CN114685965B - Fully-degradable hard polylactic acid composite material and preparation method thereof - Google Patents
Fully-degradable hard polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polymer composite materials, and discloses a fully-degradable hard polylactic acid composite material which is prepared from degradable resin polylactic acid, polybutylene succinate, an organic-inorganic composite reinforcing material and an auxiliary agent. Firstly, polylactic acid and polybutylene succinate are prepared into a degradable composite resin matrix, then mica powder and plant fibers are modified by triisocyanate to prepare an organic-inorganic composite reinforced material, and finally the degradable composite resin matrix, the organic-inorganic composite reinforced material and an auxiliary agent are melted and blended to prepare the fully degradable hard polylactic acid composite material which not only can be fully degraded, but also has excellent mechanical property, hardness and toughness, can be used for manufacturing food and drink appliances such as lunch boxes, water cups and the like, and is high-temperature resistant, safe and nontoxic.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a fully-degradable hard polylactic acid composite material and a preparation method thereof.
Background
Plastic products are widely used in various fields of our lives because of their light weight and performance. For plastic products containing food and drink, the plastic products are required not to generate toxic substances under the condition of heating, and the safe use of human bodies is guaranteed. The hard food and beverage utensils such as drinking cups, lunch boxes and the like are mainly made of PP resin, and the hard food and beverage utensils are safe, healthy and heatable. However, the problem of white pollution caused by the large amount of PP resin used as an undegradable material is getting worse, and the ecological balance of the earth is deeply affected by the environmental pollution caused by the PP resin.
It is needed to provide a composite material which is nontoxic and fully degradable when heated and used as a material of a hard food and drink appliance so as to solve the problem that the resin releases toxic substances when heated and can not be degraded to pollute the environment in the prior art. However, the currently common degradable resin has the defect of poor comprehensive mechanical property, so that the application and popularization efficiency of the degradable material is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a fully-degradable hard polylactic acid composite material which not only can be fully degraded, but also has excellent mechanical property, good hardness and toughness, can be used for manufacturing food and drink appliances such as lunch boxes, water cups and the like, and is high-temperature resistant, safe and nontoxic.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate at 50-60 ℃ for 12-24h, then carrying out melt mixing at 180-200 ℃, adding dibenzoyl peroxide accounting for 0.5-1.0% of the total mass of the polylactic acid and the polybutylene succinate, continuing melt mixing, and finally extruding, cooling and pelletizing to obtain a degradable composite resin matrix;
step two, heating and melting triisocyanate at 100-110 ℃, adding muscovite powder for banburying for 3-5min, then adding plant fibers for further banburying for 3-5min, and preparing the organic-inorganic composite reinforced material;
and step three, carrying out melt blending on the degradable composite resin matrix, the organic-inorganic composite reinforced material and the auxiliary agent at the temperature of 180-200 ℃, and after melt blending, extruding, cooling and granulating to obtain the fully-degradable hard polylactic acid composite material.
Preferably, the mass ratio of the polylactic acid to the polybutylene succinate is 50-80.
Preferably, the mass ratio of the triisocyanate to the muscovite powder to the plant fiber is 10.
Preferably, the triisocyanate comprises any one of triphenylmethane triisocyanate and L-lysine triisocyanate;
the plant fiber comprises pineapple leaf fiber;
the length of the pineapple leaf fiber is 0.1-1mm;
the particle size of the muscovite powder is 500-1500 meshes, and 800-1500 meshes are preferred.
Preferably, the auxiliary agent comprises an antioxidant and a lubricant;
the mass ratio of the antioxidant to the lubricant is 1:1-5;
the antioxidant comprises any one of an antioxidant 1600 (pentaerythritol diisodecyl diphosphite) and an antioxidant 1608 (triisooctyl phosphite);
the lubricant comprises any one of zinc stearate and calcium stearate.
Preferably, the mass ratio of the degradable composite resin matrix to the organic-inorganic composite reinforcing material to the auxiliary agent is 100-200.
