CN112795072A - Natural light-microorganism dual-degradation master batch and preparation method thereof - Google Patents
Natural light-microorganism dual-degradation master batch and preparation method thereof Download PDFInfo
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- C08K5/098—Metal salts of carboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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Abstract
The natural light-microorganism dual-degradation master batch comprises the following raw materials of polyethylene, Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant and a silane coupling agent, and the raw materials of the master batch also comprise catechin accounting for 1-7% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, and the raw materials comprise the following components in percentage by weight: 70-80% of polyethylene, 1-5% of Fischer-Tropsch wax, 3-12% of a photosensitive catalyst, 10-13% of calcium stearate, 0.1-1% of an antioxidant and 0.1-1% of a silane coupling agent. The master batch provided by the invention is applied to the existing plastic film production, the production process of the film is not changed, the master batch can be used as an additive of the film, and the effect of the film production and the operation of machine equipment are not influenced.
Description
Technical Field
The invention relates to the technical field of environment-friendly materials, in particular to plastic degradation, and specifically relates to a natural light-microorganism dual-degradation master batch and a preparation method thereof.
Background
It is known that about 160 ten thousand tons of plastics are consumed in the use of plastic bags every year in China, more than 480 ten thousand tons of petroleum are consumed in the production of the plastic bags every year in China, and the excessive use of the plastic bags can generate considerable negative effects and pressure on energy resources and environment in China. At present, the recycled plastics are less than 1% of the total amount of the plastic garbage, but account for about 10% of the solid garbage. Faced with increasingly serious environmental pollution, research and development on decomposable plastics have been strengthened by relevant departments at home and abroad in recent years.
The method conforms to the development trend of green, low-carbon and environment-friendly plastic industry in the world, and the plastic industry in China presents new characteristics in the aspects of development and technical progress. At present, technicians can adopt polylactic acid as a degradation material, but the price of the lactic acid and a polymerization process thereof determine that the cost of the polylactic acid is higher, so that the polylactic acid is widely applied as general plastic, the price of the polylactic acid is still hardly accepted by the market at present, and the problems are the key to large-scale marketization of biodegradable plastic.
Disclosure of Invention
The master batch is applied to a plastic bag, the plastic bag is degraded by natural light under natural conditions and then is broken into fragments, and the fragments are finally degraded under the action of bacterial microorganisms.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the natural light-microorganism dual-degradation master batch comprises the following raw materials of polyethylene, Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant and a silane coupling agent, and also comprises catechin accounting for 1-10% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, wherein the raw materials comprise the following components in percentage by weight: 70-80% of polyethylene, 1-5% of Fischer-Tropsch wax, 3-12% of a photosensitive catalyst, 10-13% of calcium stearate, 0.1-1% of an antioxidant and 0.1-1% of a silane coupling agent.
The polyethylene in the present invention may be replaced with petroleum-based plastics such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, PET, PUR, etc. Preferably, the polyethylene in the present invention is one or more of high density polyethylene, linear low density polyethylene and low density polyethylene.
As a preferable scheme of the invention, the polyethylene in the invention is composed of low-density polyethylene micro powder and linear low-density polyethylene particles, the low-density polyethylene micro powder has a porous structure, a polyethylene matrix has a stable structure by utilizing different particle size grading of the micro powder and the particles, the fluidity and the processability of master batches are improved, and the polyethylene can be used as a carrier of Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant, an accelerant, an additive and a silane coupling agent, so that the raw materials have good dispersibility and are prevented from agglomeration.
As a preferred scheme of the invention, the raw materials comprise the following components in percentage by weight: 75% of polyethylene, 1.5% of Fischer-Tropsch wax, 11% of a photosensitive catalyst, 11.8% of calcium stearate, 0.2% of an antioxidant and 0.5% of a silane coupling agent.
In the invention, the photosensitive catalyst is one or a combination of a lanthanide rare earth complex photosensitive catalyst, lanthanum stearate, manganese stearate and copper blue oxidase.
The antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
The silane coupling agent in the invention is r- (2, 3-epoxypropoxy) propyl trimethoxy silane.
Wherein, the master batch also comprises an accelerant, and the mass of the accelerant accounts for 0.5-1.5% of the total weight of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent.
The master batch also comprises an additive, wherein the mass of the additive accounts for 1-5.5% of the total weight of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, and the mass ratio of the additive to the additive is 70-80: 10-15: 10-15 of cellulose, chitin and chitosan.
