CN116965419A - Controlled slow-release herbicide and preparation method thereof - Google Patents
Controlled slow-release herbicide and preparation method thereof Download PDFInfo
- Publication number
- CN116965419A CN116965419A CN202310940445.7A CN202310940445A CN116965419A CN 116965419 A CN116965419 A CN 116965419A CN 202310940445 A CN202310940445 A CN 202310940445A CN 116965419 A CN116965419 A CN 116965419A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- hydrotalcite
- acrylic acid
- herbicide
- release
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004009 herbicide Substances 0.000 title claims abstract description 47
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000005562 Glyphosate Substances 0.000 claims abstract description 203
- 229940097068 glyphosate Drugs 0.000 claims abstract description 203
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 164
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 163
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 163
- -1 glyphosate anions Chemical class 0.000 claims abstract description 133
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229920000642 polymer Polymers 0.000 claims abstract description 96
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000011229 interlayer Substances 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 50
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 35
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical class COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 21
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000013270 controlled release Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- BFHKYHMIVDBCPC-UHFFFAOYSA-N 1,3,5,7-tetrahydro-[1,3]oxazolo[3,4-c][1,3]oxazol-7a-ylmethanol Chemical compound C1OCN2COCC21CO BFHKYHMIVDBCPC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- 238000009830 intercalation Methods 0.000 abstract description 11
- 230000002687 intercalation Effects 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 5
- 238000013268 sustained release Methods 0.000 abstract description 5
- 239000012730 sustained-release form Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 56
- 239000010410 layer Substances 0.000 description 55
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 39
- 239000012153 distilled water Substances 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- 238000002411 thermogravimetry Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000003971 tillage Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- GEVWHIDSUOMVRI-UHFFFAOYSA-N anisatin Chemical compound CC1(O)C(OC(=O)C2O)CC22C(C)CC(O)C2(O)C21COC2=O GEVWHIDSUOMVRI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
Abstract
The invention belongs to the technical field of pesticide sustained release agents, and particularly relates to a controllable sustained release herbicide and a preparation method thereof. The controlled slow release herbicide is hydrotalcite containing glyphosate and polymer. And (3) preparing hydrotalcite intercalated by glyphosate anions and acrylic acid radicals by a coprecipitation method, and carrying out polymerization reaction in the hydrotalcite to obtain the controlled and slow-release herbicide. The controllable slow-release herbicide disclosed by the invention is composed of glyphosate intercalation hydrotalcite and polymers between layers and particles, the glyphosate intercalation structure is stable, the herbicide is light-resistant, and is suitable for most types of soil, and meanwhile, due to the blocking of the polymers between layers and particles, the movement of the glyphosate is delayed, so that the herbicide has a long-acting slow-release effect.
Description
Technical Field
The invention belongs to the technical field of pesticide sustained release agents, and particularly relates to a controllable sustained release herbicide and a preparation method thereof.
Background
The herbicide is a pesticide for eliminating or controlling weed growth, and is mainly used for weeds or shrubs in farmlands, pastures, river courses, highways, park forest fire-fighting roads and the like. The application of the herbicide not only can obviously improve the weeding efficiency, save labor and reduce economic loss caused by weeds, but also creates conditions for changing the cultivation mode, such as changing thin planting into close planting, developing rice aircraft sowing, developing no-tillage cultivation, cultivating by a low-tillage method and the like. The traditional herbicide is affected by environmental factors such as dissolution, evaporation, decomposition and the like and unreasonable factors of artificial application in the using process, and has low actual utilization rate. This not only causes great economic loss, but also causes harm to human health and pollution to natural environment. Thus, in recent decades, researchers around the world have made tremendous efforts to increase herbicide utilization, reduce environmental and human hazards, with slow release of herbicides being one of the important directions of research. The development of a novel environment-friendly slow-release herbicide carrier realizes high drug loading by controlling the structure of a carrier material and adjusting the interaction between the carrier and the herbicide, and the controllable loading and release of the herbicide becomes a hot topic of herbicide slow release.
Glyphosate has the chemical name of N- (methyl phosphate) glycine and the chemical formula of C 3 H 8 NO 5 P is an organic phosphine systemic conduction type broad-spectrum biocidal herbicide, and is mainly prepared by inhibiting enolpyruvylshikimin phosphate synthase in plants, so that the conversion of shikimin to phenylalanine, tyrosine and tryptophan is inhibited, the protein synthesis is interfered, and the plants die. As a non-selective and residue-free biocidal herbicide, the glyphosate is very effective in killing perennial rooting weeds, can prevent and kill monocotyledonous and dicotyledonous, annual and perennial, herbaceous and shrub plants and other plants of more than 40 families, and is widely used in rubber, mulberry, tea, orchards and sugarcane fields.
