CN110551347A - Full-biodegradable PVC material and preparation method and application thereof - Google Patents
Full-biodegradable PVC material and preparation method and application thereof Download PDFInfo
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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Abstract
The application provides a full-biodegradable PVC material, a preparation method and an application thereof, wherein the full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 35-50 parts of PVC, 0.11-10 parts of a biodegradation agent, 35-50 parts of a mixed plasticizer and 0.5-2 parts of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 0.1-10: 1, and the glutamic acid composition comprises glutamic acid, glutaric acid and polylactic acid. The mixed plasticizer is added to prepare the soft PVC product, the plasticity and the fluidity of the soft PVC product are improved, the variety and the application range of the PVC product are enlarged, and the plasticizer is also beneficial to reducing the processing temperature of the PVC and improving the processing performance. The composite stabilizer can improve the thermal stability of PVC. The application provides a full biodegradable PVC material, it is full biodegradation, and is not for taking off HCl's autocatalytic reaction mode, therefore even there is the stabilizer, it still can have faster degradation speed and higher degradation efficiency.
Description
Technical Field
The application belongs to the technical field of PVC materials, and particularly relates to a full-biodegradable PVC material, and a preparation method and application thereof.
Background
Polyethylene (PVC) is one of the plastic products with the largest yield in the world, is low in price and wide in application, and polyvinyl chloride resin is white or light yellow powder. As a leading thermoplastic material, PVC has the advantages of flame retardance, wear resistance, high strength, easy forming and processing, good chemical stability and the like, so that the PVC is widely applied to the production of hard products such as doors and windows, pipelines, valves and the like, and is also used for producing soft products such as shoe materials, artificial leather, packaging films, wires and cables and the like. A proper amount of plasticizer is usually added into polyvinyl chloride resin to prepare various hard, soft and transparent products which are widely applied to national defense, chemical engineering, automobile industry and daily life.
PVC has a fatal weakness that the thermal stability is poor, and unsaturated double bonds, allyl groups, branch points, initiator residues and the like are introduced into the molecular structure of PVC in the polymerization process. At present, it is generally considered that the degradation of PVC is an autocatalytic reaction for HCl removal, which first initiates HCl removal on some unstable structures and forms some unequal number of double bonds, i.e. multiolefin segments, on the molecular chain of PVC. With increasing temperature, the PVC chains are broken continuously until they break. Therefore, a heat stabilizer is generally used in PVC processing, and the addition of the heat stabilizer can inhibit HCl removal of PVC and even reduce activation energy of photooxidation, so that degradation of the PVC is inhibited. That is, in order to meet the requirement of PVC for long-term use, a stabilizer needs to be introduced in the processing process of PVC, and the addition of the stabilizer greatly influences the chemical degradation rate of PVC, so that a new degradation mode is needed at present, and even if the stabilizer is added to meet the requirement of PVC for use, efficient and rapid degradation can be realized.
Content of application
The application aims to provide a full-biodegradable PVC material, a preparation method and application thereof, which are in a full-biodegradation mode, have high degradation speed and high degradation rate and can simultaneously take the problems of use and degradation into consideration.
In order to achieve the above object, a first aspect of the present application provides a fully biodegradable PVC material, which comprises the following raw materials in parts by weight: 35-50 parts of PVC, 0.11-10 parts of a biodegradation agent, 35-50 parts of a mixed plasticizer and 0.5-2 parts of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 0.1-10: 1, and the glutamic acid composition comprises glutamic acid, glutaric acid and polylactic acid.
Compared with the prior art, the mixed plasticizer is added to the fully biodegradable PVC material provided by the application on the basis of PVC, PVC with great acting force between molecular chains and lacking elasticity can be made into a soft polyvinyl chloride product, the plasticity and the fluidity of the product are improved, and the product variety and the application range are enlarged. Meanwhile, the polyvinyl chloride has poor thermal stability, and can be decomposed and discolored when heated to 130-140 ℃, and the plasticizer is added to facilitate the reduction of the processing temperature and the improvement of the processing performance. The addition of the composite stabilizer can improve the thermal stability of PVC and the durability of the PVC in use. The glutamic acid composition and the biological enzyme contained in the biological degradation agent can attract microorganisms in soil to attach to the fully-biodegradable PVC material, when the PVC material is buried, the number of the surrounding microorganisms reaches a certain number, the surrounding pH value can be influenced by the microorganisms, and the surrounding oxygen is converted into carbon dioxide and water. Along with the rise of the temperature of the soil after the landfill, the biological expanding agent in the material is influenced by external conditions, so that molecules in the material become larger, the outer layer of the molecules becomes thinner and thinner, meanwhile, the glutamic acid composition and the biological enzyme in the material are drawn by microbial flora to serve as nutrients, and the secreted enzyme or acidic substance gradually decomposes macromolecules into micromolecules until the degradation process is finished. The application provides a full biodegradable PVC material, it is full biodegradation, and is not for taking off HCl's autocatalytic reaction mode, therefore even there is the stabilizer, it still can have faster degradation speed and higher degradation efficiency.
