CN114702800A - High-barrier full-biodegradable mulching film raw material composition, mulching film and preparation method thereof - Google Patents
High-barrier full-biodegradable mulching film raw material composition, mulching film and preparation method thereof Download PDFInfo
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- CN114702800A CN114702800A CN202210292909.3A CN202210292909A CN114702800A CN 114702800 A CN114702800 A CN 114702800A CN 202210292909 A CN202210292909 A CN 202210292909A CN 114702800 A CN114702800 A CN 114702800A
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- mulching film
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000010096 film blowing Methods 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 claims description 2
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
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- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- 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
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- 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
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- Manufacturing & Machinery (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention relates to the technical field of macromolecules and discloses a high-barrier full-biodegradable mulching film raw material composition, a mulching film and a preparation method of the mulching film. The composition comprises, by weight, 100 parts of polyester and 0.5-1.5 parts of chain extender; based on the total mass of the polyester, the polyester comprises 60-90 wt% of PGA and 40-78 wt% of PBAT 10; the weight ratio of the PGA to the PBAT is 2.6-9: 1. the mulching film can replace the original non-degradable mulching film. After the chain extender is added, the compatibility of PBAT and PGA is effectively improved, the mulching film can be produced by a blow molding method, and the produced mulching film has the flexibility of PBAT and the strength and high barrier property of PGA. The biodegradation rate of the mulching film is up to more than 90 percent, the requirement of industrial production of the environment-friendly biodegradable plastic mulching film is met, and the preparation process is simple, easy to operate and suitable for popularization and application.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a high-barrier full-biodegradable mulching film raw material composition, a mulching film and a preparation method of the mulching film.
Background
The agricultural mulching film is an important production material of modern agriculture, has the functions of increasing temperature, preserving soil moisture, promoting microbial activity, increasing the utilization rate of high temperature and light, inhibiting saline-alkali rising and the like, and is beneficial to improving crop yield and improving agricultural benefits. The wide application of the agricultural film greatly promotes the development of agricultural production in China and causes serious white pollution to the land in China. Agricultural plastic film exposes for a long time under air, the sunshine, and constantly ageing, fragile, the crop is difficult whole piece to be retrieved after results, and most agricultural film piece is ploughed in the arable layer, causes soil hardening, and moisture can not permeate, and traditional polyethylene plastic film takes several hundred years to accomplish in soil and degrades. In recent years, some biodegradable materials have been widely used, and are expected to replace part of traditional polyethylene mulching films in the aspect of mulching films, such as polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), Polyhydroxyalkanoates (PHAs), Polyglycolide (PGA), polypropylene carbonate (PPC), and the like. These polyester polymers all have good biodegradability and processability. However, when a certain polyester is used as a mulching film material alone, the obtained product cannot meet the use requirements, such as: the water permeability of the pure PBAT mulching film is too high, pure PLA can not be blown into a film due to poor toughness, the biodegradation rate of the pure PHAs mulching film is too high, and the like.
By making up for the deficiencies of the two or more biodegradable polyesters, the two or more biodegradable polyesters can be blended to form the composite mulching film, so that the mulching film with excellent mechanical property and barrier property can be prepared. Chinese patent CN201610651212 discloses a preparation method of a PBAT/PLA composite material and a mulching film, and Chinese patent CN201810776537 discloses a preparation method of a high-barrier mulching film based on a PLA/PBAT/PGA three-component material, and the prepared composite mulching films have excellent mechanical properties and barrier properties. Polyglycolic acid (PGA) is a material with good biodegradability, and the time of in vitro degradation is about 1.5-3 months. The PGA has a glass transition temperature of 35 to 40 ℃ and a melting temperature of 220 to 230 ℃. Because the PGA molecular chain has good stereoregularity, the PGA can be crystallized quickly, and the crystallization temperature of the PGA is about 150-180 ℃. Compared with other biodegradable polymers, PGA has higher mechanical properties. The tensile strength is about 115MPa, and the Young modulus is about 7 GPa. The mechanical properties of PGA are much higher than those of other biodegradable plastics and most conventional plastics. Meanwhile, the PGA film has excellent gas barrier properties due to its regular structure. However, pure PGA material has poor film forming property, and the mulching film cannot be prepared in the traditional melt extrusion blowing mode.
