CN110615977B - Multifunctional polylactic acid composite material and preparation method thereof - Google Patents
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Abstract
The invention discloses a multifunctional polylactic acid composite material, which is prepared by the steps of carrying out mixed crosslinking reaction on biobased polyester functionalized graphene and polylactic acid/biobased polyester blend, preparing the composite material by casting film formation or melt extrusion and injection molding, and obtaining the multifunctional polylactic acid composite material with different strength and toughness by changing the addition amount of the biobased polyester functionalized graphene; wherein the addition amount of the biobased polyester functionalized graphene is 1-15% of the polylactic acid/biobased polyester blend. According to the invention, by adding the bio-based polyester functionalized graphene, the polylactic acid/bio-based polyester composite material is converted from an insulator to a semiconductor material to be applied to the antistatic field, and has excellent flame retardant property, so that the application range of the polylactic acid in the fields of flame retardant materials and antistatic materials is widened, an important function of the graphene is developed, and the application range of the graphene is greatly widened.
Description
Technical Field
The invention relates to a multifunctional polylactic acid composite material and a preparation method thereof, belonging to the technical field of composite materials.
Background
With the development of science and technology, various petroleum-based polymer materials have been integrated into the lives of people due to their excellent properties. However, the pollution caused by the petroleum-based polymer products which are widely used due to the difficulty in degradation seriously threatens the living environment of people. Biomass polymer materials have attracted increasing attention due to their excellent biodegradability, because the widespread use of biomass polymer materials not only reduces the dependence on fossil resources, but also is environmentally friendly. Polylactic acid is also called polylactide, is a novel environment-friendly polymer material obtained by ring-opening polymerization of lactic acid prepared from bio-based corn starch as a monomer, and can be finally and completely degraded into an environment-friendly end product. In recent years, the compound has been widely used in the fields of agriculture, food packaging, medical care and the like because of its advantages such as high mechanical strength, easy processing, high melting point, biodegradability and good biocompatibility. The widespread use of polylactic acid in various fields has led to a continuous demand for enhanced flame retardancy and mechanical properties of polylactic acid. The tendency of polylactic acid to burn hinders their industrial use due to its flammable nature, which is composed of elements such as carbon, hydrogen, oxygen, etc. The addition of flame retardants is a widely used strategy to inhibit the burning of polymeric materials. Halogen-based compounds are suitable choices for improving the flame retardancy of polymers, which provide high flame retardant efficiency and relatively slight deterioration of mechanical properties. However, corrosive and toxic gases generated during the combustion of halogen-based compounds have serious secondary hazards to the environment and humans, which has prompted the development of halogen-free flame retardants. Metal hydroxides are the most promising choice in the field of halogen-free flame retardants. However, the flame-retardant efficiency of metal hydroxide-based flame retardants is always low, and thus very large filler addition amounts are required to obtain satisfactory flame-retardant properties. This inevitably leads to a severe deterioration of the mechanical properties of the polymer composite.
The graphene is a two-dimensional carbon nanomaterial, has a two-dimensional carbon atom crystal of an sp2 hybrid orbit, has a honeycomb crystal structure, has the advantages of high strength, high conductivity, high barrier property and the like, and can improve the mechanical property, the flame retardance and the electrical property of the polymer nanocomposite. The raw material natural graphite has sufficient resources and low price. Therefore, the method has wide application prospect. The preparation of the nano composite material by adding the graphene into the polymer is the focus of the research on the preparation of the high-performance composite material at present. The graphene can endow the polylactic acid with excellent flame retardant property and conductive property, but the mechanical property of the polylactic acid is reduced due to the inherent rigidity of the graphene. Therefore, how to prepare polylactic acid with good mechanical toughness to widen its application range while improving its flame retardant property is very demanding.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property and a preparation method thereof
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the reaction mechanism of the invention is as follows: the method (1) regulates and controls the surface tension of graphene through solvent-free chemically synthesized bio-based polyester, and reduces the graphene to recover the excellent conductivity; (2) introducing bio-based polyester polybutylene succinate and polypropylene carbonate as a second phase of the composite material, utilizing entanglement of an active polyester chain segment on the bio-based polyester functionalized graphene and a polylactic acid molecular chain and a polybutylene succinate molecular chain to anchor the bio-based polyester functionalized graphene on an interface of a polylactic acid/polybutylene succinate mixture, and promoting the phase of the polypropylene carbonate to evolve into a network structure to toughen the polylactic acid. More importantly, the graphene layer can undergo sintering and form a dense carbon layer, which isolates oxygen and absorbs heat, reduces the temperature of the mixture during combustion, and can realize high flame retardant performance even if a small amount of bio-based polyester modified reduced graphene oxide is added, while imparting excellent antistatic performance thereto.
