CN113527659B - Polyoxyethylene polyoxypropylene amine ether, carboxylic acid polymer, preparation method and application - Google Patents
Polyoxyethylene polyoxypropylene amine ether, carboxylic acid polymer, preparation method and application Download PDFInfo
- Publication number
- CN113527659B CN113527659B CN202110592874.0A CN202110592874A CN113527659B CN 113527659 B CN113527659 B CN 113527659B CN 202110592874 A CN202110592874 A CN 202110592874A CN 113527659 B CN113527659 B CN 113527659B
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- China
- Prior art keywords
- polyoxyethylene polyoxypropylene
- ether
- carboxylic acid
- polyoxypropylene amine
- reaction
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 title claims abstract description 72
- 150000001412 amines Chemical class 0.000 title claims abstract description 49
- 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
- -1 olefin ester Chemical class 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000002270 dispersing agent Substances 0.000 claims description 33
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 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
- 239000012986 chain transfer agent Substances 0.000 claims description 13
- 230000035484 reaction time Effects 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 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
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- 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
- 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
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000000361 pesticidal effect Effects 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000725 suspension Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 238000003860 storage Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000004562 water dispersible granule Substances 0.000 description 14
- 229920005646 polycarboxylate Polymers 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 239000005906 Imidacloprid Substances 0.000 description 11
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 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
- 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
- 238000012360 testing method Methods 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
- 239000006185 dispersion Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000000375 suspending agent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
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- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 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
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical group CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- LWRXNMLZNDYFAW-UHFFFAOYSA-N 1-octylperoxyoctane Chemical compound CCCCCCCCOOCCCCCCCC LWRXNMLZNDYFAW-UHFFFAOYSA-N 0.000 description 1
- 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
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241000209094 Oryza Species 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
- 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
- 125000003277 amino group Chemical group 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
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- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000011344 liquid material Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 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
- 125000000542 sulfonic acid group Chemical group 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
-
- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 in particular relates to polyoxyethylene polyoxypropylene amine ether, a carboxylic acid polymer, a preparation method and application thereof,has a structure shown in formula (III):
Description
Technical Field
The invention belongs to the technical field of functional polymer material preparation, and particularly relates to polyoxyethylene polyoxypropylene amine ether, a carboxylic acid polymer, a preparation method and application thereof.
Background
The pesticide is an important means for preventing and controlling diseases, weeds and protecting crops, 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 pollution becomes an environmental problem of increasing attention of people. The research hot spot in the field of pesticide preparations is to reduce the pollution of pesticides to the environment through innovation of pesticide preparation technology. The development of pesticide preparations is advancing toward the development of water-based preparations and dust-free solid particle preparations which are safer, environmentally friendly and low in cost. The water suspending agent (SC) or the Water Dispersible Granule (WDG) is the dosage form with the fastest development in recent years, the most mature processing technology, the lowest cost and the largest processable pesticide active ingredient. Under the action of a dispersing agent, a water-insoluble or poorly-soluble crude drug is dispersed into water to form a uniform and stable dispersion system, and the formulation is uniformly mixed and dispersed with water in any proportion and is hardly influenced by water quality and water temperature, so that dust pollution, harm to operators and safety to surrounding environment can be avoided, and the formulation is considered as one of pesticide formulations with the most development prospect in the twenty-first century.
The polycarboxylate dispersant is a novel efficient agricultural dispersant which is widely used in water suspending agents or water dispersible granules, the dispersant has long carbon chains and more adsorption sites, and branched chain groups such as carboxyl, sulfonic acid groups, amino groups, polyoxyethylene side chains and the like can play a role in space rejection, so that the special structure of the polycarboxylate dispersant has good dispersion performance on a suspension system. The traditional polycarboxylic acid dispersing agent is generally single-arm and contains ether bond or ester bond side chain structure, and the raw materials for synthesizing the polycarboxylic acid dispersing agent mainly comprise polyethylene glycol, allyl polyethylene glycol ether and the like, however, the stability and suspension improving effect of the polycarboxylic acid dispersing agent on pesticide preparations are general, and in order to better improve the stability and suspension of the pesticide preparations, new raw materials are necessary to be developed for preparing new polycarboxylic acid dispersing agents.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of lower stability and poorer suspension property of pesticide preparations caused by the adoption of the traditional polycarboxylate dispersant in the prior art, thereby providing polyoxyethylene polyoxypropylene amine ether, carboxylic acid polymers, and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme:
the invention provides polyoxyethylene polyoxypropylene amine 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) n Refers to the whole (PO) m (EO) n There are m propoxy units PO and n ethoxy units EO, where PO and EO are randomly or statistically distributed.
The desired distribution (PO) can be obtained by processes known to the person skilled in the art, for example by sequential adjustment of the addition or simultaneous addition of ethylene oxide and propylene oxide and controlling the molar ratio to one another m (EO) n Fragments.
