CN108948701A - A kind of environmental protection high-ductility agricultural film and preparation method thereof - Google Patents
A kind of environmental protection high-ductility agricultural film and preparation method thereof Download PDFInfo
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- 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
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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Abstract
The invention discloses a kind of environmentally friendly high-ductility agricultural films and preparation method thereof, it is related to film material field, the raw material including following parts by weight meter: 65-78 parts of polylactic acid, 22-30 parts of poly-succinic fourth diester, 0.1-0.3 parts of chitosan, 0.2-0.5 parts of modified graphene oxide, 0.3-0.7 parts of nano zine oxide, 0.2-0.5 parts of sorbester p17,4-10 parts of tributyl citrate, 0.2-0.7 parts of ultra-violet stabilizer and 0.5-1.2 parts of antioxidant；Mulch of the present invention, which passes through the mating reaction between raw material, has good stretch-resistance, mechanical tenacity and resistance to ag(e)ing, while having good antibiotic property, and biodegradable, does not generate noxious material, environmentally protective.
Description
Technical field
The present invention relates to film material fields, and in particular to a kind of environmental protection high-ductility agricultural film and preparation method thereof.
Background technique
Mulch, that is, covered ground film, usually transparent or black PE film, also has green, silver thin film, covers for ground
Lid keeps soil moisture to improve the soil moisture, maintains soil texture, prevents pest attacks crop and certain micro-organisms from causing
Disease etc., promote the function of plant growth, still, existing Plastic-film disintegration effect is poor, be easy to cause soil pollution.
Mulching planting can make crop yield improve 30% or so, in the vast arid area of northern China, mulch
The advantage of plantation is especially prominent, so that mulching planting is widely applied.According to statistics, China's mulch dosage in 2011
125.5 ten thousand tons, area coverage is up to 300,000,000 mu；National 136.2 ten thousand tons of dosage, more than 3.7 hundred million mu of culture underglass area of mulch in 2013；
More than 3.8 hundred million mu of plastic film mulching cultivation area in 2014, in 142.8 ten thousand tons of sales volume of mulch year, annual dosage is all quickling increase.
Chinese patent CN102432945B discloses a kind of dry farming anti-aging long-acting autumn mulching film, and it is half-dried to meet arid
The agricultural production of nonirrigated farmland area collects the rain moisture, the requirement in autumn rain spring.Specifically, dry farming anti-aging long-acting autumn mulching film,
It is made of the raw material of following weight percentage: polymerized hindered amine light stabilizer 0.3-0.5%；Composite antioxidant 0.08-
0.16%；Linear low density polyethylene (LLDPE) 73.6-81%；Ultraviolet absorbing agent 0.06-0.12%；Low density polyethylene (LDPE) 8-15%；
Metallocene linear polyethylene 5-10%, high density polyethylene (HDPE) 5-10%；Above-mentioned each group subtotaling 100%.The present invention is produced
Dry farming anti-aging long-acting autumn mulching film, effective solution collect the rain moisture, and autumn rain spring is used, mulch during production estimation
Requirement of the ageing-resistant time up to 300-540 days is covered, but the polythene material in raw material haves the shortcomings that difficult to degrade, Yi Zao
At white pollution.
Chinese patent CN107383544A discloses a kind of preparation method of oxidative biodegradation mulch；Including resin
Additive and degradable master batch；The mass percent of the material component are as follows: resin additive 98-99.8%, degradable master batch
0.2-2.0%；Preparation process of the present invention is simple, without changing production equipment and technique；It is recyclable, do not generate waste material；?
Noxious material is not generated in production, storage, use and degradation process；The original performance of product is not influenced, but the toughness of material is owed
It is good.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of environmentally friendly high-ductility agricultural film and its preparation sides
Method, mulch of the present invention, which passes through the mating reaction between raw material, has good stretch-resistance, mechanical tenacity and resistance to ag(e)ing, has simultaneously
There is good antibiotic property, and biodegradable, does not generate noxious material, it is environmentally protective.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
65-78 parts of polylactic acid, 22-30 parts of poly-succinic fourth diester, 0.1-0.3 parts of chitosan, modified graphene oxide
0.2-0.5 parts, 0.3-0.7 parts of nano zine oxide, 0.2-0.5 parts of sorbester p17,4-10 parts of tributyl citrate, UV stable
0.2-0.7 parts and antioxidant 0.5-1.2 parts of agent.
