CN114195962B - Amphiphilic fluorine-containing block polymer and preparation method and application thereof - Google Patents
Amphiphilic fluorine-containing block polymer and preparation method and application thereof Download PDFInfo
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- CN114195962B CN114195962B CN202111642468.7A CN202111642468A CN114195962B CN 114195962 B CN114195962 B CN 114195962B CN 202111642468 A CN202111642468 A CN 202111642468A CN 114195962 B CN114195962 B CN 114195962B
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- containing block
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- 229920000642 polymer Polymers 0.000 title claims abstract description 124
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 97
- 239000011737 fluorine Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title description 26
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 48
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 82
- 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 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 20
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 18
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012987 RAFT agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 18
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000147 Styrene maleic anhydride Polymers 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 238000012360 testing method Methods 0.000 description 38
- 238000005227 gel permeation chromatography Methods 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 19
- 239000005457 ice water Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 5
- -1 perfluoro chain Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 239000004811 fluoropolymer Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241000529895 Stercorarius Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- JGHKDVSIFPFNIJ-UHFFFAOYSA-N dodecylsulfanylmethanedithioic acid Chemical group CCCCCCCCCCCCSC(S)=S JGHKDVSIFPFNIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008689 wuhua Substances 0.000 description 1
Classifications
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a synthesis method of an amphiphilic fluorine-containing block polymer, which comprises the following steps: adding a first fluorine-free solvent, a RAFT reagent and a first initiator, carrying out mixed polymerization reaction on styrene and maleic anhydride, adding a solvent to dissolve a reaction product after the reaction, adding an alcohol solvent to precipitate, filtering the precipitate and drying to obtain a solid which is a macromolecular chain transfer agent; and B, adding the macromolecular chain transfer agent obtained in the step A, a second initiator and tridecafluorooctyl acrylate into a second non-fluorine-containing solvent, and reacting to obtain a transparent solution containing the polymer. In the polymer, the repeatability of the macromolecular segment of the styrene maleic anhydride is an integer between 5 and 30, and the repeatability of the tridecyl acrylate fluorooctyl unit is an integer between 5 and 30. The polymer disclosed by the invention has the advantages of good solubility in a fluorine-free solvent, high surface activity, few synthesis steps, low toxicity in the environment, easiness in degradation and good application prospect.
Description
Technical Field
The invention relates to the field of new fluorine-containing materials, in particular to an amphiphilic fluorine-containing block polymer, and a preparation method and application thereof.
Background
Fluorosurfactants are generally composed of perfluorocarbon chains or partially fluorocarbons chains and hydrophilic groups and are characterized by high activity, high heat stability, and high chemical stability. Among fluorosurfactants, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are most widely used, but are difficult to degrade in the environment and toxic, being banned by most countries around the world.
Therefore, development of novel degradable fluorine surfactants to fully replace existing PFOS/PFOA class fluorocarbon surfactants is highly valued by the scientific and industrial circles of countries. The development orientations of alternatives can be broadly divided into two categories, (1) reducing the length of the perfluoro chain; (2) And N, O and other hetero atoms and methylene or methine are introduced into the fluorocarbon chain. However, the above orientation has the following problems: when the perfluoro chain length is reduced, the surface activity thereof is not required in many fields; after the introduction of heteroatoms in the fluorocarbon chain, its crystallinity is significantly reduced, resulting in a reduction of its surface activity. Thus, there is a need to develop new short carbon chain fluorosurfactants to meet industry requirements.
Gemini and heteroGemini surfactants are first synthesized in the 20 th century by Zana (Langmuir 1991,7,1072.) and Jaeger (Langmuir 1996,12,4314), respectively, on active agent monomers containing two hydrophobic groups (or three hydrophobic groups) and two hydrophilic groups, linked by a linker near the hydrophilic groups. Because two hydrophilic head groups in the gemini surfactant molecule are connected by chemical bonds, stronger hydrophobic interaction is easy to generate between alkyl chains, and repulsive force between the hydrophilic head groups is greatly weakened due to the action of the chemical bonds, so that the gemini surfactant can be more closely arranged. The interfacial properties of such surfactants in aqueous media are one to several orders of magnitude higher than conventional surfactants. However, such structures are often complex and complex to synthesize during the preparation process, and are still a distance from the application.
The polymerization of fluoropolymers, particularly tridecafluorooctyl acrylate, generally requires synthesis in a special fluorine-containing solvent, such as benzotrifluoride, to obtain a clear solution. In common solvents, the polymer is often precipitated, for example, yuan Jinying and other researches show that (Macromolecular Rapid Communications, 2018:1700840), the poly (dimethylaminoethyl methacrylate) is taken as a macromolecular chain transfer agent to initiate polymerization of tridecyl fluoride octyl acrylate, and the obtained block is insoluble in isopropanol, toluene, dioxane, dimethylformamide and the like, which is disadvantageous for practical application.
