CN108485207A - A kind of degradable mulch and preparation method thereof with slow-release phosphate fertilizer - Google Patents
A kind of degradable mulch and preparation method thereof with slow-release phosphate fertilizer Download PDFInfo
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- CN108485207A CN108485207A CN201810148531.3A CN201810148531A CN108485207A CN 108485207 A CN108485207 A CN 108485207A CN 201810148531 A CN201810148531 A CN 201810148531A CN 108485207 A CN108485207 A CN 108485207A
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- phosphate fertilizer
- lignin
- release phosphate
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The invention discloses a kind of degradable mulches and preparation method thereof with slow-release phosphate fertilizer, it is characterised in that the whole life cycle design of slow-release phosphate fertilizer is made in the lignin and fully biodegradable plastic blend blown film being modified using phosphatization.The present invention is effectively utilized reproducible Liginon Resource, the consumption of ground film preparation petrochina base material is reduced simultaneously, reduce biorefinery industry and problem of environmental pollution that non-degradable mulch is brought, phosphatization lignin also contributes to phosphate fertilizer utilization efficiency as the slow-release phosphate fertilizer of crops, soil is improved, thus there is good environment, resource and economic benefit.
Description
Technical field
The invention belongs to agricultural film fields, and in particular to a kind of degradable mulch with slow-release phosphate fertilizer and its system
Preparation Method.
Background technology
Exploitation degradative plastic film is the Main way for solving the problems, such as Plastic-film pollution in the world at present, and the use of degradative plastic film is saved
The link of recycling and processing residual film, brings great convenience to agricultural production.Traditional degradative plastic film is by polyethylene
(PE) compound photodegradable aid, starch etc. are prepared, and can be disintegrated into mulch fragment in the regular period, but mulch fragment mainly by
PE difficult to degrade is constituted, and long-term existence in soil, is reduced soil quality and crop yield, while endangering ecology by these fragments
Environment, thus develop can degradable mulch have become research hotspot both domestic and external now.Such as poly- pair of a variety of ester plastics
Phthalic acid/tetramethylene adipate (PBAT), polylactic acid (PLA), poly (propylene carbonate) (PPC), poly-succinic/adipic acid fourth
Diol ester (PBSA), polyhydroxyalkanoates (PHA), poly butylene succinate (PBS) etc. have been demonstrated that there is biology completely to drop
Performance is solved, can carbon dioxide and water be generated by the enzyme catabolism in multiple-microorganism and animal and plant body under field conditions (factors).But
Compared with traditional mulch, such plastics prepare ground film-strength is low, poor toughness, and cost is higher, hampers it to market
Large-scale promotion application.
Lignin is the maximum natural aromatic macromolecule of reserves, the by-product as biorefinery and paper industry in plant
Object, have the advantages that cheap and easy to get, biodegradable, be easy to derivatization etc. it is multiple, however only less than 2% industrial lignin quilt
It recycles, remaining a large amount of lignin is incinerated or abandons, and causes a large amount of wasting of resources and environmental pollution.But lignin
Itself have effects that soil improvement and antiseptic, high value added product can be converted into and be applied to agricultural and forestry production field.When
When using fertilizer element modified lignin resin needed for plant growth, fertilizer can be released slowly with the degradation of lignin,
Fertilizer efficiency time is substantially prolonged, the lignin that especially phosphatization is modified can effectively prevent phosphate fertilizer permanently to be fixed by soil, significantly
Improve the effective rate of utilization of phosphate fertilizer in ground.
By phosphatization lignin and degradation plastic blending extrusion blown film, the mechanical property of mulch can be enhanced.This method obtains
The mulch arrived still with complete biodegradable, can not only reduce consumption and the biorefinery industrial pollutants of petroleum based material
Discharge, also substantially reduce the cost of mulch.Since phosphatization lignin color is deeper, the light transmittance of mulch can be reduced, favorably
In the growth for inhibiting ground weeds.
Invention content
The technical problem to be solved in the present invention is to provide a kind of degradable mulches with slow-release phosphate fertilizer, existing to solve
There is problem ineffective existing for technology.
