CN117511152B - Environment-friendly polylactic acid plastic and preparation method and application thereof - Google Patents
Environment-friendly polylactic acid plastic and preparation method and application thereof Download PDFInfo
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- CN117511152B CN117511152B CN202311453522.2A CN202311453522A CN117511152B CN 117511152 B CN117511152 B CN 117511152B CN 202311453522 A CN202311453522 A CN 202311453522A CN 117511152 B CN117511152 B CN 117511152B
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- polylactic acid
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 71
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 71
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 46
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 46
- 229920001194 natural rubber Polymers 0.000 claims abstract description 46
- 238000001746 injection moulding Methods 0.000 claims abstract description 41
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005770 Eugenol Substances 0.000 claims abstract description 30
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229960002217 eugenol Drugs 0.000 claims abstract description 30
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 229940037312 stearamide Drugs 0.000 claims description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 2
- 239000005022 packaging material Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 19
- 239000012634 fragment Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012745 toughening agent 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an environment-friendly polylactic acid plastic and a preparation method and application thereof, wherein the preparation method of the environment-friendly polylactic acid plastic comprises the steps of crushing eugenol grafted modified natural rubber, mixing and banburying with polylactic acid, wherein the temperature of an internal mixer is 180 ℃, the rotating speed is 60rpm, after banburying for 5min, adding a nucleating agent and a vulcanizing agent, and continuously banburying for 10min to obtain a preform, wherein in the step, eugenol grafted modified natural rubber is obtained: polylactic acid: nucleating agent: the mass ratio of the vulcanizing agent is 8:100:0.05:0.04; and (3) transferring the preform into an injection molding machine for injection molding to obtain the environment-friendly polylactic acid plastic. The polylactic acid plastic prepared by the method can be used for preparing video packaging materials, and has good mechanical properties, and meanwhile, the raw materials of the plastic are environment-friendly and easy to degrade, so that the polylactic acid plastic has good application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an environment-friendly polylactic acid plastic and a preparation method and application thereof.
Background
Polylactic acid is a biodegradable polymer composed of lactic acid monomers, and the raw material is lactic acid, and the lactic acid belongs to renewable resources, so that the polylactic acid-based plastic product has a huge market prospect.
However, the crystallinity of polylactic acid is high, and the conventional polylactic acid plastic has the problem of larger brittleness, for example, a food package box prepared from the polylactic acid plastic is extremely easy to break after being pressed, which brings a certain limit to the application of the polylactic acid. At present, in order to overcome the problem of brittleness of polylactic acid plastics, blending toughening modification is generally adopted, for example, blending treatment is carried out with resin materials with toughness such as PBAT, TPU, PET. However, the compatibility deviation between the toughening material and the polylactic acid is common, which brings about a certain adverse effect on the mechanical properties and the like of the finally obtained polylactic acid plastic.
In view of this, how to obtain high-toughness polylactic acid plastics is one of the technical problems to be solved in the present day.
Disclosure of Invention
In view of the above, the invention provides an environment-friendly polylactic acid plastic, a preparation method and application thereof, and aims to improve the toughness of the polylactic acid plastic.
The technical scheme of the invention is realized as follows: the invention provides a preparation method of environment-friendly polylactic acid plastic, which comprises the following steps of:
Crushing eugenol grafted and modified natural rubber, mixing with polylactic acid, banburying at 180 ℃ and 60rpm for 5min, adding a nucleating agent and a vulcanizing agent, and continuously banburying for 10min to obtain a preform, wherein the eugenol grafted and modified natural rubber is prepared by the following steps: polylactic acid: nucleating agent: the mass ratio of the vulcanizing agent is 8:100:0.05:0.04;
And (3) transferring the preform into an injection molding machine for injection molding to obtain the environment-friendly polylactic acid plastic.
In the embodiment, the natural rubber has good toughening effect, after the eugenol is grafted and modified, the carbon chain of the natural rubber is provided with the benzene ring, and the benzene ring and the carbon chain of the polylactic acid form a riveting-like effect by utilizing the steric effect of the benzene ring, so that the compatibility between the natural rubber and the polylactic acid is improved.
In some embodiments, a method of preparing a eugenol graft modified natural rubber includes: adding natural rubber at 180 ℃ and 60rpm of an internal mixer for banburying, adding eugenol and benzoyl peroxide on the surface of the natural rubber after banburying for 20min, and continuing banburying for 5min to obtain eugenol grafted modified natural rubber, wherein the steps are as follows: eugenol: the mass ratio of benzoyl peroxide is 60:1:0.1.
In some embodiments, the nucleating agent is stearamide or stearamide grafted modified silica.
The stearamide can influence the crystal orientation of the polylactic acid, and in order to improve the toughness of the polylactic acid and reduce the single orientation crystallization of the polylactic acid, the application adopts the stearamide as a grafting modifier and adopts silica as a carrier, and the stearamide is grafted on the surface of the silica, so that the stearamide takes the silica as a center to carry out spherical divergent distribution, and the crystallization performance of the polylactic acid is improved.
In some embodiments, a method of preparing stearamide grafted modified silica comprises:
Dispersing silica in ethanol, adding surfactant 3-aminopropyl trimethyloxysilane, mixing, and heating to 60deg.C to obtain silica dispersion;
Adding stearamide into ethanol, heating to 60 ℃, stirring and dissolving to obtain a stearamide solution;
Adding the stearamide solution into the stirred silica dispersion, then carrying out heat preservation and stirring treatment for 10min, and filtering and drying to obtain the stearamide grafted modified silica.
In some embodiments, the silica: 3-aminopropyl trimethyloxysilane: the mass ratio of the stearamide is 1:0.1:0.1.
In some embodiments, the sulfiding agent is a mixture of sulfur, sulfotetraol and zinc oxide, sulfur: thiol tetrasulfide: the mass ratio of zinc oxide is 10:2:3.
In a second aspect, the invention also provides an environment-friendly polylactic acid plastic, which is prepared by adopting the preparation method.
In a third aspect, the polylactic acid plastic of the present invention may be used to prepare food packaging.
Compared with the prior art, the environment-friendly polylactic acid plastic, the preparation method and the application thereof have the following steps
The beneficial effects are that:
The environment-friendly polylactic acid plastic adopts the natural rubber as the main component for toughening modification, the toughness of the environment-friendly polylactic acid plastic is greatly improved on the premise of not influencing the environment-friendly degradation of the polylactic acid plastic, and the eugenol is adopted for grafting modification of the natural rubber, so that the compatibility and the bonding strength between the natural rubber and the polylactic acid are improved, and the impact strength and the tensile strength of the polylactic acid plastic are also improved. Compared with the conventional polylactic acid, the environment-friendly polylactic acid plastic has the advantages of improved toughness, simple overall preparation process and improved structural stability of package when being applied to preparing restaurant packages.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
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 embodiments of the invention belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications and other publications incorporated herein by reference, the definitions set forth in this section are preferentially set forth in the definitions set forth herein.
Example 1
Preparing eugenol grafted and modified natural rubber:
setting the temperature of an internal mixer at 180 ℃ and the rotating speed at 60r/min, adding 600g of natural rubber, banburying for 20min, then spraying a mixture of 10g of eugenol and 1g of benzoyl peroxide on the surface of the natural rubber, and continuing banburying for 5min after the spraying is finished, thus obtaining the eugenol grafted modified natural rubber.
Preparation of polylactic acid plastic:
The temperature of the internal mixer is set to 180 ℃ and the rotating speed is 60r/min, 400g of the prepared modified natural rubber is cut into fragments under the condition of heat preservation and no cooling, then the fragments are mixed with 5000g of polylactic acid particles, the mixture is added into the internal mixer, after banburying for 5min, 2.5g of stearamide, 13g of sulfur, 2.8g of tetrasulfide mercaptan and 4.2g of zinc oxide are added, and banburying is continued for 10min, so as to obtain a preform.
Cutting the preform into fragments under the condition of heat preservation and uncooled, then adding the fragments into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 15 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Example 2
Preparing eugenol grafted and modified natural rubber:
setting the temperature of an internal mixer at 180 ℃ and the rotating speed at 60r/min, adding 600g of natural rubber, banburying for 20min, then spraying a mixture of 10g of eugenol and 1g of benzoyl peroxide on the surface of the natural rubber, and continuing banburying for 5min after the spraying is finished, thus obtaining the eugenol grafted modified natural rubber.
Preparation of modified silica:
Dispersing 10g of silica in 200ml of absolute ethyl alcohol, adding 1g of 3-aminopropyl trimethyloxysilane, stirring and heating to 60 ℃, and preserving heat to obtain silica dispersion;
Adding 1g of stearamide into 100ml of absolute ethyl alcohol, heating to 60 ℃, and carrying out heat preservation, stirring and dissolution to obtain a stearamide solution;
Slowly adding the stearamide solution into the stirred silica dispersion, carrying out heat preservation and stirring treatment for 10min, and filtering and drying to constant weight to obtain the stearamide grafted modified silica.
Preparation of polylactic acid plastic:
the temperature of the internal mixer is set to 180 ℃ and the rotating speed is 60r/min, 400g of the prepared modified natural rubber is cut into fragments under the condition of heat preservation and no cooling, then the fragments are mixed with 5000g of polylactic acid particles, the mixture is added into the internal mixer, 2.5g of stearamide grafted modified silica, 13g of sulfur, 2.8g of tetrasulfide thiol and 4.2g of zinc oxide are added after banburying for 5min, and banburying is continued for 10min, so as to obtain a preform.
Cutting the preform into fragments under the condition of heat preservation and uncooled, then adding the fragments into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 15 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Comparative example 1
Preparation of polylactic acid plastic:
The temperature of the internal mixer is set to 180 ℃ and the rotating speed is 60r/min, 400g of natural rubber is taken, mixed with 5000g of polylactic acid particles, added into the internal mixer, banburying for 5min, added with 2.5g of stearamide, 13g of sulfur, 2.8g of tetrasulfide thiol and 4.2g of zinc oxide, and banburying is continued for 10min, thus obtaining the preform.
Cutting the preform into fragments under the condition of heat preservation and uncooled, then adding the fragments into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 15 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Comparative example 2
Preparing eugenol grafted and modified natural rubber:
setting the temperature of an internal mixer at 180 ℃ and the rotating speed at 60r/min, adding 600g of natural rubber, banburying for 20min, then spraying a mixture of 10g of eugenol and 1g of benzoyl peroxide on the surface of the natural rubber, and continuing banburying for 5min after the spraying is finished, thus obtaining the eugenol grafted modified natural rubber.
Preparation of polylactic acid plastic:
400g of the prepared modified natural rubber is taken, cut into fragments under the condition of heat preservation and no cooling, mixed with 5000g of polylactic acid particles, 2.5g of stearamide, 13g of sulfur, 2.8g of tetrasulfide mercaptan and 4.2g of zinc oxide, and then added into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area of the injection molding machine is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 15 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Comparative example 3
Preparing eugenol grafted and modified natural rubber:
setting the temperature of an internal mixer at 180 ℃ and the rotating speed at 60r/min, adding 600g of natural rubber, banburying for 20min, then spraying a mixture of 10g of eugenol and 1g of benzoyl peroxide on the surface of the natural rubber, and continuing banburying for 5min after the spraying is finished, thus obtaining the eugenol grafted modified natural rubber.
Preparation of modified silica:
Dispersing 10g of silica in 200ml of absolute ethyl alcohol, adding 1g of 3-aminopropyl trimethyloxysilane, stirring and heating to 60 ℃, and preserving heat to obtain silica dispersion;
Adding 1g of stearamide into 100ml of absolute ethyl alcohol, heating to 60 ℃, and carrying out heat preservation, stirring and dissolution to obtain a stearamide solution;
Slowly adding the stearamide solution into the stirred silica dispersion, carrying out heat preservation and stirring treatment for 10min, and filtering and drying to constant weight to obtain the stearamide grafted modified silica.
Preparation of polylactic acid plastic:
400g of the modified natural rubber prepared by the method is taken, cut into fragments under the condition of heat preservation and no cooling, mixed with 5000g of polylactic acid particles, 2.5g of stearamide grafted modified silica, 13g of sulfur, 2.8g of tetrasulfide mercaptan and 4.2g of zinc oxide, and then added into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area of the injection molding machine is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 15 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Comparative example 4
Preparation of polylactic acid plastic:
The temperature of the internal mixer is set to 180 ℃ and the rotating speed is 60r/min, 400g of natural rubber is taken, mixed with 5000g of polylactic acid particles, added into the internal mixer, banburying for 5min, added with 2.5g of stearamide, 13g of sulfur, 2.8g of tetrasulfide thiol and 4.2g of zinc oxide, and banburying is continued for 10min, thus obtaining the preform.
Cutting the preform into fragments under the condition of heat preservation and uncooled, then adding the fragments into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. After the injection molding is finished, the temperature is rapidly reduced at a cooling rate of more than 30 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Comparative example 5
Preparation of polylactic acid plastic:
The temperature of the internal mixer is set to 180 ℃ and the rotating speed is 60r/min, 400g of natural rubber is taken, mixed with 5000g of polylactic acid particles, added into the internal mixer, banburying for 5min, added with 2.5g of stearamide, 13g of sulfur, 2.8g of tetrasulfide thiol and 4.2g of zinc oxide, and banburying is continued for 10min, thus obtaining the preform.
Cutting the preform into fragments under the condition of heat preservation and uncooled, then adding the fragments into an injection molding machine, wherein the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 10 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
Blank examples
The polylactic acid particles are added into an injection molding machine, the temperature of a feeding area of the injection molding machine is 190 ℃, the temperature of a middle section of the injection molding machine is 200 ℃, and the temperature of a nozzle area is 205 ℃. And after the injection molding is finished, cooling is carried out according to the cooling rate of 10 ℃/min, and the injection molded sample bar is a dumbbell sample bar with the length of 75mm, the width of 7mm and the thickness of 2 mm.
The plastic bars of the above examples and comparative examples were respectively subjected to mechanical property tests, the test items including: tensile property testing, impact property testing and bending property testing.
Tensile property test:
And (3) placing the material at 25+/-2 ℃, carrying out balanced standing treatment for 7d, testing by a universal tensile testing machine, wherein the pulling-up speed is 5mm/min, testing the tensile strength and the elongation at break, testing for 5 times, and taking an arithmetic average value.
Impact performance test:
The reverse notch impact test is carried out by using an impact tester, the notch depth is 0.25mm, the notch is a V-shaped 45-degree cross notch, the impact is carried out on the samples by using a pendulum bob, each sample is tested 5 times, and the arithmetic average value is obtained.
Bending performance test:
The test was performed using a universal tensile tester with a support span of 60mm, bending properties were measured at a rate of 5mm/min, bending strength was recorded, each sample tested 5 times, and an arithmetic average was taken.
The following results were obtained after the measurement:
As can be seen from the experimental data of the above examples and comparative examples, the invention adopts the eugenol grafted and modified natural rubber as the toughening agent, the mechanical properties of the polylactic acid plastic are effectively improved after the polylactic acid is toughened, most of the adopted raw materials are from natural raw materials, the environment is protected, the degradation is easy, and meanwhile, the invention also adopts the hard amide as the nucleating agent, and especially when the hard amide grafted and modified silica is adopted as the nucleating agent, the mechanical properties of the obtained stearic acid plastic are obviously improved. Meanwhile, the invention adopts twice banburying operation, the first banburying is used for preparing modified natural rubber, the second banburying is used for mixing raw materials of all components, experimental comparison shows that the polylactic acid plastic prepared by banburying has better mechanical property than the polylactic acid plastic obtained by conventional direct mixing injection molding extrusion, and high aluminum can strengthen the dispersion effect of modified components in the banburying process.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The preparation method of the environment-friendly polylactic acid plastic is characterized in that the raw materials of the environment-friendly polylactic acid plastic comprise polylactic acid, eugenol grafted modified natural rubber, a nucleating agent and a vulcanizing agent, and the preparation method of the environment-friendly polylactic acid plastic comprises the following steps:
Crushing eugenol grafted and modified natural rubber, mixing with polylactic acid, banburying at 180 ℃ and 60rpm for 5min, adding a nucleating agent and a vulcanizing agent, and continuously banburying for 10min to obtain a preform, wherein in the step, the eugenol grafted and modified natural rubber is obtained: polylactic acid: nucleating agent: the mass ratio of the vulcanizing agent is 8:100:0.05:0.04;
Transferring the preform into an injection molding machine for injection molding to obtain environment-friendly polylactic acid plastic;
The preparation method of the eugenol grafted and modified natural rubber comprises the following steps: adding natural rubber at 180 ℃ and 60rpm of an internal mixer for banburying, adding eugenol and benzoyl peroxide on the surface of the natural rubber after banburying for 20min, and continuing banburying for 5min to obtain eugenol grafted modified natural rubber, wherein the steps are as follows: eugenol: the mass ratio of benzoyl peroxide is 60:1:0.1;
The nucleating agent is stearamide grafted modified silica, and the preparation method of the stearamide grafted modified silica comprises the following steps:
Dispersing silica in ethanol, adding surfactant 3-aminopropyl trimethyloxysilane, mixing, and heating to 60deg.C to obtain silica dispersion;
Adding stearamide into ethanol, heating to 60 ℃, stirring and dissolving to obtain a stearamide solution;
adding a stearamide solution into the stirred silica dispersion, then carrying out heat preservation and stirring treatment for 10min, and filtering and drying to obtain stearamide grafted modified silica;
wherein, silica: 3-aminopropyl trimethyloxysilane: the mass ratio of the stearamide is 1:0.1:0.1.
2. The method for preparing environment-friendly polylactic acid plastic according to claim 1, wherein the vulcanizing agent is a mixture of sulfur, tetrasulfide thiol and zinc oxide, and sulfur: thiol tetrasulfide: the mass ratio of zinc oxide is 10:2:3.
3. An environment-friendly polylactic acid plastic, which is characterized by being prepared by the preparation method of any one of claims 1-2.
4. The use of the environment-friendly polylactic acid plastic prepared by the preparation method of any one of claims 1-2 in preparing restaurant packages.
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| CN103642184A (en) * | 2013-11-22 | 2014-03-19 | 华南理工大学 | Dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof |
| CN106366596A (en) * | 2016-09-30 | 2017-02-01 | 青岛科技大学 | Polylactic acid/chemically modified natural rubber blend material and preparing method thereof |
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| CN102276965B (en) * | 2011-06-25 | 2013-03-06 | 四川大学 | Method for toughening and modifying polylactic acid by natural rubber |
| CN102229744B (en) * | 2011-06-25 | 2013-06-12 | 四川大学 | Toughening polylactic acid blend with excellent biocompatibility and preparation method thereof |
| CN105199249B (en) * | 2015-10-27 | 2017-07-04 | 上海工程技术大学 | A kind of preparation method of the chlorinated butyl damping rubber containing modified montmorillonoid damping agent |
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| CN103642184A (en) * | 2013-11-22 | 2014-03-19 | 华南理工大学 | Dynamically vulcanized polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof |
| CN106366596A (en) * | 2016-09-30 | 2017-02-01 | 青岛科技大学 | Polylactic acid/chemically modified natural rubber blend material and preparing method thereof |
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