Preferably, in the first step, the drying treatment temperature is 50-60 ℃, and the drying time is 12-24h; the melting and mixing temperature is 180-200 ℃;
in the second step, the heating and melting temperature of the triisocyanate is 100-110 ℃; banburying time is 3-5min, and banburying time is 3-5min;
the melt blending temperature in the third step is 180-200 ℃;
the extrusion, cooling and pelletizing specifically comprise the following steps:
the linear melt extruded from the die hole is drawn into a water cooling device through a drawing roller for cooling treatment;
forming a linear material after cooling;
carrying out grain cutting treatment on the linear material;
the linear speed of the traction is 0.1m/s-3m/s;
the temperature of the linear material formed after the cooling is finished is 30-35 ℃;
the grain size of the fully-degradable hard polylactic acid composite material obtained after the grain cutting is 0.5mm-3mm.
Preferably, the fully-degradable hard polylactic acid composite material is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, polylactic acid and polybutylene succinate are used as raw materials to prepare a degradable composite resin matrix, the polylactic acid is used as a raw material of the most common degradable material, and has the advantages of good glossiness, transparency, high tensile strength and the like, but the polylactic acid has the defects of poor hardness and toughness, lack of flexibility and elasticity, high processing difficulty, poor heat resistance and the like, and the polybutylene succinate has the characteristics of good heat resistance, good flexibility and elasticity and the like;
according to the invention, when the organic-inorganic composite reinforced material is prepared, the muscovite powder is used as the inorganic reinforced material, the mechanical hardness and toughness of the resin can be improved, the plant fiber (pineapple leaf fiber) is used as the organic reinforced material, the antibacterial and deodorant properties are good, the toughness of the resin can be improved, the muscovite powder does not contain components harmful to human health, the mechanical property and the degradability are excellent, the muscovite powder is degraded into a soil matrix, and the final products after the plant fiber is degraded are carbon dioxide and water, so that secondary pollution to the environment can not be caused;
for the muscovite powder with smaller particle size, the surface contains hydroxyl, and the hydroxyl is easy to generate bonding reaction with active groups; triisocyanate is used as a modified monomer, so that the muscovite powder and the plant fiber can be modified together, isocyanate groups (-NCO) have high reaction activity, isocyanate groups on the triisocyanate can react with hydroxyl on the surface of the muscovite powder and hydroxyl in the plant fiber respectively, the inorganic reinforced material and the organic reinforced material are connected through a formed stable chemical bond (amido bond), unreacted isocyanate groups on the triisocyanate can also react with hydroxyl on the upper end position of the degradable resin matrix, and the organic reinforced material plant fiber, the inorganic reinforced material muscovite powder and the degradable resin matrix form a net-shaped structure with good uniformity through the connection effect of the triisocyanate; the reinforcing material is connected with the degradable resin matrix through a stable chemical bond, so that the dispersibility and compatibility of the reinforcing material in the resin matrix can be improved, and the strength and toughness of the composite material are further improved;
the plant fiber is connected with the triisocyanate through the hydroxyl, so that the steric hindrance of plant fiber molecules is increased, the hydrophilicity of the plant fiber is not easily reduced due to the formation of intermolecular and intramolecular hydrogen bonds by the hydroxyl on the surface of the plant fiber, and the compatibility and the interface cohesiveness between the plant fiber and the degradable resin matrix are improved; furthermore, hydroxyl on the surface of the plant fiber and hydroxyl on the surface of the muscovite powder can be connected with carbonyl in a degradable resin matrix molecular chain in a hydrogen bond mode to form a larger network structure, and all raw materials are connected by stable chemical bonds to prepare the composite material with stable structure and performance;
the fully-degradable hard polylactic acid composite material is prepared by taking the degradable resin and the organic-inorganic composite reinforced material as main raw materials, the prepared fully-degradable hard polylactic acid composite material can be fully degraded, the composite material has excellent mechanical property under the reinforcing effect of the organic-inorganic composite reinforced material, the hardness and the toughness are both good, the raw materials are safe and nontoxic, the fully-degradable hard polylactic acid composite material can be used for manufacturing food and drink appliances such as lunch boxes and water cups, the composite material has good high-temperature resistance, toxic substances cannot be generated under the heating condition, and the safety performance is high.
