CN114507426A - Modified nano calcium carbonate composite material and preparation method thereof - Google Patents

Modified nano calcium carbonate composite material and preparation method thereof Download PDF

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CN114507426A
CN114507426A CN202210142964.4A CN202210142964A CN114507426A CN 114507426 A CN114507426 A CN 114507426A CN 202210142964 A CN202210142964 A CN 202210142964A CN 114507426 A CN114507426 A CN 114507426A
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calcium carbonate
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CN114507426B (en
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文经建
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Hunan Jinjian New Material Technology Co ltd
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract

The invention provides a modified nano calcium carbonate composite material and a preparation method thereof, belonging to the technical field of composite materials. The method comprises the following steps: s1, preparing a water phase; s2, preparing porous nano calcium carbonate hollow microspheres; s3, preparing a catalyst solution; s4, preparing modified porous polydopamine/nano calcium carbonate hollow microspheres; s5, preparing modified porous polydopamine/nano calcium carbonate hollow microspheres; s6, processing bagasse; s7, preparing the modified nano calcium carbonate composite material. The modified nano calcium carbonate/PLA composite material prepared by the invention can obviously improve the brittleness, elasticity and toughness of the PLA material, improve the mechanical property of the material, simultaneously improve the degradability and thermal stability of the PLA material, and obviously reduce the cost of the PLA material and improve the degradability and mechanical property after the modified bagasse is added, thereby having wide application prospect.

Description

Modified nano calcium carbonate composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a modified nano calcium carbonate composite material and a preparation method thereof.
Background
Polylactic acid (PLA) is a biodegradable thermoplastic polymer material synthesized by using renewable plant resources as raw materials and lactic acid as a monomer through a chemical method, and has inherent advantages of biodegradability, renewability, biocompatibility, high mechanical strength, high melting temperature, easy processability and the like, and PLA is a substitute for petroleum-based polymers with the best application prospect, and has attracted more and more researchers' attention. PLA has begun to be widely used in the fields of industry, medicine, building materials, transportation, agriculture, electronics, environmental materials, and the like. However, PLA also has significant drawbacks, such as its glassy state at room temperature, brittleness, poor toughness, low elongation at break and notch impact strength, lack of elasticity and flexibility, too slow crystallization rate, poor barrier properties, poor thermal stability, easy degradation during processing, and difficult control of degradation cycle, which limits its application in many aspects. And the PLA has higher price, which increases the cost of raw materials and limits the large-scale commercial application of the PLA. Therefore, in view of the above disadvantages and problems, modification of PLA has become the main research direction of related researchers at home and abroad in recent years. The existing PLA modification methods are many, and the physical blending modification shows obvious advantages due to the economical and practical use.
The nano calcium carbonate is also called ultra-fine calcium carbonate, and the particle size of the nano calcium carbonate is between 0.02 and 0.1 mu m. Because of the superfine nano calcium carbonate particles, the crystal structure and the surface electronic structure of the nano calcium carbonate particles are changed, and the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by the common calcium carbonate are generated. The most mature industry of nano calcium carbonate application is the plastic industry mainly applied to high-grade plastic products. Can improve the rheological property of the plastic master batch and improve the moldability of the plastic master batch. The product can be used as plastic filler with toughening and reinforcing effects, and can improve the bending strength, bending elastic modulus, thermal deformation temperature and dimensional stability of plastic, and endow plastic with heat hysteresis, so that the product can be widely applied to the industrial fields of rubber, plastic, coating and the like.
In the preparation of the traditional nano calcium carbonate reinforced PLA material, the nano calcium carbonate and the PLA resin are simply blended, extruded and granulated, and the calcium carbonate is in a nano structure and is inorganic particles, so that the phenomena of uneven distribution, agglomeration and the like in the PLA resin are easy to occur, the obvious improvement of the performance of the PLA composite material is influenced, and the performance enhancing effect of the prepared PLA composite material is not obvious.
The physical method for preparing the nano calcium carbonate is to grind and crush natural limestone to thin the limestone and then screen calcium carbonate products with different grain size grades in a grading way. But the physical crushing method is rough, the equipment is simple, and the prepared product can hardly reach the nanometer level. The existing production process of the nano calcium carbonate is complex, the production flow is long, continuous production cannot be carried out on carbonization and surface treatment due to the particularity of gas-solid reaction, batch production is adopted at home and abroad at present, the single-batch yield is generally 1000 plus 2000 kilograms, and the control factors of the reaction are wide, and the production process conditions of each batch cannot be completely consistent, so that the quality imbalance of products of each batch is caused, and the application of downstream products is seriously influenced. Meanwhile, due to batch production, the production process is long, the operation is complex, the labor intensity of workers is high, and the production energy consumption is high.
