CN113185823B - Polycaprolactone composite material and preparation method thereof - Google Patents
Polycaprolactone composite material and preparation method thereof Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a polycaprolactone composite material and a preparation method thereof. The present invention provides a composite material comprising: 100 parts of polycaprolactone; 2-40 parts of polyvinyl alcohol fiber; 2-40 parts of polyvinyl alcohol nano particles; the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 mu m, and the fiber length is 1-5 mm; the particle size of the polyvinyl alcohol nano particles is 1-50 nm. According to the invention, the polyvinyl alcohol fiber and the polyvinyl alcohol nanoparticles are simultaneously added into the polycaprolactone, and the synergistic effect of the fiber and the nanoparticles is utilized, so that the tensile strength, modulus, crystallization rate and degradation performance of the polycaprolactone material are remarkably improved, a powerful technical support is provided for further expanding the application field of the polycaprolactone, and the market prospect is wide.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a polycaprolactone composite material and a preparation method thereof.
Background
Since the 21 st century, the global environment is protected, a resource circulation type society is constructed, and a path for sustainable development becomes a global focus and urgent task. Plastics, i.e. high molecular materials, are difficult to degrade due to covalent bond and tight molecular chain arrangement, resulting in 'white pollution'. In addition, the burial and incineration of the used and discarded polymer also causes "secondary pollution". Therefore, the research and development of the biodegradable polymer have great economic and social values. The biodegradable polymer is completely decomposed into water, carbon dioxide and organic matters under the action of microorganisms and the like, and does not pollute the environment.
Polycaprolactone (PCL) is a biodegradable aliphatic polyester, a linear polymer synthesized by ring-opening polymerization of epsilon-caprolactone under the action of a catalyst at 90 ℃. The repeating structural unit of the PCL molecular chain has 5 nonpolar methylene-CH 2 And a polar ester group-COO-, the molecular chain is relatively regular and is easily crystallized, so that PCL is a semi-crystalline polymer. The PCL material is like medium density polyethylene, has waxy texture, has the same mechanical property with polyethylene, and has the tensile strength of 12-30 MPa and the breaking elongation of 300-600 percent. The C-C bond and the C-O bond in the molecular chain can rotate freely, so that the PCL has good flexibility and processabilityIt can be used for extrusion, injection molding, wire drawing, etc. Due to the existence of ester group in PCL molecular chain, PCL has biocompatibility, can be completely biodegraded, has proper degradation rate, and is one of the most promising biodegradable materials for mass production at present.
Although the PCL material has the advantages, the PCL material has the disadvantages of insufficient strength, low modulus, slow crystallization rate and degradation rate, and the like when used as engineering plastics. How to further improve the physical and chemical properties of the PCL material has important significance for widening the use field of the PCL material and improving the market competitiveness of the PCL material.
Disclosure of Invention
In view of the above, the present invention provides a polycaprolactone composite material and a preparation method thereof, and the composite material provided by the present invention has good mechanical properties, crystallization properties and degradation properties.
The invention provides a polycaprolactone composite material, which comprises the following components in parts by weight:
100 parts of polycaprolactone;
2-40 parts of polyvinyl alcohol fiber;
2-40 parts of polyvinyl alcohol nanoparticles;
the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 mu m, and the fiber length is 1-5 mm;
the particle size of the polyvinyl alcohol nano particles is 1-50 nm.
Preferably, the weight average molecular weight of the polycaprolactone is 5-30 ten thousand.
Preferably, the degree of polymerization of the polyvinyl alcohol fibers is 500 to 2000.
Preferably, the degree of alcoholysis of the polyvinyl alcohol fibers is 50 to 99%.
Preferably, the polymerization degree of the polyvinyl alcohol nanoparticles is 500 to 2000.
Preferably, the alcoholysis degree of the polyvinyl alcohol nanoparticles is 50-99%.
The invention provides a preparation method of a polycaprolactone composite material, which comprises the following steps:
melting and blending the raw materials to obtain a polycaprolactone composite material;
the raw material comprises 100 parts by weight of polycaprolactone, 2-40 parts by weight of polyvinyl alcohol fiber and 2-40 parts by weight of polyvinyl alcohol nano particles;
the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 mu m, and the fiber length is 1-5 mm;
the particle size of the polyvinyl alcohol nano particles is 1-50 nm.
Preferably, the temperature of the melt blending is 80-100 ℃; the time of melt blending is 5-10 min.
