CN116178749A - Modified straw polylactic acid degradable mulching film and preparation method thereof - Google Patents
Modified straw polylactic acid degradable mulching film and preparation method thereof Download PDFInfo
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- CN116178749A CN116178749A CN202310252774.2A CN202310252774A CN116178749A CN 116178749 A CN116178749 A CN 116178749A CN 202310252774 A CN202310252774 A CN 202310252774A CN 116178749 A CN116178749 A CN 116178749A
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- mulch film
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- 239000010902 straw Substances 0.000 title claims abstract description 109
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 46
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002362 mulch Substances 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 53
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 229920001896 polybutyrate Polymers 0.000 claims abstract 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 34
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 19
- 229930192474 thiophene Natural products 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229920001353 Dextrin Polymers 0.000 claims description 11
- 239000004375 Dextrin Substances 0.000 claims description 11
- 235000019425 dextrin Nutrition 0.000 claims description 11
- RFKWIEFTBMACPZ-UHFFFAOYSA-N 3-dodecylthiophene Chemical compound CCCCCCCCCCCCC=1C=CSC=1 RFKWIEFTBMACPZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 alkyl thiophene Chemical compound 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- HQKVUWMATDWFJI-UHFFFAOYSA-N 3-dodecoxythiophene Chemical compound CCCCCCCCCCCCOC=1C=CSC=1 HQKVUWMATDWFJI-UHFFFAOYSA-N 0.000 claims description 5
- WQYWXQCOYRZFAV-UHFFFAOYSA-N 3-octylthiophene Chemical compound CCCCCCCCC=1C=CSC=1 WQYWXQCOYRZFAV-UHFFFAOYSA-N 0.000 claims description 5
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 4
- GFJHLDVJFOQWLT-UHFFFAOYSA-N 3-hexoxythiophene Chemical compound CCCCCCOC=1C=CSC=1 GFJHLDVJFOQWLT-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
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- 238000003756 stirring Methods 0.000 claims description 4
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- RDEGOEYUQCUBPE-UHFFFAOYSA-N 3-ethoxythiophene Chemical compound CCOC=1C=CSC=1 RDEGOEYUQCUBPE-UHFFFAOYSA-N 0.000 claims 1
- SLDBAXYJAIRQMX-UHFFFAOYSA-N 3-ethylthiophene Chemical compound CCC=1C=CSC=1 SLDBAXYJAIRQMX-UHFFFAOYSA-N 0.000 claims 1
- RFSKGCVUDQRZSD-UHFFFAOYSA-N 3-methoxythiophene Chemical compound COC=1C=CSC=1 RFSKGCVUDQRZSD-UHFFFAOYSA-N 0.000 claims 1
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- GWBGGJASGYDQMF-UHFFFAOYSA-N (6-methyl-4-oxo-1h-pyrimidin-2-yl)urea Chemical compound CC1=CC(=O)N=C(NC(N)=O)N1 GWBGGJASGYDQMF-UHFFFAOYSA-N 0.000 description 2
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 229960000310 isoleucine Drugs 0.000 description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
Abstract
The invention provides a modified straw polylactic acid degradable mulching film, which comprises the following components in parts by weight: 30-90 parts of PLA, 40-70 parts of PBAT, 20-30 parts of modified straw powder, 1-4 parts of molecular chain extender, 2-5 parts of plasticizer, 1-3 parts of coupling agent and 1-2 parts of lubricant. The weight loss rate of the modified straw polylactic acid mulch film provided by the invention reaches more than 90% after 6 months, and in addition, the inventor introduces the modified straw coated by the conjugated polymer in the mulch film preparation process, so that the compatibility of the straw and the degradable high polymer material is improved, the ageing resistance of the mulch film is obviously improved, and the farmland residual film rate of the mulch film is reduced in the actual use process.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified straw polylactic acid degradable mulch film and a preparation method thereof.
Background
The mulching film is widely applied to the field of agricultural planting, has the effects of improving the ground temperature, preserving water, preserving soil and preserving fertilizer, can effectively improve the crop yield and the water utilization efficiency, has root protecting and growth promoting effects on the seedlings which just come out of the soil, and has remarkable effect on increasing the yield and income of plants.