Disclosure of Invention
The invention aims to solve the problem of replacing a fluorine-containing surfactant, and develop an environment-friendly fluorine-containing surfactant, namely a simple synthesis method of a Gemini-like fluorine-containing surfactant.
Another object of the present invention is to invent a method for synthesizing fluorine-containing block polymers with good solubility in environment-friendly solvents.
The invention solves the technical problems by adopting the following technical scheme.
An amphiphilic fluorine-containing block polymer, the structure of which is shown in a general formula (I):
in the general formula (I), R 1 Z is a stable group of the RAFT reagent, R is a leaving group of the RAFT reagent 2 Is- (CF) 2 ) 5 CF 3 Wherein m is an integer between 5 and 30 and n is an integer between 5 and 30.
As a further improvement of the amphiphilic fluorine-containing block polymer of the invention, the R 1 is-C (CH) 3 ) 2 -COOH, Z is CH 3 (CH 2 ) 11 -S-(C＝S)-S-。
As a further improvement of the amphiphilic fluorine-containing block polymer, m is an integer between 10 and 25, and n is an integer between 10 and 20.
The invention also provides a preparation method of the amphiphilic fluorine-containing block polymer, which comprises the following steps:
adding a first fluorine-free solvent, a RAFT reagent and a first initiator at the temperature of-20 ℃ to 25 ℃, and mixing styrene and maleic anhydride according to the proportion of 1 to 1.2:1, and the molar ratio of the maleic anhydride, the RAFT agent, and the first initiator is from 5 to 30:1: 0.01-0.2, setting the reaction environment as an anaerobic environment, heating to 50-90 ℃ for polymerization reaction for 8-24h, adding a solvent (such as butanone, methyl isobutyl ketone, propylene glycol methyl ether acetate and the like) to dissolve the reaction product, adding another solvent (which can be an alcohol solvent such as methanol or a non-alcohol solvent such as n-hexane, a solvent capable of precipitating a styrene-maleic anhydride macromolecular chain) to precipitate, filtering the precipitate and drying to obtain a solid macromolecular chain transfer agent;
b, adding the macromolecular chain transfer agent, the second initiator and the tridecyl acrylate into a second fluorine-free solvent, wherein the molar ratio of the tridecyl acrylate to the macromolecular chain transfer agent to the second initiator is 5-30:1:0.1-0.5, and reacting at 60-100 ℃ for 8-24 hours to obtain a transparent solution containing the polymer.
As a further improvement of the preparation method of the amphiphilic fluorine-containing block polymer, the RAFT reagent is 2- (dodecyl trithiocarbonate group) -2-methylpropanoic acid; the first initiator and the second initiator are both azobisisobutyronitrile.
As a further improvement of the preparation method of the amphiphilic fluorine-containing block polymer of the present invention, in the step a, the first fluorine-free solvent is one of butanone, acetone, methyl isobutyl ketone and propylene glycol methyl ether acetate.
As a further improvement of the preparation method of the amphiphilic fluorine-containing block polymer, in the step B, the second fluorine-free solvent is a mixed solvent of butanone and butyl acetate according to the mass ratio of 1:0.5-2.
As a further improvement of the process for the preparation of amphiphilic fluorine-containing block polymers according to the invention, in step a, styrene and maleic anhydride are reacted according to 1:1 in a molar ratio of 1.
As a further improvement of the preparation method of the amphiphilic fluorine-containing block polymer, in the step A, the molar ratio of maleic anhydride to RAFT reagent is 10-25:1; in the step B, the molar ratio of the tridecyl acrylate to the macromolecular chain transfer agent is 10-20:1.
The amphiphilic fluorine-containing block polymer is applied in a manner that the polymer is used as a surfactant in a detergent and a cosmetic.
