CN113527659A - Polyoxyethylene polyoxypropylene ether, carboxylic acid polymer, preparation method and application - Google Patents
Polyoxyethylene polyoxypropylene ether, carboxylic acid polymer, preparation method and application Download PDFInfo
- Publication number
- CN113527659A CN113527659A CN202110592874.0A CN202110592874A CN113527659A CN 113527659 A CN113527659 A CN 113527659A CN 202110592874 A CN202110592874 A CN 202110592874A CN 113527659 A CN113527659 A CN 113527659A
- Authority
- CN
- China
- Prior art keywords
- ether
- polyoxyethylene polyoxypropylene
- reaction
- carboxylic acid
- integer
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000000575 pesticide Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002270 dispersing agent Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- -1 ethylene glycol alkyl ether Chemical class 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 27
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012986 chain transfer agent Substances 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- VWQXLMJSFGLQIT-UHFFFAOYSA-N prop-2-enoyl bromide Chemical compound BrC(=O)C=C VWQXLMJSFGLQIT-UHFFFAOYSA-N 0.000 claims description 2
- GLFSWJDJMXUVEV-UHFFFAOYSA-N prop-2-enoyl iodide Chemical compound IC(=O)C=C GLFSWJDJMXUVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000725 suspension Substances 0.000 description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 229920005646 polycarboxylate Polymers 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 239000004562 water dispersible granule Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 239000005906 Imidacloprid Substances 0.000 description 11
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 11
- 229940056881 imidacloprid Drugs 0.000 description 11
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
- 239000002552 dosage form Substances 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000007900 aqueous suspension Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003090 pesticide formulation Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000002146 bilateral effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- 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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- 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
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- 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
- A01N25/30—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 characterised by the surfactants
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
Abstract
The invention belongs to the technical field of functional polymer material preparation, and particularly relates to polyoxyethylene polyoxypropylene ether, a carboxylic acid polymer, a preparation method and an application, wherein the polyoxyethylene polyoxypropylene ether has a structure shown in a formula (III):
Description
Technical Field
The invention belongs to the technical field of functional polymer material preparation, and particularly relates to a polyoxyethylene polyoxypropylene ether, a carboxylic acid polymer, a preparation method and an application thereof.
Background
As an important means for preventing and controlling diseases, pests and weeds and protecting crops, the pesticide plays an irreplaceable important role in agricultural production, but with the continuous enhancement of environmental awareness and safety awareness of people, the problem of pesticide public hazard becomes an environmental problem which is increasingly concerned by people. The research focus in the field of pesticide preparations is to reduce the pollution of pesticides to the environment by innovating pesticide preparation technology. The development of pesticide preparations is developing towards water-based preparations and dust-free solid particle preparations with safety, environmental protection and low cost. The water suspending agent (SC) or the Water Dispersible Granule (WDG) is the dosage form which is developed fastest in recent years, has the most mature processing technology and the lowest cost and can process the most pesticide active ingredients. Under the action of a dispersing agent, a raw pesticide which is insoluble or poorly soluble in water is dispersed in water to form a uniform and stable dispersion system, and the dosage form is uniformly mixed and dispersed with water in any proportion and hardly influenced by water quality and water temperature, so that dust pollution, operator harm and safety to the surrounding environment can be avoided, and the dosage form is considered as one of the pesticide dosage forms with the greatest development prospects in the twenty-first century.
The polycarboxylate dispersant is a novel high-efficiency agricultural dispersant, is widely applied to water suspending agents or water dispersible granules, has long carbon chains and more adsorption sites, and has a space exclusion effect on branched chain groups such as carboxyl, sulfonic groups, amino, polyoxyethylene side chains and the like, so that the special structure of the polycarboxylate dispersant has good dispersing performance on a suspension system. The traditional polycarboxylic acid dispersant is generally a single-arm dispersant containing ether bonds or ester bond side chain structure, the raw materials for synthesizing the polycarboxylic acid dispersant mainly comprise polyethylene glycol, allyl polyethylene glycol ether and the like, however, the stability and suspension property of the polycarboxylic acid dispersant are generally improved, and in order to better improve the stability and suspension property of the pesticide preparation, a new raw material needs to be developed for preparing a new polycarboxylate dispersant.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low stability and poor suspension property of a pesticide preparation caused by adopting a traditional polycarboxylate dispersing agent in the prior art, so that the polyoxyethylene polyoxypropylene ether and the carboxylic acid polymer as well as the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical scheme:
the invention provides polyoxyethylene polyoxypropylene ether, which has a structure shown in a formula (III):
wherein p is an integer between 2 and 4, q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10.
(PO)m(EO)nMeans whole (PO)m(EO)nIn which there are m propoxy units PO and n ethoxy units EO, where PO and EO are randomly or statistically distributed.
Can be prepared by processes known to the person skilled in the art, for example by additionThe ethylene oxide and propylene oxide are added sequentially or simultaneously and the molar ratio of each other is controlled to obtain the desired distribution of (PO)m(EO)nAnd (3) fragment.
In a preferred embodiment, the polyoxyethylene polyoxypropylene ether has the structure shown below:
the invention also provides a preparation method of the polyoxyethylene polyoxypropylene ether, which comprises the following steps:
(1) reacting ethylene glycol alkyl ether, ethylene oxide and propylene oxide under the action of an alkaline catalyst to obtain an intermediate 1;
(2) taking the intermediate 1 to react with thionyl chloride under the action of an alkaline catalyst to prepare an intermediate 2;
(3) taking the intermediate 2, potassium iodide and alkanolamine to carry out a first reaction under the action of an alkaline catalyst to obtain a reaction solution, taking the reaction solution to carry out a second reaction with acryloyl halide to obtain polyoxyethylene polyoxypropylene amine ether.
Wherein intermediate 1 has the general structural formula of formula (I):
H(PO)m(EO)nCH2CH2O(CH2)qCH3
formula (I);
wherein q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10.
Intermediate 2 has the general structural formula of formula (II):
Cl(PO)m(EO)nCH2CH2O(CH2)qCH3
formula (II);
wherein q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10.
As a preferred embodiment, any one or more of the following a to F are satisfied;
A. in the step (1), the molar ratio of the ethylene glycol alkyl ether to the ethylene oxide to the propylene oxide is 1:2-10:2-5, the reaction temperature in the step (1) is 100-;
B. the molar ratio of the ethylene glycol alkyl ether in the step (1) to the basic catalyst and the thionyl chloride in the step (2) is 1:2-4:2-6, the reaction temperature of the step (2) is 30-50 ℃, and the reaction time is 16-24 h.
C. The molar ratio of the ethylene glycol alkyl ether in the step (1) to the basic catalyst, potassium iodide, alkanolamine and acrylic halide in the step (3) is 5:4-10:30-40:2-6: 4-12; in the step (3), the first reaction is carried out under the reflux of nitrogen, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 h; the second reaction is to drop the acryloyl halide into the reaction liquid at 0-10 ℃ for 3-5 h;
D. in the step (1), the adopted glycol alkyl ether is at least one of glycol methyl ether, glycol ethyl ether and glycol propyl ether;
E. in the step (2) and/or the step (3), the adopted alkaline catalyst is at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide;
F. in the step (3), the adopted acryloyl halide is one of acryloyl chloride, acryloyl bromide and acryloyl iodide; the alkanolamine is selected from one of ethanolamine, propanolamine and butanolamine
The invention also provides a carboxylic acid copolymer or a salt thereof, which has a structural formula shown as the following formula (IV):
wherein a, b and c are positive integers, p is an integer between 2 and 4, q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10;
R1，R2independently selected from H, methyl, carboxyl;
R3，R4，R5independently selected from H, methyl, phenyl, hexyl, -CH2C(CH3)3，-CONH2，
HOCH2CH2NHCO-，HOCH2CH2CH2NHCO-，(CH3)2NCH2CH2COO-，-CONHC(CH3)2CH2SO3H，-COOCH2CH2N(CH3)2，-CH2SO3Na，
Or, R4，R5Form a ring of R4，R5Each independently of the group
Is linked to the methylene group of (a).
In a preferred embodiment, the carboxylic acid copolymers have the following structure:
the invention also provides the carboxylic acid copolymer, which at least comprises three monomers, namely:
(1) at least one polyoxyethylene polyoxypropylene ether;
(2) at least one unsaturated carboxylic acid and/or derivative thereof;
(3) at least one lipophilic unsaturated comonomer;
the polyoxyethylene polyoxypropylene amine ether is the polyoxyethylene polyoxypropylene amine ether or the polyoxyethylene polyoxypropylene amine ether prepared by any preparation method.
The three monomeric fragments are randomly or statistically distributed.
The desired distribution can be obtained by processes known to the person skilled in the art, for example by sequential or simultaneous addition of the three monomers and control of the molar ratio to one another.
Oleophilic unsaturated comonomers are comonomers that contain a carbon-carbon unsaturated double bond and are more prone to dissolution in oil-soluble solvents.
In a preferred embodiment, the carboxylic acid-based polymer has a number average molecular weight of 5000-.
The invention also provides a preparation method of the polycarboxylic acid copolymer or the salt thereof, which comprises the step of carrying out copolymerization reaction on the polyoxyethylene polyoxypropylene ether or the polyoxyethylene polyoxypropylene ether prepared by the preparation method, unsaturated carboxylic acid and/or derivatives thereof and lipophilic unsaturated comonomer in an initiator, a chain transfer agent and a solvent system to obtain the polycarboxylic acid copolymer or the salt thereof.
As a preferred embodiment, the production method further satisfies any one or more of the following (1) to (3):
(1) the mass ratio of the polyoxyethylene polyoxypropylene ether, the unsaturated carboxylic acid and/or the derivative thereof, the lipophilic unsaturated comonomer, the initiator and the chain transfer agent is 100:50-300:50-150:5-20:1-15, in the copolymerization reaction, the reaction temperature is 50-90 ℃, and the reaction time is 3.5-7 h;
(2) the solvent system comprises water and an organic solvent, preferably, the organic solvent is one or a mixed solvent of more of acetonitrile, acetone, butanone, tetrahydrofuran, ethanol, methanol, isopropyl formate, methyl acetate, ethyl acetate and isopropyl acetate, and the mass ratio of the organic solvent to the water is 1:1-1: 5;
(3) the unsaturated carboxylic acid is one or a mixture of acrylic acid, methacrylic acid, maleic acid and fumaric acid; the unsaturated carboxylic acid derivative is maleic anhydride; and/or the lipophilic unsaturated comonomer is one or a mixture of more of 1-octene, dicyclopentadiene, styrene, alpha-methylstyrene, diisobutylene, hydroxyethyl acrylamide, hydroxypropyl acrylamide, vinyl pyrrolidone, sodium styrene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, dimethylaminoethyl methacrylate and sodium allylsulfonate; and/or the chain transfer agent is one or a mixture of more of mercaptoethanol, isopropanol, sodium bisulfite and sodium methallyl sulfonate; and/or the initiator is selected from one or a mixture of more of persulfate initiator, azo initiator and peroxide initiator.
In particular embodiments, the persulfate initiator is potassium persulfate and/or ammonium persulfate; the peroxide initiator is one or a mixture of more of dibenzoyl peroxide, diacetyl peroxide, dioctanoyl peroxide and dilauroyl peroxide; the azo initiator is one or a mixture of more of azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyronitrile dimethyl ester, azoisobutyronitrile formamide and azodicyclohexyl formonitrile.
The invention also provides application of the polycarboxylic acid copolymer or the salt thereof in improving the dispersibility of materials or serving as a dispersing agent, wherein the polycarboxylic acid copolymer is the polycarboxylic acid copolymer or the salt thereof prepared by the preparation method.
In which the dispersibility of the material is improved, the dispersant of the present invention can be used for dispersing one solid substance into another solid substance, and can also be used for dispersing into another liquid substance or a semisolid substance. For example in pesticide formulations.
The invention also provides a pesticide preparation which comprises the polycarboxylic acid copolymer or the polycarboxylic acid copolymer prepared by the preparation method.
Specifically, the pesticide preparation is a pesticide preparation conventional in the field, and can be, but is not limited to, an aqueous suspension or a water dispersible granule.
The technical scheme of the invention has the following advantages:
1. the polyoxyethylene polyoxypropylene amine ether provided by the invention has a structure of double-arm unsaturated olefin ester and amine ether, and is used as a raw material for synthesizing carboxylic acid polymers with excellent dispersibility and stability for pesticides.
2. The preparation method of the polyoxyethylene polyoxypropylene amine ether provided by the invention comprises the steps of firstly reacting ethylene glycol alkyl ether with ethylene oxide and propylene oxide to prepare hydroxyl-terminated polyoxyethylene polyoxypropylene ether, then reacting with thionyl chloride to prepare chlorine atom-terminated polyoxyethylene polyoxypropylene ether, and reacting with alkanolamine and acryloyl halide in sequence to finally prepare the polyoxyethylene polyoxypropylene amine ether.
3. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether, the molar ratio of ethylene glycol alkyl ether in the step (1) to the basic catalyst and thionyl chloride in the step (2) is 1:2-4:2-6, the reaction temperature is controlled to be 30-50 ℃, the reaction time is 16-24 hours, and the substitution rate of chloro groups can be obviously improved by controlling the molar ratio of the substances and the reaction conditions, so that the yield and the purity of an intermediate 2 are improved, and the generation of the polyoxyethylene polyoxypropylene amine ether is promoted.
4. The preparation method of polyoxyethylene polyoxypropylene ether provided by the invention comprises the following steps of (3), carrying out the first reaction under nitrogen reflux at the reaction temperature of 60-80 ℃ for 16-24 h; the second reaction is that acryloyl chloride is dripped into the reaction liquid with the temperature of 0-10 ℃ and the reaction time is 3-5 h; the molar ratio of the ethylene glycol alkyl ether to the basic catalyst, potassium iodide, alkanolamine and acrylic halide in the step (1) is 5:4-10:30-40:2-6:4-12, and the two hydrogen atoms on the primary amino group in the intermediate 2 can be promoted to be completely substituted by controlling the molar ratio, the reaction time and the reaction temperature, so that the synthesis of the dipodal polyoxyethylene polyoxypropylene ether is promoted, and the yield and the purity of the target product are improved.
5. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether provided by the invention, in the step (1), the molar ratio of the ethylene glycol alkyl ether to the ethylene oxide to the propylene oxide is 1:2-10:2-5, the introduction of the ethylene oxide and the propylene oxide can inhibit the austenite curing process of pesticide particles, the stability is improved, and researches show that the preparation method can be more suitable for realizing different types of pesticide particles by adjusting the ratio of the ethylene oxide to the propylene oxide.
6. The carboxylic acid polymer provided by the invention has excellent dispersibility, disintegration and stability, is colorless or light yellow in color, and can be used in occasions with high requirements on color.
7. According to the preparation method of the polyoxyethylene polyoxypropylene ether provided by the invention, the reaction is carried out in a mixed system of water and an organic solvent, so that the phenomenon of implosion or layering can be effectively avoided, the reaction is easy to control and operate, and the problems of uneven reaction, layering, excessive solvent consumption, safety risk and the like caused by the independent adoption of water or the organic solvent are effectively avoided.
8. The preparation method of the polyoxyethylene polyoxypropylene amine ether provided by the invention comprises the following steps of (1) preparing polyoxyethylene polyoxypropylene amine ether, unsaturated carboxylic acid and/or derivatives thereof, lipophilic unsaturated comonomer, initiator and chain transfer agent according to the mass ratio of 100:50-300:50-150:5-20:1-15, and the mass ratio of organic solvent to water according to 1:1-1:5, wherein in the copolymerization reaction, the reaction temperature is 50-90 ℃, and the reaction time is 3.5-7 h; through the control of the mass of each monomer, the mass of the initiator and the chain transfer agent, the mass ratio of the organic solvent to the water in the solvent, the reaction temperature and the reaction time, the carboxylic acid polymer with the proper molecular weight is obtained, the number average molecular weight of the carboxylic acid polymer is 5000-50000, the carboxylic acid polymer with the molecular weight can exert the effects of dispersing and stabilizing pesticide particles to the maximum extent, if the molecular weight is too low, the steric hindrance generated by the molecular side chain is too small, and the pesticide particles are easy to agglomerate; if the molecular weight is too high, chain entanglement of too long molecular side chains occurs easily to each other, thereby lowering the stability of the preparation.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The purities of the chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 and the unsaturated double-bond polyoxyethylene polyoxypropylene amine ether intermediate 3 are measured by a High Performance Liquid Chromatography (HPLC), and the test conditions are as follows: an Shimadzu high performance liquid chromatograph LC-20A system, a mobile phase (volume ratio) methanol/water solution (75/25), a flow rate of 1.0mL/min, a chromatographic column Inertsil ODS-SP, 5 μm, 4.6mm x 150mm, a sample injection volume of 25 μ L, a column temperature of 40 ℃, a detection wavelength of 360nm, and isocratic elution.
Example 1
This example provides a polyoxyethylene polyoxypropylene ether, which has the following structural formula:
the preparation method comprises the following steps:
(1) mixing 76kg (1Kmol) of ethylene glycol monomethyl ether and 5.6kg of basic catalyst KOH, heating to 100 ℃, adding 88kg (2Kmol) of ethylene oxide and 116kg (2Kmol) of propylene oxide, keeping 100 ℃ after 1h of material addition, continuing to react for 3h to obtain 280kg of intermediate 1, and testing the EO polymerization degree to be 2, the PO polymerization degree to be 2 and the number average molecular weight to be 280 in the intermediate 1 by a nuclear magnetic resonance hydrogen spectrometer.
(2) 238kg of thionyl chloride (2Kmol) was dissolved in 156kg of dimethyl sulfoxide to obtain a thionyl chloride solution. 280kg of the intermediate 1 and 276kg of potassium carbonate (2Kmol) are placed in 500L of dimethyl sulfoxide, the thionyl chloride solution is dropwise added to react for 16 hours at 30 ℃, and 320kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 is obtained after filtration, desalination and reduced pressure distillation, wherein the yield is 62%, and the purity is 90%.
(3) 320kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2(1Kmol) is dissolved in 328kg of acetonitrile, 110kg of potassium carbonate (0.8Kmol), 996kg of potassium iodide (6Kmol) and 25kg of ethanolamine (0.4Kmol) are added to react under the reflux of nitrogen at 60 ℃ for 16 hours, 72kg of acryloyl chloride solution (solvent is acetonitrile) with the mass percent of 50 percent is dropped after filtration to react for 3 hours at 0 ℃, and 383kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, the yield is 25 percent, and the purity is 92 percent.
This example provides a carboxylic acid copolymer as a polycarboxylate dispersant having the formula:
the preparation method comprises the following steps:
60kg of methanol and 60kg of water are added in a mixed system of methanol and water at 50 ℃.2kg of initiator potassium persulfate and 0.4kg of chain transfer agent mercaptoethanol are added into the mixed system. 40kg of polyoxyethylene polyoxypropylene ether, 20kg of methacrylic acid and 20kg of styrene are mixed and then dripped into the reaction system, after dripping is finished for 2 hours, heat preservation reaction is continuously carried out for 1.5 hours at the temperature of 50 ℃. The resulting mixture was neutralized with 32% by mass of an aqueous NaOH solution to pH 5.5, and the solvent was distilled off under reduced pressure at 50 ℃ to obtain polycarboxylate dispersant AGC-1 having a number average molecular weight of 49800 (measured by GPC).
Example 2
This example provides a polyoxyethylene polyoxypropylene ether, which has the following structural formula:
the preparation method comprises the following steps:
(1) mixing 90kg (1Kmol) of ethylene glycol ethyl ether and 5.6kg of basic catalyst KOH, heating to 110 ℃, adding 440kg (10Kmol) of ethylene oxide and 290kg (5Kmol) of propylene oxide, reacting for 4h after 2h of material addition to obtain 820kg of intermediate 1, wherein the EO polymerization degree in the intermediate 1 is 10, the PO polymer is 5, and the number average molecular weight is 800 according to a nuclear magnetic resonance hydrogen spectrometer test.
(2) 476kg of thionyl chloride (4Kmol) was dissolved in 250kg of methylene chloride to obtain a thionyl chloride solution. 820kg of intermediate 1(1Kmol) and 552kg of potassium carbonate (4Kmol) were placed in 800L of dichloromethane, the thionyl chloride solution was added dropwise, the reaction was carried out at 50 ℃ for 24 hours, and 970kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 was obtained after filtration, desalting and reduced pressure distillation, with the yield of 75% and the purity of 89%.
(3) 970kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2(1Kmol) is taken and dissolved in 500kg of tetrahydrofuran, 276kg of potassium carbonate (2Kmol), 1328kg of potassium iodide (8Kmol) and 74kg of ethanolamine (1.2Kmol) are added, reaction is carried out at 80 ℃ under nitrogen reflux for 24 hours, 216kg of acryloyl chloride solution (solvent is tetrahydrofuran) with the mass percent of 60 percent is dripped after filtration, reaction is carried out at 10 ℃ for 24 hours, 1390kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, the yield is 48%, and the purity is 91%.
This example provides a carboxylic acid copolymer useful as a polycarboxylate dispersant, having the formula:
the preparation method comprises the following steps:
in a mixed system of butanone and water at 80 ℃, 20kg of butanone and 100kg of water are added. 8kg of initiator diacetyl peroxide and 6kg of chain transfer agent isopropanol are added into the mixed system. 40kg of unsaturated double-bond polyoxyethylene polyoxypropylene ether intermediate 3, 60kg of acrylic acid, 60kg of maleic anhydride and 60kg of sodium styrene sulfonate are mixed and dripped, after dripping is finished for 4 hours, the reaction is continued for 5 hours at the temperature of 80 ℃. Neutralized to pH 8 with triethanolamine and the solvent was distilled off at 80 ℃ under reduced pressure to give polycarboxylate dispersant AGC-2 having a number average molecular weight of 5120 (measured by GPC).
Example 3
This example provides a polyoxyethylene polyoxypropylene ether, which has the following structural formula:
the preparation method comprises the following steps:
(1) 104kg (1Kmol) of ethylene glycol propyl ether and 5.6kg of basic catalyst KOH are mixed, the temperature is raised to 105 ℃, 220kg (5Kmol) of ethylene oxide and 174kg (3Kmol) of propylene oxide are added, the reaction lasts for 4h after 1h of addition, 498kg of intermediate 1 is obtained, the polymerization degree of EO in the intermediate 1 is 5, the polymerization degree of PO is 3 and the number average molecular weight is 500 as tested by a nuclear magnetic resonance hydrogen spectrometer.
(2) 357kg of thionyl chloride (3Kmol) was dissolved in 200kg of acetone to obtain a thionyl chloride solution. 498kg of intermediate 1(1Kmol) and 414kg of potassium carbonate (3Kmol) are placed in 600L of acetone, the thionyl chloride solution is added dropwise, the reaction is carried out for 20 hours at the temperature of 40 ℃, and after filtering, desalting and reduced pressure distillation, 633kg of chlorinated end capping polyoxyethylene polyoxypropylene ether intermediate 2 is obtained, the yield is 74%, and the purity is 97%.
(3) 633kg of chlorinated end capping polyoxyethylene polyoxypropylene ether intermediate 2(1Kmol) is taken and dissolved in 350kg of isopropyl formate, then 170kg of sodium carbonate (1.6Kmol), 1162kg of potassium iodide (7Kmol) and 49kg of ethanolamine (0.8Kmol) are added to react under the reflux of nitrogen at 70 ℃ for 20h, 144kg of acryloyl chloride solution with the mass percent of 55% (the solvent is isopropyl formate) is added dropwise after filtration to react for 20h at 5 ℃, and 915kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, the yield is 42%, and the purity is 90%.
This example provides a carboxylic acid copolymer useful as a polycarboxylate dispersant, having the formula:
the preparation method comprises the following steps:
in a mixed system of acetonitrile and water at 70 ℃, the mixture comprises 40kg of acetonitrile and 80kg of water. 4kg of initiator azobisisobutyronitrile and 3kg of chain transfer agent sodium methyl propylene sulfonate are added into the mixed system. 40kg of unsaturated double-bond polyoxyethylene polyoxypropylene ether intermediate 3, 30kg of maleic acid, 30kg of maleic anhydride, 20kg of hydroxyethyl acrylamide and 20kg of vinyl pyrrolidone are mixed and dripped, after 3 hours of dripping, the reaction is continued for 2 hours at 70 ℃. Neutralized with 32% by weight potassium hydroxide solution to pH 7, and the solvent was distilled off under reduced pressure at 70 ℃ to obtain a polycarboxylate dispersant AGC-3 having a number average molecular weight of 36930 (measured by GPC).
Example 4
This example provides a polyoxyethylene polyoxypropylene ether, which has the following structural formula:
the preparation method is basically the same as that of example 1, except for the step (3), in the step (3) of the present example, 320kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2(1Kmol) is taken and dissolved in 328kg of acetonitrile, then 110kg of potassium carbonate (0.8Kmol), 996kg of potassium iodide (6Kmol) and 30kg of propanolamine (0.4Kmol) are added, the reaction is carried out under nitrogen reflux at 60 ℃ for 16h, 72kg of 50% by mass of acryloyl chloride solution (the solvent is acetonitrile) is added dropwise after filtration, the reaction is carried out at 0 ℃ for 3h, and 385kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, the yield is 25%, and the purity is 91%.
This example provides a carboxylic acid copolymer useful as a polycarboxylate dispersant, having the formula:
the preparation method comprises the following steps:
60kg of methanol and 60kg of water are added in a mixed system of methanol and water at 50 ℃.2kg of initiator potassium persulfate and 0.4kg of chain transfer agent mercaptoethanol are added into the mixed system. 40kg of unsaturated double-bond polyoxyethylene polyoxypropylene ether intermediate 3, 20kg of methacrylic acid and 20kg of styrene are mixed and then dripped into the reaction system, after dripping for 2 hours, the reaction is continued for 1.5 hours at 50 ℃. The resulting mixture was neutralized with 32% by mass aqueous NaOH solution to pH 5.5, and the solvent was distilled off under reduced pressure at 50 ℃ to obtain polycarboxylate dispersant AGC-4 having a number average molecular weight of 46600 (measured by GPC).
Example 5
This example provides a method for preparing polyoxyethylene polyoxypropylene ether and carboxylic acid polymer, which is substantially the same as example 1, except that in the preparation of carboxylic acid polymer, 1kg of initiator potassium persulfate and 0.2kg of chain transfer agent mercaptoethanol are added to the mixed system, the rest of the reagents and reaction conditions are the same as example 1, and polycarboxylate dispersant with number average molecular weight of 63200 (measured by GPC) is obtained.
Example 6
This example provides a method for preparing polyoxyethylene polyoxypropylene ether and carboxylic acid polymer, which is substantially the same as example 1, except that 10kg of initiator potassium persulfate and 8kg of chain transfer agent mercaptoethanol are added to the mixed system during the carboxylic acid polymer preparation, and the remaining reagents and reaction conditions are the same as example 1, to obtain a polycarboxylate dispersant having a number average molecular weight of 3880 (measured by GPC).
Example 7
This example provides a method for producing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is substantially the same as example 1, except that the solvent system is different from that in the production of the carboxylic acid polymer, the solvent system in this example is a mixed system of water and methanol, the mass of water is 110kg, the mass of methanol is 10kg, the remaining reagents and reaction conditions are the same as example 1, and the carboxylic acid polymer having a number average molecular weight of 75800 (measured by GPC) is obtained by the reaction.
Example 8
This example provides a method for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is substantially the same as example 1, except that the solvent system is different from that in the preparation of the carboxylic acid polymer, the solvent system in this example is a mixed system of water and methanol, the mass of water is 20kg, the mass of methanol is 120kg, the other reagents and reaction conditions are the same as example 1, and the carboxylic acid polymer with the number average molecular weight of 34860 (measured by GPC) is obtained by the reaction.
Comparative example 1
This example provides a method for producing a polyoxyethylene polyoxypropylene amine ether and a carboxylic acid-based polymer, which is substantially the same as in example 1, except that in the step (1) of producing a polyoxyethylene polyoxypropylene amine ether, propylene oxide is omitted, ethylene oxide is added in an amount of 176kg, and the remaining reagents and reaction conditions are the same as in example 1.
Comparative example 2
This example provides a method for producing a polyoxyethylene polyoxypropylene ether and a carboxylic acid-based polymer, which is substantially the same as in example 1, except that in the step (3) of producing a polyoxyethylene polyoxypropylene ether, ethanolamine is replaced with the same mole of N-methylethanolamine, i.e., 30kg of N-methylethanolamine to obtain 385kg of polyoxyethylene polyoxypropylene ether, with a yield of 25% and a purity of 91%.
Experimental example 1
The powder obtained by spray drying the carboxylic acid polymer prepared in each example and comparative example is used as a dispersing agent in a pesticide dispersible granule (WDG) to prepare 90% of atrazine technical by mass, and the specific preparation method comprises the following steps: 90kg of atrazine technical, 5kg of dispersing agent prepared in the invention, 1kg of wetting agent (703D optimized chemistry), 1kg of dry starch and the balance of magnesium aluminum silicate which is complemented to 100 kg. Mixing the above materials at the above ratio, and micronizing with jet mill to obtain fine powder with particle size of 2-5 μm. Adding water with the mass of 10kg of fine powder, kneading for 0.5h, granulating, drying in an airflow dryer, and screening to obtain 90% atrazine WDG.
The particle size, suspension rate, disintegration, dispersibility and storage stability of 90% atrazine WDG were tested, respectively, and the specific test method was:
the particle size test method is that 1g of 90% atrazine WDG is dispersed in 100ml of water, the particle size is measured by an optical microscope or a laser particle sizer, the experimental example adopts the laser particle sizer for measurement, and the average particle size of the water suspending agent obtained in the embodiment of the invention is about 0.2-5 microns. The smaller the particle size, the more desirable the dispersing effect of the granules.
The suspension percentage (CIPAC MT161, MT184) was measured by placing 40ml of water in a beaker, adding 4g (W1) of 90% atrazine WDG, placing for 30s, and stirring for 90 s. It was then transferred to a 250ml graduated cylinder and diluted to 250ml with water, the cylinder was inverted 15 times, left to stand for 30 minutes and the upper 225ml of suspension was pumped off with water. The bottom 25ml were transferred in their entirety to a weighing pan and dried to constant weight (W2), and the suspension rate was calculated as follows: the suspension percentage is (W1-W2)/W2 × 100%.
The disintegration property was measured by adding 100ml of water to a 250ml measuring cylinder, then pouring 0.5g of 90% atrazine WDG, and starting to examine its wettability and looseness by visual observation until the particles settled to the bottom of the measuring cylinder. The evaluation was carried out according to the following criteria. a. Almost all the granules are disintegrated and excellent; b. about half of the granules had disintegrated and were good; c. little granule disintegration, poor.
Dispersion (CIPAC MT160) and visual observation, 1g of atrazine WDG was added to a 250ml measuring cylinder containing 250ml of the desired 3-fold standard hard water (1026ppm) and temperature (30 ℃ C.) water. It is desirable that the dispersion is cloudy, and it is inferior that the dispersion is dropped in granular form.
Storage stability (CIPAC MT39.3, MT46.3) like other pesticide formulations, at-5. + -. 2 ℃ and 54. + -. 2 ℃ for two weeks, no change in appearance and degradation of the active ingredient occurred during storage, and the suspension percentage after storage was determined, with suspension percentages > 90% satisfying the requirements and the higher the suspension percentage the better the stability of the formulation.
The results are shown in Table 1.
Table 1 performance evaluation results of different dispersants in 90% atrazine WDG
Note: SD-819 is a polycarboxylic acid type dispersant derived from Shanghai, a large polymer materials Co., Ltd; huntsman 2700 is a polycarboxylic acid type dispersant from the hensman manufacturer.
As is clear from the data in the tables, when the molecular weight and the water/solvent mass ratio of the carboxylic acid-based polymer were controlled to 5000-; according to the comparison between the examples 1 to 4 and the comparative examples 1 to 2 and the products on the market, the appropriate amount of PO and the bilateral branched chain structure are introduced, so that the dispersibility, the suspension rate and the disintegration of 90% atrazine WDG after hot storage, cold storage and normal temperature storage can meet the requirements, and the product performance is superior to the product performance of the same type on the market.
Experimental example 2
The carboxylic acid polymer prepared in each example and comparative example is used as a dispersant in a pesticide aqueous suspension, and the imidacloprid Suspension (SC) with the mass percentage of 50% is prepared, and the specific preparation method comprises the following steps: 50kg of imidacloprid technical, 5kg of dispersing agent prepared in the invention, 2kg of emulsifying agent (703D optimized chemical), 0.1kg of defoaming agent (XEP5303 optimized chemical), 0.1kg of xanthan gum and the balance of water to 100 kg. The raw materials are mixed according to the proportion, and a final sample, namely the 50% imidacloprid SC, can be obtained after sanding and filtering by a sand mill.
The particle size, suspension percentage, dispersibility, fluidity and storage stability of the imidacloprid SC are respectively tested, and the specific test method comprises the following steps:
the particle size test method is that 1g of 50% imidacloprid SC is dispersed in 100ml of water, the particle size is measured by an optical microscope or a laser particle sizer, the experimental example adopts the laser particle sizer for measurement, and the average particle size of the aqueous suspension agent obtained in the embodiment of the invention is about 0.2-5 microns. The smaller the particle size, the more desirable the suspending agent.
The suspension percentage (CIPAC MT161, MT184) was measured by placing 40ml of water in a beaker, adding 4g (W1) of 50% imidacloprid SC, standing for 30s, and stirring for another 90 s. It was then transferred to a 250ml graduated cylinder and diluted to 250ml with water, the cylinder was inverted 15 times, left to stand for 30 minutes and the upper 225ml of suspension was pumped off with water. The bottom 25ml were transferred in their entirety to a weighing pan and dried to constant weight (W2), and the suspension rate was calculated as follows: the suspension percentage is (W1-W2)/W2 × 100%.
Dispersion (CIPAC MT160) and visual observation, 1g of 50% imidacloprid SC suspension was added to a 250ml graduated cylinder containing 250ml of the desired standard hard water (342ppm) and temperature (30 ℃ C.) water. It is desirable that the dispersion is cloudy, and it is inferior that the dispersion is dropped in granular form.
Flowability is characterized by the viscosity of the formulation, measured with a B-type-viscometer (NDJ-1) to determine the viscosity of a 50% imidacloprid SC suspension, the lower the suspension viscosity, the better the flowability. The viscosity is generally between 100 and 500 centipoises, and no problem exists in the specific implementation process.
Storage stability (CIPAC MT39.3, MT46.3) like other pesticide formulations, at 0. + -. 2 ℃ and 54. + -. 2 ℃ for two weeks, no change in appearance and degradation of the active ingredient can occur during storage, and the suspension percentage after storage is determined, with suspension percentages > 90% being sufficient and the higher the suspension percentage the better the stability of the formulation.
The results are shown in Table 2.
TABLE 2 evaluation of the Performance of different dispersants in 50% Imidacloprid SC
Note: SD-811 is a polycarboxylic acid type dispersant derived from Shanghai, a large polymer materials Co., Ltd; agrilan 788 is a polycarboxylic acid type dispersant from noreon manufacturers.
As can be seen from the data in the table, when the molecular weight of the carboxylic acid polymer and the mass ratio of water to solvent are controlled to 5000-; according to the comparison between the examples 1-4 and the comparative examples 1-2 and the products on the market, the appropriate amount of PO and the bilateral branched chain structure are introduced, so that the dispersibility, the suspension rate and the fluidity of 50 percent imidacloprid SC after hot storage, cold storage and normal temperature storage meet the requirements, and the imidacloprid SC is superior to the products of the same type on the market in performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A polyoxyethylene polyoxypropylene ether having a structure represented by formula (III):
wherein p is an integer between 2 and 4, q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10.
2. The polyoxyethylene polyoxypropylene amine ether according to claim 1, wherein the polyoxyethylene polyoxypropylene amine ether has a structure shown as follows:
3. a preparation method of polyoxyethylene polyoxypropylene ether is characterized by comprising the following steps:
(1) reacting ethylene glycol alkyl ether, ethylene oxide and propylene oxide under the action of an alkaline catalyst to obtain an intermediate 1;
(2) taking the intermediate 1 to react with thionyl chloride under the action of an alkaline catalyst to prepare an intermediate 2;
(3) taking the intermediate 2, potassium iodide and alkanolamine to carry out a first reaction under the action of an alkaline catalyst to obtain a reaction solution, taking the reaction solution to carry out a second reaction with acryloyl halide to obtain polyoxyethylene polyoxypropylene amine ether.
4. The method for producing a polyoxyethylene polyoxypropylene ether according to claim 3, wherein any one or more of the following A to F is satisfied:
A. in the step (1), the molar ratio of the ethylene glycol alkyl ether to the ethylene oxide to the propylene oxide is 1:2-10:2-5, the reaction temperature in the step (1) is 100-;
B. the molar ratio of the ethylene glycol alkyl ether in the step (1) to the basic catalyst and the thionyl chloride in the step (2) is 1:2-4:2-6, wherein the reaction temperature in the step (2) is 30-50 ℃, and the reaction time is 16-24 h;
C. the molar ratio of the ethylene glycol alkyl ether in the step (1) to the basic catalyst, potassium iodide, alkanolamine and acrylic halide in the step (3) is 5:4-10:30-40:2-6: 4-12; in the step (3), the first reaction is carried out under the reflux of nitrogen, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 h; the second reaction is to drop the acryloyl halide into the reaction liquid at 0-10 ℃ for 3-5 h;
D. in the step (1), the adopted glycol alkyl ether is at least one of glycol methyl ether, glycol ethyl ether and glycol propyl ether;
E. in the step (2) and/or the step (3), the adopted alkaline catalyst is at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide;
F. in the step (3), the adopted acryloyl halide is one of acryloyl chloride, acryloyl bromide and acryloyl iodide; the alkanolamine is selected from one of ethanolamine, propanolamine and butanolamine.
5. A carboxylic acid-based copolymer or a salt thereof, characterized in that the carboxylic acid-based copolymer has a structure represented by the formula (IV):
wherein a, b and c are positive integers, p is an integer between 2 and 4, q is an integer between 0 and 2, m is an integer between 2 and 5, and n is an integer between 2 and 10;
R1，R2independently selected from H, methyl, carboxyl;
R3，R4，R5independently selected from H, methyl, phenyl, hexyl, -CH2C(CH3)3，-CONH2，
HOCH2CH2NHCO-，HOCH2CH2CH2NHCO-，(CH3)2NCH2CH2COO-，-CONHC(CH3)2CH2SO3H，-COOCH2CH2N(CH3)2，-CH2SO3Na，
Or, R4，R5Form a ring of R4，R5Each independently of the group
Is linked to the methylene group of (a).
6. A polycarboxylic acid-based copolymer or a salt thereof, wherein the monomers of the polycarboxylic acid-based copolymer include:
(1) at least one unsaturated carboxylic acid and/or derivative thereof;
(2) at least one lipophilic unsaturated comonomer;
(3) at least one polyoxyethylene polyoxypropylene amine ether, which is the polyoxyethylene polyoxypropylene amine ether according to claim 1 or 2 or the polyoxyethylene polyoxypropylene amine ether obtained by the production method according to claim 3 or 4.
7. The polycarboxylic acid-based copolymer or the salt thereof according to claim 5 or 6, characterized in that the number average molecular weight of said carboxylic acid-based polymer is 5000-50000.
8. A method for preparing a polycarboxylic acid copolymer or a salt thereof, which comprises copolymerizing the polyoxyethylene polyoxypropylene ether according to claim 1 or 2 or the polyoxyethylene polyoxypropylene ether obtained by the method according to claim 3 or 4, an unsaturated carboxylic acid and/or a derivative thereof, and a lipophilic unsaturated comonomer in an initiator, a chain transfer agent, and a solvent system;
preferably, any one or more of the following (1) to (5) are also satisfied:
(1) the mass ratio of the polyoxyethylene polyoxypropylene ether, the unsaturated carboxylic acid and/or the derivative thereof, the lipophilic unsaturated comonomer, the initiator and the chain transfer agent is 100:50-300:50-150:5-20:1-15, in the copolymerization reaction, the reaction temperature is 50-90 ℃, the reaction time is 3.5-7h, and the solvent system comprises the following components in a mass ratio of 1:1-1:5 with water;
(2) the unsaturated carboxylic acid is one or a mixture of acrylic acid, methacrylic acid, maleic acid and fumaric acid; the unsaturated carboxylic acid derivative is maleic anhydride;
(3) the lipophilic unsaturated comonomer is one or a mixture of more of 1-octene, dicyclopentadiene, styrene, alpha-methylstyrene, diisobutylene, hydroxyethyl acrylamide, hydroxypropyl acrylamide, vinyl pyrrolidone, sodium styrene sulfonate, 2-acrylamide-2-methylpropanesulfonic acid, dimethylaminoethyl methacrylate and sodium allylsulfonate;
(4) the chain transfer agent is one or a mixture of more of mercaptoethanol, isopropanol, sodium bisulfite and sodium methallyl sulfonate;
(5) the initiator is selected from one or a mixture of more of persulfate initiator, azo initiator and peroxide initiator.
9. Use of a polycarboxylic acid-based copolymer or a salt thereof for improving dispersibility of materials or as a dispersant, characterized in that the polycarboxylic acid-based copolymer or a salt thereof is the polycarboxylic acid-based copolymer or a salt thereof according to any one of claims 5 to 7, or the polycarboxylic acid-based copolymer or a salt thereof is the polycarboxylic acid-based copolymer or a salt thereof produced by the production method according to claim 8.
10. A pesticide preparation comprising the polycarboxylic acid-based copolymer or the salt thereof according to any one of claims 5 to 7 or the polycarboxylic acid-based copolymer or the salt thereof produced by the production method according to claim 8.
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