The mulch film is generally laid in farmland, so natural conditions such as sun exposure and the like can accelerate the aging speed, experienced growers know that most of the mulch film in farmland can be formed into unshaped fragments until the mulch film is uncovered, and therefore part of the mulch film cannot be collected and is directly buried in soil. The degradation period of the conventional mulching film is generally 200 years, toxic substances can be released in the degradation process, and the growth and development of crops can be positively influenced under long-term accumulation. Therefore, it is necessary to develop a degradable mulch film with high aging resistance, so that the mulch film can keep the shape intact as much as possible in the service period, the film can be completely uncovered, the film residue rate of farmland can be reduced, and even if unavoidable residues exist, the degradability of the mulch film can also reduce soil pollution.
Polylactic acid (PLA) and poly (butylene adipate/terephthalate) (PBAT) are common raw materials for the preparation of biodegradable materials. The PLA has good biocompatibility, transparency and mechanical strength, but has low elongation at break and large brittleness, so that the application of the PLA is limited; the PBAT has the characteristics of Poly (PBA) adipate and polybutylene terephthalate (PBT), and has better ductility, elongation at break, heat resistance and impact property. Therefore, it is a common approach to improve the overall properties of the material by blending PLA with PBAT, but conventionally, the PBAT is larger in a ratio of about 70%, but the overall manufacturing cost is increased due to the 2-3 times of the PBAT price compared to the common plastics.
The straw fiber has the advantages of low price, sufficient raw materials, high specific modulus, small processing energy consumption and the like, so that the straw fiber is used as a reinforcing body to form a composite material with a high polymer to become a research hot spot, thus not only reducing the production cost, but also improving the added value of the straw. However, as the surface of the straw contains a large amount of polar alcohol hydroxyl and phenolic hydroxyl functional groups, the straw has stronger chemical polarity and poor compatibility with a polymer substrate.
As disclosed in patent document CN 110218424A, a straw powder/PLA/PBAT biomass fully degradable plastic is disclosed, wherein the fully degradable plastic comprises the following components in parts by weight: 15-30 parts of straw powder, 35-50 parts of PLA (polylactic acid), 35-50 parts of PBAT (Poly urethane), 2-4 parts of plasticizer, 1-3 parts of coupling agent, 1-3 parts of chain extender, 1-3 parts of lubricant, 1-3 parts of heat stabilizer and 0.1-0.3 part of antioxidant. Although the inventor carries out complex pretreatment on the straw powder, the problem of compatibility of the straw powder with PLA and PBAT is still not completely solved, and the tensile strength of the prepared plastic product is between 18 and 28MPa, and the requirement of the mulching film on the tensile strength is not met.
In order to increase the compatibility of the straw powder and the degradable high polymer material, the patent document CN 111534071A modifies the straw powder by a method of spraying paraffin miniemulsion; patent documents CN 114395229A and CN 113881208A respectively use 2, 4-diamino-6-methyl-1, 3, 5-triazine grafted polyvinyl acetate and 2-ureido-4-hydroxy-6-methylpyrimidine functionalized isoleucine to modify the straw, and aim to bond modified molecules with the surface of the straw and increase the compatibility of the straw and degradable high polymer materials. Although 2, 4-diamino-6-methyl-1, 3, 5-triazine grafted polyvinyl acetate and 2-ureido-4-hydroxy-6-methylpyrimidine functionalized isoleucine have the effect of increasing the compatibility of straws and high polymer materials, the effect of improving the aging resistance of the mulching film is not obviously enhanced.
Based on the background, the invention provides the polylactic acid mulching film which has good aging resistance, can effectively reduce the residual film rate of farmlands, and meanwhile, the straw modification method provided by the invention can not only increase the compatibility of straw and degradable high polymer materials, but also obviously improve the elongation of the mulching film and improve the mechanical property.
Disclosure of Invention
The invention aims to provide a modified straw polylactic acid degradable mulch film, and another aim of the invention is to provide a preparation method of the modified straw polylactic acid degradable mulch film. The aim of the invention is realized by the following technical scheme:
in a first aspect, a degradable mulching film of modified straw polylactic acid is characterized in that modified straw in the mulching film is prepared by the following method:
(1) Crushing straw, and sieving with a 80-200 mesh standard sieve to obtain straw powder;
(2) Straw powder is added in NaOH or NaHCO 3 Pretreating in the solution to obtain pretreated straw powder;
(3) Dispersing the pretreated straw powder into an organic solution 1 containing conjugated polymer monomers, taking out and drying after 1-5 min;
(4) And dispersing the straw powder obtained in the previous step into an organic solution 2 containing an initiator, taking out and drying after 1-2min to obtain the modified straw powder.