Layered composite metal hydroxide (Layered Double Hydroxides), also known as hydrotalcite-like compound, may be abbreviated as LDHs, consisting of hydrotalcite and hydrotalcite-like compound. LDHs are a class of ionic layered compounds consisting of positively charged brucite-like layers and interlayer regions containing charge compensation, with anions and small solvent molecules (typically water molecules) being interlayer guests. The metal cations occupy the centers of the edge-sharing octahedra, and the vertices are connected with hydroxide ions to form an infinite two-dimensional lamellar structure. The chemical composition of LDHs is [ M ] 2+ 1-x M 3+ x (OH) 2 ] x+ (A n– ) x/n ·mH 2 O。M 2+ And M 3+ I.e. divalent and trivalent metal cations, with exchangeable anions A between the layers n- To maintain charge balance. The elements among hydrotalcite laminates have strong covalent bond effect, interlayer anions and the laminates are attracted to each other by electrostatic attraction, and the whole crystal is electrically neutral. Because of the adjustability of laminate metal ions and interlayer anions, hydrotalcite-like materials have been widely used in the fields of catalysis, absorption, drug release, ion exchange and the like.
The release performance of the glyphosate intercalated magnesium aluminum hydrotalcite MgAl-LDH-gly is studied, the chemical report of higher schools, vol 25, no 10, 1869-1874, zhang Xian and the like adopt a nucleation/crystallization isolation method to assemble the glyphosate intercalated hydrotalcite between water talcum layers, the physicochemical properties of the intercalated hydrotalcite are analyzed, the release performance of the glyphosate in water and sodium carbonate solution is inspected, and the release mechanism is primarily discussed. In the method, glyphosate is easily exchanged by other anions, so that the slow release time is very short (when the pH value is 7.6, the slow release reaches equilibrium at 70h, when the pH value is 6.6, the slow release reaches equilibrium at 70h, when the pH value is 5.6, the slow release reaches equilibrium at 81 h), and in addition, the method does not mention the influence of an interlayer polymer on the slow release rate.
Preparation of AA/AMPS-LDH intercalation polymerization and organic/inorganic composite super absorbent resin and performance research, the paper of Beijing university of chemical industry, guo Fang adopts an ion exchange method to prepare Acrylic Acid (AA), 2-acrylamido-2-methylsulfonic Acid (AMPS) single intercalation hydrotalcite and co-intercalation hydrotalcite, and in-situ polymerization reaction of AA and AMPS between hydrotalcite layers is realized under the condition of external initiator heat treatment. The structural characteristics of intercalated hydrotalcite and polymerized hydrotalcite materials are studied by adopting analytical means such as XRD. However, the study did not relate to the effect of the interlayer polymer on interlayer movement and slow release properties of other anions between the layers.
Chinese patent CN1507778A discloses a sustained release agent of glyphosate with supermolecular structure and its preparation method, which uses anion layered material LDH as main body, glyphosate as intercalation guest, and the mixed salt solution prepared by two soluble metal salts and alkaline solution of glyphosate are assembled in one step to obtain the GLy-LDHs with supermolecular structure, the chemical formula is: (M) 2+ ) 1－x (M 3+ ) x (OH) 2 (GLY － ) a1 (GLY 2－ ) a2 (GLY 3－ ) a3 (B n－ ) b ·mH 2 O. The method does not mention the effect of the interlayer polymer on the slow release rate.
Although glyphosate is widely applied in the weeding field, the glyphosate has the defects that the glyphosate is far away from crops when in use, is easy to complex with calcium, magnesium, aluminum and the like to lose activity, and needs to be sprayed regularly, so that the application of the glyphosate is limited. The glyphosate is intercalated between hydrotalcite layers, and the slow release effect can be achieved, but the slow release speed is still high and the speed is not controllable.
Disclosure of Invention
The invention aims to provide a controllable slow-release herbicide which consists of glyphosate intercalated hydrotalcite and polymers between layers and particles, and the movement of the glyphosate is delayed due to the blocking of the polymers between the layers and the particles, so that the controllable slow-release herbicide has a long-acting slow-release effect; the invention also provides a preparation method of the controllable slow-release herbicide.
The controllable slow-release herbicide disclosed by the invention is hydrotalcite containing glyphosate and a polymer, and has the following chemical formula:
[(M 2+ ) 1-x (M 3+ ) x (OH) 2 ] x+ (gyl 2- ) a (AA - ) b (D) c ·mH 2 O
wherein x=0.25-0.33, 2a+b=x, m=3-6, c=0.5-1, m is the number of interlayer crystal water moleculesAmount of M 2+ Is a divalent metal ion, M 3+ Is trivalent metal ion gyl 2- Is glyphosate acid radical, AA - Is acrylate, and D is acrylate.
Said M 2+ Is Mg 2+ 、Ni 2+ Or Zn 2+ One of them.
Said M 3+ Is Al 3+ 。
The acrylic ester is one of Methyl Acrylate (MA), ethyl Acrylate (EA) or Propyl Acrylate (PA).
The preparation method of the controllable slow-release herbicide comprises the following steps:
(1) Co-precipitation process to prepare hydrotalcite intercalated with glyphosate anion and acrylate:
will M 2+ Soluble salts of (C) and M 3+ Preparing a mixed solution A by using soluble salts of glyphosate and acrylic acid, and dissolving the glyphosate and the acrylic acid in an alkali solution to obtain a mixed solution B; n at room temperature 2 Stirring the mixed solution A and the mixed solution B under the protection condition, and regulating the pH value to obtain slurry; crystallizing, washing and drying slurry to obtain hydrotalcite intercalated by glyphosate anions and acrylic acid radical;
(2) Polymerization in hydrotalcite:
adding the hydrotalcite intercalated by glyphosate anions and acrylic acid radical obtained in the step (1) into an aqueous-ethanol solution of acrylic acid ester, then adding potassium persulfate, soaking, and N 2 Heating to 70-75 ℃ under protection, reacting for 2-4h under stirring, heating to 85-90 ℃, and reacting for 2-3h under stirring; and washing and drying the product to obtain the controlled slow-release herbicide.