The master batch is also added with titanocene dichloride with the mass accounting for 1-5% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent.
Preferably, the additive is prepared from the following components in a mass ratio of 70: 15: 15, the nano cellulose, the chitin and the chitosan can be used as a culture medium of bacterial microorganisms, and the microorganisms can destroy macromolecular chains in the plastic fragments while acquiring nutrient substances, so that the plastic fragments are decomposed under the action of the bacterial microorganisms.
The 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and catechin contained in the invention can play a role in protecting active metal ions by utilizing the synergistic effect of synthetic and natural antioxidant products, and avoid the strength reduction of the plastic caused by the normal use process. Meanwhile, the catechin contains polyphenol substances capable of absorbing ultraviolet rays in natural light, and the catechin is compounded with the lanthanide rare earth complex photosensitive catalyst, lanthanum stearate, manganese stearate and copper blue oxidase, so that the wavelength range of natural light absorption of the master batch is widened, and when the plastic is cracked into fragments, an automatic oxidation reaction is generated under the action of the ultraviolet rays, and the polymer is degraded.
A preparation method of natural light-microorganism dual-degradation master batch comprises the following steps: adding the raw materials of the master batch into a high-speed stirrer, stirring and mixing, controlling the temperature of the raw materials to be 90-130 ℃, placing the raw materials into an internal mixer, mixing for 5-10min, discharging, cooling the raw materials to be treated to be below 40 ℃, and performing extrusion granulation at the temperature of 140 ℃ and 170 ℃ by using a parallel double-screw extruder to obtain the master batch.
The invention is a master batch granule, which takes polyethylene as a matrix, and is added with Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant, a silane coupling agent, and also can be added with titanocene dichloride, an accelerant and/or an additive, wherein the calcium stearate has good lubricity and no toxicity; the active metal ions such as copper, titanium, lanthanum, manganese and the like contained in the master batch can be embedded into a polyethylene plastic matrix, and when the plastic is cracked into fragments, the metal ions are exposed in ultraviolet rays or activated when encountering heat energy, and then begin to degrade. The combined action of various active metal ions can shorten the time of plastic degradation and improve the degradation efficiency.
Because plastics generally have stable chemical structure, the long chain structure of its inside is difficult for microbial cell to get into, after the master batch of the invention is applied to the plastic bag, the plastic bag breaks into pieces after certain time of natural light irradiation, thus improve the surface area contacting with microorganism, through the function of the microbial bacterium, carry on the final degradation.
The master batch of the invention can be added in the production process of plastic bags to produce plastic films which are degradable by photochemistry and microorganisms, and once exposed to ultraviolet rays, the degradation reaction is initiated and continued, even in the night, and the degradation speed is accelerated after being heated. Many studies have shown that biodegradation occurs as soon as the plastic bag breaks into pieces, and that biodegradation begins when the molecular weight is reduced drastically and the surface area of the plastic crumbles is enlarged. The end products of biodegradation are carbon dioxide, water and a small portion of the remaining non-toxic inert mineral substances. The plastic bag can not be decomposed by itself before being irradiated by ultraviolet rays, the residual substances degraded by the plastic bag are nontoxic and harmless, and the cost of the applied raw materials is lower.
The master batch provided by the invention is applied to the existing plastic film production, the production process of the film is not changed, the master batch can be used as an additive master batch of the film, and the effect of producing the film and the operation of machine equipment are not influenced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The following detailed description of embodiments of the invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The natural light-microorganism dual-degradation master batch comprises the following raw materials of polyethylene, Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant and a silane coupling agent, and also comprises catechin accounting for 1-10% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, wherein the raw materials comprise the following components in percentage by weight: 70-80% of polyethylene, 1-5% of Fischer-Tropsch wax, 3-12% of a photosensitive catalyst, 10-13% of calcium stearate, 0.1-1% of an antioxidant and 0.1-1% of a silane coupling agent.
The present invention will be described in further detail with reference to examples.
Example 1
The natural light-microorganism dual-degradation master batch comprises the following raw materials in percentage by weight: 75% of high-density polyethylene, 1.5% of Fischer-Tropsch wax, 7.2% of lanthanide rare earth complex photosensitive catalyst, 3.8% of manganese stearate, 11.8% of calcium stearate, 0.2% of antioxidant and 0.5% of silane coupling agent.
