CN110922707A - Composite biodegradable material and preparation method thereof - Google Patents
Composite biodegradable material and preparation method thereof Download PDFInfo
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- CN110922707A CN110922707A CN201911277371.3A CN201911277371A CN110922707A CN 110922707 A CN110922707 A CN 110922707A CN 201911277371 A CN201911277371 A CN 201911277371A CN 110922707 A CN110922707 A CN 110922707A
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- intermediate product
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- thermoplastic starch
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 42
- 239000004626 polylactic acid Substances 0.000 claims abstract description 42
- 239000013067 intermediate product Substances 0.000 claims abstract description 33
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 32
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 229920000728 polyester Polymers 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- 229920002472 Starch Polymers 0.000 claims description 20
- 235000019698 starch Nutrition 0.000 claims description 20
- 239000008107 starch Substances 0.000 claims description 20
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 12
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- 239000004386 Erythritol Substances 0.000 claims description 11
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 11
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 11
- 235000019414 erythritol Nutrition 0.000 claims description 11
- 229940009714 erythritol Drugs 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- -1 polybutylene succinate Polymers 0.000 claims description 4
- 229920002961 polybutylene succinate Polymers 0.000 claims description 4
- 239000004631 polybutylene succinate Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 239000000806 elastomer Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920006238 degradable plastic Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- NDEIPVVSKGHSTL-UHFFFAOYSA-N butane-1,1,1,2-tetrol Chemical compound CCC(O)C(O)(O)O NDEIPVVSKGHSTL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Abstract
The invention relates to a composite biodegradable material and a preparation method thereof, which comprises the steps of firstly mixing linear polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide, then carrying out reactive extrusion to obtain an intermediate product, and then compounding the intermediate product with a polylactic acid base material to obtain the composite biodegradable material; in the reactive extrusion process, dicumyl peroxide initiates maleic anhydride to simultaneously react with linear polyester and thermoplastic starch to form an interpenetrating network structure, so that the prepared intermediate product becomes an elastomer with giant molecular free space, and the impact resistance of the polylactic acid substrate can be greatly improved. The prepared composite biodegradable material has good impact resistance, biodegradability, thermal stability and water resistance.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a composite biodegradable material and a preparation method thereof.
Background
The application of the traditional non-degradable plastics brings convenience to the production and life of human beings and brings hazards such as polluted soil, water, ocean and the like. With the gradual increase of human environmental awareness and the increasing desire for degradable and environmentally friendly materials, more than ten degradable plastics including polylactic acid have been developed, but the application of the degradable plastics in real life is greatly limited due to more or less defects of the degradable plastics.
Polylactic acid (PLLA) is a biodegradable material with wide application prospect, the raw material is starch with wide source, but the defect of poor impact resistance greatly limits the application of the material, in order to further expand the application field of the PLLA, especially to meet the requirement of the field with high requirement on the impact resistance of the material, researchers have conducted many exploration and research on the aspect of improving the impact resistance of the PLLA, at present, the impact resistance is improved mainly by adding a toughening agent or a plasticizer into PLLA resin, however, the traditional toughening agent or the plasticizer has poor compatibility with the polylactic acid, and the plasticizer is separated out in the using process of the PLLA material, so that the physical property, the mechanical property and the heat resistance of the polylactic acid are reduced, the biodegradability of the polylactic acid is influenced, the cost is high, and the large-scale application is not facilitated.
Disclosure of Invention
Based on the above, the invention provides a composite biodegradable material and a preparation method thereof.
The technical scheme of the invention is as follows.
One aspect of the invention provides a preparation method of a composite biodegradable material, which comprises the following steps:
mixing linear polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide to obtain premix 1;
carrying out reaction extrusion on the premix 1 to obtain an intermediate product;
mixing the intermediate product and polylactic acid to obtain premix 2;
melting and extruding the premix 2 to obtain a composite biodegradable material;
wherein the linear polyester is selected from at least one of polycaprolactone or polybutylene succinate;
according to the mass parts, the dosage ratio of the intermediate product to the polylactic acid is 100: (12-35).