Disclosure of Invention
The invention aims to overcome the problems of poor film forming property and poor thermal stability of PGA in the prior art, and provides a raw material composition of a high-barrier full-biodegradable mulching film, the mulching film and a preparation method thereof.
In order to achieve the above purpose, the invention provides, in a first aspect, a high-barrier full-biodegradable mulch raw material composition, which comprises, by weight, 100 parts of polyester and 0.5-1.5 parts of a chain extender; based on the total mass of the polyester, the polyester comprises 60-90 wt% of PGA and 10-40 wt% of PBAT; the weight ratio of the PGA to the PBAT is 2.6-9: 1.
the invention provides a preparation method of a high-barrier full-biodegradable mulching film, which comprises the following steps:
(1) blending the raw material composition according to a proportion, and uniformly dispersing to obtain a mixture;
(2) extruding, cooling and dicing the mixture to obtain granules;
(3) and extruding and blowing the granules to obtain the mulching film.
In a third aspect, the invention provides a biodegradable mulching film prepared by the method of the invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the performance requirement of the plastic mulching film is met;
(2) the compatibility of the PBAT and the PGA is improved, the PGA/PBAT mulching film is produced by a blow molding method, and the produced mulching film has the flexibility of the PBAT and the strength and high barrier property of the PGA;
(3) the mulching film has good mechanical property and oxygen and water vapor barrier property, and the oxygen transmission rate of the obtained film is lower than 3.12cm3/(m224h) oxygen transmission coefficient of less than 1.89X 10-13cm3·cm/(cm2s.cmHg), water vapor transmission rate of less than 14.57g/(m2Day), coefficient of moisture permeability lower than 2.39X 10-14g.cm/cm2s.Pa, and an intrinsic viscosity at 0.1rad/s of not less than 245 Pa.s.
(4) The biodegradable plastic mulching film has good biodegradability, the biodegradation rate can reach more than 90 percent according to GB/T19277.1 test, the industrial production requirement of the environment-friendly biodegradable plastic mulching film is met, and the preparation process is simple, easy to operate and suitable for popularization and application.
Drawings
FIG. 1 is a graph of rheological property tests of examples 1 to 3 and comparative examples 1 to 3;
FIG. 2 is an electron micrograph of the mulching film of example 5;
FIG. 3 is an electron micrograph of the mulching film of example 7.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a high-barrier full-biodegradable mulch raw material composition, which comprises, by weight, 100 parts of polyester and 0.5-1.5 parts of chain extender; based on the total mass of the polyester, the polyester comprises 60-90 wt% of PGA and 10-40 wt% of PBAT; the weight ratio of the PGA to the PBAT is 2.6-9: 1 (e.g., 2.6:1, 3:1, 5:1, 6:1, 7: 1, 9: 1, etc.); preferably 3 to 5: 1. the PGA and PBAT are used as main materials, the biodegradation rate of the obtained composite material is more than 90%, and the requirement that the biodegradation rate of the biodegradable material in the national standard GB/T20197 is more than or equal to 60% is met.
According to a preferred embodiment of the present invention, the chain extender contains at least 2 active epoxy groups (e.g., 2 active epoxy groups, 4 active epoxy groups, 6 active epoxy groups, 7 active epoxy groups, 9 active epoxy groups, 12 active epoxy groups) on the molecular chain; further preferably, the molecular chain of the chain extender contains 7-10 active epoxy groups. By adopting the embodiment, the compatibility between PBAT and PGA is effectively improved, the performance of the composite material is greatly improved, and a certain guiding function is provided for the selection of the formula in the actual production and processing.
According to a preferred embodiment of the present invention, the weight average molecular weight of the chain extender is 4800-9000 (e.g. 4800, 5000, 5500, 5800, 6500, 6800, 7200, 8000), more preferably 6000-7200; and/or the chain extender has an epoxy equivalent weight of greater than 168g/mol (e.g., greater than 168g/mol, greater than 180g/mol, greater than 200g/mol, greater than 230g/mol, greater than 255g/mol, greater than 285g/mol, greater than 325g/mol), and more preferably 230-325 g/mol.
