CN109575144A - A kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-and its application in cell member herbicide - Google Patents
A kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-and its application in cell member herbicide Download PDFInfo
- Publication number
- CN109575144A CN109575144A CN201811463372.2A CN201811463372A CN109575144A CN 109575144 A CN109575144 A CN 109575144A CN 201811463372 A CN201811463372 A CN 201811463372A CN 109575144 A CN109575144 A CN 109575144A
- Authority
- CN
- China
- Prior art keywords
- microcrystalline cellulose
- sulfonated
- quaternary ammonium
- stabilizer
- herbicide
- 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.)
- Granted
Links
- 229920000168 Microcrystalline cellulose Polymers 0.000 title claims abstract description 80
- 235000019813 microcrystalline cellulose Nutrition 0.000 title claims abstract description 80
- 239000008108 microcrystalline cellulose Substances 0.000 title claims abstract description 80
- 229940016286 microcrystalline cellulose Drugs 0.000 title claims abstract description 80
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 56
- 239000004009 herbicide Substances 0.000 title claims abstract description 49
- 239000003381 stabilizer Substances 0.000 title claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- 239000012065 filter cake Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical group CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- -1 polyoxy Polymers 0.000 claims description 6
- 206010001497 Agitation Diseases 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000230 xanthan gum Substances 0.000 claims description 5
- 235000010493 xanthan gum Nutrition 0.000 claims description 5
- 229920001285 xanthan gum Polymers 0.000 claims description 5
- 229940082509 xanthan gum Drugs 0.000 claims description 5
- 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 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- RCYXGFWYLSKLKH-UHFFFAOYSA-M sodium;4-(prop-2-enoylamino)benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(NC(=O)C=C)C=C1 RCYXGFWYLSKLKH-UHFFFAOYSA-M 0.000 claims description 4
- XNYBUIUOTDPTMX-UHFFFAOYSA-N 2-(prop-2-enoylamino)hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCC(CS(O)(=O)=O)NC(=O)C=C XNYBUIUOTDPTMX-UHFFFAOYSA-N 0.000 claims description 3
- ZQOCDOFDUXPNGM-UHFFFAOYSA-N 3-(4-methylimidazol-1-yl)-5-(trifluoromethyl)benzoic acid Chemical compound C1=NC(C)=CN1C1=CC(C(O)=O)=CC(C(F)(F)F)=C1 ZQOCDOFDUXPNGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005500 Clopyralid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- HUBANNPOLNYSAD-UHFFFAOYSA-N clopyralid Chemical compound OC(=O)C1=NC(Cl)=CC=C1Cl HUBANNPOLNYSAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 claims 1
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 235000009508 confectionery Nutrition 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 3
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 3
- 239000001263 FEMA 3042 Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940033123 tannic acid Drugs 0.000 description 3
- 235000015523 tannic acid Nutrition 0.000 description 3
- 229920002258 tannic acid Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005913 Maltodextrin Substances 0.000 description 2
- 229920002774 Maltodextrin Polymers 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229940035034 maltodextrin Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- NNZGNZHUGJAKKT-UHFFFAOYSA-M 3-bromopropyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCBr NNZGNZHUGJAKKT-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- 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
-
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
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Abstract
The invention discloses a kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-and its applications in cell member herbicide.The sulfonated microcrystalline cellulose stabilizer of the quaternary ammonium-is prepared by following step: (1) microcrystalline cellulose being carried out alkali process；(2) it reacts to obtain quaternized microcrystalline cellulose with 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride after alkali process；(3) it will react to obtain the sulfonated microcrystalline cellulose stabilizer of the quaternary ammonium-with ammonium ceric nitrate, sulfonating reagent under obtained quaternized microcrystalline cellulose again nitrogen protection.Compared with prior art, the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-of the invention is applied in cell member herbicide, the cell member herbicide being prepared, with efficient, wide spectrum herbicidal performance, dispersion performance is good, and suspension is good, has the characteristics that efficiently disintegration rapidly.The scientific matching of quaternary ammonium-through the invention sulfonated microcrystalline cellulose stabilizer and emulsifier and carrier, improves disintegration rate, dispersibility and suspension stability and greatly improves herbicidal effect.
Description
Technical field
The present invention relates to a kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-and its applications in cell member herbicide.
Background technique
Herbicide compared with insecticide, fungicide its using technology requirement it is higher.Insecticide, fungicide use mistake for the moment
When, may only influence control efficiency.And herbicide improper use, then concerning the safety of plant growth.
It the discovery of herbicide and applies on a large scale, is the most important mark of the agriculture green revolution occurred in 20th century
One, rural labor production method is greatly changed, the modernization of agricultural is promoted, to ensure that world food production safety is made
Tremendous contribution.So far, the whole world has been developed that more than 30 major class, more than 20 a action targets, about 400~500 chemical weed controls
The weeds chemical control product technology system of agent kind.But since current herbicide is poor in the prevalence of slow release, once
Application action time is short, and effective component is rapidly losing by rainfall, needs multiple, a large amount of applications.And it depends on unduly and long-term big
Amount uses single herbicide, results in the generation and development of herbicide resistance, so that drug effect reduces, dosage increases, cost mentions
It is high, also more aggravated pollution, directly threaten herbicide continue to use and agricultural production security.
How to develop a kind of efficient herbicide becomes urgent problem to be solved.The sulfonated crystallite of quaternary ammonium-of the invention is fine
Stabilising system can be played by tieing up plain being added in cell member herbicide for stabilizer, balancing charge distribution, to enhance sustained release
The effect of active constituent, so that herbicide is more efficient.
Summary of the invention
One of the objects of the present invention is to provide a kind of sulfonated microcrystalline cellulose stabilizers of quaternary ammonium-
The second object of the present invention is to provide the sulfonated microcrystalline cellulose stabilizer of above-mentioned quaternary ammonium-in cell member herbicide
In application.
The present invention adopts the following technical scheme that:
A kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-, is prepared using following methods:
Microcrystalline cellulose is added in sodium hydrate aqueous solution S1, in 92-96 DEG C of isothermal reaction 50-70min, takes out after cooling
Filter, filter cake is added in sodium hydrate aqueous solution, is stood, is filtered, filtration cakes torrefaction to constant weight obtains alkali process microcrystalline cellulose；
S2 is by the alkali process microcrystalline cellulose adding into acetone in step S1, under stiring 8-12mL sodium hydroxide is added dropwise
Aqueous solution adds 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, in 42-48 DEG C of isothermal reaction 2.5-3.5h, then adjusts pH value
It to 6.9-7.1, filters, by Washing of Filter Cake, drying to constant weight, obtains quaternized microcrystalline cellulose；
Quaternized microcrystalline cellulose in step S2 is added to the water by S3, under nitrogen protection, is being uniformly mixed, so
After be added ammonium ceric nitrate, add sulfonating reagent after reacting 15-25min, react 45-60min, then heat to 48-52 DEG C,
It in 48-52 DEG C of heat preservation 2-3h, filters while hot, and by Washing of Filter Cake, drying to constant weight, it is fine to obtain the sulfonated crystallite of the quaternary ammonium-
Tie up plain stabilizer.
A kind of preferred technical solution, the sulfonated microcrystalline cellulose stabilizer of the quaternary ammonium-, using following methods system
It is standby to obtain:
The NaOH aqueous solution that 250-400mL mass concentration is 0.4%-0.6% is added in microcrystalline cellulose 10-15g by S1
In, it is warming up to 92-96 DEG C, in 92-96 DEG C of heat preservation 50-70min, is filtered after being cooled to 25-30 DEG C, filter cake is added to 250-
400mL mass concentration is in the NaOH aqueous solution of 8%-11%, and 25-28 DEG C of standing 120-180min is filtered, and filter cake is in 25-30
It is DEG C dry to constant weight, obtain alkali process microcrystalline cellulose.
S2 weighs alkali process microcrystalline cellulose 7.5-8.5g in step S1, is added in 180-220mL acetone, 25-30 DEG C,
8-12mL mass concentration is added dropwise as the NaOH of 8%-12% with 0.8-1.5mL/min speed under 150-300 revs/min of magnetic agitation
Aqueous solution adds 14-17g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, is warming up to 42-48 DEG C, in 42-48 DEG C of reaction 2.5-
3.5h is filtered then with 0.8-1.5mol/L salt acid for adjusting pH value to 6.9-7.1, filter cake is successively used 150-300mL methanol,
The washing of 150-300mL dehydrated alcohol, it is then dry to constant weight at 55-65 DEG C, obtain quaternized microcrystalline cellulose.
S3 weighs quaternized microcrystalline cellulose 5-5.5g in step S2, is added in 180-220mL water, under nitrogen protection,
25-30 DEG C, with 250-400 revs/min of stirring 10-20min, 8-10g ammonium ceric nitrate is then added, adds again after reacting 15-25min
Enter 0.06-0.1mol sulfonating reagent, reacts 45-60min, then heat to 48-52 DEG C, in 48-52 DEG C of heat preservation 2-3h, while hot
It filters, and filter cake is successively washed with 200mL water, 200mL acetone, 200mL ether, it is then dry to constant weight at 25-30 DEG C, it obtains
To the sulfonated microcrystalline cellulose stabilizer of the quaternary ammonium-.
The sulfonating reagent is 2- acrylamide-2-methyl propane sulfonic, 4- acrylamido benzenesulfonic acid sodium salt, 2- acryloyl
One of amido hexadecane sulfonic acid.It is further preferred that the sulfonating reagent is 2- acrylamide-2-methyl propane sulfonic.
The invention also discloses the sulfonated microcrystalline cellulose stabilizer of above-mentioned quaternary ammonium-answering in cell member herbicide
With.
It is specific as follows:
A kind of efficient fater disintegration cell member herbicide is grouped as by following group by weight: 40-70 parts of herbicide,
10-15 parts of wetting agent, 3-7 parts of disintegrating agent, 3-10 parts of above-mentioned quaternary ammonium-sulfonated microcrystalline cellulose stabilizer, carrier 30 as one kind -60
Part, 420-460 parts of emulsifier solution, 3-7 parts of binder；Each raw material is weighed by weight, is mixed, in 28-30 DEG C, 300-800
Rev/min stirring 30-60 minutes, be then ground to D90 partial size less than 5 μm with grinding machine, obtain slurry, slurry is pumped into pressure type
Granulation is dried in spray dryer, and spray press control is in 3-5MPa, and dry gas intake air temperature is 120-145 DEG C, outlet
Temperature is 60-80 DEG C, and material is screened after granulation obtains 50-100 aim cell member herbicide.
The herbicide is one of alachlor, clopyralid, glyphosate choline or a variety of；The herbicide is preferred
For one of alachlor, clopyralid or a variety of.
The wetting agent is aliphatic alcohol sulfate, fatty alcohol polyoxyethylene ether, sodium sulfate of polyethenoxy ether of fatty alcohol, alkyl
One of benzene sulfonic acid alkali metal salt, dialkyl succinylsuccinate ester sulfonate sodium, lignosulfonates are a variety of；The wetting agent is preferred
For sldium lauryl sulfate.
The binder is one of gelatin, xanthan gum, Arabic gum, polyvinyl alcohol, dextrin or a variety of；The bonding
Agent is preferably maltodextrin and xanthan gum is 1:(2-4 in mass ratio) mixture.
The disintegrating agent be one of ammonium sulfate, sodium chloride, calcium chloride, magnesium chloride, aluminium chloride, urea, sodium sulphate or
It is a variety of；It is (1-2) that the disintegrating agent is preferably urea, sodium chloride in mass ratio: the mixture of (1-2).
Solvent is water in the emulsifier solution, and the mass fraction of emulsifier is 0.5%-1.0%, cream in emulsifier solution
Agent be (3- bromopropyl) trimethylammonium bromide, chlorination N, N '-hexamethyl second diammonium bi-quaternary ammonium salt, chlorination N, N '-hexamethyl oneself
One of diammonium bi-quaternary ammonium salt；The emulsifier is preferably chlorination N, N '-hexamethyl second diammonium bi-quaternary ammonium salt.
The carrier is improved ferroferric oxide and/or modified molecular screen.It is further preferred that the carrier is modified four
The mass ratio of the mixture of Fe 3 O and modified molecular screen, the improved ferroferric oxide and modified molecular screen is (1-3):
(1-3).The improved ferroferric oxide the preparation method is as follows: take 80-120mL, concentration be 0.3-0.6mol/L citric acid
Sodium water solution and 80-120mL, the tannic acid aqueous solution that mass fraction is 0.5%-1.5%, are uniformly mixed, lead to nitrogen and remove air,
Then 0.8-1.2g Fe is taken3O4Powder is add to the above mixed solution, frequency be 20-60KHz, power 200-500W
Condition ultrasound 25-40min, it is to be cooled to arrive then under 55-65 DEG C, nitrogen protection, with 250-350 revs/min of stirring 10-14h
After 28-30 DEG C, product is separated with magnet from water phase, and is done product vacuum with after 280-320mL water washing product
Dry (vacuum drying temperature be 28-30 DEG C, vacuum degree 30-35kPa, drying time 20-26h), crushed 100-200 mesh
Sieve, obtains improved ferroferric oxide.
The modified molecular screen the preparation method is as follows: under nitrogen protection, 200-250mL is added in 8-12g molecular sieve
In toluene, 35-40 DEG C, 150-250 revs/min stirring 25-40 minutes, then with 0.06-0.12g/s speed be added KH550,
Continue 35-40 DEG C, 150-250 revs/min stirring 2-4 hours, be cooled to 28-30 DEG C, addition 280-320g mass fraction is
The polyacrylic acid aqueous solution of 10%-15%, 28-30 DEG C, 250-350 revs/min stirring 2-4 hours, filter, filter cake 250-
(vacuum drying temperature is 28-30 DEG C, vacuum degree 30-35kPa, drying time for vacuum drying after the washing of 400g dehydrated alcohol
For 20-26h), it crushed 100-200 mesh, obtain modified molecular screen.
The molecular sieve is 13X type molecular sieve.
13X type molecular sieve, is also sodium X-type molecular sieve, is alkali metal aluminosilicate, has certain alkalinity, belongs to one kind
Solid base, chemical formula Na2O·A12O3·2.45SiO2·6.0H20, aperture 10A adsorb more than 3.64A and appoint less than 10A
What molecule.
Improved ferroferric oxide surface has carboxyl, has negative electrical charge.Molecular sieve passes through polyacrylic acid modified rear surface band
Negative electrical charge.Emulsifier used in herbicide (positively charged) can form micella and be coated on herbicide active active ingredients surface, into
And it is adsorbed on the electronegative improved ferroferric oxide in surface, on modified molecular screen, herbicide active active ingredients are released to realize
It puts.
Being added in cell member herbicide for the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-more plays stabilising system,
Balancing charge distribution, to enhance the effect of slow-release.
By the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-and emulsifier, carrier scientific matching of the invention, cooperate,
The disintegration rate of herbicide in water and dispersibility in water can be improved.
The sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-of the invention is applied in cell member herbicide, is prepared
Cell member herbicide has efficient, wide spectrum herbicidal performance, and dispersion performance is good, and suspension is good, has the spy being efficiently disintegrated rapidly
Point.The scientific matching of quaternary ammonium-through the invention sulfonated microcrystalline cellulose stabilizer and emulsifier and carrier, improves and collapses
Solution speed, dispersibility and suspension stability greatly improve herbicidal effect.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can be each preferably to get the present invention in any combination
Embodiment.
Specific embodiment
In following embodiments, part material is described below:
Alachlor, CAS:15972-60-8.
Xanthan gum, CAS:11138-66-2, product number G104873, Aladdin reagent.
Microcrystalline cellulose, CAS:9004-34-6, product number C104841, Aladdin reagent.
3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, CAS:3327-22-8.
2- acrylamide-2-methyl propane sulfonic, English name 2-Acrylamide-2-methylpro panesulfonic
Acid (abbreviation AMPS), CAS:15214-89-8.
4- acrylamido benzenesulfonic acid sodium salt, can be by commercially available or be prepared, the 4- acrylamido benzene in embodiment
Sodium sulfonate is prepared according to 102363603 B embodiment 1 of Chinese invention patent CN.
2- acrylamido hexadecane sulfonic acid, can be by commercially available or be prepared, the 2- acrylamido in embodiment
Hexadecane sulfonic acid is prepared according to 103044294 B embodiment 1 of Chinese invention patent CN.
Ammonium ceric nitrate, CAS:16774-21-3.
Chlorination N, N '-hexamethyl second diammonium bi-quaternary ammonium salt, can be according to public affairs by buying or being prepared, in embodiment
The number of opening is that the Chinese invention patent embodiment 1 of 101973887 B of CN is prepared.
The own diammonium bi-quaternary ammonium salt of chlorination N, N '-hexamethyl can be according to public affairs by buying or being prepared, in embodiment
The number of opening is that the Chinese invention patent embodiment 5 of 101973887 B of CN is prepared.
(3- bromopropyl) trimethylammonium bromide, CAS:3779-42-8.
Fe3O4Powder, 300 mesh of partial size.
Tannic acid, CAS:1401-55-4.
Sodium citrate, Na3C6H5O7·2H2O。
KH550, CAS:919-30-2.
Polyacrylic acid, CAS:9003-01-4, product number P131659, Aladdin reagent.
Molecular sieve is 13X molecular sieve.Shape: bar shaped, diameter: 1.5-1.7mm, bulk density/()≤0.61 g/mL.On
Extra large honest honest industry Development Co., Ltd provides, and the use of the preceding partial size that is first crushed to is 300 mesh.
The present invention is further illustrated below by the mode of embodiment.
Embodiment 1
A kind of efficient quickly disintegrated cell member herbicide, the raw material including following weight parts are prepared:
55 parts of herbicide, 13 parts of wetting agent, 5 parts of disintegrating agent, 7 parts of the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-, carrier
40 parts, 450 parts of the emulsifier aqueous solution that mass fraction is 0.8%, 5 parts of binder.
The herbicide is alachlor.The wetting agent is sldium lauryl sulfate.The disintegrating agent is urea, sodium chloride is pressed
Mass ratio is the mixture of 1:1.The binder is the mixture that maltodextrin and xanthan gum are 1:3 in mass ratio.
The sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-the preparation method is as follows: weigh microcrystalline cellulose 12g, be added
In the NaOH aqueous solution that 300mL mass concentration is 0.5%, 95 DEG C are warming up to, in 95 DEG C of heat preservation 60min, is taken out after being cooled to 30 DEG C
Filter cake is added in the NaOH aqueous solution that 300mL mass concentration is 10%, 25 DEG C of standing 150min by filter, is filtered, filter cake is 30
It is DEG C dry to constant weight, obtain alkali process microcrystalline cellulose.8.0g alkali process microcrystalline cellulose is taken, is added in 200mL acetone, 25
DEG C, the NaOH aqueous solution that 10mL mass concentration is 10% is added dropwise with 1mL/min speed under 200 revs/min of magnetic agitations, add
16g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, is warming up to 45 DEG C, in 45 DEG C of reaction 3h, then uses 1mol/L salt acid for adjusting pH
Value filters to 7.0, filter cake is successively washed with 200mL methanol, 200mL dehydrated alcohol, then obtain in 60 DEG C of dryings to constant weight
To quaternized microcrystalline cellulose.The quaternized microcrystalline cellulose of 5.2g is taken, is added in 200mL water, under nitrogen protection, at 25 DEG C, with
Then 9g ammonium ceric nitrate is added in 300 revs/min of stirring 15min, add 0.08mol sulfonating reagent after reacting 20min, instead
50min is answered, then heats to 50 DEG C, in 50 DEG C of heat preservation 2.5h, is filtered while hot, and filter cake is successively used to 200mL water, 200mL third
Ketone, the washing of 200mL ether, it is then dry to constant weight at 30 DEG C, obtain the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-.The sulphur
Acidizing reagent is 2- acrylamide-2-methyl propane sulfonic.
The carrier is the mixture of improved ferroferric oxide and modified molecular screen, the improved ferroferric oxide and modification
The mass ratio of molecular sieve is 1:1.
The improved ferroferric oxide the preparation method is as follows: take 100mL, concentration be 0.5mol/L sodium citrate it is water-soluble
Liquid and 100mL, the tannic acid aqueous solution that mass fraction is 1%, are uniformly mixed, lead to nitrogen and remove air, then take 1.00g Fe3O4
Powder is add to the above mixed solution, frequency is 40KHz, power is 300W condition ultrasound 30min, then in 60 DEG C, nitrogen
Under gas shielded, with 300 revs/min of stirring 12h, after to be cooled to 28 DEG C, product is separated from water phase with magnet, is used in combination
By product vacuum, dry (vacuum drying temperature is 30 DEG C, vacuum degree 35kPa, and drying time is after 300mL water washing product
For 24 hours), it then crushes and sieves with 100 mesh sieve, obtain improved ferroferric oxide.
The modified molecular screen the preparation method is as follows: under nitrogen protection, 10g molecular sieve is added in 220mL toluene,
It is stirred 30 minutes in 37 DEG C, 200 revs/min, KH550 is then added with 0.1g/s speed, continuation is stirred in 37 DEG C, 200 revs/min
It mixes 3 hours, is cooled to 28 DEG C, the polyacrylic acid aqueous solution that 300g mass fraction is 13% is added, is stirred in 28 DEG C, 300 revs/min
It mixes 3 hours, filters, (vacuum drying temperature is 30 DEG C, vacuum degree is for vacuum drying after filter cake is washed with 300g dehydrated alcohol
35kPa, drying time are for 24 hours), it then crushes and sieves with 100 mesh sieve, obtain modified molecular screen.
The emulsifier is chlorination N, N '-hexamethyl second diammonium bi-quaternary ammonium salt.
The efficiently quickly disintegrated cell member herbicide the preparation method is as follows: weigh each raw material by weight, mix,
It is stirred 40 minutes in 28 DEG C, 500 revs/min, is then ground to D90 partial size less than 5 μm with grinding machine, obtains slurry, mashing pump
Enter press spray drier and granulation is dried, spray press control is in 4MPa, and dry gas intake air temperature is 140 DEG C, out
Temperature degree is 75 DEG C, and material is screened after granulation obtains the efficiently quickly disintegrated cell member herbicide of 80 purposes.
Embodiment 2
With embodiment 1, difference is only that, in the present embodiment 2, the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-
The preparation method is as follows: weighing microcrystalline cellulose 12g, it is added in the NaOH aqueous solution that 300mL mass concentration is 0.5%, is warming up to
It 95 DEG C, in 95 DEG C of heat preservation 60min, is filtered after being cooled to 30 DEG C, filter cake is added to the NaOH water that 300mL mass concentration is 10%
In solution, 25 DEG C of standing 150min are filtered, and filter cake is dry to constant weight at 30 DEG C, obtain alkali process microcrystalline cellulose.It takes at 8.0g alkali
Microcrystalline cellulose is managed, is added in 200mL acetone, 10mL is added dropwise with 1mL/min speed under 25 DEG C, 200 revs/min of magnetic agitations
The NaOH aqueous solution that mass concentration is 10%, adds 16g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, is warming up to 45 DEG C,
45 DEG C of reaction 3h filter then with 1mol/L salt acid for adjusting pH value to 7.0, successively use 200mL methanol, 200mL anhydrous filter cake
Ethanol washing, it is then dry to constant weight at 60 DEG C, obtain quaternized microcrystalline cellulose.The quaternized microcrystalline cellulose of 5.2g is taken, is added
Enter in 200mL water, under nitrogen protection, at 25 DEG C, with 300 revs/min of stirring 15min, 9g ammonium ceric nitrate, reaction is then added
0.08mol sulfonating reagent is added after 20min, is reacted 50min, is then heated to 50 DEG C, in 50 DEG C of heat preservation 2.5h, take out while hot
Filter, and filter cake is successively washed with 200mL water, 200mL acetone, 200mL ether, it is then dry to constant weight at 30 DEG C, obtain season
The sulfonated microcrystalline cellulose stabilizer of ammonium-.The sulfonating reagent is 4- acrylamido benzenesulfonic acid sodium salt.
Embodiment 3
With embodiment 1, difference is only that, in the present embodiment 3, the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-
The preparation method is as follows: weighing microcrystalline cellulose 12g, it is added in the NaOH aqueous solution that 300mL mass concentration is 0.5%, is warming up to
It 95 DEG C, in 95 DEG C of heat preservation 60min, is filtered after being cooled to 30 DEG C, filter cake is added to the NaOH water that 300mL mass concentration is 10%
In solution, 25 DEG C of standing 150min are filtered, and filter cake is dry to constant weight at 30 DEG C, obtain alkali process microcrystalline cellulose.It takes at 8.0g alkali
Microcrystalline cellulose is managed, is added in 200mL acetone, 10mL is added dropwise with 1mL/min speed under 25 DEG C, 200 revs/min of magnetic agitations
The NaOH aqueous solution that mass concentration is 10%, adds 16g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, is warming up to 45 DEG C,
45 DEG C of reaction 3h filter then with 1mol/L salt acid for adjusting pH value to 7.0, successively use 200mL methanol, 200mL anhydrous filter cake
Ethanol washing, it is then dry to constant weight at 60 DEG C, obtain quaternized microcrystalline cellulose.The quaternized microcrystalline cellulose of 5.2g is taken, is added
Enter in 200mL water, under nitrogen protection, at 25 DEG C, with 300 revs/min of stirring 15min, 9g ammonium ceric nitrate, reaction is then added
0.08mol sulfonating reagent is added after 20min, is reacted 50min, is then heated to 50 DEG C, in 50 DEG C of heat preservation 2.5h, take out while hot
Filter, and filter cake is successively washed with 200mL water, 200mL acetone, 200mL ether, it is then dry to constant weight at 30 DEG C, obtain season
The sulfonated microcrystalline cellulose stabilizer of ammonium-.The sulfonating reagent is 2- acrylamido hexadecane sulfonic acid.
Comparative example 1
Substantially the same manner as Example 1, difference is only that, efficient quickly disintegrated cell member herbicide, including following weight
The raw material of part is prepared: 55 parts of herbicide, 13 parts of wetting agent, 5 parts of disintegrating agent, 7 parts of microcrystalline cellulose, 40 parts of carrier, quality
Emulsifier aqueous solution 450 part, binder 5 part of the score for 0.8%.It as stabilizer is microcrystalline cellulose i.e. in this comparative example 1
Element, and in embodiment 1 it is the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-.
Embodiment 4
Substantially the same manner as Example 1, difference is only that, in the present embodiment 4, the emulsifier is (3- bromopropyl) front three
Base ammonium bromide.
Embodiment 5
Substantially the same manner as Example 1, difference is only that, in the present embodiment 5, the emulsifier is chlorination N, N '-pregnancy
The own diammonium bi-quaternary ammonium salt of base.
Embodiment 6
Substantially the same manner as Example 1, difference is only that: carrier described in the present embodiment 6 is only improved ferroferric oxide.
The preparation method of improved ferroferric oxide is same as Example 1.
Embodiment 7
Substantially the same manner as Example 1, difference is only that: carrier described in the present embodiment 7 is only modified molecular screen.It is modified
The preparation method of molecular sieve is same as Example 1.
Comparative example 2
Substantially the same manner as Example 1, difference is only that: carrier described in this comparative example 2 is ferroso-ferric oxide and molecular sieve
Mixture, the mass ratio of the ferroso-ferric oxide and molecular sieve is 1:1.
Test case
Efficient quickly disintegrated cell member herbicide of the invention is subjected to following test.
1, disintegration time is tested: being indicated with measuring disintegration time length, it is qualification that general provision, which is less than 3min,.Method is such as
Under: efficiently quickly disintegrated cell member herbicide is added in 25 DEG C in the 100mL tool plug graduated cylinder of Xiang Shengyou 90mL standard hard water
0.5g clamps in the middle part of graduated cylinder, clogs nozzle, is rotated with 8 turns/min speed along center, until disintegration is sample completely in water
Only, the record time is disintegration time.
2, dispersion rate is tested: the standard hard water of 900mL (20 ± 1 DEG C) is added in the beaker weighed；By blender
Carefully in beaker, it is located at the bottom of stirrer paddle in bottom of the beaker at 15mm, the screw pitch of stirrer paddle and direction of rotation
Water can be promoted to turning over, make agitator speed 300r/min.The efficiently quickly disintegrated cell member herbicide of 9g is weighed, accurately extremely
(± 0.1g), is added in the water of stirring, continues to stir 1min；It is then shut off blender, stands 1min.With vacuum syringe pump method extraction ten
/ nine (810mL) suspension, will maintain glass tip just under the suspension level of whereabouts, in completing in 40~60s
Operation, and pay attention to making to minimize the interference of suspension.Contained with the solids that gravimetric detemination stays in the 90mL in beaker
Amount, the dry temperature of solids are 65 DEG C.With following formula calculate dispersion rate: dispersion rate (%)=10/9 × [(m-M)/m] ×
100%.The W is the quality (g) of solids after drying；The m is the quality of efficient quickly disintegrated cell member herbicide
(g)。
3, sustained release performance is tested: in the Buchner funnel that internal diameter is 8cm, tile 2cm thickness soil, sprinkling distilled water wetting soil
Earth is extremely saturated.After 12h, efficient quickly disintegrated cell member herbicide 10mg is taken, 10mL is watered, is uniformly sprayed at soil surface.
After naturally dry 1h, water spray is distilled with 40mL, collects leachates, using removing in efficient liquid-phase chromatography method analysis leachates
Careless agent active constituent alachlor content.It is 10 times total to spray distilled water, every minor tick 1h.Calculate the accumulative herbicidal activity drenched out
Component content accounts for the percentage of initial application total amount, is release rate (%).
Table 1: test result table
The sulfonated microcrystalline cellulose stabilizer of the quaternary ammonium-of invention is applied to the height being prepared in cell member herbicide
Quickly disintegrated cell member herbicide is imitated, there is efficient, wide spectrum herbicidal performance, dispersion performance is good, and suspension is good, has efficient
Rapidly the characteristics of disintegration.By screening research and develop improve the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-, and with emulsifier and carrier
Scientific matching improves disintegration rate, dispersibility and suspension stability, greatly improves herbicidal effect.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (6)
1. a kind of sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-, which is characterized in that be prepared using following methods:
Microcrystalline cellulose is added in sodium hydrate aqueous solution S1, in 92-96 DEG C of isothermal reaction 50-70min, filters after cooling,
Filter cake is added in sodium hydrate aqueous solution, stands, filter, filtration cakes torrefaction to constant weight obtains alkali process microcrystalline cellulose；
S2 is water-soluble 8-12mL sodium hydroxide is added dropwise under stiring by the alkali process microcrystalline cellulose adding into acetone in step S1
Liquid adds 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, in 42-48 DEG C of isothermal reaction 2.5-3.5h, then adjust pH value to
6.9-7.1 is filtered, and by Washing of Filter Cake, drying to constant weight, obtains quaternized microcrystalline cellulose；
Quaternized microcrystalline cellulose in step S2 is added to the water by S3, under nitrogen protection, is being uniformly mixed, then plus
Enter ammonium ceric nitrate, adds sulfonating reagent after reacting 15-25min, react 45-60min, then heat to 48-52 DEG C,
48-52 DEG C of heat preservation 2-3h, filters while hot, and Washing of Filter Cake, drying are obtained the sulfonated microcrystalline cellulose of the quaternary ammonium-to constant weight
Plain stabilizer.
2. the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-as described in claim 1, which is characterized in that use following methods system
It is standby to obtain:
Microcrystalline cellulose 10-15g is added in the NaOH aqueous solution that 250-400mL mass concentration is 0.4%-0.6%, is risen by S1
Temperature in 92-96 DEG C of heat preservation 50-70min, filters after being cooled to 25-30 DEG C to 92-96 DEG C, filter cake is added to 250-400mL matter
It measures in the NaOH aqueous solution that concentration is 8%-11%, 25-28 DEG C of standing 120-180min is filtered, and filter cake is dried extremely at 25-30 DEG C
Constant weight obtains alkali process microcrystalline cellulose.
S2 weighs alkali process microcrystalline cellulose 7.5-8.5g in step S1, is added in 180-220mL acetone, in 25-30 DEG C, 150-
It is water-soluble for the NaOH of 8%-12% with 0.8-1.5mL/min speed dropwise addition 8-12mL mass concentration under 300 revs/min of magnetic agitations
Liquid adds 14-17g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride, is warming up to 42-48 DEG C, in 42-48 DEG C of reaction 2.5-
3.5h is filtered then with 0.8-1.5mol/L salt acid for adjusting pH value to 6.9-7.1, filter cake is successively used 150-300mL methanol,
The washing of 150-300mL dehydrated alcohol, it is then dry to constant weight at 55-65 DEG C, obtain quaternized microcrystalline cellulose.
S3 weighs quaternized microcrystalline cellulose 5-5.5g in step S2, is added in 180-220mL water, under nitrogen protection, in 25-30
DEG C, with 250-400 revs/min of stirring 10-20min, 8-10g ammonium ceric nitrate is then added, is added after reacting 15-25min
0.06-0.1mol sulfonating reagent reacts 45-60min, then heats to 48-52 DEG C, in 48-52 DEG C of heat preservation 2-3h, take out while hot
Filter, and filter cake is successively washed with 200mL water, 200mL acetone, 200mL ether, it is then dry to constant weight at 25-30 DEG C, it obtains
The sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-.
3. the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-as claimed in claim 1 or 2, it is characterised in that: described sulfonated
Reagent is 2- acrylamide-2-methyl propane sulfonic, in 4- acrylamido benzenesulfonic acid sodium salt, 2- acrylamido hexadecane sulfonic acid
It is a kind of.
4. the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-as claimed in claim 1 or 2, it is characterised in that: described sulfonated
Reagent is 2- acrylamide-2-methyl propane sulfonic.
5. if the sulfonated microcrystalline cellulose stabilizer of the described in any item quaternary ammoniums-of Claims 1 to 4 is in cell member herbicide
Application.
6. application of the sulfonated microcrystalline cellulose stabilizer of quaternary ammonium-as claimed in claim 5 in cell member herbicide,
Be characterized in that: the cell member herbicide is grouped as by following group by weight: 40-70 parts of herbicide, wetting agent 10-15
Part, 3-7 parts of disintegrating agent, 3-10 parts of the described in any item quaternary ammoniums-of such as Claims 1 to 4 sulfonated microcrystalline cellulose stabilizer,
- 60 parts of carrier 30 as one kind, 420-460 parts of emulsifier solution, 3-7 parts of binder；The herbicide is alachlor, clopyralid, grass
One of sweet phosphine choline is a variety of；The wetting agent is aliphatic alcohol sulfate, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxy second
One of alkene ether sodium sulfate, benzene sulfonamide acid alkali metal salt, dialkyl succinylsuccinate ester sulfonate sodium, lignosulfonates are more
Kind；The binder is one of gelatin, xanthan gum, Arabic gum, polyvinyl alcohol, dextrin or a variety of；The disintegrating agent is
One of ammonium sulfate, sodium chloride, calcium chloride, magnesium chloride, aluminium chloride, urea, sodium sulphate are a variety of；The stabilizer is season
The sulfonated microcrystalline cellulose of ammonium-；Solvent is water in the emulsifier solution, and the mass fraction of emulsifier is in emulsifier solution
0.5%-1.0%, emulsifier are (3- bromopropyl) trimethylammonium bromide, chlorination N, N '-hexamethyl second diammonium bi-quaternary ammonium salt, chlorination
One of own diammonium bi-quaternary ammonium salt of N, N '-hexamethyl；The carrier is improved ferroferric oxide and/or modified molecular screen.
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| CN113980293A (en) * | 2021-10-12 | 2022-01-28 | 昆明理工大学 | Preparation method of cellulose microgel compound suspension rheology modifier |
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| CN113980293B (en) * | 2021-10-12 | 2024-05-10 | 昆明理工大学 | Preparation method of cellulose microgel compound suspension rheology modifier |
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Denomination of invention: A Quaternary Ammonium Sulfonated Microcrystalline Cellulose Stabilizer and Its Application in Cellular Herbicides Effective date of registration: 20230914 Granted publication date: 20210702 Pledgee: Bank of Beijing Co.,Ltd. Jinan Branch Pledgor: JINAN TIANBANG CHEMICAL Co.,Ltd. Registration number: Y2023980056643 |