CN113402741B - Rare earth modified fiber reinforced polylactic acid and preparation method thereof - Google Patents
Rare earth modified fiber reinforced polylactic acid and preparation method thereof Download PDFInfo
- Publication number
- CN113402741B CN113402741B CN202110755637.1A CN202110755637A CN113402741B CN 113402741 B CN113402741 B CN 113402741B CN 202110755637 A CN202110755637 A CN 202110755637A CN 113402741 B CN113402741 B CN 113402741B
- Authority
- CN
- China
- Prior art keywords
- solution
- polylactic acid
- rare earth
- fiber
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides rare earth modified fiber reinforced polylactic acid and a preparation method thereof, and relates to the technical field of biodegradable packaging materials. The invention combines the solution blending method and the hot pressing method to prepare the high-content fiber-filled polylactic acid composition with good mechanical property. Firstly, the rare earth modified cellulose fiber can reduce the hydrophilicity of the hydroxyl on the surface of the cellulose fiber, and can improve the compatibility of the cellulose fiber and polylactic acid through the strong coordination relationship between rare earth ions and oxygen in the polylactic acid; the flocculant is added, so that the uniform mixing of the cellulose fibers and the polylactic acid can be effectively kept, and the delamination caused by sedimentation is prevented; then, the invention adopts hot pressing to improve the compactness of the cellulose fiber and the polylactic acid and fix the orientation of the cellulose fiber; finally, the biodegradable rare earth modified fiber reinforced polylactic acid with ultrahigh tensile strength and tensile modulus is obtained.
Description
Technical Field
The invention relates to the technical field of biodegradable packaging materials, in particular to rare earth modified fiber reinforced polylactic acid and a preparation method thereof.
Background
The bio-based material is one of strategic emerging industries of the country and is also one of materials which are put forward to be developed intensively by the country. Abundant biomass resources are fully utilized, environment-friendly biodegradable materials are developed, traditional high polymer materials are replaced to the maximum extent, and the problem of environmental pollution caused by plastic wastes difficult to degrade is expected to be relieved. Among several developed biodegradable materials, polylactic acid is called one of the most potential products due to its better mechanical properties, but its mechanical properties need to be improved compared with the conventional engineering plastics.
Cellulose fibers have high tensile strength and high tensile modulus, and the filling of modified polylactic acid with the cellulose fibers is an effective way for improving the mechanical properties of the cellulose fibers.
Disclosure of Invention
The invention aims to provide rare earth modified fiber reinforced polylactic acid and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of rare earth modified fiber reinforced polylactic acid, which comprises the following steps:
mixing a rare earth compound, cellulose fiber and water to obtain a solution A;
dissolving polylactic acid in an organic solvent to obtain a solution B;
blending the solution A and the solution B to obtain a solution C;
mixing the solution C with a flocculating agent to obtain a solution D;
removing water and organic solvent from the solution D to obtain a solid E;
and carrying out hot pressing on the solid E to obtain the rare earth modified fiber reinforced polylactic acid.
Preferably, the mass ratio of the polylactic acid to the cellulose fiber to the rare earth compound to the flocculating agent is 20-90: 5-70: 1-10: 1 to 10.
Preferably, theThe rare earth compound comprises LnO2、Ln2O3、Ln(NO3)3、Ln(CO3)2、Ln2(CO3)3、Ln(P2O4)3、Ln(P5O7)3、Ln2(SO4)3、Ln2(C2O4)3、Ln(C8H15O2)3And Ln (ClO)3At least one of; wherein Ln is at least one of La, Ce, Tb, Pr, Dy, Yb, Eu, Tm, Sm and Nd.
Preferably, the rare earth compound comprises CeO2、La2O3、Ce(CO3)2、Tm2(CO3)3、Yb2(SO4)3、Pr(NO3)3、Ce(P2O4)3、Ce(C8H15O2)3、La(P5O7)3、Eu2(C2O4)3、La(ClO)3And Sm (ClO)3At least one of (1).