The preparation method comprises the following steps: adding the master batch raw material into a high-speed stirrer, stirring and mixing, controlling the temperature of the raw material to be 100-fold-over-120 ℃, placing the raw material into an internal mixer, mixing for 8min, discharging, cooling the raw material to be treated to be below 40 ℃, and extruding and granulating at 155-fold-over-160 ℃ by using a parallel double-screw extruder to obtain the master batch.
Example 2
The natural light-microorganism dual-degradation master batch comprises the following raw materials in percentage by weight: 80% of high-density polyethylene, 1.1% of Fischer-Tropsch wax, 4.8% of lanthanide rare earth complex photosensitive catalyst, 1.6% of manganese stearate, 1.2% of ceruloplasmin oxidase, 10.5% of calcium stearate, 0.1% of antioxidant and 0.7% of silane coupling agent, and the master batch is also added with titanocene dichloride, 0.7% of cellulose, 4.6% of catechin, 0.15% of chitin and 0.15% of chitosan, wherein the mass of the titanocene dichloride is 2.5% of the total mass of the high-density polyethylene, the Fischer-Tropsch wax, the lanthanide rare earth complex photosensitive catalyst, the manganese stearate, the calcium stearate, the antioxidant and the silane coupling agent.
Example 3
The natural light-microorganism dual-degradation master batch comprises the following raw materials in percentage by weight: 76% of high-density polyethylene, 2.0% of Fischer-Tropsch wax, 6.5% of lanthanum stearate, 3.9% of manganese stearate, 0.4% of ceruloplasmin oxidase, 11% of calcium stearate, 0.1% of antioxidant and 0.1% of silane coupling agent, and the master batch is also added with titanocene dichloride, 1.4% of catechin and 1.5% of accelerator, wherein the mass of titanocene dichloride, the mass of lanthanum stearate, the mass of manganese stearate, the mass of ceruloplasmin oxidase, the mass of calcium stearate, the mass of antioxidant and the total mass of silane coupling agent are 1.0%.
Example 4
The natural light-microorganism dual-degradation master batch comprises the following raw materials in percentage by weight: 78% of high-density polyethylene, 1.2% of Fischer-Tropsch wax, 5.1% of lanthanide rare earth complex photosensitive catalyst, 1.0% of lanthanum stearate, 1.3% of manganese stearate, 0.8% of ceruloblue oxidase, 12.3% of calcium stearate, 0.15% of antioxidant and 0.15% of silane coupling agent, wherein dichlorotitanocene, 1.0% of accelerator, 0.8% of cellulose, 0.10% of chitin and 0.10% of chitosan are also added into the master batch, wherein the mass of dichlorotitanocene accounts for 4.0% of the total mass of the low-density polyethylene, the Fischer-Tropsch wax, the lanthanide rare earth complex photosensitive catalyst, the lanthanum stearate, the manganese stearate, the ceruloblue oxidase, the calcium stearate, the antioxidant and the silane coupling agent.
Example 5
The natural light-microorganism dual-degradation master batch comprises the following raw materials in percentage by weight: 80% of high-density polyethylene, 1.0% of Fischer-Tropsch wax, 5.2% of lanthanide rare earth complex photosensitive catalyst, 3.4% of manganese stearate, 10.0% of calcium stearate, 0.2% of antioxidant and 0.2% of silane coupling agent, and cellulose, 0.11% of chitin, 6.5% of catechin and 0.11% of chitosan are also added into the master batch, wherein the cellulose accounts for 0.78% of the total mass of the high-density polyethylene, the Fischer-Tropsch wax, the lanthanide rare earth complex photosensitive catalyst, the manganese stearate, the calcium stearate, the antioxidant and the silane coupling agent.
In the other examples, the master batch is prepared by referring to the preparation method in example 1, and the degradable plastic product is prepared by adding the master batch into the existing production process of the plastic product.
The invention uses lanthanide rare earth complex photosensitive catalyst, lanthanum stearate, manganese stearate, copper blue oxidase, titanocene dichloride and catechin to absorb natural light ultraviolet rays and convert the ultraviolet rays into heat energy to be released, so that the plastic bag is accelerated to be degraded and cracked into fragments, and then the second-level degradation is carried out by using the action of soil bacteria microorganisms under natural conditions. The master batch is applied to the plastic production process, the traditional plastic product process is not changed, and the production cost is greatly reduced.
