CN111363174B - Preparation method of starch/polycaprolactone composite material - Google Patents

Preparation method of starch/polycaprolactone composite material Download PDF

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CN111363174B
CN111363174B CN202010262629.9A CN202010262629A CN111363174B CN 111363174 B CN111363174 B CN 111363174B CN 202010262629 A CN202010262629 A CN 202010262629A CN 111363174 B CN111363174 B CN 111363174B
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polycaprolactone
starch
dispersing
polyethylene glycol
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CN111363174A (en
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唐洁净
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Ningbo Plastic Metal Product Co ltd
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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • 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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Abstract

A preparation method of starch/polycaprolactone composite material comprises dispersing dried starch and polyethylene glycol 2000 into acetone to obtain suspension; weighing dried polycaprolactone and polyethylene glycol 6000, and dispersing into acetone to obtain polycaprolactone dispersed liquid; and mixing the suspension and the polycaprolactone dispersion liquid, performing high-energy ball milling, washing after reaction, filtering, drying, and performing compression molding to obtain the starch/polycaprolactone composite material. The method can still uniformly disperse the starch and the polycaprolactone when a large amount of cheap starch is used, and can improve the mechanical property.

Description

Preparation method of starch/polycaprolactone composite material
Technical Field
The invention relates to a high-molecular composite material and a preparation method thereof, in particular to a preparation method of a starch/polycaprolactone composite material.
Background
Polycaprolactone, also known as polyepsilon caprolactone, has the advantages of good thermal stability, large elongation at break, good toughness and degradability, and can be completely degraded into water and carbon dioxide in water and soil, so that attention is paid. However, polycaprolactone has the disadvantages of low modulus, low melting point and high price, so that the large-scale development of polycaprolactone is limited. In recent years, degradable natural biomaterials, such as starch, have been introduced into degradable polymers, thereby reducing the cost of the degradable materials and improving the mechanical properties of the polymers. The starch is a completely degradable pure natural material, has low cost, is reproducible, has high degradation speed, and can be completely used for overcoming the defect that the cost of polycaprolactone is higher. However, since natural materials such as starch have hydrophilicity, and the interfacial bonding force with polymers is weak, the compatibility is generally poor, so that the mechanical properties of the composite material are rather reduced, especially when the content of starch is large (for example, more than 40%), the phenomenon is further aggravated, and the mechanical properties of the composite material are greatly reduced. How to uniformly disperse starch and polycaprolactone and still maintain or even improve the mechanical properties when cheap starch is used in a large amount is still a problem to be solved.
Disclosure of Invention
The invention relates to a preparation method of a starch/polycaprolactone composite material, aiming at solving the technical problems that when a large amount of cheap starch is used, the starch and polycaprolactone can still be uniformly dispersed, and the mechanical property is improved.
A preparation method of a starch/polycaprolactone composite material comprises the following steps:
1) weighing starch, drying in vacuum at 80 ℃ to constant weight, dispersing the dried starch in acetone, adding polyethylene glycol 2000, and stirring and dispersing uniformly to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, and uniformly stirring and dispersing to obtain polycaprolactone dispersed feed liquid;
3) mixing the suspension obtained in the step 1) with the polycaprolactone dispersed liquid obtained in the step 2), uniformly dispersing, transferring the obtained mixed liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 4-5h, wherein the stirring speed is 5000-6000rpm, zirconium oxide is used as grinding balls, and the ball-to-material ratio is 10-13: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product to obtain the starch/polycaprolactone composite material.
Wherein the mass ratio of the starch to the polycaprolactone is 0.4-0.6: 1.
Wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is about 1: 0.3-0.4. Wherein the mass ratio of the starch to the polyethylene glycol 2000 is about 1: 0.08-0.15.
Wherein the temperature of the compression molding is 90 ℃, the pressure is 20MPa, and the time is 5 min.
Advantageous effects
The invention completes the compounding of the starch and the polycaprolactone by one step by using a method of high-energy ball milling to assist the dispersion of the polyethylene glycol with specific molecular weight, and the starch is uniformly dispersed in the continuous phase of the polycaprolactone by controlling the high-energy ball milling parameters and the molecular weight and the dosage of the polyethylene glycol. The low molecular weight polyethylene glycol has stronger hydrophilicity and can be combined with starch, the high molecular weight polyethylene glycol has lower hydrophilicity and can be combined with polycaprolactone, the polyethylene glycols with different molecular weights still have certain compatibility, the starch and the polycaprolactone combined with the polyethylene glycols with different molecular weights can be well dispersed under the action of the polyethylene glycols, and the high-energy ball milling process is strongly impacted, ground and stirred, so that the dispersion is further optimized, and further, the high-molecular weight polyethylene glycol can still have good dispersibility and compatibility when the starch content is higher, the mechanical property of the composite material is improved, and the cost of the degradable material is effectively reduced.
Detailed Description
The tensile strength of the composite was measured using GB/T1040-92 at a test speed of 2mm/min and a sample size of 250mm 25mm 3 mm.
Example 1
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 20.3 MPa.
Example 2
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.15, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.4, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.4: 1, uniformly dispersing, transferring the obtained mixture liquid into a high-energy ball mill, performing high-energy ball milling reaction for 4 hours, stirring at 6000rpm, taking zirconium oxide as grinding balls, and the ball-material ratio is 13: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 19.8 MPa.
Example 3
1) Weighing starch, drying in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the starch to the polyethylene glycol 6000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 5.7 MPa.
Example 4
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 2000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 8.5 MPa.
Example 5
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 4000, wherein the mass ratio of the starch to the polyethylene glycol 4000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 4000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 4000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 11.2 MPa.
Example 6
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.2, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 14.1MPa through testing.
Example 7
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.2, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 10.9 MPa.
Example 8
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixture liquid into a high-energy ball mill, performing high-energy ball milling reaction for 5 hours, stirring at the speed of 4000rpm, and taking zirconium oxide as grinding balls, wherein the ball-to-material ratio is 10: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 12.7 MPa.
Example 9
1) Weighing starch, drying the starch in vacuum at 80 ℃ to constant weight, dispersing the dried starch into acetone, adding polyethylene glycol 2000, wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.1, and uniformly stirring and dispersing to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3, and uniformly stirring and dispersing to obtain polycaprolactone dispersed material liquid;
3) mixing the suspension obtained in the step 1) with the dispersed material liquid of polycaprolactone obtained in the step 2), wherein the mass ratio of starch to polycaprolactone is 0.6: 1, uniformly dispersing, transferring the obtained mixed material liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 5 hours, wherein the stirring speed is 5000rpm, zirconium oxide is used as grinding balls, and the ball-material ratio is 15: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) and pressing and molding the dried product at 90 ℃ and 20MPa for 5min to obtain the starch/polycaprolactone composite material.
The tensile strength of the composite material is 8.6 MPa.

Claims (3)

1. A preparation method of a starch/polycaprolactone composite material is characterized by comprising the following steps: the method comprises the following steps:
1) weighing starch, drying in vacuum at 80 ℃ to constant weight, dispersing the dried starch in acetone, adding polyethylene glycol 2000, and stirring and dispersing uniformly to obtain a suspension;
2) weighing dried polycaprolactone, dispersing the dried polycaprolactone into acetone, adding polyethylene glycol 6000, and uniformly stirring and dispersing to obtain polycaprolactone dispersed feed liquid;
3) mixing the suspension obtained in the step 1) with the polycaprolactone dispersed liquid obtained in the step 2), uniformly dispersing, transferring the obtained mixed liquid into a high-energy ball mill, carrying out high-energy ball milling reaction for 4-5h, wherein the stirring speed is 5000-6000rpm, zirconium oxide is used as grinding balls, and the ball-to-material ratio is 10-13: 1;
4) washing the reaction product with ethanol, filtering, drying, and distilling and recovering the washing filtrate;
5) pressing and molding the dried product to obtain a starch/polycaprolactone composite material;
wherein the mass ratio of the polycaprolactone to the polyethylene glycol 6000 is 1: 0.3-0.4;
wherein the mass ratio of the starch to the polyethylene glycol 2000 is 1: 0.08-0.15.
2. The method of claim 1, wherein: wherein, the weight ratio of starch: the mass ratio of the polycaprolactone is 0.4-0.6: 1.
3. The method of claim 1, wherein: wherein the temperature of the compression molding is 90 ℃, the pressure is 20MPa, and the time is 5 min.
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