Preferably, the cellulose fibers comprise at least one of nanocellulose, softwood fibers, hardwood fibers, and gramineous fibers.
Preferably, the polylactic acid includes at least one of levorotatory polylactic acid, dextrorotatory polylactic acid, and a copolymer of levorotatory polylactic acid and dextrorotatory polylactic acid.
Preferably, the flocculant comprises at least one of polyacrylamide, ferric aluminium polysilicate, ferric polysilicate sulfate and polydimethyl diallyl ammonium chloride.
Preferably, the organic solvent includes at least one of dichloromethane, chloroform, toluene, xylene, and acetone.
Preferably, the pressure of the hot pressing is 10-30 MPa; the hot pressing temperature is 170-200 ℃; and the hot pressing time is 2-6 min.
The invention provides the rare earth modified fiber reinforced polylactic acid prepared by the preparation method in the technical scheme.
The invention provides a preparation method of rare earth modified fiber reinforced polylactic acid, which comprises the following steps: mixing a rare earth compound, cellulose fiber and water to obtain a solution A; dissolving polylactic acid in an organic solvent to obtain a solution B; blending the solution A and the solution B to obtain a solution C; mixing the solution C with a flocculating agent to obtain a solution D; removing water and organic solvent from the solution D to obtain a solid E; and carrying out hot pressing on the solid E to obtain the rare earth modified fiber reinforced polylactic acid. The invention combines the solution blending method and the hot pressing method to prepare the high-content fiber-filled polylactic acid composition with good mechanical property. Firstly, the rare earth modified cellulose fiber can reduce the hydrophilicity of the hydroxyl on the surface of the cellulose fiber, and can improve the compatibility of the cellulose fiber and polylactic acid through the strong coordination relationship between rare earth ions and oxygen in the polylactic acid; the flocculant is added, so that the uniform mixing of the cellulose fibers and the polylactic acid can be effectively kept, and the delamination caused by sedimentation is prevented; then, the invention adopts hot pressing to improve the compactness of the cellulose fiber and the polylactic acid and fix the orientation of the cellulose fiber; finally, the biodegradable rare earth modified fiber reinforced polylactic acid with ultrahigh tensile strength and tensile modulus is obtained.
Detailed Description
The invention provides a preparation method of rare earth modified fiber reinforced polylactic acid, which comprises the following steps:
mixing a rare earth compound, cellulose fiber and water to obtain a solution A;
dissolving polylactic acid in an organic solvent to obtain a solution B;
blending the solution A and the solution B to obtain a solution C;
mixing the solution C with a flocculating agent to obtain a solution D;
removing water and organic solvent from the solution D to obtain a solid E;
and carrying out hot pressing on the solid E to obtain the rare earth modified fiber reinforced polylactic acid.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes rare earth compound, cellulose fiber and water to obtain solution A. In the invention, the mass ratio of the rare earth compound to the cellulose fiber is preferably 1-10: 5-70, more preferably 3-5: 10-60, and further preferably 3-5: 20 to 50.
In the present invention, the rare earth compound preferably includes LnO2、Ln2O3、Ln(NO3)3、Ln(CO3)2、Ln2(CO3)3、Ln(P2O4)3、Ln(P5O7)3、Ln2(SO4)3、Ln2(C2O4)3、Ln(C8H15O2)3And Ln (ClO)3At least one of; wherein Ln is at least one of La, Ce, Tb, Pr, Dy, Yb, Eu, Tm, Sm and Nd. Preferably, the rare earth compound preferably comprises CeO2、La2O3、Ce(CO3)2、Tm2(CO3)3、Yb2(SO4)3、Pr(NO3)3、Ce(P2O4)3、Ce(C8H15O2)3、La(P5O7)3、Eu2(C2O4)3、La(ClO)3And Sm (ClO)3At least one of (1). In a particular embodiment of the invention, when the rare earth compound is Ce (P)2O4)3And Ce (C)8H15O2)3In the case of the mixture of (1), the Ce (P)2O4)3And Ce (C)8H15O2)3Is preferably 2: 3; when the rare earth compound is CeO2And La (ClO)3In the mixture of (1), the CeO2And La (ClO)3The mass ratio of (a) to (b) is preferably 1: 1; when the rare earth compound is Sm (ClO)3、Pr(NO3)3And Ce (C)8H15O2)3In the case of a mixture of (1), Sm (ClO)3、Pr(NO3)3And Ce (C)8H15O2)3The mass ratio of (b) is preferably 1:1: 1.