M as described in step (1) 2+ The soluble salt of (C) is its hydrochloride or nitrate, M 3+ Is its hydrochloride or nitrate; in the mixed solution A, M 2+ Soluble salts of (C) and M 3+ The same species as the soluble salts of (a).
M as described in step (1) 2+ And M is as follows 3+ The molar ratio of (C) is 2-3, M in the mixed solution A 2+ The molar concentration of (C) is 0.1-1.0M, M in the mixed solution A 3+ The molar concentration of (2) is 0.05-0.5M。
The alkali solution in the step (1) is NaOH solution, and the molar concentration of the alkali solution is 1.0-5.0M.
The ratio of the glyphosate to the acrylic acid to the alkali solution in the step (1) is 4-10:2-5:200, wherein the glyphosate is calculated by g, the acrylic acid is calculated by g, and the alkali solution is calculated by ml.
The pH value of the step (1) is adjusted to 7.5-8.5 by adopting 0.1-5.0M NaOH solution.
The crystallization temperature in the step (1) is 60-90 ℃ and the crystallization time is 12-72h.
The drying temperature in the step (1) is 50-90 ℃ and the drying time is 20-48h.
The concentration of the acrylic ester in the water-ethanol solution of the acrylic ester in the step (2) is 40-80g/L, the volume ratio of water to ethanol is 3:2-9, and the mass ratio of the acrylic ester to potassium persulfate is 25:1-2.
The soaking time in the step (2) is 5-8h.
The drying temperature in the step (2) is 50-90 ℃ and the drying time is 20-48h.
The controlled slow-release herbicide is hydrotalcite co-assembled by glyphosate and a polymer, the polymer comprises an interlayer polymer and a polymer among particles, wherein the interlayer polymer is polymerized by acrylate and acrylic ester, and the polymer among particles is polymerized by acrylic ester.
The preparation method of the controllable slow-release herbicide comprises the following specific steps:
(1) Co-precipitation process to prepare hydrotalcite intercalated with glyphosate anion and acrylate:
will M 2+ Soluble salts of (C) and M 3+ Preparing a mixed solution A by using soluble salts of glyphosate and acrylic acid, and dissolving the glyphosate and the acrylic acid in an alkali solution to obtain a mixed solution B; n at room temperature 2 Under the protection condition, adding the mixed solution A and the mixed solution B into a four-mouth bottle by adopting a double-drop method, stirring, regulating the pH value to 7.5-8.5 by using NaOH solution, crystallizing the obtained slurry at 60-90 ℃ for 12-72h, and removing CO from the product 2 Washing with water to neutrality; taking out the sample, drying at 50-90deg.C for 20-48 hr to obtain glyphosate yinHydrotalcite intercalated with ions and acrylic acid radical;
(2) Polymerization in hydrotalcite:
preparing an aqueous-ethanol solution of acrylic ester, adding the glyphosate anion and the hydrotalcite intercalated by acrylic acid radical obtained in the step (1) into the solution, adding potassium persulfate, and soaking for 5-8h, N 2 Heating to 70-75 deg.C under stirring for 2-4 hr, heating to 85-90 deg.C, and stirring for 2-3 hr. CO removal of the product 2 Washing with water to neutrality, and drying at 50-90deg.C for 20-48 hr to obtain controlled-release herbicide.
According to the invention, the glyphosate is intercalated between hydrotalcite layers, then an acrylic acid-acrylic acid ester copolymer is introduced between hydrotalcite layers, and acrylic acid ester self-polymers are introduced into gaps of hydrotalcite particles, so that the movement of the glyphosate in hydrotalcite can be obviously blocked by the polymer, and the controlled glyphosate slow release is realized.
According to the invention, the glyphosate anion and the acrylic acid radical are intercalated into the hydrotalcite interlayer, and the glyphosate anion can form a hydrogen bond with the acrylic acid radical, so that the stability of the glyphosate between the layers is improved; and then the hydrotalcite is put into water-ethanol solution of acrylic ester for full soaking, firstly, potassium persulfate is used for initiating polymerization of acrylic ester in gaps of hydrotalcite particles at a lower temperature, and then the temperature is increased for initiating polymerization of acrylic acid radical/acrylic ester among hydrotalcite layers, so that hydrotalcite containing glyphosate and polymer is obtained.
The reason why the gradient heating polymerization is adopted in the invention is as follows:
the difficulty of the inter-layer polymerization of hydrotalcite is different from that of the inter-particle polymerization, so that the inter-layer polymerization is difficult and a higher temperature is required. If the polymerization is carried out at a relatively high temperature at the beginning, the degree of polymerization between layers and between particles is too high, and if the temperature is too high, delamination of the hydrotalcite laminate may be caused. Therefore, the invention adopts a gradient heating polymerization mode to control the polymerization degree between layers and between particles, and avoids overlarge polymerization degree.