In a preferred embodiment, the polyoxyethylene polyoxypropylene amine ether has the structure shown below:
the invention also provides a preparation method of the polyoxyethylene polyoxypropylene amine 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 intermediate 2, potassium iodide and alkanolamine to react for the first time under the action of an alkaline catalyst to obtain a reaction solution, and taking the reaction solution to react with acryloyl halide for the second time to obtain polyoxyethylene polyoxypropylene amine ether.
Wherein intermediate 1 has the general structural formula of formula (I):
H(PO) m (EO) n CH 2 CH 2 O(CH 2 ) q CH 3
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) n CH 2 CH 2 O(CH 2 ) q CH 3
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-F are satisfied;
A. the molar ratio of the glycol alkyl ether, the ethylene oxide and the propylene oxide in the step (1) is 1:2-10:2-5, wherein the reaction temperature in the step (1) is 100-110 ℃, and the reaction time is 3-6h;
B. the molar ratio of the glycol alkyl ether in the step (1) to the basic catalyst in the step (2) to the thionyl chloride is 1:2-4:2-6, the reaction temperature in the step (2) is 30-50 ℃ and the reaction time is 16-24h.
C. The molar ratio of the glycol alkyl ether in the step (1) to the alkaline catalyst, potassium iodide, alkanolamine and the acryloyl 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 condition of nitrogen reflux, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 hours; the second reaction is to drop the acryl halide into the reaction liquid with the temperature of 0-10 ℃ for 3-5h;
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 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 one selected from ethanolamine, propanolamine and butanolamine
The invention also provides a carboxylic acid copolymer or salt thereof, which has a structural formula shown in the following formula (IV):
wherein a, b, 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;
R 1 ，R 2 independently selected from H, methyl, carboxyl;
R 3 ，R 4 ，R 5 independently selected from H, methyl, phenyl, hexyl, -CH 2 C(CH 3 ) 3 ，-CONH 2 ，HOCH 2 CH 2 NHCO-，HOCH 2 CH 2 CH 2 NHCO-，(CH 3 ) 2 NCH 2 CH 2 COO-，-CONHC(CH 3 ) 2 CH 2 SO 3 H，-COOCH 2 CH 2 N(CH 3 ) 2 ，-CH 2 SO 3 Na，/>Alternatively, R 4 ，R 5 Form a ring, R 4 ，R 5 Respectively with the radicals->Methylene linkage of (c).
In a preferred embodiment, the partial carboxylic acid copolymer has the following structure:
the invention also provides the carboxylic acid copolymer, which at least comprises three monomers, namely:
(1) At least one polyoxyethylene polyoxypropylene amine 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 any polyoxyethylene polyoxypropylene amine ether or polyoxyethylene polyoxypropylene amine ether prepared by any preparation method.
The three monomer 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 adjusting the sequence of addition or by adding the three monomers simultaneously and controlling the molar ratio to one another.
Lipophilic unsaturated comonomers are comonomers which contain carbon-carbon unsaturated double bonds and which are more prone to dissolution in oil-soluble solvents.
In a preferred embodiment, the carboxylic acid polymer has a number average molecular weight of 5000 to 50000.
The invention also provides a preparation method of the polycarboxylic acid copolymer or the salt thereof, which comprises the steps of taking any one of the polyoxyethylene polyoxypropylene amine ether or the polyoxyethylene polyoxypropylene amine ether prepared by any one of the preparation methods, unsaturated carboxylic acid and/or the derivative thereof and lipophilic unsaturated comonomer, and carrying out copolymerization reaction under the conditions of an initiator, a chain transfer agent and a solvent system.
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 amine 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 3.5-7h;
(2) The solvent system comprises water and an organic solvent, and preferably the organic solvent is one or a mixed solvent of a plurality 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 several 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 bisulphite and sodium methallyl sulfonate; and/or the initiator is selected from one or a mixture of a plurality of persulfate initiators, azo initiators and peroxide initiators.
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, dioctyl peroxide and dilauroyl peroxide; the azo initiator is one or a mixture of a plurality of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, azoi Ding Qingji formamide and azodicyclohexyl carbonitrile.
The invention also provides an application of the polycarboxylic acid copolymer or the salt thereof in improving the dispersibility of materials or being used as a dispersing agent, wherein the local carboxylic acid copolymer is any one of the polycarboxylic acid copolymer or the salt thereof prepared by the preparation method.
Wherein the dispersibility of the materials is improved, the dispersants of the present invention can be used for dispersing one solid material into another solid material, and also for dispersing into another liquid material or semisolid material. 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 art, and can be, but is not limited to, a water suspension agent 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 double-arm unsaturated olefin ester and amine ether structure, and is used as a raw material for synthesizing a carboxylic acid polymer with excellent dispersibility and stability on pesticides.
2. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether, the hydroxyl-terminated polyoxyethylene polyoxypropylene ether is prepared by reacting ethylene glycol alkyl ether with ethylene oxide and propylene oxide, then the chlorine-terminated polyoxyethylene polyoxypropylene ether is prepared by reacting with thionyl chloride, and finally the polyoxyethylene polyoxypropylene amine ether is prepared by reacting with alkanolamine and acrylic halide in sequence.
3. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether, the molar ratio of the glycol alkyl ether in the step (1) to the basic catalyst in the step (2) to the thionyl chloride is 1:2-4:2-6, the reaction temperature is controlled to be 30-50 ℃, the reaction time is controlled to be 16-24 hours, and the substitution rate of a chloro group can be obviously improved through the control of the combination reaction conditions of the molar ratio of the substances, so that the yield and the purity of the intermediate 2 are improved, and the generation of the polyoxyethylene polyoxypropylene amine ether is promoted.
4. In the step (3), the first reaction is carried out under the condition of nitrogen reflux, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 hours; the second reaction is to drop the acryloyl chloride into the reaction liquid at 0-10 ℃ for 3-5h; the molar ratio of the glycol alkyl ether in the step (1) to the alkaline catalyst, potassium iodide, alkanolamine and acryloyl halide in the step (3) is 5:4-10:30-40:2-6:4-12, and through the control of the molar ratio of the substances, the reaction time and the reaction temperature, the complete substitution of two hydrogen atoms on a primary amino group in the intermediate 2 can be promoted, so that the synthesis of the double-arm polyoxyethylene polyoxypropylene amine ether is promoted, and the yield and the purity of a target product are improved.
5. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether, in the step (1), the mol ratio of ethylene glycol alkyl ether to ethylene oxide to propylene oxide is 1:2-10:2-5, the Oryza curing process of pesticide particles can be inhibited by introducing the ethylene oxide to the propylene oxide, the stability is improved, and the research shows that the 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 not only has excellent dispersibility, disintegrability and stability, but also has colorless or pale yellow color, and can be used in occasions with high color requirement.
7. The preparation method of the polyoxyethylene polyoxypropylene amine ether provided by the invention discovers that the reaction is carried out under a mixed system of water and an organic solvent, so that the phenomena of bursting or layering can be effectively avoided, the reaction is easy to control and operate, and the problems of uneven reaction, layering, safety risks caused by overlarge solvent consumption and the like caused by independently adopting water or the organic solvent are effectively avoided.
8. According to the preparation method of the polyoxyethylene polyoxypropylene amine ether, the mass ratio of the polyoxyethylene polyoxypropylene amine ether, unsaturated carboxylic acid and/or derivatives thereof, lipophilic unsaturated comonomer, initiator and chain transfer agent is 100:50-300:50-150:5-20:1-15, and the mass ratio of organic solvent and water is 1:1-1:5, and in the copolymerization reaction, the reaction temperature is 50-90 ℃ and the reaction time is 3.5-7h; through the control of the mass of each monomer, the mass ratio of the initiator to water in the solvent, the reaction temperature and the reaction time, the carboxylic acid polymer with proper molecular weight and number average molecular weight of 5000-50000 is obtained, the carboxylic acid polymer with molecular weight can exert the effect of dispersing and stabilizing pesticide particles to the greatest extent, and if the molecular weight is too low, the steric hindrance generated by a molecular side chain is too small, and the pesticide particles are easy to agglomerate; if the molecular weight is too high, too long molecular side chains thereof are liable to be entangled with each other, thereby lowering the stability of the formulation.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In the invention, the purity of the chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 and the purity of the unsaturated double-bond polyoxyethylene polyoxypropylene amine ether intermediate 3 are measured by a High Performance Liquid Chromatograph (HPLC), and the test conditions are as follows: the Shimadzu high performance liquid chromatograph LC-20A system, mobile phase (volume ratio) methanol/water solution (75/25), flow rate 1.0mL/min, chromatographic column Inertsil ODS-SP,5 μm,4.6mm×150mm, sample injection volume 25. Mu.L, column temperature 40 ℃, detection wavelength 360nm, isocratic elution.
Example 1
The embodiment provides polyoxyethylene polyoxypropylene amine ether, the structural formula of which is shown as the following formula:
the preparation method comprises the following steps:
(1) Ethylene glycol methyl ether 76kg (1 Kmol) and an alkaline catalyst KOH 5.6kg are mixed, the temperature is raised to 100 ℃, 88kg (2 Kmol) of ethylene oxide and 116kg (2 Kmol) of propylene oxide are added, after the addition of the materials is completed for 1 hour, the reaction is continued for 3 hours at 100 ℃ to obtain 280kg of intermediate 1, and the EO polymerization degree in the intermediate 1 is 2, the PO polymerization degree is 2 and the number average molecular weight is 280 after the test of a nuclear magnetic resonance hydrogen spectrometer.
(2) 238kg of thionyl chloride (2 Kmol) was dissolved in 156kg of dimethyl sulfoxide to obtain a thionyl chloride solution. 280kg of intermediate 1 and 276kg of potassium carbonate (2 Kmol) are placed in 500L of dimethyl sulfoxide, the thionyl chloride solution is added dropwise, the reaction is carried out 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, the yield is 62%, and the purity is 90%.
(3) 320kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 (1 Kmol) is taken and dissolved in 328kg of acetonitrile, then 110kg of potassium carbonate (0.8 Kmol), 996kg of potassium iodide (6 Kmol) and 25kg of ethanolamine (0.4 Kmol) are added for reaction under the condition of nitrogen reflux at 60 ℃ for 16 hours, 72kg of 50% by mass of acryloyl chloride solution (acetonitrile as solvent) is dripped after filtration, the reaction is carried out for 3 hours at 0 ℃, 383kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, and the yield is 25% and the purity is 92%.
The present example provides a carboxylic acid copolymer as a polycarboxylate dispersant having the structural formula:
the preparation method comprises the following steps:
60kg of methanol and 60kg of water are mixed in a mixed system of methanol and water at 50 ℃. To the mixed system, 2kg of potassium persulfate as an initiator and 0.4kg of mercaptoethanol as a chain transfer agent were added. 40kg of polyoxyethylene polyoxypropylene amine ether, 20kg of methacrylic acid and 20kg of styrene are taken and dropwise added into the reaction system after being mixed, and the reaction is continued at 50 ℃ for 1.5 hours after the completion of the dropwise addition. The solvent was distilled off under reduced pressure at 50℃after neutralization to pH 5.5 with 32% by mass of an aqueous NaOH solution, to give polycarboxylate dispersant AGC-1 having a number average molecular weight of 49800 (GPC).
Example 2
The embodiment provides polyoxyethylene polyoxypropylene amine ether, the structural formula of which is shown as the following formula:
the preparation method comprises the following steps:
(1) 90kg (1 Kmol) of ethylene glycol diethyl ether and 5.6kg of alkaline catalyst KOH are mixed, the temperature is raised to 110 ℃, 440kg (10 Kmol) of ethylene oxide and 290kg (5 Kmol) of propylene oxide are added, after 2 hours of addition, the mixture is reacted for 4 hours, 820kg of intermediate 1 is obtained, EO polymerization degree in the intermediate 1 is 10, PO polymer is 5 and number average molecular weight is 800 in the nuclear magnetic resonance hydrogen spectrometer test.
(2) 476kg of thionyl chloride (4 Kmol) was dissolved in 250kg of methylene chloride to obtain a thionyl chloride solution. 820kg of intermediate 1 (1 Kmol) and 552kg of potassium carbonate (4 Kmol) are placed in 800L of dichloromethane, the thionyl chloride solution is added dropwise, the mixture is reacted for 24 hours at 50 ℃, and 970kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 is obtained after filtration, desalination and reduced pressure distillation, the yield is 75%, and the purity is 89%.
(3) 970kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 (1 Kmol) is taken and dissolved in 500kg of tetrahydrofuran, then 276kg of potassium carbonate (2 Kmol), 1328kg of potassium iodide (8 Kmol) and 74kg of ethanolamine (1.2 Kmol) are added to react under reflux of nitrogen at 80 ℃ for 24 hours, 216kg of 60% acrylic chloride solution (solvent is tetrahydrofuran) by mass percent is dripped into the mixture after filtering, the mixture is reacted for 24 hours at 10 ℃, and 1390kg of polyoxyethylene polyoxypropylene ether is obtained after filtering and reduced pressure distillation, the yield is 48%, and the purity is 91%.
The present embodiment provides a carboxylic acid copolymer which can be used as a polycarboxylate dispersant, and has a structural formula shown as follows:
the preparation method comprises the following steps:
in a mixed system of butanone and water at 80 ℃, the butanone is 20kg and the water is 100kg. 8kg of diacetyl peroxide as an initiator and 6kg of isopropyl alcohol as a chain transfer agent are added into the mixed system. Mixing and dripping 40kg of unsaturated double bond polyoxyethylene polyoxypropylene amine ether intermediate 3, 60kg of acrylic acid, 60kg of maleic anhydride and 60kg of sodium styrene sulfonate, and keeping the temperature at 80 ℃ for 5 hours after the dripping is completed. The solvent was distilled off under reduced pressure at 80℃after neutralization with triethanolamine to pH 8, to give polycarboxylate dispersant AGC-2 having a number average molecular weight of 5120 (GPC).
Example 3
The embodiment provides polyoxyethylene polyoxypropylene amine ether, the structural formula of which is shown as the following formula:
the preparation method comprises the following steps:
(1) 104kg (1 Kmol) of ethylene glycol propyl ether and 5.6kg of alkaline catalyst KOH are mixed, the temperature is raised to 105 ℃, 220kg (5 Kmol) of ethylene oxide and 174kg (3 Kmol) of propylene oxide are added, and after the addition of the materials is completed for 1 hour, the reaction is carried out for 4 hours, 498kg of intermediate 1 is obtained, and the EO polymerization degree in the intermediate 1 is 5, the PO polymer is 3 and the number average molecular weight is 500 after the test of a nuclear magnetic resonance hydrogen spectrometer.
(2) 357kg of thionyl chloride (3 Kmol) was dissolved in 200kg of acetone to obtain a thionyl chloride solution. 498kg of intermediate 1 (1 Kmol) and 414kg of potassium carbonate (3 Kmol) are placed in 600L of acetone, the thionyl chloride solution is added dropwise, the reaction is carried out for 20 hours at 40 ℃, and 633kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 is obtained after filtration, desalination and reduced pressure distillation, the yield is 74%, and the purity is 97%.
(3) Taking 633kg of chlorinated end-capped polyoxyethylene polyoxypropylene ether intermediate 2 (1 Kmol), dissolving in 350kg of isopropyl formate, then adding 170kg of sodium carbonate (1.6 Kmol), 1162kg of potassium iodide (7 Kmol) and 49kg of ethanolamine (0.8 Kmol), reacting under reflux of nitrogen at 70 ℃ for 20 hours, filtering, dripping 144kg of 55% by mass of acrylic chloride solution (the solvent is isopropyl formate), reacting for 20 hours at 5 ℃, filtering and distilling under reduced pressure to obtain 915kg of polyoxyethylene polyoxypropylene ether, wherein the yield is 42% and the purity is 90%.
The present embodiment provides a carboxylic acid copolymer which can be used as a polycarboxylate dispersant, and has a structural formula shown as follows:
the preparation method comprises the following steps:
in a mixed system of acetonitrile and water at 70 ℃, 40kg of acetonitrile and 80kg of water are adopted. 4kg of initiator azobisisobutyronitrile and 3kg of chain transfer agent sodium methacrylate sulfonate were added to the mixed system. Mixing and dripping 40kg of unsaturated double bond polyoxyethylene polyoxypropylene amine ether intermediate 3, 30kg of maleic acid, 30kg of maleic anhydride, 20kg of hydroxyethyl acrylamide and 20kg of vinyl pyrrolidone for 3 hours, and keeping the temperature at 70 ℃ for 2 hours. The solvent was distilled off under reduced pressure at 70℃after neutralization to pH 7 with 32% by mass of potassium hydroxide solution, to give polycarboxylate dispersant AGC-3 having a number average molecular weight of 36930 (GPC).
Example 4
The embodiment provides polyoxyethylene polyoxypropylene amine ether, the structural formula of which is shown as the following formula:
the preparation method is basically the same as that of example 1, except that in step (3), 320kg of the chlorinated and capped polyoxyethylene polyoxypropylene ether intermediate 2 (1 Kmol) is taken and dissolved in 328kg of acetonitrile, then 110kg of potassium carbonate (0.8 Kmol), 996kg of potassium iodide (6 Kmol) and 30kg of propanolamine (0.4 Kmol) are added, the mixture is reacted under the condition of 60 ℃ nitrogen reflux, 16 hours of reaction is carried out, after filtration, 72kg of an acryloyl chloride solution (solvent is acetonitrile) with the mass percentage of 50% is dripped, the reaction is carried out for 3 hours at 0 ℃, 385kg of polyoxyethylene polyoxypropylene ether is obtained after filtration and reduced pressure distillation, and the yield is 25% and the purity is 91%.
The present embodiment provides a carboxylic acid copolymer which can be used as a polycarboxylate dispersant, and has a structural formula shown as follows:
the preparation method comprises the following steps:
60kg of methanol and 60kg of water are mixed in a mixed system of methanol and water at 50 ℃. To the mixed system, 2kg of potassium persulfate as an initiator and 0.4kg of mercaptoethanol as a chain transfer agent were added. 40kg of unsaturated double bond polyoxyethylene polyoxypropylene amine ether intermediate 3, 20kg of methacrylic acid and 20kg of styrene are taken and dropwise added into the reaction system after being mixed, and the reaction is continued at 50 ℃ for 1.5h after the dropwise addition is completed. The solvent was distilled off under reduced pressure at 50℃after neutralization to pH 5.5 with 32% by mass of aqueous NaOH solution, to give polycarboxylate dispersant AGC-4 having a number average molecular weight of 46600 (GPC).
Example 5
This example provides a process for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is substantially the same as example 1, except that 1kg of potassium persulfate as an initiator and 0.2kg of mercaptoethanol as a chain transfer agent are added to the mixed system during the preparation of the carboxylic acid polymer, and the remaining reagents and reaction conditions are the same as those of example 1, to obtain a polycarboxylate dispersant having a number average molecular weight of 63200 (GPC).
Example 6
This example provides a process for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is substantially the same as example 1, except that 10kg of potassium persulfate as an initiator and 8kg of mercaptoethanol as a chain transfer agent are added to the mixed system during the preparation of the carboxylic acid polymer, 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 (GPC).
Example 7
The present example provides a method for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is basically the same as example 1, except that the solvent system in the preparation process of the carboxylic acid polymer is different, the solvent system in the present example is a mixed system of water and methanol, the mass of water is 110kg, the mass of methanol is 10kg, the rest of reagents and reaction conditions are the same as example 1, and the carboxylic acid polymer with a number average molecular weight of 75800 (measured by GPC) is obtained through the reaction.
Example 8
The present example provides a method for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is basically the same as example 1, except that the solvent system in the preparation process of the carboxylic acid polymer is different, the solvent system in the present example is a mixed system of water and methanol, the mass of water is 20kg, the mass of methanol is 120kg, the rest of reagents and reaction conditions are the same as example 1, and the carboxylic acid polymer with a number average molecular weight of 34860 (measured by GPC) is obtained through the reaction.
Comparative example 1
This example provides a process for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid-based polymer, which is substantially the same as example 1, except that in the step (1) of preparing a polyoxyethylene polyoxypropylene ether, propylene oxide is omitted, the amount of ethylene oxide added is 176kg, and the remaining reagents and reaction conditions are the same as example 1.
Comparative example 2
This example provides a process for preparing a polyoxyethylene polyoxypropylene ether and a carboxylic acid polymer, which is substantially identical to example 1, except that in step (3) of preparing a polyoxyethylene polyoxypropylene ether, ethanolamine is replaced with N-methylethanolamine, i.e., N-methylethanolamine, in an equimolar amount of 30kg to give 385kg of polyoxyethylene polyoxypropylene ether in a yield of 25% and a purity of 91%.
Experimental example 1
The powder obtained after spray drying of the carboxylic acid polymers prepared in each example and comparative example is used as a dispersing agent in pesticide dispersible granules (WDG) to prepare atrazine technical product with the mass percentage of 90 percent, 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 optimization chemical), 1kg of dry starch and the balance of magnesium aluminum silicate to 100kg. Mixing above materials at the above ratio, adding into jet mill, and superfine pulverizing to particle size of 2-5 μm to obtain fine powder. Adding 10kg of water with the mass of the fine powder, kneading for 0.5h, granulating, sending into an air flow dryer for drying, and screening to obtain the atrazine WDG with the mass of 90%.
The particle size, suspension rate, disintegration, dispersibility and storage stability of 90% atrazine WDG were tested separately, and the specific test method was:
particle size measurement method 1g of 90% atrazine WDG was dispersed in 100ml of water, and its particle size was measured with an optical microscope or a laser particle sizer, and the average particle size of the aqueous suspension obtained in the examples of the present invention was about 0.2 to 5 μm, as measured with a laser particle sizer. The smaller the particle diameter, the more desirable the particle dispersing effect.
The suspension ratio (CIPAC MT161, MT 184) was measured by placing 40ml of water in a beaker, adding 4g (W1) of 90% atrazine WDG, standing for 30s, and stirring for another 90s. It was then transferred to a 250ml measuring cylinder and diluted with water to 250ml, the cylinder was inverted 15 times, left to stand for 30 minutes and the upper 225ml suspension was pumped off with water. The bottom 25ml was transferred in its entirety to a weighing pan and dried to constant weight (W2), the suspension ratio was calculated as follows: suspension% = (W1-W2)/w2×100%.
The disintegration test was carried out 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 granules were settled to the bottom of the measuring cylinder. The evaluation was performed as follows. a. Almost all particles have disintegrated, preferably; b. about half of the granules disintegrated well; c. few particles disintegrated, poor.
Dispersibility (CIPAC MT 160), visual observation, 1g of atrazine WDG was added to a 250ml graduated cylinder containing 250ml of the required 3-fold standard hard water (1026 ppm) and temperature (30 ℃ C.) water. Dispersion in a cloud form is desirable, and dispersion in a granular form is poor.
Storage stability (CIPAC MT39.3, MT 46.3) like other pesticide formulations, no change in appearance and degradation of the active ingredient occurred during storage for two weeks at-5±2 ℃ and 54±2 ℃, and the suspension rate after storage was determined, the suspension rate being >90% satisfying the requirements and the higher the suspension rate, the better the stability of the formulation.
The test results are shown in Table 1.
TABLE 1 evaluation results of the Performance of different dispersants in 90% atrazine WDG
Note that: SD-819 is a polycarboxylic acid type dispersant from Shanghai, a company of high polymer materials, inc.; huntsman 2700 is a polycarboxylic acid type dispersant from the hensman manufacturer.
As can be seen from the data in the table, when the molecular weight of the carboxylic acid polymer and the water/solvent mass ratio are controlled to be 5000-50000 and 1:1-5:1 respectively, the final 90% atrazine WDG is better in dispersibility, suspension rate and disintegration after heat storage, cold storage and normal temperature storage according to comparison of examples 1-4 and examples 5-8; according to comparison of examples 1-4 with comparative examples 1-2 and products on the market, the introduction of a proper amount of PO and a double-side branched structure can make 90% atrazine WDG meet the requirements on dispersibility, suspension rate and disintegration after heat storage, cold storage and normal-temperature storage, and is superior to the properties of the same type of products on the market.
Experimental example 2
The carboxylic acid polymers prepared in each example and comparative example are used as dispersing agents in pesticide water suspending agents to prepare 50% imidacloprid suspending agents (SC), and the specific preparation method is as follows: 50kg of imidacloprid active compound, 5kg of dispersing agent prepared in the invention, 2kg of emulsifying agent (703D optimization chemistry), 0.1kg of defoaming agent (XEP 5303 optimization chemistry), 0.1kg of xanthan gum and the balance of water to 100kg. Mixing the raw materials according to the proportion, and grinding by adopting a sand mill and filtering to obtain a final sample, namely 50% imidacloprid SC.
The particle size, suspension rate, dispersibility, fluidity and storage stability of imidacloprid SC were tested separately, and the specific test method was:
particle size measurement method 1g of 50% imidacloprid SC was dispersed in 100ml of water, and its particle size was measured with an optical microscope or a laser particle sizer, and the average particle size of the aqueous suspension obtained in the examples of the present invention was about 0.2 to 5. Mu.m. The smaller the particle size, the more desirable the suspending agent.
Suspension ratio (CIPAC MT161, MT 184) was measured by placing 40ml of water in a beaker, adding 4g (W1) of 50% imidacloprid SC, standing for 30s, and stirring for another 90s. It was then transferred to a 250ml measuring cylinder and diluted with water to 250ml, the cylinder was inverted 15 times, left to stand for 30 minutes and the upper 225ml suspension was pumped off with water. The bottom 25ml was transferred in its entirety to a weighing pan and dried to constant weight (W2), the suspension ratio was calculated as follows: suspension% = (W1-W2)/w2×100%.
Dispersibility (CIPAC MT 160), 1g of 50% imidacloprid SC suspension was visually added to a 250ml graduated cylinder containing 250ml of the required standard hard water (342 ppm) and temperature (30 ℃ C.) water. Dispersion in a cloud form is desirable, and dispersion in a granular form is poor.
Flowability is characterized by the viscosity of the formulation, the viscosity of a 50% imidacloprid SC suspension is measured with a B-type viscometer (NDJ-1), the lower the viscosity of the suspension, the better the flowability. Typically, the viscosity is between 100 and 500 centipoise, and no problem exists in the implementation process.
Storage stability (CIPAC MT39.3, MT 46.3) like other pesticide formulations, no change in appearance and degradation of the active ingredient occurred during storage for two weeks at 0±2 ℃ and 54±2 ℃, and the suspension rate after storage was determined, the suspension rate >90% meeting the requirements and the higher the suspension rate, the better the stability of the formulation.
The test results are shown in Table 2.
TABLE 2 evaluation results of the Performance of different dispersants in 50% Imidacloprid SC
Note that: SD-811 is a polycarboxylic acid type dispersant derived from Shanghai which is a large polymer materials Co., ltd; agrilan 788 is a polycarboxylic acid type dispersant from the nuleon manufacturer.
As can be seen from the data in the table, when the molecular weight of the carboxylic acid polymer and the water/solvent mass ratio are controlled to be 5000-50000 and 1:1-5:1 respectively, the final 50% imidacloprid SC is better in dispersibility, suspension rate and fluidity after heat storage, cold storage and normal-temperature storage according to comparison of examples 1-4 and examples 5-8; according to comparison of examples 1-4 with comparative examples 1-2 and products on the market, the addition of a proper amount of PO and a double-side branched structure can enable 50% imidacloprid SC to meet the requirements of heat storage, cold storage, dispersibility after normal-temperature storage, suspension rate and fluidity, and is superior to the performances of the products on the same type on the market.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A polyoxyethylene polyoxypropylene amine ether having the structure of formula (III):
（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 of claim 1, wherein the polyoxyethylene polyoxypropylene amine ether has the structure shown below:
。
3. a method for preparing the polyoxyethylene polyoxypropylene amine ether of claim 1 or 2, comprising the steps of:
(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 intermediate 2, potassium iodide and alkanolamine to react for the first time under the action of an alkaline catalyst to obtain a reaction solution, and taking the reaction solution to react with acryloyl halide for the second time to obtain polyoxyethylene polyoxypropylene amine ether.
4. A method of preparing a polyoxyethylene polyoxypropylene amine ether according to claim 3, wherein any one or more of the following a-F is satisfied:
A. the molar ratio of the glycol alkyl ether, the ethylene oxide and the propylene oxide in the step (1) is 1:2-10:2-5, wherein the reaction temperature in the step (1) is 100-110 ℃, and the reaction time is 3-6h;
B. the molar ratio of the glycol alkyl ether in the step (1) to the basic catalyst in the step (2) to the thionyl chloride is 1:2-4:2-6, wherein the reaction temperature in the step (2) is 30-50 ℃ and the reaction time is 16-24h;
C. the molar ratio of the glycol alkyl ether in the step (1) to the alkaline catalyst, potassium iodide, alkanolamine and the acryloyl 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 condition of nitrogen reflux, the reaction temperature is 60-80 ℃, and the reaction time is 16-24 hours; the second reaction is to drop the acryl halide into the reaction liquid with the temperature of 0-10 ℃ for 3-5h;
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 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 formula (IV):
（IV）；
wherein a, b, 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;
R 1 ，R 2 independently selected from H, methyl, carboxyl;
R 3 ，R 4 ，R 5 independently selected from H, methyl, phenyl, hexyl, -CH 2 C(CH 3 ) 3 ，-CONH 2 ，，HOCH 2 CH 2 NHCO-，HOCH 2 CH 2 CH 2 NHCO-，(CH 3 ) 2 NCH 2 CH 2 COO-，-CONHC(CH 3 ) 2 CH 2 SO 3 H，-COOCH 2 CH 2 N(CH 3 ) 2 ， -CH 2 SO 3 Na，/>Alternatively, R 4 ，R 5 Form a ring, R 4 ，R 5 Respectively with the radicals->The number average molecular weight of the carboxylic acid polymer is 5000-50000; wherein->And->The short horizontal line in (a) is a connecting key.
6. A polycarboxylic acid-based copolymer or a salt thereof, characterized in that the monomers of the polycarboxylic acid-based copolymer comprise:
(1) At least one unsaturated carboxylic acid and/or derivative thereof; the unsaturated carboxylic acid derivative is maleic anhydride;
(2) At least one lipophilic unsaturated comonomer;
(3) At least one polyoxyethylene polyoxypropylene amine ether, wherein the polyoxyethylene polyoxypropylene amine ether is the polyoxyethylene polyoxypropylene amine ether of claim 1 or 2 or the polyoxyethylene polyoxypropylene amine ether prepared by the preparation method of claim 3 or 4, and the number average molecular weight of the polycarboxylic acid copolymer is 5000-50000.
7. A process for preparing a polycarboxylic acid copolymer or a salt thereof, which comprises copolymerizing a polyoxyethylene polyoxypropylene amine ether according to claim 1 or 2 or a polyoxyethylene polyoxypropylene amine ether prepared by the process according to claim 3 or 4, an unsaturated carboxylic acid and/or a derivative thereof and a lipophilic unsaturated comonomer in the presence of an initiator, a chain transfer agent and a solvent system, wherein the unsaturated carboxylic acid derivative is maleic anhydride.
8. The production method according to claim 7, wherein any one or more of the following (1) to (5) is also satisfied:
(1) The mass ratio of the polyoxyethylene polyoxypropylene amine 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 percentage by mass: 1-1:5 an organic solvent and water;
(2) The unsaturated carboxylic acid is one or a mixture of several of acrylic acid, methacrylic acid, maleic acid and fumaric acid;
(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 bisulphite and sodium methacrylate sulfonate;
(5) The initiator is selected from one or a mixture of a plurality of persulfate initiators, azo initiators and peroxide initiators.
9. The application of the polycarboxylic acid copolymer or the salt thereof in improving the dispersibility of materials or being used as a dispersing agent is characterized in that the polycarboxylic acid copolymer or the salt thereof is the polycarboxylic acid copolymer or the salt thereof according to claim 5 or 6, or the polycarboxylic acid copolymer or the salt thereof is the polycarboxylic acid copolymer or the salt thereof prepared by the preparation method according to claim 7 or 8.
10. A pesticidal preparation comprising the polycarboxylic acid copolymer or a salt thereof according to claim 5 or 6 or the polycarboxylic acid copolymer or a salt thereof produced by the production method according to claim 7 or 8.
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