CN114836013A - Full-biodegradable plastic mulching film master batch, preparation method and application thereof - Google Patents
Full-biodegradable plastic mulching film master batch, preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention provides a fully-degradable plastic mulching film master batch, a preparation method and application thereof. In the processing process, silane or epoxy groups are in key joint with hydroxyl or carboxyl in a degradable high polymer material structure, unsaturated bonds in unsaturated monomers are introduced into the degradable high polymer structure, and then are in key joint with free radicals on a biodegradable high polymer chain in the presence of an initiator to form a micro-crosslinking structure, so that the ultraviolet aging resistance of the material is obviously improved, meanwhile, a mulching film material with the thickness of less than 6 microns can be prepared, and the problems of difficulty in blowing, over-quick aging and the like of the conventional low-thickness full-biodegradable mulching film are solved.
Description
Technical Field
The invention belongs to the technical field of biodegradable plastic materials, and particularly relates to a fully-degradable plastic mulching film master batch, a preparation method and application thereof.
Background
In the 50 s of the 20 th century, plastic mulching technology is introduced into the field of agricultural planting along with the development of plastic science, and is mainly used for planting strawberries at first. The mulching can obviously improve the soil temperature, prevent the soil moisture from evaporating, keep the soil loose, prevent weeds and the like and is beneficial to promoting the seed germination and the crop growth, so the application crop types are gradually developed from economic crops to main grain crops such as corn, wheat, rice and the like, the application range and the area are continuously expanded, and the agricultural productivity is effectively improved. However, the mulching film also brings about a serious residual pollution problem of the mulching film, and causes serious white pollution.
In recent years, the development of fully biodegradable plastics provides possibility for solving the problem, and as the degradable high molecular materials can be decomposed by microorganisms and finally degraded into water and carbon dioxide, the mulching film product prepared by taking the degradable high molecular materials as the raw material can be gradually degraded in soil after being used, so that a large amount of accumulation can not be caused, and the pollution to the soil and the surrounding environment can be avoided. However, due to the difference of the growth cycles of different crops in different regions, the requirements for the degradation speed of the degradable mulching film are greatly different, and the current fully-degradable mulching film product still has the defects of short rupture time, poor degradation controllability and the like, so that the heating and soil moisture preserving functions are poor, the growth requirements of different weather conditions and different crops are difficult to meet, and the application and popularization of the fully-biodegradable mulching film are greatly limited. The prior documents and patent reports mainly focus on pursuing the degradation performance of the mulching film (CN201310458050.X), but ignore the difference of the use cycle of the mulching film, the used degraded mulching film is often degraded prematurely, the mechanical performance is deteriorated to cause film breakage, and the heat preservation, moisture retention and weed suppression capabilities are lost, although the anti-aging performance of the degraded mulching film (CN201310736299.2) can be improved by simply adding an ultraviolet absorbent or a light stabilizer, the simultaneous addition of a large amount of the ultraviolet absorbent and the light stabilizer not only increases the production cost of materials, but also has the problem that the requirements of crops with long life cycle cannot be met.
Aiming at the technical problems, the invention provides a full-biodegradable mulching film master batch and a preparation method thereof, and mainly solves the problems that a full-biodegradable plastic material is poor in ultraviolet resistance and aging resistance, and the service cycle of a mulching film is too short.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide the master batch of the full-biodegradable plastic mulching film with light aging resistance and the preparation method thereof, and the full-biodegradable plastic mulching film prepared by the master batch can avoid premature aging and cracking of the film in the using process without influencing the final degradation performance of the film.
The object of the present invention is achieved by the following means.
The master batch for the fully biodegradable plastic mulching film preferably comprises the following raw materials in parts by weight:
fully-degradable high polymer material: 100 to 150 parts of
Antioxidant: 0.2 to 1.2 portions of
Initiator: 0.01 to 0.05 portion
Inorganic filler: 5 to 50 parts of
Unsaturated modifier: 0.1 to 50 portions
Stabilizing aid: 0.5 to 8 portions of
Preferably, the fully degradable high molecular material is one or more of polybutylene adipate/terephthalate, polylactic acid, polyhydroxybutyrate-valerate, polypropylene carbonate and polybutylene succinate.
Preferably, the stabilizing aid is a uv stabilizer.
Preferably, the inorganic filler is one or more of nano silica, modified talcum powder, nano calcium carbonate and the like.
Preferably, the unsaturated modifier is one or more of vinyltrimethylsilane, vinyltrimethoxysilane, allyl glycidyl ether and glycidyl methacrylate.
Preferably, the initiator is one or a mixture of two of dibenzoyl peroxide and dicumyl peroxide.
Preferably, the antioxidant is one or more of 1010, 168 and 1076.