Because the volume of the acrylic acid and the acrylic ester is smaller and is convenient to enter hydrotalcite interlamination and particle gaps, the size of the interlaminar copolymer is equivalent to the interlamellar spacing by controlling the polymerization condition, the volume of the self-polymer in the particle gaps is equivalent to the gap size, the purposes of preventing glyphosate ions from moving between hydrotalcite interlamination and in the particle gaps can be achieved, and the hydrotalcite laminate is not peeled off, so that the effect of controllable slow release is achieved.
The beneficial effects of the invention are as follows:
(1) The controllable slow-release herbicide has the advantage of wide application range, can be used at the temperature of 0-40 ℃, is suitable for acidic or alkaline soil, and does not influence the slow-release effect even if being irradiated for a long time.
(2) The controlled-release rate of the glyphosate in the controlled-release herbicide is influenced by the steric hindrance of the polymer, and researches show that the larger the polymer molecule is, the slower the slow-release rate of the glyphosate is, otherwise, the slow-release of the glyphosate is quickened. The invention controls the polymerization degree of polymers between layers and among particles by changing the polymerization reaction condition and adjusting the quantity of monomers, thereby regulating and controlling the slow release rate of the glyphosate.
(3) The hydrotalcite material prepared by the invention is subjected to X-ray diffraction characterization, and the result shows that the glyphosate and acrylic acid radical co-intercalation hydrotalcite is successfully prepared first, and then acrylic acid-acrylic acid ester polymerization between hydrotalcite layers is realized. The XRD structural parameters show that the glyphosate anions adopt a monolayer arrangement mode that the axes of the glyphosate anions are perpendicular to the layers of hydrotalcite, and the acrylic acid radical molecules are smaller, and the interlayer spacing is determined by the glyphosate anions. After polymerization, the interlayer spacing and the unit cell parameter a value are not changed obviously, which indicates that the hydrotalcite structure is kept good after polymerization, and the glyphosate anions are still among hydrotalcite layers. After hydrotalcite containing glyphosate and polymer is dissolved in an acid solution layer plate, the molecular weight of the polymer is measured by a boiling point elevation method, and the molecular weight is calculated to be 4000-10000, so that the polymerization reaction is proved. From the aspect that the product releases glyphosate in aqueous solution, each gram of hydrotalcite containing glyphosate and polymer can release glyphosate for more than 77 days.
(4) The controllable slow-release herbicide disclosed by the invention is composed of glyphosate intercalation hydrotalcite and polymers between layers and particles, the glyphosate intercalation structure is stable, the herbicide is light-resistant, and is suitable for most types of soil, and meanwhile, due to the blocking of the polymers between layers and particles, the movement of the glyphosate is delayed, so that the herbicide has a long-acting slow-release effect. Therefore, hydrotalcite containing glyphosate and polymer can be used as a slow-release herbicide, and has high application value.
Drawings
FIG. 1 is a schematic structural diagram of a controlled slow-release herbicide of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of hydrotalcite comprising glyphosate and a polymer prepared in example 1; in the figure: a is nitrate radical intercalated hydrotalcite, b is hydrotalcite intercalated by glyphosate anions and acrylic acid radical, c is hydrotalcite containing glyphosate and polymer;
FIG. 3 is a thermogravimetric analysis of hydrotalcite containing glyphosate and polymer prepared in example 1.
FIG. 4 is a graph of the release profile of glyphosate from hydrotalcite containing glyphosate and polymer prepared in example 5.
Detailed Description
The invention is further described below with reference to examples.
Example 1
(1) 35.8g Zn (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 6.8g of glyphosate and 2.9g of acrylic acid were dissolved in 200ml of a 1.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 0.1mol/L NaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 60deg.C for 72 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 50deg.C for 48 hr to obtain hydrotalcite gyl/AA-LDHs intercalated with glyphosate anion and acrylate.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 Heating to 75 ℃ under stirring for 2h, heating to 85 ℃ and reacting for 3h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (EA) 0.72 ·4H 2 O. The X-ray powder diffraction pattern of the product is shown in FIG. 2. As can be seen from fig. 2, hydrotalcite has a more ideal hexagonal layered structure, and has a single crystal phase and a better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization.
After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The hydrotalcite containing glyphosate and polymer was subjected to thermogravimetric analysis (air) using a thermogravimetric/differential thermal integrated thermal analyzer, and the thermogravimetric analysis spectrum is shown in fig. 3. As can be seen from fig. 3, as the temperature increases, the hydrotalcite quality decreases, and the weight loss process can be roughly divided into three stages. A first stage, room temperature to about 180 ℃, of losing adsorbed water and bound water and other volatile components in the hydrotalcite; in the second stage, the temperature is 180-340 ℃, and a significant exothermic peak is observed in a DTA curve when the weight is lost, so that the process of burning and decomposing the high polymer in the hydrotalcite gaps in the air is adopted; in the third stage, the obvious exothermic peak is also observed in the DTA curve at the same time of weight loss at 340-470 ℃, and is the combustion and decomposition process of hydrotalcite interlayer intercalation polymer and glyphosate in air. The results show that the high polymers exist between hydrotalcite layers and among gaps, the hydrotalcite laminate can effectively protect the interlayer high polymers and the glyphosate, the high temperature resistance of the hydrotalcite laminate is improved, and the temperature at which combustion decomposition occurs is obviously improved. In contrast, the thermal decomposition temperature of the inter-hydrotalcite-void polymers is significantly lower.
In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the glyphosate is basically released and balanced after 83 days, and the total release amount is 0.0724g.
Example 2
(1) 31.0g of Mg (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 5.0g of glyphosate and 4.3g of acrylic acid were dissolved in 200ml of a 1.5mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 7.5 by using 5.0mol/L NaOH solution, so that slurry is obtained. Crystallizing the obtained slurry at 90deg.C for 12 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 90 deg.C for 20 hr to obtain hydrotalcite gyl/AA-LDHs intercalated with glyphosate anions and acrylate.
(2) Adding 7.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:1) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.50g of potassium persulfate, and soaking for 8h, N 2 Heating to 75 ℃ under stirring for 2h, heating to 90 ℃ and reacting for 2.5h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 90deg.C for 20 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Mg) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.09 (AA - ) 0.15 (EA) 0.85 ·5H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.38nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.90nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is not substantially affected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, glyphosate is continuously released by soaking 1g of hydrotalcite in 100mL of distilled water, and the glyphosate is basically released and balanced after 96 days, and the total release amount is 0.0501g.
Example 3
(1) 34.8g Ni (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.4g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 9.0g of glyphosate and 2.8g of acrylic acid were dissolved in 200ml of a 3.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8.5 by using 1.0mol/L NaOH solution, so that slurry is obtained. Crystallizing the obtained slurry at 80deg.C for 30 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 50deg.C for 48 hr to obtain hydrotalcite intercalated with glyphosate anions and acrylic acid radical, gyl/AA-LDHs.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 3:2) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.20g of potassium persulfate, and soaking for 6h, N 2 Heating to 72 ℃ under protection, reacting for 3h under stirring, heating to 88 ℃, and reacting for 2.5h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 70deg.C for 30 hr to obtain the final product containing glyphosate and poly (glyphosate)Hydrotalcite of the compound.
In this example, the product chemical formula is: [ (Ni) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.14 (AA - ) 0.05 (EA) 0.66 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the glyphosate is basically released and balanced after 79 days, and the total release amount is 0.0926g.
Example 4
(1) 16.4g ZnCl was weighed out 2 And 14.5g AlCl 3 ﹒6H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 7.0g of glyphosate and 3.0g of acrylic acid were dissolved in 200ml of 2.0mol/L NaOH solution to obtain a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 2.0mol/LNaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 80deg.C for 30 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 70deg.C for 30 hr to obtain hydrotalcite intercalated with glyphosate anions and acrylic acid radical, gyl/AA-LDHs.
(2) 5.0g of ethyl acrylate was added to 100mL of a water-ethanol solution (water and ethanolThe volume ratio is 1: 1) Adding the obtained water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of hydrotalcite gyl/AA-LDHs intercalated by glyphosate anions and acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 7h, N 2 Heating to 73 ℃ under protection, reacting for 3h under stirring, heating to 88 ℃, and reacting for 2h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 80deg.C for 25 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (EA) 0.70 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. This lamina expansion suggests successful intercalation of glyphosate anions and acrylates between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the glyphosate is basically released and balanced after 79 days, and the total release amount is 0.0733g.
Example 5
(1) 53.5g Zn (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 In waterA mixed solution A was prepared, and 6.0g of glyphosate and 4.0g of acrylic acid were dissolved in 200ml of a 1.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 2.0mol/L NaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 80deg.C for 30 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 70deg.C for 30 hr to obtain hydrotalcite intercalated with glyphosate anions and acrylic acid radical, gyl/AA-LDHs.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:1) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 Heating to 75 ℃ under stirring for reaction for 4 hours, heating to 85 ℃, and reacting for 2 hours under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 80deg.C for 25 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.75 (Al 3+ ) 0.25 (OH) 2 ] 0.25+ (gyl 2- ) 0.08 (AA - ) 0.09 (EA) 0.78 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.38nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.90nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. Thermogravimetric analysis of the product revealed the presence of both hydrotalcite interlayers and interstitialsIn the high polymer, the thermal decomposition temperature of the interlayer high polymer and the glyphosate is obviously higher than that of the high polymer in the gaps due to the protective effect of the laminate. In addition, the glyphosate is continuously released by soaking 1g of hydrotalcite in 100mL of distilled water, and the balance is basically released after 77 days, and the total release amount is 0.0483g.
Example 6
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of methyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of methyl acrylate, adding the water-ethanol solution of methyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 8h, wherein N is the same as that of the solution of methyl acrylate 2 Heating to 70 ℃ under stirring for 2h, heating to 90 ℃ and reacting for 3h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (MA) 0.84 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the interlayer and the gap between hydrotalcite layers have high polymer, and the thermal decomposition temperature of the interlayer high polymer and the glyphosate is obviously higher than that of the gap due to the protection effect of the laminateMedium and high polymers. In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the balance is basically released after 81 days, and the total release amount is 0.0756g.
