CN106188646A - A kind of interpolation corn straw degradable starch based agricultural mulching film - Google Patents
A kind of interpolation corn straw degradable starch based agricultural mulching film Download PDFInfo
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- CN106188646A CN106188646A CN201610601052.3A CN201610601052A CN106188646A CN 106188646 A CN106188646 A CN 106188646A CN 201610601052 A CN201610601052 A CN 201610601052A CN 106188646 A CN106188646 A CN 106188646A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
- C08L3/08—Ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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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
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/08—Ethers
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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
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses and a kind of add corn straw degradable starch based agricultural mulching film, be made up of the raw material of following weight portion: butt corn starch 64 70, ethanol 23 26, chloroacetic acid 11 15, silica 14 16, epoxychloropropane 0.08 0.1, dimethylformamide 60 80, phosphorous acid lipid stabilizer 23, thiourea 34, carbamide 45, corn straw 16 20, gelatin 34, formaldehyde 0.05 0.07, Dormant oils 23, Pulvis Talci 56, antioxidant 23,85% ethanol solution is appropriate, deionized water is appropriate；Starch film intensity prepared by the present invention is high, water-fast, oil resistant, and raw material is simple and easy to get, it is simple to industry is big to be produced, and service life is long, and production cost is low, can enhance vigour for soil after degraded, ecological, environmental protective.
Description
Technical field
The present invention relates to agricultural mulching technical field, particularly relate to a kind of interpolation corn straw degradable starch base agricultural
Mulch film.
Background technology
At present, film-mulching technique is widely popularized in agricultural, be applied to Semen Tritici aestivi, Oryza sativa L., corn and soybean,
In the plantation of the crop such as Sorghum vulgare Pers., Cotton Gossypii, effect of increasing production is obvious, owing to the most a large amount of mulch films used are nondegradable macromolecules
Compound, neither by microbial attack, can not decompose voluntarily.If things go on like this, insoluble dirt will necessarily be brought to descendant
Dye harm.Therefore, research degradable mulch gradually comes into one's own.Starch is the Renewable resource that nature is abundant, its nontoxic nothing
Evil, fully biodegradable, but poor mechanical property and water resistance but limit its application.Its application is restricted.
Starch is a kind of Renewable resource, and not only wide material sources are cheap, and its goods in use have the feature of environmental protection of excellence
Can, can degrade rapidly after discarding, come from nature, back to nature.But, owing to starch is a kind of highly polar crystal material,
Intramolecular also exists substantial amounts of hydrogen bond with intermolecular, and under generic condition, thermoplasticity is poor, it is difficult to machine-shaping, and obtained product
Also exist that mechanical strength is low, poor water resistance and the shortcoming such as wet strength is low, therefore, how to improve the intensity of starch material, toughness and
Water proofing property is a urgent problem of the real substituted for plastic raw material of starch based full-biodegradable material energy.By to starch
Modification, starch granules expands, and structure changes, and degree of crystallinity reduces, and has certain molecular flexibility, and good film-forming property, with
The compatibility of macromolecule resin improves, and is so greatly improved the performance of starch mulch film so that it is range of application is wider.
In " research of hydrophobic modification starch/PVA biodegradable plastic mulch film " literary composition, author is former with corn starch
Material, through carboxymethyl etherification, the double modification of crosslinking, wherein etherification temperature is 74.44 DEG C, the molar ratio of sodium hydroxide/starch
1.85, etherification time 2.33h, concentration of alcohol is 84.65%, cross-linking modified during, use epoxychloropropane as cross-linking agent,
Consumption is 0.05%, and crosslinking time is 1.0h, and sodium hydroxide concentration is 1.5%, then obtains the cross-linking carboxymethyl that thermoplasticity is stronger
Starch, recycles it and is blended with PVA, and through crosslinking, speedup, hydrophobic modification, the mechanical property of film reaches standard-required, water suction
Rate is substantially reduced, but its combination property does not also reach actually used needs, needs its further modification is met various making
By demand, to improve the mechanical performance of starch film, toughness, intensity and other attributes, expand range of application.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of interpolation corn straw degradable starch
Based agricultural mulching film.
