CN114806106A

CN114806106A - PBAT-based biodegradable mulch film special material

Info

Publication number: CN114806106A
Application number: CN202210464620.5A
Authority: CN
Inventors: 郝艳平; 田洪池; 陈军; 王凡; 王泽芳; 牛茂平; 邱焕玲; 王红; 李双利; 刘杨; 马德琳
Original assignee: Kpic Dawn Polymer Shanghai Co ltd; Qingdao Rioh Plastic New Material Co ltd; Qingdao Zhoushi Plastic Packing Co ltd; Shandong Dawn Degradable Materials Co ltd; SHANDONG DAWN POLYMER CO Ltd
Current assignee: Kpic Dawn Polymer Shanghai Co ltd; Qingdao Rioh Plastic New Material Co ltd; Qingdao Zhoushi Plastic Packing Co ltd; Shandong Dawn Degradable Materials Co ltd; SHANDONG DAWN POLYMER CO Ltd
Priority date: 2022-04-29
Filing date: 2022-04-29
Publication date: 2022-07-29

Abstract

PBAT-based biodegradable mulching film special material, including the following raw materials: 61.5-91.6 parts of PBAT melt, 5-20 parts of solid particle modifier, 3-15 parts of enhancer, 0.1-0.5 parts of compatibilizer, lubricant 0.1-0.5 part, UV absorber 0.1-1.0 part, light stabilizer 0.1-1.0 part, anti-hydrolysis agent 0.1-0.5 part. The invention overcomes the problems of poor mechanical properties and high production cost caused by thermal degradation of PBAT during the secondary processing of preparing the PBAT-based biodegradable mulch film in the prior art, and provides a method for preparing the PBAT-based biodegradable mulch film by melt on-line modification The device and method for the special material avoid the degradation of PBAT due to secondary processing, so that the prepared PBAT-based biodegradable mulch film has higher mechanical properties and can reduce production costs.

Description

PBAT-based biodegradable mulch film special material

Technical Field

The invention belongs to the field of preparation of biodegradable mulching films, and particularly relates to a PBAT-based biodegradable mulching film special material.

Background

The mulching film is the fourth agricultural production data following seeds, pesticides and fertilizers, and the application of the mulching film technology drives the agricultural productivity of China. The functions of increasing temperature, preserving soil moisture, preventing diseases, resisting insects, inhibiting weeds and the like of the mulching film cover enable the grain crops to increase the yield by 30-50 percent and the economic crops to increase the yield by 20-60 percent, thereby making a great contribution to guaranteeing the safe supply of Chinese food. According to statistics, the mulching area of the mulching film in China is about 2.8 hundred million acres, the using amount reaches 150 ten thousand tons, and the mulching area of the mulching film in China is increased at a speed of 10% per year in the next 10 years. However, because of the disposable use of mulching films, a large amount of residual mulching films are left in the soil every year. The traditional mulching film is difficult to degrade in nature, and the fragments of the mulching film can form a barrier layer in soil, so that the flow of water, gas, fertilizer and the like in the soil is blocked, the soil structure is hardened, the ecological environment is seriously damaged, white pollution is caused, and the green development of agriculture in China is severely restricted. Therefore, solving the problem of soil pollution caused by residual mulching has become a urgent task in the technology of mulching cultivation, and in order to solve this problem, research on biodegradation and mulching film degradation is in force.

The fully biodegradable mulching film mainly takes PBAT as a main component, then is modified, can be completely decomposed by bacteria and microorganisms in 1-2 plant growth cycles after being used, and is finally completely degraded into water and carbon dioxide, so that the fully biodegradable mulching film has zero harm to soil and crops. In recent years, research and application of biodegradable mulching films have been advanced to a certain extent, and PBAT raw material production enterprises such as tunghe in blue mountains of Xinjiang, Guangzhou Jinhui technology, and Jinhuilong have carried out research and popularization work on biodegradable mulching films. At present, in order to prepare a biodegradable mulching film product, a PBAT (poly (butylene adipate-co-terephthalate)) is modified to prepare a biodegradable mulching film modified material, and then the biodegradable mulching film product is produced. CN111978691A discloses a biodegradable mulch film and a preparation method thereof, the method comprises mixing PBAT and various modifiers to obtain a premix, then extruding and granulating the premix through a double-screw extruder to obtain modified film-forming resin, and then blowing the modified film-forming resin through a film blowing machine to obtain a biodegradable mulch film product. CN110452507A discloses a high-barrier high-strength ultrathin full-biodegradable mulch film and a preparation method thereof, the method comprises the steps of mixing PBAT and various modifiers in a stirrer to obtain a mixture, then putting the mixture into a double-screw extruder to extrude and granulate to obtain film blowing master batches, and then blowing the modified master batches through a film blowing machine to obtain a full-biodegradable mulch film product.