Disclosure of Invention
The invention aims to provide a modified nano calcium carbonate composite material and a preparation method thereof, which can obviously improve the brittleness, elasticity and toughness of a PLA material, improve the mechanical property of the material, improve the degradability and thermal stability of the PLA material, obviously reduce the cost of the PLA material after adding modified bagasse, improve the degradability and mechanical property and have wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a modified nano calcium carbonate composite material, which comprises the following steps:
s1, preparation of a water phase: adding a first pore forming agent into the saturated solution of calcium hydroxide to obtain a water phase;
s2, preparing porous nano calcium carbonate hollow microspheres: adding the water phase prepared in the step S1 into an organic solvent containing a surfactant, emulsifying at a high speed, introducing carbon dioxide gas into the obtained emulsion, repeating the emulsifying and ventilating steps, centrifuging, and drying to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution to obtain catalyst solution;
s4, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing the porous nano calcium carbonate hollow microspheres prepared in the step S2 in water, adding the catalyst solution prepared in the step S3, dopamine hydrochloride and a second pore-forming agent, stirring for reaction, filtering, and washing with water to obtain porous polydopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4 and a first coupling agent into an ethanol water solution, heating for reaction, centrifuging, and drying to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying bagasse, crushing, sieving, adding NaOH solution, stirring, mixing, reacting, filtering, washing to neutrality, drying, adding ethanol solution, adding a second coupling agent, heating for reaction, filtering, and drying to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (4) adding the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, the modified bagasse prepared in the step S6 and PLA resin into a continuous mixing roll for mixing and granulation to obtain a continuous mixing master batch, and feeding the continuous mixing master batch into a double-screw extruder for extrusion and granulation to obtain the modified nano calcium carbonate composite material.
As a further improvement of the present invention, in step S1, the first pore-forming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene octyl phenyl ether and polyoxyethylene sorbitan fatty acid ester; the content of the pore-forming agent in the water phase is 1-3 wt%.
As a further improvement of the invention, the surfactant in step S2 is selected from at least one of span-80, glyceryl monostearate, monoalkyl ether phosphate, cetyl palmitate, starch octenyl succinate; the content of the surfactant in the organic solvent is 2-5 wt%; the organic solvent is at least one selected from toluene, xylene, cyclohexane, n-hexane, petroleum ether, ethyl acetate, methyl acetate, dichloromethane, trichloromethane and chloroform; the rotating speed in the high-speed emulsification is 10000-12000r/min, and the emulsification time is 5-10 min; introducing carbon dioxide for 10-15min, and ventilating at 5-10L/min; the emulsification and aeration steps were repeated 3-7 times. Water-in-oil surfactants are beneficial for faster and more stable formation of water-in-oil microemulsions, thereby forming stable water-in-oil micro-droplets.
As a further improvement of the present invention, in step S3, the cobalt salt is at least one selected from cobalt chloride, cobalt sulfate and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.5-8.5; co in the catalyst solution2+The ion concentration is 3-5 wt%. Containing Co2+The ionic Tris-HCl buffer solution can effectively catalyze the reaction speed of the polydopamine.
As a further improvement of the present invention, in step S4, the second porogen is selected from at least one of cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20, PEO106-PPO70-PEO 106; the mass ratio of the porous nano calcium carbonate hollow microspheres to the catalyst solution to the dopamine hydrochloride to the second pore-foaming agent is 100: (5-10): (15-30): (0.2-0.7). After the porous polydopamine/nano calcium carbonate hollow microspheres are formed under the action of the first pore-forming agent and the second pore-forming agent and added into PLA resin, PLA molecular chains can penetrate through the microspheres from the pores, so that the molecular chains are not broken to influence the performance of the material.
As a further improvement of the invention, in the step S5, the first coupling agent comprises an aluminate coupling agent and a first titanate coupling agent, and the mass ratio is (2-5): (1-3); the aluminate coupling agent is selected from at least one of SG-Al821, DL-411AF, DL-411D, DL-411DF and ASA; the first titanate coupling agent is selected from at least one of TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-2, TMC-27 and TMC-4; the ethanol content in the ethanol water solution is 50-70 wt%; the mass ratio of the porous polydopamine/nano calcium carbonate hollow microspheres to the first coupling agent is 100: (3-8); the heating temperature is 65-80 ℃, and the reaction time is 3-5 h.
As a further improvement of the invention, the mesh number of the sieved screen in the step S6 is 200-500 meshes; the concentration of the NaOH solution is 5-10 wt%; the solid-liquid ratio of the bagasse to the NaOH solution is 1: (5-10) g/mL; the second coupling agent is a second titanate coupling agent; at least one selected from TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-2, TMC-27 and TMC-4; the mass ratio of the bagasse to the second titanate coupling agent is 100: (2-5); the heating reaction temperature is 70-80 ℃, and the time is 3-5 h.
