CN1010654B - 联吡啶季盐固态除草剂组合物的制备方法 - Google Patents
联吡啶季盐固态除草剂组合物的制备方法Info
- Publication number
- CN1010654B CN1010654B CN85106125A CN85106125A CN1010654B CN 1010654 B CN1010654 B CN 1010654B CN 85106125 A CN85106125 A CN 85106125A CN 85106125 A CN85106125 A CN 85106125A CN 1010654 B CN1010654 B CN 1010654B
- Authority
- CN
- China
- Prior art keywords
- bipyridyl
- algin
- dichloride
- alginic acid
- methyl
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000003839 salts Chemical group 0.000 title claims abstract description 13
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 75
- 229920000615 alginic acid Polymers 0.000 claims abstract description 75
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000000783 alginic acid Substances 0.000 claims description 36
- 229960001126 alginic acid Drugs 0.000 claims description 36
- 150000004781 alginic acids Chemical class 0.000 claims description 36
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- OVLLDIFWPZHRRQ-UHFFFAOYSA-N 3-chloro-2-(3-chloropyridin-2-yl)pyridine Chemical compound ClC1=CC=CN=C1C1=NC=CC=C1Cl OVLLDIFWPZHRRQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005054 agglomeration Methods 0.000 claims description 13
- 230000002776 aggregation Effects 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000004009 herbicide Substances 0.000 claims description 12
- 239000010451 perlite Substances 0.000 claims description 7
- 235000019362 perlite Nutrition 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000000728 ammonium alginate Substances 0.000 claims description 6
- 235000010407 ammonium alginate Nutrition 0.000 claims description 6
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- -1 mosanom Substances 0.000 claims 1
- 235000010408 potassium alginate Nutrition 0.000 claims 1
- 239000000737 potassium alginate Substances 0.000 claims 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 claims 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 claims 1
- 239000004563 wettable powder Substances 0.000 abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 2