The present invention is achieved by the following technical solutions:
A kind of interpolation corn straw degradable starch based agricultural mulching film, is made up of the raw material of following weight portion: butt is beautiful
Rice starch 64-70, ethanol 23-2 chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane 0.08-0.1, dimethyl formyl
Amine 60-80, phosphorous acid lipid stabilizer 2-3, thiourea 3-4, carbamide 4-5, corn straw 16-20, gelatin 3-4, formaldehyde 0.05-
0.07, Dormant oils 2-3, Pulvis Talci 5-6, antioxidant 2-3,85% ethanol solution is appropriate, deionized water is appropriate.
Described a kind of interpolation corn straw degradable starch based agricultural mulching film, is made up of step in detail below:
(1) by the sodium hydroxide mix homogeneously of butt corn starch and 6-10 times amount, forwarding to stir in reactor, rotating speed is 80-
100r/min, at 35 DEG C, stirring reaction 30min, after ethanol solution and chloroacetic acid mix homogeneously, is sprayed on starch surface and continues
Continuous stirring 10min, after reaction terminates, is cooled to room temperature, then washs above-mentioned modified starch with 85% ethanol solution and adds appropriate
Glacial acetic acid, regulation pH is 7.0, sucking filtration, continues to wash filter cake 2-3 time with 85% ethanol water, then in blast drier 50
It is dried 2-3h at DEG C, pulverizes, be sieving through 100 mesh, obtain carboxymethyl starch；
(2) carboxymethyl starch prepared by step (1) is added to furnishing slurry in alkaline solution, alkaline solution and carboxymethyl starch press
Mix than ml:g1.5-2:1 according to volume mass, be subsequently placed in the thermostat water bath of 70-80 DEG C and be stirred continuously, by epoxy chloropropionate
Alkane is dissolved in appropriate alkaline liquor, all instills in starch milk, react 1-3h, use hydrochloric acid conditioning solution after completion of the reaction in 3-5min
Ph value to 6-7, stand a period of time, washing, sucking filtration, be placed in drying baker at 55 DEG C of dry 4h, prepare cross-linking carboxymethyl and form sediment
Powder；
(3) by corn straw smashing, adding 40% sodium hydroxide solution according to solid-to-liquid ratio 1:14-18, at 60-90 DEG C, stirring is anti-
Answer 2-3h, filter, be washed with deionized and be dried in neutral final vacuum, more dried corn stalk powder is broken to 400-600
Mesh is standby, thiourea and carbamide is mixed and is added in the deionized water of total amount 22-30 times amount be uniformly dissolved, is cooled to-12--6 DEG C in advance,
Again above-mentioned corn straw is dissolved in mixed aqueous solution, after stirring 20-30min, adds gelatin, formaldehyde and Pulvis Talci, at 50-70
At DEG C, stirring is standby after reacting 1-2h；
(4) product prepared by step (2) is configured to the starch milk that concentration is 38-48g/L, adds product prepared by step (3)
Stirring 30-40min at 95-100 DEG C, stirring adds remaining surplus materials and continues stirring 50-60min after terminating, then will mixing
Emulsion is transferred to homogenizer 18000r/min homogenizing 5min, forms uniform film forming liquid, then by film forming liquid in 0.09MPa vacuum
Deaerate under degree 20min, casting film-forming.
Described a kind of starch base agricultural mulching adding plant fiber degradable, described alkaline solution be by sodium hydroxide and
Sodium chloride mixes according to mass ratio 2-3:1, is then uniformly mixing to obtain with the deionized water dissolving of gross weight 3-4 times amount.