Preferably, the rotating speed of the melt blending is 40-120 r/min.
Preferably, the raw materials are dried to the water content of less than or equal to 200ppm before being subjected to melt blending.
Compared with the prior art, the invention provides a polycaprolactone composite material and a preparation method thereof. The present invention provides a composite material comprising: 100 parts of polycaprolactone; 2-40 parts of polyvinyl alcohol fiber; 2-40 parts of polyvinyl alcohol nano particles; the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 mu m, and the fiber length is 1-5 mm; the particle size of the polyvinyl alcohol nano particles is 1-50 nm. According to the invention, the polyvinyl alcohol fiber and the polyvinyl alcohol nanoparticles are simultaneously added into the polycaprolactone, and the synergistic effect of the fiber and the nanoparticles is utilized, so that the tensile strength, modulus, crystallization rate and degradation performance of the polycaprolactone material are remarkably improved, a powerful technical support is provided for further expanding the application field of the polycaprolactone, and the market prospect is wide. The experimental results show that: the polycaprolactone composite material provided by the invention has the highest tensile strength of 49MPa, the highest Young modulus of 508MPa, the isothermal and non-isothermal crystallization rates are obviously improved, and the degradation rate is improved and controlled.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polycaprolactone composite material, which comprises the following components in parts by weight:
100 parts of polycaprolactone;
2-40 parts of polyvinyl alcohol fiber;
2-40 parts of polyvinyl alcohol nano particles.
In the polycaprolactone composite material provided by the invention, the weight average molecular weight of the Polycaprolactone (PCL) is preferably 5 to 30 ten thousand, and specifically may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 ten thousand.
In the polycaprolactone composite material provided by the invention, the fiber diameter of the polyvinyl alcohol (PVA) fiber is 0.1-50 μm, specifically 0.1 μm, 0.3 μm, 0.5 μm, 0.7 μm, 1 μm, 3 μm, 5 μm, 7 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm; the length of the polyvinyl alcohol fiber is 1-5 mm, and specifically can be 1mm, 1.2mm, 1.5mm, 1.7mm, 2mm, 2.3mm, 2.5mm, 2.7mm, 3mm, 3.2mm, 3.5mm, 3.7mm, 4mm, 4.2mm, 4.5mm, 4.7mm or 5mm; the polymerization degree of the polyvinyl alcohol fiber is preferably 500-2000, and specifically can be 500, 700, 1000, 1300, 1500, 1800 or 2000; the degree of alcoholysis of the polyvinyl alcohol fibers is preferably 50 to 99%, and specifically may be 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 97%, or 99%.
In the polycaprolactone composite material provided by the invention, based on 100 parts by weight of polycaprolactone in the composite material, the content of the polyvinyl alcohol fiber in the composite material is 2-40 parts by weight, specifically 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 37 parts by weight or 40 parts by weight.
In the polycaprolactone composite material provided by the invention, the particle size of the polyvinyl alcohol (PVA) nano particles is 1-50 nm, and specifically can be 1nm, 2nm, 5nm, 7nm, 10nm, 12nm, 15nm, 17nm, 20nm, 23nm, 25nm, 27nm, 30nm, 32nm, 35nm, 37nm, 40nm, 42nm, 45nm, 47nm or 50nm; the polymerization degree of the polyvinyl alcohol nanoparticles is preferably 500-2000, and specifically can be 500, 700, 1000, 1300, 1500, 1800 or 2000; the degree of alcoholysis of the polyvinyl alcohol nanoparticles is preferably 50 to 99%, and specifically can be 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 97%, or 99%.
In the polycaprolactone composite material provided by the invention, the content of the polyvinyl alcohol nanoparticles in the composite material is 2-40 parts by weight, specifically 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 30 parts by weight, 32 parts by weight, 35 parts by weight, 37 parts by weight or 40 parts by weight, based on 100 parts by weight of polycaprolactone in the composite material.
The invention also provides a preparation method of the polycaprolactone composite material, which comprises the following steps:
melting and blending the raw materials to obtain a polycaprolactone composite material;
the raw materials comprise polycaprolactone, polyvinyl alcohol fiber and polyvinyl alcohol nanoparticles.