Preferably, the raw material including following parts by weight meter: 70-75 parts of polylactic acid, 25-28 parts of poly-succinic fourth diester, shell
0.15-0.25 parts of glycan, 0.28-0.42 parts of modified graphene oxide, 0.45-0.57 parts of nano zine oxide, sorbester p17 0.3-
0.4 part, 5-9 parts of tributyl citrate, 0.3-0.6 parts of ultra-violet stabilizer and 0.7-1.0 parts of antioxidant.
Preferably, the raw material including following parts by weight meter: 73 parts of polylactic acid, 26 parts of poly-succinic fourth diester, chitosan
0.21 part, 0.34 part of modified graphene oxide, 0.48 part of nano zine oxide, 0.35 part of sorbester p17,7 parts of tributyl citrate, purple
0.45 part and 0.86 part of antioxidant of outside line stabilizer.
Preferably, the modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 20-25 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 500-600 revs/min of speed, it is stirred to react 38-45 hours；
(3) mixture of step (2) is poured into 50-60 degrees Celsius of ethyl alcohol, with the power of 300-400W, ultrasonic disperse
It after 50-60 minutes, filters, after being filtered 5 times with 50-60 degrees Celsius of ethyl alcohol repeated washing, filtrate is placed in vacuum oven
Under 70-80 degrees Celsius, it is dry to constant weight to get.
Preferably, the organic solvent in the step (1) is thionyl chloride and n,N-Dimethylformamide according to mass ratio
20:1, which is uniformly mixed, to be made.
Preferably, the ultra-violet stabilizer is 2-hydroxy-4-n-octoxybenzophenone, 2- hydroxyl -4- methoxyl group two
Benzophenone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole and 2- (2- hydroxyl -5- (1,1,3,3- tetramethyl
Butyl) phenyl) one or more of benzotriazole combines.
Preferably, the antioxidant is three (2,4- di-tert-butyl-phenyl) phosphites, β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionate, one or more of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester
In conjunction with.
A kind of preparation method of above-mentioned environmentally friendly high-ductility agricultural film is also disclosed in the present invention, specifically, including following step
It is rapid:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 600-
After 800 revs/min, grinding 4-6 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
It is 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 8-15 minutes in mixing machine under 50-60 degrees Celsius, obtain mixture
Expect B；
(4) mixed material A and mixed material B is added in high-speed mixer, under 40-50 degrees Celsius, with 1200-1500
Rev/min speed be stirred 15-20 minutes after, be added parallel dual-screw extruding machine in be granulated, squeeze out batten pass through water cooling
But pelletizing after, pellet are put into 110-120 degrees Celsius of baking oven and dry to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
Preferably, one to five area's temperature of parallel dual-screw extruding machine in the step (4) is successively set are as follows: 145 is Celsius
Degree, 150 degrees Celsius, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Preferably, each phase temperature of extruder that the single screw rod in the step (5) squeezes out in inflation film manufacturing machine is successively set are as follows:
190 degrees Celsius, 198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 Celsius
Degree, blow-up ratio 3.0, hauling speed are 5 ms/min.
The present invention have it is following the utility model has the advantages that
(1) mulch of the present invention has good stretch-resistance, mechanical tenacity and ageing-resistant by the mating reaction between raw material
Property, while there is good antibiotic property, and biodegradable, and noxious material is not generated, it is environmentally protective.
(2) present invention uses polylactic acid and poly-succinic fourth diester as base-material, and polylactic acid is from a wealth of sources, biological can drop
Solution, it is environmentally protective, there is good intensity and modulus, but polylactic acid the shortcomings that there are easy friability, it equally can be complete by addition
Biological degradation plastics poly-succinic fourth diester, poly-succinic fourth diester flexible have good toughness and processing performance, can
To improve polylactic acid toughness, composite material still can be degradable, while remaining the excellent performance of the two.
(3) present invention enhances the mechanical mechanics of mulch, together by addition modified graphene oxide and nano zine oxide
When enhance the wearability and ageing resistance of mulch, the antibiotic property of addition chitosan enhancing mulch.