A multifunctional polylactic acid composite material is prepared by mixing and crosslinking bio-based polyester functionalized graphene (RGP) and polylactic acid/bio-based polyester blend, and preparing the composite material by casting film formation or melt extrusion and injection molding; wherein the addition amount of the bio-based polyester functionalized graphene is 1-15% of the mass of the polylactic acid/bio-based polyester blend.
Further, the polylactic acid/bio-based polyester blend is a polylactic acid/polybutylene succinate blend, and the mass ratio of the polylactic acid to the polybutylene succinate is one of 9:1, 8:2, 7:3 and 6: 4.
Further, the polylactic acid/bio-based polyester blend is a polylactic acid/polypropylene carbonate blend, and the mass ratio of the polylactic acid to the local propylene carbonate is one of 9:1, 8:2, 7:3 and 6: 4.
A preparation method of a multifunctional polylactic acid composite material comprises the following steps:
dispersing graphene oxide in tetrahydrofuran, and dropwise adding toluene diisocyanate and 1, 4-butanediol to react to obtain functionalized graphene oxide; then, carrying out a high-temperature polycondensation reaction on citric acid and polyethylene glycol to obtain a prepolymer, and adding 2, 2-bis (hydroxymethyl) propionic acid, glycerol and the functionalized graphene oxide into the prepolymer to react to obtain bio-based polyester functionalized graphene oxide;
uniformly dispersing the bio-based polyester functionalized graphene oxide in deionized water, and adding ammonia water and hydrazine hydrate for reduction reaction to obtain the bio-based polyester functionalized graphene;
adding bio-based polyester functionalized graphene into a trichloromethane solution of a polylactic acid/bio-based polyester blend, stirring for reaction, and volatilizing a solvent to obtain the multifunctional polylactic acid composite material;
or uniformly mixing the polylactic acid/biobased polyester blend and the biobased polyester functionalized graphene, and performing melt extrusion molding to obtain the multifunctional polylactic acid composite material.
Further, the mass ratio of the graphene oxide to the toluene diisocyanate is 4: 1.
further, the mass ratio of the polylactic acid/bio-based polyester blend to the chloroform is 1: 10.
Further, the addition amount of the bio-based polyester functionalized graphene is 1-15% of the mass of the polylactic acid/bio-based polyester blend.
Further, the polylactic acid/bio-based polyester blend is a polylactic acid/polybutylene succinate blend or a polylactic acid/polypropylene carbonate blend.
The invention achieves the following beneficial effects:
(1) the bio-based polyester functionalized graphene, polylactic acid, poly (butylene succinate) and poly (propylene carbonate) are subjected to solution mixing and casting film forming or melt extrusion and injection molding to prepare the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property. Compared with pure polylactic acid/poly (butylene succinate), the toughness of the polylactic acid/poly (propylene carbonate) composite material is increased by 22.6% and 27.4%, and the polylactic acid/poly (butylene succinate) and the polylactic acid/poly (propylene carbonate) composite material are converted from an insulator to a semiconductor material to be applied to the antistatic field, have excellent flame retardant property and widen the application range of the polylactic acid in the fields of flame retardant materials and antistatic materials;
(2) the application range of the graphene is greatly expanded, the surface tension of the graphene is controlled by performing bio-based polyester functionalization on the surface of the graphene, so that the two phases of the polylactic acid composite material have different distribution tendencies, the graphene is positioned in a polylactic acid/polybutylene succinate and polylactic acid/polypropylene carbonate matrix to realize controllable adjustment, the graphene is used as a toughening agent, a flame retardant and multiple roles of a conductive network in the polylactic acid matrix, an important function of the graphene is developed, and a new application direction is developed for the graphene which is industrially produced in the future.