The invention have the advantage that the present invention utilizes corn starch for raw material, through carboxymethyl etherification, the double modification of crosslinking, make
Obtaining modified corn starch, greatly add the surface group of starch, the chemical bonding effect that intermolecular existence is strong, to flowing
The viscous drag produced increases, and apparent viscosity rises, and hinders rearranging and associating between straight chain molecule in gelatinized corn starch, increases
The water-retaining property of starch low temperature disperse system, greatly reduces retrogradation and gel tendency, and improves light transmittance and reduce parent
Aqueous, meets the crops requirement to illumination, and improves Optimality and the stability of film forming, and polysaccharide has special
Long-chain helical molecular structure, stable chemical nature, filming performance is preferable, and gas barrier property is the most excellent, and moisture barrier property is poor, utilizes farming
Cellulose abundant in thing refuse corn straw, is dissolved out as modifying agent modified to talcum powder, can not only
The cost of reduction preparation, and effectively raise the combination property of starch film, starch film intensity prepared by the present invention is high, resistance to
Water, oil resistant, raw material is simple and easy to get, it is simple to industry is big to be produced, and service life is long, and production cost is low, can increase for soil after degraded
Add vigor, ecological, environmental protective.
Detailed description of the invention
A kind of interpolation corn straw degradable starch based agricultural mulching film, is prepared system by the raw material of following weight portion (kilogram)
Become: butt corn starch 64, ethanol 23, chloroacetic acid 11, silica 14, epoxychloropropane 0.08, dimethylformamide 60,
Phosphorous acid lipid stabilizer 2, thiourea 3, carbamide 4, corn straw 16, gelatin 3, formaldehyde 0.05, Dormant oils 2, Pulvis Talci 5, antioxidant
2,85% ethanol solution is appropriate, deionized water is appropriate.
Described a kind of interpolation corn straw degradable starch based agricultural mulching film, is made up of step in detail below:
(1) by the sodium hydroxide mix homogeneously of butt corn starch and 6 times amount, forwarding to stir in reactor, rotating speed is 80r/
Min, stirring reaction 30min at 35 DEG C, after ethanol solution and chloroacetic acid mix homogeneously, be sprayed on starch surface and continue stirring
10min, after reaction terminates, is cooled to room temperature, then washs above-mentioned modified starch with 85% ethanol solution and adds appropriate ice vinegar
Acid, regulation pH is 7.0, sucking filtration, continues to wash filter cake 2 times with 85% ethanol water, then dry at 50 DEG C in blast drier
Dry 2h, pulverizes, is sieving through 100 mesh, obtain carboxymethyl starch；
(2) carboxymethyl starch prepared by step (1) is added to furnishing slurry in alkaline solution, alkaline solution and carboxymethyl starch press
Mix than ml:g1.5:1 according to volume mass, be subsequently placed in the thermostat water bath of 70 DEG C and be stirred continuously, epoxychloropropane is dissolved
In appropriate alkaline liquor, all instill in starch milk in 3min, react 1h, after completion of the reaction by the ph value of hydrochloric acid conditioning solution to 6,
Stand a period of time, washing, sucking filtration, it is placed in drying baker at 55 DEG C of dry 4h, prepares crosslinked carboxymethyl fecula；
(3) by corn straw smashing, 40% sodium hydroxide solution is added according to solid-to-liquid ratio 1:14, stirring reaction 2h, mistake at 60 DEG C
Filter, is washed with deionized and is dried in neutral final vacuum, then it is standby, by thiourea that dried corn stalk powder is broken to 400 mesh
It is added in the deionized water of total amount 22 times amount be uniformly dissolved with carbamide mixing, is cooled in advance DEG C, more above-mentioned corn straw is dissolved in mixed
In Heshui solution, after stirring 20min, add gelatin, formaldehyde and Pulvis Talci, standby after stirring reaction 1h at 50 DEG C；
(4) product prepared by step (2) being configured to the starch milk that concentration is 38g/L, product prepared by addition step (3) is 95
Stirring 30min at DEG C, stirring adds remaining surplus materials and continues stirring 50min after terminating, then mixed emulsion is transferred to homogenizing
Device 18000r/min homogenizing 5min, forms uniform film forming liquid, and then deaerate under 0.09MPa vacuum 20min by film forming liquid,
Casting film-forming.
