CN115449195A - Super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material and preparation method thereof - Google Patents
Super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 31
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 63
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 230000014759 maintenance of location Effects 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 229920001896 polybutyrate Polymers 0.000 claims abstract 4
- 239000003963 antioxidant agent Substances 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 25
- 239000004611 light stabiliser Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 230000003020 moisturizing effect Effects 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000010902 jet-milling Methods 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 150000001343 alkyl silanes Chemical group 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 238000010096 film blowing Methods 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000002362 mulch Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 3
- 230000006870 function Effects 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 229920001610 polycaprolactone Polymers 0.000 description 20
- 239000004632 polycaprolactone Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000012528 membrane Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- -1 polybutylene terephthalate-adipate Polymers 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000011707 mineral Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- ZGZUKKMFYTUYHA-HNNXBMFYSA-N (2s)-2-amino-3-(4-phenylmethoxyphenyl)propane-1-thiol Chemical compound C1=CC(C[C@@H](CS)N)=CC=C1OCC1=CC=CC=C1 ZGZUKKMFYTUYHA-HNNXBMFYSA-N 0.000 description 1
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
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- 239000003209 petroleum derivative Substances 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 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
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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 super-hydrophobic high-barrier moisture retention humidification anti-aging full-biodegradable mulching film material and a preparation method thereof, wherein the material comprises 35-63 parts of PBAT, 7-15 parts of PPC, 10-20 parts of PCL, 20-30 parts of hydrophobically modified calcium carbonate, 0.8-1.2 parts of silane coupling agent and 2.5-3.3 parts of auxiliary agent by weight. According to the parameters of the extruder: a first stage: 100 to 120 ℃; and (2) second stage: 120-140 ℃; and (3) three stages: 130 to 150 ℃; extruding and blowing the film at the temperature of 160-160 ℃ to obtain the fully biodegradable mulching film material. The invention takes PBAT, PPC and PCL as basic polymers, adopts ultrafine calcium carbonate which is subjected to airflow pulverization and hydrophobic modification as a filler, and is assisted by a silane coupling agent, and finally prepares the fully biodegradable mulching film material with the functions of super hydrophobicity, high barrier property, soil moisture conservation, humidification and aging resistance.
Description
Technical Field
The invention relates to the technical field of degradable mulching film preparation, in particular to a super-hydrophobic high-barrier soil moisture-retention humidifying anti-aging fully-biodegradable mulching film material and a preparation method thereof.
Background
The biodegradable mulching film mainly refers to components such as carbon dioxide and water which can be decomposed into nature by microorganisms under the composting condition. The biodegradable mulching film material is mainly derived from two sources, the bio-based material is mainly obtained from components such as starch, cellulose, lignin and the like, the bio-based material represents PLA material, the petroleum-based product is mainly obtained by cracking petroleum product into small molecules and polymerizing, and the representative material comprises PBAT, PPC, PCL, PHB, PBS and the like. Among them, the biodegradable high molecular polymer poly (butylene terephthalate-adipate) (PBAT) has become the mainstream material for preparing biodegradable mulching films because the processability is comparable with that of PE and the mechanical property is excellent.
PBAT are semi-crystalline polymers that, when melted, form a wide distribution of small crystals, with amorphous and crystalline regions in a single crystalline unit. PBAT simultaneously takes the flexibility of aliphatic polymers and the rigidity of aromatic polymers into consideration, and has good heat resistance, impact resistance and biodegradability. But the PBAT mulching film has poor water vapor barrier property and low moisture retention and increasing capacity, and the application of the PBAT mulching film in agriculture is limited.
Analysis is carried out on the principle, and water vapor mainly permeates through the mulching film in three steps: the water vapor contacts the mulching film and is adsorbed and dissolved on the surface of the mulching film close to the ground surface side; then under the action of the concentration difference of the water vapor, the water vapor in the mulching film is diffused to the surface of the mulching film far away from the ground surface side; and finally water vapor is desorbed from the surface of the mulching film far away from the ground surface side. The traditional PBAT material has higher polarity than that of PE material, so that the PBAT material is easy to absorb water, and the water vapor barrier property is poorer. The traditional modification means is that a certain amount of mineral powder (talcum powder, calcium carbonate and the like) is added into the PBAT component for filling, and the surface of the mineral powder has hydrophilic and oleophobic properties due to lower surface energy, so that the water absorption of the PBAT base material and the filling material is higher than that of the PE material when water vapor contacts the mulching film; meanwhile, PBAT molecular groups contain large-size benzene ring structures, so that the molecular gaps are too large, and water vapor permeates the mulching film in the second step much faster than PE, so that the water vapor blocking performance of the PBAT molecular groups is inferior to that of the PE mulching film.