Example 7
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of propyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of the propyl acrylate, adding the water-ethanol solution of the propyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 Heating to 70 ℃ under stirring for 2h, heating to 90 ℃ and reacting for 3h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (PA) 0.51 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, after 1g of hydrotalcite was immersed in 100mL of distilled water, glyphosate was continuously released, after 87 daysThe equilibrium is essentially released and the total release is 0.0808g.
Example 8
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 Heating to 75 ℃ under stirring for 2h, heating to 85 ℃ and reacting for 2h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (EA) 0.70 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, glyphosate is continuously released by soaking 1g of hydrotalcite in 100mL of distilled water, and the glyphosate is basically released and balanced after 80 days, and the total release amount is 0.0736g.
Example 9
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 Heating to 75 ℃ under stirring for 2h, heating to 90 ℃ and reacting for 3h under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.12 (AA - ) 0.09 (EA) 0.78 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the glyphosate is basically released and balanced after 89 days, and the total release amount is 0.0715g.
Example 10
(1) 35.8g Zn (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 6.8g of glyphosate and 5.0g of acrylic acid were dissolved in 200ml of a 1.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 0.1mol/L NaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 60deg.C for 72 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 50deg.C for 48 hr to obtain hydrotalcite gyl/AA-LDHs intercalated with glyphosate anion and acrylate.
(2) Step (2) was performed as in example 1.
In this example, the product chemical formula is: [ (Zn) 2+ ) 0.67 (Al 3+ ) 0.33 (OH) 2 ] 0.33+ (gyl 2- ) 0.10 (AA - ) 0.13 (EA) 0.71 ·4H 2 O. The product is proved by X-ray powder diffraction to have ideal hexagonal lamellar structure, single crystalline phase and better crystallinity. D of glyphosate anion and acrylate intercalated hydrotalcite gyl/AA-LDHs 003 The interlayer spacing is 1.37nm, the thickness of the hydrotalcite laminate is subtracted by 0.48nm, the height of the inner space is 0.89nm, which is equivalent to the height of the glyphosate anion, and the result shows that the glyphosate anion and the acrylic acid radical are successfully inserted between LDHs layers. D after polymerization 003 The interlayer spacing remains substantially unchanged at 1.38nm, indicating that the arrangement of glyphosate anions between the layers is substantially unaffected during polymerization. After the product was dissolved in the laminate with an acid, the molecular weight of the polymer was measured by a boiling point elevation method, confirming that polymerization took place. The thermogravimetric analysis of the product shows that the polymers exist between hydrotalcite layers and among gaps, and the thermal decomposition temperature of the interlayer polymers and glyphosate is obviously higher than that of the polymers in the gaps due to the protective effect of the laminate. In addition, by immersing 1g of the hydrotalcite in 100mL of distilled water, glyphosate is continuously released, and the glyphosate is basically released and balanced after 93 days, and the total release amount is 0.0621g.
Comparative example 1
35.8g Zn (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 6.8g of glyphosate was dissolved in 200ml of a 1.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 0.1mol/L NaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 60deg.C for 72 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 50deg.C for 48 hr to obtain hydrotalcite gyl-LDHs intercalated with glyphosate anions.
1g of this hydrotalcite was immersed in 100mL of distilled water, and after 13 days it was substantially released from equilibrium. Comparative example 1 is only a hydrotalcite intercalated with glyphosate, the structure of which is not blocked by polymer, and the slow release speed of glyphosate from hydrotalcite is faster.
Comparative example 2
(1) 35.8g Zn (NO) was weighed out 3 ) 2 ﹒6H 2 O and 22.6g Al (NO) 3 ) 3 ﹒9H 2 O is dissolved in 200ml to remove CO 2 A mixed solution A was prepared in water, and 6.8g of glyphosate and 2.9g of acrylic acid were dissolved in 200ml of a 1.0mol/L NaOH solution to give a mixed solution B. N at room temperature 2 Under the protection condition, the mixed solution A and the mixed solution B are added into a four-mouth bottle by adopting a double-drop method, and are strongly stirred, and the pH value is regulated to 8 by using 0.1mol/L NaOH solution, so as to obtain slurry. Crystallizing the obtained slurry at 60deg.C for 72 hr, removing CO 2 Washing with water to neutrality, taking out the sample, and drying at 50deg.C for 48 hr to obtain hydrotalcite gyl/AA-LDHs intercalated with glyphosate anion and acrylate.
(2) 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) is added into a four-mouth bottle, 10g of hydrotalcite gyl/AA-LDHs intercalated by glyphosate anions and acrylic acid radical in the step (1) is added, 0.25g of potassium persulfate is added, and the mixture is added into a four-mouth bottle in N 2 The reaction is carried out for 4 hours at 85 ℃ under the protection and stirring, and the CO is removed from the product 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain glyphosate and polyacrylate co-intercalated hydrotalcite gyl/PAA-LDHs.
1g of this hydrotalcite was immersed in 100mL of distilled water, and after 47 days it was substantially released from equilibrium. Comparative example 2 is a hydrotalcite intercalated with glyphosate and acrylate, and initiator was used to promote the polymerization of acrylate between hydrotalcite layers. In comparative example 2, only the interlaminar acrylic acid radical forms a polymer, the blocking effect on the glyphosate in hydrotalcite is still smaller, and the slow release speed of the glyphosate from hydrotalcite is faster.
