CN106146907A - The starch base composite mulching film that a kind of block-water performance is good - Google Patents
The starch base composite mulching film that a kind of block-water performance is good Download PDFInfo
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- CN106146907A CN106146907A CN201610600999.2A CN201610600999A CN106146907A CN 106146907 A CN106146907 A CN 106146907A CN 201610600999 A CN201610600999 A CN 201610600999A CN 106146907 A CN106146907 A CN 106146907A
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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
-
- 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
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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
- C08B31/006—Crosslinking of derivatives of 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
- C08B31/08—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
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses the starch base composite mulching film that a kind of block-water performance is good, 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, silicone 45, viscose glue 45, fucoidin 23, glutaraldehyde 0.05 0.08, polyacrylonitrile-based carbon fibre 45, dioctyl phthalate 35, antioxidant BHT 0.2 0.3,85% ethanol solution is appropriate, deionized water is appropriate；The degradable agricultural film of the present invention, it is possible to decomposed completely by microorganism, does not interferes with environment, and excellent performance, there is good water preventing ability, ageing-resistant, impact resistance, filming performance is excellent, and production efficiency is high, reduces cost.
Description
Technical field
The present invention relates to agricultural mulching technical field, particularly relate to the starch base composite mulching film that a kind of block-water performance is good.
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 compound ground of starch base that a kind of block-water performance is good
Film.
The present invention is achieved by the following technical solutions:
The starch base composite mulching film that a kind of block-water performance is good, is made up of the raw material of following weight portion: butt corn starch 64-
70, ethanol 23-2 chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane 0.08-0.1, dimethylformamide 60-80,
Silicone 4-5, viscose glue 4-5, fucoidin 2-3, glutaraldehyde 0.05-0.08, polyacrylonitrile-based carbon fibre 4-5, phthalic acid two
Monooctyl ester 3-5, antioxidant BHT 0.2-0.3,85% ethanol solution is appropriate, deionized water is appropriate.
The starch base composite mulching film that described a kind of block-water performance is good, 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) being added to fucoidin in deionized water at 90 DEG C stir 1-1.5h, wherein concentration is 3-5g/L, reduces temperature extremely
Dripping glutaraldehyde reaction 30-45min when 80 DEG C, reaction adds dioctyl phthalate and continues reaction 30-40min after terminating,
Polyacrylonitrile-based carbon fibre is added in fucoidin solution stirring, adds appropriate formalin after being uniformly dispersed in 80-90 DEG C
Lower reaction 1-2h, reaction terminates rear drying for standby；
(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 starch base composite mulching film that described a kind of block-water performance is good, described alkaline solution be by sodium hydroxide and sodium chloride by
Mix according to mass ratio 2-3:1, be 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 Brown algae
The cross-linking agent such as polysaccharide, formaldehyde is modified to polyacrylonitrile-based carbon fibre so that it is have good block water, water repelling property, and forming sediment
In powder paste, dispersibility and the compatibility are good, effectively raise tensile strength and the water repelling property of film, the degradable agriculture of the present invention
With mulch film, it is possible to decomposed completely by microorganism, do not interfere with environment, and excellent performance, have good water preventing ability, resistance to always
Change, impact resistance, filming performance is excellent, and production efficiency is high, reduces cost.
Detailed description of the invention
The starch base composite mulching film that a kind of block-water performance is good, is made up of the raw material of following weight portion (kilogram): butt
Corn starch 64, ethanol 23, chloroacetic acid 11, silica 14, epoxychloropropane 0.08, dimethylformamide 60, silicone 4,
Viscose glue 4, fucoidin 2, glutaraldehyde 0.05, polyacrylonitrile-based carbon fibre 4, dioctyl phthalate 3, antioxidant BHT 0.2,
85% ethanol solution is appropriate, deionized water is appropriate.
The starch base composite mulching film that described a kind of block-water performance is good, 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) being added to fucoidin in deionized water at 90 DEG C stir 1h, wherein concentration is 3g/L, when reducing temperature to 80 DEG C
Dropping glutaraldehyde reaction 30min, reaction adds dioctyl phthalate and continues reaction 30min, by polyacrylonitrile-radical after terminating
Carbon fiber is added in fucoidin solution stirring, adds appropriate formalin and react 1h, reaction knot at 80 DEG C after being uniformly dispersed
Drying for standby after bundle；
(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 starch base composite mulching film that described a kind of block-water performance is good, described alkaline solution be by sodium hydroxide and sodium chloride by
Mix according to mass ratio 2:1, be 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): 52.2；Elongation at break (%): 315%；Light transmittance (600nm, %): 72.5；Moisture-vapor transmission
(g.cm.cm-2.s-1.Pa-1): 1.81 × 10-12；Water absorption rate (%): 6.3.
Claims (3)
1. the starch base composite mulching film that a block-water performance is good, it is characterised in that be made up of the raw material of following weight portion: dry
Base corn starch 64-70, ethanol 23-26, chloroacetic acid 11-15, silica 1 4-16, epoxychloropropane 0.08-0.1, diformazan
Base Methanamide 60-80, silicone 4-5, viscose glue 4-5, fucoidin 2-3, glutaraldehyde 0.05-0.08, polyacrylonitrile-based carbon fibre 4-
5, dioctyl phthalate 3-5, antioxidant BHT 0.2-0.3,85% ethanol solution is appropriate, deionized water is appropriate.
The starch base composite mulching film that a kind of block-water performance is good, it is characterised in that by walking in detail below
Suddenly make:
(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) being added to fucoidin in deionized water at 90 DEG C stir 1-1.5h, wherein concentration is 3-5g/L, reduces temperature extremely
Dripping glutaraldehyde reaction 30-45min when 80 DEG C, reaction adds dioctyl phthalate and continues reaction 30-40min after terminating,
Polyacrylonitrile-based carbon fibre is added in fucoidin solution stirring, adds appropriate formalin after being uniformly dispersed in 80-90 DEG C
Lower reaction 1-2h, reaction terminates rear drying for standby；
(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 starch base composite mulching film that a kind of block-water performance is good, it is characterised in that described alkaline solution
It is to be mixed according to mass ratio 2-3:1 by sodium hydroxide and sodium chloride, then with the deionized water dissolving stirring of gross weight 3-4 times amount
Uniformly obtain.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610600999.2A CN106146907A (en) | 2016-07-28 | 2016-07-28 | The starch base composite mulching film that a kind of block-water performance is good |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610600999.2A CN106146907A (en) | 2016-07-28 | 2016-07-28 | The starch base composite mulching film that a kind of block-water performance is good |
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| CN201610600999.2A Withdrawn CN106146907A (en) | 2016-07-28 | 2016-07-28 | The starch base composite mulching film that a kind of block-water performance is good |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265754A (en) * | 2017-07-17 | 2019-01-25 | 金华金年火腿有限公司 | A kind of edible composite film and its preparation method for ham processing |
| CN110183859A (en) * | 2019-05-30 | 2019-08-30 | 李全峰 | A kind of preparation method of tension waterproof starch film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-07-28 CN CN201610600999.2A patent/CN106146907A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 曹龙奎等: ""交联羧甲基玉米淀粉/PVA复合膜制备工艺的研究"", 《包装工程》 * |
| 王霞等: ""几种成膜助剂对CCMS/PVA可降解薄膜力学及耐水性能影响的研究"", 《黑龙江八一农垦大学学报》 * |
| 闫美珍: ""疏水化改性淀粉/PVA生物降解塑料地膜的研究"", 《中国优秀硕士学位论文全文数据库 农业科技辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265754A (en) * | 2017-07-17 | 2019-01-25 | 金华金年火腿有限公司 | A kind of edible composite film and its preparation method for ham processing |
| CN110183859A (en) * | 2019-05-30 | 2019-08-30 | 李全峰 | A kind of preparation method of tension waterproof starch film |
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