The source of the chain extender is not limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the chain extender is manufactured by BASF
ADR-4368. With the foregoing embodiments, not only the weight ratio of PGA to PBAT can be as high as 9: 1, the compatibility of the two is improved, the melt strength can be increased, and the bubble stability in the film blowing process is improved.
According to a preferred embodiment of the invention, the PBAT and PGA each have a moisture content of less than 0.02 wt%, and/or the composition further comprises one or more of an antioxidant, a light stabilizer, an ultraviolet absorber.
In the present invention, the moisture content of each of the PBAT and PGA may be made lower than 0.02 wt% by drying, as long as the object of the present invention can be achieved, wherein the manner of drying is not limited as long as the moisture content of each of the PBAT and PGA can be made lower than 0.02 wt%. In a preferred embodiment of the present invention, the PBAT and PGA are dried in the following manners: the drying temperature is 80-100 deg.C, and the drying time is 8-12 h.
According to a preferred embodiment of the invention, the composition further comprises: 0.1-0.5 part by weight of antioxidant; and/or 0.1 to 1 part by weight of a light stabilizer; and/or 0.1-2 parts by weight of an ultraviolet absorber. By adopting the embodiment, the service life of the mulching film is effectively prolonged, the melt processing performance is improved, the preparation process flow is simple, the operation is easy, and the method is suitable for popularization and application.
In the present invention, the kinds of the antioxidant, the light stabilizer and the ultraviolet absorber are not limited as long as the object of the present invention can be achieved, and in a preferred embodiment of the present invention, the antioxidant is one or more selected from hindered phenol-based antioxidants, phosphite-based antioxidants and thioether-based antioxidants, and is preferably a hindered phenol-based antioxidant; and/or the light stabilizer comprises a hindered amine light stabilizer.
According to a preferred embodiment of the invention, the hindered phenolic antioxidant comprises one or more of antioxidant 264, antioxidant 330, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 5057 and antioxidant KY-616, and is preferably antioxidant 1010 and/or antioxidant 1076; and/or the hindered amine light stabilizer comprises one or more of light stabilizer 119, light stabilizer 622, light stabilizer 944, light stabilizer 3346, light stabilizer NOR371, preferably light stabilizer 622 and/or light stabilizer 3346; and/or the ultraviolet light absorber comprises one or more of an ultraviolet light absorber UV-P, an ultraviolet light absorber UV-234, an ultraviolet light absorber UV-326, an ultraviolet light absorber UV-327, and an ultraviolet light absorber UV-320.
In the present invention, the thickness of the mulching film may be selected as needed as long as the object of the present invention is achieved, and in a preferred embodiment of the present invention, the thickness of the mulching film is 10 to 40 μm, preferably 20 to 30 μm.
The invention provides a method for preparing a mulching film by using a high-barrier full-biodegradable mulching film raw material composition, which comprises the following steps:
(1) blending the raw material composition according to a proportion, and uniformly dispersing to obtain a mixture;
(2) extruding, cooling and dicing the mixture to obtain granules;
(3) and extruding and blowing the granules to obtain the mulching film. The blending conditions in the step (1) are not limited as long as the object of the present invention can be achieved, and in a preferred embodiment of the present invention, the blending temperature in the step (1) is room temperature and the blending time is 5 to 10min (e.g., 5min, 6min, 7min, 8min, 9min, 10 min).
In the present invention, the term "room temperature" means 10 to 30 ℃.
In the present invention, the manner of extrusion and dicing is not limited as long as the mixture in step (2) can be melt-extruded and diced, and in a preferred embodiment of the present invention, the manner of extrusion in step (2) is: adding the mixture into a double-screw extruder, mixing and plasticizing, and extruding through a machine head.
The cooling method in step (2) is not limited as long as the object of the present invention can be achieved, and in a preferred embodiment of the present invention, the cooling method in step (2) is an air cooling method.
The extrusion conditions of the twin-screw extruder are not limited as long as the object of the present invention can be achieved, and in a preferred embodiment of the present invention, the temperature of the twin-screw extruder is 160-230 ℃; and/or the rotation speed of the twin-screw extruder is 80-200 rpm.
Wherein the number of stages of the twin-screw extruder is not limited, as long as the temperature of each stage is maintained at 160 ℃ and 230 ℃ to achieve the object of the present invention.