However, the PBAT is very easy to degrade during processing due to the poor thermal stability of the PBAT, which results in the decrease of the molecular weight and influences the mechanical properties of the mulching film product. At present, the method adopted for preparing the biodegradable mulching film product is subjected to secondary processing, so that the molecular weight and the mechanical property of PBAT are reduced, and the cost is increased.

Disclosure of Invention

The invention provides a PBAT-based biodegradable mulching film special material, which is used for overcoming the defects in the prior art.

The invention is realized by the following technical scheme:

the PBAT-based biodegradable mulch film special material comprises the following raw materials in parts by weight: 61.5-91.6 parts of PBAT melt, 5-20 parts of solid particle modifier, 3-15 parts of reinforcing agent, 0.1-0.5 part of compatilizer, 0.1-0.5 part of lubricant, 0.1-1.0 part of ultraviolet absorbent, 0.1-1.0 part of light stabilizer and 0.1-0.5 part of hydrolysis resistant agent.

The PBAT-based biodegradable mulch film special material comprises the following components in parts by weight: BDO, PTA and AA in the proportions BDO, PTA and AA in the range of 2-4: 3-4: 2-4, then pumping the mixture to a first esterification kettle through a slurry pump, and carrying out esterification reaction to obtain an esterified substance; feeding the esterified substance into a second esterification kettle, and continuously carrying out esterification reaction to obtain an oligomer; and pumping the oligomer into a polycondensation reaction kettle for polycondensation reaction to obtain a PBAT melt.

The PBAT-based biodegradable mulch film special material comprises a solid particle modifier, wherein the solid particle modifier is any one of polylactic acid (PLA), polypropylene carbonate (PPC) and polybutylene succinate (PBS) or a mixture of any two of the two in any proportion.

The special PBAT-based biodegradable mulch film material comprises a reinforcing agent, wherein the reinforcing agent is any one or a mixture of any two of talcum powder, calcium carbonate, diatomite and nano silica which are mixed in any proportion.

The special PBAT-based biodegradable mulch film material comprises a compatilizer, wherein the compatilizer is any one or a mixture of any two of polyphenyl polymethylpolyisocyanate (PAPI), diphenylmethane diisocyanate (MDI) and di-tert-butylperoxy Diisopropylbenzene (DCP) mixed in any proportion.

The special PBAT-based biodegradable mulch film material comprises any one or a mixture of any two of ethylene bis stearamide, oleamide, zinc stearate, calcium stearate and ethylene-acrylic acid which are mixed in any proportion.

The PBAT-based biodegradable mulch film special material comprises the ultraviolet absorbent which is any one of UV-234 and UV-326.

The PBAT-based biodegradable mulch special material comprises one of UV-770 and UV-944.

The PBAT-based biodegradable mulch film special material comprises 2,2', 6,6' -tetraisopropyl diphenyl carbodiimide (AHA-98).

The preparation method of the special PBAT-based biodegradable mulch film material comprises the following steps:

the method comprises the following steps: accurately weighing various substances according to the proportion;

step two: the PBAT melt obtained by polymerization is extruded into a zone B of a double screw through a PBAT melt conveying pipeline;

step three: feeding a solid particle modifier into a zone of a double screw A through a solid particle modifier hopper; mechanically and uniformly mixing a reinforcing agent, a compatilizer, a lubricant, an ultraviolet absorbent, a light stabilizer and an anti-hydrolysis agent, and feeding the mixture into a second area of a double screw A through a powder modifier hopper; (4) the PBAT melt, the solid particle modifier, the reinforcing agent, the compatilizer, the lubricant, the ultraviolet absorbent, the light stabilizer and the hydrolysis resistant agent are extruded by a double-screw extruder B to prepare the special material for the PBAT-based biodegradable mulching film.