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 37
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 239000000908 ammonium hydroxide Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000002036 drum drying Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001767 cationic compounds Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- INFDPOAKFNIJBF-UHFFFAOYSA-N paraquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 INFDPOAKFNIJBF-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100493820 Caenorhabditis elegans best-1 gene Proteins 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007058 Halophila ovalis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- LGDAGYXJBDILKZ-UHFFFAOYSA-N [2-methyl-1,1-dioxo-3-(pyridin-2-ylcarbamoyl)-1$l^{6},2-benzothiazin-4-yl] 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=CC=CC=N1 LGDAGYXJBDILKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009333 weeding Methods 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- 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
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明涉及吡啶季盐固态除草剂组合物制备方法,该固态组合物是吡啶盐和藻朊的络合物,是干的、自由流动的可湿性粉末。
Description
联吡啶鎓季盐例如按美国专利4,118,218所载是有效的除草剂。其中,百草枯(1,1′-二甲基-4,4′-联吡啶鎓二氯化物)和杀草快〔6,7-二氢联吡啶并(1.2-a;2′.1′-c)吡嗪二鎓二溴化物〕是最通用的。这些化合物在商业上一般以含水组合物销售。试图将这些盐制备成自由流动的可湿性粉末制剂还没有成功。在英国专利2,100,603描述可湿性粉末组合物是采用粉状的硅酸钙作为载体。在J5 6152-401(Asahi Chemical)描述的粉末状的组合物包括无机硫酸盐如硫酸钠、硫酸镁等,和防结块剂如白炭黑(二氧化硅),硼砂,硅胶等。在美国专利4,118,218里介绍制备粒状除草剂组合物的方法,包括在惰性载体上沉积联吡啶鎓季盐的水溶液,载体最好用氯化钙或氯化钠。这专利也提及各种日本和英国专利申请中介绍了固态除草剂组合物,但这些组合物中没有一种在商业上是成功的。一般而言,先有技术的化合物没有充分浓集其有效成分,也没有适当地水合或者防止有效成分结晶,于是对于干粉末的使用者有潜在危险性。除草剂联吡啶鎓盐的水溶液干燥时,出现结晶。晶体也出现在这些盐的干燥组合物内。
现在已能制备高浓度固态的联吡啶鎓盐除草剂组合物。这些组合物不出现表面结晶。制备的方法是将藻朊酸与联吡啶鎓盐混合,中和混合物使其生成一种络合物,然后干燥。
本发明的组合物是固态的,除草剂联吡啶鎓季盐与藻朊的络合物,其中有14~52%(重量)是联吡啶鎓盐(按阳离子计算)。最好该藻朊
是藻酸,尤其是粘度低的〔小于20厘泊,10%溶液〕藻酸。其中较好的联吡啶鎓盐是:
1,1′-亚乙基-2,2′-联吡啶鎓二溴化物,
1,1′-二甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-2-羟乙基-4,4′-联吡啶鎓二氯化物,
1,1′-双-3,5-二甲基吗啉代羰基甲基-4,4′-联吡啶鎓二氯化物,