In the present invention, the cellulose fiber preferably includes at least one of nanocellulose (20 to 100nm), softwood fiber (1.5 to 5.6mm in length and 30 to 75 μm in width), hardwood fiber (0.7 to 1.7mm in length and 20 to 40 μm in width), and gramineous plant fiber (1 to 1.5mm in length and 10 to 20 μm in width). In a specific embodiment of the present invention, when the cellulose fiber is a mixture of nanocellulose and softwood fiber, the mass ratio of nanocellulose to softwood fiber is preferably 4: 3; when the cellulose fiber is a mixture of hardwood fibers and gramineous plant fibers, the mass ratio of the hardwood fibers to the gramineous plant fibers is preferably 1: 1; when the cellulose fiber is a mixture of nano-cellulose, hardwood fiber and gramineous plant fiber, the mass ratio of the nano-cellulose, the hardwood fiber and the gramineous plant fiber is preferably 1:1: 2; when the cellulose fiber is a mixture of nanocellulose and gramineous plant fibers, the mass ratio of nanocellulose to gramineous plant fibers is preferably 1: 1.
In the invention, the mass ratio of the cellulose fibers to the water is preferably 5-70: 120-1600, more preferably 10-60: 300-1100, and further preferably 20-50: 460-1000.
In the invention, the mixing of the rare earth compound, the cellulose fiber and the water is preferably carried out under the ultrasonic condition, and the ultrasonic time is preferably 1-48 h, more preferably 2-18 h, and further preferably 6-12 h; the temperature of the ultrasonic wave is preferably 30-90 ℃, and more preferably 50-60 ℃.
After the solution A is obtained, the polylactic acid is dissolved in the organic solvent to obtain the solution B. In the present invention, the polylactic acid preferably includes at least one of levorotatory polylactic acid (PLLA), dextrorotatory polylactic acid (PDLA), and a copolymer of levorotatory polylactic acid and dextrorotatory polylactic acid (PLDLLA). The polymerization degree of the PLDLLA is not specially required, and the PLDLLA can be sold as a commodity. In the present invention, when the polylactic acid is a mixture of PDLA and PLDLLA, the mass ratio of PDLA to PLDLLA is preferably 50: 27; when the polylactic acid is a mixture of PLLA and PLDLLA, the mass ratio of the PLLA to the PLDLLA is preferably 1: 1; when the polylactic acid is a mixture of PLLA and PDLA, the mass ratio of PLLA to PDLA is preferably 30: 24.
In the present invention, the organic solvent preferably includes at least one of dichloromethane, chloroform, toluene, xylene, and acetone.
In the invention, the mass ratio of the polylactic acid to the cellulose fiber is preferably 20-90: 5 to 70, preferably 30 to 77:10 to 60, and more preferably 40 to 54:20 to 50. In the invention, the mass ratio of the polylactic acid to the organic solvent is preferably 20-90: 200 to 1800, more preferably 30 to 77:600 to 1500, and still more preferably 40 to 54:800 to 1100.
After the solution B is obtained, the solution A and the solution B are blended to obtain the solution C. In the invention, the blending time is preferably 30-120 min, more preferably 60-90 min, and further preferably 70-80 min.
