower oil is 6.2 to 6.6 percent, and the epoxy value of the epoxidized corn oil is 6.0 to 6.4 percent.
9. The preparation method of the biomass antibacterial plastic material as claimed in claim 1, wherein the diameter of the bamboo charcoal fiber is 3-9 μm, the length-diameter ratio is (10-15): 1; the temperature of the extrusion molding is 190-230 ℃.
10. The biomass antibacterial plastic material prepared by the preparation method of the biomass antibacterial plastic material according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113232388A (en) * | 2021-06-21 | 2021-08-10 | 宁波长阳科技股份有限公司 | Composite film and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113232388A (en) * | 2021-06-21 | 2021-08-10 | 宁波长阳科技股份有限公司 | Composite film and preparation method and application thereof |
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Application publication date: 20210423 |