Drawings
FIG. 1 is a heat release rate curve of the polylactic acid composite of example 1;
FIG. 2 is a heat release rate curve of the polylactic acid composite of example 2;
FIG. 3 is a graph of the conductivity of a polylactic acid composite;
FIG. 4 is a graph of the mechanical properties of the polylactic acid/polypropylene carbonate composite material;
FIG. 5 is a graph showing the mechanical properties of the polylactic acid/polybutylene succinate composite material.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
(1) Preparation of bio-based polyester functionalized graphene
Firstly, graphene oxide was prepared by a modified Hummers method, graphene oxide was dispersed in tetrahydrofuran by ultrasonic treatment, the dispersed graphene oxide was placed in a three-necked flask equipped with a stirrer and a nitrogen inlet, and toluene diisocyanate was added dropwise to the above graphene oxide suspension at room temperature, wherein the mass ratio of graphene oxide to toluene diisocyanate was 4: 1, adding 1, 4-butanediol into the mixture to obtain the required functionalized graphene oxide. The free reactants/components were separated by centrifugation and the functionalized graphene oxide was washed with tetrahydrofuran. The obtained functionalized graphene oxide was dried in a vacuum oven.
Then reacting citric acid with polyethylene glycol-200 at 140 ℃ to obtain a prepolymer, adding 2, 2-bis (hydroxymethyl) propionic acid and glycerol with the functionalized graphene oxide to obtain bio-based polyester functionalized graphene oxide, and reducing by using hydrazine hydrate, wherein the reduction reaction temperature is 100 ℃. And cooling to room temperature, filtering and washing by using a Buchner funnel to obtain filter residue, and then carrying out freeze drying for 48 hours by using a freeze dryer to obtain the bio-based polyester functionalized graphene.
(2) Preparation of polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property
Taking 1g of dried polylactic acid/polybutylene succinate, wherein the mass ratio of polylactic acid to polybutylene succinate is 9:1, dissolving the polylactic acid/polybutylene succinate in 20g of trichloromethane solution, magnetically stirring the solution at room temperature for 7h to obtain a clear and transparent solution, adding 0.05g of functionalized bio-based polyester functionalized graphene, continuously stirring the solution for 12h to prepare a flat and regular film material, pouring the solution after reaction into an evaporation dish of polytetrafluoroethylene, and volatilizing the solvent at room temperature for 1 week to obtain the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property.
Or uniformly mixing the polylactic acid/polybutylene succinate and the bio-based polyester functionalized graphene in the same mass ratio in the steps, and then performing melt extrusion molding to prepare the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property.
Example 2
(1) Preparation of bio-based polyester functionalized graphene
Preparation of biobased polyester functionalized graphene as per example 1
(2) Preparation of polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property
1g of dried polylactic acid/polypropylene carbonate (the mass ratio of polylactic acid to polypropylene carbonate is 8: 2) is dissolved in 20g of trichloromethane solution, the solution is magnetically stirred at room temperature for 7h to obtain clear and transparent solution, 0.05g of functionalized bio-based polyester functionalized graphene is added, the solution is continuously stirred for 12h to prepare a flat and regular film material, the reacted solution is poured into an evaporation dish of polytetrafluoroethylene, and the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property is obtained after the solvent is volatilized at room temperature for 1 week.
Or uniformly mixing the polylactic acid/polybutylene succinate and the bio-based polyester functionalized graphene in the same mass ratio in the steps, and then performing melt extrusion molding to prepare the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property.
Example 3
(1) Preparation of bio-based polyester functionalized graphene
Preparation of biobased polyester functionalized graphene as per example 1
(2) Preparation of polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property
1g of dried polylactic acid/polypropylene carbonate (the mass ratio of polylactic acid to polypropylene carbonate is 8: 2) is dissolved in 20g of trichloromethane solution, the solution is magnetically stirred at room temperature for 7h to obtain clear and transparent solution, 0.07g of bio-based polyester functionalized graphene is added, then the stirring is continued for 12h to prepare a flat and regular film material, the reacted solution is poured into an evaporation dish of polytetrafluoroethylene, and the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property is obtained after the solvent is volatilized for 1 week at room temperature.
Or uniformly mixing the polylactic acid/polybutylene succinate and the bio-based polyester functionalized graphene in the same mass ratio in the steps, and then performing melt extrusion molding to prepare the polylactic acid composite material with high toughness, excellent flame retardant property and antistatic property.
Comparative example 1
The polylactic acid/polybutylene succinate composite material is characterized in that the mass ratio of polylactic acid to polybutylene succinate is 9: 1.
Comparative example 2
Uniformly dispersing graphene oxide in deionized water, adding ammonia water and hydrazine hydrate for reduction reaction at the reaction temperature of 100 ℃ to obtain the reduced graphene oxide.