(4) graphene oxide specific surface area with higher, surface functional group rich in, passes through modified graphite
There is good compatibility and interface binding power between alkene and polylactic acid, improve the comprehensive performance of material.
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention, and following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
65 parts of polylactic acid, 22 parts of poly-succinic fourth diester, 0.1 part of chitosan, 0.2 part of modified graphene oxide, nano oxygen
0.3 part of zinc of change, 0.2 part of sorbester p17,4 parts of tributyl citrate, 0.2 part of ultra-violet stabilizer and 0.5 part of antioxidant.
Modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 20 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 500 revs/min of speed, it is stirred to react 38 hours；
(3) mixture of step (2) is poured into 50 degrees Celsius of ethyl alcohol, with the power of 300W, after ultrasonic disperse 50 minutes,
It filters, after being filtered 5 times with 50 degrees Celsius of ethyl alcohol repeated washings, filtrate is placed in vacuum oven under 70 degrees Celsius, is done
It is dry to constant weight to get.
Organic solvent in step (1) is that thionyl chloride and N,N-dimethylformamide are uniformly mixed according to mass ratio 20:1
It is made.
Ultra-violet stabilizer is 2-hydroxy-4-n-octoxybenzophenone.
Antioxidant is three (2,4- di-tert-butyl-phenyl) phosphites.
The preparation method of environmentally friendly high-ductility agricultural film in the present embodiment, specifically, comprising the following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 600
Rev/min, after grinding 4 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
In mixing machine at 50 c, 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 8 minutes, obtain mixed material B；
(4) mixed material A and mixed material B is added in high-speed mixer, under 40 degrees Celsius, with 1200 revs/min
Speed be stirred 15 minutes after, be added in parallel dual-screw extruding machine and be granulated, squeeze out batten pelletizing after water is cooling, grain
Material is put into 110 degrees Celsius of baking oven and dries to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
One to five area's temperature of parallel dual-screw extruding machine in step (4) is successively set are as follows: 145 degrees Celsius, 150 is Celsius
Degree, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Each phase temperature of extruder that single screw rod in step (5) squeezes out in inflation film manufacturing machine is successively set are as follows: and 190 degrees Celsius,
198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 degrees Celsius, and blow-up ratio is
3.0, hauling speed is 5 ms/min.
Embodiment 2
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
78 parts of polylactic acid, 30 parts of poly-succinic fourth diester, 0.3 part of chitosan, 0.5 part of modified graphene oxide, nano oxygen
0.7 part of zinc of change, 0.5 part of sorbester p17,10 parts of tributyl citrate, 0.7 part of ultra-violet stabilizer and 1.2 parts of antioxidant.
Modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 25 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 600 revs/min of speed, it is stirred to react 45 hours；
(3) mixture of step (2) is poured into 60 degrees Celsius of ethyl alcohol, with the power of 400W, ultrasonic disperse after sixty minutes,
It filters, after being filtered 5 times with 60 degrees Celsius of ethyl alcohol repeated washings, filtrate is placed in vacuum oven at 80 degrees celsius, is done
It is dry to constant weight to get.
Organic solvent in step (1) is that thionyl chloride and N,N-dimethylformamide are uniformly mixed according to mass ratio 20:1
It is made.
Ultra-violet stabilizer is ESCALOL 567.
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionate.
The preparation method of environmentally friendly high-ductility agricultural film in the present embodiment, specifically, comprising the following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 800
Rev/min, after grinding 6 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
In mixing machine at 60 c, 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 15 minutes, obtain mixed material B；
(4) mixed material A and mixed material B is added in high-speed mixer, at 50 c, with 1500 revs/min
Speed be stirred after twenty minutes, be added in parallel dual-screw extruding machine and be granulated, squeeze out batten pelletizing after water is cooling, grain
Material is put into 120 degrees Celsius of baking oven and dries to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
One to five area's temperature of parallel dual-screw extruding machine in step (4) is successively set are as follows: 145 degrees Celsius, 150 is Celsius
Degree, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Each phase temperature of extruder that single screw rod in step (5) squeezes out in inflation film manufacturing machine is successively set are as follows: and 190 degrees Celsius,
198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 degrees Celsius, and blow-up ratio is
3.0, hauling speed is 5 ms/min.
