CN115895217A - Blow molding-grade biodegradable material applied to chemical container and preparation method thereof - Google Patents
Blow molding-grade biodegradable material applied to chemical container and preparation method thereof Download PDFInfo
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- CN115895217A CN115895217A CN202211620742.5A CN202211620742A CN115895217A CN 115895217 A CN115895217 A CN 115895217A CN 202211620742 A CN202211620742 A CN 202211620742A CN 115895217 A CN115895217 A CN 115895217A
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- 238000000071 blow moulding Methods 0.000 claims abstract description 43
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
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- 238000002156 mixing Methods 0.000 claims description 18
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- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
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- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 239000002537 cosmetic Substances 0.000 abstract description 7
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- 235000011187 glycerol Nutrition 0.000 description 16
- 229920002472 Starch Polymers 0.000 description 6
- 229920000704 biodegradable plastic Polymers 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 2
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- ZLPOWNUXKJLCFE-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione hexanedioic acid terephthalic acid Chemical compound C1(C2=CC=C(C(=O)OCCCCO1)C=C2)=O.C(C2=CC=C(C(=O)O)C=C2)(=O)O.C(CCCCC(=O)O)(=O)O ZLPOWNUXKJLCFE-UHFFFAOYSA-N 0.000 description 1
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 238000009264 composting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
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- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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Classifications
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- 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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- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a blow molding level biodegradable material applied to chemical containers and a preparation method thereof, wherein the material comprises 20-30 parts of polybutylene terephthalate-adipate (PBAT), 60-80 parts of carbon nanotube modified polylactic acid (PLA), 10-20 parts of polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), 5-10 parts of polyolefin elastomer (POE), 10-15 parts of titanium dioxide, 1-4 parts of glycerol, 0.1-0.5 part of B900 antioxidant and 0.1-0.5 part of oleamide lubricant. The degradable material has good degradation rate, and the container obtained by blow molding also has excellent mechanical properties such as tensile strength, impact strength, high toughness and the like, and has good appearance transparency and good texture. Can be effectively used for the holding of the cosmetic, can give good visual impact to consumers, and then enhance the purchase intention of the consumers.
Description
Technical Field
The invention relates to the field of chemical containers, in particular to a blow molding level biodegradable material applied to the chemical containers and a preparation method thereof.
Background
Blow molding containers is the formation of a blank from a polymeric material and the addition of an auxiliary agent using an extrusion or injection apparatus, and then blow molding the container through a corresponding mold. Blow molded containers, in addition to having the advantages common to most polymeric containers, can be made into containers of different shapes and volumes, have good shape stability, can be sealed in various forms and methods, are widely used in life and industry, and specifically can be used for packaging meat, milk and fish processed products, fuels, lubricating materials, chemical raw materials, and the like, and cosmetics, pharmaceuticals, and the like. Due to their wide range of applications, the large number of uses necessarily results in a great environmental stress from waste. With the increasing strictness of requirements and standards, blow-molded containers of the fully biodegradable type have been developed. PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact property; in addition, the biodegradable plastic has excellent biodegradability, and is one of the most popular degradable materials for the research and market application of biodegradable plastics. Polylactic acid (PLA) is a new biodegradable material made using starch feedstock proposed by renewable plant resources such as corn. The starch raw material is saccharified to obtain glucose, the glucose and certain strains are fermented to prepare high-purity lactic acid, and the polylactic acid with certain molecular weight is synthesized by a chemical synthesis method.
Chinese patent CN108250696A discloses a cellulose full-biodegradation blow molding material, which comprises the following preparation raw materials in percentage by mass: polybutylene terephthalate adipate, polylactic acid, polyvinyl alcohol, straw powder, a compatilizer, an additive and a nano rigid organic material; wherein the compatilizer is at least one of polyethylene glycol, silane coupling agent, aluminum titanate and titanate; the additive is one or more of a plasticizer, a cross-linking agent and an internal lubricant; the nano rigid organic material is cellulose nano crystal or cellulose nano fibril. Chinese patent CN113736233A discloses a PBAT/PLA starch-based completely biodegradable material composition, particles, composite film and a preparation method thereof, the material composition includes: 30-60 parts of PBAT, 3-10 parts of PLA, 10-40 parts of starch, 10-20 parts of plasticizer, 0.2-0.8 part of lubricant, 0.1-0.5 part of compatilizer and 0.1-0.5 part of chain extender. Although the fully biodegradable blow molding material is prepared by blending PBAT and PLA, the space for further improvement on the aspects of degradation performance, mechanical property and the like is provided.
The blow-molded container for cosmetics, which is aimed at by different application scenes, is required to have excellent mechanical properties and high requirements on appearance and vision of packaging; the method for preparing the cosmetic container with noble appearance, exquisite appearance and transparency also has wide prospect.
Disclosure of Invention
Based on the requirements of the existing products, the invention aims to provide a blow-molding-grade biodegradable material applied to a chemical container and a preparation method thereof, wherein the biodegradable material has a good degradation rate, and the container obtained by blow molding also has excellent mechanical properties such as tensile strength, impact strength and high toughness, and has good appearance transparency and good texture. Can be effectively used for the holding of the cosmetic, can give good visual impact to consumers, and then enhance the purchase intention of the consumers.
In order to achieve the purpose, the invention adopts the technical scheme that: a blow molding level biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight:
20 to 30 portions of polybutylene terephthalate-adipate (PBAT),
60-80 parts of carbon nano tube modified polylactic acid (PLA),
10-20 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG),
5-10 parts of polyolefin elastomer (POE),
10 to 15 portions of titanium dioxide,
1 to 4 portions of glycerol,
0.1 to 0.5 portion of B900 antioxidant,
0.1 to 0.5 portion of oleamide lubricant.
Further, the blow molding grade biodegradable material comprises the following raw materials in parts by weight:
23 to 27 portions of polybutylene terephthalate-adipate (PBAT),
65-75 parts of carbon nano tube modified polylactic acid (PLA),
12 to 18 portions of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG),
7 to 8 portions of polyolefin elastomer (POE),
12 to 13 portions of titanium dioxide,
2 to 3 portions of glycerol,
0.3 to 0.4 portion of B900 antioxidant,
0.2 to 0.4 portion of oleamide lubricant.
Further, the preparation steps of the carbon nanotube modified polylactic acid (PLA) are as follows: (1) Pre-drying PLA granules in a vacuum furnace at the temperature of 75-85 ℃ for 3-4 h; (2) Dissolving 20-25 parts of PLA in 5-10L of tetrahydrofuran, heating to 50-60 ℃, and stirring for 1-2 h; (3) Dispersing 2-3 parts by weight of carbon nano tubes in 1-3L of tetrahydrofuran, and carrying out ultrasonic treatment for 1-2 h; (4) After ultrasonic treatment, adding the carbon nanotube-tetrahydrofuran dispersion liquid obtained in the step (3) into the polylactic acid solution obtained in the step (2); then continuously stirring for 2-3 h at 40-50 ℃; (5) And (4) evaporating tetrahydrofuran from the mixture obtained in the step (4), and drying the solid at room temperature to obtain the carbon nano tube modified polylactic acid. (6) And (3) sending the dried solid into a torque rheometer to obtain the carbon nano tube modified polylactic acid with good dispersion, wherein the temperature is set to be 190-200 ℃, and the rotating speed is set to be 30-40 rpm/min.
Further, the blow-molding grade biodegradable material further comprises a polyethylene glycol plasticizer; the weight portion of the stabilizer is 0.05-0.1 portion.
Further, the blow molding grade biodegradable material also comprises a polyurethane chain extender; the weight portion of the chain extender is 0.1-0.3 portion.
The invention also provides a preparation method of the blow molding level biodegradable material, which comprises the following steps:
(1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio;
(2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material.
Further, the length-diameter ratio of the double-screw extruder is (50-55): 1. the rotating speed of the screw is controlled to be 400-500 r/min.
Further, the set temperature of the twin-screw extruder is as follows: a first stage: 125-155 ℃, and the second stage: 125-155 ℃, three sections: 140-170 ℃, four sections: 135-165 ℃ and five sections: 140-170 ℃ and six stages: 140-170 ℃, seven sections: 135-175 ℃, eight sections: 150-180 ℃, nine sections: 150-180 ℃, head: 155 to 185 ℃.
The invention also provides a chemical product container which is prepared by adopting the blow molding-grade biodegradable material through blow molding.
PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact property; in addition, the biodegradable plastic has excellent biodegradability, and is one of the most popular degradable materials for the research and market application of biodegradable plastics. Polylactic acid (PLA) is a new biodegradable material made using starch feedstock proposed by renewable plant resources such as corn. The starch raw material is saccharified to obtain glucose, the glucose and certain strains are fermented to prepare high-purity lactic acid, and the polylactic acid with certain molecular weight is synthesized by a chemical synthesis method. By blending PBAT with PLA, the rigidity of blow-molded grade biodegradable materials is increased, making the blends useful for forming containers for use as cosmetics, benefiting from a good balance of strength, stiffness, flexibility and toughness. The invention further utilizes the carbon nano tube to modify PLA, and can further improve the mechanical properties of the container, such as excellent tensile strength, impact strength, high toughness and the like.
The degradation rate of polylactic acid (PLA) is lower than that of polybutylene terephthalate-adipate (PBAT); and the degradation temperature of polylactic acid (PLA) is higher than that of polybutylene terephthalate adipate (PBAT); therefore, under the same compost degradation condition, the overall degradation time is easily inconsistent; in particular, although the improvement of the mechanical property is expected, the degradation rate is further reduced, and the degradation temperature is further increased, which is disadvantageous, the applicant has selected to add a certain amount of glycerin into the biodegradable material through a large number of experiments, and compared with the discovery that the addition of glycerin can enable the PLA to be biodegraded at a lower temperature. The degradation process is as follows:
PETG resin is applied to cosmetic containers, and is an ideal container material; and the decoration treatment on the surface of the container can be enhanced, the transparency of the container is still good after the ultraviolet-resistant treatment, and the appearance of the container is similar to that of glass. However, the container molded by the material mainly containing the PETG resin is soft to touch, and the applicant applies the PETG resin as a secondary component to blow molding of the container, and the container and the carbon nanotube modified polylactic acid can effectively improve the texture of the container body after being blended, approach the touch with a glass material, and enhance the touch of consumers.
Polyolefin elastomer (POE) is a thermoplastic elastomer with a narrow relative molecular mass distribution and a uniform distribution of short chain branches; can be used for improving the toughness and the shock resistance of the high polymer material.
The composite antioxidant B900 is a high-efficiency composite antioxidant, has good light stability and excellent color fastness, has good intermiscibility with most polymers, and is particularly suitable for high-temperature production and processing of various polymer formed materials.
Compared with the prior art, the invention has the following beneficial effects: (1) Taking 65-75 parts of poly (butylene terephthalate-adipate terephthalate) (PBAT) and polylactic acid (PLA) as main components, modifying the polylactic acid by using carbon nano tubes on the basis of meeting the basic requirements of degradability and material mechanical properties, and further improving the mechanical properties such as tensile strength, impact strength, high toughness and the like; and the degradation performance is also improved. (2) Through compounding of the raw material components, the container for the food is good in appearance transparency and texture, can be effectively used for containing the shaped food, can give good visual impact to consumers, and further enhances the purchase intention of the consumers.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and clearly describe the scope of the present invention.
Example 1
Preparing carbon nanotube modified polylactic acid (PLA), wherein the preparation steps of the carbon nanotube modified polylactic acid (PLA) are as follows: (1) Pre-drying PLA granules in a vacuum furnace at the temperature of 80 ℃ for 4 hours; (2) Dissolving 20 parts by weight of PLA in 6-tetrahydrofuran, heating to 60 ℃, and stirring for 2 hours; (3) Dispersing 3 parts of carbon nano tubes in 2 tetrahydrofuran, and carrying out ultrasonic treatment for 2h; (4) After ultrasonic treatment, adding the carbon nano tube-tetrahydrofuran dispersion liquid obtained in the step (3) into the polylactic acid solution obtained in the step (2); then continuously stirring for 2h at 50 ℃; (5) And (4) evaporating tetrahydrofuran from the mixture obtained in the step (4), and drying the solid at room temperature to obtain the carbon nano tube modified polylactic acid. (6) And (3) feeding the dried solid into a torque rheometer to obtain the carbon nano tube modified polylactic acid with good dispersion, wherein the temperature is set to be 200 ℃, and the rotating speed is set to be 40rpm/min.
Example 2
A blow molding level biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 20 parts of polybutylene terephthalate-adipate (PBAT), 60 parts of carbon nanotube modified polylactic acid (PLA), 10 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG), 5 parts of polyolefin elastomer (POE), 10 parts of titanium dioxide, 1 part of glycerol, 0.1 part of B900 antioxidant and 0.1 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material comprises the following steps: (1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 50: 1. the control of the rotating speed of the screw is set to 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 135 ℃ and a second stage: 135 ℃ and three stages: 150 ℃ and four stages: 145 ℃ and five stages: 145 ℃ and six stages: 150 ℃ and seven stages: 155 ℃ and eight stages: 160 ℃ and nine stages: 160 ℃, head: 165 ℃.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
Example 3
A blow molding level biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 30 parts of polybutylene terephthalate-adipate (PBAT), 80 parts of carbon nanotube modified polylactic acid (PLA), 20 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG), 10 parts of polyolefin elastomer (POE), 15 parts of titanium dioxide, 4 parts of glycerol, 0.5 part of B900 antioxidant and 0.5 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material specifically comprises the following steps: (1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 55: 1. the control of the rotating speed of the screw is set to 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 145 ℃ and a second stage: 145 ℃ and three stages: 160 ℃ and four stages: 155 ℃ and five stages: 155 ℃ and six stages: 160 ℃ and seven stages: 165 ℃ and eight stages: 170 ℃ and nine stages: 170 ℃ and a machine head: 175 ℃.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
Example 4
A blow molding grade biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 25 parts of polybutylene terephthalate-adipate (PBAT), 70 parts of carbon nanotube modified polylactic acid (PLA), 15 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG), 7 parts of polyolefin elastomer (POE), 13 parts of titanium dioxide, 2 parts of glycerol, 0.3 part of B900 antioxidant and 0.2 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material specifically comprises the following steps: (1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 55: 1. the rotating speed of the screw is controlled to be 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 140 ℃ and a second stage: 140 ℃ and three sections: 155 ℃ and four stages: 150 ℃ and five stages: 150 ℃ and six stages: 155 ℃ and seven stages: 160 ℃ and eight stages: 165 ℃ and nine stages: 165 ℃ and a machine head: 170 deg.C.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
Comparative example 1
A blow molding grade biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 25 parts of polybutylene terephthalate-adipate (PBAT), 70 parts of polylactic acid (PLA), 15 parts of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester (PETG), 7 parts of polyolefin elastomer (POE), 13 parts of titanium dioxide, 2 parts of glycerol, 0.3 part of B900 antioxidant and 0.2 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material specifically comprises the following steps: (1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 55: 1. the rotating speed of the screw is controlled to be 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 140 ℃ and a second stage: 140 ℃ and three stages: 155 ℃ and four stages: 150 ℃ and five stages: 150 ℃ and six stages: 155 ℃ and seven stages: 160 ℃ and eight stages: 165 ℃ and nine stages: 165 ℃ and a machine head: 170 deg.C.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
Comparative example 2
A blow molding level biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 25 parts of polybutylene terephthalate-adipate (PBAT), 70 parts of carbon nanotube modified polylactic acid (PLA), 7 parts of polyolefin elastomer (POE), 13 parts of titanium dioxide, 2 parts of glycerol, 0.3 part of B900 antioxidant and 0.2 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material specifically comprises the following steps: (1) Uniformly mixing poly (butylene terephthalate-adipate) (PBAT), carbon nanotube modified polylactic acid (PLA), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 55: 1. the rotating speed of the screw is controlled to be 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 140 ℃ and second stage: 140 ℃ and three stages: 155 ℃ and four stages: 150 ℃ and five stages: 150 ℃ and six stages: 155 ℃ and seven stages: 160 ℃ and eight stages: 165 ℃ and nine stages: 165 ℃ and a machine head: 170 deg.C.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
Comparative example 3
A blow molding grade biodegradable material applied to a chemical product container comprises the following raw materials in parts by weight: 25 parts of polybutylene terephthalate-adipate (PBAT), 70 parts of carbon nano tube modified polylactic acid (PLA), 15 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG), 7 parts of polyolefin elastomer (POE), 13 parts of titanium dioxide, 0.3 part of B900 antioxidant and 0.2 part of oleamide lubricant.
The preparation method of the blow molding-grade biodegradable material specifically comprises the following steps: (1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), B900 antioxidant and oleamide lubricant according to the weight part ratio; (2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material. Wherein the length-diameter ratio of the double-screw extruder is 55: 1. the control of the rotating speed of the screw is set to 400r/min; the set temperature of the double-screw extruder is as follows: a first stage: 140 ℃ and a second stage: 140 ℃ and three stages: 155 ℃ and four stages: 150 ℃ and five stages: 150 ℃ and six stages: 155 ℃ and seven stages: 160 ℃ and eight stages: 165 ℃ and nine stages: 165 ℃ and a machine head: 170 deg.C.
The containers are obtained from the above-mentioned biodegradable materials by blow moulding.
The properties of the blow-molding grade biodegradable materials prepared in examples 1-4 and comparative examples 1-3 were tested. The results are reported in table 1.
As can be seen from the mechanical property tests in Table 1, the blow-molding-grade biodegradable material applied to the chemical container provided by the application has excellent tensile strength, impact strength and high toughness.
The films prepared by the above operations were tested for degradation rates of 60 days and 90 days by a composting method, and the degradation rates are recorded in table 2.
According to the data in table 2, the blow-molding-grade biodegradable material applied to the chemical container provided by the present application has excellent degradation performance. According to the data of comparative example 3, the degradation rate is far lower than that of the present application, so that the degradation of PLA and carbon nanotube modified PLA by glycerol can be found to be beneficial.
The above description is only for the preferred embodiment of the present invention, and it should be noted that any modification, equivalent replacement, improvement, etc. made by those skilled in the art without departing from the principle of the present invention shall be included in the protection scope of the present invention.
Claims (9)
1. A blow molding grade biodegradable material applied to a chemical product container is characterized by comprising the following raw materials in parts by weight:
20 to 30 portions of polybutylene terephthalate-adipate (PBAT),
60-80 parts of carbon nano tube modified polylactic acid (PLA),
10-20 parts of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG),
5-10 parts of polyolefin elastomer (POE),
10 to 15 portions of titanium dioxide,
1 to 4 portions of glycerol,
0.1 to 0.5 portion of B900 antioxidant,
0.1-0.5 part of oleamide lubricant.
2. The blow molding grade biodegradable material according to claim 1, characterized by comprising the following raw materials in parts by weight: 23 to 27 portions of polybutylene terephthalate-adipate (PBAT),
65-75 parts of carbon nano tube modified polylactic acid (PLA),
12 to 18 portions of polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester (PETG),
7-8 parts of polyolefin elastomer (POE),
12 to 13 portions of titanium dioxide,
2 to 3 portions of glycerol,
0.3 to 0.4 portion of B900 antioxidant,
0.2-0.4 part of oleamide lubricant.
3. The blow molding grade biodegradable material according to claim 1 or 2, wherein the carbon nanotube modified polylactic acid (PLA) is prepared by the steps of: (1) Pre-drying PLA granules in a vacuum furnace at the temperature of 75-85 ℃ for 3-4 h; (2) Dissolving 20-25 parts of PLA in 5-10L of tetrahydrofuran, heating to 50-60 ℃, and stirring for 1-2 h; (3) Dispersing 2-3 parts by weight of carbon nano tubes in 1-3L of tetrahydrofuran, and carrying out ultrasonic treatment for 1-2 h; (4) After ultrasonic treatment, adding the carbon nanotube-tetrahydrofuran dispersion liquid obtained in the step (3) into the polylactic acid solution obtained in the step (2); then continuously stirring for 2-3 h at 40-50 ℃; (5) And (5) evaporating tetrahydrofuran from the mixture obtained in the step (4), and then drying the solid at room temperature to obtain the carbon nano tube modified polylactic acid. (6) And (3) sending the dried solid into a torque rheometer to obtain the carbon nano tube modified polylactic acid with good dispersion, wherein the temperature is set to be 190-200 ℃, and the rotating speed is set to be 30-40 rpm/min.
4. The blow-molded grade biodegradable material according to claim 1 or 2, wherein said blow-molded grade biodegradable material further comprises a polyethylene glycol plasticizer; the weight portion of the stabilizer is 0.05-0.1 portion.
5. The blow molding grade biodegradable material according to claim 1 or 2, characterized in that the blow molding grade biodegradable material further comprises a polyurethane chain extender; the weight portion of the chain extender is 0.1-0.3 portion.
6. The preparation method of the blow molding grade biodegradable material according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) Uniformly mixing polybutylene terephthalate-adipate (PBAT), carbon nanotube modified polylactic acid (PLA), polyethylene terephthalate-1, 4-cyclohexanedimethanol (PETG), polyolefin elastomer (POE), glycerol, B900 antioxidant and oleamide lubricant according to the weight part ratio;
(2) And (2) feeding the mixture obtained in the step (1) through main feeding, feeding titanium dioxide through side feeding, melting by a double-screw extruder, mixing, extruding and granulating to obtain the blow molding biodegradable material.
7. The method according to claim 6, wherein the twin-screw extruder has an aspect ratio of (50-55): 1. the control of the rotating speed of the screw is set to be 400-500 r/min.
8. The method of claim 6, wherein the twin screw extruder is set to a temperature of: a first stage: 125-155 ℃, and the second stage: 125-155 ℃, three sections: 140-170 ℃, four sections: 135-165 ℃ and five sections: 140-170 ℃ and six stages: 140-170 ℃, seven sections: 135175 ℃, eight stages: 150-180 ℃, nine sections: 150-180 ℃, head: 155 to 185 ℃.
9. The chemical product container is characterized by being prepared from the blow-molding-grade biodegradable material obtained by the preparation method of any one of claims 6 to 8 through blow molding.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659488A (en) * | 2018-04-19 | 2018-10-16 | 武汉金发科技有限公司 | A kind of carbon nanotube high tenacity flame-proof polylactic acid composite material and preparation method |
| KR102222764B1 (en) * | 2020-09-17 | 2021-03-04 | 주식회사 엠보틀 | Eco-friendly cosmetic container and manufacturing method thereof |
| CN112920392A (en) * | 2021-01-20 | 2021-06-08 | 银金达(上海)新材料有限公司 | High-transparency PETG material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659488A (en) * | 2018-04-19 | 2018-10-16 | 武汉金发科技有限公司 | A kind of carbon nanotube high tenacity flame-proof polylactic acid composite material and preparation method |
| KR102222764B1 (en) * | 2020-09-17 | 2021-03-04 | 주식회사 엠보틀 | Eco-friendly cosmetic container and manufacturing method thereof |
| CN112920392A (en) * | 2021-01-20 | 2021-06-08 | 银金达(上海)新材料有限公司 | High-transparency PETG material and application thereof |
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| NAWADON PETCHWATTANA ET AL: "Plasticization of Biodegradable Poly(Lactic Acid) by Different Triglyceride Molecular Sizes: A Comparative Study with Glycerol", 《JOURNAL OF POLYMERS AND THE ENVIRONMENT》, vol. 26, 2 May 2017 (2017-05-02), pages 1160, XP036444580, DOI: 10.1007/s10924-017-1012-7 * |
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