As a further improvement of the invention, the mass ratio of the modified porous polydopamine/nano calcium carbonate hollow microspheres, the modified bagasse and the PLA resin in the step S7 is (2-7): (5-12): 100, respectively; the mixing temperature is 110-120 ℃, the extrusion temperature is 150-170 ℃, the die head temperature is 145-155 ℃, and the mixing speed is 30-50 r/min; the extrusion granulation temperature is 140-170 ℃, and the screw rotation speed is 150-200 r/min.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, preparation of a water phase: adding a first pore-forming agent into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the pore-forming agent is 1-3 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding the water phase prepared in the step S1 into an organic solvent containing 2-5 wt% of a surfactant, emulsifying for 5-10min at the rotating speed of 10000-12000r/min, introducing carbon dioxide gas into the obtained emulsion for 10-15min, wherein the air flow is 5-10L/min, repeating the emulsifying and air introducing steps for 3-7 times, centrifuging, and drying to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution with pH value of 7.5-8.5 to obtain Co2+A catalyst solution having an ion concentration of 3 to 5 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in water, adding 5-10 parts by weight of the catalyst solution prepared in the step S3, 15-30 parts by weight of dopamine hydrochloride and 0.2-0.7 part by weight of a second pore-forming agent, stirring for reaction, filtering and washing to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 2-5 parts by weight of an aluminate coupling agent and 1-3 parts by weight of a first titanate coupling agent into 50-70 wt% of ethanol water solution, heating to 65-80 ℃, reacting for 3-5h, centrifuging, and drying to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving with a 200-mesh sieve and a 500-mesh sieve, adding into a 5-10 wt% NaOH solution, stirring, mixing, reacting, filtering, washing to neutrality, drying, then adding into an ethanol solution, adding 2-5 parts by weight of a second titanate coupling agent, heating to 70-80 ℃, reacting for 3-5h, filtering, and drying to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: adding 2-7 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 5-12 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulation, wherein the mixing temperature is 110-120 ℃, the extrusion temperature is 150-170 ℃, the die head temperature is 145-155 ℃, and the mixing rotation speed is 30-50r/min, so as to obtain a continuous mixing master batch, and then feeding the continuous mixing master batch into a double-screw extruder for extrusion granulation, wherein the extrusion granulation temperature is 140-170 ℃, and the screw rotation speed is 150-200r/min, so as to obtain the modified nano calcium carbonate composite material.
The invention further protects the modified nano calcium carbonate composite material prepared by the preparation method.
The invention has the following beneficial effects: in the presence of a surfactant, mixing and emulsifying a calcium hydroxide saturated solution and an organic solvent to form uniform and stable single-phase microemulsion, introducing carbon dioxide, forming a calcium carbonate shell layer on the surface of a microemulsion droplet, and forming porous calcium carbonate nano hollow microspheres under the action of a pore-forming agent; further, the surface of the prepared porous nano calcium carbonate hollow microsphere is further coated with a poly dopamine layer, the polyhydroxy structure of poly dopamine enables the prepared porous poly dopamine/nano calcium carbonate hollow microsphere to be easily subjected to hydrogen bond formation with an ester group of a PLA molecular chain in subsequent mixing with PLA resin, so that the dispersibility and compatibility of the nano microsphere are improved, and in addition, the heat stability of the resin can be improved when the poly dopamine modified microsphere is added into the PLA resin; then, modifying the surfaces of an aluminate coupling agent and a titanate coupling agent, wherein alkyl groups of the titanate coupling agent and the aluminate coupling agent are partially hydrolyzed and combined with hydroxyl groups on the surfaces of the microspheres, so that the surfaces of the calcium carbonate nano microspheres are hydrophobic, and the other ends of the calcium carbonate nano microspheres can be further wound with PLA molecular chains in subsequent reactions, thereby improving the dispersibility of the microspheres in PLA resin; the synergistic modification of the titanate coupling agent and the aluminate coupling agent can not only improve the dispersibility of the microspheres in the PLA resin, but also enhance the toughness and elasticity of the prepared composite material; after the porous polydopamine/nano calcium carbonate hollow microspheres are formed under the action of the first pore-forming agent and the second pore-forming agent and added into PLA resin, PLA molecular chains can penetrate through the microspheres from the pores, so that the molecular chains are not broken to influence the performance of the material;
after the nano calcium carbonate is added into the PLA material, the calcium carbonate particles increase the distance between the plastic macromolecule molecules, weaken the acting force between PLA molecule chain segments, hinder the re-crosslinking of macromolecule free radicals and accelerate the biodegradability of the PLA material; meanwhile, in a buried humid environment, calcium carbonate is chemically corroded, can be directly utilized as a carbon source by part of inorganic nutritional microorganisms, and can be improved in solubility under the synergistic effect of organic acid generated by the microorganisms in the soil, nitric acid and sulfuric acid generated by nitrobacteria and sulfuration bacteria, so that the degradation process of the PLA material is greatly accelerated by the calcium carbonate.
The bagasse is fibrous residue obtained after sugarcane juice is extracted from the sugarcane through crushing and squeezing, is also a main byproduct of the sugar industry, is low in cost, and is subjected to alkali treatment, a large number of hydroxyl groups are formed on the surface and are further modified with a titanate coupling agent, the alkyl end of the titanate coupling agent is hydrolyzed and connected with the hydroxyl groups on the surface of the bagasse, and the other end of the titanate coupling agent can be wound with a PLA molecular chain, so that the dispersibility of the bagasse in PLA resin is improved; the cost of the PLA resin added with the modified bagasse is obviously reduced, and meanwhile, the mechanical property is improved to a certain extent;
the modified nano calcium carbonate/PLA composite material prepared by the invention can obviously improve the brittleness, elasticity and toughness of the PLA material, improve the mechanical property of the material, simultaneously improve the degradability and thermal stability of the PLA material, and obviously reduce the cost of the PLA material and improve the degradability and mechanical property after the modified bagasse is added, thereby having wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in example 1 of the present invention;
FIG. 2 is a TEM image of the modified porous polydopamine/nano calcium carbonate hollow microsphere prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Bagasse was purchased from Xianggui Co., Ltd, guest, Guangxi province;
the nano calcium carbonate added in comparative example 1 was purchased from Guangxi Virbon calcium science, Inc.
