CN115340473B - 环境友好含氟非离子Gemini表面活性剂及其制备方法和应用 - Google Patents
环境友好含氟非离子Gemini表面活性剂及其制备方法和应用 Download PDFInfo
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- CN115340473B CN115340473B CN202110463766.3A CN202110463766A CN115340473B CN 115340473 B CN115340473 B CN 115340473B CN 202110463766 A CN202110463766 A CN 202110463766A CN 115340473 B CN115340473 B CN 115340473B
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 96
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 93
- 239000011737 fluorine Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000003756 stirring Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 239000002736 nonionic surfactant Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
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- 230000015556 catabolic process Effects 0.000 claims description 14
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000005907 Indoxacarb Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- VBCVPMMZEGZULK-NRFANRHFSA-N indoxacarb Chemical compound C([C@@]1(OC2)C(=O)OC)C3=CC(Cl)=CC=C3C1=NN2C(=O)N(C(=O)OC)C1=CC=C(OC(F)(F)F)C=C1 VBCVPMMZEGZULK-NRFANRHFSA-N 0.000 claims description 13
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- 239000000693 micelle Substances 0.000 claims description 12
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- 239000002904 solvent Substances 0.000 claims description 12
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 11
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- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
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- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- 230000002195 synergetic effect Effects 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 4
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- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
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- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000012267 brine Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
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- 239000005562 Glyphosate Substances 0.000 description 7
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
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- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 2
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 description 2
- OXTJFBHLOXGCPW-UHFFFAOYSA-N 6-cyanatohexyl cyanate Chemical compound N#COCCCCCCOC#N OXTJFBHLOXGCPW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
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- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- GGDYAKVUZMZKRV-UHFFFAOYSA-N 2-fluoroethanol Chemical compound OCCF GGDYAKVUZMZKRV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- -1 polymethylene chain Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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Classifications
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- 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
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- 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
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
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- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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- C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
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- C07C43/10—Saturated ethers of polyhydroxy compounds
- C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
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- C07C43/115—Saturated ethers containing carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C43/02—Ethers
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- C07C43/164—Unsaturated ethers containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及含氟非离子Gemini表面活性剂技术领域,具体涉及一种环境友好含氟非离子Gemini表面活性剂及其制备方法和应用,结构式中各基团的意义见说明书。本发明提供的制备方法简单、条件温和、易于工业化开发、成本低。本发明提供的表面活性剂具有环境友好、表面活性优异且可调控等优点。
Description
技术领域
本发明涉及含氟非离子Gemini表面活性剂技术领域,具体涉及一种环境友好含氟非离子Gemini表面活性剂及其制备方法和应用。
背景技术
含氟表面活性剂作为特种表面活性剂中重要的一类,是指碳氢表面活性剂碳氢链上的氢原子全部或部分被氟原子取代,形成以氟碳链为疏水基的一类表面活性剂。按亲水基极性的不同,可分为离子型含氟表面活性剂和非离子型含氟表面活性剂。相比于离子型含氟表面活性剂,非离子型含氟表面活性剂具有其独特的性能,比如在水中不电离,对溶液的pH值的变化和电解质的存在不敏感,可溶解在酸、碱的溶液中等。
氟碳键的特殊结构赋予了含氟表面活性剂具有常规表面活性剂不可比拟的性质:高表面活性、高化学稳定性、高耐热稳定性以及氟碳链既憎水又憎油的特性。但是,长氟碳链(连有氟的碳原子的个数大于等于8)的含氟化合物难以在环境中降解,并且具有生物积累性,会沿食物链在生物体内富集,危害人类健康。比如全氟辛烷磺酸(PFOS)在人体内的“半排出时间”长达8.7年,不但会造成呼吸系统的伤害,甚至会导致新生婴儿死亡。因此,研制性能优异且环境友好的含氟非离子表面活性剂具有十分重要的意义。
双子表面活性剂(Gemini)又称二聚表面活性剂,包含两条疏水链和两个亲水基团,通过与连接桥形成共价键连接而成,连接桥可以是聚亚甲基链、包含杂原子(N、O和S)的亚甲基链和刚性的芳香基团。自Bunton团队合成双溴化季铵盐Gemini表面活性剂以来,这类表面活性剂因其独特的性能而受到越来越多的关注。与传统表面活性剂相比,Gemini表面活性剂具有较低的临界胶束浓度(CMC)、较低的Krafft、特殊的流变性能和良好的润湿性。目前已有许多碳氢Gemini表面活性剂合成的报道,但对含氟Gemini表面活性剂的研究相对较少,尤其是含碳氟短链的非离子Gemini表面活性剂尚无报道。
因此,研制含碳氟短链的环境友好非离子Gemini表面活性剂具有十分重要的意义。
发明内容
本发明的第一目的是针对现有技术的不足,提供一种新的、环境友好、含氟非离子Gemini表面活性剂。
本发明的第二目的是提供制备上述新的、环境友好、含氟非离子Gemini表面活性剂的方法。
本发明的第三目的是提供了一种新的、环境友好、含氟非离子Gemini表面活性剂在精细化学品中的应用。
为达到发明的目的,本发明在进行分子设计时,选择了具有优异的生物相容性、生物降解性的聚乙二醇和环境友好连有氟的碳原子的个数小于等于4的氟醇来制备具有环境友好和表面活性可调控的含氟非离子Gemini表面活性剂,其结构如下:
式中R1为-(CH2)6-,/>Rf为1~4个碳的氟烷基链,m整数,1≤m≤44。
本发明提供的制备上述环境友好含氟非离子Gemini表面活性剂的方法,其特征在于,包含以下步骤:将聚乙二醇与环氧溴丙烷按摩尔比为1∶1~1∶3溶解于溶剂1中,搅拌,加入摩尔分数为20~80%的催化剂1,室温反应12~24h后,即得中间体,将所得的中间体与氟醇按摩尔比为1∶1~1∶3溶解于溶剂2中,搅拌,加入摩尔分数为30~80%的催化剂2,温度Ta下反应12~24h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶于溶剂3中,除水,再按摩尔比1∶1加入二异氰酸酯,搅拌,温度Tb下反应8~15h,得到环境友好含氟非离子Gemini表面活性剂。其反应通式为:
式中R1为-(CH2)6-,/>Rf为1~4个碳的氟烷基链,m为整数,1≤m≤44。
作为本发明的一种优选的技术方案,以上方法所用溶剂1为丙酮、N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、二氧六环中的一种。
作为本发明的一种优选的技术方案,以上方法所用催化剂1为正丁基锂、叔丁基锂、叔丁醇钾、叔丁醇钠、氢化钠中的一种。
作为本发明的一种优选的技术方案,以上方法所用溶剂2为丙酮、二甲基亚砜、四氢呋喃、乙腈、二氧六环中的一种。
作为本发明的一种优选的技术方案,以上方法所用催化剂2为正丁基锂、仲丁基锂、叔丁醇钾、叔丁醇钠、氢化钠中的一种。
作为本发明的一种优选的技术方案,以上方法所用温度Ta为50℃~100℃。
作为本发明的一种优选的技术方案,以上方法所用溶剂3为丙酮、N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、乙腈、二氯乙烷、甲苯、二氧六环中的一种。
作为本发明的一种优选的技术方案,以上方法所用温度Tb为50℃~120℃。
上述环境友好含氟非离子表面活性剂,临界胶束浓度为0.01g/L~1.2g/L,表面张力为18mN/m~30mN/m。
上述环境友好含氟非离子表面活性剂,作为茚虫威水悬浮剂、草甘膦异丙胺盐水剂的添加剂,对茚虫威水悬浮剂、草甘膦异丙胺盐水剂具有增效作用。
本发明具有以下优点:
1.本发明提供的一种环境友好含氟非离子Gemini表面活性剂是以聚乙二醇、环氧溴丙烷、连有氟的碳原子的个数小于等于4的氟醇为原料制得,因而不仅为含氟表面活性剂领域增添了一种可供选择的新品种,且该含氟非离子Gemini表面活性剂还具有环境友好性,28天的降解率为75%~95%,高于目前使用的含氟表面活性剂全氟辛酸的降解率,全氟辛酸28天的降解率为11%。
2.本发明提供的一种环境友好含氟非离子Gemini表面活性剂可以通过原料种类和比例的调节实现表面活性性能的调控。
3.本发明提供的制备方法,合成路线短,反应条件容易控制,易于工业化开发,成本低。
4.本发明提供的一种环境友好含氟非离子Gemini表面活性剂降低表面张力的效率优异,临界胶束浓度为0.01g/L~1.2g/L。
5.本发明提供的一种环境友好含氟非离子Gemini表面活性剂降低表面活性的能力优异,表面张力为18mN/m~30mN/m,低于商品化的非离子表面活性剂的表面张力。
6.本发明提供的一种环境友好含氟非离子Gemini表面活性剂对生态安全,对大鼠急性毒性测定结果均为低毒。
7.本发明提供的一种环境友好含氟非离子Gemini表面活性剂作为茚虫威水悬浮剂、草甘膦异丙胺盐水剂的添加剂,对茚虫威水悬浮剂、草甘膦异丙胺盐水剂具有增效作用。
具体实施方式
下面给出实施例以对本发明作进一步说明。有必要指出的是以下实施例不能理解为对本发明保护范围的限制,如果该领域的技术熟练人员根据上述本发明内容对本发明做出一些非本质的改进和调整,仍属于本发明保护的范围。
另外,需要说明的是:
1.所述环境友好含氟非离子Gemini表面活性剂表面张力的测定方法:配置一系列不同浓度的环境友好含氟表面活性剂,采用吊环法由JK99M全自动静态表面张力仪进行表面张力测试(外径20.30mm,铂丝0.30mm,周长61.89mm,密度0.998g/cm3,温度25±1℃)。仪器在测试前后均用纯水校准。
2.所述环境友好含氟非离子Gemini表面活性剂降解率的测定方法:《化学品:快速生物降解性呼吸计量法试验(GB/T 21801-2008)》。采用呼吸计量法,向一定体积并已接种的无机物培养基中加入适量环境友好含氟表面活性剂作为唯一的有机碳源,密闭瓶在恒温下连续搅拌28天,测得其耗氧量,进而确定样品的降解率。
3.所述环境友好含氟非离子Gemini表面活性剂对大鼠急性毒性的测定方法:将实验动物(大鼠)随机分组,给药前一天禁食药品现配现用,按照体重经口给药。观察给药后大鼠对于药品的反应,记录下来进行结果判定。将样品对大鼠毒性登记划分为四个等级:
实施例1
将分子量为1954g/mol的聚乙二醇与环氧溴丙烷按摩尔比为1∶2溶解于四氢呋喃中,搅拌,加入摩尔分数为50%的叔丁醇钠,室温反应16h后,即得中间体。将所得的中间体与1H,1H-五氟丙醇按摩尔比为1∶3溶解于乙腈中,搅拌,加入摩尔分数为53%的仲丁基锂,70℃下反应16h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶于二甲基亚砜中,除水,再按摩尔比1∶1加入1,4-环己烷二异氰酸酯,搅拌,温度120℃下反应15h,得到含氟非离子双子表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为0.2g/L,所对应表面张力为30mN/m,28天的降解率为75%,对大鼠急性毒性等级为低毒。
实施例2
将分子量为1000g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶1.2溶解于二氧六环中,搅拌,加入摩尔分数为68%的氢化钠,室温反应12h后,即得中间体。将所得的中间体与2-氟乙醇按摩尔比为1∶1.8溶解于丙酮中,搅拌,加入摩尔分数为30%的叔丁醇钠,50℃下反应18h后,即得环境友好含氟非离子表面活性剂,然后将单链表面活性剂溶于二氧六环中,除水,再按摩尔比1∶1加入二甲苯烷二异氰酸酯,搅拌,温度100℃下反应13h,得到含氟非离子双子表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为1.2g/L,所对应表面张力为27mN/m,28天的降解率为95%,对大鼠急性毒性等级为低毒。
实施例3
将分子量为500g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶1.2溶解于丙酮中,搅拌,加入摩尔分数为20%的正丁基锂,室温反应12h后,即得中间体。将所得的中间体与全氟丁醇按摩尔比为1∶1溶解于二甲基亚砜中,搅拌,加入摩尔分数为60%的叔丁醇钾,70℃下反应24h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于乙腈中,除水,搅拌,加入当量六亚甲基二氰酸酯,100℃反应12h后,即得环境友好含氟非离子Gemini表面活性剂。
经测试,本实施例制备的环境友好含氟非离子Gemini表面活性剂的临界胶束浓度为0.01g/L,所对应表面张力为20mN/m,28天的降解率为90%,对大鼠急性毒性等级为低毒。
实施例4
将分子量为200g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶1.2溶解于N,N-二甲基甲酰胺中,搅拌,加入摩尔分数为80%的叔丁醇钾,室温反应24h后,即得中间体。将所得的中间体与2,2,3,3,4,4,5,5-八氟-1-戊醇按摩尔比为1∶1.8溶解于二氧六环中,搅拌,加入摩尔分数为30%的正丁基锂,50℃下反应12h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于四氢呋喃中,除水,搅拌,加入当量六亚甲基二氰酸酯,80℃反应12h后,即得环境友好含氟非离子Gemini表面活性剂。
经测试,本实施例制备的环境友好含氟非离子Gemini表面活性剂的临界胶束浓度为0.08g/L,所对应表面张力为24mN/m,28天的降解率为80%,对大鼠急性毒性等级为低毒。
实施例5
将分子量为76g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶3溶解于二甲基亚砜中,搅拌,加入摩尔分数为46%的叔丁基锂,室温反应22h后,即得中间体。将所得的中间体与全氟丁醇按摩尔比为1∶1.5溶解于四氢呋喃中,搅拌,加入摩尔分数为80%的氢化钠,50℃下反应24h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于N,N-二甲基甲酰胺中,除水,搅拌,加入当量间苯二异氰酸酯,110℃反应8h后,即得环境友好含氟非离子Gemini表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为0.04g/L,所对应表面张力为18mN/m,28天的降解率为86%,对大鼠急性毒性等级为低毒。
实施例6
将分子量为500g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶1.2溶解于丙酮中,搅拌,加入摩尔分数为20%的正丁基锂,室温反应12h后,即得中间体。将所得的中间体与全氟丁醇按摩尔比为1∶1溶解于二甲基亚砜中,搅拌,加入摩尔分数为60%的叔丁醇钾,70℃下反应24h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于二氯乙烷中,除水,搅拌,加入当量对苯二氰酸酯,90℃反应12h后,即得环境友好含氟非离子双子表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为0.02g/L,所对应表面张力为21mN/m,28天的降解率为85%,对大鼠急性毒性等级为低毒。
实施例7
将分子量为200g/mol的聚乙二醇单甲醚与环氧溴丙烷按摩尔比为1∶1.2溶解于N,N-二甲基甲酰胺中,搅拌,加入摩尔分数为80%的叔丁醇钾,室温反应24h后,即得中间体。将所得的中间体与2,2,3,3,4,4,5,5-八氟-1-戊醇按摩尔比为1∶1.8溶解于二氧六环中,搅拌,加入摩尔分数为30%的正丁基锂,100℃下反应12h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于甲苯中,除水,搅拌,加入当量1,4-环己烷二异氰酸酯,100℃反应12h后,即得环境友好含氟非离子双子表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为0.05g/L,所对应表面张力为22mN/m,28天的降解率为75%,对大鼠急性毒性等级为低毒。
实施例8
将分子量为1954g/mol的聚乙二醇与环氧溴丙烷按摩尔比为1∶2溶解于四氢呋喃中,搅拌,加入摩尔分数为50%的叔丁醇钠,室温反应16h后,即得中间体。将所得的中间体与1H,1H-五氟丙醇按摩尔比为1∶3溶解于乙腈中,搅拌,加入摩尔分数为53%的仲丁基锂,70℃下反应16h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶解于丙酮中,除水,搅拌,加入当量对苯二氰酸酯,50℃反应12h后,即得环境友好含氟非离子双子表面活性剂。
经测试,本实施例制备的环境友好含氟非离子表面活性剂的临界胶束浓度为0.09g/L,所对应表面张力为27mN/m,28天的降解率为83%,对大鼠急性毒性等级为低毒。
实施例9
供试杀虫剂茚虫威的用量为30g a.i/hm2,选用实施例3中制备的环境友好含氟非离子Gemini表面活性剂作为添加剂,添加量为茚虫威喷洒液的含量的0.01%(w/w),采用国际抗性行动委员会(IRAC)提出的喷雾法,用立式喷雾塔,喷雾量10mL,选取三龄小菜蛾幼虫,放入喷雾塔中进行制剂室内测定实验,每次使用试虫16头,每个浓度2次重复。48h后检查死亡率,计算LC50值(致死率为50%时的实际药液浓度)。
实施例10
供试杀虫剂茚虫威的用量为30g a.i/hm2,选用实施例4中制备的环境友好含氟非离子表面活性剂作为添加剂,添加量为茚虫威喷洒液的含量的0.03%(w/w),采用国际抗性行动委员会(IRAC)提出的喷雾法,用立式喷雾塔,喷雾量10mL,选取三龄小菜蛾幼虫,放入喷雾塔中进行制剂室内测定实验,每次使用试虫16头,每个浓度2次重复,48h后检查死亡率,计算LC50值(致死率为50%时的实际药液浓度)。
实施例11
空白对照,供试杀虫剂茚虫威的用量为30g a.i/hm2,不添加含氟非离子Gemini表面活性剂,直接将药液喷洒,采用国际抗性行动委员会(IRAC)提出的喷雾法,用立式喷雾塔,喷雾量10mL,选取三龄小菜蛾幼虫,放入喷雾塔中进行制剂室内测定实验,每次使用试虫16头,每个浓度2次重复,48h后检查死亡率,计算LC50值(致死率为50%时的实际药液浓度)。
实施例12
供试杀虫剂草甘膦的用量为350g a.i/hm2,选用实施例5中制备的环境友好含氟非离子表面活性剂作为添加剂,添加量为草甘膦喷洒液含量的0.05%(w/w)。采用室内盆栽法,每个花盆中挑入一定数量的稗草(20株),加入药剂,注意保持稗草大小尽量一致,颜色鲜绿一致,并保持其完整性,在温室中(25℃)培养观察,根据分级标准作好记录,根据稗草的受害情况进行评判药剂效果,计算EC50值(半最大效应浓度)。
实施例13
供试杀虫剂草甘膦的用量为350g a.i/hm2,选用实施例6中制备的环境友好含氟非离子表面活性剂作为添加剂,添加量为草甘膦喷洒液含量的0.1%(w/w)。采用室内盆栽法,每个花盆中挑入一定数量的稗草(20株),加入药剂,注意保持稗草大小尽量一致,颜色鲜绿一致,并保持其完整性,在温室中(25℃)培养观察,根据分级标准作好记录,根据稗草的受害情况进行评判药剂效果,计算EC50值(半最大效应浓度)。
实施例14
空白对照,供试杀虫剂草甘膦的用量为350g a.i/hm2,不添加含氟非离子Gemini表面活性剂,直接将药液喷洒。采用室内盆栽法,每个花盆中挑入一定数量的稗草(20株),加入药剂,注意保持稗草大小尽量一致,颜色鲜绿一致,并保持其完整性,在温室中(25℃)培养观察,根据分级标准作好记录,根据稗草的受害情况进行评判药剂效果,计算EC50值(半最大效应浓度)。
表1环境友好含氟非离子Gemini表面活性剂对茚虫威杀小菜蛾的增效作用
表2环境友好含氟非离子Gemini表面活性剂对草甘膦杀稗草的增效作用
通过以上数据,可以说明,本发明提供的环境友好含氟非离子Gemini表面活性剂对茚虫威水悬浮剂和草甘膦水剂有增效作用。
Claims (13)
1.一种环境友好含氟非离子Gemini表面活性剂,
式中R1为-(CH2)6-,/>Rf为1~4个碳的氟烷基链,m整数,1≤m≤44。
2.一种制备权利要求1所述的环境友好含氟非离子Gemini表面活性剂的方法,其特征在于,包含以下步骤:将聚乙二醇与环氧溴丙烷按摩尔比为1∶1~1∶3溶解于溶剂1中,搅拌,加入摩尔分数为20~80%的催化剂1,室温反应12~24h后,即得中间体,将所得的中间体与氟醇按摩尔比为1∶1~1∶3溶解于溶剂2中,搅拌,加入摩尔分数为30~80%的催化剂2,温度Ta下反应12~24h后,即得环境友好单链含氟非离子表面活性剂,然后将单链表面活性剂溶于溶剂3中,除水,再按摩尔比1∶1加入二异氰酸酯,搅拌,温度Tb下反应8~15h,得到环境友好含氟非离子Gemini表面活性剂,其反应通式为:
式中R1为-(CH2)6-,/>Rf为1~4个碳的氟烷基链,m为整数,1≤m≤44。
3.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述溶剂1为丙酮、N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、二氧六环中的一种。
4.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述催化剂1为正丁基锂、叔丁基锂、叔丁醇钾、叔丁醇钠、氢化钠中的一种。
5.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述溶剂2为丙酮、二甲基亚砜、四氢呋喃、乙腈、二氧六环中的一种。
6.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述催化剂2为正丁基锂、仲丁基锂、叔丁醇钾、叔丁醇钠、氢化钠中的一种。
7.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述温度Ta为50℃~100℃。
8.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述溶剂3为丙酮、N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃、乙腈、二氯乙烷、甲苯、二氧六环中的一种。
9.根据权利要求2所述的环境友好含氟非离子Gemini表面活性剂的制备方法,其特征在于,所述温度Tb为50℃~120℃。
10.根据权利要求1所述的环境友好含氟非离子Gemini表面活性剂,其特征在于,临界胶束浓度为0.01g/L~1.2g/L,表面张力为18mN/m~30mN/m。
11.根据权利要求1所述的环境友好含氟非离子Gemini表面活性剂,其特征在于,28天的降解率为75%~95%,对大鼠急性毒性测定结果均为低毒。
12.根据权利要求1所述的环境友好含氟非离子Gemini表面活性剂的应用,其特征在于,作为茚虫威水悬浮剂的添加剂,对茚虫威水悬浮剂具有增效作用。
13.根据权利要求1所述的环境友好含氟非离子Gemini表面活性剂的应用,其特征在于,作为草甘膦异丙胺盐水剂的添加剂,对草甘膦异丙胺盐水剂具有增效作用。
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