The beneficial effects of the invention are as follows: a simple synthesis method of the Gemini-like fluorine-containing surfactant is developed, and the environment-friendly amphiphilic fluorine-containing block polymer is obtained. In the polymer, the repeatability (indicated by m, hydrophilic group) of the macromolecular segment of styrene maleic anhydride is an integer between 5 and 30, and the repeatability (indicated by n, hydrophobic group) of the tridecyl acrylate unit is an integer between 5 and 30. During synthesis, the activity of the obtained polymer is gradually reduced along with the chain length growth of the polystyrene maleic anhydride macromolecular transfer agent, and the amphiphilic fluorine-containing block polymer has the property of transiting from a Gemini-like fluorine-containing surfactant to a macromolecular fluorine-containing surfactant. Meanwhile, the length of the macromolecular chain transfer agent has obvious influence on the solvent property of the amphiphilic fluorine-containing block polymer, and when the number of monomer units in the molecule is less than 5, the solubility in a common solvent is obviously reduced. The surface activity of the amphiphilic fluorine-containing block polymer is related to the amount of fluorine-containing monomers, and when the content of tridecyl acrylate in the block polymer is less than 5, the property of reducing the surface tension is not obvious; and when the content thereof is more than 30, the resulting fluorine-containing block polymer is insoluble in a common solvent. The polymer provided by the invention has good solubility in fluorine-free solvents (such as isopropanol, toluene, dioxane and dimethylformamide), high surface activity, few synthesis steps, low toxicity in the environment, easiness in degradation and good application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The amphiphilic fluorine-containing block polymer and the preparation method thereof of the present invention are specifically described below.
The invention provides an amphiphilic fluorine-containing block polymer, the structure of which is shown as a general formula (I):
R 1 z is a stable group of the RAFT reagent, R is a leaving group of the RAFT reagent 2 Is- (CF) 2 ) 5 CF 3 Wherein m is an integer between 5 and 30 and n is an integer between 5 and 30.
RAFT agents are a class of compounds with reversible addition-fragmentation chain transfer properties that should have chemical bonds in their molecular structure that are susceptible to both addition and fragmentation reactions, and have the function of controlling the molecular weight of the polymer.
A preferred RAFT agent is 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (DDMAT, CAS: 461642-78-4). R1 is-C (CH 3) 2-COOH, and Z is CH3 (CH 2) 11-S- (C=S) -S-.
Common trithioesters and dithioesters are common RAFT agents, and the structural formula and use thereof can be referred to: macromolecules 2012,45,13,5321-5342; compared with other RAFT reagents, the DDMAT is easy to synthesize and good in regulation performance, and the molecular weight distribution of the obtained polymer is narrow, so that the DDMAT is the best choice for regulating and preparing the block polymer.
Further, the amphiphilic fluoropolymer has m being an integer between 10 and 25, n being an integer between 10 and 20, and the fluoropolymer has better solubility and surface activity than the fluoropolymer outside the range.
In the polymer, the subscript m inner group is an alternating copolymerization chain formed by styrene and maleic anhydride, the length of the chain influences the surface activity of the final polymer, the activity of the obtained fluorine-containing surfactant gradually decreases along with the chain length growth of the polystyrene maleic anhydride macromolecular transfer agent, and the amphiphilic fluorine-containing block polymer has the property of being similar to a gemini fluorine-containing surfactant and transiting to the macromolecular fluorine-containing surfactant. Meanwhile, the length of the macromolecular chain transfer agent has obvious influence on the solvent property of the amphiphilic fluorine-containing block polymer, and when the number of monomer units in the molecule is less than 5, the solubility in a common solvent is obviously reduced. The surface activity of the amphiphilic fluorine-containing block polymer is related to the amount of fluorine-containing monomers, and when the content of tridecafluorooctyl acrylate (the group indicated by the subscript n) in the block polymer is less than 5, the property of reducing the surface tension is not obvious; and when the content thereof is more than 30, the resulting fluorine-containing block polymer is insoluble in a common solvent.
The invention also provides a preparation method of the amphiphilic fluorine-containing block polymer, which comprises the following steps: firstly, styrene and maleic anhydride are mixed according to the proportion of 1 to 1.2 under the condition of adding RAFT reagent and free radical initiator in water bath with the temperature of-20 to 25 ℃ below zero: 1, and the mole ratio of maleic anhydride, RAFT reagent and initiator is 5-30: 1: 0.01-0.2, vacuumizing, introducing nitrogen, heating to 50-90 ℃, reacting for 8-24 hours, adding acetone, butanone, methyl isobutyl ketone or propylene glycol methyl ether acetate for dissolving, precipitating in methanol or other alcohol solvents, filtering to obtain precipitate, and drying to obtain the solid macromolecular chain transfer agent. The radical initiator may be azo type such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and the like; peroxides such as dibenzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, dilauroyl peroxide, and the like are also contemplated. The preferred RAFT agent is DDMAT ((2-dodecyl trithiocarbonate) -2-methylpropanoic acid), which is easy to synthesize and has good regulatory properties for the system. The preferred initiator is Azobisisobutyronitrile (AIBN), with a 1:1 molar ratio of styrene to maleic anhydride, because maleic anhydride and styrene readily form an electron-complexing copolymer and maleic anhydride is not readily homopolymerized, and when in excess, only oligomers are obtained; styrene, although homopolymerizing, has a slow rate of polymerization, and therefore a molar ratio of styrene to maleic anhydride of 1:1 is selected as the chain transfer agent for the synthetic macromolecule.