A preparation method of a full-biodegradable plastic mulching film master batch preferably comprises the following specific steps:
(1) drying the fully-degradable high polymer material at 45-80 ℃ for 6-24 h;
(2) after uniformly mixing the fully-degradable high polymer material and the inorganic filler, adding an antioxidant, an initiator, an unsaturated modifier and a stabilizing auxiliary agent for full mixing;
(3) and (3) putting the mixture obtained in the step (2) into an extruder, and melting, extruding and granulating at 120-220 ℃.
Preferably, the fully degradable high molecular material is one or more of polybutylene adipate/terephthalate, polylactic acid, polyhydroxybutyrate-valerate, polypropylene carbonate and polybutylene succinate.
Preferably, the stabilizing aid is an ultraviolet light stabilizer.
Further preferably, the ultraviolet stabilizer is one or a mixture of two or more selected from the group consisting of bis (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate, 1-methyl-8- (1,2,2,6, 6-pentamethyl-4-piperidine) sebacate, polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidine ethanol) ester, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 2- (2 '-hydroxy-5' - (2, 4-tert-butyl) phenyl) benzotriazole.
Preferably, the inorganic filler is one or more of nano silica, modified talcum powder, nano calcium carbonate and the like.
Preferably, the unsaturated modifier is one or more of vinyltrimethylsilane, vinyltrimethoxysilane, allyl glycidyl ether and glycidyl methacrylate.
Preferably, the initiator is one or a mixture of two of dibenzoyl peroxide and dicumyl peroxide.
Preferably, the antioxidant is one or more of 1010, 168 and 1076.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention introduces silane or epoxy compound containing unsaturated double bond into full biodegradable high molecular material, and adds free radical initiator. In the process of melting and blending, silane or epoxy groups can be in key joint with hydroxyl or carboxyl in a degradable high polymer material structure, unsaturated bonds in unsaturated monomers are introduced into the degradable high polymer structure, the unsaturated bonds can be in key joint with free radicals on a biodegradable high polymer chain to form a micro-crosslinking structure, the micro-crosslinking phenomenon can also occur under the condition of natural illumination, the performance reduction caused by degradation of the degradable high polymer can be reduced to a certain extent, and the ultraviolet aging resistance of the material is obviously improved. Meanwhile, the viscosity of the material melt is increased due to the micro-crosslinking structure, so that the possibility is provided for preparing a fully-degradable mulching film material with the thickness of less than 6 microns, and the problems of difficult blowing, too fast aging and the like of the conventional low-thickness fully-biodegradable mulching film are solved.
Detailed Description
The following examples are given to further illustrate the practice of the present invention, but the present invention is not limited thereto.
The raw materials used in the examples are all commercially available products. The poly (butylene adipate/terephthalate) was purchased from basf, germany or tunhe, xinjiang; polylactic acid is available from Natureworks; polyhydroxybutyrate-hydroxyvalerate was purchased from Tianan organisms; the polypropylene carbonate is a self-made copolymer of carbon dioxide and propylene oxide, the number average molecular weight is 16.8 ten thousand, and the molecular weight distribution is 2.8; polybutylene succinate is available from Anqing and Xingjing industries.
Aging test the experiments were carried out in a GT-QUV/SPRAY UV light box manufactured by high-speed rail inspection instruments Inc. with reference to the test standards G B/T16585-1996. The mechanical property of the mulching film is tested by referring to GB/T1040.3-2006,
example 1
100 parts by weight of polybutylene adipate/terephthalate are dried at 45 ℃ for 24 h. 5 parts by weight of nano-silica, 0.2 part of 1010, 0.01 part of dibenzoyl peroxide, 0.5 part of vinyltrimethylsilane and 0.5 part of polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) were added thereto and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Example 2
100 parts by weight of poly (butylene adipate/terephthalate), 15 parts by weight of polylactic acid, 5 parts by weight of poly (hydroxybutyrate-valerate) and 10 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 8 hours. 10 parts by weight of nano-silica, 1.0 part of 1010, 0.02 part of dibenzoyl peroxide, 5.0 parts of vinyltrimethoxysilane and 1.0 part of polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester are added and fully mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film, thus obtaining the full-biodegradable mulching film with the thickness of 6 microns.
Example 3
100 parts by weight of poly (butylene adipate/terephthalate), 25 parts by weight of polylactic acid, 5 parts by weight of poly (hydroxybutyrate-valerate) and 20 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 6 hours. 20 parts by weight of nano silica, 1.2 parts by weight of 1010 parts by weight of dicumyl peroxide, 10 parts by weight of vinyltrimethylsilane and 2.0 parts by weight of poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate were added and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film, thus obtaining the full-biodegradable mulching film with the thickness of 6 microns.