The conditions for the extrusion blown film in the step (3) are not limited as long as the object of the present invention can be achieved, and in a preferred embodiment of the present invention, the temperature of the extrusion blown film is 200-220 ℃; and/or the stretch ratio of the blown film is 2 to 4. By adopting the embodiment, the barrier property of the mulching film can be better increased.
The number of stages of the extrusion blown film in the extrusion using an extruder is not required as long as the temperature of each stage is 200-220 ℃.
In a third aspect, the invention provides a biodegradable mulch film prepared by the method of the invention, the mulch film comprising: oxygen transmission rate is lower than 3.12cm3/(m224 h); and/or; oxygen permeability coefficient of less than 1.89 x 10-13cm3·cm/(cm2S cmHg); the water vapor transmission rate is lower than 14.57 g/(m)2Day); and/or a coefficient of moisture permeability of less than 2.39 x 10- 14g.cm/cm2s.Pa; and/or the intrinsic viscosity at 0.1rad/s is not less than 245 Pa.s.
The present invention will be described in detail below by way of examples. In the following examples, the films were tested for tensile strength and elongation at break according to GB/T1040; tear strength was measured by the method of GB/T16578; the oxygen permeability and the oxygen permeability coefficient are tested by a GB/T19789 method; the moisture permeability coefficient and the moisture permeability are respectively measured by the GB/T1037 method.
FIG. 1 is a graph of rheological property test at 200 ℃ of examples 1 to 3 and comparative examples 1 to 3, wherein the ordinate represents intrinsic viscosity and the abscissa represents oscillation frequency, and the larger the value of the ordinate, the better the intrinsic viscosity, the higher the melt strength, and the better the film forming stability in the film blowing process.
The chain extender of examples 1-7 was a base by BASF corporation brand of
A commercially available product of ADR-4368.
Example 1
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 0.5 part of chain extender, 10100.5 parts of antioxidant, 6220.6 parts of light stabilizer and 1.5 parts of ultraviolet absorbent UV-P;
based on the total mass of the polyester, the polyester comprises 60 wt% of PGA and 40 wt% of PBAT;
the preparation method of the mulching film comprises the following steps:
(1) drying the PBAT and the PGA, controlling the respective moisture content of the PBAT and the PGA to be lower than 0.02 wt%, wherein the drying temperature of the PBAT is 80 ℃ and the drying time of the PBAT is 8h, and the drying temperature of the PGA is 80 ℃ and the drying time of the PGA is 8 h;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder for mixing and plasticizing, and extruding, air cooling and granulating through a machine head to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
(4) extruding the granules and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 215 ℃ at the first section, 217 ℃ at the second section, 217 ℃ at the third section and 217 ℃ at the fourth section; the stretch ratio of the blown film is 2;
the thickness of the mulching film is 30 mu m;
the mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Example 2
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 1 part of chain extender, 10100.5 parts of antioxidant, 6220.6 parts of light stabilizer and 1.5 parts of ultraviolet absorbent UV-P;
based on the total mass of the polyester, the polyester comprises 60 wt% of PGA and 40 wt% of PBAT;
the preparation method of the mulching film comprises the following steps:
(1) drying the PBAT and the PGA, controlling the respective moisture content of the PBAT and the PGA to be lower than 0.02 wt%, wherein the drying temperature of the PBAT is 80 ℃ and the drying time of the PBAT is 8h, and the drying temperature of the PGA is 80 ℃ and the drying time of the PGA is 8 h;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
(4) extruding the granules and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 215 ℃ at the first section, 217 ℃ at the second section, 217 ℃ at the third section and 217 ℃ at the fourth section; the stretch ratio of the blown film is 2;
the thickness of the mulching film is 30 mu m;
the mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Example 3
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 1.5 parts of chain extender, 10100.5 parts of antioxidant, 6220.6 parts of light stabilizer and 1.5 parts of ultraviolet absorbent UV-P;
based on the total mass of the polyester, the polyester comprises 60 wt% of PGA and 40 wt% of PBAT;
the preparation method of the mulching film comprises the following steps:
(1) drying PBAT and PGA, controlling the respective moisture content of the PBAT and the PGA to be lower than 0.02 wt%, drying the PBAT at the temperature of 80 ℃ for 8 hours, and drying the PGA at the temperature of 120 ℃ for 3 hours;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