After the solution C is obtained, the solution C is mixed with a flocculating agent to obtain a solution D. In the present invention, the flocculant preferably includes at least one of polyacrylamide, polyaluminum ferric silicate, polyferric silicate sulfate, and polydimethyldiallyl ammonium chloride. In a specific embodiment of the present invention, when the flocculant is a mixture of polyacrylamide and polysilicate aluminum ferric, the mass ratio of the polyacrylamide to the polysilicate aluminum ferric is preferably 1: 1; when the flocculating agent is a mixture of polyacrylamide and poly dimethyl diallyl ammonium chloride, the mass ratio of the polyacrylamide to the poly dimethyl diallyl ammonium chloride is preferably 2-7: 3; when the flocculating agent is a mixture of polyacrylamide and ferric polysilicate sulfate, the mass ratio of the polyacrylamide to the ferric polysilicate sulfate is preferably 2: 1.
In the invention, the mass ratio of the flocculating agent to the polylactic acid is preferably 1-10: 20-90, more preferably 3-8: 30-77, and further preferably 5-7: 40-54.
The invention preferably adds the flocculant into the C solution for blending. In the invention, the mixing time of the solution C and the flocculating agent is preferably 1-6 h, and more preferably 2-3 h; the mixing temperature is preferably 20 to 60 ℃, and more preferably 30 to 40 ℃.
After the solution D is obtained, the invention removes water and organic solvent in the solution D to obtain solid E. In the present invention, the method for removing water and an organic solvent from the D solution preferably includes: heating and concentrating the solution D to obtain colloid; the colloid was filtered and dried to give solid E. In the present invention, the concentration by heating is preferably carried out in a rotary evaporator. The invention has no special requirements on the parameters of heating and concentration, and the colloid with high concentration can be obtained. The present invention has no special requirement on the filtration and drying parameters, and the water and organic solvent in the colloid can be removed by the operation method known by the skilled person.
After the solid E is obtained, the solid E is hot-pressed to obtain the rare earth modified fiber reinforced polylactic acid. The solid E is preferably placed between two stainless steel plates and hot-pressed in the invention.
In the invention, the pressure of the hot pressing is preferably 10-30 MPa, and more preferably 20 MPa; the temperature of hot pressing is preferably 170-200 ℃, and more preferably 180-190 ℃; the time for hot pressing is preferably 2-6 min, and more preferably 3-5 min.
The invention also provides the rare earth modified fiber reinforced polylactic acid prepared by the preparation method of the technical scheme. The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared by the method is preferably 50-120 MPa; the tensile modulus is preferably 4-9 GPa.
The preparation method provided by the invention can fill cellulose fiber with high proportion in polylactic acid, thereby obtaining biodegradable material with excellent mechanical property.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
According to the parts by weight, 5 parts of Ce (C)8H15O2)3Mixing 50 parts of nano cellulose and 1100 parts of water at 30 ℃ for 12 hours by ultrasonic waves to obtain a solution A;
dissolving 40 parts of PLLA in 800 parts of dichloromethane to obtain a solution B;
blending the solution A and the solution B for 60min and stirring evenly to obtain a solution C;
adding 8 parts of polyacrylamide into the solution C, blending for 3 hours at 30 ℃, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and placing the solid E between two stainless steel plates, and performing hot press molding for 2min at 180 ℃ under 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 105MPa, and the tensile modulus is 8 GPa.
Example 2
According to the parts by weight, 3 parts of La (ClO)3Ultrasonically mixing 20 parts of softwood fiber and 460 parts of water at 50 ℃ for 6 hours to obtain a solution A;
dissolving 50 parts of PDLA and 27 parts of PLDLLA in 1500 parts of toluene to obtain a solution B;
blending the solution A and the solution B for 90min and stirring evenly to obtain a solution C;
adding 5 parts of polyacrylamide and 5 parts of ferric aluminum polysilicate into the solution C, blending at 40 ℃ for 2h, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and placing the solid E between two stainless steel plates, and performing hot press molding for 3min at 190 ℃ under 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 70MPa, and the tensile modulus is 6 GPa.