Preferably, the mass concentration of NaOH solution for pretreatment of the straw powder in the step (2) is selected from 4-6%, naHCO 3 The mass concentration of the solution is selected from 15-20%.
Preferably, the conjugated polymer monomer in the step (3) is selected from one or more than two of pyrrole, N-alkyl pyrrole, thiophene, alkyl thiophene and alkoxy thiophene. The organic solution 1 is ethanol and cyclohexane according to the volume ratio of 1: (0.5-1). The mass fraction of conjugated polymer monomer in the organic solution 1 is 0.01-0.05%.
Preferably, the alkyl is a C1-C12 straight chain/branched alkyl, and the alkoxy is selected from the group consisting of C1-C12 straight chain/branched alkoxy.
In a specific embodiment of the present invention, the conjugated polymer monomer is selected from the group consisting of pyrrole, thiophene, 3-octyl thiophene, 3-dodecyl thiophene, 3-hexyloxy thiophene, and combinations of two or more of 3-dodecyloxy thiophene.
Also preferably, the conjugated polymer monomer is a combination of pyrrole and thiophene, 3-octylthiophene, 3-dodecylthiophene, 3-hexyloxythiophene or 3-dodecyloxythiophene.
In a most preferred embodiment of the invention, the conjugated polymer monomer is a combination of pyrrole and 3-dodecylthiophene, or a combination of pyrrole and 3-dodecylthiophene.
Preferably, the initiator in the step (4) is selected from one of peracetic acid and benzoyl peroxide. The organic solution 2 is methanol solution, and the mass fraction of the initiator in the methanol solution is 0.1-0.5%.
In a more preferred embodiment of the present invention, the method for preparing modified straw further comprises: soaking the pretreated straw powder in the dispersion liquid for 20-30min, taking out and drying. The dispersion liquid is a solution prepared from one of polyethylene glycol, polyvinyl alcohol and dextrin, and the concentration of the solution is 3-10mg/mL.
Preferably, the dispersion is an aqueous dextrin solution, for example, an aqueous dextrin solution having a concentration of 5 mg/mL.
Further, the modified straw polylactic acid degradable mulch film provided by the invention is prepared from the following components in parts by weight:
PLA used in the invention is a compound of L-type PLA and D-type PLA, the optical purity is more than 80%, and the weight average molecular weight is 10000-20000; the mass ratio of the L-type PLA to the D-type PLA is 2 (0.2-1). The weight average molecular weight of the PBAT is 30000-100000.
The molecular chain extender is a polyurethane chain extender or an epoxy chain extender, and in a preferred embodiment of the invention, the molecular chain extender is selected from the group consisting of the basf chain extender ADR4370S.
The plasticizer is selected from one or more than two of epoxidized soybean oil, polyethylene glycol 400 and acetyl tributyl citrate.
The coupling agent is selected from silane coupling agents, specifically KH560 and KH 570.
The lubricant is selected from one or more of stearic acid, ethylene bis-stearamide and polyethylene wax.
In the specific embodiment of the invention, the modified straw polylactic acid degradable mulch film is prepared from the following components in parts by weight:
in a second aspect, the invention provides a method for preparing a modified straw polylactic acid degradable mulch film, which comprises the following steps: and at normal temperature, stirring PLA, PBAT, a molecular chain extender, a plasticizer, a coupling agent and a lubricant by using a high-speed stirrer according to parts by weight, adding modified straw powder, uniformly mixing, adopting a double-screw extruder for blending extrusion, drying, granulating, and adopting a film blowing machine to prepare the degradable mulch film.
Preferably, the temperature of the twin-screw extruder is 140-170 ℃, the screw rotating speed is 150-200rpm, the feeding frequency is 1-2Hz, and the granulator frequency is 10-12Hz.