(4) extruding the granules and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 215 ℃ at the first section, 217 ℃ at the second section, 217 ℃ at the third section and 217 ℃ at the fourth section; the stretch ratio of the blown film is 2;
the thickness of the mulching film is 30 micrometers;
the mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Example 4
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 1.5 parts of chain extender, 10100.5 parts of antioxidant, 6220.6 parts of light stabilizer and 1.5 parts of ultraviolet absorbent UV-P;
based on the total mass of the polyester, the polyester comprises 70 wt% of PGA and 30 wt% of PBAT;
the preparation method of the mulching film comprises the following steps:
(1) drying the PBAT and the PGA, controlling the moisture content of the PBAT and the PGA to be lower than 0.02 wt%, drying the PBAT at the temperature of 80 ℃ for 8 hours, and drying the PGA at the temperature of 120 ℃ for 3 hours;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
(4) extruding the granules and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 215 ℃ at the first section, 217 ℃ at the second section, 217 ℃ at the third section and 217 ℃ at the fourth section; the stretch ratio of the blown film is 2;
the thickness of the mulching film is 30 micrometers;
the mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Example 5
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 1.5 parts of chain extender, 10760.3 parts of antioxidant, 33460.8 parts of light stabilizer and UV-3261 parts of ultraviolet absorbent;
based on the total mass of the polyester, the polyester comprises 80 wt% of PGA80 wt% and 20 wt% of PBAT;
the preparation method of the mulching film comprises the following steps:
(1) respectively drying the PBAT and the PGA, controlling the respective moisture content of the PBAT and the PGA to be lower than 0.02 wt%, drying the PBAT at the temperature of 80 ℃ for 8 hours, and drying the PGA at the temperature of 120 ℃ for 3 hours;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
(4) extruding and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 215 ℃ at the first stage, 217 ℃ at the second stage, 217 ℃ at the third stage and 217 ℃ at the fourth stage; the stretch ratio of the blown film is 2;
the mechanical properties of the mulching film are shown in a table 1, and the thermal stability and the oxygen permeation and water permeability are shown in a table 2;
the thickness of the mulching film is 35 mu m;
the scanning electron microscope of the mulching film is shown in FIG. 2: the holes in fig. 2 are left after the PBAT phase is etched away by dichloromethane, and the morphology of the holes reflects the dispersion of the PBAT in the matrix of the mulching film. As can be seen from FIG. 2, the PBAT phase is dispersed in a fibrous form, and the mulching film has good mechanical property and barrier property.
Example 6
The same as example 5 except that the polyester comprises PGA 40 wt%, PBAT 60 wt% and a blown film stretching ratio of 3, based on the total mass of the polyester.
The mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Example 7
The procedure of example 5 was repeated, except that the draw ratio was 1.
The scanning electron microscope of the mulching film is shown in FIG. 3: the holes in fig. 3 are left after the PBAT phase is etched away by dichloromethane, and the morphology of the holes reflects the dispersion of PBAT in the matrix of the geomembrane. From fig. 3, it can be seen that PBAT is nearly dispersed in granular form, the mechanical and barrier properties of the mulching film are not good, and the size of the film is thick.
Comparative example 1
The raw materials of the mulching film comprise, by weight, 100 parts of polyester, 43681.5 parts of chain extender ADR-43681.5 parts, 10100.5 parts of antioxidant, 6220.6 parts of light stabilizer and 1.5 parts of ultraviolet absorbent UV-P;
the polyester is PBAT;
the preparation method of the mulching film comprises the following steps:
(1) drying the PBAT, controlling the moisture content of the PBAT to be lower than 0.02 wt%, wherein the drying temperature of the PBAT is 80 ℃ and the drying time is 8 h;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 110 ℃, the second-stage temperature is 120 ℃, the third-stage temperature is 120 ℃, the fourth-stage temperature is 125 ℃, the fifth-stage temperature is 125 ℃, the sixth-stage temperature is 120 ℃, the seventh-stage temperature is 120 ℃, the eighth-stage temperature is 120 ℃ and the die head temperature is 120 ℃;
(4) extruding the granules and blowing the granules to obtain a mulching film, wherein the extrusion temperature is 115 ℃ at the first section, 120 ℃ at the second section, 120 ℃ at the third section and 120 ℃ at the fourth section; the stretch ratio of the blown film is 3;
the thickness of the mulching film is 20 micrometers;
the mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
Comparative example 2
The remainder of the process was the same as in example 4 except that no chain extender was added.
