CN103172788A - Preparation method of dispersing agent - Google Patents
Preparation method of dispersing agent Download PDFInfo
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- CN103172788A CN103172788A CN201310100419XA CN201310100419A CN103172788A CN 103172788 A CN103172788 A CN 103172788A CN 201310100419X A CN201310100419X A CN 201310100419XA CN 201310100419 A CN201310100419 A CN 201310100419A CN 103172788 A CN103172788 A CN 103172788A
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- Prior art keywords
- monomer
- dispersion agent
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- vinyl
- acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 239000006185 dispersion Substances 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 vinyl compound Chemical class 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 229940087305 limonene Drugs 0.000 claims description 5
- 235000001510 limonene Nutrition 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-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
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-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
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 229930006722 beta-pinene Natural products 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005574 norbornylene group Chemical group 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
- 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 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 150000003839 salts Chemical group 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000004562 water dispersible granule Substances 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000003090 pesticide formulation Substances 0.000 description 5
- 239000008234 soft water Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000005906 Imidacloprid Substances 0.000 description 2
- 101000663001 Mus musculus TNFAIP3-interacting protein 1 Proteins 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 2
- 229940056881 imidacloprid Drugs 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- ZDWZXBJFITXZBL-UHFFFAOYSA-N S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] Chemical compound S(=O)(=O)(O)C=CC1=CC=CC=C1.[Na] ZDWZXBJFITXZBL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000012395 formulation development Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a dispersing agent. The preparation method comprises the following steps of: carrying out free radical polymerization reaction onto a lipophilic monomer (A), a functional adsorption monomer (B), a hydrophilic monomer (C) and molecular weight regulator in a solvent after initiating by virtue of an initiator; removing the solvent after the free radical polymerization reaction is finished, adjusting the pH value to 7.0-10.0 by using inorganic alkali to prepare the dispersing agent. The dispersing agent, which is synthesized by the lipophilic monomer (A), the functional adsorption monomer (B) and the hydrophilic monomer (C), is insoluble in water, however, the dispersing agent can be converted into a salt form, so that the product has the advantages of good water-solubility, good dispersion and good dispersion stability.
Description
Technical field
The present invention relates to a kind of dispersion agent, be specifically related to a kind of preparation method of many anchor points macromolecule dispersing agent.
Background technology
Agricultural chemicals is that the mankind prevent and treat Crops Pests Control of Diseases Insects And Weeds Pests of Crops, improves crop yield and important means, in agriculture production, plays a part very importantly, and tensio-active agent has indispensable vital role in Pesticide formulation, is described as " industrial monosodium glutamate ".For a long time, because the class of China's pesticide surfactant does not get a promotion, cause China's pesticide formulation still to take missible oil, wettable powder, pulvis and the large formulation of granule four as main.Now, along with the requirement to environment and safety performance is more and more higher, the pesticide formulation also present the trend of hydrotropismsization, high-content future development.In the last few years, the development of water-based pesticide formulation, particularly water suspending agent (SC), water dispersible granules (WG) was very rapid, had pollution-free, high content of dispersion, good dispersity, and the advantages such as complete processing maturation, have good market outlook.
Along with agricultural chemicals hydrotropismsization future development, must develop supporting its use of a series of New-type adjuvant.Dispersion agent is most important in pesticide preparation, is also a class tensio-active agent of consumption maximum, plays in pharmaceutical formulation and stops former medicine particle to gather, and makes formulation of pesticide form a long stable dispersion homogeneous system, easy to use and raising drug effect.