The modified straw polylactic acid degradable mulching film provided by the invention has the following advantages:
(1) The degradable mulching film has excellent aging resistance, and in an aging resistance experiment, the mechanical performance of the mulching film is remarkably slowed down along with ultraviolet irradiation compared with that of a conventional mulching film, because the inventor introduces a conjugated polymer protective layer on the surface of straw in the process of modifying the straw, and the conjugated polymer protective layer has a unique continuous conjugated double bond structure and can absorb part of ultraviolet rays, so that the aging resistance of the degradable mulching film is improved;
(2) The invention uses conjugated polymer monomer to form conjugated polymer protective layer on the surface of straw under the induction of peroxidation initiator in modified straw, the conjugated polymer protective layer not only has the function of improving the ultraviolet resistance of the mulching film, but also can increase the compatibility of straw with degradable high polymer materials PLA and PBAT, and improve the elongation of the mulching film;
(3) In order to further improve the compatibility of the straw, the pretreated straw powder is reprocessed by using the dextrin solution, and the inventor unexpectedly discovers that the mechanical property of the degradable mulch film is further improved due to better compatibility of the straw powder treated by the dextrin solution;
(4) According to the standard test method for determining the aerobic biodegradation of plastics in soil by ASTM D5988-12, the weight loss rate of the degradable mulching film prepared by the method provided by the invention in 6 months is more than 90%.
Drawings
FIG. 1 shows the aging resistance trend of comparative examples and examples 1, 2 and 5.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation of modified straw powder
Preparation example 1
S1: crushing corn straw by using a crusher, and sieving the crushed corn straw by using a 100-target standard sieve to obtain straw powder;
s2: preparing NaHCO with mass concentration of 15% 3 Adding straw powder into the aqueous solution according to the solid-to-liquid ratio of 1:2, soaking for 15min at 100-120 ℃, washing with clear water, and drying to obtain pretreated straw powder;
s3: mixing ethanol and cyclohexane according to a volume ratio of 1:1 to form an organic solution 1, adding thiophene into the organic solution 1 to form a solution with a mass fraction of 0.05%, immersing the pretreated straw powder in the solution for 5min, taking out and airing;
s4: adding benzoyl peroxide into a methanol solution to form a solution with the mass fraction of 0.5%, immersing the dried straw powder in the solution for 1min, and drying to obtain the modified straw powder 1.
Preparation example 2
The preparation method and the raw materials are the same as in preparation example 1, except that the conjugated polymer monomer in step S3 is different, specifically: pyrrole and thiophene are mixed according to a molar mass ratio of 1:1 to obtain a mixture, the mixture is added into the organic solution 1 to form a solution with a mass fraction of 0.05%, and other steps are the same as those of the preparation example 1, so that modified straw powder 2 is obtained.
Preparation example 3
The preparation method and the raw materials are the same as in preparation example 1, except that the conjugated polymer monomer in step S3 is different, specifically: pyrrole and 3-methylthiophene are mixed according to a molar mass ratio of 1:1 to obtain a mixture, the mixture is added into the organic solution 1 to form a solution with a mass fraction of 0.05%, and the other steps are the same as those of the preparation example 1, so that the modified straw powder 3 is prepared.
Preparation example 4
The preparation method and the raw materials are the same as in preparation example 1, except that the conjugated polymer monomer in step S3 is different, specifically: pyrrole and 3-octyl thiophene are mixed according to a molar mass ratio of 1:1 to obtain a mixture, the mixture is added into the organic solution 1 to form a solution with a mass fraction of 0.05%, and the other steps are the same as those of the preparation example 1, so that modified straw powder 4 is prepared.
Preparation example 5
The preparation method and the raw materials are the same as in preparation example 1, except that the conjugated polymer monomer in step S3 is different, specifically: pyrrole and 3-dodecyl thiophene are mixed according to a molar mass ratio of 1:1 to obtain a mixture, the mixture is added into the organic solution 1 to form a solution with a mass fraction of 0.05%, and the other steps are the same as those of the preparation example 1, so that modified straw powder 5 is prepared.
Preparation example 6
The preparation method and the raw materials are the same as in preparation example 1, except that the conjugated polymer monomer in step S3 is different, specifically: pyrrole and 3-dodecyloxy thiophene are mixed according to a molar mass ratio of 1:1 to obtain a mixture, the mixture is added into an organic solution 1 to form a solution with a mass fraction of 0.05%, and the other steps are the same as those of preparation example 1, so that modified straw powder 6 is prepared.
Preparation examples 7 to 12
On the basis of preparation examples 1-6, respectively, the pretreated straw powder is immersed in dextrin aqueous solution (5 mg/mL) for 20min, taken out and dried, and then conjugated polymer coating operation is carried out, and modified straw powder 7-12 is prepared according to the method.