Example 1
The embodiment provides a preparation method of a modified nano calcium carbonate composite material, which specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 1 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of methyl acetate containing 2 wt% of monoalkyl ether phosphate, emulsifying for 5min at the rotating speed of 10000r/min, introducing carbon dioxide gas into the obtained emulsion for 10min, introducing the air flow for 5L/min, repeating the emulsifying and air introducing steps for 3 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt sulfate in Tris-HCl buffer solution with pH value of 7.5 to obtain Co2+A catalyst solution having an ion concentration of 3 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 5 parts by weight of the catalyst solution prepared in the step S3, 15 parts by weight of dopamine hydrochloride and 0.2 part by weight of hexadecyl trimethyl ammonium bromide, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 2 parts by weight of aluminate coupling agent DL-411DF and 1 part by weight of acid ester coupling agent TMC-102 into 200 parts by weight of 50 wt% ethanol water solution, heating to 65 ℃, reacting for 3h, centrifuging at 3000r/min for 15min, and drying at 70 ℃ for 2h to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres; fig. 1 is an SEM image of the prepared modified porous polydopamine/nano calcium carbonate hollow microsphere, and it can be seen from the SEM image that many pores are formed on the surface of the microsphere prepared by the present invention, and the particle size is generally less than 200 nm; fig. 2 is a TEM image of the prepared modified porous polydopamine/nano calcium carbonate hollow microsphere, and it can be seen from the TEM image that the modified porous polydopamine/nano calcium carbonate hollow microsphere prepared by the invention has a hollow structure.
S6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 200-mesh sieve, adding 200 parts by weight of a 5 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of an ethanol solution, adding 2 parts by weight of a titanate coupling agent TMC-201, heating to 70 ℃, reacting for 3 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: adding 2 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 5 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulation, wherein the mixing temperature is 110 ℃, the extrusion temperature is 150 ℃, the die head temperature is 145 ℃, the mixing rotation speed is 30r/min, so as to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extrusion granulation, the extrusion granulation temperature is 140 ℃, and the screw rotation speed is 150r/min, so as to obtain the modified nano calcium carbonate composite material.
Example 2
The embodiment provides a preparation method of a modified nano calcium carbonate composite material, which specifically comprises the following steps:
s1, preparation of a water phase: adding polyethylene glycol octyl phenyl ether into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyethylene glycol octyl phenyl ether is 3 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of cyclohexane containing 5 wt% of octenyl succinate starch, emulsifying for 10min at the rotating speed of 12000r/min, introducing carbon dioxide gas into the obtained emulsion for 15min, introducing the air flow for 10L/min, repeating the emulsifying and air introducing steps for 7 times, centrifuging for 15min at 3000r/min, and drying at 70 ℃ for 2h to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8.5 to obtain Co2+A catalyst solution having an ion concentration of 5 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 10 parts by weight of the catalyst solution prepared in the step S3, 30 parts by weight of dopamine hydrochloride and 0.7 part by weight of oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous polydopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 5 parts by weight of aluminate coupling agent SG-Al821 and 3 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 70 wt% ethanol aqueous solution, heating to 80 ℃, reacting for 5 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 500-mesh sieve, adding 200 parts by weight of 10 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 5 parts by weight of titanate coupling agent TMC-27, heating to 80 ℃, reacting for 5 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: adding 7 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 12 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 120 ℃, the extrusion temperature is 170 ℃, the die head temperature is 155 ℃, the mixing rotation speed is 50r/min, so as to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extrusion and granulation, the extrusion and granulation temperature is 170 ℃, and the screw rotation speed is 200r/min, so as to obtain the modified nano calcium carbonate composite material.
Example 3
The embodiment provides a preparation method of a modified nano calcium carbonate composite material, which specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 3.5 parts by weight of aluminate coupling agent DL-411 and 2 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol aqueous solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 9 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, and the mixing rotation speed is 40r/min to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extruding and granulating, wherein the extruding and granulating temperature is 155 ℃, and the screw rotation speed is 170r/min to obtain the modified nano calcium carbonate composite material.
Example 4
In step S5, the aluminate coupling agent DL-411 was not added, as compared with example 3, and the other conditions were not changed.
The method specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4 and 5.5 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol aqueous solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 9 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, and the mixing rotation speed is 40r/min to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extruding and granulating, wherein the extruding and granulating temperature is 155 ℃, and the screw rotation speed is 170r/min to obtain the modified nano calcium carbonate composite material.
Example 5
Compared with the example 3, the titanate coupling agent TMC-101 is not added in the step S5, and other conditions are not changed.
The method specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microsphere prepared in the step S4 and 5.5 parts by weight of aluminate coupling agent DL-411 into 200 parts by weight of 60 wt% ethanol aqueous solution, heating to 72 ℃, reacting for 4h, centrifuging at 3000r/min for 15min, and drying at 70 ℃ for 2h to prepare a modified porous polydopamine/nano calcium carbonate hollow microsphere;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 9 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, and the mixing rotation speed is 40r/min to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extruding and granulating, wherein the extruding and granulating temperature is 155 ℃, and the screw rotation speed is 170r/min to obtain the modified nano calcium carbonate composite material.