Example 3
2 parts of Ce (P) by weight2O4)33 parts of Ce (C)8H15O2)3Mixing 40 parts of nano cellulose, 30 parts of softwood fiber and 1600 parts of water at 90 ℃ for 48 hours by ultrasonic waves to obtain a solution A;
dissolving 20 parts of PDLA in 600 parts of trichloromethane to obtain a solution B;
mixing the solution A and the solution B for 120min and stirring uniformly to obtain a solution C;
adding 2 parts of polyacrylamide and 3 parts of poly dimethyl diallyl ammonium chloride into the solution C, blending at 30 ℃ for 3 hours, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and placing the solid E between two stainless steel plates, and performing hot press molding for 5min at 190 ℃ under 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 115MPa, and the tensile modulus is 8.5 GPa.
Example 4
According to the parts by weight, 5 parts of CeO25 parts of La (ClO)3Ultrasonic mixing 30 parts of broadleaf wood fiber and 1000 parts of water at 60 ℃ for 18 hours to obtain a solution A;
dissolving 25 parts of PLLA and 25 parts of PLDLLA in 1000 parts of trichloromethane to obtain a solution B;
blending the solution A and the solution B for 70min and stirring uniformly to obtain a solution C;
adding 7 parts of polyacrylamide and 3 parts of poly dimethyl diallyl ammonium chloride into the solution C, blending at 60 ℃ for 6 hours, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and (3) placing the solid E between two stainless steel plates, and carrying out hot press molding for 2min at 185 ℃ and 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 90MPa, and the tensile modulus is 7.5 GPa.
Example 5
According to the parts by weight, 3 parts of Sm (ClO)3Ultrasonically mixing 30 parts of broadleaf wood fiber, 30 parts of gramineous plant fiber and 1000 parts of water at 90 ℃ for 12 hours to obtain a solution A;
dissolving 30 parts of PLLA in 600 parts of trichloromethane to obtain a solution B;
mixing the solution A and the solution B for 120min and stirring uniformly to obtain a solution C;
adding 7 parts of ferric polysilicate sulfate into the solution C, blending for 1h at the temperature of 40 ℃, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and placing the solid E between two stainless steel plates, and performing hot press molding for 2min at 180 ℃ under 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared by the embodiment is 95MPa, and the tensile modulus is 8 GPa.
Example 6
According to the parts by weight, 1 part of Sm (ClO)31 part of Pr (NO)3)31 part of Ce (C)8H15O2)3Ultrasonically mixing 10 parts of nano cellulose, 10 parts of broadleaf wood fiber, 20 parts of gramineous plant fiber and 1100 parts of water at 50 ℃ for 6 hours to obtain a solution A;
dissolving 54 parts of PLDLLA in 1100 parts of acetone to obtain a solution B;
mixing the solution A and the solution B for 30min and stirring evenly to obtain solution C;
adding 2 parts of polyacrylamide and 1 part of ferric polysilicate sulfate into the solution C, blending at 20 ℃ for 6 hours, and uniformly stirring to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and (3) placing the solid E between two stainless steel plates, and performing hot press molding for 4min at the temperature of 170 ℃ and under the pressure of 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 70MPa, and the tensile modulus is 6 GPa.
Example 7
According to the parts by weight, 3 parts of Ce (CO)3)2Ultrasonically mixing 5 parts of nano cellulose, 5 parts of gramineous plant fiber and 300 parts of water at 50 ℃ for 2 hours to obtain a solution A;
dissolving 30 parts of PLLA and 24 parts of PDLA in 1100 parts of dichloromethane to obtain a solution B;
blending the solution A and the solution B for 60min and stirring uniformly to obtain a solution C;
adding 1 part of polyacrylamide into the solution C, blending for 2 hours at 40 ℃, and uniformly stirring to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and placing the solid E between two stainless steel plates, and performing hot press molding for 2min at 180 ℃ under 20MPa to obtain the rare earth modified fiber reinforced polylactic acid.