Comparative preparation example 1
S1: crushing corn straw by using a crusher, and sieving the crushed corn straw by using a 100-target standard sieve to obtain straw powder;
s2: preparing NaHCO with mass concentration of 15% 3 Adding straw powder into the aqueous solution according to the solid-to-liquid ratio of 1:2, soaking for 15min at 100-120 ℃, washing with clear water, and drying to obtain the pretreated straw powder.
Preparation of degradable mulch film
Example 1
S1: weighing 90 parts of PLA (L-shaped PLA: D-shaped PLA=5:1), 70 parts of PBAT, 3 parts of ADR4370S, 4 parts of epoxidized soybean oil, 1 part of KH560 and 1.5 parts of stearic acid according to parts by weight at normal temperature for standby, and stirring at 300rpm for 15min by using a high-speed stirrer;
s2: adding 30 parts of the modified straw powder obtained in preparation example 1 into the mixed system, and slowly stirring and uniformly mixing;
s3: and adopting a double-screw extruder to carry out blending extrusion, drying, granulating and film blowing machine to obtain the degradable mulching film, wherein the temperature of the double-screw extruder is 140-170 ℃, the rotating speed of a screw is 200rpm, the feeding frequency is 2Hz, and the frequency of a granulator is 12Hz.
Examples 2 to 12
The preparation method and the raw materials are the same as those in example 1, except that the straw powder added in the step S2 is the modified straw powder 2-12 prepared in the preparation examples 2-12 respectively, and the rest steps are the same as those in example 1, so as to prepare the degradable mulch film.
Comparative example 1
The preparation method and the raw materials are the same as those in example 1, except that the straw powder added in the step S2 is the pretreated straw powder prepared in comparative preparation example 1, and the rest steps are the same as those in example 1, so as to prepare the degradable mulch film.
Effect example 1 detection of mechanical Properties of degradable mulch
The purpose is as follows: the degradable mulch films prepared in examples 1 to 12 of the present invention and comparative example 1 were examined for longitudinal tensile strength and longitudinal elongation.
The method comprises the following steps: testing is carried out on an electronic universal tensile testing machine according to the requirements of national standard GB/T1040.2-2006, the tensile rate is 50mm/min, 10 samples are measured in parallel for each sample, and the average value is obtained. The results are shown in the following table.
TABLE 1 degradable mulch mechanical property data
| Test sample number | Tensile strength in machine direction/MPa | Elongation at break in machine direction/% |
| Example 1 | 37.6 | 389 |
| Example 2 | 42.9 | 400 |
| Example 3 | 45.3 | 405 |
| Example 4 | 46.1 | 419 |
| Example 5 | 49.8 | 423 |
| Example 6 | 50.2 | 429 |
| Example 7 | 39.2 | 388 |
| Example 8 | 44.0 | 402 |
| Example 9 | 46.7 | 406 |
| Example 10 | 48.2 | 420 |
| Example 11 | 51.3 | 423 |
| Example 12 | 52.5 | 431 |
| Comparative examples | 30.8 | 362 |
As can be seen from the data in table 1, compared with the comparative examples, when the surface of the straw powder is coated with the conjugated polymer protective layer (examples 1 to 6), the longitudinal tensile strength of the mulching film is improved from 30.8MPa to 37.6 to 50.2MPa, and the tensile strength is remarkably improved. The technical staff analysis holds that the conjugated polymer protective layer has a continuous double bond structure, and the originally folded chain segments are stretched to form ordered arrangement in the longitudinal stretching process, so that orientation force is generated, and the longitudinal stretching strength is increased. In addition, the inventor also finds that the polymer effect formed by the combination of pyrrole and thiophene is better than that of single thiophene polymer, and the longer the branched structure of thiophene is, the better the mechanical property of the mulching film is improved.
As can be seen from the comparison of the tensile strength data of examples 7-12 and examples 1-6, the tensile strength of the finally prepared mulch film is improved when the surface of the straw powder is treated by the dextrin solution and then coated with the conjugated polymer. This is because the dextrin molecule contains a large number of hydroxyl groups, and forms bonding with the surface of the straw powder, so that the compatibility of the straw powder with the conjugated polymer is increased.