Example 4
100 parts by weight of poly (butylene adipate/terephthalate), 10 parts by weight of polylactic acid, 10 parts by weight of poly (hydroxybutyrate-valerate) and 5 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 8 hours. 30 parts by weight of nano-silica, 0.5 part of 1010 and 0.5 part of 1076 antioxidant, 0.02 part of dibenzoyl peroxide, 15 parts of vinyltrimethylsilane and 2.0 part of 2- (2 '-hydroxy-5' - (2, 4-tert-butyl) phenyl) benzotriazole were added and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Example 5
100 parts by weight of polybutylene adipate/terephthalate, 25 parts by weight of polypropylene carbonate and 15 parts by weight of polybutylene succinate were dried at 60 ℃ for 24 hours. 35 parts by weight of nano calcium carbonate, 0.5 part of 1010, 0.05 part of dibenzoyl peroxide, 20 parts of allyl glycidyl ether and 4.0 parts of polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester are added and fully mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Example 6
120 parts by weight of poly (butylene adipate/terephthalate) and 30 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 24 h. 20 parts by weight of nano silica, 0.5 part of 1010, 0.05 part of dibenzoyl peroxide, 50 parts of allyl glycidyl ether and 8.0 parts of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate were added thereto and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Comparative example 1: the other formulation was the same as in example 4 without addition of vinyltrimethylsilane
100 parts by weight of poly (butylene adipate/terephthalate), 10 parts by weight of polylactic acid, 10 parts by weight of poly (hydroxybutyrate-valerate) and 5 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 8 hours. 30 parts by weight of nano silica, 0.5 part by weight of 1010 and 0.5 part by weight of 1076 antioxidant, 0.02 part by weight of dibenzoyl peroxide and 2.0 part by weight of 2- (2 '-hydroxy-5' - (2, 4-tert-butyl) phenyl) benzotriazole were added and mixed thoroughly in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Comparative example 2: the initiator and vinyltrimethylsilane were not added, and the other formulation was the same as in example 4
100 parts by weight of poly (butylene adipate/terephthalate), 10 parts by weight of polylactic acid, 10 parts by weight of poly (hydroxybutyrate-co-valerate) and 5 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 8 hours. 30 parts by weight of nano-silica, 0.5 part by weight of 1010 and 0.5 part by weight of 1076 antioxidant and 2.0 parts by weight of 2- (2 '-hydroxy-5' - (2, 4-tert-butyl) phenyl) benzotriazole were added and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
Comparative example 3: the formulation is otherwise the same as in example 4 without initiator addition
100 parts by weight of poly (butylene adipate/terephthalate), 10 parts by weight of polylactic acid, 10 parts by weight of poly (hydroxybutyrate-valerate) and 5 parts by weight of poly (butylene succinate) were dried at 60 ℃ for 8 hours. 30 parts by weight of nano-silica, 0.5 part of 1010 and 0.5 part of 1076 antioxidant, 15 parts of vinyltrimethylsilane and 2.0 parts of 2- (2 '-hydroxy-5' - (2, 4-tert-butyl) phenyl) benzotriazole were added and sufficiently mixed in a mixer. Then adding the obtained mixture into a double screw to perform extrusion granulation at the temperature of 150-220 ℃ to obtain master batch particles. And carrying out blow molding on the obtained plastic particles on a single-screw film blowing machine to form a film so as to obtain the full-biodegradable mulching film with the thickness of 6 microns.
The mechanical properties of the mulching films prepared in the examples and the comparative examples are as follows:
the experimental results show that the aging resistance of the mulching film modified by the method is obviously improved, and parameters such as tensile strength, elongation at break and the like are not obviously reduced after being irradiated for 48 hours by ultraviolet. The ultraviolet resistance and the aging resistance of the degradable high polymer material can be effectively improved by the method.
In order to further investigate the performance of the prepared film material, the rupture time of the mulching film is checked by covering peanuts in a natural environment, and the experimental place is a certain place in Shandong province. The mulching films prepared in example 4 and comparative example 2 were each covered with 10 ridges of 10-meter-long peanuts. In the experiment, the peanut is set to 150 days from planting to harvesting, and the integrity of the mulching film in the whole process is as follows:
| days of experiment (sky) | Example 4 | Comparative example 2 |
| 65 | Intact | 2 ridges are broken |
| 75 | Intact | Cracking of 8 ridges |
| 90 | Intact | 10 ridges all appeared cracked |
| 105 | 1 ridge is broken | —— |
| 120 | 3 ridges are broken | —— |
| 150 | 4 ridges appeared cracked and the rest was more intact | —— |
The experimental data show that the modified mulching film can still keep good integrity after being covered for 100 days, only 1 ridge is broken, and considering that the performance requirements of crops on the mulching film such as weeding and the like are obviously reduced after being planted for 100 days, the mulching film provided in the embodiment can meet the actual peanut planting requirements. And the unmodified mulching film is cracked greatly at 75 days, so that the growth of crops is influenced. The modification master batch and the mulching film product provided by the invention can meet the actual production requirements.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. The master batch is characterized by comprising the following raw materials in parts by weight:
fully-degradable high polymer material: 100 to 150 parts by weight
Antioxidant: 0.2 to 1.2 portions of
Initiator: 0.01 to 0.05 portion
Inorganic filler: 5 to 50 parts of
Unsaturated modifier: 0.1 to 50 portions
Stabilizing auxiliary agent: 0.5 to 8 portions of
Wherein the fully degradable high molecular material is one or more of poly (butylene adipate/terephthalate), polylactic acid, poly (hydroxybutyrate-co-valerate), poly (propylene carbonate) and poly (butylene succinate);
the stabilizing auxiliary agent is an ultraviolet stabilizer;
the inorganic filler is one or more of nano silicon dioxide, modified talcum powder, nano calcium carbonate and the like.