Therefore, there is a need to design an improved super-hydrophobic high-barrier moisture-retention moisturizing anti-aging fully biodegradable mulching film material and a preparation method thereof to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a super-hydrophobic high-barrier moisture retention humidification aging-resistant fully biodegradable mulching film material and a preparation method thereof.
In order to achieve the purpose, the invention provides a super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material which comprises, by mass, 35-63 parts of PBAT, 7-15 parts of PPC, 10-20 parts of PCL, 20-30 parts of hydrophobically modified calcium carbonate, 0.8-1.2 parts of silane coupling agent and 2.5-3.3 parts of assistant.
Furthermore, the hydrophobic modified calcium carbonate is obtained by mixing calcium carbonate with a hydrophobic modifier in the jet milling process.
Further, the hydrophobic modifier is stearic acid.
Further, the particle size of the hydrophobic modified calcium carbonate is 1-3 μm.
Further, the molecular weight of the PCL is 50000-60000.
Further, the silane coupling agent is an alkyl silane coupling agent with 1-30 carbon atoms.
Further, the auxiliary agent comprises the following main antioxidants in parts by mass: 0.2-0.4 part; auxiliary antioxidant: 0.3-0.6; ultraviolet absorber: 0.3-0.5; light stabilizer: 0.7-1.3; a slipping agent: 1.0-1.5.
Further, the antioxidant is one or more of 1010, 168 and 1076;
the slipping agent is one or two of erucamide and oleamide;
the ultraviolet absorbent is one or more of UV-P, UV-234 and UV-326;
the light stabilizer is one or two of 770 and UV-1084.
The preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material comprises the following steps:
s1, uniformly mixing membrane-grade PBAT, PPC and PCL in an extruder, adding hydrophobic modified calcium carbonate and a silane coupling agent, uniformly mixing, and finally adding an auxiliary agent, and uniformly mixing;
s2, extruding and granulating the uniformly mixed materials in the step S1, and then blowing out the granules through a single-screw film blowing machine to obtain a mulching film; the temperature of each zone during extrusion of the extruder is as follows: a first stage: 100 to 120 ℃; and (2) second stage: 120-140 ℃; and (3) three stages: 130 to 150 ℃; the temperature of the machine head is 160-160 ℃.
Further, the thickness of the mulching film is 5-30 μm.
The invention has the beneficial effects that:
1. the invention provides a super-hydrophobic high-barrier moisture retention humidification aging-resistant fully biodegradable mulching film material, which is prepared by taking PBAT, PPC and PCL as basic polymers, adopting ultrafine calcium carbonate subjected to airflow pulverization and hydrophobic modification as a filler and a silane coupling agent as an auxiliary material through regulating and controlling a formula ratio.
2. The invention adopts the jet milling method to firstly carry out ultrafine milling surface modification on calcium carbonate, and the calcium carbonate after high-speed jet milling is used to refine the size of the calcium carbonate, improve the surface energy, reduce the agglomeration trend of the calcium carbonate and change the surface of the powder from water absorption to hydrophobic; PCL (polycaprolactone) is used as a fully biodegradable material with good biocompatibility and good water vapor permeability, so that the surface does not have a condensation phenomenon; the silane coupling agent not only can promote the adhesive force between the powder and the particle surface, but also has a hydrophobic effect. Finally, the comprehensive performance of the mulching film is obviously improved.
Drawings
Fig. 1 is a schematic view of a preparation process of the biodegradable mulch film material of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments. It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a super-hydrophobic high-barrier moisture retention humidification anti-aging full-biodegradable mulching film material which comprises, by mass, 35-63 parts of PBAT, 7-15 parts of PPC, 10-20 parts of PCL, 20-30 parts of hydrophobically modified calcium carbonate, 0.8-1.2 parts of a silane coupling agent and 2.5-3.3 parts of an auxiliary agent. The invention finally prepares the fully biodegradable mulching film material with the functions of super-hydrophobicity, high barrier, soil moisture conservation, humidification and aging resistance by taking PBAT, PPC and PCL as basic polymers, adopting hydrophobic modified superfine calcium carbonate as a filler and assisting a silane coupling agent and regulating and controlling a proper formula ratio.