The obtained mulching film is discontinuous and has a plurality of holes, and the film with good uniformity cannot be formed.
Comparative example 3
The raw materials of the mulching film comprise 100 parts of polyester, 10100.5 parts of chain extender ADR-43681.5 parts, antioxidant, light stabilizer 6220.6 parts and ultraviolet absorbent UV-P1.5 parts;
the preparation method of the mulching film comprises the following steps:
(1) drying PGA, controlling the water content of the PGA to be lower than 0.02 wt%, wherein the drying temperature of the PGA is 80 ℃, and the drying time is 8 hours;
(2) blending the raw materials of the mulching film in a high-speed mixer for 8min at room temperature to obtain a mixture;
(3) adding the mixture into a double-screw extruder, mixing and plasticizing, extruding through a machine head, cooling by air, and pelletizing to obtain granules, wherein the temperature of each section in the double-screw extruder is respectively set as follows: the first-stage temperature is 160 ℃, the second-stage temperature is 180 ℃, the third-stage temperature is 200 ℃, the fourth-stage temperature is 215 ℃, the fifth-stage temperature is 225 ℃, the sixth-stage temperature is 230 ℃, the seventh-stage temperature is 230 ℃, the eighth-stage temperature is 225 ℃ and the die head temperature is 215 ℃;
finally, the film can not be formed when the film is extruded and blown.
The mechanical properties of the mulching film are shown in table 1, and the thermal stability and oxygen permeation and water permeability properties are shown in table 2.
TABLE 1
TABLE 2
As can be seen from the results of tables 1-2, example 5 using the present invention has significantly better oxygen and water blocking effects.
From the mechanical data of the embodiments 1 to 3, it can be seen that the longitudinal and transverse tensile strengths of the mulching film are gradually reduced along with the increase of the content of the chain extender, and meanwhile, the longitudinal and transverse breaking elongations are gradually increased; the longitudinal tear strength gradually decreases and the transverse tear strength gradually increases. This is probably due to the difference in the form of the dispersion of the PBAT as a dispersed phase in the PGA matrix. When the addition amount of the chain extender is gradually increased, the chain extender can play a plasticizing role and reduce the strong interaction among PGA molecular chains, thereby playing a role of a lubricant and having good film-forming property.
As can be seen from the oxygen permeation and water permeation data of the examples, with the increase of the content of the chain extender, the oxygen permeation and water permeation coefficients of the mulching film are gradually reduced, wherein the oxygen permeation coefficient in the example 5 is 2 orders of magnitude lower than that of pure PBAT in the comparative example 1, and the water permeation coefficient is 2 orders of magnitude lower than that of pure PBAT in the comparative example 1. The moisture permeability coefficient of the prepared mulching film is close to that of the traditional LDPE film, and the oxygen permeability coefficient is 1 order of magnitude lower than that of the LDPE film. Therefore, the mulching film can well replace the traditional mulching film and has more outstanding advantages in the aspects of temperature rise and soil moisture conservation.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. The high-barrier full-biodegradable mulching film raw material composition is characterized by comprising, by weight, 100 parts of polyester and 0.5-1.5 parts of chain extender; based on the total mass of the polyester, the polyester comprises 60-90 wt% of PGA and 10-40 wt% of PBAT; the weight ratio of the PGA to the PBAT is 2.6-9: 1.
2. the composition according to claim 1, wherein,
the molecular chain of the chain extender contains at least 2 active epoxy groups; and/or
The weight average molecular weight of the chain extender is 4800-9000, preferably 6000-7200; and/or
The epoxy equivalent of the chain extender is more than 168g/mol, preferably 230-325 g/mol; and/or
The type of the chain extender is
ADR-4368。
3. The composition of claim 1 or 2,
the moisture content of each of PBAT and PGA was less than 0.02 wt%; and/or
The composition also comprises one or more of an antioxidant, a light stabilizer and an ultraviolet absorber.