Further, PVC is specifically but not limited to 35 parts, 38 parts, 40 parts, 42 parts, 45 parts and 50 parts; the biological degradation agent is specifically but not limited to 0.11 part, 0.5 part, 1 part, 3 parts, 5 parts, 7 parts, 9 parts and 10 parts; the mixed plasticizer is specifically but not limited to 35 parts, 38 parts, 40 parts, 42 parts, 45 parts and 50 parts; the composite stabilizer is specifically but not limited to 0.5 part, 0.8 part, 1.0 part, 1.4 parts, 1.8 parts and 2 parts. The weight ratio of the biological bulking agent, glutamic acid composition, and biological enzyme is specifically, but not limited to, 0.1:0.1:1, 0.1:1:1, 0.1:5:1, 0.1:10:1, 1:0.1:1, 1:1:1, 1:5:1, 1:10:1, 5:0.1:1, 5:1:1, 5:5:1, 2:2:1, 1:1:2, and 10:10: 1.
Further, the biological enzyme is at least one of oxidoreductase, transferase, hydrolase, lyase, and ligase. The glutamic acid composition comprises glutamic acid, glutaric acid and polylactic acid, wherein the glutamic acid participates in a plurality of reactions in a microorganism body, is an important nutrient substance for metabolism of the microorganism and can attract the aggregation of the microorganism in soil; the biological complex enzyme comprises one or more of oxidoreductase, transferase, hydrolase, lyase and ligase. The biological compound enzyme promotes the catabolism of substances in nature, wherein, the redox enzyme catalyzes an oxidation-reduction reaction, the transferase catalyzes a chemical functional group transfer, the hydrolase catalyzes a hydrolysis reaction, the lyase catalyzes and increases a double bond reaction, the isomerase catalyzes an isomerization reaction, and the ligase catalyzes ATP to form a new construction. The biological complex enzyme is protein, and can be hydrolyzed into amino acid in some cases, and the amino acid can be absorbed and utilized as nutrient substances. The biological expanding agent is a mixture of polyurethane and vegetable protein, and the weight ratio of the polyurethane to the vegetable protein is 1: 1.
Further, the mixed plasticizer is a mixture of dioctyl terephthalate (DOTP) and dioctyl adipate (DOA), and the dioctyl adipate accounts for 5-20% of the weight of the dioctyl terephthalate. The dioctyl terephthalate serving as a main plasticizer is matched with the dioctyl adipate to improve the heat resistance, cold resistance, difficult volatilization, extraction resistance, flexibility, electric insulation and other properties, so that the PVC product shows excellent durability, soap water resistance and low-temperature flexibility.
Further, the composite stabilizer is a stearate compound of lead, cadmium, barium, calcium and zinc, or an oleate compound of lead, cadmium, barium, calcium and zinc. The PVC is usually a binary or ternary composite system, such as lead barium, cadmium barium zinc, calcium zinc system and the like, and due to the synergistic thermal stability among the components in the system, the PVC is processed to have good color and luster and very good long-term stability.
furthermore, the preparation raw materials also comprise 0.1-2 parts of lignin and 0.1-2 parts of organic resin. The lignin in PVC material products can obviously improve the mechanical property of PVC materials, and the lignin has low price and can reduce the production cost. The lignin is a biological full-biodegradable material, and the specific surface area of the full-biodegradable PVC material is gradually increased along with the degradation of the lignin, so that the degradation rate of the full-biodegradable PVC material is effectively improved. The carrier resin is favorable for uniformly mixing all the components and can accelerate biodegradation, and the carrier resin can be phenolic resin.
Further, the preparation raw materials further comprise 0.5-2 parts of an auxiliary plasticizer, and the auxiliary plasticizer is epoxidized soybean oil. In the processing, the addition of the epoxidized soybean oil can obviously improve the physical properties of the product and prolong the aging time. In addition, the epoxidized soybean oil has good intermiscibility with PVC resin, and the intramolecular epoxy group plays a role in absorbing HCl decomposed from PVC, so the epoxidized soybean oil also can play a role in stability.
furthermore, the preparation raw materials also comprise 0.1-2 parts of a lubricant, the lubricant is a mixture of polyethylene wax and zinc stearate, and the mixture of the polyethylene wax and the zinc stearate has a stronger internal lubricating effect.
Furthermore, the preparation raw materials also comprise 2-18 parts of inorganic filler, preferably the inorganic filler is calcium carbonate, which can improve the mechanical property, the processing property, the heat resistance and the dimensional stability of the PVC product, especially in soft polyvinyl chloride, the hardness gradually increases along with the addition of calcium carbonate, and the elongation rate decreases along with the increase of the hardness. Fine particles, large oil absorption value and high hardness increment rate. On the contrary, the calcium carbonate with coarse particles and small oil absorption value has small hardness growth rate of the plastic. In soft polyvinyl chloride, the hardness increase rate of heavy calcium carbonate is the smallest, and precipitated calcium carbonate (light) is the second.
The second aspect of the application provides a preparation method of a full-biodegradable PVC material, weighing the PVC, the biodegradable agent, the mixed plasticizer and the composite stabilizer in formula amounts, mixing and banburying in an internal mixer, and extruding and granulating after banburying, wherein the biodegradable agent is added in the mixing and banburying process and below 130 ℃. The biodegradable agent is added below 130 ℃ to avoid the influence of high temperature on the performance of the biodegradable agent.
In a third aspect, the present application provides a use of the above degradable PVC material in PVC products.
Detailed Description
The fully biodegradable PVC material of the present application will be further described in detail with reference to the following specific examples, which should not be construed as limiting the scope of the present application.
The fully biodegradable PVC material of the present application will be further described in detail with reference to the following specific examples, which should not be construed as limiting the scope of the present application.
Example 1
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer and 1 part of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer and a composite stabilizer according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 2
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 35 parts of PVC, 5 parts of a biodegradation agent, 50 parts of a mixed plasticizer and 0.5 part of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 2:2:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 45 parts of DOTP and 5 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer and a composite stabilizer according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 3
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 50 parts of PVC, 10 parts of a biodegradation agent, 35 parts of a mixed plasticizer and 2 parts of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 5:10:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 30 parts of DOTP and 5 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
the preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer and a composite stabilizer according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 4
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer and 1 part of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of di-n-butyl phthalate (DBP) and 4 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer and a composite stabilizer according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 5
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer and 1 part of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of transferase, hydrolase and lyase with equal content, the biological swelling agent is a mixture of polyurethane and vegetable protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a calcium and zinc oleate compound.
The preparation method comprises the following steps:
weighing PVC, a biodegradation agent, a mixed plasticizer and a composite stabilizer according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 6
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer, 1 part of a composite stabilizer, 1 part of lignin and 1 part of phenolic resin, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
the preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer, a composite stabilizer, lignin and phenolic resin according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying, wherein the biodegradation agent is added in the mixing and banburying process at a temperature below 130 ℃.
Example 7
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer, 1 part of a composite stabilizer and 2 parts of epoxidized soybean oil, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer, a composite stabilizer and epoxidized soybean oil according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature below 130 ℃.
Example 8
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer, 1 part of a composite stabilizer and 1 part of a lubricant, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, the composite stabilizer is a lead barium stearate compound, and the lubricant is a mixture of polyethylene wax and zinc stearate with the weight ratio of 1: 1.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer, a composite stabilizer and a lubricant according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Example 9
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer, 1 part of a composite stabilizer and 8 parts of calcium carbonate, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological swelling agent is a mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead barium stearate compound.
The preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer, a composite stabilizer and calcium carbonate according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature below 130 ℃.
Example 10
A full-biodegradable PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 3 parts of a biodegradation agent, 41 parts of a mixed plasticizer, 1 part of a composite stabilizer, 0.8 part of lignin, 0.8 part of phenolic resin, 1 part of an auxiliary plasticizer, 0.4 part of a lubricant and 10 parts of an inorganic filler, wherein the biodegradation agent comprises a biological expansion agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological expansion agent to the glutamic acid composition to the biological enzyme is 1:1:1, the glutamic acid composition is the mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is the mixture of oxidoreductase, transferase and hydrolase with equal content, the biological expansion agent is the mixture of polyurethane and plant protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, the composite stabilizer is a lead barium stearate compound, the auxiliary plasticizer is epoxy soybean oil, the lubricant is the mixture of polyethylene wax and zinc stearate with the weight ratio of 1:1, the inorganic filler is calcium carbonate.
the preparation method comprises the following steps:
Weighing PVC, a biodegradation agent, a mixed plasticizer, a composite stabilizer, lignin, phenolic resin, an auxiliary plasticizer, a lubricant and an inorganic filler according to the formula ratio, mixing and banburying in an internal mixer, and extruding and granulating after banburying is finished, wherein the biodegradation agent is added in the mixing and banburying process at a temperature of below 130 ℃.
Comparative example 1
42 parts of PVC, 41 parts of mixed plasticizer and 1 part of composite stabilizer are mixed and internally mixed in an internal mixer, extrusion granulation is carried out after internal mixing is finished, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is lead barium stearate compound.
Comparative example 2
The PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 41 parts of mixed plasticizer and 1 part of composite stabilizer, wherein the biodegradation agent comprises a biological expanding agent and a glutamic acid composition, the weight ratio of the biological expanding agent to the glutamic acid composition is 1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological expanding agent is a mixture of polyurethane and vegetable protein with the weight ratio of 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead-barium stearate compound.
The preparation method comprises the following steps: weighing the components according to the formula ratio, banburying the PVC, the mixed plasticizer and the composite stabilizer, adding the biological expanding agent and the glutamic acid composition at the temperature of below 130 ℃, and mixing, extruding and granulating in an extruder.
Comparative example 3
The PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 41 parts of mixed plasticizer and 1 part of composite stabilizer, wherein the biodegradation agent comprises glutamic acid composition and biological enzyme, the weight ratio of the glutamic acid composition to the biological enzyme is 1:1, the glutamic acid composition is a mixture of glutamic acid, glutaric acid and polylactic acid with equal content, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is lead barium stearate compound.
The preparation method comprises the following steps: weighing the components according to the formula ratio, banburying the PVC, the mixed plasticizer and the composite stabilizer, adding the glutamic acid composition and the biological enzyme at the temperature of below 130 ℃, and mixing, extruding and granulating in an extruder.
Comparative example 4
The PVC material comprises the following preparation raw materials in parts by weight: 42 parts of PVC, 41 parts of mixed plasticizer and 1 part of composite stabilizer, wherein the biodegradation agent comprises a biological expanding agent and biological enzyme, the weight ratio of the biological expanding agent to the biological enzyme is 1:2, the biological enzyme is a mixture of oxidoreductase, transferase and hydrolase with equal content, the biological expanding agent is a mixture of polyurethane and vegetable protein, the weight ratio of the biological expanding agent to the biological enzyme is 1:1, the mixed plasticizer is 37 parts of DOTP and 4 parts of DOA, and the composite stabilizer is a lead-barium stearate compound.
The preparation method comprises the following steps: weighing the components according to the formula ratio, banburying the PVC, the mixed plasticizer and the composite stabilizer, adding the biological expanding agent and the biological enzyme at the temperature of below 130 ℃, and mixing, extruding and granulating in an extruder.
The fully biodegradable PVC materials of examples 1-10 and the PVC materials of comparative examples 1-4 were made into PVC products, and after being buried in a simulated landfill environment for 833 days, the degradation rate was tested according to ASTM-D5511, and the degradation results are shown in Table 1.
TABLE 1 degradation Rate test results in examples 1 to 10 and comparative examples 1 to 4
As can be seen from Table 1, the degradation rate of the product was higher after the addition of lignin and organic resin.
The PVC product of example 10 was subjected to composition testing after 833 days of degradation, the results of which are shown in table 2.
TABLE 2 degradation results for the PVC articles of example 10
| Degraded component | Example 10 |
| Total gas volume (mL) | 9040.00 |
| CH4Content (%) | 44.00 |
| CH4Volume (mL) | 3977.60 |
| CO2Content (%) | 34.00 |
| CO2Volume (mL) | 3073.60 |
As can be seen from Table 2, the fully biodegradable PVC material in the application can be degraded into methane and carbon dioxide after being buried, and the methane can be recycled as a novel energy source.
the fully biodegradable PVC material is improved in formula technology on the basis that various physical and chemical properties of traditional PVC are not influenced, and the original processing technology and mechanical equipment are not changed, so that a novel fully biodegradable PVC formula is prepared, and the degradation efficiency is 330 times faster than that of the traditional PVC (the traditional degradation is long for 1000 years, and the degradation time in the application is about 833 days).
Compared with the prior art, the mixed plasticizer is added to the fully biodegradable PVC material provided by the application on the basis of PVC, PVC with great acting force between molecular chains and lacking elasticity can be made into a soft polyvinyl chloride product, the plasticity and the fluidity of the product are improved, and the product variety and the application range are enlarged. Meanwhile, the polyvinyl chloride has poor thermal stability, and can be decomposed and discolored when heated to 130-140 ℃, and the plasticizer is added to facilitate the reduction of the processing temperature and the improvement of the processing performance. The addition of the composite stabilizer can improve the thermal stability of PVC and the durability of the PVC in use. The glutamic acid composition and the biological enzyme contained in the biological degradation agent can attract microorganisms in soil to attach to the fully-biodegradable PVC material, and when the microorganisms around the material reach a certain amount, the surrounding pH value can be influenced by the microorganisms to convert the surrounding oxygen into carbon dioxide and water. Along with the rise of the temperature of the soil after the landfill, the biological expanding agent in the material is influenced by external conditions, so that molecules in the material become larger, the outer layer of the molecules becomes thinner and thinner, meanwhile, the glutamic acid composition and the biological enzyme in the material are drawn by microbial flora to serve as nutrients, and the secreted enzyme or acidic substance gradually decomposes macromolecules into micromolecules until the degradation process is finished. The application provides a full biodegradable PVC material, it is full biodegradation, and is not for taking off HCl's autocatalytic reaction mode, therefore even there is the stabilizer, it still can have faster degradation speed and higher degradation efficiency.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The full-biodegradable PVC material is characterized by comprising the following raw materials in parts by weight: 35-50 parts of PVC, 0.11-10 parts of a biodegradation agent, 35-50 parts of a mixed plasticizer and 0.5-2 parts of a composite stabilizer, wherein the biodegradation agent comprises a biological swelling agent, a glutamic acid composition and a biological enzyme, the weight ratio of the biological swelling agent to the glutamic acid composition to the biological enzyme is 0.1-10: 1, and the glutamic acid composition comprises glutamic acid, glutaric acid and polylactic acid.
2. The fully biodegradable PVC material according to claim 1, wherein said bio-enzyme is at least one of an oxidoreductase, a transferase, a hydrolase, a lyase and a ligase.
3. The fully biodegradable PVC material according to claim 1, wherein the mixed plasticizer is a mixture of dioctyl terephthalate and dioctyl adipate, wherein the dioctyl adipate accounts for 5-20% by weight of the dioctyl terephthalate.
4. The fully biodegradable PVC material according to claim 1, wherein said composite stabilizer is stearate complex of lead, cadmium, barium, calcium, zinc or oleate complex of lead, cadmium, barium, calcium, zinc.
5. The fully biodegradable PVC material according to claim 1, wherein the raw materials for preparation further comprise 0.1-2 parts of lignin and 0.1-2 parts of organic resin.
6. The fully biodegradable PVC material according to claim 1, wherein the raw materials for preparation further comprise 0.5-2 parts of an auxiliary plasticizer, and the auxiliary plasticizer is epoxidized soybean oil.
7. The fully biodegradable PVC material according to claim 1, wherein the raw materials for preparation further comprise 0.1-2 parts of lubricant, and the lubricant is a mixture of polyethylene wax and zinc stearate.
8. The fully biodegradable PVC material according to claim 1, wherein the raw materials for preparation further comprise 2-18 parts of inorganic filler.
9. The method for preparing the fully biodegradable PVC material according to any one of claims 1 to 8, wherein the PVC, the biodegradable agent, the mixed plasticizer and the composite stabilizer are weighed according to the formula, mixed and banburying in an internal mixer, and extruded and granulated after banburying, wherein the biodegradable agent is added during the mixing and banburying process and at a temperature of 130 ℃ or below.
10. An application of the fully biodegradable PVC material prepared by the method for preparing the fully biodegradable PVC material according to any one of claims 1 to 8 or the fully biodegradable PVC material according to claim 9 in PVC products.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063149A (en) * | 2020-09-18 | 2020-12-11 | 深圳市百奥降解材料科技有限公司 | Degradable plastic with good stability and preparation method thereof |
| CN115028935A (en) * | 2021-03-05 | 2022-09-09 | 普裕兴业股份有限公司 | Biodegradable material |
| DE102021106156A1 (en) | 2021-03-12 | 2022-09-15 | Sunta Chemical Corporation | BIODEGRADABLE POLYMER COMPOUND |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063149A (en) * | 2020-09-18 | 2020-12-11 | 深圳市百奥降解材料科技有限公司 | Degradable plastic with good stability and preparation method thereof |
| CN115028935A (en) * | 2021-03-05 | 2022-09-09 | 普裕兴业股份有限公司 | Biodegradable material |
| DE102021106156A1 (en) | 2021-03-12 | 2022-09-15 | Sunta Chemical Corporation | BIODEGRADABLE POLYMER COMPOUND |
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