Comparative example 1
Compared with the example 3, the steps S1 and S2 are not carried out, the purchased nano calcium carbonate is directly added, and other conditions are not changed.
The method specifically comprises the following steps:
s1, preparation of a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s2, preparing polydopamine/nano calcium carbonate: uniformly dispersing 100 parts by weight of nano calcium carbonate in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain polydopamine/nano calcium carbonate;
s3, preparing modified polydopamine/nano calcium carbonate: adding 100 parts by weight of polydopamine/nano calcium carbonate prepared in the step S2, 3.5 parts by weight of aluminate coupling agent DL-411 and 2 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol water solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified polydopamine/nano calcium carbonate;
s4, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s5, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified polydopamine/nano calcium carbonate prepared in the step S3, 9 parts by weight of the modified bagasse prepared in the step S4 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, the mixing rotating speed is 40r/min, so as to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extrusion and granulation, the extrusion and granulation temperature is 155 ℃, and the screw rotating speed is 170r/min, so as to obtain the modified nano calcium carbonate composite material.
Comparative example 2
Steps S3 and S4 were not performed, and other conditions were not changed, as compared with example 3.
The method specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing the modified porous nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2, 3.5 parts by weight of aluminate coupling agent DL-411 and 2 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol water solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous nano calcium carbonate hollow microspheres;
s4, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s5, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S3, 9 parts by weight of the modified bagasse prepared in the step S4 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, and the mixing rotation speed is 40r/min to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extruding and granulating, wherein the extruding and granulating temperature is 155 ℃, and the screw rotation speed is 170r/min to obtain the modified nano calcium carbonate composite material.
Comparative example 3
Compared with the example 3, the titanate coupling agent TMC-4 is not modified in the step S6, and other conditions are not changed.
The method specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 3.5 parts by weight of aluminate coupling agent DL-411 and 2 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol aqueous solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, and drying at 70 ℃ for 2 hours to obtain bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (2) adding 5 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 9 parts by weight of the bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, the mixing rotating speed is 40r/min, so as to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extrusion and granulation, the extrusion and granulation temperature is 155 ℃, and the screw rotating speed is 170r/min, so as to obtain the modified nano calcium carbonate composite material.
Comparative example 4
Compared with example 3, no modified bagasse was added, and other conditions were not changed.
The method specifically comprises the following steps:
s1, preparation of a water phase: adding polyoxyethylene sorbitan fatty acid ester into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the polyoxyethylene sorbitan fatty acid ester is 2 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding 50 parts by weight of the water phase prepared in the step S1 into 70 parts by weight of ethyl acetate containing 3.5 wt% of span-80, emulsifying for 7min at the rotating speed of 11000r/min, introducing carbon dioxide gas into the obtained emulsion for 12min, introducing air flow of 7L/min, repeating the emulsifying and air introducing steps for 5 times, centrifuging for 15min at 3000r/min, and drying for 2h at 70 ℃ to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain Co2+A catalyst solution having an ion concentration of 4 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in 200 parts by weight of water, adding 7 parts by weight of the catalyst solution prepared in the step S3, 22 parts by weight of dopamine hydrochloride and 0.5 part by weight of PEO106-PPO70-PEO106, heating to 40 ℃, stirring for reaction for 5 hours, filtering, and washing with deionized water to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 3.5 parts by weight of aluminate coupling agent DL-411 and 2 parts by weight of titanate coupling agent TMC-101 into 200 parts by weight of 60 wt% ethanol aqueous solution, heating to 72 ℃, reacting for 4 hours, centrifuging at 3000r/min for 15 minutes, and drying at 70 ℃ for 2 hours to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, preparing the modified nano calcium carbonate composite material: and (2) adding 14 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5 and 100 parts by weight of PLA resin into a continuous mixing roll for mixing and granulating, wherein the mixing temperature is 115 ℃, the extrusion temperature is 160 ℃, the die head temperature is 150 ℃, the mixing rotating speed is 40r/min, so as to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder for extruding and granulating, the extrusion and granulating temperature is 155 ℃, and the screw rotating speed is 170r/min, so as to obtain the modified nano calcium carbonate composite material.
Comparative example 5
Compared with the example 3, the modified porous polydopamine/nano calcium carbonate hollow microspheres are not added, and other conditions are not changed.
The method specifically comprises the following steps:
s1, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving the crushed bagasse with a 300-mesh sieve, adding 200 parts by weight of 7 wt% NaOH solution, stirring, mixing, reacting, filtering, washing with water to neutrality, drying at 70 ℃ for 2 hours, then adding 200 parts by weight of ethanol solution, adding 3.5 parts by weight of titanate coupling agent TMC-4, heating to 75 ℃, reacting for 4 hours, filtering, and drying at 70 ℃ for 2 hours to obtain modified bagasse;
s2, preparing the modified nano calcium carbonate composite material: and (2) adding 14 parts by weight of the modified bagasse obtained in the step S2 and 100 parts by weight of PLA resin into a continuous mixing roll, mixing and granulating at the mixing temperature of 115 ℃, the extrusion temperature of 160 ℃, the die head temperature of 150 ℃ and the mixing rotation speed of 40r/min to obtain a continuous mixing master batch, feeding the continuous mixing master batch into a double-screw extruder, and extruding and granulating at the extrusion granulation temperature of 155 ℃ and the screw rotation speed of 170r/min to obtain the modified nano calcium carbonate composite material.