The present invention also technical problems to be solved are to provide the preparation of the above-mentioned degradable mulch with slow-release phosphate fertilizer
Method.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of degradable mulch with slow-release phosphate fertilizer, it includes the component of following mass fraction：
Wherein, the component of preferably following mass fraction：
Wherein, the degradation plastic be poly terephthalic acid/tetramethylene adipate (PBAT), polylactic acid (PLA),
Poly (propylene carbonate) (PPC), poly-succinic/tetramethylene adipate (PBSA), polyhydroxyalkanoates (PHA) and poly-succinic fourth
Any one or the combination of several of them in diol ester (PBS), preferably poly terephthalic acid/tetramethylene adipate (PBAT).
Wherein, the phosphatization lignin is lignin through polyphosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphoric anhydride, acid
It is obtained after the phosphorization reagents phosphatization such as phosphate, phosphorus oxychloride or phosphorus thiochloride, it is preferable to use polyphosphoric acid carries out phosphatization.
Wherein, the method for bonderizing is：
Phosphorization reagent is added into lignin, after stirring 60~80h, is drying to obtain phosphatization lignin；Wherein, lignin and
The mass ratio of phosphorization reagent is 1：3~5.
Wherein, the lignin be alkali lignin, it is enzymolysis xylogen, papermaking lignin, organic solvent lignin, wooden
Any one or the combination of several of them in plain sulfonate, grain size are 100~1000 mesh.
Wherein, the plasticizer is dibutyl sebacate, glyceryl triacetate, polyethylene glycol and citric acid ester type plasticising
Any one or the combination of several of them in agent；Wherein, citric acid ester plasticizer includes tributyl citrate, acetyl tributyl citrate three
Butyl ester and triethyl citrate.
Wherein, the chain extender is hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, Isosorbide-5-Nitrae-fourth
Any one or the combination of several of them in glycol and diisocyanates chain extender；Wherein, diisocyanates chain extender includes
Methyl diphenylene diisocyanate and Toluene-2,4-diisocyanate, 4- diisocyanate.
Wherein, the antioxidant is butylated hydroxy anisole, dibutyl hydroxy toluene, tert-butyl hydroquinone, season
Penta tetrol bis-phosphite, ten caprylate of 3- (3,5- di-tert-butyl-hydroxy phenyls) propionic acid and the bimonthly osmanthus of thio-2 acid
Any one or the combination of several of them in ester.
Wherein, the heat stabilizer is maleic anhydride and/or epoxidized soybean oil.
Wherein, the lubricant is appointing in pentaerythritol stearate, zinc stearate, calcium stearate and oleamide
The combination for one or more of anticipating.
Further, the component of preferably following mass fraction：
Further, the component of preferably following mass fraction：
The preparation method of the above-mentioned degradable mulch with slow-release phosphate fertilizer, it includes the following steps：
By the degradation plastic of formula ratio, phosphatization lignin, plasticizer, chain extender, antioxidant, heat stabilizer and lubrication
After agent is sufficiently mixed in high mixer, through dual-screw pelletizer extruding pelletization, the compound grain of plastics of phosphatization lignin modification is obtained
Son；The plastics compound particle of phosphatization lignin modification has effects that the degradable mulch of slow-release phosphate fertilizer through Blown Film.
Wherein, in high mixer, temperature be 100~110 DEG C, rotating speed be 800~1000rpm, incorporation time be 10~
20min；When extruding pelletization, temperature is 120~180 DEG C；When Blown Film, temperature is 125~150 DEG C.
Advantageous effect：
The present invention, which uses in degradation process, has effects that the biodegradable plastic system of the phosphatization lignin modification of slow-release phosphate fertilizer
Standby whole life cycle design, had both been effectively utilized reproducible Liginon Resource, and had reduced biorefinery and paper industry is brought
Problem of environmental pollution, and the white pollution problems in the consumption and agricultural production of petroleum based material can be reduced, additionally aided
Phosphate fertilizer utilization efficiency is improved, soil is improved, saves fertilizer volume increase, thus there is good environment, resource and economic benefit.Phosphatization lignin
Use also advantageously improve the mechanical property of degradable mulch, inhibit the growth of weeds.It, can be with since lignin is cheap and easy to get
The production cost for effectively reducing mulch, is conducive to marketing.
Specific implementation mode
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Embodiment 1
Specific preparation method includes the following steps：
(1) 90 parts of polyphosphoric acids are added into 20 parts by weight alkali lignins, stirs 60 hours, is dried to obtain phosphatization lignin；
(2) 50 parts of PBAT, 20 parts of PLA, the phosphatization lignin described in 30 parts of steps (1), 0.6 part of lemon are added in high mixer
Lemon acid tributyl, 0.8 part of bisphenol-A, 0.3 part of tert-butyl hydroquinone, 0.5 part of epoxidized soybean oil, 0.2 part of zinc stearate, 105
At DEG C, with the rotating speed of 1000rpm, 15min is mixed, mixed material is obtained；
(3) mixed material described in step (2) is obtained through double-screw extruding pelletizing controlled at 150~160 DEG C
The plastics compound particle of phosphatization lignin modification；
(4) compound particle described in step (3) at 140~150 DEG C is subjected to Blown Film, obtained with slow-release phosphate fertilizer
The degradable mulch of effect.
Embodiment 2
Specific preparation method includes the following steps：
(1) 140 parts of polyphosphoric acids are added into 40 parts by weight enzymolysis xylogens, stirs 80 hours, it is wooden to be dried to obtain phosphatization
Element；
(2) be added in high mixer 55 parts of PBAT, 25 parts of PBSA, the phosphatization lignin described in 20 parts of steps (1), 0.6 part
Glyceryl triacetate, 0.3 part of 1,4- butanediol, 0.4 part of dibutyl hydroxy toluene, 0.6 part of maleic anhydride, 0.15 part of tristearin
Sour calcium, with the rotating speed of 1000rpm, mixes 15min, obtains mixed material at 105 DEG C；
(3) mixed material described in step (2) is obtained through double-screw extruding pelletizing controlled at 140~150 DEG C
The plastics compound particle of phosphatization lignin modification；
(4) compound particle described in step (3) at 130~140 DEG C is subjected to Blown Film, obtained with slow-release phosphate fertilizer
The degradable mulch of effect.
Comparative example 1
The PBAT of phosphatization lignin homogenous quantities in embodiment 1 is replaced, the mulch prepared with reference to the step of embodiment 1
As a comparison case 1.
Performance test
The tensile strength of 1 material of above-described embodiment 1,2 and comparative example is measured using tensilon, and to above-mentioned
Material carries out biological compost degradation experiment, and specific testing result is as shown in table 1.
Table 1
| Tensile strength (MPa) | 6 months compost degradation rates (%) | |
| Embodiment 1 | 33 | >99% |
| Embodiment 2 | 30 | >99% |
| Comparative example 1 | 20 | >99% |
As can be seen that the tensile strength of the mulch of phosphatization lignin modification is shown from test result shown in table 1
Ground enhancing is write, and meets degradable requirement.
By in embodiment 1,2 and comparative example 1 mulch carry out potted plant experiment, periodically to phosphorus element content in soil into
Row measures (in 1 group of comparative example, applies phosphate fertilizer, phosphorus element content in 1 mulch of phosphorus element content and embodiment before experiment starts
It is identical), phosphorus fertilizer slow release situation is as shown in table 2.
Table 2
| Time/day | 0 | 30 | 60 | 90 |
| Embodiment 1 (mg/kg) | 0 | 15.8 | 36.0 | 55.9 |
| Embodiment 2 (mg/kg) | 0 | 13.1 | 32.2 | 48.8 |
| Comparative example 1 (mg/kg) | 0 | 12.5 | 14.0 | 14.2 |
Table 2 the result shows that the present invention mulch have the effect of slow-release phosphate fertilizer, to soil release phosphate fertilizer can continue 90 days, fertilizer
It is long to imitate the time.
Specific embodiments of the present invention are explained in detail above, but the present invention is not limited to above-described embodiment, because
This do not depart from the spirit of the present invention and under the premise of objective made by change and modification, should all cover in the scope of the present invention
It is interior.
Claims (11)
1. a kind of degradable mulch with slow-release phosphate fertilizer, which is characterized in that it includes the component of following mass fraction：
2. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that described is degradable
Plastics are poly terephthalic acid/tetramethylene adipate, polylactic acid, poly (propylene carbonate), poly-succinic/adipic acid butanediol
Any one or the combination of several of them in ester, polyhydroxyalkanoates and poly butylene succinate.
3. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that the phosphatization wood
Quality is lignin through polyphosphoric acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphoric anhydride, acid phosphate, phosphorus oxychloride or phosphorus thiochloride
It is obtained after phosphatization.
4. the degradable mulch with slow-release phosphate fertilizer according to claim 3, which is characterized in that the lignin
For in alkali lignin, enzymolysis xylogen, papermaking lignin, organic solvent lignin, lignosulfonates any one or it is several
The combination of kind, grain size are 100~1000 mesh.
5. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that the plasticizer
For any one or a few the group in dibutyl sebacate, glyceryl triacetate, polyethylene glycol and citric acid ester plasticizer
It closes.
6. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that the chain extender
For hydroquinone two hydroxy ethyl ether, resorcinol dihydroxyethyl ether, bisphenol-A, 1,4- butanediols and diisocyanates chain extender
In any one or the combination of several of them.
7. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that described is anti-oxidant
Agent is butylated hydroxy anisole, dibutyl hydroxy toluene, tert-butyl hydroquinone, pentaerythritol bis-phosphite, 3- (3,5- bis-
Tert-butyl-hydroxy phenyl) any one or the combination of several of them of the propionic acid ten in the double lauryls of caprylate and thio-2 acid.
8. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that the thermostabilization
Agent is maleic anhydride and/or epoxidized soybean oil.
9. the degradable mulch with slow-release phosphate fertilizer according to claim 1, which is characterized in that the lubricant
For any one or the combination of several of them in pentaerythritol stearate, zinc stearate, calcium stearate and oleamide.
10. the preparation method of the degradable mulch with slow-release phosphate fertilizer described in claim 1, which is characterized in that it is wrapped
Include following steps：
The degradation plastic of formula ratio, phosphatization lignin, plasticizer, chain extender, antioxidant, heat stabilizer and lubricant are existed
After being sufficiently mixed in high mixer, through dual-screw pelletizer extruding pelletization, the plastics compound particle of phosphatization lignin modification is obtained；Phosphorus
The plastics compound particle for changing lignin modification has effects that the degradable mulch of slow-release phosphate fertilizer through Blown Film.
11. preparation method according to claim 10, which is characterized in that in high mixer, temperature is 100~110 DEG C, rotating speed
For 800~1000rpm, incorporation time is 10~20min；When extruding pelletization, temperature is 120~180 DEG C；When Blown Film, temperature
Degree is 125~150 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810148531.3A CN108485207A (en) | 2018-02-13 | 2018-02-13 | A kind of degradable mulch and preparation method thereof with slow-release phosphate fertilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088047A (en) * | 2021-04-02 | 2021-07-09 | 中国农业科学院蔬菜花卉研究所 | Application of full-biodegradable mulching film in production of melons in autumn and winter stubbles |
| CN114163787A (en) * | 2021-11-23 | 2022-03-11 | 武汉俱源科技有限公司 | Biodegradable fertilizer-effect agricultural film and preparation method and application thereof |
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| 王娟等: ""黑液中木质素的提取及其资源化利用的研究进展"", 《黑龙江造纸》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088047A (en) * | 2021-04-02 | 2021-07-09 | 中国农业科学院蔬菜花卉研究所 | Application of full-biodegradable mulching film in production of melons in autumn and winter stubbles |
| CN114163787A (en) * | 2021-11-23 | 2022-03-11 | 武汉俱源科技有限公司 | Biodegradable fertilizer-effect agricultural film and preparation method and application thereof |
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Application publication date: 20180904 |