The tensile strength of the rare earth modified fiber reinforced polylactic acid prepared in the embodiment is 60MPa, and the tensile modulus is 5 GPa.
Comparative example 1
According to the weight portion, 30 parts of broadleaf wood fiber, 30 parts of gramineous plant fiber and 1000 parts of water are ultrasonically mixed for 12 hours at 90 ℃ to obtain solution A;
dissolving 33 parts of PLLA in 600 parts of chloroform to obtain a solution B;
mixing the solution A and the solution B for 120min and stirring uniformly to obtain a solution C;
adding 7 parts of ferric polysilicate sulfate into the solution C, blending for 1h at the temperature of 40 ℃, and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and (3) placing the solid E between two stainless steel plates, and carrying out hot press molding for 2min at 180 ℃ under 20MPa to obtain the modified polylactic acid composition.
The modified polylactic acid composition prepared in the comparative example has a tensile strength of 70MPa and a tensile modulus of 6 GPa.
Comparing the comparative example with the example 5, it can be seen that the performance of the polylactic acid obtained by rare earth modification of the cellulose fiber is obviously improved and the tensile strength is improved from 70MPa to 95MPa on the premise of filling the same amount of the cellulose fiber; the tensile modulus is improved from 6GPa to 8 GPa.
Comparative example 2
According to the parts by weight, 3 parts of Sm (ClO)3Ultrasonically mixing 30 parts of broadleaf wood fiber, 30 parts of gramineous plant fiber and 1000 parts of water at 90 ℃ for 12 hours to obtain a solution A;
dissolving 37 parts of PLLA in 600 parts of chloroform to obtain a solution B;
mixing the solution A and the solution B for 120min and stirring uniformly to obtain a solution C;
blending the solution C at 40 ℃ for 1h and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and (3) placing the solid E between two stainless steel plates, and carrying out hot press molding for 2min at 180 ℃ under 20MPa to obtain the modified polylactic acid composition.
The modified polylactic acid composition prepared in the comparative example had a tensile strength of 65MPa and a tensile modulus of 5.5 GPa.
Comparing the comparative example with the example 5, it can be seen that the performance of the polylactic acid is obviously improved and the tensile strength is improved from 65MPa to 95MPa after the flocculant is added on the premise of filling the same amount of cellulose fibers; the tensile modulus is improved from 5.5GPa to 8 GPa.
Comparative example 3
According to the weight portion, 40 portions of nano cellulose, 30 portions of softwood fiber and 1600 portions of water are ultrasonically mixed for 48 hours at 90 ℃ to obtain solution A;
dissolving 30 parts of PLDA in 600 parts of trichloromethane to obtain a solution B;
mixing the solution A and the solution B for 120min and stirring uniformly to obtain a solution C;
blending the solution C at 30 ℃ for 3h and stirring uniformly to obtain a solution D;
heating and concentrating the solution D on a rotary evaporator to obtain colloid; filtering and drying the colloid to obtain a solid E;
and (3) placing the solid E between two stainless steel plates, and carrying out hot press molding for 5min at 190 ℃ under 20MPa to obtain the modified polylactic acid composition.
The modified polylactic acid composition prepared in the comparative example has a tensile strength of 60MPa and a tensile modulus of 4.5 GPa.
Comparing the comparative example with the example 3, it can be seen that on the premise of filling the same amount of cellulose fiber, the performance of the obtained polylactic acid is obviously improved after the cellulose fiber is modified by rare earth and the flocculating agent is added, and the tensile strength is improved from 60MPa to 115 MPa; the tensile modulus is improved from 4.5GPa to 8.5 GPa.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of rare earth modified fiber reinforced polylactic acid comprises the following steps:
mixing a rare earth compound, cellulose fiber and water to obtain a solution A;
dissolving polylactic acid in an organic solvent to obtain a solution B;
blending the solution A and the solution B to obtain a solution C;
mixing the solution C with a flocculating agent to obtain a solution D;
removing water and organic solvent from the solution D to obtain a solid E;
carrying out hot pressing on the solid E to obtain rare earth modified fiber reinforced polylactic acid;
the mass ratio of the polylactic acid to the cellulose fiber to the rare earth compound to the flocculating agent is 20-90: 5-70: 1-10: 1 to 10.
2. The method of claim 1, wherein the rare earth compound comprises LnO2、Ln2O3、Ln(NO3)3、Ln(CO3)2、Ln2(CO3)3、Ln(P2O4)3、Ln(P5O7)3、Ln2(SO4)3、Ln2(C2O4)3、Ln(C8H15O2)3And Ln (ClO)3At least one of; wherein Ln is at least one of La, Ce, Tb, Pr, Dy, Yb, Eu, Tm, Sm and Nd.
3. The method according to claim 2, wherein the rare earth compound comprises CeO2、La2O3、Ce(CO3)2、Tm2(CO3)3、Yb2(SO4)3、Pr(NO3)3、Ce(P2O4)3、Ce(C8H15O2)3、La(P5O7)3、Eu2(C2O4)3、La(ClO)3And Sm (ClO)3At least one of (1).
4. The method of claim 1, wherein the cellulose fiber comprises at least one of nanocellulose, softwood fiber, hardwood fiber, and gramineous fiber.
5. The method according to claim 1, wherein the polylactic acid comprises at least one of a poly (L-lactic acid), a poly (D-lactic acid), and a copolymer of poly (L-lactic acid) and poly (D-lactic acid).
6. The method of claim 1, wherein the flocculant comprises at least one of polyacrylamide, ferric aluminum polysilicate, ferric polyferric polysilicate, and poly dimethyl diallyl ammonium chloride.
7. The method of claim 1, wherein the organic solvent comprises at least one of dichloromethane, chloroform, toluene, xylene, and acetone.
8. The method according to claim 1, wherein the pressure of the hot pressing is 10 to 30 MPa; the hot pressing temperature is 170-200 ℃; and the hot pressing time is 2-6 min.
9. The rare earth modified fiber reinforced polylactic acid prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110755637.1A CN113402741B (en) | 2021-07-05 | 2021-07-05 | Rare earth modified fiber reinforced polylactic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110755637.1A CN113402741B (en) | 2021-07-05 | 2021-07-05 | Rare earth modified fiber reinforced polylactic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113402741A CN113402741A (en) | 2021-09-17 |
| CN113402741B true CN113402741B (en) | 2022-05-06 |
Family
ID=77681236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110755637.1A Active CN113402741B (en) | 2021-07-05 | 2021-07-05 | Rare earth modified fiber reinforced polylactic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113402741B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163906A (en) * | 1996-02-09 | 1997-11-05 | 希巴特殊化学控股公司 | Antistatically treated polymers |
| CN101955640A (en) * | 2010-10-15 | 2011-01-26 | 华中科技大学 | Modified biopolymer fiber reinforced polylactic acid composite material and preparation method thereof |
| CN108997636A (en) * | 2018-08-20 | 2018-12-14 | 江苏华昌织物有限公司 | A kind of sunshade net of organic light conversion agents and preparation method thereof containing rare earth luminous ion |
| WO2019241603A1 (en) * | 2018-06-13 | 2019-12-19 | The Regents Of The University Of Colorado, A Body Corporate | Bacterial cellulose gels, process for producing and methods of use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190245155A1 (en) * | 2018-01-24 | 2019-08-08 | Stephan HEATH | Methods, products, and systems relating to making, providing, and using nanocrystalline cellulose superlattice solar cells to produce electricity |
-
2021
- 2021-07-05 CN CN202110755637.1A patent/CN113402741B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163906A (en) * | 1996-02-09 | 1997-11-05 | 希巴特殊化学控股公司 | Antistatically treated polymers |
| CN101955640A (en) * | 2010-10-15 | 2011-01-26 | 华中科技大学 | Modified biopolymer fiber reinforced polylactic acid composite material and preparation method thereof |
| WO2019241603A1 (en) * | 2018-06-13 | 2019-12-19 | The Regents Of The University Of Colorado, A Body Corporate | Bacterial cellulose gels, process for producing and methods of use |
| CN108997636A (en) * | 2018-08-20 | 2018-12-14 | 江苏华昌织物有限公司 | A kind of sunshade net of organic light conversion agents and preparation method thereof containing rare earth luminous ion |
Non-Patent Citations (3)
| Title |
|---|
| Poly(L-lactic acid) bio-composites reinforced by oligo(D-lactic acid) grafted chitosan for simultaneously improved ductility, strength and modulus;Li, W等;《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES 》;20190115;第131卷;第495-504页 * |
| Preparation of cellulose-graft-polylactic acid via melt copolycondensation for use in polylactic acid based composites: synthesis, characterization and properties;Hua, S等;《RSC ADVANCES》;20160203;第6卷(第3期);第1973-1983页 * |
| 生物降解聚乳酸合金最新进展及展望;田虎虎等;《橡塑技术与装备》;20210430;第47卷(第8期);第16-22页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113402741A (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Self-reinforced melt processable composites of sisal | |
| CN101700705B (en) | Thermosetting resin glass fiber laminating composite material and preparation method thereof | |
| CN104693464A (en) | Preparation method of lignin-nanocelluose reinforced polylactic acid composite film | |
| Qian et al. | Effect of low‐concentration alkali solution pretreatment on the properties of bamboo particles reinforced poly (lactic acid) composites | |
| CN101135075A (en) | Wood liquefied carbide fiber, protofilament and preparation method thereof | |
| Li et al. | Thermally stable and tough coatings and films using vinyl silylated lignin | |
| Xiao et al. | Preparation, structure, and properties of chitosan/cellulose/multiwalled carbon nanotube composite membranes and fibers | |
| CN103552353A (en) | Method for preparing holocellulose composite laminated material | |
| CN105482052A (en) | Thermosetting resin and preparation method | |
| Zhang et al. | Reinforcing effect of nanocrystalline cellulose and office waste paper fibers on mechanical and thermal properties of poly (lactic acid) composites | |
| CN113402741B (en) | Rare earth modified fiber reinforced polylactic acid and preparation method thereof | |
| Liu et al. | Reactive toughening of urea–formaldehyde resin with poly (vinyl alcohol) by formation of interpenetrating networks | |
| Abdelkawy et al. | Thermal and morphological characterization of biowaste date palm fiber‐reinforced polybenzoxazine and epoxy composites | |
| CN117124621A (en) | Degradable PPC composite board and preparation method thereof | |
| CN114196165B (en) | Preparation method of modified jute fiber reinforced bio-based epoxy resin composite material | |
| CN104893241A (en) | Preparation method of degradable plastic filling material taking waste bank note paper as substrate | |
| JP2006007534A (en) | Manufacturing method of cellulosic fiberboard | |
| Lu et al. | The preparation of self-reinforced sisal fiber composites | |
| CN105175342A (en) | Ionic liquid and method for homogeneous phase-modified reed-reinforced PE (polyethylene) composite material thereof | |
| Mishra et al. | Compatibilizing effect of different anhydrides on cane bagasse pith and melamine–formaldehyde‐resin composites | |
| CN105885396B (en) | A kind of natural ramie fiber enhancing cast composite nylon material and preparation method thereof | |
| JP6847102B2 (en) | Manufacturing method of molded product | |
| CN101831158B (en) | Composite crosslinking amylomaize based fully degradable material and preparation method thereof | |
| CN114479011A (en) | Epoxy glass polymer material based on dynamic reversible covalent bond and preparation method thereof | |
| JPH0343442A (en) | Production of lignocelulose-phenol resin molded product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |