CN106633722B - Tear-resistant high-toughness biodegradable material and preparation method thereof - Google Patents
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Abstract
The invention discloses a tear-resistant high-toughness biodegradable material which comprises the following substances in percentage by mass: 30-96.3% of PLA, 5-60% of PBAT, 1-30% of plasticizer, 0.5-15% of nano material, 0-20% of mineral powder, 0.1-0.5% of epoxy chain extender, 0.1-2% of coupling agent and 0.1-1% of antioxidant. The material is prepared by adopting a two-step melt blending process: (1) after the surface treatment is carried out on the nano material by a high-speed mixer, a PBAT/nano material one-step material is prepared by a high-rotating-speed and high-torque double-screw extruder; (2) adopts a double-screw extruder, finishes reaction plasticization at the front section of the extruder by a step-by-step feeding method, and realizes reactive chain extension and compatibilization at the middle and rear sections. The material has the advantages of high tear strength and good flexibility, and has good application prospect in the fields of express delivery, food, clothing, daily necessity packaging and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, particularly relates to a tear-resistant high-toughness biodegradable material and a preparation method thereof, and particularly relates to a nano-material modified and acetyl epoxidized vegetable oil acid adipic acid glyceride plasticized and toughened biodegradable material and a preparation method thereof. The material has the advantages of tear resistance, high toughness and the like.
Background
In recent years, online shopping has become an important shopping mode. The national express business volume reaches 206 hundred million pieces in 2015, the year increases by 48 percent, 29.6 hundred million woven bags, 82.6 hundred million plastic bags, 99 hundred million packing boxes, 169.5 hundred million adhesive tapes and CO are consumed2Discharging 2300 million tons.
At present, the packaging bag for express is provided with a plastic bag, a file seal, a bubble bag, a woven bag and the like. The express delivery plastic bag made of Polyethylene (PE) has the advantages of low cost, convenience in use, good waterproof performance and the like, and is a main material for express delivery packaging. However, because polyethylene cannot be degraded and the recovery cost is high, the produced express packaging garbage has wide coverage and great harm to the environment.
In 2016, the green movement plan is started by a vegetable and bird network with 32 global logistics partners, and 50% of packaging materials are replaced by 100% degradable green packaging materials in the promise of 2020. The biodegradable material shows good application prospect in the fields of express packaging and the like, and is one of effective means for solving packaging garbage pollution, protecting the earth and reducing carbon and emission.
At present, the biodegradable materials are polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), and the like. Wherein, PLA is a biodegradable material which has low price, is derived from plant starch and can truly realize complete recycling. PLA has high tensile strength, good transparency and excellent printing performance, but has poor toughness and low tearing strength, and can not meet the requirements of express packaging. The PBAT has good flexibility and high elongation at break, but has low tensile strength, poor tearing strength and higher price, and is not ideal for express packaging directly.
PLA/PBAT is blended and modified, and the biodegradable material with good tear resistance, high toughness and moderate price is obtained by plasticizing, compatibilization, toughening and nano anchoring technologies, so that the biodegradable material has wide application prospect in the fields of express packaging, commodity packaging, medical product packaging, food packaging and the like.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and providing a tear-resistant high-toughness biodegradable material. The invention takes PLA/PBAT as a base material, adds components such as nano material, coupling agent, plasticizer, epoxy chain extender and the like, and adopts a two-step melt blending process to prepare the composite material.
The invention also aims to provide a preparation method of the tear-resistant high-toughness biodegradable material.
The purpose of the invention is realized by the following technical scheme: a tear-resistant high-toughness biodegradable material comprises the following substances in percentage by mass: 30 to 96.3 percent of PLA, 5 to 60 percent of PBAT, 1 to 30 percent of plasticizer, 0.5 to 15 percent of nano material, 0 to 20 percent of mineral powder, 0.1 to 0.5 percent of epoxy chain extender, 0.1 to 2 percent of coupling agent and 0.1 to 1 percent of antioxidant.
The PLA is polylactic acid with the number average molecular weight of 50000-200000, preferably the number average molecular weight of 80000-120000.
The PBAT is polybutylene adipate/terephthalate with the number average molecular weight of 30000-120000, and is preferably polybutylene adipate/terephthalate with the number average molecular weight of 50000-100000.
The plasticizer is acetyl epoxidized fatty acid ester, and preferably acetyl epoxidized vegetable oil acid adipic acid glyceride oligomer.
The structure of the acetyl epoxidized vegetable oil acid adipic acid glyceride oligomer is as follows:
wherein m is 6-8, n is 8-6, k is 3-4, and the molecular weight is 2000-3000.
The nano material is one or a mixture of several of nano silicon dioxide and carbon nano tubes with the diameter of 0.1-20 nm.
The mineral powder is one or a mixture of at least two of calcium carbonate, talcum powder and barium sulfate.
The epoxy chain extender is a copolymer of acrylic ester, glycidyl methacrylate and styrene, and the epoxy equivalent is 6-8.
The coupling agent is siloxane containing epoxy groups, and glycidyl ether oxypropyl trimethoxy silane is preferred.
The antioxidant is an antioxidant for plastic processing, and is preferably a phenolic antioxidant.
The phenolic antioxidant is preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010) or/and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076).
The tear-resistant and high-toughness biodegradable material can be prepared by adopting a single-screw extrusion process, an internal mixing process or a double-screw extrusion process.
Preferably, the tear-resistant and high-toughness biodegradable material is prepared by a two-step melt mixing method, and comprises the following steps:
(1) surface treatment and high-shear melting, mixing and dispersing of nano material
Firstly, carrying out surface treatment on a nano material by adopting a high-speed mixer, and then preparing a PBAT/nano material one-step material by adopting a high-rotating-speed and high-torque double-screw extruder to realize high dispersion of the nano material;
(2) preparation of PLA/PBAT special material
The method adopts a double-screw extruder with a large length-diameter ratio (L/D is more than or equal to 48:1), realizes the reaction plasticization at the front section of the extruder by a step-by-step feeding method, and realizes the reactive chain extension and the compatibilization at the middle and rear sections.
Compared with the prior art, the invention has the following advantages and effects:
(1) the method comprises the following steps of pretreating the surface of a nano SiO2 or carbon nano tube by glycidyl ether oxypropyltrimethoxysilane, then melting and blending the nano SiO2 or carbon nano tube with PBAT, hydrolyzing methoxy, bonding the methoxy with silicon dioxide or the carbon nano tube, reacting epoxy groups of the methoxy with PBAT end groups, realizing nano-scale dispersion by high shearing and reactive compatibilization, generating an anchoring effect, and improving the tear strength;
(2) the method adopts acetyl epoxidized vegetable oil acid adipate as a plasticizer, utilizes the chemical reaction between the epoxy group of the plasticizer and the end group of PLA to realize reactive plasticization, overcomes the problems that the plasticizer is easy to separate out and the dosage cannot be increased, and obtains good plasticization and toughening effects.
Drawings
FIG. 1 is a flow chart of the surface treatment of the nanomaterial of example 1;
FIG. 2 is a flow diagram of the preparation of a PBAT/nanomaterial batch of example 1;
fig. 3 is a flow chart of the preparation of the tear-resistant high-toughness biodegradable material of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the following examples, PLA 4060D, PLA101 is available from Natrueworks and zhejiang haizheng, respectively; PBAT TH801 from Xinjiang blue Tunghe; the acetyl epoxidized vegetable oil adipate is provided by Guangzhou sea Fang Ma vegetable oil Co; the nano silicon dioxide is purchased from Haonian chemical industry HN-200; carbon nanotubes CNTS-5 (average tube diameter of 5nm) and CNTS-10 (average tube diameter of 10nm) were purchased from Sanshun Zhongke New Material Co., Ltd, Shenzhen, City; silane coupling agent KH-560 available from Nanjing Processinger chemical; the epoxy chain extender is 4370, is purchased from Shanxi chemical research institute, and is a raw material and a reagent which can be obtained from commercial approaches such as the conventional market and the like unless specially stated.
Example 1
Accurately weighing 98kg of nano-silica HN-200, heating to 80 ℃ by adopting a high-speed mixer, mixing at high speed, adding 2kg of KH-560 in a spraying manner, and mixing for 20 minutes to obtain surface-treated nano-SiO2。
Accurately weighing 20kg of the surface-treated nano SiO2 and 80kg of PBAT TH801, and then adopting a length-diameter ratio of 40: 1, melting and mixing the mixture by a double-screw extruder at the extrusion temperature of 160-170 ℃ and the screw rotation speed of 800rpm to prepare PBAT/SiO2And (5) carrying out one-step material preparation.
Accurately weighing 10kg of PLA 4060D and 75kg of PBAT/SiO2The raw materials comprise a first step material, 10kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 4.7kg of calcium carbonate, 0.2kg of epoxy chain extender 4370 and 0.1kg of antioxidant 1010. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and 300rpm to prepare the tear-resistant high-toughness degradable material.
Example 2
Accurately weighing 95kg HN-200, heating to 80 deg.C with high speed mixer, high speed mixing, adding 5kg KH-560 by spray, and mixing for 20 min to obtain surface treated nanometer SiO2。
Accurately weighing 10kg of the above-mentioned surface partNano SiO22And 90kg of PBAT TH801, then using a ratio of length to diameter of 40: 1, melting and mixing the mixture by a double-screw extruder at the extrusion temperature of 160-170 ℃ and the screw rotation speed of 800rpm to prepare PBAT/SiO2And (5) carrying out one-step material preparation.
Accurately weighing 40kg of PLA 4060D and 30kg of PBAT/SiO2The raw materials comprise a first-step material, 15kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 14.8kg of talcum powder, 0.1kg of epoxy chain extender 4370 and 0.1kg of antioxidant 1076. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Example 3
Surface treatment of nano-silica and PBAT/SiO2The one-step material preparation method is the same as example 2.
50kg of PLA 4060D and 19.3kg of PBAT/SiO are accurately weighed2One-step material, 30kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 0.5kg of epoxy chain extender 4370 and 0.2kg of antioxidant 1076. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and 500rpm to prepare the tear-resistant high-toughness degradable material.
Example 4
Surface treatment of nano-silica and PBAT/SiO2The one-step material preparation method is the same as example 2.
75kg of PLA101 and 20kg of PBAT/SiO are accurately weighed2One-step material, 4.5kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 0.3kg of epoxy chain extender 4370 and 0.2kg of antioxidant 1076. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and 500rpm to prepare the tear-resistant high-toughness degradable material.
Example 5
Surface treatment of nano-silica and PBAT/SiO2The one-step material preparation method is the same as example 2.
Accurately weighing 90kg of PLA101 and 5.5kg of PBAT/SiO2One-step material, 4kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 0.3kg of epoxy chain extender 4370 and 0.2kg of antioxidant 1076. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and 500rpm to prepare the tear-resistant high-toughness degradable material.
Example 6
Accurately weighing 95kg of carbon nanotube CNTS-5, heating to 80 ℃ by adopting a high-speed mixer, mixing at high speed, adding 5kg of KH-560 in a spraying manner, and mixing for 20 minutes to obtain the surface-treated carbon nanotube CNTS-5.
Accurately weighing 10kg of the surface-treated nanocarbon CNTS-5 and 90kg of PBAT TH801, mixing for 10 minutes by adopting an internal mixer at 160 ℃ and 40rpm, and then adopting a mixing machine with a length-diameter ratio of 40: 1, melting and mixing the mixture by using a single-screw extruder at the extrusion temperature of 160-170 ℃ and the screw rotating speed of 800rpm to prepare the PBAT/CNTS-5 one-step material.
40kg of PLA101, 30kg of PBAT/CNTS-5 one-step material, 15kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 14.4kg of talcum powder, 0.1kg of epoxy chain extender 4370 and 0.5kg of antioxidant 1076 are accurately weighed. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Example 7
50kg of nano-silica and 45kg of carbon nanotube CNTS-10 are accurately weighed, heated to 80 ℃ by a high-speed mixer, mixed at high speed, added with 5kg of KH-560 in a spraying manner, and mixed for 20 minutes to prepare a nano-material mixture with a surface treated.
Accurately weighing 10kg of the surface-treated nanomaterial mixture and 90kg of PBAT TH801, and then adopting a length-diameter ratio of 40: 1, melting and mixing the mixture by a double-screw extruder at the extrusion temperature of 160-170 ℃ and the screw rotation speed of 800rpm to prepare the PBAT/nano material mixture one-step material.
40kg of PLA, 30kg of PBAT/nano material mixture one-step material, 15kg of acetyl epoxidized vegetable oil acid adipic acid glyceride, 13.9kg of barium sulfate, 0.1kg of epoxy chain extender 4370 and 1kg of antioxidant 1076 are accurately weighed. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Comparative example 1
40kg of PLA, 30kg of PBAT, 15kg of acetyl epoxidized vegetable oil acid glyceryl adipate, 14.8kg of talcum powder, 0.1kg of epoxy chain extender 4370 and 0.1kg of antioxidant 1010 are accurately weighed. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Comparative example 2
PBAT/SiO2The procedure for the preparation of one batch was as in example 1.
Accurately weighing 75kg of PLA and 24.5kg of PBAT/SiO2One step, 0.3kg of epoxy chain extender 4370 and 0.2kg of antioxidant 1076. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and 500rpm to prepare the tear-resistant high-toughness degradable material.
Comparative example 3
The preparation method of PBAT/CNTS-5 one-step material is the same as that of example 6.
40kg of PLA, 30kg of PBAT/CNTS-5 one-step material, 13.9kg of barium sulfate, 0.1kg of epoxy chain extender 4370 and 1kg of antioxidant 1076 are accurately weighed. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Comparative example 4
The procedure for the preparation of the PBAT/nanomaterial mixture was the same as in example 7.
40kg of PLA, 45kg of PBAT/nano material mixture, 14.4kg of talcum powder, 0.1kg of epoxy chain extender 4370 and 0.5kg of antioxidant 1010 are accurately weighed. The components are uniformly mixed in advance, a double-screw extruder is adopted for melting and mixing, and the temperature of a heating zone of the extruder from a feed opening to a machine head is set as follows in sequence: 130 ℃, 180 ℃ and the rotation speed of 200rpm to prepare the tear-resistant high-toughness degradable material.
Effects of the embodiment
The tear-resistant high-toughness biodegradable materials prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to performance tests according to the following test methods, and the test results are shown in table 1.
The melt index is tested according to GB 3682-2000, the temperature is 190 ℃, and the load is 2.16 Kg.
The tensile strength and elongation at break were measured according to GB/T1040.3-2006, with a tensile rate of 200 mm/min.
Tear strength was performed as described in GB/T16578-.
Table 1 results of performance testing of examples
Table 2 examples performance test results
TABLE 3 comparative examples Performance test results
From examples 1 to 7, it is clear that as the content of the plasticizer increases, the elongation at break of the material increases and the toughness improves; with nano SiO2Or the content of the carbon nano tube is increased, and the tearing strength of the material is increased; meanwhile, the nano material and the acetyl epoxidized vegetable oil acid adipic acid glyceride are added to prepare the biodegradable material with high elongation at break and good tearing strength, and the melt flow rate is relatively high. In the comparative example, the tear strength of the material was poor, the elongation at break was low, and the melt flow rate was low, since the two components were not added simultaneously.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. The tear-resistant high-toughness biodegradable material is characterized by comprising the following substances in percentage by mass: 30-96.3% of PLA, 5-60% of PBAT, 1-30% of plasticizer, 0.5-15% of nano material, 0-20% of mineral powder, 0.1-0.5% of epoxy chain extender, 0.1-2% of coupling agent and 0.1-1% of antioxidant; the plasticizer is acetyl epoxidized vegetable oil acid adipic acid glyceride oligomer; the nano material is one or a mixture of several of nano silicon dioxide and carbon nano tubes with the diameter of 0.1-20 nm;
the tear-resistant high-toughness biodegradable material is prepared by a two-step melt mixing method, and comprises the following steps:
(1) surface treatment and high-shear melting, mixing and dispersing of nano material
Firstly, carrying out surface treatment on a nano material by adopting a high-speed mixer, and then preparing a PBAT/nano material one-step material by adopting a high-rotating-speed and high-torque double-screw extruder to realize high dispersion of the nano material;
(2) preparation of PLA/PBAT special material
A large length-diameter ratio L/D is more than or equal to 48:1 double-screw extruder is adopted, reaction plasticization is completed at the front section of the extruder by a step-by-step feeding method, and reactive chain extension and compatibilization are realized at the middle and rear sections;
the structure of the acetyl epoxidized vegetable oil acid adipic acid glyceride oligomer is as follows:
wherein m is 6-8, n is 8-6, k is 3-4, and the molecular weight is 2000-3000;
the mineral powder is one or a mixture of at least two of calcium carbonate, talcum powder and barium sulfate;
the epoxy chain extender is a copolymer of acrylic ester, glycidyl methacrylate and styrene, and the epoxy equivalent is 6-8;
the coupling agent is glycidyl ether oxypropyltrimethoxysilane.
2. The tear-resistant high-toughness biodegradable material according to claim 1, wherein the PLA is polylactic acid with a number average molecular weight of 50000-200000.
3. The tear-resistant high-toughness biodegradable material according to claim 1, wherein the PBAT is polybutylene adipate/terephthalate with a number average molecular weight of 30000-120000.
4. The tear-resistant high-toughness biodegradable material according to claim 1, wherein the antioxidant is a phenolic antioxidant.
5. The tear-resistant high-toughness biodegradable material according to claim 4, wherein the phenolic antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] or/and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
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| CN113045879B (en) * | 2021-03-16 | 2023-05-09 | 漯河市瑞博塑胶有限公司 | High-tear-resistance PLA-PBAT composite degradable resin and preparation method and application thereof |
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