In the preparation method provided by the invention, the raw materials are firstly melt blended according to the dosage proportion. Wherein, the specific physicochemical indexes and the dosage proportion of the raw materials are introduced in the above, and are not described again; before the raw materials are subjected to melt blending, the raw materials are preferably dried to the water content of less than or equal to 200ppm; the melt blending temperature is preferably 80-100 deg.C, and specifically may be 80 deg.C, 81 deg.C, 82 deg.C, 84 deg.C, 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C, 90 deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C, 99 deg.C or 100 deg.C; the rotation speed of the melt blending is preferably 40-120 r/min, and specifically can be 40 r/min, 50 r/min, 60 r/min, 70 r/min, 80 r/min, 90 r/min, 100 r/min, 110 r/min or 120 r/min; the time for melt blending is preferably 5-10 min, and specifically can be 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10min; the equipment used for melt blending is preferably a torque rheometer. And after the melt blending is finished, cooling the obtained melt to room temperature to obtain the polycaprolactone composite material provided by the invention.
In the preparation method provided by the invention, in order to facilitate performance detection, the cooled polycaprolactone composite material is preferably placed on a flat vulcanizing machine for pressing to obtain a film or sheet with the thickness meeting the detection requirement, and then the film or sheet is placed in a cold press for pressure maintaining and cooling to room temperature. Wherein the pressing temperature is preferably 80-100 ℃, and specifically can be 80 ℃, 81 ℃, 82 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃; the pressing pressure is preferably 7-15 MPa, and specifically can be 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa or 15MPa; the pressure for pressure-maintaining cooling is preferably 7 to 15MPa, and specifically may be 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa or 15MPa.
According to the technical scheme provided by the invention, the polyvinyl alcohol fiber and the polyvinyl alcohol nanoparticles are simultaneously added into the polycaprolactone, and the tensile strength, modulus, crystallization rate and degradation performance of the polycaprolactone material are obviously improved through the synergistic effect of the fiber and the nanoparticles, so that a powerful technical support is provided for further expanding the application field of the polycaprolactone, and the market prospect is wide. The experimental results show that: the polycaprolactone composite material provided by the invention has the highest tensile strength of 49MPa, the highest Young modulus of 508MPa, the isothermal and non-isothermal crystallization rates are obviously improved, and the degradation rate is improved and controlled.
For the sake of clarity, the following examples and comparative examples are provided in detail.
In the following examples and comparative examples of the present invention, the performance evaluation methods according to the present invention were as follows:
1) Crystallization rate:
non-isothermal crystallization: heating the obtained sample to 80 ℃ by a Differential Scanning Calorimeter (DSC) at 100 ℃/min for melting for 3min, and then cooling to-20 ℃ at the speed of 10 ℃/min;
isothermal crystallization: the obtained sample is heated to 80 ℃ by a Differential Scanning Calorimeter (DSC) at 100 ℃/min for melting for 3min, and then is cooled to 40 ℃ at the speed of 100 ℃/min for isothermal crystallization.
2) Tensile strength and modulus:
the sample is cut into strips with the length of 150mm and the width of 15mm along the direction to be measured, the distance between the clamps is 100mm, and the test speed is 100mm/min. Test specimens 5 were tested and averaged.
3) Biodegradability:
measured according to the method of the national standard GB/T28206-2011.
Example 1
Drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 5 ten thousand, 2 parts by weight of polyvinyl alcohol fiber (the diameter is 0.1 mu m, the length is 1mm, the polymerization degree is 500, the alcoholysis degree is 50%) and 2 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 1nm, the polymerization degree is 500, and the alcoholysis degree is 50%), putting the dried materials into a torque rheometer, and melting and stirring the materials at the temperature of 80 ℃, wherein the stirring speed is 110 r/min, and the stirring time is 5min; after the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at the temperature of 80 ℃ and under the pressure of 10MPa for testing, and then quickly placed under a cold press at the pressure of 10MPa for pressure maintaining and cooling to room temperature, so as to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 21.5 ℃, the isothermal crystallization half-life at 40 ℃ is 3.1min, the tensile strength is 39MPa, the Young modulus is 322MPa, and the required days when the biological decomposition rate reaches 90 percent is 150 days.