Test example 1 mechanical Properties and thermo-oxidative aging resistance test
The modified nano calcium carbonate composite materials prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to mechanical property test, followed by aging at 100 ℃ for 50 hours, and the same property test was performed.
The tensile strength is tested according to GB/T1040.1-2018, the tensile speed is 50mm/min, and each sample is tested for 5 times and the average value is taken.
The bending strength is tested according to GB/T9341-2008, the speed is 2mm/min, and each sample is tested for 5 times and an average value is taken;
notched impact strength was tested according to GB/T1843-2008, V notch, and the prepared specimens were left at room temperature for 24 hours before testing.
The hardness is carried out according to GB/T3512-2014, a digital display Shore A durometer is utilized, and 5-point average test is adopted to test the hardness of the material.
The results are shown in Table 1.
TABLE 1
Figure BDA0003507186460000221
Figure BDA0003507186460000231
As can be seen from the table above, the modified nano calcium carbonate composite material prepared by the invention has good mechanical property and thermal-oxidative aging resistance.
Test example 2 degradable Property test
Method for determining the final aerobic biological decomposition capacity of a material under controlled composting conditions, according to GB/T19277.1-2011 part 1 of the method for determining the carbon dioxide released: general method the modified nano calcium carbonate composite materials prepared in examples 1 to 5 and comparative examples 1 to 5 were tested for degradability with a treatment time of 30 days, and the results are shown in table 2.
TABLE 2
Group of Biological decomposition Rate (%)
Example 1 94
Example 2 95
Example 3 97
Example 4 92
Example 5 91
Comparative example 1 90
Comparative example 2 89
Comparative example 3 78
Comparative example 4 67
Comparative example 5 69
As can be seen from the table above, the modified nano calcium carbonate composite material prepared by the invention has good biodegradability.
Compared with the embodiment 3, the embodiment 4 and the embodiment 5 adopt a single titanate coupling agent or aluminate coupling agent for modification, and the mechanical property of the prepared composite material is slightly reduced, wherein the bending strength is obviously reduced. According to the invention, an aluminate coupling agent and a titanate coupling agent are modified on the surfaces, alkyl groups of the titanate coupling agent and the aluminate coupling agent are partially hydrolyzed and combined with hydroxyl groups on the surfaces of the microspheres, so that the surfaces of the calcium carbonate nano microspheres are hydrophobic, and the other ends of the calcium carbonate nano microspheres can be further wound with PLA molecular chains in subsequent reactions, thereby improving the dispersibility of the microspheres in PLA resin; the synergistic modification of the titanate coupling agent and the aluminate coupling agent can not only improve the dispersibility of the microspheres in the PLA resin, but also enhance the toughness and elasticity of the prepared composite material.
Compared with the example 3, the comparative example 1 has no steps of S1 and S2, directly adds the purchased nano calcium carbonate, is a solid nano material, and has poorer dispersibility and compatibility in PLA resin than the example 3 although being coated by polydopamine and modified by a coupling agent, thereby leading to the reduction of mechanical property; according to the invention, the coupling agent is modified on the surface, alkyl groups of the titanate coupling agent and the aluminate coupling agent are partially hydrolyzed and combined with hydroxyl groups on the surface of the microsphere, so that the surface of the calcium carbonate nano microsphere is hydrophobic, and the other end of the calcium carbonate nano microsphere can be further wound with a PLA molecular chain in the subsequent reaction, thereby improving the dispersibility of the microsphere in the PLA resin; the synergistic modification of the titanate coupling agent and the aluminate coupling agent can not only improve the dispersibility of the microspheres in the PLA resin, but also enhance the toughness and elasticity of the prepared composite material; after the porous polydopamine/nano calcium carbonate hollow microspheres are formed under the action of the first pore-forming agent and the second pore-forming agent and added into PLA resin, PLA molecular chains can penetrate through the microspheres from the pores, so that the molecular chains are not broken to influence the performance of the material.
Compared with the example 3, the steps S3 and S4 are not carried out, and the prepared porous nano calcium carbonate hollow microspheres are not modified by polydopamine, so that the mechanical property and the thermo-oxidative aging resistance are reduced. The surface of the prepared porous nano calcium carbonate hollow microsphere is further coated with a polydopamine layer, the polyhydroxy structure of polydopamine enables the prepared porous polydopamine/nano calcium carbonate hollow microsphere to be easily subjected to hydrogen bond formation with an ester group of a PLA molecular chain in subsequent mixing with PLA resin, so that the dispersibility and compatibility of the nano microsphere are improved, and in addition, the heat stability of the resin can be improved by adding the microsphere into the PLA resin after polydopamine modification
Compared with the example 3, the bagasse in the step S6 is not modified by the titanate coupling agent TMC-4, and the mechanical property and the degradability are reduced, because a large amount of hydroxyl groups are formed on the surface of the bagasse after alkali treatment, and are further modified by the titanate coupling agent, the alkyl terminal of the titanate coupling agent is hydrolyzed and connected with the hydroxyl groups on the surface of the bagasse, and the other end of the titanate coupling agent can be wound with a PLA molecular chain, so that the dispersibility of the bagasse in PLA resin is improved; the cost of the PLA resin added with the modified bagasse is obviously reduced, and the mechanical property is improved to a certain extent.