1-(2-羟乙基)-1′-甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-氨基甲酰基甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-N,N-二甲基氨基甲酰基甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-N,N-二乙基氨基甲酰基甲基-4,4′-联吡啶鎓二氯化物,
1,1-双-(哌啶子基羰基甲基)-4,4′-联吡啶鎓二氯化物,
1,1′-二丙酮基-4,4′-联吡啶鎓二氯化物,
1,1′-二乙氧羰基甲基-4,4′-联吡啶鎓二溴化物,
1,1′-二烯丙基-4′-联吡啶鎓二溴化物。
其中以1,1′-亚乙基-2,2′-联吡啶鎓二溴化物
和1,1′-二甲基-4,4′-联吡啶鎓二氯化物为最好。
本发明的络合物的制备是将联吡啶鎓盐与藻朊酸起反应。所谓藻朊指的是藻酸及其盐。主要从海草得到的藻酸在工业上是现有的产品如KELACID
(Kelco Div.,Merck & Co.Ltd)。这些盐包括适宜的金属盐,如碱金属、碱土金属,铵盐,还有有机衍生物,如链烷二醇、丙二醇等的衍生物。这些盐最好是水溶性的。较好的是钠、铵、钾和丙二醇的藻酸盐或酯。在本发明中,如需要很快水合,最好用粘度很低的藻酸(或它的盐)(10%溶液,小于20厘泊)。(在这里,所有的粘度
值都是用Brookfield LVT粘度计测量,采用适当的旋转轴,60转/分)。需要较慢水合时,则可采用较高粘度的藻酸或藻酸盐。将联吡啶鎓盐和藻朊混合并中和,便可形成络合物。可以采用几种方法,例如:盘附聚;转鼓式干燥,烘箱烘干或喷雾干燥藻朊溶液;流化床干燥器附聚;以及将联吡啶鎓盐与藻朊溶液在非溶剂中沉淀。简便方式,可将一种碱加入藻朊与联吡啶鎓盐的混合物中并测量pH值,以达到中和的目的。另一种方法,也可在混合之前,使预定量的碱存在于藻朊或联吡啶鎓盐之中。可用的碱包括氨、氢氧化铵,氢氧化钠和氢氧化钾。下面详细地描述这些方法。各种变化,如液滴大小,干燥温度和时间,各组分浓度等变化都包括在本发明的范围之内。
盘附聚
将藻朊粉末放入盘式附聚器中,制成一种干燥藻朊的流动床。然后把联吡啶鎓盐溶液喷射到移动着的藻朊床上面,使藻朊粉末附聚成小颗粒。喷雾是通过一个喷管,形成大小约为500微米的雾滴。当所有的藻朊已附聚和所有的联吡啶鎓盐溶液已加入后,用氨气对这些附聚物进行氨化使潮湿颗粒的pH值为7.0至8.0,这些络合物小颗粒进入一个流化床干燥器内烘干,入口温度为120℃,烘干10分钟。生成一种自由流动颗粒状的含有高浓度有效除草成分的产品。市上可买到的用于本方法的设备是Ferrotech盘式附聚器,型号:FC 016-02(Ferrotech Co.,地址:Wyandotte,Mich.)。
转鼓式干燥
使联吡啶鎓盐溶液与藻朊混合10分钟。然后用氨气或者28%氢氧化铵溶液来氨化该混合物。这时的产物是一种粘稠的、接近糊状的液体。再混合15分钟之后就可以用常用方法对络合物进行转鼓式烘干。
烘箱烘干或喷雾干燥法
当体系中有大量水分时,可以将络合物放在烘箱或常用的喷雾干燥
设备中烘干来代替转鼓烘干。
非溶剂中沉淀
将藻朊悬浮在水和非溶剂的混合物中。此混合物应含足够的水致使藻朊溶胀但基本上不溶解。建议用50∶50的水和异丙醇。加入碱和联吡啶鎓盐溶液。接着将此混合物在室温搅拌18小时,过滤,用此混合液洗涤,再过滤,然后干燥。
珍珠岩
也可以将藻朊和珍珠岩的组合物与联吡啶鎓盐溶液混合而获得络合物。珍珠岩有助于除草溶液的吸收从而改进其使用性能。藻朊与珍珠岩以3∶1到1∶3掺合(最好1∶1),再与联吡啶鎓盐溶液混合,中和,干燥。该产物中不存在晶体并且容易溶解,但在水溶液中出现絮状物。珍珠岩是商业上通用的(例,Dicaperl HP-200,HP210或HP-1000,Grefco,Inc产品)。由于产生絮状物,含珍珠岩组合物局限于高固体物含量的制剂,如悬浮液化肥。
利用这些方法,可以制备成具有高浓度联吡啶鎓盐(14~50%,以阳离子计算)的络合物。其优点是采用很低粘度的藻朊酸时,这些络合物很容易溶解于水中。在不需要快速溶解的场合,可采用较高粘度的藻酸或藻酸盐。已溶解了的络合物可以采用农业用的喷雾设备来施喷。
本发明的藻朊与联吡啶鎓络合物的有利性能是其他成分的混合物或络合物所不具备的。曾经对百草枯与下面组分的混合物进行过试验。
结果
1.淀粉接枝共聚物 百草枯被吸收但大约10%被永久性束缚在
(美国专利3,935,009) 聚合体上,因此降低了除草效果。
2.微晶纤维素 不溶胀,不吸收百草枯。
(Avicel 101)
3.硅藻土 不吸收百草枯。
4.可溶于冷水的罗望子胶 吸收百草枯,但在颗粒表面形成结晶
5.聚丙烯酸酯类固体物 使得晶体生长。
〔得自(Acrysol/
RM-4〕
6.木素磺酸钠 与百草枯起反应,但形成不溶性的沉淀物。
7.羧甲基纤维素 吸收百草枯,但在表面形成结晶。
(Drispac Super Low)