B, adding the macromolecular chain transfer agent, the initiator and the tridecyl fluooctyl acrylate obtained in the step A into a solvent which does not contain fluorine, wherein the molar ratio of the tridecyl fluooctyl acrylate, the macromolecular chain transfer agent and the initiator is 5-30:1:0.1-0.5, and reacting for 8-24 hours at the temperature of 60-100 ℃ to obtain a transparent polymer solution. The tridecafluorooctyl acrylate monomer is soluble in common solvents such as acetone, butanone, ethyl acetate, butyl acetate and the like, but the polymer thereof is insoluble in common solvents, and a special solvent such as a fluorine-containing solvent and the like is generally required. Thus, the present invention increases its solubility by first introducing an SMA copolymer (styrene maleic anhydride) that is easily soluble in a common solvent, while introducing hydrophilic groups, while controlling the chain length of tridecyl polyacrylate by living controlled polymerization, and the present invention found that when the repeating units of tridecyl acrylate are controlled to 30 or less, the polymer is soluble in a common solvent, whereas above 30, precipitation occurs.
Common solvents such as acetone, butanone, methyl isobutyl ketone, propylene glycol methyl ether acetate, or other solvents capable of solvent SMA polymers may be used as solvents for polymerization in the preparation of SMA (styrene-maleic anhydride) macromolecular chain transfer agents. In preparing the copolymer of tridecafluorooctyl acrylate, a lipid solvent is added to improve the solubility, and butyl acetate is a good choice.
The molar ratio of styrene and maleic anhydride to RAFT agent determines the molecular weight of the macromolecular chain transfer agent, in order to maintain the resulting fluorine-containing block polymer with good solubility and surface tension reducing properties, in step a the molar ratio of styrene to maleic anhydride is chosen to be 1:1 and the molar ratio of maleic anhydride to RAFT agent is chosen to be 10-25:1, such that m=10-25. In the step B, the molar ratio of the tridecyl acrylate and the macromolecular chain transfer agent is 10-20:1, so that n=10-20. The molecular weight of the macromolecular chain transfer agent increases to improve the solubility thereof, but the final surface tension lowering performance is lowered.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 5.58g (0.0153 mol) of DDMAT and 0.251g (0.00153 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 70 ℃ for 12 hours of reaction. Add Ding TongrongDissolving, precipitating in methanol to obtain macromolecular chain transfer agent, filtering to obtain precipitate, vacuum drying at 100deg.C to obtain solid 35.6g with 97.6% yield, wherein macromolecular chain transfer agent (i.e. precipitate) has chemical composition DDMAT- (maleic anhydride-styrene macromolecular chain) m . GPC (gel permeation chromatography) tests molecular weight of macromolecular chain transfer agent, mn=2400, m P =2590, pdi=1.08. Wherein Mn is the number average molecular weight of the macromolecular chain transfer agent. M is M P Is the highest molecular weight of the macromolecular chain transfer agent. The PDI is the dispersion coefficient of the macromolecular chain transfer agent, and the more the PDI is close to 1, the more uniform the molecular weight of the macromolecular chain transfer agent. Wherein, the molecular weight Mr1=98, the molecular weight Mr2=104, and the molecular weight Mr3=365. From the structural formula (I), it can be seen that m= (Mn-Mr 3)/(mr1+mr2) = (2400-365)/(98+104) =10.1.
And B, adding 8g (0.0033 mol) of the macromolecular chain transfer agent prepared in the step A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 14g (0.0335 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 1.082g (0.00066 mol) of azodiisobutyronitrile, reacting for 12 hours at 80 ℃ to obtain a pale yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Test of the conversion of tridecafluorooctyl acrylate to 95.2%, GPC test Polymer molecular weight, mn=6440, M P 7400, pdi=1.15. Wherein Mn is the number average molecular weight of the polymer. M is M P Is the highest molecular weight of the polymer. The PDI is the dispersion coefficient of the polymer, and the more the PDI is close to 1, the more uniform the molecular weight of the polymer is. Molecular weight Mr4 = 418 of tridecafluorooctyl acrylate. From the structural formula (I), n= (6440-2400)/(mr4=4040/(418=9.7) can be found.