The PBAT-based biodegradable mulch special material is described.

The invention has the advantages that: the invention overcomes the problems of poor mechanical property and high production cost caused by thermal degradation of PBAT in the secondary processing process of preparing the PBAT-based biodegradable mulching film in the prior art, and provides a device and a method for preparing a special material for the PBAT-based biodegradable mulching film by melt online modification.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a schematic view of a production apparatus of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1: (1) 85.6kg of PBAT melt obtained by polymerization is extruded into a zone B by a twin screw through a PBAT melt conveying pipeline; (2) feeding 8kg of PLA via a solid particle modifier into a zone entering the twin screw A; (3) mechanically and uniformly mixing 5kg of talcum powder, 0.1kg of PAPI, 0.2kg of ethylene bis stearamide, 0.5kg of UV-234, 0.5kg of UV-770 and 0.1kg of AHA-98, and feeding the mixture into a second area of a double screw A through a powder modifier hopper; (4) and extruding the PBAT melt, the solid particle modifier and the powder modifier by a double-screw extruder B to prepare the special PBAT-based biodegradable mulching film material.

Example 2 (1) 70.7kg of PBAT melt obtained from the polymerization was fed via a PBAT melt feed line into a zone of a twin-screw extrusion B; (2) feeding 20kg of PPC via a solid particle modifier into a zone entering twin-screw A; (3) mechanically and uniformly mixing 8kg of talcum powder, 0.1kg of MDI, 0.2kg of oleamide, 0.2kg of UV-234, 0.5kg of UV-770 and 0.3kg of AHA-98, and feeding the mixture into a second area of a double screw A through a powder modifier hopper; (4) and extruding the PBAT melt, the solid particle modifier and the powder modifier by a double-screw extruder B to prepare the special PBAT-based biodegradable mulching film material.

Example 3: (1) 80.3kg of PBAT melt obtained by polymerization is fed into a first zone of a double-screw extruder B through a PBAT melt conveying pipeline; (2) mechanically and uniformly mixing 5kg of PLA and 10kg of PPC, and feeding the mixture into a first area of a double screw A through a solid particle modifier; (3) 3kg of calcium carbonate, 0.2kg of PAPI, 0.2kg of ethylene bis stearamide, 0.5kg of UV-326, 0.5kg of UV-944 and 0.3kg of AHA-98 are mechanically and uniformly mixed and then enter a second area of a double screw A through a powder modifier hopper; (4) and extruding the PBAT melt, the solid particle modifier and the powder modifier by a double-screw extruder B to prepare the special PBAT-based biodegradable mulching film material.

Example 4: (1) 79.3kg of PBAT melt obtained by polymerization is extruded into a zone B of a double screw through a PBAT melt conveying pipeline; (2) feeding 12kg of PLA via a solid particle modifier into a zone entering the twin screw A; (3) mechanically and uniformly mixing 5kg of diatomite, 2kg of nano silicon dioxide, 0.2kg of DCP, 0.2kg of calcium stearate, 0.5kg of UV-234, 0.4kg of UV-994 and 0.4kg of AHA-98, and feeding the mixture into a second area of a double screw A through a powder modifier hopper; (4) and extruding the PBAT melt, the solid particle modifier and the powder modifier by a double-screw extruder B to prepare the special PBAT-based biodegradable mulching film material.

Example 5: (1) 81.4kg of PBAT melt obtained by polymerization is fed into a zone B of twin-screw extrusion through a PBAT melt conveying pipeline; (2) feeding 6kg of PLA and 5kg of PBS through a solid particle modifier into a zone entering the twin screw A; (3) 3kg of silicon dioxide, 3kg of calcium carbonate, 0.3kg of PAPI, 0.2kg of ethylene-acrylic acid, 0.3kg of UV-326, 0.3kg of UV-770 and 0.5kg of AHA-98 are mechanically and uniformly mixed and then enter a second area of a double screw A through a powder modifier hopper; (4) and extruding the PBAT melt, the solid particle modifier and the powder modifier by a double-screw extruder B to prepare the special PBAT-based biodegradable mulching film material.