联吡啶鎓盐的除草用途在本技术领域已为公知。本发明的固态络合物是在溶解之后用作除草剂,关于用量、组成、设备、方法等方面,使用联吡啶鎓盐的用户也已十分通晓。引用下面的制备方法和实例来进一步说明本发明,但这仅仅是属于说明性的,本发明并不受此限制。
制备1
低粘度的藻酸
一种10%粘度为1400厘泊的藻酸以1%盐酸溶液处理并加热到90℃,时间为5,10,15和20分钟。在每个时间里取一个样品,然后分成两份,一份在室温干燥而另一份在65.5℃烘干。由这些样品制备藻朊与联吡啶鎓盐的络合物并测定其溶解性。表1说明络合物的溶解速率是取决于该酸的粘度。
提高干燥温度会促进聚合物的降解。正如,反应时间5分钟后,室温的那份样品粘度为105厘泊,而在65℃干燥的为28厘泊。
表 Ⅰ
酸的粘度与溶解速率的关系
反应时间 10%酸的粘度(室温干燥) 络合物
(分钟) (厘泊) 溶解时间(分钟)
5 105 5
10 45 3
15 38 3
20 31 2
25 20 1
利用另一藻酸样品,所得对比结果列于表Ⅱ
表 Ⅱ
酸的粘度与溶解速率的关系
10%酸的粘度(室温干燥) 络合物
(厘泊) 溶解时间(分钟)
1600 15
1000 13
10 少于1
8 少于1
制备2
低粘度的藻酸盐
希望应用低粘度藻酸盐来代替藻酸时,可以采用按照制备1的方法制得的低粘度的藻酸,用标准方法制成藻酸盐。
本发明将引用下面的实例来进一步详细说明,但这仅仅是属于说明性的而本发明不受此局限。
溶解速率和百草枯二氯化物的分析测定如下。以5.00克亚硫酸氢钠,
2.00克氢氧化钠和93.00克去离子水制成一种亚硫酸氢盐溶液。将1.00克干产品溶解于999.00克STW(人造自来水)中,分别在1,2,5和10分钟的时刻取1毫升样品。将1毫升样品加98.0克STW并混合。然后加入1毫升亚硫酸氢盐溶液并混合。采用Pye Unicam SP1750分光光度计,测得394毫微米的吸收度。样品的吸收度与对照图表上的一定浓度的百草枯二氯化物的吸收度对照,得到百草枯二氯化物的百分含量。
人造自来水(STW)是含有1000ppm Na Cl和40ppm Ca++(147ppm Ca Cl2·2H2O)的去离子水。
实例 1
盘附聚
将30.0克藻酸(1600厘泊,10%溶液)放在一个盘附聚器内。然后将68.7克的百草枯CL(Chevron Chem·Co.)(配成29.1%二氯化物活性物溶液),溶液喷射成500微米的小雾滴,喷到移动着的酸床层上,使这些酸附聚。附聚后,用氨气处理这些混合物至pH值为7.0~8.0(在潮湿的小颗粒上测量)。将络合物小颗粒在流化床干燥器中烘干。入口温度为120℃,10分钟后成为自由流动颗粒状产品。干产品颗粒表面见不到有结晶或有白色的绒毛存在。在STW中的溶解速率为13分钟。
实例 2
盘附聚
按照实例1的方法,不同之处是使用103.1克百草枯CL的29.1%溶液,制备成一种干的产品。
此干产品颗粒表面见不到有结晶或有白色的绒毛存在。在STW中的溶解速率为13分钟。
实例 3
盘附聚
按照实例1的方法,不同之处是使用27.0克藻酸(1600厘泊,10%溶液),68.7克百草枯CL的29.1%溶液,和3.0克乙二次氮基四乙酸(螯合剂),制成一种干产品。
此干产品颗粒表面见不到有结晶或有白色的绒毛存在。在STW中的溶解速率为10分钟。
实例 4
转鼓式干燥
15.0克藻酸(8厘泊,10%溶液)与30.0克百草枯溶液(43.5%活性物)混合,加入氢氧化铵使pH值升到7.0。生成一种粘稠糊状物,然后采用转鼓式烘干,利用100℃的水蒸汽作为热源。接着把这些藻朊与百草枯的络合物碾磨并用18和40目的筛网进行筛选。此干产品颗粒表面见不到有结晶或有白色绒毛存在。在STW中的溶解速率短于1分钟。
这产品中的联吡啶鎓盐含量是43.2%(以百草枯二氯化物计算)
实例 5
转鼓式干燥
按照实例4的方法,不同之处是使用100.0克藻酸(12厘泊,10%溶液)和300.0克百草枯溶液(43.5%活性物,按二氯化物计)制备成一种干产品。
此干产品颗粒表面见不到有结晶或有白色的绒毛存在。在STW中的溶解速率短于1分钟。
这产品中的联吡啶鎓盐含量是45.0%(以百草枯二氯化物计算)
实例 6
盘附聚
按照例1的方法,不同之处是使用15.0克藻酸(10厘泊,10%溶液)与15.0克珍珠岩(Dicaperl HP-200,Grefco,Inc.供应)和55.0克百草枯溶液(43.5%活性物,按二氯化物计),制备成一种干产品。
在颗粒表面见不到有结晶或有白色绒毛存在。溶解速率为1分钟。珍珠岩形成一种絮凝体。
实例 7
极低粘度的藻酸铵
将200磅低灰分的藻酸(20%固体物)加热到190°F并保持温度3小时。从中取150磅物料,用28%氢氧化铵中和到pH值8.8。然后,在搅拌下再将这些产物加热到180°F,经历8小时,使此液态产物浓缩。接着,将它放在180°F的烘干盘上烘干72小时,然后碾磨并过325网目的筛。最后的藻酸铵产品的pH值为4.7,10%溶液的粘度为12厘泊。
实例 8
采用实例7的藻酸铵制成50%(重量)的百草枯阳离子体系:
配方:
30.00 克 43.5% 百草枯二氯化物溶液
1.00 克 28% 氢氧化铵
3.44 克 藻酸铵(12厘泊,10%溶液)
方法:
首先将氢氧化铵与百草枯溶液混合。然后在搅拌下慢慢加入藻酸铵。在搅拌下将混合物加热到180°F,历时1小时,以便使体系浓缩。将这些浓缩物用转鼓式干燥机干燥之后进行碾磨和筛分。然后对藻朊与百草枯的络合物进行试验,测试其溶解性和百草枯的结晶状况。数据列于下表:
数据:
外观 溶解性 百草枯浓度
无表面结晶 <1分钟 48.5%阳离子化合物
实例 9
采用极低粘度的藻酸制成50%(重量)百草枯阳离子体系:
配方:
30.00 克 43.5% 百草枯二氯化物溶液
2.50 克 28% 氢氧化铵
3.34 克 藻酸(15厘泊,10%溶液)
方法:
首先将氢氧化铵与百草枯溶液混合。然后在搅拌下慢慢加入藻酸。加热这混合物并搅拌,在180°F历经1小时使其浓缩。浓缩物用转鼓烘干之后碾磨及筛分。然后试验藻酸与百草枯络合物的溶解性和百草枯的结晶状况。
数据:
外观 溶解性 百草枯浓度
无表面结晶 <1分钟 48.0%阳离子化合物
对于盘附聚技术,有可能通过提高藻酸的粘度即使10%溶液的粘度为100-300厘泊,最好是150-250厘泊,来取消藻朊与百草枯络合物的浓缩过程。采用较高粘度藻酸盐,则其络合物溶液足够粘稠以致应用热转鼓时不会发生流泄。用转鼓干燥时,络合物仍然溶解迅速,并可防止晶体增大。
实例 10
按照制备1的方法处理藻酸,制成10%浓度的粘度为200厘泊的产品,然后采用转鼓式干燥法用此藻酸生产一种百草枯络合物。
配方:
30.00 克 47.5% 百草枯二氯化物溶液
2.50 克 28% 氢氧化铵
1.43 克 藻酸(200厘泊,10%溶液)
方法:
首先将氢氧化铵与百草枯溶液混合。然后在搅拌下慢慢加入藻酸。搅拌混合物半小时以保证藻酸溶解,接着用转鼓烘干,碾磨和筛分。然后将此藻酸与百草枯络合物进行试验,测试其溶解性和百草枯的结晶状况。
数据:
外观 溶解性 百草枯的浓度
无表面结晶 <1分钟 51%阳离子化合物
因此本发明的另一实施方案是一种高粘度的藻朊(藻酸、其盐或它的衍生物)。所谓高粘度指的是其10%水溶液粘度为100厘泊或以上,100-300厘泊较好;最好是150-250厘泊。
Claims (6)
1、一种联吡啶鎓季盐和藻朊的固态络合物除草剂的制备方法,包括:
a.在含水条件下混合并中和藻朊和联吡啶鎓季盐,形成一种络合物,
b.烘干上述络合物,
该方法的特征在于,所用藻朊的10%溶液粘度小于20厘泊,并且是藻酸、藻酸钠、藻酸钾、藻酸铵或丙二醇藻酸酯,所得到的络合物按阳离子计算含有14-52%(重量)联吡啶鎓季盐,并且是形成干的、自由流动的可湿性固体组合物。
2、根据权利要求1的方法,其特征在于所用联吡啶鎓季盐是:
1,1′-亚乙基-2,2′-联吡啶鎓二溴化物,
1,1′-二甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-2-羟乙基-4,4′-联吡啶鎓二氯化物,
1,1′-双-3,5-二甲基吗啉代羰基甲基-4,4′-联吡啶鎓二氯化物,
1-(2-羟乙基)-1′-甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-氨基甲酰甲基甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-N,N-二甲基氨基甲酰基甲基-4,4′-联吡啶鎓二氯化物,
1,1′-双-N,N-二乙基氨基甲酰基甲基-4,4′-联吡啶鎓二氯化物,
1,1-双-(哌啶子基羰基甲基)-4,4′-联吡啶鎓二氯化物,
1,1′-双丙酮基-4,4′-联吡啶鎓二氯化物,
1,1′-二乙氧羰基甲基-4,4′-联吡啶鎓二溴化物,
1,1′-二烯丙基-4′-联吡啶鎓二溴化物。
3、根据权利要求1的方法,其特征在于将藻朊首先按步骤(a)与珍珠岩以3∶1到1∶3的比率混合。
4、根据权利要求1的方法,其特征在于采用盘附聚法使藻朊和联吡啶鎓盐形成一种混合物,并用氨中和该混合物。
5、根据权利要求1的方法,其特征在于该藻朊是低粘度藻酸或其盐。
6、根据权利要求1的方法,其特征在于该藻朊是高粘度藻酸或其盐。
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JPS6178704A (ja) * | 1984-09-26 | 1986-04-22 | S D S Baiotetsuku:Kk | 難嚥下農薬組成物 |
EP0253035A1 (fr) * | 1986-07-17 | 1988-01-20 | Goemar S.A. | Produit à base d'algues, application comme fongicide ou bactéricide et procédé de traitement de plantes utilisant un tel produit |
US4874423A (en) * | 1985-10-08 | 1989-10-17 | Merck & Co., Inc. | Solid, herbicidal complexes |
FR2588723B1 (fr) * | 1985-11-12 | 1990-04-13 | Sds Biotech Kk | Composition herbicide solide anti-deglutition contenant du paraquat et un agent epaississant |
AU588009B2 (en) * | 1985-11-12 | 1989-09-07 | Sds Biotech K.K. | Contradeglutitious solid herbicidal composition |
FR2736508B1 (fr) * | 1995-07-13 | 1997-09-19 | Francais Prod Ind Cfpi | Nouvelle forme solide de stockage et de commercialisation pour compositions phytosanitaires et moyens pour sa preparation |
CA2430277A1 (en) * | 1999-11-30 | 2001-07-06 | Chuanxing Yu | The alginate having low molecular weight, methods of manufacturing it and its use |
GB0107651D0 (en) * | 2001-03-27 | 2001-05-16 | Syngenta Ltd | Composition |
KR100699672B1 (ko) * | 2005-10-28 | 2007-03-23 | 시논 코포레이션 | 제초제 조성물 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2979499A (en) * | 1954-03-11 | 1961-04-11 | Kelco Co | Derivatives of water-soluble gums |
GB976301A (en) * | 1960-10-27 | 1964-11-25 | Calmic Ltd | Preparation and use of alginates |
GB1271575A (en) * | 1968-07-24 | 1972-04-19 | Galdonost Dynamics Nz Ltd | Improvements in or relating to fertilizer compositions |
JPS5049425A (zh) * | 1973-09-03 | 1975-05-02 | ||
US4118218A (en) * | 1975-06-16 | 1978-10-03 | Imperial Chemical Industries Limited | Formulation process |
US4226855A (en) * | 1976-12-16 | 1980-10-07 | Mitsubishi Chemical Industries Ltd. | Plant viral disease preventive alginate containing compositions |
US4401456A (en) * | 1980-01-09 | 1983-08-30 | The United States Of America As Represented By The Secretary Of Agriculture | Controlled release of bioactive materials using alginate gel beads |
US4764206A (en) * | 1985-10-10 | 1988-08-16 | S D S Bioteck K.K. | Contradeglutitious solid herbicidal composition |
-
1984
- 1984-12-24 US US06/685,809 patent/US4832730A/en not_active Expired - Fee Related
- 1984-12-24 CN CN85106125A patent/CN1010654B/zh not_active Expired
-
1985
- 1985-08-01 NZ NZ212951A patent/NZ212951A/xx unknown
- 1985-08-02 IL IL76007A patent/IL76007A0/xx not_active IP Right Cessation
- 1985-08-05 DE DE8585305566T patent/DE3573705D1/de not_active Expired
- 1985-08-05 GR GR851914A patent/GR851914B/el unknown
- 1985-08-05 EP EP85305566A patent/EP0174101B1/en not_active Expired
- 1985-08-06 IE IE193585A patent/IE58651B1/en not_active IP Right Cessation
- 1985-08-06 CA CA000488105A patent/CA1268172A/en not_active Expired - Lifetime
- 1985-08-08 ES ES546012A patent/ES8700237A1/es not_active Expired
- 1985-08-08 HU HU853070A patent/HU200326B/hu not_active IP Right Cessation
- 1985-08-09 JP JP17439385A patent/JPH0699250B2/ja not_active Expired - Lifetime
- 1985-08-09 PT PT80932A patent/PT80932B/pt not_active IP Right Cessation
- 1985-08-09 KR KR1019850005753A patent/KR920002302B1/ko not_active IP Right Cessation
- 1985-08-09 DK DK362985A patent/DK163704C/da not_active IP Right Cessation
- 1985-08-09 AU AU45965/85A patent/AU576613B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
AU4596585A (en) | 1986-02-13 |
GR851914B (zh) | 1985-12-06 |
IE851935L (en) | 1986-02-10 |
IL76007A0 (en) | 1985-12-31 |
CA1268172C (en) | 1990-04-24 |
CN85106125A (zh) | 1986-07-02 |
CA1268172A (en) | 1990-04-24 |
DK163704C (da) | 1992-08-24 |
NZ212951A (en) | 1989-04-26 |
JPH0699250B2 (ja) | 1994-12-07 |
DK362985D0 (da) | 1985-08-09 |
HUT39725A (en) | 1986-10-29 |
KR920002302B1 (ko) | 1992-03-21 |
DE3573705D1 (en) | 1989-11-23 |
ES546012A0 (es) | 1986-10-16 |
US4832730A (en) | 1989-05-23 |
DK163704B (da) | 1992-03-30 |
EP0174101B1 (en) | 1989-10-18 |
EP0174101A1 (en) | 1986-03-12 |
JPS6147402A (ja) | 1986-03-07 |
DK362985A (da) | 1986-02-11 |
KR870001765A (ko) | 1987-03-28 |
ES8700237A1 (es) | 1986-10-16 |
PT80932B (pt) | 1987-12-30 |
AU576613B2 (en) | 1988-09-01 |
HU200326B (en) | 1990-05-28 |
PT80932A (en) | 1985-09-01 |
IE58651B1 (en) | 1993-11-03 |
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