Taking 1g of dried polylactic acid/poly butylene succinate, wherein the mass ratio of the polylactic acid to the poly butylene succinate is 9:1, dissolving the polylactic acid/poly butylene succinate in 20g of chloroform solution, magnetically stirring the solution at room temperature for 7 hours to obtain clear and transparent solution, and adding 0.05g of reduced graphene oxide. And then continuously stirring for 12h, pouring the reacted solution into an evaporation dish of polytetrafluoroethylene to prepare a flat and regular membrane material, and volatilizing the solvent at room temperature for 1 week to obtain the polylactic acid/polybutylene succinate/reduced graphene oxide composite material.
Comparative example 3
The polylactic acid/polypropylene carbonate composite material is characterized in that the mass ratio of the polylactic acid to the polypropylene carbonate is 8: 2.
Comparative example 4
Uniformly dispersing graphene oxide in deionized water, adding ammonia water and hydrazine hydrate for reduction reaction at the reaction temperature of 100 ℃ to obtain the reduced graphene oxide.
Dissolving 1g of dried polylactic acid/polypropylene carbonate (the mass ratio of polylactic acid to polypropylene carbonate is 8: 2) in 20g of chloroform solution, magnetically stirring at room temperature for 7h to obtain a clear and transparent solution, adding 0.05g of reduced graphene oxide, and then continuously stirring for 12h to prepare a flat and regular membrane material, pouring the reacted solution into an evaporation dish of polytetrafluoroethylene, and volatilizing the solvent at room temperature for 1 week to obtain the polylactic acid/polypropylene carbonate/reduced graphene oxide composite material.
The tensile properties of the polylactic acid/polybutylene succinate/graphene, polylactic acid/polypropylene carbonate/graphene prepared in the above examples and comparative examples are shown in table 1.
TABLE 1 comparison of tensile Properties of polylactic acid composites
In table 1, PLA is polylactic acid, PBS is polybutylene succinate, PPC is polypropylene carbonate, RGO is reduced graphene oxide, and RGP is bio-based polyester functionalized graphene.
The heat release rate curve of the polylactic acid composite material measured by a micro calorimeter is shown in figure 1 and figure 2, and the heat release rate of the pure polylactic acid/polybutylene succinate and pure polylactic acid/polypropylene carbonate composite material is very high and reaches 603.52Wg-1And 573.12Wg-1When 5% reduced graphene oxide and 5% bio-based polyester functionalized graphene are added respectively, the peak heat release rates of the polylactic acid/polybutylene succinate and polylactic acid/polypropylene carbonate composite materials are from 603.52Wg-1Reduced to 464.92Wg-1And 492.93Wg-1，573.12Wg-1Reduced to 431.59Wg-1And 490.22Wg-1. Due to the physical barrier effect of the graphene in the matrix, the polymer and a heat source are mutually isolated, so that the flame retardant property is improved. The peak heat release rate of the composite containing biobased polyester functionalized graphene was slightly higher than the peak heat release rate of the composite containing reduced graphene oxide, which may be attributed to the oxygen-containing groups on the surface of the labile biobased polyester functionalized graphene that may lead to outgassing behavior between layers in the polymer matrix during the test. Then graphene layers are damaged or stacked together, so that the thermal stability and the flame retardance are slightly reduced, but compared with pure polylactic acid/polybutylene succinate, the polylactic acid/polypropylene carbonate composite material still has good flame retardance and high mechanical toughness, which is excellent mechanical property which cannot be achieved by the graphene-containing composite material, and the flame retardance is inevitably lost while the mechanical property is improved.
In addition, due to the excellent conductivity of the graphene, the electrical properties of the polylactic acid composite material can be improved. The conductivity of the polylactic acid composite material was measured using four probes, and the corresponding curve and image are shown in fig. 3. In our previous studies, the conductivity of the pure polylactic acid composite was probably 1 x 10-16Left and right, but when addedWhen 5% of the bio-based polyester functionalized graphene is adopted, the conductivity of the composite material of the polylactic acid/polypropylene carbonate/5% of the bio-based polyester functionalized graphene and the polylactic acid/polybutylene succinate/5% of the bio-based polyester functionalized graphene reaches 8.09 to 10-5S/m and 1.65 x 10-5S/m, the required conductivity range of the antistatic material is reached. This is mainly due to the fact that the bio-based polyester functionalized graphene forms a stable 3D conductive network inside the polylactic acid composite. Although the electrical conductivity is slightly lower than that of a composite material containing graphene in the same addition amount, the mechanical toughness is excellent, and the composite material can be used for an antistatic material, which is a multiple of performances that cannot be achieved by a composite material containing graphene.