2. The masterbatch for full biodegradable plastic mulch film according to claim 1, wherein said unsaturated modifier is one or more of vinyltrimethylsilane, vinyltrimethoxysilane, allyl glycidyl ether, glycidyl methacrylate.
3. The masterbatch for full biodegradable plastic mulch film according to claim 1, wherein said initiator is one or a mixture of two of dibenzoyl peroxide and dicumyl peroxide.
4. The master batch for full biodegradable plastic mulching film according to claim 1, wherein the antioxidant is one or more of 1010, 168 and 1076.
5. The preparation method of the master batch of the full biodegradable plastic mulching film according to the claims 1-4, which is characterized by comprising the following specific steps:
(1) drying the fully-degradable high polymer material at 45-80 ℃ for 6-24 h;
(2) after uniformly mixing the fully-degradable high polymer material and the inorganic filler, adding an antioxidant, an initiator, an unsaturated modifier and a stabilizing auxiliary agent for full mixing;
(3) putting the mixture obtained in the step (2) into an extruder, and melting, extruding and granulating at 120-220 ℃;
wherein the fully degradable high molecular material is one or more of poly (butylene adipate/terephthalate), polylactic acid, poly (hydroxybutyrate-valerate), polypropylene carbonate and poly (butylene succinate);
the stabilizing auxiliary agent is an ultraviolet stabilizer;
the inorganic filler is one or more of nano silicon dioxide, modified talcum powder, nano calcium carbonate and the like.
6. The method for preparing the master batch for the full biodegradable plastic mulching film according to claim 5, wherein the unsaturated modifier is one or more of vinyltrimethylsilane, vinyltrimethoxysilane, allyl glycidyl ether and glycidyl methacrylate.
7. The method for preparing a masterbatch for full biodegradable plastic mulch film according to claim 5, wherein the initiator is one or a mixture of two of dibenzoyl peroxide and dicumyl peroxide.
8. The method for preparing a masterbatch for full biodegradable plastic mulch film according to claim 5, wherein the antioxidant is one or more of 1010, 168 and 1076.
9. A full biodegradable plastic mulching film, characterized in that it contains the master batch of the full biodegradable plastic mulching film according to any one of claims 1 to 4 or the master batch of the full biodegradable plastic mulching film prepared by the preparation method according to any one of claims 5 to 8.
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| CN101265356A (en) * | 2008-05-07 | 2008-09-17 | 江苏琼花集团有限公司 | Degradation-type composite material and preparation method thereof |
| US20120288650A1 (en) * | 2011-05-10 | 2012-11-15 | Basf Se | Biodegradable polyester film |
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| CN112874099A (en) * | 2020-12-31 | 2021-06-01 | 东莞市普凯塑料科技有限公司 | Biodegradable multilayer composite barrier film and preparation method thereof |
| CN112980153A (en) * | 2021-03-01 | 2021-06-18 | 北京惠林苑生物科技有限公司 | Full-biodegradable plastic mulching film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265356A (en) * | 2008-05-07 | 2008-09-17 | 江苏琼花集团有限公司 | Degradation-type composite material and preparation method thereof |
| US20120288650A1 (en) * | 2011-05-10 | 2012-11-15 | Basf Se | Biodegradable polyester film |
| CN111748184A (en) * | 2020-07-21 | 2020-10-09 | 苏州环诺新材料科技有限公司 | Fully-degradable high-fluidity PLA composite material and preparation method thereof |
| CN112874099A (en) * | 2020-12-31 | 2021-06-01 | 东莞市普凯塑料科技有限公司 | Biodegradable multilayer composite barrier film and preparation method thereof |
| CN112980153A (en) * | 2021-03-01 | 2021-06-18 | 北京惠林苑生物科技有限公司 | Full-biodegradable plastic mulching film and preparation method and application thereof |
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