The silane coupling agent is an alkyl silane coupling agent with 1-30 carbon atoms, such as propyl trimethoxy silane, dodecyl trimethoxy silane, hexadecyl trimethoxy silane, etc. Preferably an alkylsilane coupling agent having 10 to 18 carbon atoms. The alkoxy of the silane coupling agent promotes the compatibility of calcium carbonate and a polymer matrix, the hydrophobicity of an alkyl chain improves the hydrophobicity of the mulching film on one hand, and the compatibility of a carbon chain polymer on the other hand, so that the porosity of the mulching film is reduced, the water evaporation rate is further reduced, when the number of carbon atoms is too small, the hydrophobic effect is not good, when the number of carbon atoms is too large, the processing performance is influenced, and the porosity is improved.
Preferably, the following components are included:
PBAT (polybutylene terephthalate-adipate, film grade): 35-63 parts;
PPC (polymethyl ethylene carbonate, MFI:3-5g/10 min): 7-15 parts;
PCL (polycaprolactone, molecular weight 50000-60000): 10-20 parts;
jet milling surface modified calcium carbonate (mesh number about 8000-10000 mesh): 20-30 parts of a solvent; the modifier is preferably stearic acid. The particle size of the hydrophobic modified calcium carbonate is 1-3 mu m; the calcium carbonate which is easy to agglomerate is refined to be less than 5um by high-speed physical airflow crushing, and the stearic acid has the effect of surface modification in the physical high-speed crushing process and has more obvious effect than the common high-mixing modification.
Hexadecyl trimethoxy silane: 0.8-1.2;
main antioxidant: 0.2-0.4;
auxiliary antioxidant: 0.3-0.6;
ultraviolet light absorber: 0.3-0.5;
light stabilizer: 0.7-1.3;
a slipping agent: 1.0-1.5.
The auxiliary agent comprises the following main antioxidant in parts by mass: 0.2-0.4 part; auxiliary antioxidant: 0.3-0.6; ultraviolet absorber: 0.3-0.5; light stabilizer: 0.7-1.3; a slipping agent: 1.0-1.5.
The antioxidant is one or more of 1010 (phenolic antioxidant), 168 (phosphite ester auxiliary antioxidant) and 1076 (octadecyl pure ester).
The slipping agent is one or two of erucamide and oleamide.
The ultraviolet absorbent is one or more of UV-P (benzotriazole light stabilizer), UV-234 and UV-326.
The light stabilizer is one or two of 770 (bis-2, 6-tetramethylpiperidinol sebacate) and UV-1084 novel thioamine high-efficiency stabilizers.
Referring to fig. 1, a method for preparing a super-hydrophobic, high-barrier, moisture-preserving, moisturizing, aging-resistant and fully biodegradable mulching film material includes the following steps:
s1, uniformly mixing membrane-grade PBAT, PPC and PCL in an extruder, adding hydrophobic modified calcium carbonate and a silane coupling agent, uniformly mixing, and finally adding an auxiliary agent, and uniformly mixing;
s2, extruding and granulating the uniformly mixed materials in the step S1, and then blowing out the materials through a single-screw film blowing machine to obtain a mulching film; the temperature of each zone is as follows when the extruder extrudes; a first stage: 100 to 120 ℃; and (2) second stage: 120-140 ℃; and (3) three stages: 130 to 150 ℃; the temperature of the machine head is 160-160 ℃.
Further, the thickness of the mulching film is 5-30 μm.
Example 1
A preparation method of a super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulching film material comprises the following steps: PBAT (membrane stage): 60 parts; PPC:8 parts of a mixture; PCL:12 parts of (1); pretreatment of calcium carbonate: 20 parts of (1); hexadecyl trimethoxy silane: 0.9 part; main antioxidant: 0.2 part; auxiliary antioxidant: 0.3 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.1 parts. The method comprises the following steps:
firstly, carrying out high-speed airflow crushing on common calcium carbonate by using an airflow crusher, adding stearic acid with a certain metering ratio in the crushing process for surface modification to obtain stearic acid modified calcium carbonate, wherein the pulverized calcium carbonate has higher surface energy and is not easy to agglomerate, and the surface of the calcium carbonate is changed from hydrophilic to hydrophobic;
then uniformly mixing the particles in a membrane-grade PBAT (MFI: 3-5g/10 min), PPC and PCL low-mixing pot, and then adding stearic acid modified calcium carbonate and hexadecyl trimethoxy silane for uniform low-mixing;
finally, adding various auxiliary agents into the mixture to be highly mixed uniformly, wherein the temperature of each zone of the extruder is as follows; a first stage: 100 to 120 ℃; and a second stage: 120-140 ℃; and (3) three stages: 130 to 150 ℃; the temperature of the machine head is 160-160 ℃. And (4) conveying the extruded material strips to room temperature through crawler belt air cooling, and granulating through a granulator. Then blow out the plastic film of thickness 10um thickness through single screw rod inflation film manufacturing machine.