Embodiment 3
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
70 parts of polylactic acid, 25 parts of poly-succinic fourth diester, 0.15 part of chitosan, modified graphene oxide 0.28 part, nanometer
0.45 part of zinc oxide, 0.3 part of sorbester p17,5 parts of tributyl citrate, 0.3 part of ultra-violet stabilizer and 0.7 part of antioxidant.
Modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 22 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 550 revs/min of speed, it is stirred to react 42 hours；
(3) mixture of step (2) is poured into 54 degrees Celsius of ethyl alcohol, with the power of 360W, after ultrasonic disperse 58 minutes,
It filters, after being filtered 5 times with 54 degrees Celsius of ethyl alcohol repeated washings, filtrate is placed in vacuum oven under 78 degrees Celsius, is done
It is dry to constant weight to get.
Organic solvent in step (1) is that thionyl chloride and N,N-dimethylformamide are uniformly mixed according to mass ratio 20:1
It is made.
Ultra-violet stabilizer is 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole.
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionate.
The preparation method of environmentally friendly high-ductility agricultural film in the present embodiment, specifically, comprising the following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 750
Rev/min, after grinding 5 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
It is 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 12 minutes in mixing machine under 58 degrees Celsius, obtain mixed material B；
(4) mixed material A and mixed material B is added in high-speed mixer, under 46 degrees Celsius, with 1300 revs/min
Speed be stirred 18 minutes after, be added in parallel dual-screw extruding machine and be granulated, squeeze out batten pelletizing after water is cooling, grain
Material is put into 117 degrees Celsius of baking oven and dries to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
One to five area's temperature of parallel dual-screw extruding machine in step (4) is successively set are as follows: 145 degrees Celsius, 150 is Celsius
Degree, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Each phase temperature of extruder that single screw rod in step (5) squeezes out in inflation film manufacturing machine is successively set are as follows: and 190 degrees Celsius,
198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 degrees Celsius, and blow-up ratio is
3.0, hauling speed is 5 ms/min.
Embodiment 4
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
75 parts of polylactic acid, 28 parts of poly-succinic fourth diester, 0.25 part of chitosan, modified graphene oxide 0.42 part, nanometer
0.57 part of zinc oxide, 0.4 part of sorbester p17,9 parts of tributyl citrate, 0.6 part of ultra-violet stabilizer and 1.0 parts of antioxidant.
Modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 24 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 570 revs/min of speed, it is stirred to react 43 hours；
(3) mixture of step (2) is poured into 58 degrees Celsius of ethyl alcohol, with the power of 380W, after ultrasonic disperse 56 minutes,
It filters, after being filtered 5 times with 58 degrees Celsius of ethyl alcohol repeated washings, filtrate is placed in vacuum oven under 72 degrees Celsius, is done
It is dry to constant weight to get.
Organic solvent in step (1) is that thionyl chloride and N,N-dimethylformamide are uniformly mixed according to mass ratio 20:1
It is made.
Ultra-violet stabilizer is 2- (2- hydroxyl -5- (1,1,3,3- tetramethyl butyl) phenyl) benzotriazole.
Antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester.
The preparation method of environmentally friendly high-ductility agricultural film in the present embodiment, specifically, comprising the following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 650
Rev/min, after grinding 5.8 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
It is 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 13 minutes in mixing machine under 52 degrees Celsius, obtain mixed material B；
(4) mixed material A and mixed material B is added in high-speed mixer, under 44 degrees Celsius, with 1400 revs/min
Speed be stirred 17 minutes after, be added in parallel dual-screw extruding machine and be granulated, squeeze out batten pelletizing after water is cooling, grain
Material is put into 112 degrees Celsius of baking oven and dries to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
One to five area's temperature of parallel dual-screw extruding machine in step (4) is successively set are as follows: 145 degrees Celsius, 150 is Celsius
Degree, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Each phase temperature of extruder that single screw rod in step (5) squeezes out in inflation film manufacturing machine is successively set are as follows: and 190 degrees Celsius,
198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 degrees Celsius, and blow-up ratio is
3.0, hauling speed is 5 ms/min.