Comparative example: the special PBAT-based biodegradable plastic film material is prepared by the same method as the example 1, except that PBAT resin is adopted, according to the formula of the example 1, 85.6kg of PBAT resin, 8kg of PLA, 5kg of talcum powder, 0.1kg of PAPI, 0.2kg of ethylene bis stearamide, 0.5kg of UV-234, 0.5kg of UV-770 and 0.1kg of AHA-98 are mechanically and uniformly mixed, and then are extruded and granulated by a double screw to obtain the special PBAT-based biodegradable material.

The PBAT-based full-biodegradable mulching film products obtained by blowing the films of examples 1-5 and comparative example by using a film blowing machine were subjected to mechanical property tests, and the results are shown in Table I.

Watch 1

As can be seen from the table I, the transverse and longitudinal tensile strength of the biodegradable mulching film prepared by the device and the method of the invention is greater than that of the comparative example, the transverse and longitudinal tensile strength reaches more than 20MPa, and meanwhile, the production cost is 1250 yuan/ton lower than that of the comparative example.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. PBAT-based biodegradable mulching film special material, is characterized in that: comprises the following raw materials: 61.5-91.6 parts of PBAT melt, 5-20 parts of solid particle modifier, 3-15 parts of reinforcing agent, 0.1 part of compatibilizer -0.5 part, lubricant 0.1-0.5 part, UV absorber 0.1-1.0 part, light stabilizer 0.1-1.0 part, anti-hydrolysis agent 0.1-0.5 part.

2. The special material for PBAT-based biodegradable mulch film according to claim 1, characterized in that: the preparation method of the PBAT melt is: BDO, PTA and AA according to 2-4:3-4:2-4 The molar ratio is mixed, and then the slurry is pumped to the first esterification kettle, and the esterification reaction is carried out to obtain the esterified product; the esterified product is sent to the second esterification kettle, and the esterification reaction is continued to obtain the oligomer; The material is pumped into the polycondensation reaction kettle, and the polycondensation reaction is carried out to obtain the PBAT melt.

3. The special material for PBAT-based biodegradable mulch film according to claim 1, wherein the solid particle modifier is any one of polylactic acid, polypropylene carbonate and polybutylene succinate. A mixture of one or any two in any ratio.

4. PBAT-based biodegradable plastic film special material according to claim 1, is characterized in that: described reinforcing agent is any one or any two of wherein talcum powder, calcium carbonate, diatomite, nano-silica Mixtures mixed in any ratio.

5. PBAT-based biodegradable mulch special material according to claim 1, is characterized in that: described compatibilizer is polyphenyl polymethyl polyisocyanate, diphenylmethane diisocyanate, di-tert-butyl peroxide A mixture of any one or any two of the diisopropylbenzenes mixed in any proportion.

6. PBAT-based biodegradable mulch special material according to claim 1, is characterized in that: wherein described ethylene bis-stearic acid amide, oleic acid amide, zinc stearate, calcium stearate, ethylene-acrylic acid A mixture of any one or any two in any ratio.

7. The special material for PBAT-based biodegradable mulch film according to claim 1, wherein the ultraviolet absorber is any one of UV-234 and UV-326.

8. The special material for PBAT-based biodegradable mulch film according to claim 1, wherein the light stabilizer is any one of UV-770 and UV-944.

9 . The special material for PBAT-based biodegradable mulch film according to claim 1 , wherein the anti-hydrolysis agent is 2,2′,6,6′-tetraisopropyldiphenylcarbodiimide. 10 .

10. PBAT-based biodegradable plastic film special material according to claim 1, is characterized in that: its preparation method comprises the steps:

Step 1: Accurately weigh various substances according to the ratio;

Step 2: the PBAT melt obtained by polymerization will enter the first area of twin-screw extrusion B through the PBAT melt conveying pipeline;

Step 3: pass the solid particle modifier through the solid particle modifier hopper to the first zone of the twin screw A; mechanically mix the reinforcing agent, compatibilizer, lubricant, ultraviolet absorber, light stabilizer, and anti-hydrolysis agent evenly Afterwards, it enters the second zone of the twin screw A through the powder modifier hopper; (4) the PBAT melt, solid particle modifier, reinforcing agent, compatibilizer, lubricant, ultraviolet absorber, light stabilizer, The anti-hydrolysis agent is prepared by extruding the twin-screw extruder B to obtain the special material for PBAT-based biodegradable mulch film.