Described a kind of starch base agricultural mulching adding plant fiber degradable, described alkaline solution be by sodium hydroxide and
Sodium chloride mixes according to mass ratio 2:1, is then uniformly mixing to obtain with the deionized water dissolving of gross weight 3 times amount.
Preparing starch film according to the method for embodiment, it is carried out performance test, result is as follows:
Tensile strength (MPa): 53.5；Elongation at break (%): 346%；Light transmittance (600nm, %): 73.5；Moisture-vapor transmission
(g.cm.cm-2.s-1.Pa-1): 1.83 × 10-12；Water absorption rate (%): 5.2.
Claims (3)
1. one kind is added corn straw degradable starch based agricultural mulching film, it is characterised in that by the raw material system of following weight portion
Prepare into: butt corn starch 64-70, ethanol 23-26, chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane
0.08-0.1, dimethylformamide 60-80, phosphorous acid lipid stabilizer 2-3, thiourea 3-4, carbamide 4-5, corn straw 16-20,
Gelatin 3-4, formaldehyde 0.05-0.07, Dormant oils 2-3, Pulvis Talci 5-6, antioxidant 2-3,85% ethanol solution are appropriate, deionized water is fitted
Amount.
A kind of add corn straw degradable starch based agricultural mulching film, it is characterised in that by with
Lower concrete steps are made:
(1) by the sodium hydroxide mix homogeneously of butt corn starch and 6-10 times amount, forwarding to stir in reactor, rotating speed is 80-
100r/min, at 35 DEG C, stirring reaction 30min, after ethanol solution and chloroacetic acid mix homogeneously, is sprayed on starch surface and continues
Continuous stirring 10min, after reaction terminates, is cooled to room temperature, then washs above-mentioned modified starch with 85% ethanol solution and adds appropriate
Glacial acetic acid, regulation pH is 7.0, sucking filtration, continues to wash filter cake 2-3 time with 85% ethanol water, then in blast drier 50
It is dried 2-3h at DEG C, pulverizes, be sieving through 100 mesh, obtain carboxymethyl starch；
(2) carboxymethyl starch prepared by step (1) is added to furnishing slurry in alkaline solution, alkaline solution and carboxymethyl starch press
Mix than ml:g1.5-2:1 according to volume mass, be subsequently placed in the thermostat water bath of 70-80 DEG C and be stirred continuously, by epoxy chloropropionate
Alkane is dissolved in appropriate alkaline liquor, all instills in starch milk, react 1-3h, use hydrochloric acid conditioning solution after completion of the reaction in 3-5min
Ph value to 6-7, stand a period of time, washing, sucking filtration, be placed in drying baker at 55 DEG C of dry 4h, prepare cross-linking carboxymethyl and form sediment
Powder；
(3) by corn straw smashing, adding 40% sodium hydroxide solution according to solid-to-liquid ratio 1:14-18, at 60-90 DEG C, stirring is anti-
Answer 2-3h, filter, be washed with deionized and be dried in neutral final vacuum, more dried corn stalk powder is broken to 400-600
Mesh is standby, thiourea and carbamide is mixed and is added in the deionized water of total amount 22-30 times amount be uniformly dissolved, is cooled to-12--6 DEG C in advance,
Again above-mentioned corn straw is dissolved in mixed aqueous solution, after stirring 20-30min, adds gelatin, formaldehyde and Pulvis Talci, at 50-70
At DEG C, stirring is standby after reacting 1-2h；
(4) product prepared by step (2) is configured to the starch milk that concentration is 38-48g/L, adds product prepared by step (3)
Stirring 30-40min at 95-100 DEG C, stirring adds remaining surplus materials and continues stirring 50-60min after terminating, then will mixing
Emulsion is transferred to homogenizer 18000r/min homogenizing 5min, forms uniform film forming liquid, then by film forming liquid in 0.09MPa vacuum
Deaerate under degree 20min, casting film-forming.
A kind of starch base agricultural mulching adding plant fiber degradable, it is characterised in that described
Alkaline solution is to be mixed according to mass ratio 2-3:1 by sodium hydroxide and sodium chloride, then with the deionized water of gross weight 3-4 times amount
Dissolving is uniformly mixing to obtain.
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| CN201610601052.3A CN106188646A (en) | 2016-07-28 | 2016-07-28 | A kind of interpolation corn straw degradable starch based agricultural mulching film |
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| CN201610601052.3A CN106188646A (en) | 2016-07-28 | 2016-07-28 | A kind of interpolation corn straw degradable starch based agricultural mulching film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286689A (en) * | 2017-06-30 | 2017-10-24 | 长沙天闰电子商务有限公司 | A kind of soil cover layer |
| CN107815927A (en) * | 2017-09-29 | 2018-03-20 | 当涂县瑞龙果树种植专业合作社 | A kind of Environmental-protection agricultural paper mulch sheet with enhanced water resistance energy and preparation method thereof |
| CN112646237A (en) * | 2020-12-23 | 2021-04-13 | 哈尔滨学院 | Preparation method of low-cost degradable mulching film |
| CN113402985A (en) * | 2021-06-29 | 2021-09-17 | 西安建筑科技大学 | Hydrogel material for protecting ancient building tiles and application method thereof |
| CN115160677A (en) * | 2022-08-18 | 2022-10-11 | 甘肃宏鑫农业科技有限公司 | Agricultural mulching film for high-standard farmland and preparation method thereof |
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| CN104098792A (en) * | 2014-06-30 | 2014-10-15 | 安徽巢湖南方膜业有限责任公司 | Corn starch degradable plastic film and preparation method thereof |
| CN104725721A (en) * | 2015-03-18 | 2015-06-24 | 陈广田 | Degradable composite film as well as preparation method and application thereof |
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| CN104098792A (en) * | 2014-06-30 | 2014-10-15 | 安徽巢湖南方膜业有限责任公司 | Corn starch degradable plastic film and preparation method thereof |
| CN104725721A (en) * | 2015-03-18 | 2015-06-24 | 陈广田 | Degradable composite film as well as preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286689A (en) * | 2017-06-30 | 2017-10-24 | 长沙天闰电子商务有限公司 | A kind of soil cover layer |
| CN107815927A (en) * | 2017-09-29 | 2018-03-20 | 当涂县瑞龙果树种植专业合作社 | A kind of Environmental-protection agricultural paper mulch sheet with enhanced water resistance energy and preparation method thereof |
| CN112646237A (en) * | 2020-12-23 | 2021-04-13 | 哈尔滨学院 | Preparation method of low-cost degradable mulching film |
| CN112646237B (en) * | 2020-12-23 | 2022-04-12 | 哈尔滨学院 | Preparation method of low-cost degradable mulching film |
| CN113402985A (en) * | 2021-06-29 | 2021-09-17 | 西安建筑科技大学 | Hydrogel material for protecting ancient building tiles and application method thereof |
| CN113402985B (en) * | 2021-06-29 | 2022-07-08 | 西安建筑科技大学 | Hydrogel material for protecting ancient building tiles and application method thereof |
| CN115160677A (en) * | 2022-08-18 | 2022-10-11 | 甘肃宏鑫农业科技有限公司 | Agricultural mulching film for high-standard farmland and preparation method thereof |
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Application publication date: 20161207 |
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