Drawings
FIG. 1 is a schematic diagram of a fully degradable rigid polylactic acid composite material;
FIG. 2 is a schematic diagram of the preparation of an organic-inorganic composite reinforcing material;
FIG. 3 is a schematic diagram of the preparation of a degradable composite resin matrix;
FIG. 4 is a schematic diagram of triisocyanate connecting plant fibers, muscovite powder, degradable resin matrix;
FIG. 5 is a schematic diagram showing the tensile property test results of fully degradable rigid polylactic acid composite materials prepared in examples 1 to 15 and comparative examples 1 to 6;
FIG. 6 is a schematic diagram showing the bending property test results of the fully degradable rigid polylactic acid composite materials prepared in examples 1 to 15 and comparative examples 1 to 6;
FIG. 7 is a schematic diagram of the impact performance test results of fully degradable rigid polylactic acid composite materials prepared in examples 1 to 15 and comparative examples 1 to 6;
FIG. 8 is a schematic diagram of the results of the degradation performance test of the fully degradable rigid polylactic acid composite materials prepared in examples 1 to 15;
wherein R in FIG. 4 is a triphenylmethane group or an L-lysine group.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 80 at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 0.5 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant zinc stearate at the temperature of 180 ℃ according to the mass ratio of 100.5, drawing the linear melt extruded from the die hole into a water cooling device through a drawing roller for cooling treatment after the melting and blending, wherein the linear drawing speed is 0.1m/s, and cutting the linear material into particles after the temperature of the linear material formed after cooling is 30 ℃ to obtain the fully-degradable hard polylactic acid composite material with the particle size of 0.5 mm.
Example 2
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 80 to 20 at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, then adding dibenzoyl peroxide accounting for 0.5 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing to melt and mix, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1608 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 200 to 1, after melting and blending, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment, wherein the linear drawing speed is 3m/s, and after the temperature of the linear material formed after cooling is finished is 35 ℃, cutting the linear material into granules to obtain the fully-degradable hard polylactic acid composite material with the particle size of 3mm.
Example 3
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 80 to 20 at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, then adding dibenzoyl peroxide accounting for 0.5 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing to melt and mix, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforced material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150 to 1, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment after melting and blending, wherein the linear drawing speed is 2.5m/s, and cutting the linear material into granules after the temperature of the linear material formed after cooling is 30 ℃ to obtain the fully-degradable hard polylactic acid composite material with the particle size of 1 mm.
Example 4
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 70;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for continuously banburying for 4min, and preparing the organic-inorganic composite reinforced material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforced material, the antioxidant 1600 and the lubricant zinc stearate at the temperature of 180 ℃ according to the mass ratio of 0.5 to 0.5, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment after melting and blending, wherein the linear drawing speed is 2m/s, and cutting the linear material into particles after the temperature of the linear material formed after cooling is 30 ℃ to obtain the fully-degradable hard polylactic acid composite material with the particle size of 1.5 mm.
Example 5
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 70;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1608 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 200 to 1, after melting and blending, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment, wherein the linear drawing speed is 1.5m/s, and after the temperature of the linear material formed after cooling is finished is 30 ℃, cutting the linear material into granules to obtain the fully-degradable hard polylactic acid composite material with the particle size of 2 mm.
Example 6
Step one, drying polylactic acid and polybutylene succinate with the mass ratio of 70;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
Example 7
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 60 at 60 ℃ for 24h, then carrying out melt mixing at 180 ℃, adding dibenzoyl peroxide accounting for 0.8% of the total mass of the polylactic acid and the polybutylene succinate, continuing melt mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant zinc stearate at the temperature of 180 ℃ according to the mass ratio of 100.5, drawing the linear melt extruded from the die hole into a water cooling device through a drawing roller for cooling treatment after the melting and blending, wherein the linear drawing speed is 0.5m/s, and cutting the linear material into particles after the temperature of the linear material formed after cooling is 30 ℃ to obtain the fully-degradable hard polylactic acid composite material with the particle size of 2.5 mm.
Example 8
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 60 at 60 ℃ for 24h, then carrying out melt mixing at 180 ℃, adding dibenzoyl peroxide accounting for 0.8% of the total mass of the polylactic acid and the polybutylene succinate, continuing melt mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1608 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 200 to 1, after melting and blending, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment, wherein the linear drawing speed is 1m/s, and after the temperature of the linear material formed after cooling is finished is 35 ℃, cutting the linear material into granules to obtain the fully-degradable hard polylactic acid composite material with the particle size of 1 mm.
Example 9
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 60 at 60 ℃ for 24h, then carrying out melt mixing at 180 ℃, adding dibenzoyl peroxide accounting for 0.8% of the total mass of the polylactic acid and the polybutylene succinate, continuing melt mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for continuously banburying for 4min, and preparing the organic-inorganic composite reinforced material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
Example 10
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying 50 mass percent of polylactic acid and 50 mass percent of polybutylene succinate at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 1 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforced material, the antioxidant 1600 and the lubricant zinc stearate at the temperature of 180 ℃ according to the mass ratio of 0.5 to 0.5, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment after melting and blending, wherein the linear drawing speed is 2m/s, and cutting the linear material into particles after the temperature of the linear material formed after cooling is 30 ℃ to obtain the fully-degradable hard polylactic acid composite material with the particle size of 1 mm.
Example 11
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying 50 mass percent of polylactic acid and 50 mass percent of polybutylene succinate at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 1 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1608 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 200 to 1, after melting and blending, drawing the linear melt extruded from the die hole to a water cooling device through a drawing roll for cooling treatment, wherein the linear drawing speed is 2m/s, and after the temperature of the linear material formed after cooling is finished is 30 ℃, cutting the linear material into granules to obtain the fully-degradable hard polylactic acid composite material with the particle size of 1.5 mm.
Example 12
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying 50 mass percent of polylactic acid and 50 mass percent of polybutylene succinate at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 1 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
Example 13
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 50 at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, then adding dibenzoyl peroxide accounting for 1% of the total mass of the polylactic acid and the polybutylene succinate, continuing to melt and mix, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking L-lysine triisocyanate, muscovite powder and pineapple leaf fiber according to the mass ratio of 10;
heating and melting L-lysine triisocyanate at 110 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fiber for continuously banburying for 4min to prepare an organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
Example 14
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying 50 mass percent of polylactic acid and 50 mass percent of polybutylene succinate at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 1 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
Example 15
The preparation method of the fully-degradable hard polylactic acid composite material comprises the following steps:
step one, drying 50 mass percent of polylactic acid and 50 mass percent of polybutylene succinate at 60 ℃ for 24 hours, then melting and mixing at 180 ℃, adding dibenzoyl peroxide accounting for 1 percent of the total mass of the polylactic acid and the polybutylene succinate, continuing melting and mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, melting and blending the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
In examples 1 to 15, muscovite powder was supplied from silver ring chemical limited, guangzhou, having a particle size of 1250 mesh; polylactic acid is provided by anshi Feng Yuanfu tela polylactic acid, ltd, translucent-transparent particles, brand: FY801; polybutylene succinate (also known as polybutylene succinate, PBS) is produced by basf, germany, as off-white granules, cat #: n2350; the pineapple leaf fiber is provided by Yiwuweiwei science and technology Limited, the fiber length is 32-42mm, and the pineapple leaf fiber is used after being cut into the fiber length of 0.5 mm; the CAS number for triphenylmethane triisocyanate is 2422-91-5, supplied by Xin Mingtai chemical Co., ltd, hubei; the CAS number of L-lysine triisocyanate is 69878-18-8, provided by Shanghai-based Bioreagent, inc.; zinc stearate was supplied by guangdong schrader blue, ltd, cat #: S-919C zinc stearate (special for plastics); calcium stearate is supplied by Guangdong Shuddlan chemical Co., ltd, cat No.: s-818 calcium stearate (aqueous process).