Example 2
After drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 30 ten thousand, 40 parts by weight of polyvinyl alcohol fiber (the diameter is 50 mu m, the length is 5mm, the polymerization degree is 2000, and the alcoholysis degree is 99%) and 40 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 50nm, the polymerization degree is 2000, and the alcoholysis degree is 99%), putting the dried polyvinyl alcohol fibers and the dried polyvinyl alcohol nanoparticles into a torque rheometer, and melting and stirring the dried polyvinyl alcohol fibers and the dried polyvinyl alcohol nanoparticles at 90 ℃, wherein the stirring speed is 100 r/min, and the stirring time is 6min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ and under the pressure of 10MPa for testing, and then rapidly placed under a cold press at 10MPa for pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 23.4 ℃, the isothermal crystallization half-life period at 40 ℃ is 8.7min, the tensile strength is 24MPa, the Young modulus is 213MPa, and the number of days required when the biological decomposition rate reaches 90% is 98 days.
Example 3
After drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 20 ten thousand, 10 parts by weight of polyvinyl alcohol fiber (the diameter is 0.5 mu m, the length is 2mm, the polymerization degree is 1000, and the alcoholysis degree is 80%) and 10 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 2nm, the polymerization degree is 1300, and the alcoholysis degree is 70%), placing the dried materials in a torque rheometer to be melted and stirred at the temperature of 90 ℃, wherein the stirring speed is 80 r/min, and the stirring time is 8min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ and under the pressure of 10MPa for testing, and then rapidly placed under a cold press at 10MPa for pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 32.7 ℃, the isothermal crystallization half-life period at 40 ℃ is 1.9min, the tensile strength is 49MPa, the Young modulus is 508MPa, and the required days for 90 percent biological decomposition are 101 days.
Example 4
After drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 15 ten thousand, 8 parts by weight of polyvinyl alcohol fiber (the diameter is 5 mu m, the length is 4mm, the polymerization degree is 1500, and the alcoholysis degree is 90%), and 30 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 20nm, the polymerization degree is 700, and the alcoholysis degree is 60%), the dried polyvinyl alcohol fibers and the dried polyvinyl alcohol nanoparticles are placed in a torque rheometer to be melted and stirred at the temperature of 80 ℃, the stirring speed is 50 r/min, and the stirring time is 10min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature and cut into small pieces, the small pieces are pressed into a film with the thickness of 1mm on a flat vulcanizing machine at the temperature of 80 ℃ and under the pressure of 10MPa for testing, and then the film is rapidly placed under a cold press at the pressure of 10MPa for pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 26.7 ℃, the isothermal crystallization half-life period at 40 ℃ is 4.5min, the tensile strength is 40MPa, the Young modulus is 412MPa, and the number of days required when the biological decomposition rate reaches 90% is 98 days.
Example 5
100 parts of polycaprolactone with the weight average molecular weight of 20 ten thousand, 35 parts of polyvinyl alcohol fiber (the diameter is 15 mu m, the length is 5mm, the polymerization degree is 1000, the alcoholysis degree is 60%) and 15 parts of polyvinyl alcohol nano particles (the diameter is 15nm, the polymerization degree is 1800 and the alcoholysis degree is 70%) are dried and then placed in a torque rheometer to be melted and stirred at the temperature of 90 ℃, the stirring speed is 80 r/min and the stirring time is 10min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at the temperature of 80 ℃ and under the pressure of 10MPa for testing, and then quickly placed under a cold press at the pressure of 10MPa for pressure maintaining and cooling to room temperature, so as to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 22.37 ℃, the isothermal crystallization half-life period at 40 ℃ is 9.1min, the tensile strength is 38MPa, the Young modulus is 472MPa, and the required days when the biological decomposition rate reaches 90% is 96 days.
Comparative example 1
Drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 30 ten thousand, putting the polycaprolactone into a torque rheometer, and melting and stirring the polycaprolactone at 90 ℃, wherein the stirring speed is 100 r/min, and the stirring time is 6min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ and under the pressure of 10MPa for testing, and then rapidly placed under a cold press at 10MPa for pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 17.0 ℃, the isothermal crystallization half-life period at 40 ℃ is 12.3min, the tensile strength is 34MPa, the Young modulus is 191MPa, and the number of days required for the biological decomposition rate to reach 90% is 165 days.