The invention endows the graphene with multiple functions of serving as a toughening agent, a flame retardant and a conductive network in a polylactic acid matrix, so that the polylactic acid composite material has high toughness, flame retardant performance and antistatic performance, and simultaneously solves the problem that the high toughness, the flame retardant performance and the antistatic performance of the material are difficult to coexist in the material. The defect of original brittleness is overcome, the flame retardant property and the antistatic property of the antistatic flame retardant polymer material are greatly improved, the application field of the antistatic flame retardant polymer material is greatly widened, an optimized solution is particularly provided on the design of the antistatic flame retardant polymer material, and the antistatic flame retardant polymer material conforms to the concept of sustainable development of a modern green bio-based material.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The multifunctional polylactic acid composite material is characterized by being prepared by mixing and crosslinking bio-based polyester functionalized graphene and polylactic acid/bio-based polyester blend, wherein the addition amount of the bio-based polyester functionalized graphene is 1-15% of the mass of the polylactic acid/bio-based polyester blend;
the preparation method of the multifunctional polylactic acid composite material comprises the following steps:
dispersing graphene oxide in tetrahydrofuran, and dropwise adding toluene diisocyanate and 1, 4-butanediol to react to obtain functionalized graphene oxide; then, carrying out polycondensation reaction on citric acid and polyethylene glycol to obtain a prepolymer, and adding 2, 2-bis (hydroxymethyl) propionic acid, glycerol and the functionalized graphene oxide into the prepolymer for reaction to obtain bio-based polyester functionalized graphene oxide;
uniformly dispersing the bio-based polyester functionalized graphene oxide in deionized water, and adding ammonia water and hydrazine hydrate for reduction reaction to obtain the bio-based polyester functionalized graphene;
preparing a trichloromethane solution of polylactic acid/bio-based polyester blend, adding bio-based polyester functionalized graphene, stirring for reaction, and volatilizing a solvent to obtain the multifunctional polylactic acid composite material; or uniformly mixing the polylactic acid/bio-based polyester blend with the bio-based polyester functionalized graphene, and performing melt extrusion molding to obtain the multifunctional polylactic acid composite material.
2. The multifunctional polylactic acid composite material as claimed in claim 1, wherein the polylactic acid/bio-based polyester blend is a polylactic acid/polybutylene succinate blend, and the mass ratio of the polylactic acid to the polybutylene succinate is one of 9:1, 8:2, 7:3 and 6: 4.
3. The multifunctional polylactic acid composite material as claimed in claim 1, wherein the polylactic acid/bio-based polyester blend is a polylactic acid/polypropylene carbonate blend, and the mass ratio of the polylactic acid to the polypropylene carbonate is one of 9:1, 8:2, 7:3 and 6: 4.
4. A preparation method of a multifunctional polylactic acid composite material is characterized by comprising the following steps:
dispersing graphene oxide in tetrahydrofuran, and dropwise adding toluene diisocyanate and 1, 4-butanediol to react to obtain functionalized graphene oxide; then, carrying out polycondensation reaction on citric acid and polyethylene glycol to obtain a prepolymer, and adding 2, 2-bis (hydroxymethyl) propionic acid, glycerol and the functionalized graphene oxide into the prepolymer for reaction to obtain bio-based polyester functionalized graphene oxide;
uniformly dispersing the bio-based polyester functionalized graphene oxide in deionized water, and adding ammonia water and hydrazine hydrate for reduction reaction to obtain the bio-based polyester functionalized graphene;
preparing a trichloromethane solution of polylactic acid/bio-based polyester blend, adding bio-based polyester functionalized graphene, stirring for reaction, and volatilizing a solvent to obtain the multifunctional polylactic acid composite material; or uniformly mixing the polylactic acid/bio-based polyester blend with the bio-based polyester functionalized graphene, and performing melt extrusion molding to obtain the multifunctional polylactic acid composite material.
5. The preparation method of the multifunctional polylactic acid composite material as claimed in claim 4, wherein the mass ratio of the graphene oxide to the toluene diisocyanate is 4: 1.
6. the method for preparing the multifunctional polylactic acid composite material as claimed in claim 4, wherein the mass ratio of the polylactic acid/bio-based polyester blend to the chloroform is 1: 10.
7. The preparation method of the multifunctional polylactic acid composite material as claimed in claim 4, wherein the addition amount of the bio-based polyester functionalized graphene is 1-15% of the mass of the polylactic acid/bio-based polyester blend.
8. The method of any one of claims 4, 6 or 7, wherein the polylactic acid/bio-based polyester blend is a polylactic acid/polybutylene succinate blend or a polylactic acid/polypropylene carbonate blend.
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