Comparative example 1
Compared with the embodiment 1, the degradable composite resin matrix is not prepared in the comparative example 1, only polylactic acid is used as the degradable resin matrix, and the polylactic acid, the organic-inorganic composite reinforcing material and the auxiliary agent are subjected to melt blending to prepare the fully degradable hard polylactic acid composite material, and other conditions are not changed.
Comparative example 2
Compared with the embodiment 1, in the comparative example 2, the organic-inorganic composite reinforcing material is not prepared, the muscovite powder is only used as the reinforcing material, and the fully-degradable hard polylactic acid composite material is prepared by melt blending with the degradable composite resin matrix and the auxiliary agent, and other conditions are not changed.
Comparative example 3
Compared with the embodiment 1, in the comparative example 3, the organic-inorganic composite reinforcing material is not prepared, only the pineapple leaf fiber is used as the reinforcing material, and the pineapple leaf fiber, the degradable composite resin matrix and the auxiliary agent are subjected to melt blending to prepare the fully-degradable hard polylactic acid composite material, and other conditions are not changed.
Comparative example 4
Compared with the embodiment 1, in the comparative example 4, the degradable composite resin matrix and the auxiliary agent are only subjected to melt blending without adding the reinforcing material to prepare the fully-degradable hard polylactic acid composite material, and other conditions are not changed.
Comparative example 5
Compared with the embodiment 1, in the comparative example 5, the organic-inorganic composite reinforced material is not prepared, and the muscovite powder, the pineapple leaf fiber, the degradable composite resin matrix and the auxiliary agent are subjected to melt blending to prepare the fully-degradable hard polylactic acid composite material, and other conditions are not changed.
Test examples
(1) Mechanical property tests were performed on the fully degradable rigid polylactic acid composite materials prepared in examples 1 to 15 and comparative examples 1 to 5:
and (3) testing tensile property: testing according to GB/T1040.2-2006, and testing the bending performance: testing according to GB/T9341-2008, and testing impact performance: the test is carried out according to GB/T1043.1-2018, and the test result is shown in Table 1;
(2) The degradation performance test of the fully degradable hard polylactic acid composite materials prepared in the examples 1 to 15 is carried out: method for determining the carbon dioxide released, using a determination of the ultimate aerobic biological decomposition capacity of the material under controlled composting conditions, according to the standard: GB/T19277.1-2011 (IDTISO 14855-1 2005), the reference material is cellulose, the compost age is 3 months, the test volume is 3L, and the method for measuring carbon dioxide comprises the following steps: the mixed gas at the outlet of the test container is continuously measured by an infrared carbon dioxide analyzer, the amount of the released carbon dioxide is collected and calculated, and the basic characteristics and the detection results of the sample are respectively shown in tables 2 and 3:
TABLE 1
TABLE 2
TABLE 3
As can be seen from Table 1, the fully-degradable hard polylactic acid composite material prepared by the method has excellent mechanical properties, the strength of the composite material can be obviously improved by adding the organic-inorganic composite reinforcing material, so that the mechanical properties of the composite material are improved, and the higher the adding proportion of the organic-inorganic composite reinforcing material is, the better the mechanical properties of the composite material are; the polylactic acid can provide the hardness of the composite material, the polybutylene succinate can endow the composite material with flexibility, the impact performance of the composite material is improved, and the impact performance of the composite material is better along with the improvement of the adding proportion of the polybutylene succinate;
as shown in Table 3, the fully-degradable hard polylactic acid composite material prepared by the invention has excellent degradation performance and high degradation speed, can realize full degradation, and is environment-friendly.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the fully-degradable hard polylactic acid composite material is characterized by comprising the following steps:
step one, drying polylactic acid and polybutylene succinate, then melting and mixing, then adding dibenzoyl peroxide, continuing mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, after heating and melting the triisocyanate, adding muscovite powder for banburying, then adding pineapple leaf fibers for continuously banburying to prepare the organic-inorganic composite reinforced material;
step three, carrying out melt blending on the degradable composite resin matrix, the organic-inorganic composite reinforced material and the auxiliary agent, and after melt blending, extruding, cooling and granulating to obtain a fully degradable hard polylactic acid composite material;
the mass ratio of the polylactic acid to the polybutylene succinate is 50-80;
the mass ratio of the triisocyanate to the muscovite powder to the pineapple leaf fibers is 10-50;
the mass ratio of the degradable composite resin matrix to the organic-inorganic composite reinforcing material to the auxiliary agent is (100-200).