Comparative example 3
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of propyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of the propyl acrylate, adding the water-ethanol solution of the propyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 The mixture was heated to 70℃under stirring for 2 hours. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer.
1g of this hydrotalcite was immersed in 100mL of distilled water, and after 31 days it was substantially released from equilibrium. In comparative example 3, because the polymerization temperature is low, the initiator promotes the polymerization of the acrylic ester among particles, only part of the acrylic acid radical and the acrylic ester among layers are polymerized, the volume of the formed polymer is small, the blocking effect on the glyphosate in hydrotalcite is small, and the slow release speed of the glyphosate from hydrotalcite is high.
Comparative example 4
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of propyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of the propyl acrylate, adding the water-ethanol solution of the propyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), adding 0.25g of potassium persulfate, and soaking for 5h, N 2 The mixture is heated to 90 ℃ under protection and is reacted for 10 hours under stirring. CO removal for products 2 Washing with water to neutrality, and drying at 50deg.C for 48 hr to obtain hydrotalcite containing glyphosate and polymer, wherein X-ray powder diffraction shows that part of hydrotalcite has been exfoliated.
1g of this hydrotalcite was immersed in 100mL of distilled water, and after 12 days it was substantially released from equilibrium.
Comparative example 5
(1) Step (1) was performed as in example 1.
(2) Adding 5.0g of ethyl acrylate into 100mL of water-ethanol solution (the volume ratio of water to ethanol is 1:3) to obtain the water-ethanol solution of ethyl acrylate, adding the water-ethanol solution of ethyl acrylate into a four-mouth bottle, adding 10g of glyphosate anion and hydrotalcite gyl/AA-LDHs intercalated by acrylic acid radical obtained in the step (1), soaking for 10h, and removing a large amount of CO 2 Washing with water for 5 times. Then 100mL of water-ethanol solution (volume ratio of water to ethanol is 1:3) is added, 0.25g of potassium persulfate and N 2 Heating to 75 ℃ under stirring for 2h, heating to 85 ℃ and reacting for 3h under stirring. And drying the product at 50 ℃ for 48 hours to obtain hydrotalcite containing glyphosate and polymer, wherein the hydrotalcite is provided with high polymer between layers and no polymer in gaps.
1g of this hydrotalcite was immersed in 100mL of distilled water, and after 53 days it was substantially released from equilibrium. In comparative example 5, a large amount of CO was removed before polymerization 2 Washing with water for 5 times, and cleaning ethyl acrylate in hydrotalcite gaps. The polymerization reaction only forms high polymer between hydrotalcite layers, and the gaps are free of polymer, so that the overall inhibition effect of the glyphosate in the hydrotalcite is small, and the slow release speed of the glyphosate from the hydrotalcite is high.
As can be seen from examples 1-10, hydrotalcite containing glyphosate and polymer can release glyphosate for 77 days or more, while comparative examples 1-5 all have shorter glyphosate release times. Therefore, the hydrotalcite containing the glyphosate and the polymer is adopted, so that the long-acting slow release effect of the glyphosate from the hydrotalcite is ensured, and the slow release time can be changed by changing the addition amount of the monomer.
Claims (10)
1. The controlled slow release herbicide is characterized by comprising hydrotalcite containing glyphosate and a polymer, and has the following chemical formula:
[(M 2+ ) 1-x (M 3+ ) x (OH) 2 ] x+ (gyl 2- ) a (AA - ) b (D) c ·mH 2 O
wherein x=0.25-0.33, 2a+b=x, m=3-6, c=0.5-1, M is the number of interlayer crystal water molecules, M 2+ Is a divalent metal ion, M 3+ Is trivalent metal ion gyl 2- Is glyphosate acid radical, AA - Is acrylate, and D is acrylate.
2. A controlled slow release herbicide as claimed in claim 1, characterised in that M 2+ Is Mg 2+ 、Ni 2+ Or Zn 2+ One of (a), M 3+ Is Al 3+ 。
3. The controlled release herbicide of claim 1, wherein the acrylate is one of methyl acrylate, ethyl acrylate or propyl acrylate.
4. A process for the preparation of a controlled release herbicide as claimed in any one of claims 1 to 3 comprising the steps of:
(1) Co-precipitation process to prepare hydrotalcite intercalated with glyphosate anion and acrylate:
will M 2+ Soluble salts of (C) and M 3+ Preparing a mixed solution A by using soluble salts of glyphosate and acrylic acid, and dissolving the glyphosate and the acrylic acid in an alkali solution to obtain a mixed solution B; n at room temperature 2 Stirring the mixed solution A and the mixed solution B under the protection condition, and regulating the pH value to obtain slurry; crystallizing, washing and drying slurry to obtain hydrotalcite intercalated by glyphosate anions and acrylic acid radical;
(2) Polymerization in hydrotalcite:
adding the hydrotalcite intercalated by glyphosate anions and acrylic acid radical obtained in the step (1) into an aqueous-ethanol solution of acrylic acid ester, then adding potassium persulfate, soaking, and N 2 Heating to 70-75 ℃ under protection, reacting for 2-4h under stirring, heating to 85-90 ℃, and reacting for 2-3h under stirring; and washing and drying the product to obtain the controlled slow-release herbicide.