At SC, in the WG formulation, while using traditional dispersion agent as polycondensation naphthalenesulfonate, lignin sulfonate, alkylaryl sulphonate class, there are the problems such as dispersing property is undesirable, dispersion stabilization is poor, can not meet the requirement of formulation development.In the last few years, the development of agricultural high score subclass dispersion agent was very rapid, and because structure can be adjusted, molecular weight is controlled, therefore had the incomparable performance of traditional dispersion agent, was applied in the pesticide formulation, can reach desirable dispersion effect.Patent US11726200 and US2007/0244216 adopt SMA or PIBSA resin to prepare dispersion agent through the Amino Terminated polyether(ATPE) modification, have good dispersing property, but Amino Terminated polyether(ATPE) only have fewer companies production, and cost is too high and buying is inconvenient.Patent US6339043 and US6855763 employing unsaturated acid (acid anhydrides) carry out polymerization with а-vinyl toluene class monomer and prepare dispersion agent, but the dispersion agent of preparation adds cost in the aq. type formula, are more than 2 times of conventional products.Patent CN200710052016.7 discloses a kind of amphipathic graft copolymer dispersion agent, can be for the aq. type formulation of pesticide, but need to adopt the method for catalytic chain transfer polymerization (CCTP), industrial production realizes difficulty at present.Patent CN200810201807.6 discloses dispersion agent prepared by a kind of rosin derivative and vinylformic acid, styrene sulfonic acid sodium polymerization, can be for the G-30027 water dispersible granules, but the rosin derivative of setting forth preparation is complicated, is unfavorable for industrial production.The comb-shaped copolymer of patent CN200710025659.2 and CN200910157864.3 invention, there is good dispersing property and retention in water suspending agent, but the dispersion agent side chain of synthesized is the polyoxyethylene ether, though have good water-soluble, but molecule easily is wound around, and dispersion agent itself is difficult to be processed into pulvis, can only in formula, use with the form of its aqueous solution.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method with macromolecule dispersing agent of many anchor points adsorption group is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of dispersion agent, the steps include: under nitrogen atmosphere, lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) in corresponding solvent, carry out Raolical polymerizable after causing by initiator with molecular weight regulator; After Raolical polymerizable finishes, except desolventizing, with mineral alkali, regulate pH=7.0～10.0, make dispersion agent;
Further, its concrete steps are: in reactor, add solvent and initiator, N
2displacement 30 ± 10min, keep nitrogen atmosphere, reactor is warming up to 65～80 ℃ and keep this temperature of reaction, drip lipophilicity monomer (A), functional absorption monomer (B), the mixture that hydrophilic monomer (C) and molecular weight regulator form, the control time for adding is 3～6h, dropwise, keeping reactor temperature is 65～80 ℃, stir 1 ± 0.5h, underpressure distillation is except desolventizing, add mineral alkali again in reactor, in stirring and 1.5 ± 0.5h, control pH=7.0～10.0, prepare dispersion agent, now dispersion agent is thick liquid, further dispersion agent being made to the aqueous solution directly uses, or dispersion agent is made to white powder with micronizer mill.The weight-average molecular weight of described dispersion agent is 1000～40000g/mol, is preferably 6000～12000g/mol(weight-average molecular weight and is regulated by the consumption of molecular weight regulator in polymerization process).
In the preparation process of described dispersion agent, monomer and initiator can adopt dropping, the disposable feed way that feeds intake to drop in reactor, and for fear of the generation of implode reaction, the present invention adopts the method for dropping to be fed intake, monomer and initiator need be dripped respectively, immiscible.
Described lipophilicity monomer (A) is selected from least one in alicyclic ring same clan monomer, phenyl ring class monomer, heterocyclic vinyl monomer; Not only play in molecular structure the effect of lipophilicity anchoring group is provided, also make molecular structure there is rigidity, effectively prevent the upset of molecular structure by steric hindrance.
Described functional absorption monomer (B) is for having the vinyl monomer of ester group, morpholine group, pyridine groups or furan group; Functional absorption monomer (B) purpose is on the basis of the effective anchoring of (A) monomer, increases with the agricultural chemicals surface and can produce the adsorption group of anchorage effect, thereby reach the multi-point-anchoring effect, strengthens dispersiveness and dispersion stabilization.
The vinyl compound of described hydrophilic monomer (C) for containing acid, acid anhydrides or sulfonic acid group; Give the hydrophilicity that dispersant molecule is good, and can, by the ion from ionizing out, by electrostatic interaction, reach stable dispersion effect in the aqueous solution.
The total mass of described lipophilicity monomer (A) and functional absorption monomer (B) accounts for the 30-65% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass;
Described hydrophilic monomer (C) quality used accounts for the 70%-35% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described molecular weight regulator is mercaptoethanol, Thiovanic acid, alkyl sulfhydryl; Described molecular weight regulator consumption accounts for the 0.1%-1% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described lipophilicity monomer (A) is selected from a kind of in following substances: vinyl pentamethylene, vinyl cyclohexane, vinyl naphthalene, vinylbenzene, а-vinyl toluene, limonene, norbornylene, beta-pinene.
Described lipophilicity monomer (A) is a kind of in following substances preferably: vinyl pentamethylene, vinyl cyclohexane, vinylbenzene, а-vinyl toluene, limonene, vinyl naphthalene.
Described functional absorption monomer (B) is selected from a kind of of following substances: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-vinyl morpholine, vinyl pyridine.
Described hydrophilic monomer (C) is selected from a kind of of following substances: vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, myristic acid, vinyl phosphoric acid, Sodium styrene sulfonate, sodium vinyl sulfonate.
Described hydrophilic monomer (C) is following substances a kind of preferably: methacrylic acid, toxilic acid, maleic anhydride, vinyl phosphoric acid.
Described solvent is aromatic hydrocarbon solvent or ketones solvent (carry out in this type of solution in preparation process, can better control molecular weight and molecualr weight distribution).
Described ketones solvent is selected from a kind of in following solvents: acetone, butanone, methyl ethyl ketone, pimelinketone.Preferably ketones solvent, as the solvent of polyreaction, because ketone is stronger to the dissolving power of macromolecule dispersing agent, can effectively prevent that the precipitation of macromolecule dispersing agent in polymerization process from producing.
Described initiator is superoxide or azo compound; Described initiator quality used accounts for the 0.5%-3% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described initiator is preferably H
2o
2, benzoyl peroxide (BPO), dilauroyl peroxide (LPO), peroxidized t-butyl perbenzoate (BPB), Diisopropyl azodicarboxylate (ABIN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN).
Described initiator is benzoyl peroxide (BPO), peroxidized t-butyl perbenzoate (BPB) or Diisopropyl azodicarboxylate (ABIN) more preferably.
Described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Beneficial effect of the present invention:
The synthetic dispersion agent itself of described lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) is water insoluble, but by converting thereof into the form of salt, just product has good water-solublely, has good dispersiveness and dispersion stabilization simultaneously.Other Neutralizing modes, as with neutralizations such as thanomin, diethanolamine, trolamines, be unfavorable for the raising of dispersion agent dispersing property, also is unfavorable for that product is processed into powder simultaneously.
In process of production, slough solvent and carry out recycling by underpressure distillation, final dispersion agent finished product is owing to having good processing characteristics, can make its aqueous solution directly uses, also can carry out powder process by the comminution by gas stream drying machine, obtain the white powder finished product, be convenient to transportation and use.
The accompanying drawing explanation
The preparation flow figure that Fig. 1 is dispersion agent.
Embodiment
Following examples are that the present invention is carried out to more detailed description, but the present invention are not produced to any restriction.
Embodiment 1
To with agitator, A constant pressure dropping groove (2Kg acetone solution 90g azo-bis-isobutyl cyanide, standby) and B constant pressure dropping groove (the a-vinyl toluene of 2.1kg, 0.3Kg butyl methacrylate, 3.0Kg toxilic acid, 30g lauryl mercaptan 5Kg acetone solution, standby), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.1Kg acetone and 0.6Kg toxilic acid, N
2replace after 30 minutes, be warming up to 65 ℃, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 65～70 ℃ of temperature of reaction, after 5h, B dropwise adding tank material drips off, 5.5h rear A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.5Kg, in the 45%NaOH that adds 5.66Kg in reactor and 6.8Kg technique soft water and after 1.5h, the stream pulverizer of supplying gas is pulverized to obtain the white powder finished product, is labeled as Y-1, and the weight-average molecular weight of surveying through GPC is 7890g/mol.
Embodiment 2
To with agitator, A constant pressure dropping groove, (the 2Kg butanone dissolves 120g azo two cyanogen in different heptan, standby) and B constant pressure dropping groove (vinylbenzene of 2.128kg, 0.912Kg N-vinyl morpholine, 2.50Kg maleic anhydride, 5Kg butanone dissolving for the 18.2g lauryl mercaptan, standby), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.2Kg acetone and 0.54Kg maleic anhydride, N
2replace after 30 minutes, be warming up to 66 ℃, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 65～70 ℃ of temperature of reaction, 3.5h rear B dropwise adding tank material drips off, 4.0h rear A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent butanone 8.7Kg, in the 45%NaOH that adds 5.58Kg in reactor and 7Kg technique soft water and after 1.5h, the stream pulverizer of supplying gas is pulverized to obtain the white powder finished product, is labeled as Y-2, and the weight-average molecular weight of surveying through GPC is 11430g/mol.
Embodiment 3
To with agitator, A constant pressure dropping groove, (the 2Kg butanone dissolves the 100g azo-bis-isobutyl cyanide, standby) and B constant pressure dropping groove (vinyl naphthalene of 1.5kg, 0.50Kg N-vinyl morpholine, 3.50Kg vinyl phosphoric acid, 5Kg butanone dissolving for the 9.0g lauryl mercaptan, standby), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.0Kg acetone and 0.50Kg vinyl phosphoric acid, N
2replace after 30 minutes, be warming up to 75 ℃, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 75～80 ℃ of temperature of reaction, 4.0h rear B dropwise adding tank material drips off, 4.5h rear A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent butanone 8.7Kg, in the 45%NaOH that adds 8.20Kg in reactor and 5.5Kg technique soft water and after 1.5h, the stream pulverizer of supplying gas is pulverized to obtain the white powder finished product, is labeled as Y-3, and the weight-average molecular weight of surveying through GPC is 7860g/mol.
Embodiment 4
To with agitator, A constant pressure dropping groove, (the 2Kg butanone dissolves the 152g benzoyl peroxide, standby) and B constant pressure dropping groove (the a-vinyl toluene of 2.50kg, 0.50Kg vinyl pyridine, 2.50Kg toxilic acid, 5Kg butanone dissolving for the 10g lauryl mercaptan, standby), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.50Kg butanone and 0.6Kg toxilic acid, N
2replace after 30 minutes, be warming up to 70 ℃, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 70～75 ℃ of temperature of reaction, after 3h, B dropwise adding tank material drips off, 3.5h rear A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.8Kg, in the 45%NaOH that adds 5.62Kg in reactor and 6.9Kg technique soft water and after 1.5h, the stream pulverizer of supplying gas is pulverized to obtain the white powder finished product, is labeled as Y-4, and the weight-average molecular weight of surveying through GPC is 10087g/mol.
Embodiment 5
To with agitator, A constant pressure dropping groove, (the 2Kg butanone dissolves 170g azo two cyanogen in different heptan, standby) and B constant pressure dropping groove (limonene of 1.55kg, 0.50Kg butyl methacrylate, 3.55Kg methacrylic acid, 5Kg butanone dissolving for the 62g lauryl mercaptan, standby), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.50Kg butanone and 0.60Kg methacrylic acid, N
2replace after 30 minutes, be warming up to 70 ℃, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 70～75 ℃ of temperature of reaction, 5.5h rear B dropwise adding tank material drips off, 6.0h rear A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.40Kg, in the 45%NaOH that adds 4.28Kg in reactor and 7.6Kg technique soft water and after 1.5h, the stream pulverizer of supplying gas is pulverized to obtain the white powder finished product, is labeled as Y-5, and the weight-average molecular weight of surveying through GPC is 8701g/mol.
Embodiment 6
Apply above-mentioned synthetic dispersion agent product, in the situation that other auxiliary agent kinds are identical with consumption, prepared 70% imidacloprid water dispersible granule (fluidized bed granulation) and 500g/L G-30027 water suspending agent in laboratory.Estimate initial dispersion performance and the dispersion stabilization of dispersion agent, the consumption of dispersion agent in formula is between 4%～6%.Dispersed and cold and hot storage stability as shown in Table 1 and Table 2.Experimental result shows, this dispersion agent as dispersion agent, is a kind of good novel dispersant in WDG and SC formulation.
The applicating evaluating of table 1 embodiment dispersion agent in 70% imidacloprid water dispersible granule formula
| Dispersion agent | Y-1 | Y-2 | Y-3 | Y-4 | Y-5 |
| Initial suspensibility % | 92.2 | 90.7 | 90.3 | 93.5 | 86.2 |
| Suspensibility %(54 ± 2 ℃, 14 days) | 90.8 | 89.8 | 81.6 | 92.8 | 83.2 |
| Suspensibility %(-5 ± 2 ℃, 14 days) | 90.4 | 89.9 | 82.4 | 92.8 | 82.6 |
The applicating evaluating of table 2 embodiment dispersion agent in 500g/L G-30027 water suspending agent formula
| Dispersion agent | Y-1 | Y-2 | Y-3 | Y-4 | Y-5 |
| Dispersed | Excellent | Excellent | Good | Excellent | Poor |
| Initial suspensibility % | 90.1 | 92.7 | 85.6 | 93.0 | 72.7 |
| Suspensibility %(54 ± 2 ℃, 14 days) | 91.8 | 89.8 | 82.6 | 90.1 | 69.3 |
| Suspensibility %(-5 ± 2 ℃, 14 days) | 90.8 | 89.9 | 83.4 | 90.5 | 67.9 |
Claims (15)
1. the preparation method of a dispersion agent, the steps include: under nitrogen atmosphere, lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) in corresponding solvent, carry out Raolical polymerizable after causing by initiator with molecular weight regulator; After Raolical polymerizable finishes, except desolventizing, with mineral alkali, regulate pH=7.0～10.0, make dispersion agent.
2. the preparation method of a kind of dispersion agent according to claim 1, it is characterized in that: described Raolical polymerizable is that the dropwise reaction mode is carried out, and temperature of reaction is 65～80 ℃.
3. the preparation method of a kind of dispersion agent according to claim 1, it is characterized in that: described lipophilicity monomer (A) is selected from least one in alicyclic ring same clan monomer, phenyl ring class monomer, heterocyclic vinyl monomer; Described functional absorption monomer (B) is for having the vinyl monomer of ester group, morpholine group, pyridine groups or furan group; The vinyl compound of described hydrophilic monomer (C) for containing acid, acid anhydrides or sulfonic acid group;
The total mass of described lipophilicity monomer (A) and functional absorption monomer (B) accounts for the 30-65% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
4. the preparation method of a kind of dispersion agent according to claim 1, it is characterized in that: described molecular weight regulator is mercaptoethanol, Thiovanic acid, alkyl sulfhydryl; Described molecular weight regulator consumption accounts for the 0.1%-1% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
5. according to the preparation method of the described a kind of dispersion agent of 1 to 4 arbitrary claim, it is characterized in that: described lipophilicity monomer (A) is selected from a kind of in following substances: vinyl pentamethylene, vinyl cyclohexane, vinyl naphthalene, vinylbenzene, alpha-methyl styrene, limonene, norbornylene, beta-pinene.
6. the preparation method of a kind of dispersion agent according to claim 5 is characterized in that: described lipophilicity monomer (A) is selected from a kind of in following substances: vinyl pentamethylene, vinyl cyclohexane, vinylbenzene, alpha-methyl styrene, limonene, vinyl naphthalene.
7. according to the preparation method of the described a kind of dispersion agent of 1 to 4 arbitrary claim, it is characterized in that: described functional absorption monomer (B) is selected from a kind of of following substances: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-vinyl morpholine, vinyl pyridine.
8. according to the preparation method of the described a kind of dispersion agent of 1 to 4 arbitrary claim, it is characterized in that: described hydrophilic monomer (C) is selected from a kind of of following substances: vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, myristic acid, vinyl phosphoric acid, Sodium styrene sulfonate, sodium vinyl sulfonate.
9. the preparation method of a kind of dispersion agent according to claim 8, it is characterized in that: described hydrophilic monomer (C) is selected from a kind of of following substances: methacrylic acid, toxilic acid, maleic anhydride, vinyl phosphoric acid.
10. according to the preparation method of the described a kind of dispersion agent of 1 to 4 arbitrary claim, it is characterized in that: described solvent is aromatic hydrocarbon solvent or ketones solvent.
11. the preparation method of a kind of dispersion agent according to claim 10 is characterized in that: described ketones solvent is selected from a kind of in following solvents: acetone, butanone, methyl ethyl ketone, pimelinketone.
12. the preparation method according to the described a kind of dispersion agent of 1 to 4 arbitrary claim is characterized in that: described initiator is superoxide or azo compound; Described initiator amount accounts for the 0.5%-3% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
13. the preparation method of a kind of dispersion agent according to claim 12 is characterized in that: described initiator is hydrogen peroxide, benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
14. the preparation method of a kind of dispersion agent according to claim 13 is characterized in that: described initiator is benzoyl peroxide, peroxidized t-butyl perbenzoate or Diisopropyl azodicarboxylate.
15. the preparation method of a kind of dispersion agent according to claim 1 is characterized in that: described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
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| CN104211195A (en) * | 2014-09-15 | 2014-12-17 | 山东天庆科技发展有限公司 | Composite water treatment agent with effects of scale inhibition, corrosion inhibition and sterilization and preparation method thereof |
| CN106031855A (en) * | 2015-03-19 | 2016-10-19 | 托贾（上海）高分子材料有限公司 | Preparation and applications of carboxylate binary copolymer dispersing agents |
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| CN104211195A (en) * | 2014-09-15 | 2014-12-17 | 山东天庆科技发展有限公司 | Composite water treatment agent with effects of scale inhibition, corrosion inhibition and sterilization and preparation method thereof |
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| CN106031855A (en) * | 2015-03-19 | 2016-10-19 | 托贾（上海）高分子材料有限公司 | Preparation and applications of carboxylate binary copolymer dispersing agents |
| CN110035818A (en) * | 2016-12-09 | 2019-07-19 | 路博润先进材料公司 | The aliphatic ceramic dispersants obtained are reacted with non-polymeric amino ethers/alcohol by PIBSA |
| CN110035818B (en) * | 2016-12-09 | 2022-04-19 | 路博润先进材料公司 | Aliphatic ceramic dispersants obtained by reacting PIBSA with non-polymeric aminoethers/alcohols |
| CN109503776A (en) * | 2018-12-03 | 2019-03-22 | 广东科隆智谷新材料股份有限公司 | A kind of preparation method of polyocarboxy acid type ceramic dispersants |
| CN111003971A (en) * | 2019-09-30 | 2020-04-14 | 上海晶阳商品混凝土有限公司 | Low-slump loss concrete and preparation method thereof |
| CN111057176A (en) * | 2019-12-29 | 2020-04-24 | 权冉(银川)科技有限公司 | Tracer agent suitable for complex geological environment energy development and interpretation method thereof |
| CN111057176B (en) * | 2019-12-29 | 2020-12-04 | 权冉(银川)科技有限公司 | Tracer agent suitable for complex geological environment energy development and interpretation method thereof |
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