Compared with the embodiment 3, the modified bagasse is not added, the mechanical property is slightly reduced, the degradability is obviously reduced, the cost of the PLA material is obviously reduced, the degradability and the mechanical property are improved after the modified bagasse is added, and the application prospect is wide.
Compared with the embodiment 3, the modified porous polydopamine/nano calcium carbonate hollow microspheres are not added, the mechanical property is greatly reduced, and the thermo-oxidative aging resistance is obviously reduced. The modified porous polydopamine/nano calcium carbonate hollow microspheres have small particle size, enter a PLA matrix, occupy the space in the PLA matrix material, destroy the interaction between PLA molecular chains, have adhesive force between the nano particles and polylactic acid, form a plurality of physical entanglement points, and bear larger acting force at the formed entanglement points, thereby increasing the notch impact strength. After the nano calcium carbonate is added into the PLA material, the calcium carbonate particles increase the distance between the plastic macromolecule molecules, weaken the acting force between PLA molecule chain segments, hinder the re-crosslinking of macromolecule free radicals and accelerate the biodegradability of the PLA material; meanwhile, in a buried humid environment, calcium carbonate is chemically corroded, can be directly utilized as a carbon source by part of inorganic nutritional microorganisms, and can be improved in solubility under the synergistic effect of organic acid generated by the microorganisms in the soil, nitric acid and sulfuric acid generated by nitrobacteria and sulfuration bacteria, so that the degradation process of the PLA material is greatly accelerated by the calcium carbonate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The preparation method of the modified nano calcium carbonate composite material is characterized by comprising the following steps:
s1, preparation of a water phase: adding a first pore forming agent into the saturated solution of calcium hydroxide to obtain a water phase;
s2, preparing porous nano calcium carbonate hollow microspheres: adding the water phase prepared in the step S1 into an organic solvent containing a surfactant, emulsifying at a high speed, introducing carbon dioxide gas into the obtained emulsion, repeating the emulsifying and ventilating steps, centrifuging, and drying to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution to obtain catalyst solution;
s4, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing the porous nano calcium carbonate hollow microspheres prepared in the step S2 in water, adding the catalyst solution prepared in the step S3, dopamine hydrochloride and a second pore-forming agent, stirring for reaction, filtering, and washing with water to obtain porous polydopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4 and a first coupling agent into an ethanol water solution, heating for reaction, centrifuging, and drying to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, bagasse treatment: drying bagasse, crushing, sieving, adding NaOH solution, stirring, mixing, reacting, filtering, washing to neutrality, drying, adding ethanol solution, adding a second coupling agent, heating for reaction, filtering, and drying to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: and (4) adding the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, the modified bagasse prepared in the step S6 and PLA resin into a continuous mixing roll for mixing and granulation to obtain a continuous mixing master batch, and feeding the continuous mixing master batch into a double-screw extruder for extrusion and granulation to obtain the modified nano calcium carbonate composite material.
2. The method for preparing a modified nano calcium carbonate composite material according to claim 1, wherein the first pore-forming agent in step S1 is at least one selected from the group consisting of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene octylphenyl ether, and polyoxyethylene sorbitan fatty acid ester; the content of the pore-forming agent in the water phase is 1-3 wt%.
3. The method for preparing a modified nano calcium carbonate composite material according to claim 1, wherein the surfactant is selected from at least one of span-80, glyceryl monostearate, monoalkyl ether phosphate, cetyl palmitate and starch octenyl succinate in step S2; the content of the surfactant in the organic solvent is 2-5 wt%; the organic solvent is at least one selected from toluene, xylene, cyclohexane, n-hexane, petroleum ether, ethyl acetate, methyl acetate, dichloromethane, trichloromethane and chloroform; the rotating speed in the high-speed emulsification is 10000-12000r/min, and the emulsification time is 5-10 min; introducing carbon dioxide for 10-15min, and ventilating at 5-10L/min; the emulsification and aeration steps were repeated 3-7 times.
4. According to claim 1The preparation method of the modified nano calcium carbonate composite material is characterized in that in the step S3, the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.5-8.5; co in the catalyst solution2+The ion concentration is 3-5 wt%.
5. The method for preparing the modified nano calcium carbonate composite material according to claim 1, wherein the second pore-forming agent in the step S4 is at least one selected from cetyl trimethyl ammonium bromide, oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20, PEO106-PPO70-PEO 106; the mass ratio of the porous nano calcium carbonate hollow microspheres to the catalyst solution to the dopamine hydrochloride to the second pore-foaming agent is 100: (5-10): (15-30): (0.2-0.7).