5. The method for producing a controlled-release herbicide as claimed in claim 4, characterized in that M is as defined in the step (1) 2+ The soluble salt of (C) is its hydrochloride or nitrate, M 3+ Is its hydrochloride or nitrate; in the mixed solution A, M 2+ Soluble salts of (C) and M 3+ The same species as the soluble salts of (a); m is M 2+ And M is as follows 3+ The molar ratio of (C) is 2-3, M in the mixed solution A 2+ The molar concentration of (C) is 0.1-1.0M, M in the mixed solution A 3+ The molar concentration of (2) is 0.05-0.5M.
6. The method for preparing a controlled-release herbicide as claimed in claim 4, wherein the alkaline solution in the step (1) is NaOH solution, and the molar concentration of the alkaline solution is 1.0-5.0M; the ratio of the glyphosate to the acrylic acid to the alkali solution is 4-10:2-5:200, wherein the glyphosate is calculated by g, the acrylic acid is calculated by g, and the alkali solution is calculated by ml.
7. The method for preparing a controlled-release herbicide as claimed in claim 4, wherein the pH adjustment in the step (1) is carried out by adjusting the pH to 7.5-8.5 with 0.1-5.0M NaOH solution.
8. The method for preparing a controlled-release herbicide as claimed in claim 4, wherein the crystallization temperature in the step (1) is 60-90 ℃, the crystallization time is 12-72h, the drying temperature is 50-90 ℃ and the drying time is 20-48h.
9. The method for preparing a controlled-release herbicide as claimed in claim 4, wherein the concentration of the acrylic ester in the aqueous-ethanol solution of the acrylic ester in the step (2) is 40-80g/L, the volume ratio of water to ethanol is 3:2-9, and the mass ratio of the acrylic ester to potassium persulfate is 25:1-2.
10. The method for preparing a controlled-release herbicide according to claim 4, wherein the soaking time in the step (2) is 5-8 hours, the drying temperature is 50-90 ℃ and the drying time is 20-48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940445.7A CN116965419A (en) | 2023-07-28 | 2023-07-28 | Controlled slow-release herbicide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940445.7A CN116965419A (en) | 2023-07-28 | 2023-07-28 | Controlled slow-release herbicide and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116965419A true CN116965419A (en) | 2023-10-31 |
Family
ID=88470826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310940445.7A Pending CN116965419A (en) | 2023-07-28 | 2023-07-28 | Controlled slow-release herbicide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116965419A (en) |
-
2023
- 2023-07-28 CN CN202310940445.7A patent/CN116965419A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110663683B (en) | Slow-release type weeding and sterilizing double-effect pesticide and preparation method thereof | |
| CN100542966C (en) | Rod hydrotalcite-like compound and preparation method thereof | |
| GB2267085A (en) | Process for producing antimicrobial phosphates | |
| CN100341776C (en) | Method for prenaring spherical hydroxy-apatite nano crystal | |
| KR101207553B1 (en) | Injectable drug carrier comprising layered double hydroxide | |
| CN101194624B (en) | Imidacloprid/hydrotalcite-like compounds nano hybridisation article and method for producing the same | |
| de Castro et al. | Alginate beads containing layered double hydroxide intercalated with borate: A potential slow-release boron fertilizer for application in sandy soils | |
| CN116965419A (en) | Controlled slow-release herbicide and preparation method thereof | |
| CN109694095A (en) | The preparation method of high-ratio surface nano hydrotalcite | |
| CN102631685A (en) | Coprecipitation method for preparing methotrexate/ layered double hydroxides nanocomposite material | |
| CN110622991B (en) | Slow-release phoxim pesticide and preparation method thereof | |
| CN110663682A (en) | Slow-release type double-effect pesticide and preparation method thereof | |
| CN1245079C (en) | Supermolecular structure glyphosate slow release agent and preparing method thereof | |
| CN112806357B (en) | Mepighiaum controlled-release agent and application thereof in chemical regulation of crops | |
| CN101234756A (en) | Method of preparing spherical nano hydroxyapatite material | |
| KR102188686B1 (en) | Light-cleavage metal organic frameworks and method of synthesis therof | |
| JP4759662B2 (en) | Method for producing clay mineral composite material having bioactive function | |
| CN114620698B (en) | Large-particle zirconium phosphate and preparation method thereof | |
| Qiu et al. | Biomimetic synthesis of spherical nano-hydroxyapatite with polyvinylpyrrolidone as template | |
| CN115109588A (en) | Rare earth doped hydrotalcite nanometer optical fertilizer and preparation method and application thereof | |
| KR20090128679A (en) | Controled-release fertilizer comprising layered metal double hydroxide-based reservoir and the preparation method thereof | |
| Bohari et al. | The synthesis and characterization of layered hydroxide salt interleaved with 4-chlorophenoxyacetic acid and its control release study as herbicide | |
| CN105748300A (en) | Strontium nano-hydroxyapatite procyanidine complex and preparation method thereof | |
| CN110734554A (en) | Zn (II) three-dimensional blending coordination polymer and preparation method thereof | |
| CN111153444B (en) | Method for rapidly preparing carbonate hydrotalcite-like single-layer nanosheets at low temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |