CN106220902A - A kind of degradable agricultural starch base composite mulching film of antioxidation low cost - Google Patents

A kind of degradable agricultural starch base composite mulching film of antioxidation low cost Download PDF

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Publication number
CN106220902A
CN106220902A CN201610601015.2A CN201610601015A CN106220902A CN 106220902 A CN106220902 A CN 106220902A CN 201610601015 A CN201610601015 A CN 201610601015A CN 106220902 A CN106220902 A CN 106220902A
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starch
antioxidation
low cost
appropriate
base composite
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高绍彬
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MAANSHAN WUGU POULTRY INDUSTRY SPECIALIZED COOPERATIVE
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MAANSHAN WUGU POULTRY INDUSTRY SPECIALIZED COOPERATIVE
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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
    • 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
    • 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
    • C08B31/18—Oxidised starch
    • C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses the degradable agricultural starch base composite mulching film of a kind of antioxidation low cost, 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, maltose alcohol 13, medical stone fibre 46, Pericarpium Citri tangerinae powder 14 17, tea polysaccharide 45, polyvinyl alcohol 56, barium zinc heat stabilizer 23,85% ethanol solution is appropriate, deionized water is appropriate；The degradable agricultural mulching of the present invention, has good heat insulating ability, deinsectization and a non-oxidizability, and the gas barrier properties well easy film forming that blocks water, can be by the degradable digestion of microorganism in nature, environmental protection.

Description

A kind of degradable agricultural starch base composite mulching film of antioxidation low cost
Technical field
The present invention relates to agricultural mulching technical field, particularly relate to the degradable agricultural starch base of a kind of antioxidation low cost Composite mulching 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 the degradable agricultural of a kind of antioxidation low cost Starch base composite mulching film.
The present invention is achieved by the following technical solutions:
The degradable agricultural starch base composite mulching film of a kind of antioxidation low cost, is made up of the raw material of following weight portion: dry Base corn starch 64-70, ethanol 23-2 chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane 0.08-0.1, dimethyl Methanamide 60-80, maltose alcohol 1-3, medical stone fibre 4-6, Pericarpium Citri tangerinae powder 14-17, tea polysaccharide 4-5, polyvinyl alcohol 5-6, barium zinc Heat stabilizer 2-3,85% ethanol solution is appropriate, deionized water is appropriate.
The degradable agricultural starch base composite mulching film of described a kind of antioxidation low cost, by the preparation system of step in detail below Become:
(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) Pericarpium Citri tangerinae powder and deionized water being mixed according to solid-to-liquid ratio 1:8-10, be placed in the ultrasound wave of 120-150W, the time is 20-35min, is collected by filtration filtrate, and the 1/3 of rotary evaporation to original volume is standby；It is added to tea polysaccharide in deionized water make Mass percent concentration is 2-5g/L, then will be added to after medical stone fibre chopped in tea polysaccharide solution, adds after ultrasonic disperse is uniform Entering Pericarpium Citri tangerinae concentrated solution and polyvinyl alcohol, limit heating becomes stirs to forming dope, is subsequently placed in baking oven drying；
(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.
The degradable agricultural starch base composite mulching film of described a kind of antioxidation low cost, described alkaline solution is by hydroxide Sodium and sodium chloride mix according to mass ratio 2-3:1, are 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 Pericarpium Citri tangerinae The antioxygenic property of self and tea polysaccharide are modified to medical stone fibre, improve its dispersibility in gelatinized corn starch, and also solve Determine the pollution problem to environment of the Pericarpium Citri tangerinae of bulk deposition, it is achieved refuse secondary utilizes, the degradable agricultural mulching of the present invention, There is good heat insulating ability, deinsectization and non-oxidizability, and the gas barrier properties well easy film forming that blocks water, can be by microorganism in nature Degradable digestion, environmental protection.
Detailed description of the invention
The degradable agricultural starch base composite mulching film of a kind of antioxidation low cost, by the raw material system of following weight portion (kilogram) Prepare into: butt corn starch 64, ethanol 23, chloroacetic acid 11, silica 14, epoxychloropropane 0.08, dimethyl formyl Amine 60, maltose alcohol 1, medical stone fibre 4, Pericarpium Citri tangerinae powder 14, tea polysaccharide 4, polyvinyl alcohol 5, barium zinc heat stabilizer 2,85% ethanol are molten Liquid is appropriate, deionized water is appropriate.
The degradable agricultural starch base composite mulching film of described a kind of antioxidation low cost, by the preparation system of step in detail below Become:
(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) Pericarpium Citri tangerinae powder and deionized water being mixed according to solid-to-liquid ratio 1:8, be placed in the ultrasound wave of 120W, the time is 20min, mistake Filtrate is collected in filter, and the 1/3 of rotary evaporation to original volume is standby；Tea polysaccharide is added in deionized water makes mass percent dense Degree is for 2g/L, then will be added to after medical stone fibre chopped in tea polysaccharide solution, ultrasonic disperse adds the most afterwards Pericarpium Citri tangerinae concentrated solution with Polyvinyl alcohol, limit heating becomes stirs to forming dope, is subsequently placed in baking oven drying；
(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.
The degradable agricultural starch base composite mulching film of described a kind of antioxidation low cost, described alkaline solution is by hydroxide Sodium and sodium chloride mix according to mass ratio 2:1, are 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): 54.8；Elongation at break (%): 341%；Light transmittance (600nm, %): 71.8；Moisture-vapor transmission (g.cm.cm-2.s-1.Pa-1): 1.87 × 10-12；Water absorption rate (%): 6.2.

Claims (3)

1. the degradable agricultural starch base composite mulching film of an antioxidation low cost, it is characterised in that former by following weight portion Material preparation is made: butt corn starch 64-70, ethanol 23-26, chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane 0.08-0.1, dimethylformamide 60-80, maltose alcohol 1-3, medical stone fibre 4-6, Pericarpium Citri tangerinae powder 14-17, tea polysaccharide 4-5, poly- Vinyl alcohol 5-6, barium zinc heat stabilizer 2-3,85% ethanol solution is appropriate, deionized water is appropriate.
A kind of degradable agricultural starch base composite mulching film of antioxidation low cost, it is characterised in that It 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) Pericarpium Citri tangerinae powder and deionized water being mixed according to solid-to-liquid ratio 1:8-10, be placed in the ultrasound wave of 120-150W, the time is 20-35min, is collected by filtration filtrate, and the 1/3 of rotary evaporation to original volume is standby；It is added to tea polysaccharide in deionized water make Mass percent concentration is 2-5g/L, then will be added to after medical stone fibre chopped in tea polysaccharide solution, adds after ultrasonic disperse is uniform Entering Pericarpium Citri tangerinae concentrated solution and polyvinyl alcohol, limit heating becomes stirs to forming dope, is subsequently placed in baking oven drying；
(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 degradable agricultural starch base composite mulching film of antioxidation low cost, 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 gross weight 3-4 times amount go from Sub-water dissolution is uniformly mixing to obtain.
CN201610601015.2A 2016-07-28 2016-07-28 A kind of degradable agricultural starch base composite mulching film of antioxidation low cost Withdrawn CN106220902A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107619565A (en) * 2017-09-29 2018-01-23 当涂县瑞龙果树种植专业合作社 A kind of agricultural native flour nutrition liquid film with enhanced water resistance energy and preparation method thereof
CN107722524A (en) * 2017-09-29 2018-02-23 当涂县瑞龙果树种植专业合作社 A kind of agricultural solid mulch film of high water resistance being modified using wet strength agent and preparation method thereof
CN107815047A (en) * 2017-09-29 2018-03-20 当涂县瑞龙果树种植专业合作社 A kind of agricultural solid mulch film of slow release chemical fertilizer type water resistance and preparation method thereof
CN117886569A (en) * 2023-12-28 2024-04-16 珠海汇茂环保科技有限公司 Multicomponent concrete for prefabricated member and production method thereof

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CN104004230A (en) * 2014-06-10 2014-08-27 杨云 Degradable mulching film and preparation method thereof
CN104098781A (en) * 2014-06-20 2014-10-15 华中农业大学 Method utilizing tabasheer waste to produce degradable liquid mulching film

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CN104004230A (en) * 2014-06-10 2014-08-27 杨云 Degradable mulching film and preparation method thereof
CN104098781A (en) * 2014-06-20 2014-10-15 华中农业大学 Method utilizing tabasheer waste to produce degradable liquid mulching film

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107619565A (en) * 2017-09-29 2018-01-23 当涂县瑞龙果树种植专业合作社 A kind of agricultural native flour nutrition liquid film with enhanced water resistance energy and preparation method thereof
CN107722524A (en) * 2017-09-29 2018-02-23 当涂县瑞龙果树种植专业合作社 A kind of agricultural solid mulch film of high water resistance being modified using wet strength agent and preparation method thereof
CN107815047A (en) * 2017-09-29 2018-03-20 当涂县瑞龙果树种植专业合作社 A kind of agricultural solid mulch film of slow release chemical fertilizer type water resistance and preparation method thereof
CN117886569A (en) * 2023-12-28 2024-04-16 珠海汇茂环保科技有限公司 Multicomponent concrete for prefabricated member and production method thereof
CN117886569B (en) * 2023-12-28 2024-07-02 珠海汇茂环保科技有限公司 Multicomponent concrete for prefabricated member and production method thereof

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