6. The method for preparing the modified nano calcium carbonate composite material according to claim 1, wherein the first coupling agent in the step S5 comprises an aluminate coupling agent and a first titanate coupling agent, and the mass ratio is (2-5): (1-3); the aluminate coupling agent is selected from at least one of SG-Al821, DL-411AF, DL-411D, DL-411DF and ASA; the first titanate coupling agent is selected from at least one of TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-2, TMC-27 and TMC-4; the ethanol content in the ethanol water solution is 50-70 wt%; the mass ratio of the porous polydopamine/nano calcium carbonate hollow microspheres to the first coupling agent is 100: (3-8); the heating temperature is 65-80 ℃, and the reaction time is 3-5 h.
7. The method for preparing modified nano calcium carbonate composite material as claimed in claim 1, wherein the mesh number of the sieved mesh in step S6 is 200-500 meshes; the concentration of the NaOH solution is 5-10 wt%; the solid-liquid ratio of the bagasse to the NaOH solution is 1: (5-10) g/mL; the second coupling agent is a second titanate coupling agent; at least one selected from TMC-201, TMC-102, TMC-101, TMC-311w, TMC-311, TMC-3, TMC-2, TMC-27 and TMC-4; the mass ratio of the bagasse to the second titanate coupling agent is 100: (2-5); the heating reaction temperature is 70-80 ℃, and the time is 3-5 h.
8. The preparation method of the modified nano calcium carbonate composite material according to claim 1, wherein the mass ratio of the modified porous polydopamine/nano calcium carbonate hollow microspheres, the modified bagasse and the PLA resin in step S7 is (2-7): (5-12): 100, respectively; the mixing temperature is 110-120 ℃, the extrusion temperature is 150-170 ℃, the die head temperature is 145-155 ℃, and the mixing speed is 30-50 r/min; the extrusion granulation temperature is 140-170 ℃, and the screw rotation speed is 150-200 r/min.
9. The method for preparing the modified nano calcium carbonate composite material according to any one of claims 1 to 8, which is characterized by comprising the following steps:
s1, preparation of a water phase: adding a first pore-forming agent into the calcium hydroxide saturated solution to obtain a water phase, wherein the content of the pore-forming agent is 1-3 wt%;
s2, preparing porous nano calcium carbonate hollow microspheres: adding the water phase prepared in the step S1 into an organic solvent containing 2-5 wt% of a surfactant, emulsifying for 5-10min at the rotating speed of 10000-12000r/min, introducing carbon dioxide gas into the obtained emulsion for 10-15min, wherein the air flow is 5-10L/min, repeating the emulsifying and air introducing steps for 3-7 times, centrifuging, and drying to obtain the porous nano calcium carbonate hollow microspheres;
s3, preparing a catalyst solution: dissolving cobalt salt in Tris-HCl buffer solution with pH value of 7.5-8.5 to obtain Co2+A catalyst solution having an ion concentration of 3 to 5 wt%;
s4, preparing porous polydopamine/nano calcium carbonate hollow microspheres: uniformly dispersing 100 parts by weight of the porous nano calcium carbonate hollow microspheres prepared in the step S2 in water, adding 5-10 parts by weight of the catalyst solution prepared in the step S3, 15-30 parts by weight of dopamine hydrochloride and 0.2-0.7 part by weight of a second pore-forming agent, stirring for reaction, filtering and washing to obtain porous poly dopamine/nano calcium carbonate hollow microspheres;
s5, preparing the modified porous polydopamine/nano calcium carbonate hollow microspheres: adding 100 parts by weight of the porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S4, 2-5 parts by weight of an aluminate coupling agent and 1-3 parts by weight of a first titanate coupling agent into 50-70 wt% of ethanol water solution, heating to 65-80 ℃, reacting for 3-5h, centrifuging, and drying to prepare modified porous polydopamine/nano calcium carbonate hollow microspheres;
s6, processing bagasse: drying and crushing 100 parts by weight of bagasse, sieving with a 200-mesh sieve and a 500-mesh sieve, adding into a 5-10 wt% NaOH solution, stirring, mixing, reacting, filtering, washing to neutrality, drying, then adding into an ethanol solution, adding 2-5 parts by weight of a second titanate coupling agent, heating to 70-80 ℃, reacting for 3-5h, filtering, and drying to obtain modified bagasse;
s7, preparing the modified nano calcium carbonate composite material: adding 2-7 parts by weight of the modified porous polydopamine/nano calcium carbonate hollow microspheres prepared in the step S5, 5-12 parts by weight of the modified bagasse prepared in the step S6 and 100 parts by weight of PLA resin into a continuous mixing mill for mixing and granulation, wherein the mixing temperature is 110-120 ℃, the extrusion temperature is 150-170 ℃, the die head temperature is 145-155 ℃ and the mixing rotation speed is 30-50r/min, so as to obtain a continuous mixing master batch, and then feeding the continuous mixing master batch into a double-screw extruder for extrusion granulation, wherein the extrusion granulation temperature is 140-170 ℃, and the screw rotation speed is 150-200r/min, so as to obtain the modified nano calcium carbonate composite material.
10. A modified nano calcium carbonate composite material prepared by the preparation method according to any one of claims 1 to 9.
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