Comparative example 2
100 parts by weight of polycaprolactone with the weight-average molecular weight of 30 ten thousand and 80 parts by weight of polyvinyl alcohol fiber (the diameter is 50 mu m, the length is 5mm, the polymerization degree is 2000, and the alcoholysis degree is 99%) are dried, then are placed in a torque rheometer to be melted and stirred at the temperature of 90 ℃, the stirring speed is 100 r/min, and the stirring time is 6min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature and cut into small pieces, the small pieces are pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ under the pressure of 10MPa for testing, and then the small pieces are rapidly placed under a cold press for 10MPa pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 15.1 ℃, the half-life of isothermal crystallization at 40 ℃ is 19.4min, the tensile strength is 26MPa, the Young modulus is 189MPa, and the required days are 91 days when the biological decomposition rate is 90%.
Comparative example 3
After drying 100 parts by weight of polycaprolactone with the weight-average molecular weight of 30 ten thousand and 80 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 50nm, the polymerization degree is 2000 and the alcoholysis degree is 99%), putting the dried polycaprolactone and the dried polyvinyl alcohol nanoparticles into a torque rheometer, and melting and stirring the polycaprolactone and the dried polyvinyl alcohol nanoparticles at 90 ℃, wherein the stirring speed is 100 r/min and the stirring time is 6min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature, cut into small blocks, pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ and under the pressure of 10MPa for testing, and then rapidly placed under a cold press at 10MPa for pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature is 16.2 ℃, the isothermal crystallization half-life period at 40 ℃ is 13.4min, the tensile strength is 27MPa, the Young modulus is 209MPa, and the required days for 90 percent of the biological decomposition rate are 90 days.
Comparative example 4
100 parts by weight of polycaprolactone with the weight-average molecular weight of 30 ten thousand, 50 parts by weight of polyvinyl alcohol fiber (the diameter is 50 mu m, the length is 5mm, the polymerization degree is 2000, and the alcoholysis degree is 99%) and 50 parts by weight of polyvinyl alcohol nanoparticles (the diameter is 50nm, the polymerization degree is 2000, and the alcoholysis degree is 99%) are dried and then placed in a torque rheometer to be melted and stirred at the temperature of 90 ℃, the stirring speed is 100 r/min, and the stirring time is 6min. After the melting and stirring are finished, the melt is directly cooled in the air state at room temperature and cut into small pieces, the small pieces are pressed into a film with the thickness of 1mm on a flat vulcanizing machine at 90 ℃ under the pressure of 10MPa for testing, and then the small pieces are rapidly placed under a cold press for 10MPa pressure maintaining and cooling to room temperature to obtain the polycaprolactone composite material.
The performance of the prepared polycaprolactone composite material is detected, and the result is as follows: the non-isothermal crystallization temperature was 14.2 ℃, the isothermal crystallization half-life at 40 ℃ was 15.1min, the tensile strength was 25MPa, the Young's modulus was 189MPa, and the number of days required until the biological decomposition rate reached 90% was 89 days.
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 (3)
1. A polycaprolactone composite material comprises the following components in parts by weight:
100 parts of polycaprolactone;
2-40 parts of polyvinyl alcohol fiber;
2-40 parts of polyvinyl alcohol nanoparticles;
the weight average molecular weight of the polycaprolactone is 5-30 ten thousand;
the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 μm, the fiber length is 1-5 mm, the polymerization degree is 500-2000, and the alcoholysis degree is 50-99%;
the polyvinyl alcohol nanoparticles have the particle size of 1 to 50nm, the polymerization degree of 500 to 2000 and the alcoholysis degree of 50 to 99 percent.
2. A preparation method of a polycaprolactone composite material comprises the following steps:
melting and blending the raw materials to obtain a polycaprolactone composite material;
the raw material comprises 100 parts by weight of polycaprolactone, 2 to 40 parts by weight of polyvinyl alcohol fiber and 2 to 40 parts by weight of polyvinyl alcohol nanoparticles;
the weight average molecular weight of the polycaprolactone is 5-30 ten thousand;
the fiber diameter of the polyvinyl alcohol fiber is 0.1-50 μm, the fiber length is 1-5 mm, the polymerization degree is 500-2000, and the alcoholysis degree is 50-99%;
the particle size of the polyvinyl alcohol nano particles is 1 to 50nm, the polymerization degree is 500 to 2000, and the alcoholysis degree is 50 to 99 percent;
before the raw materials are subjected to melt blending, the raw materials are dried until the water content is less than or equal to 200ppm;
the temperature of the melt blending is 80 to 100 ℃; the time for melt blending is 5 to 10min.
3. The method according to claim 2, wherein the melt blending is performed at a rotation speed of 40 to 120 rpm.
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