In the above preparation method, the ratio of the amount of the intermediate product to the amount of the polylactic acid is 100: (12-20).
In the above production method, the mass ratio of the linear polyester, the thermoplastic starch, the maleic anhydride, and the dicumyl peroxide is (60 to 100): (6-15): (0.5-1.5): 1.
in the preparation method, the reactive extrusion is carried out by adopting a screw extruder, wherein the temperature of the screw extruder is as follows according to the advancing direction of the materials: 95-115 ℃, 110-135 ℃, 130-155 ℃, 140-160 ℃, 155-165 ℃ and the head temperature is 150-160 ℃.
In the preparation method, the particle size of the intermediate product is controlled to be less than 3 mm.
The preparation method also comprises the following steps of: mixing esterified starch, glycerol, 1, 6-hexanediol, erythritol and stearic acid to obtain premix 3;
and (3) carrying out melt extrusion on the premix 3 to obtain the thermoplastic starch.
In the preparation method, the esterified starch, the glycerol, the 1, 6-hexanediol, the erythritol and the stearic acid are mixed for 10 to 30 minutes at a temperature of between 45 and 75 ℃.
In the above production method, the mass ratio of the esterified starch, the glycerin, the 1, 6-hexanediol, the erythritol, and the stearic acid is (30 to 50): (2-5): (1-3): (1-2): 1.
in the preparation method, the melt extrusion of the premix 3 is carried out by adopting a screw extruder, wherein the temperature of the screw extruder is as follows in sequence according to the advancing direction of the materials: 75-95 ℃, 90-115 ℃, 110-135 ℃, 130-145 ℃, 140-155 ℃ and the head temperature is 135-150 ℃.
The invention also provides the composite biodegradable material prepared by the preparation method.
Advantageous effects
The preparation method comprises the steps of firstly mixing linear polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide, then carrying out reaction extrusion to obtain an intermediate product, and then compounding the intermediate product with a polylactic acid base material to obtain a composite biodegradable material; dicumyl peroxide is used as an initiator to initiate maleic anhydride to simultaneously react with linear polyester and thermoplastic starch to form an interpenetrating network structure, so that a prepared intermediate product becomes an elastomer with a giant molecular free space, when the elastomer is acted by an external force, the elastomer consumes stress through large deformation, and meanwhile, the deformation and a shear band of the elastomer can be used for preventing the silver lines from expanding and increasing, so that the weak parts are prevented from generating micro lines due to stress concentration, and further, the shock resistance of the polylactic acid base material can be greatly improved. In addition, the linear polyester and the polylactic acid have similar structures and are linear high molecular materials which contain ester groups and can be completely degraded, an intermediate product prepared by taking the linear polyester as a main material has good compatibility with the polylactic acid, and the prepared composite biodegradable material can keep excellent biodegradability.
Furthermore, the thermoplastic starch provided by the invention is prepared from esterified starch, glycerol, 1, 6-hexanediol, erythritol and stearic acid, wherein the esterified starch is a product obtained by esterifying hydroxyl of starch with inorganic acid or organic acid, the water absorption of polylactic acid can be improved, and the degradation caused by water absorption of the product in the processes of storage and use is prevented, so that the service life of the material is prolonged.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a method for preparing a composite biodegradable material, including the following steps S1-S4.
S1, mixing the linear polyester, the thermoplastic starch, the maleic anhydride and the dicumyl peroxide to obtain the premix 1.
Wherein the linear polyester is at least one selected from polycaprolactone or polybutylene succinate.
In one embodiment, the mixing is performed in a high speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
S2, carrying out reaction extrusion on the premix 1 obtained in the step S1 to obtain an intermediate product.
In one embodiment, the mass ratio of the linear polyester to the thermoplastic starch to the maleic anhydride to the dicumyl peroxide is (60-100): (6-15): (0.5-1.5): 1.
in one embodiment, the reactive extrusion in the above step is performed by using a screw extruder, wherein the temperature of the screw extruder is, in order according to the material advancing direction: 95-115 ℃, 110-135 ℃, 130-155 ℃, 140-160 ℃, 155-165 ℃ and the head temperature is 150-160 ℃. Further, the rotation speed of the screw is 80rpm to 110 rpm.
In the reaction extrusion process, the maleic anhydride initiated by dicumyl peroxide simultaneously reacts with polylactic acid and thermoplastic starch, and fully reacts to form an interpenetrating network structure through the gradual heating process, so that the prepared intermediate product becomes an elastomer with huge molecular free space.
In one embodiment, step S2 further includes crushing the intermediate product to control the particle size of the intermediate product to be less than 3 mm.
It will be appreciated that the crushing may be carried out using a crusher, or other apparatus capable of effecting crushing of material.
And S3, mixing the intermediate product obtained in the step S2 with polylactic acid to obtain premix 2.
Wherein the dosage ratio of the intermediate product to the polylactic acid is 100: (12-35).
In one embodiment, the ratio of the amount of the intermediate product to the amount of the polylactic acid is 100: (12-20).
In one embodiment, the mixing is performed in a high speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
S4, carrying out melt extrusion on the premix 2 obtained in the step S3 to obtain the composite biodegradable material.
In one embodiment, the melt extrusion of premix 2 is carried out using a screw extruder, wherein the temperature of the screw extruder is, in order of the material advance direction: 120-145 ℃, 135-155 ℃, 145-165 ℃, 155-175 ℃, 165-180 ℃ and the head temperature is 160-170 ℃. Further, the rotation speed of the screw machine is 90 rpm-110 rpm.
The preparation method comprises the steps of firstly mixing linear polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide, then carrying out reaction extrusion to obtain an intermediate product, and then introducing the intermediate product into a polylactic acid substrate to obtain a composite biodegradable material; dicumyl peroxide is used as an initiator to initiate maleic anhydride to simultaneously react with linear polyester and thermoplastic starch to form an interpenetrating network structure, so that the prepared intermediate product becomes an elastomer with a giant molecular free space, when the elastomer is acted by external force, the elastomer consumes stress through large deformation, and simultaneously can prevent silver lines from expanding and growing by utilizing deformation and a shear band of the elastomer, so that the phenomenon that cracks are generated due to stress concentration at weak parts is avoided, and the impact resistance of the polylactic acid substrate can be greatly improved.
The thermoplastic starch, polycaprolactone and poly (butylene succinate) used in the invention are linear high molecular materials, and molecular chains have good flexibility and toughness, so that the mechanical property of the composite material can be further improved. In addition, the linear polyester and the polylactic acid have similar structures and are linear high molecular materials which contain ester groups and can be completely degraded, an intermediate product prepared by taking the linear polyester as a main material has good compatibility with the polylactic acid, and the prepared composite biodegradable material can keep excellent biodegradability.
In one embodiment, the above preparation method further includes steps S11-S12 of preparing thermoplastic starch.
S11, mixing the esterified starch, the glycerol, the 1, 6-hexanediol, the erythritol and the stearic acid to obtain premix 3.
In one embodiment, the mass ratio of the esterified starch, the glycerol, the 1, 6-hexanediol, the erythritol and the stearic acid is (30-50): (2-5): (1-3): (1-2): 1.
in one embodiment, the esterified starch, glycerol, 1, 6-hexanediol, erythritol, and stearic acid are mixed at 45 ℃ to 75 ℃ for 10min to 30 min.
The esterified starch is a product obtained by esterifying hydroxyl of starch with inorganic acid or organic acid, can improve the water absorption of polylactic acid, and prevents the product from being degraded due to water absorption in the processes of storage and use, thereby prolonging the service life of the material.
S12, melt-extruding the premix 3 obtained in the step S12 to obtain thermoplastic starch.
In one embodiment, the melt extrusion of premix 3 is carried out using a screw extruder, wherein the temperature of the screw extruder is, in order of the material advancing direction: 75-95 ℃, 90-115 ℃, 110-135 ℃, 130-145 ℃, 140-155 ℃ and the head temperature is 135-150 ℃. Further, the rotation speed of the screw is 80rpm to 120 rpm.
In one embodiment, step S12 further includes pulverizing the thermoplastic starch to facilitate mixing with polybutylene succinate and maleic anhydride for preparing the intermediate product.
The thermoplastic starch is prepared from esterified starch, glycerol, 1, 6-hexanediol, erythritol and stearic acid, the thermoplastic starch is a linear polymer, the molecular chain has good flexibility and toughness, and polylactic acid is introduced into an intermediate product obtained by using dicumyl oxide as a trigger to react maleic anhydride with linear polyester and the thermoplastic starch, so that the impact resistance of a polylactic acid base material can be greatly improved, the mechanical property of the material can be further improved, the water absorption of the polylactic acid can be improved, the reduction of the material performance caused by the water absorption of the product in the processes of storage and use can be prevented, the service life of the material can be prolonged, and the prepared composite biodegradable material can keep excellent biodegradability.
It is to be understood that the thermoplastic starch may also be a commercially available thermoplastic starch.
An embodiment of the invention also provides the composite biodegradable material prepared by the preparation method.
The composite biodegradable material has excellent shock resistance, thermal stability, toughness and water resistance, and keeps excellent biodegradability.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The composite biodegradable material and the method for preparing the same according to the present invention are exemplified herein, but the present invention is not limited to the following examples.
The preparation steps of the composite biodegradable materials of examples 1-7 and comparative examples 1-3 are as follows:
1) 80g of esterified starch, 10g of glycerol, 5g of 1, 6-hexanediol, 3g of butanetetraol and 2g of stearic acid were mixed in a high-speed mixer at 50 ℃ for 10 minutes to give a premix which was ready for use in step 2).
2) And (2) performing reaction extrusion on the premix by using a double-screw extruder, wherein the temperature of the double-screw extruder is as follows according to the advancing direction of the materials: 90 ℃, 110 ℃, 130 ℃, 140 ℃, 150 ℃, 145 ℃ and 110rpm of a double-screw extruder) to obtain thermoplastic starch, and crushing the thermoplastic starch in a crusher to obtain powdery thermoplastic starch for later use in the step 3).
3) Weighing thermoplastic polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide according to the table 1, adding the weighed thermoplastic polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide into a high-speed mixer, mixing to obtain a premix, and using the premix in the step 4).
4) And extruding the premix through a double-screw extruder, wherein the temperature of the double-screw extruder is as follows according to the advancing direction of the materials: first zone 100 deg.C, second zone 120 deg.C, third zone 140 deg.C, fourth zone 150 deg.C, fifth zone 155 deg.C, head 150 deg.C, and rotation speed of twin-screw extruder 110rpm) to obtain modifier, pulverizing elastomer in pulverizer, controlling size of elastomer to be less than 2mm, and preparing in step 4).
5) Weighing polylactic acid and the intermediate product according to the table 2, adding the polylactic acid and the intermediate product into a high-speed mixer, mixing to obtain a primary mixed material, and using the primary mixed material in the step 5).
6) And melting and extruding the initial mixed material through a double-screw extruder (the temperature of the double-screw extruder is as follows according to the advancing direction of the material: the first zone is 125 ℃, the second zone is 145 ℃, the third zone is 155 ℃, the fourth zone is 165 ℃, the fifth zone is 175 ℃, the head is 170 ℃, and the rotating speed of the double-screw extruder is 100rpm), thus obtaining the composite biodegradable material.
TABLE 1
TABLE 2
| Raw materials (g) | Intermediate product | Polylactic acid |
| Example 1 | 12 | 100 |
| Example 2 | 15 | 100 |
| Example 3 | 25 | 100 |
| Example 4 | 33 | 100 |
| Example 5 | 17 | 100 |
| Example 6 | 20 | 100 |
| Example 7 | 35 | 100 |
| Comparative example 1 | 15 | 100 |
| Comparative example 2 | 38 | 100 |
Example 8
Example 8 is essentially the same as example 2, except that the esterified starch in step 1) of example 2 is replaced by unesterified starch.
Performance testing
1) And carrying out an impact resistance test on the composite biodegradable material prepared in the examples 1-8 and the comparative examples 1-2 and the polylactic acid as the raw material: performed according to standard GB1943-2007, the results are shown in table 3.
2) The tensile strength of the composite biodegradable material and the polylactic acid as the raw material prepared in examples 1 to 8 and comparative examples 1 to 2 was measured: the results are shown in Table 3, performed according to the standard GB 1040-92.
3) The biodegradability of the composite biodegradable materials and polylactic acid as the raw material prepared in examples 1 to 8 and comparative examples 1 to 2 was tested: performed according to the standard GB/T19277, the results are shown in Table 3.
4) The water absorption performance of the composite biodegradable material and the polylactic acid as the raw material prepared in examples 1 to 8 and comparative examples 1 to 2 was tested: performed according to standard GB/T1034-1998, the results are shown in Table 3.
TABLE 3
The results in table 3 show that the impact strength of the composite biodegradable materials of examples 1 to 8 is greater than that of the composite materials of comparative examples 1 to 2, which indicates that the composite biodegradable materials of examples 1 to 8 have excellent impact resistance, and the composite biodegradable materials of examples 1 to 7 have excellent thermal stability and toughness, and can maintain good biodegradability, and compared with the composite biodegradable materials prepared by preparing thermoplastic starch from unesterified starch in example 8, the composite biodegradable materials of examples 1 to 7 have lower water absorption, and can prevent the products from absorbing water to cause degradation during storage and use, thereby prolonging the service life of the materials.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the composite biodegradable material is characterized by comprising the following steps of:
mixing linear polyester, thermoplastic starch, maleic anhydride and dicumyl peroxide to obtain premix 1;
reacting and extruding the premix 1 to obtain an intermediate product;
mixing the intermediate product and polylactic acid to obtain premix 2;
melting and extruding the premix 2 to obtain a composite biodegradable material;
wherein the linear polyester is selected from at least one of polycaprolactone or polybutylene succinate;
according to the mass parts, the dosage ratio of the intermediate product to the polylactic acid is 100: (12-35).
2. The method of claim 1, wherein the ratio of the amount of the intermediate product to the amount of the polylactic acid is 100: (12-20).
3. The method according to claim 1, wherein the mass ratio of the linear polyester to the thermoplastic starch to the maleic anhydride to the dicumyl peroxide is (60 to 100): (6-15): (0.5-1.5): 1.
4. the process according to any one of claims 1 to 3, wherein the reactive extrusion is carried out using a screw extruder, wherein the temperature of the screw extruder, in the direction of advance of the material, is, in order: 95-115 ℃, 110-135 ℃, 130-155 ℃, 140-160 ℃, 155-165 ℃ and the head temperature is 150-160 ℃.
5. The production method according to any one of claims 1 to 3, wherein the particle size of the intermediate product is controlled to be less than 3 mm.
6. The production method according to any one of claims 1 to 3, further comprising a step of producing the thermoplastic starch: mixing esterified starch, glycerol, 1, 6-hexanediol, erythritol and stearic acid to obtain premix 3;
and melting and extruding the premix 3 to obtain the thermoplastic starch.
7. The method according to claim 6, wherein the esterified starch, glycerin, 1, 6-hexanediol, erythritol and stearic acid are mixed at 45 to 75 ℃ for 10 to 30 minutes.
8. The method according to claim 6, wherein the mass ratio of the esterified starch, the glycerin, the 1, 6-hexanediol, the erythritol, and the stearic acid is (30-50): (2-5): (1-3): (1-2): 1.
9. the process according to claim 6, wherein the melt extrusion of premix 3 is carried out using a screw extruder, wherein the temperature of the screw extruder, in the direction of advance of the material, is, in order: 75-95 ℃, 90-115 ℃, 110-135 ℃, 130-145 ℃, 140-155 ℃ and the head temperature is 135-150 ℃.
10. The composite biodegradable material prepared by the preparation method according to any one of claims 1 to 9.
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