The mulch film of the comparative example had a longitudinal elongation at break of 362% but had a transverse elongation at break of 443%, and the mulch film had a significantly lower longitudinal elongation at break than the transverse elongation at break due to more longitudinal stretching during blowing and rolling. As can be seen from the elongation at break data of examples 1-6, coating the conjugated polymer on the surface of the straw can obviously increase the longitudinal elongation at break of the mulching film. The elongation at break parameters of comparative examples 7-12 and examples 1-6 can be found that the treatment of the surface of the straw with the dextrin solution has no significant effect on the change in elongation at break.
Effect example 2 degradable mulch ageing resistance detection
The purpose is as follows: the aging resistance of the degradable mulch films prepared in examples 1 to 12 and comparative example 1 of the present invention was examined.
The method comprises the following steps: the mulch films to be tested are cut according to the sample size of 300mm multiplied by 70mm, and 20 samples are cut for each mulch film. The setting of the experimental conditions of the ultraviolet rapid aging box is operated according to the national experimental standard of GB/T14522-2008, a sample is firstly irradiated for 8 hours under ultraviolet light at 60 ℃, then placed for 4 hours in a dark environment at 50 ℃, and the light and shade cycle is repeatedly carried out for 10 times by taking 12 hours as one cycle. In the experimental period of 5 days, 2 samples are collected after every two cycles, enough deionized water is supplemented into a water tank, and the obtained samples are naturally dried for performance characterization. Testing is carried out on an electronic universal tensile testing machine according to the requirements of national standard GB/T1040.2-2006, and the stretching rate is 50mm/min. The results are shown in the following table.
Table 2 longitudinal tensile Strength data in degradable mulch aging resistance test
The data in table 2 reflects the trend of decreasing the longitudinal tensile strength of the degradable mulch film prepared by the invention under the irradiation of 5 days of ultraviolet cycle, and as can be seen from table 2 and the attached drawing 1 in the specification, the mulch film prepared by the comparative example has very significant decrease of the tensile strength under the irradiation of ultraviolet because no conjugated polymer is doped, compared with the comparative example, the mulch film of example 1 is doped with the conjugated polymer formed by thiophene, the aging rate is obviously slowed down, but the effect is not obvious in example 2, the conjugated polymer of example 2 is formed by the co-polymerization of thiophene and pyrrole, and the anti-ultraviolet effect is better. Further, when the polymer monomer has a long chain branch such as dodecyl, the ultraviolet resistance tends not to change much, but it can be seen from the figure that the overall tensile strength of the mulch film is improved.
The inventor analyzes and considers that conjugated polymer monomers are selected to be used in the process of modifying the straw, and a conjugated polymer protective layer is formed on the surface of the straw under the induction of a peroxidation initiator, and has a unique continuous conjugated double bond structure, can absorb part of ultraviolet light and obviously improves the ageing resistance of the degradable mulch film. In addition, the aging resistance of comparative examples 7 to 12 and examples 1 to 6 can be found that the aging resistance improving effect of the dextrin solution treatment on the mulching film is not remarkable.
Effect example 3 degradable mulch degradation Performance detection
The weight loss rate of the degradable mulch film prepared by the invention under the condition of soil burial is detected by referring to a standard test method for determining the aerobic biodegradation of plastics in soil by ASTM D5988-12. The experimental method comprises the following steps: the degradable mulch films prepared in examples 1 to 12 and comparative example were cut into strip-shaped samples having a size of 5cm×2cm, 3 samples each, and weighed and dried to constant weight (W 0 ) Marking and burying under the same ground surface under the same conditions such as humidity for about 10cm, taking out corresponding sample strips 1,3 and 6 months after burying, cleaning, drying and weighing (W n ) n is 1, 2, 3, and the weight loss ratio (%) = (W) is calculated 0 -W n )/W 0 X 100. The experimental results are shown in the following table.
TABLE 3 degradation Performance detection of degradable mulch film
According to the experimental data in the table, the mulch film prepared by the method provided by the invention is implemented according to the ASTM D5988-12 operation standard, and the weight loss rate of the mulch film under the condition of soil burial for 6 months is more than 90%, and optimally more than 95%. Compared with the degradable performance of the mulching film prepared by the comparative example, the inventor finds that the degradable performance of the mulching film can be better improved by introducing the conjugated polymer into the mulching film, because conjugated unsaturated bonds are introduced into materials PLA and PBAT which originally have the degradable performance, and under the condition of soil burying, the double bond decomposition part of microorganisms is easier to break, so that the chains of the high polymer material break, and the microbial degradation rate is accelerated.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The modified straw polylactic acid degradable mulch film is characterized in that the modified straw in the mulch film is prepared by the following method:
(1) Crushing straw, and sieving with a 80-200 mesh standard sieve to obtain straw powder;
(2) Straw powder is added in NaOH or NaHCO 3 Pretreating in the solution to obtain pretreated straw powder;
(3) Dispersing the pretreated straw powder into an organic solution 1 containing conjugated polymer monomers, taking out and drying after 1-5 min;
(4) And dispersing the straw powder obtained in the previous step into an organic solution 2 containing an initiator, taking out and drying after 1-2min to obtain the modified straw powder.
2. The modified straw polylactic acid degradable mulch film according to claim 1, wherein the mass concentration of NaOH solution for pretreatment of straw powder in the step (2) is selected from 4-6%, naHCO 3 The mass concentration of the solution is selected from 15-20%; the conjugated polymer monomer in the step (3) is selected from one or more than two of pyrrole, N-alkyl pyrrole, thiophene, alkyl thiophene and alkoxy thiophene; the organic solution 1 is ethanol and cyclohexane according to the volume ratio of 1: (0.5-1).
3. The modified straw polylactic acid degradable mulch film according to claim 2, wherein the conjugated polymer monomer is selected from one or more of pyrrole, N-methylpyrrole, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-octylthiophene, 3-dodecylthiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-hexyloxythiophene, 3-dodecyloxythiophene.
4. The modified straw polylactic acid degradable mulch film according to claim 3, wherein the conjugated polymer monomer is selected from the group consisting of pyrrole, thiophene, 3-octyl thiophene, 3-dodecyl thiophene, 3-hexyloxy thiophene, and 3-dodecyloxy thiophene.
5. The modified stalk polylactic acid degradable mulch film according to claim 4, wherein the conjugated polymer monomer is a combination of pyrrole and 3-dodecylthiophene or a combination of pyrrole and 3-dodecylthiophene.
6. The modified straw polylactic acid degradable mulch film according to claim 1, wherein the initiator in the step (4) is selected from one of peracetic acid and benzoyl peroxide, the organic solution 2 is a methanol solution, and the mass fraction of the initiator in the methanol solution is 0.1-0.5%.
7. The modified straw polylactic acid degradable mulch film according to claim 1, wherein the preparation method of the modified straw further comprises: soaking the pretreated straw powder in the dispersion liquid for 20-30min, taking out and drying. The dispersion liquid is a solution prepared from one of polyethylene glycol, polyvinyl alcohol and dextrin, and the concentration of the solution is 3-10mg/mL.
8. The modified straw polylactic acid degradable mulch film according to claim 1, wherein the modified straw polylactic acid degradable mulch film comprises the following components in parts by mass:
the PLA is a compound of L-type PLA and D-type PLA, the optical purity is more than 80%, and the weight average molecular weight is 10000-20000; the mass ratio of the L-type PLA to the D-type PLA is 2 (0.2-1); the weight average molecular weight of the PBAT is 30000-100000;
the molecular chain extender is a polyurethane chain extender or an epoxy chain extender; the plasticizer is selected from one or more than two of epoxidized soybean oil, polyethylene glycol 400 and acetyl tributyl citrate; the coupling agent is selected from silane coupling agents; the lubricant is one or more selected from stearic acid, ethylene bisstearamide and polyethylene wax.
9. The modified straw polylactic acid degradable mulch film according to claim 8, wherein the modified straw polylactic acid degradable mulch film comprises the following components in parts by mass:
10. a method of making the modified straw polylactic acid degradable mulch film of claim 1, the method comprising: at normal temperature, stirring PLA, PBAT, a molecular chain extender, a plasticizer, a coupling agent and a lubricant by using a high-speed stirrer according to parts by weight, adding modified straw powder, uniformly mixing, adopting a double-screw extruder for blending extrusion, drying, granulating, and adopting a film blowing machine to prepare a degradable mulching film; the temperature of the twin-screw extruder is 140-170 ℃, the screw rotating speed is 150-200rpm, the feeding frequency is 1-2Hz, and the frequency of the granulator is 10-12Hz.
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