Example 2
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material has the following advantages that:
PBAT (membrane grade): 40 parts of a mixture; PPC:12 parts of (1); PCL:18 parts of a mixture; pretreatment of calcium carbonate: 30 parts of (1); hexadecyl trimethoxy silane: 1.2 parts; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.5 part; light stabilizer: 1.0 part; a slipping agent: 1.2 parts.
Example 3
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulching film material is characterized in that the formula is as follows:
PBAT (membrane grade): 50 parts of a mixture; PPC:10 parts of (A); PCL:15 parts of a mixture; pretreatment of calcium carbonate: 25 parts of (1); hexadecyl trimethoxy silane: 1.0 part; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.0 part.
Example 4
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material has the following advantages that:
PBAT (membrane grade): 50 parts of a mixture; PPC:10 parts of (A); PCL:15 parts of (1); untreated calcium carbonate: 25 parts of a binder; hexadecyl trimethoxy silane: 1.0 part; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.0 part.
Example 5
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulching film material is characterized in that the formula is as follows:
PBAT (membrane grade): 60 parts; PPC:0 part of (C); PCL:15 parts of a mixture; pretreatment of calcium carbonate: 25 parts of (1); hexadecyl trimethoxy silane: 1.0 part; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.0 part.
Example 6
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulching film material is characterized in that the formula is as follows:
PBAT (membrane stage): 50 parts of a mixture; PPC:10 parts of (A); PCL:15 parts of (1); pretreatment of calcium carbonate: 25 parts of (1); hexadecyl trimethoxy silane: 1.0 part; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.0 part. (the processing temperature is 140-160 ℃ in the first section, 160-180 ℃ in the second section, 160-200 ℃ in the third section and 200-210 ℃ in the machine head.
Example 7
Compared with the example 1, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material has the following advantages that:
PBAT (membrane grade): 75 parts of a mixture; PPC:0 part of (C); PCL:0 part of (C); ordinary calcium carbonate: 25 parts of (1); hexadecyl trimethoxy silane: 1.0 part; main antioxidant: 0.4 part; auxiliary antioxidant: 0.5 part; ultraviolet absorber: 0.3 part; light stabilizer: 0.7 part; a slipping agent: 1.0 part.
Table 2 results of performance testing of examples 3 and 8-10
As can be seen from Table 1, the combination of the composition system of the present invention and the formulation of example 3 is the best, and the water vapor transmission rate is as low as 117g/m 2 24h, the film surface contact angle is as high as 159 ℃, and the nominal strain is reduced by only 16% after aging. When ordinary calcium carbonate was used (example 4), the water contact angle was reduced to 86 °, the nominal strain after aging was reduced by 44%, and the nominal strain before aging was also lower than that of the present invention. When the PPC is not added, the nominal strain after aging is obviously reduced, the water vapor transmission rate is low and is obviously improved, and the PPC is beneficial to improving the water resistance and aging resistance of the mulching film. The combination properties all drop significantly as the processing temperature increases. The overall performance also drops significantly when PBAT alone is employed.
Example 8
Compared with the embodiment 3, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material has the advantage that a mechanical damage machine is adopted to modify and grind calcium carbonate.
Example 9
Compared with the preparation method of the example 3, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging fully biodegradable mulching film material has the disadvantage that hexadecyl trimethoxy silane is replaced by propyl trimethoxy silane.
Example 10
Compared with the example 3, the preparation method of the super-hydrophobic high-barrier moisture-retention humidifying anti-aging fully biodegradable mulching film material is characterized in that hexadecyl trimethoxy silane is replaced by eicosyl trimethoxy silane.
As can be seen from Table 2, both the calcium carbonate modification mode and the alkyl chain length of the silane coupling agent have an effect on the overall performance.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. The super-hydrophobic high-barrier moisture-retention humidifying anti-aging full-biodegradable mulching film material is characterized by comprising 35-63 parts of PBAT, 7-15 parts of PPC, 10-20 parts of PCL, 20-30 parts of hydrophobically modified calcium carbonate, 0.8-1.2 parts of silane coupling agent and 2.5-3.3 parts of auxiliary agent by mass.
2. The super-hydrophobic high-barrier moisture-retention moisturizing anti-aging fully-biodegradable mulching film material as claimed in claim 1, wherein the hydrophobically modified calcium carbonate is obtained by mixing calcium carbonate with a hydrophobic modifier in a jet milling process.
3. The super-hydrophobic high-barrier moisture-retention moisturizing anti-aging fully-biodegradable mulching film material as claimed in claim 2, wherein the hydrophobic modifier is stearic acid.
4. The super-hydrophobic high-barrier moisture-retention moisturizing anti-aging fully-biodegradable mulching film material as claimed in claim 2, wherein the particle size of the hydrophobically modified calcium carbonate is 1-3 μm.
5. The super-hydrophobic high-barrier moisture-retention moisturizing aging-resistant fully-biodegradable mulching film material according to claim 1, wherein the molecular weight of the PCL is 50000-60000.
6. The super-hydrophobic high-barrier moisture-retention moisturizing anti-aging fully-biodegradable mulching film material as claimed in claim 1, wherein the silane coupling agent is an alkyl silane coupling agent with a carbon atom number of 1-30.
7. The super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulching film material as claimed in claim 1, wherein the auxiliary agent comprises a main antioxidant in parts by mass: 0.2-0.4 part; auxiliary antioxidant: 0.3-0.6; ultraviolet absorber: 0.3-0.5; light stabilizer: 0.7-1.3; a slipping agent: 1.0-1.5.
8. The super-hydrophobic high-barrier moisture retention and humidification resistant aging full-biodegradable mulching film material as claimed in claim 7, wherein the antioxidant is one or more of 1010, 168 and 1076;
the slipping agent is one or two of erucamide and oleamide;
the ultraviolet absorbent is one or more of UV-P, UV-234 and UV-326;
the light stabilizer is one or two of 770 and UV-1084.
9. The preparation method of the super-hydrophobic high-barrier moisture-preserving humidifying anti-aging full-biodegradable mulch film material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
s1, uniformly mixing membrane-grade PBAT, PPC and PCL in an extruder, adding hydrophobic modified calcium carbonate and a silane coupling agent, uniformly mixing, and finally adding an auxiliary agent, and uniformly mixing;
s2, extruding and granulating the uniformly mixed materials in the step S1, and then blowing out the materials through a single-screw film blowing machine to obtain a mulching film; the temperature of each zone during extrusion of the extruder is as follows: a first stage: 100 to 120 ℃; and (2) second stage: 120-140 ℃; and (3) three stages: 130 to 150 ℃; the temperature of the machine head is 160-160 ℃.
10. The preparation method of the superhydrophobic high-barrier moisture retention and humidification resistant aging fully biodegradable mulching film material according to claim 9, wherein the thickness of the mulching film is 5-30 μm.
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| CN1803937A (en) * | 2005-12-20 | 2006-07-19 | 中国地质大学（武汉） | Dry process mechanical force and chemical modification method of superfine calcium carbonate |
| CN101724244A (en) * | 2009-12-11 | 2010-06-09 | 内蒙古蒙西高新技术集团有限公司 | Blend of PPC, PBAT and PCL and preparation method thereof |
| CN109593330A (en) * | 2018-12-12 | 2019-04-09 | 池州市锐强新材料有限公司 | For manufacturing the PP Pipe Compound and preparation method thereof of biodegradable antibacterial, ventilating film |
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| CN1803937A (en) * | 2005-12-20 | 2006-07-19 | 中国地质大学（武汉） | Dry process mechanical force and chemical modification method of superfine calcium carbonate |
| CN101724244A (en) * | 2009-12-11 | 2010-06-09 | 内蒙古蒙西高新技术集团有限公司 | Blend of PPC, PBAT and PCL and preparation method thereof |
| CN109593330A (en) * | 2018-12-12 | 2019-04-09 | 池州市锐强新材料有限公司 | For manufacturing the PP Pipe Compound and preparation method thereof of biodegradable antibacterial, ventilating film |
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