Embodiment 5
A kind of environmental protection high-ductility agricultural film, the raw material including following parts by weight meter:
73 parts of polylactic acid, 26 parts of poly-succinic fourth diester, 0.21 part of chitosan, modified graphene oxide 0.34 part, nanometer
0.48 part of zinc oxide, 0.35 part of sorbester p17,7 parts of tributyl citrate, 0.45 part of ultra-violet stabilizer and 0.86 part of antioxidant.
Modified graphene oxide the preparation method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, 70 degrees Celsius of merging
It in oil bath pan, flows back 24 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil of 120 degrees Celsius of merging are added into the product of step (1)
In bath, with 600 revs/min of speed, it is stirred to react 42 hours；
(3) mixture of step (2) is poured into 55 degrees Celsius of ethyl alcohol, with the power of 400W, after ultrasonic disperse 55 minutes,
It filters, after being filtered 5 times with 58 degrees Celsius of ethyl alcohol repeated washings, filtrate is placed in vacuum oven under 75 degrees Celsius, is done
It is dry to constant weight to get.
Organic solvent in step (1) is that thionyl chloride and N,N-dimethylformamide are uniformly mixed according to mass ratio 20:1
It is made.
Ultra-violet stabilizer is 2-hydroxy-4-n-octoxybenzophenone.
Antioxidant is three (2,4- di-tert-butyl-phenyl) phosphites.
The preparation method of environmentally friendly high-ductility agricultural film in the present embodiment, specifically, comprising the following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 720
Rev/min, after grinding 5.5 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
It is 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 15 minutes in mixing machine under 55 degrees Celsius, obtain mixed material B；
(4) mixed material A and mixed material B is added in high-speed mixer, at 50 c, with 1300 revs/min
Speed be stirred 18 minutes after, be added in parallel dual-screw extruding machine and be granulated, squeeze out batten pelletizing after water is cooling, grain
Material is put into 116 degrees Celsius of baking oven and dries to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, it is small places 24 at room temperature
When, it cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
One to five area's temperature of parallel dual-screw extruding machine in step (4) is successively set are as follows: 145 degrees Celsius, 150 is Celsius
Degree, 185 degrees Celsius, 185 degrees Celsius, 165 degrees Celsius.
Each phase temperature of extruder that single screw rod in step (5) squeezes out in inflation film manufacturing machine is successively set are as follows: and 190 degrees Celsius,
198 degrees Celsius, 204 degrees Celsius, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature is 190 degrees Celsius, and blow-up ratio is
3.0, hauling speed is 5 ms/min.
Comparative example 1: in addition to not adding poly-succinic fourth diester, remaining raw material and preparation method are identical as embodiment；
Mulch made from environmentally friendly high-ductility agricultural film and comparative example 1 is made in embodiment 1-5 to be tested for the property, as a result such as
The following table 1:
In conclusion the invention has the following advantages that
(1) mulch of the present invention has good stretch-resistance, mechanical tenacity and ageing-resistant by the mating reaction between raw material
Property, while there is good antibiotic property, and biodegradable, and noxious material is not generated, it is environmentally protective.
(2) present invention uses polylactic acid and poly-succinic fourth diester as base-material, and polylactic acid is from a wealth of sources, biological can drop
Solution, it is environmentally protective, there is good intensity and modulus, but polylactic acid the shortcomings that there are easy friability, it equally can be complete by addition
Biological degradation plastics poly-succinic fourth diester, poly-succinic fourth diester flexible have good toughness and processing performance, can
To improve polylactic acid toughness, composite material still can be degradable, while remaining the excellent performance of the two.
(3) present invention enhances the mechanical mechanics of mulch, together by addition modified graphene oxide and nano zine oxide
When enhance the wearability and ageing resistance of mulch, the antibiotic property of addition chitosan enhancing mulch.
(4) graphene oxide specific surface area with higher, surface functional group rich in, passes through modified graphite
There is good compatibility and interface binding power between alkene and polylactic acid, improve the comprehensive performance of material.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of environmental protection high-ductility agricultural film, which comprises the following steps: 65-78 parts of polylactic acid is gathered
22-30 parts of succinic acid fourth diester, 0.1-0.3 parts of chitosan, 0.2-0.5 parts of modified graphene oxide, nano zine oxide 0.3-0.7
Part, 0.2-0.5 parts of sorbester p17,4-10 parts of tributyl citrate, 0.2-0.7 parts of ultra-violet stabilizer and antioxidant 0.5-1.2
Part.
2. environmental protection high-ductility agricultural film according to claim 1, which is characterized in that the raw material including following parts by weight meter:
70-75 parts of polylactic acid, 25-28 parts of poly-succinic fourth diester, 0.15-0.25 parts of chitosan, modified graphene oxide 0.28-0.42
Part, 0.45-0.57 parts of nano zine oxide, 0.3-0.4 parts of sorbester p17,5-9 parts of tributyl citrate, ultra-violet stabilizer 0.3-
0.6 part and antioxidant 0.7-1.0 parts.
3. environmental protection high-ductility agricultural film according to claim 1, which is characterized in that the raw material including following parts by weight meter:
73 parts of polylactic acid, 26 parts of poly-succinic fourth diester, 0.21 part of chitosan, 0.34 part of modified graphene oxide, nano zine oxide
0.48 part, 0.35 part of sorbester p17,7 parts of tributyl citrate, 0.45 part of ultra-violet stabilizer and 0.86 part of antioxidant.
4. environmental protection high-ductility agricultural film according to claim 1, which is characterized in that the preparation of the modified graphene oxide
Method is as follows:
(1) it after being freeze-dried graphene oxide, is added in organic solvent after being uniformly mixed, the oil bath of 70 degrees Celsius of merging
It in pot, flows back 20-25 hours, and dry with calcium chloride tube；Distillation removal excessive organic solvent；
(2) octadecylamine of quite 10 times of its weight, the oil bath pan of 120 degrees Celsius of merging are added into the product of step (1)
In, with 500-600 revs/min of speed, it is stirred to react 38-45 hours；
(3) mixture of step (2) is poured into 50-60 degrees Celsius of ethyl alcohol, with the power of 300-400W, ultrasonic disperse 50-60
It after minute, filters, after being filtered 5 times with 50-60 degrees Celsius of ethyl alcohol repeated washing, filtrate is placed in vacuum oven in 70-
Under 80 degrees Celsius, it is dry to constant weight to get.
5. environmental protection high-ductility agricultural film according to claim 4, which is characterized in that the organic solvent in the step (1)
It is uniformly mixed and is made according to mass ratio 20:1 for thionyl chloride and N,N-dimethylformamide.
6. environmental protection high-ductility agricultural film according to claim 1, which is characterized in that the ultra-violet stabilizer is 2- hydroxyl
Base -4- oxy-octyl benzophenone, ESCALOL 567,2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5-
One or more of chlorobenzotriazole and 2- (2- hydroxyl -5- (1,1,3,3- tetramethyl butyl) phenyl) benzotriazole combine.
7. environmental protection high-ductility agricultural film according to claim 1, which is characterized in that the antioxidant is three (2,4- bis- uncles
Butyl phenyl) phosphite, β-(3,5- di-tert-butyl-hydroxy phenyl) propionate, β-(3,5- di-t-butyl-
4- hydroxy phenyl) one or more of propionic acid octadecanol ester combines.
8. a kind of preparation method of the described in any item environmentally friendly high-ductility agricultural films of such as claim 1-7, which is characterized in that including
Following steps:
(1) each component is weighed according to the raw material weight number of environmentally friendly high-ductility agricultural film；
(2) chitosan, modified graphene oxide, nano zine oxide and sorbester p17 are mixed and is added in grinder, with 600-800
Rev/min, after grinding 4-6 hours, drying 4 hours in 60 degrees Celsius of baking oven are placed in, mixed material A is obtained；
(3) mixed at high speed is added in polylactic acid, poly-succinic fourth diester, tributyl citrate, ultra-violet stabilizer and antioxidant
It is 4 hours dry in the baking oven of 80 degrees Celsius of merging after mixing 8-15 minutes in machine under 50-60 degrees Celsius, obtain mixed material B；
(4) mixed material A and mixed material B are added in high-speed mixer, under 40-50 degrees Celsius, turned with 1200-1500/
It after the speed of minute is stirred 15-20 minutes, is added in parallel dual-screw extruding machine and is granulated, squeeze out batten after water is cooling
Pelletizing, pellet are put into 110-120 degrees Celsius of baking oven and dry to constant weight；
(5) single screw rod is added in pellet made from step (4) to squeeze out in inflation film manufacturing machine after blowfilm shaping, is placed 24 hours at room temperature,
It cuts, to get the environmentally friendly high-ductility agricultural film after packaging.
9. the preparation method of environmental protection high-ductility agricultural film according to claim 8, which is characterized in that in the step (4)
One to five area's temperature of parallel dual-screw extruding machine successively set are as follows: 145 degrees Celsius, 150 degrees Celsius, 185 degrees Celsius, 185 take the photograph
Family name's degree, 165 degrees Celsius.
10. the preparation method of environmental protection high-ductility agricultural film according to claim 8, which is characterized in that in the step (5)
Single screw rod squeeze out inflation film manufacturing machine in each phase temperature of extruder successively set are as follows: 190 degrees Celsius, 198 degrees Celsius, 204 is Celsius
Degree, 204 degrees Celsius, 195 degrees Celsius；Blown-film die die temperature be 190 degrees Celsius, blow-up ratio 3.0, hauling speed be 5 meters/
Minute.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117413A (en) * | 2019-05-31 | 2019-08-13 | 兰州鑫银环橡塑制品有限公司 | Plateau vegetable cultivation degradable mulch and its preparation method and application |
| CN111303519A (en) * | 2020-03-20 | 2020-06-19 | 杨海青 | Corrosion-resistant heat-insulation building material surface composite film and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686790A (en) * | 1985-10-29 | 1987-08-18 | Kuwait Institute For Scientific Research | Degradable agricultural plastic articles, e.g., mulching film, comprising slowly released multinutrients in matrix of thermoplastic, and process for preparing same |
| CN103171219A (en) * | 2011-12-20 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Membrane consisting of inner-layer structure and outer-layer structure |
| CN106543669A (en) * | 2016-11-25 | 2017-03-29 | 陕西品达石化有限公司 | The preparation method of polylactic acid functionalization graphene nano compound film |
| CN106675017A (en) * | 2017-01-03 | 2017-05-17 | 江苏华生塑业有限公司 | High-strength anti-puncturing graphene modified plastic |
| CN107880784A (en) * | 2017-12-04 | 2018-04-06 | 苏州市宽道模具机械有限公司 | A kind of high-performance polishing fluid and preparation method thereof |
-
2018
- 2018-07-31 CN CN201810855775.5A patent/CN108948701A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686790A (en) * | 1985-10-29 | 1987-08-18 | Kuwait Institute For Scientific Research | Degradable agricultural plastic articles, e.g., mulching film, comprising slowly released multinutrients in matrix of thermoplastic, and process for preparing same |
| CN103171219A (en) * | 2011-12-20 | 2013-06-26 | 东丽纤维研究所（中国）有限公司 | Membrane consisting of inner-layer structure and outer-layer structure |
| CN106543669A (en) * | 2016-11-25 | 2017-03-29 | 陕西品达石化有限公司 | The preparation method of polylactic acid functionalization graphene nano compound film |
| CN106675017A (en) * | 2017-01-03 | 2017-05-17 | 江苏华生塑业有限公司 | High-strength anti-puncturing graphene modified plastic |
| CN107880784A (en) * | 2017-12-04 | 2018-04-06 | 苏州市宽道模具机械有限公司 | A kind of high-performance polishing fluid and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117413A (en) * | 2019-05-31 | 2019-08-13 | 兰州鑫银环橡塑制品有限公司 | Plateau vegetable cultivation degradable mulch and its preparation method and application |
| CN110117413B (en) * | 2019-05-31 | 2021-06-29 | 兰州鑫银环橡塑制品有限公司 | Degradable mulching film for plateau vegetable planting and preparation method and application thereof |
| CN111303519A (en) * | 2020-03-20 | 2020-06-19 | 杨海青 | Corrosion-resistant heat-insulation building material surface composite film and preparation process thereof |
| CN111303519B (en) * | 2020-03-20 | 2023-04-28 | 镇江富又康新型装饰材料有限公司 | Corrosion-resistant heat-insulating building material surface composite film and preparation process thereof |
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