2. The method of claim 1, wherein the triisocyanate comprises any one of triphenylmethane triisocyanate, L-lysine triisocyanate;
the particle size of the muscovite powder is 500-1500 meshes.
3. The method of claim 1, wherein the adjuvants comprise antioxidants, lubricants;
the mass ratio of the antioxidant to the lubricant is 1:1-5;
the antioxidant comprises any one of an antioxidant 1600 and an antioxidant 1608;
the lubricant comprises any one of zinc stearate and calcium stearate.
4. The method according to claim 1, wherein the dibenzoyl peroxide is added in an amount of 0.5-1.0% by mass based on the total mass of the polylactic acid and the polybutylene succinate in the first step.
5. The method according to claim 1, wherein in the first step, the drying treatment temperature is 50-60 ℃, and the drying time is 12-24h; the melting and mixing temperature is 180-200 ℃;
in the second step, the heating melting temperature of the triisocyanate is 100-110 ℃; banburying time is 3-5min, and banburying time is 3-5min;
the melt blending temperature in the third step is 180-200 ℃;
the extrusion, cooling and pelletizing specifically comprise the following steps:
the linear melt extruded from the die hole is drawn into a water cooling device through a drawing roller for cooling treatment;
forming a linear material after cooling;
carrying out grain cutting treatment on the linear material;
the linear speed of the traction is 0.1m/s-3m/s;
the temperature of the linear material formed after the cooling is finished is 30-35 ℃;
the grain size of the fully-degradable hard polylactic acid composite material obtained after the grain cutting is 0.5mm-3mm.
6. The method of claim 1, comprising the steps of:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 70;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, carrying out melt blending on the degradable composite resin matrix, the organic-inorganic composite reinforcing material, the antioxidant 1600 and the lubricant calcium stearate at the temperature of 180 ℃ according to the mass ratio of 150.
7. The method of claim 1, comprising the steps of:
step one, drying polylactic acid and polybutylene succinate with the mass ratio of 60 at 60 ℃ for 24h, then carrying out melt mixing at 180 ℃, adding dibenzoyl peroxide accounting for 0.8% of the total mass of the polylactic acid and the polybutylene succinate, continuing melt mixing, and finally extruding, cooling and granulating to obtain a degradable composite resin matrix;
step two, taking triphenylmethane triisocyanate, muscovite powder and pineapple leaf fibers according to the mass ratio of 10;
heating and melting triphenylmethane triisocyanate at 100 ℃, adding muscovite powder for banburying for 4min, then adding pineapple leaf fibers for further banburying for 4min, and preparing the organic-inorganic composite reinforcing material;
and step three, carrying out melt blending on the degradable composite resin matrix, the organic-inorganic composite reinforced material, the antioxidant 1600 and the lubricant zinc stearate at the temperature of 180 ℃ according to the mass ratio of 100.5.
8. A fully-degradable hard polylactic acid composite material is characterized in that: the fully-degradable hard polylactic acid composite material is prepared by the preparation method according to any one of claims 1 to 7.
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