4. The composition of claim 3, wherein the composition further comprises:
0.1-0.5 weight part of antioxidant; and/or
0.1-1 part by weight of light stabilizer; and/or
0.1-2 parts of ultraviolet absorbent.
5. The composition according to claim 4, wherein,
the antioxidant is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioether antioxidants, and is preferably hindered phenol antioxidants; and/or
The light stabilizer includes a hindered amine light stabilizer.
6. The composition of claim 5, wherein,
the hindered phenol antioxidant comprises one or more of antioxidant 264, antioxidant 330, antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 5057 and antioxidant KY-616; and/or
The hindered amine light stabilizer comprises one or more of light stabilizer 119, light stabilizer 622, light stabilizer 944, light stabilizer 3346 and light stabilizer NOR 371; and/or
The ultraviolet absorbent comprises one or more of ultraviolet absorbent UV-P, ultraviolet absorbent UV-234, ultraviolet absorbent UV-326, ultraviolet absorbent UV-327 and ultraviolet absorbent UV-320.
7. The composition according to any one of claims 1 to 6,
the thickness of the mulching film is 10-40 μm, preferably 20-30 μm.
8. A method for preparing mulching film using the raw material composition according to any one of claims 1 to 7, comprising:
(1) blending the raw material composition according to a proportion, and uniformly dispersing to obtain a mixture;
(2) extruding, cooling and dicing the mixture to obtain granules;
(3) and extruding and blowing the granules to obtain the mulching film.
9. The method for preparing a mulching film according to claim 8,
the blending temperature in the step (1) is room temperature and the blending time is 5-10 min; and/or
The extrusion mode in the step (2) is as follows: adding the mixture into a double-screw extruder, mixing, plasticizing and extruding through a machine head.
10. The method for preparing the mulching film as claimed in claim 9, wherein the temperature of the twin-screw extruder is 160-230 ℃; and/or
The rotating speed of the double-screw extruder is 80-200 rpm; and/or
The temperature of the extrusion film blowing is 200-220 ℃; and/or
The stretch ratio of the blown film is 2-4.
11. The mulch film according to any one of claims 8 to 10, preferably the mulch film comprises: oxygen transmission rate is lower than 3.12cm3/(m224 h); and/or;
oxygen permeability coefficient of less than 1.89X 10-13cm3·cm/(cm2S cmHg); and/or
The water vapor transmission rate is lower than 14.57 g/(m)2Day); and/or
The moisture permeability coefficient is lower than 2.39 multiplied by 10-14g.cm/cm2s.Pa; and/or
The intrinsic viscosity at 0.1rad/s is not less than 245 Pa.s.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139395A (en) * | 2003-11-10 | 2005-06-02 | Maruzen Petrochem Co Ltd | Mulching film |
| CN101851345A (en) * | 2009-04-03 | 2010-10-06 | 上海日之升新技术发展有限公司 | Chain extension method of engineering resin and reclaimed material thereof |
| CN107304285A (en) * | 2016-04-21 | 2017-10-31 | 上海浦景化工技术股份有限公司 | A kind of preparation method of polyester modification material and its membrane product |
| CN113956630A (en) * | 2021-11-29 | 2022-01-21 | 江苏碧升生物新材料有限公司 | Completely biodegradable film and preparation method thereof |
-
2022
- 2022-03-23 CN CN202210292909.3A patent/CN114702800A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005139395A (en) * | 2003-11-10 | 2005-06-02 | Maruzen Petrochem Co Ltd | Mulching film |
| CN101851345A (en) * | 2009-04-03 | 2010-10-06 | 上海日之升新技术发展有限公司 | Chain extension method of engineering resin and reclaimed material thereof |
| CN107304285A (en) * | 2016-04-21 | 2017-10-31 | 上海浦景化工技术股份有限公司 | A kind of preparation method of polyester modification material and its membrane product |
| CN113956630A (en) * | 2021-11-29 | 2022-01-21 | 江苏碧升生物新材料有限公司 | Completely biodegradable film and preparation method thereof |
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