The specific gravity of the master batch can reach 0.92g/cm3The volume density can reach 0.55g/L, and the water content is less than 0.15 percent.
The master batch disclosed by the invention is added into the existing production process of the PE plastic bag, 50 produced plastic bags are randomly extracted for detection, and the detection items are photodegradation experiments according to GB/T20197-.
The experimental conditions are as follows:
1. the hernia lamp is exposed in an artificial accelerated aging box with irradiance of 0.51W (m)2Nm) @340nm, illumination for 102min, black mark temperature of 65 + -5 deg.C, relative humidity of 65 + -5% RH, illumination and spraying for 18min, and filter Daylight; the exposure time was 120 h.
2. Laboratory environment, 23 + -2 deg.C, 60 + -5% RH; specimen width 10mm, thickness 0.023mm, test speed 50mm/min, chuck distance 50mm, specimen: GB 13022-1991 type IV. The test specimen is cut from the sample.
Wherein the retention (%) is a value after photoaging/a value of normality ×%; the weight-average relative molecular mass decrease rate (%) was (weight-average relative molecular weight before photoaging-weight-average relative molecular weight after photoaging)/weight-average relative molecular weight before photoaging x 100.
The results of the tests of examples 1-5 are shown in the following table:
the master batch is added into the existing plastic bag production process, and the field natural light degradation time is generally 3-6 months under the natural condition of the produced plastic bag.
The above description is only a preferred embodiment of the present application, and not intended to limit the present application, and the claims are intended to cover all modifications of the structure and the scope of the application.
Claims (10)
1. The master batch comprises Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant and a silane coupling agent, and the master batch also comprises catechin which accounts for 1-7% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, wherein the master batch comprises the following components in percentage by weight: 70-80% of polyethylene, 1-5% of Fischer-Tropsch wax, 3-12% of a photosensitive catalyst, 10-13% of calcium stearate, 0.1-1% of an antioxidant and 0.1-1% of a silane coupling agent.
2. The natural light-microorganism double-degradation master batch according to claim 1, characterized in that: the raw materials comprise the following components in percentage by weight: 75% of polyethylene, 1.5% of Fischer-Tropsch wax, 11% of a photosensitive catalyst, 11.8% of calcium stearate, 0.2% of an antioxidant and 0.5% of a silane coupling agent.
3. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the polyethylene is one or a combination of a plurality of high density polyethylene, linear low density polyethylene and low density polyethylene.
4. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the photosensitive catalyst is one or a combination of a lanthanide rare earth complex photosensitive catalyst, lanthanum stearate, manganese stearate and copper blue oxidase.
5. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
6. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the silane coupling agent is r- (2, 3-epoxypropoxy) propyl trimethoxy silane.
7. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the master batch also comprises an accelerant, wherein the mass of the accelerant accounts for 0.5-1.5% of the total weight of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent.
8. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the master batch also comprises an additive, wherein the mass of the additive accounts for 1-5.5% of the total weight of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent, and the mass ratio of the additive is 70-80: 10-15: 10-15 of cellulose, chitin and chitosan.
9. The natural light-microorganism double degradation master batch according to claim 1 or 2, characterized in that: the master batch is also added with titanocene dichloride with the mass accounting for 1-5% of the total mass of the polyethylene, the Fischer-Tropsch wax, the photosensitive catalyst, the calcium stearate, the antioxidant and the silane coupling agent.
10. The method for preparing the natural light-microorganism double degradation master batch as claimed in any one of claims 1-2, comprising the following steps: adding polyethylene, Fischer-Tropsch wax, a photosensitive catalyst, calcium stearate, an antioxidant and a silane coupling agent into a high-speed stirrer, stirring and mixing, controlling the temperature of raw materials to be 90-130 ℃, placing the raw materials into an internal mixer, mixing for 5-10min, discharging materials, cooling the raw materials to be treated to be below 40 ℃, and extruding and granulating the raw materials at the temperature of 140 ℃ and 170 ℃ by using a parallel double-screw extruder to obtain the master batch.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023176452A1 (en) * | 2022-03-14 | 2023-09-21 | 古河電気工業株式会社 | Masterbatch |
| CN117603522A (en) * | 2024-01-23 | 2024-02-27 | 四川腾达峰橡塑科技有限公司 | Full-biodegradation plastic master batch and preparation method and application thereof |
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