Example 2
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of methyl isobutyl ketone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 5.58g (0.0153 mol) of DDMAT and 0.251g (0.00153 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, and the mixture is vacuumized and introduced with nitrogenCirculating for 3 times, regulating the temperature to 75 ℃ and reacting for 16h. Dissolving methyl isobutyl ketone, precipitating in methanol, filtering to obtain precipitate, and vacuum drying at 100deg.C to obtain solid (macromolecular chain transfer agent) 35.1g with 96.2% yield, GPC test molecular weight, mn=2300, M P ＝2490，PDI＝1.08。m＝(Mn-Mr3)÷(Mr1+Mr2)＝(2300-365)÷(98+104)＝9.6。
And B, adding 8g (0.0035 mol) of the macromolecular chain transfer agent prepared in the step A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 14.84g (0.0355 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 1.082g (0.00066 mol) of azodiisobutyronitrile, reacting for 16 hours at 85 ℃ to obtain a pale yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Test of the conversion of tridecafluorooctyl acrylate to 95.6%, GPC test Polymer molecular weight, mn=6350, M P ＝7240，PDI＝1.14。n＝(6350-2300)÷418＝9.7。
Example 3
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of methyl isobutyl ketone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 2.79g (0.0077 mol) of DDMAT and 0.126g (0.00077 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then the temperature is regulated to 90 ℃ for reaction for 8 hours. Methyl isobutyl ketone was added to dissolve, then precipitated in methanol, and the precipitate was filtered and dried under vacuum at 100℃to give 32.1g of solid (macromolecular chain transfer agent) in 95.3% yield, GPC test molecular weight, mn=4280, M P ＝4540，PDI＝1.06。m＝(4280-365)÷(98+104)＝19.4。
And B, adding 8g (0.0018 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 14.38g (0.0188 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 1.082g (0.00066 mol) of azodiisobutyronitrile, reacting for 24 hours at 100 ℃ to obtain a pale yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Test of tridecafluoroacrylic acidOctyl ester conversion was 95.9%, GPC test polymer molecular weight, mn=8450, M P ＝9550，PDI＝1.13。n＝(8450-4280)÷418＝10.0。
Example 4
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 3.71g (0.0102 mol) of DDMAT and 0.167g (0.00102 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 60 ℃ for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 32.5g of solid (macromolecular chain transfer agent) with the yield of 93.9%, GPC test molecular weight, mn=3380, M P ＝3620，PDI＝1.07。m＝(3380-365)÷(98+104)＝14.9。
And B, adding 8g (0.0024 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 15.1g (0.037 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048 mol) of azodiisobutyronitrile, and reacting the mixture at 60 ℃ for 8 hours to obtain a pale yellow transparent solution, wherein the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 97.6%, GPC test Polymer molecular weight, mn=9660, M P ＝11850，PDI＝1.23。n＝(9660-3380)÷418＝15.0。
Example 5
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of propylene glycol methyl ether acetate, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 2.23g (0.0061 mol) of DDMAT and 0.167g (0.00102 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen introducing are carried out for 3 times, and the temperature is regulated to 80 ℃ for 24 hours. Dissolving in propylene glycol methyl ether acetate, precipitating in methanol, and filtering to obtain precipitateVacuum drying at 100deg.C gave 31.4g of solid (macromolecular chain transfer agent) in 94.8% yield, GPC test molecular weight, mn=5350, M P ＝5830，PDI＝1.09。m＝(5350-365)÷(98+104)＝24.7。
And B, adding 8g (0.0015 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 12.65g (0.0303 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048 mol) of azodiisobutyronitrile, and reacting the mixture at 70 ℃ for 16 hours to obtain a pale yellow transparent solution, wherein the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 98.3%, GPC test Polymer molecular weight, mn=13660, M P ＝16800，PDI＝1.23。n＝(13660-5350)÷418＝19.9。
Example 6
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 11.3g (0.031 mol) of DDMAT and 0.167g (0.00102 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 60 ℃ for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 39.83g of solid (macromolecular chain transfer agent) with the yield of 94.4%, GPC test molecular weight, mn=1350, M P ＝1480，PDI＝1.1。m＝(1350-365)÷(98+104)＝4.9。
And B, adding 8g (0.0059 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 12.89g (0.0308 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0969g (0.00059 mol) of azodiisobutyronitrile, and reacting the mixture at 80 ℃ for 16 hours to obtain a pale yellow transparent solution, wherein the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 96.6%, GPC test Polymer molecular weight, mn=3460, M P ＝4150，PDI＝1.20。n＝(3460-1350)÷418＝5.0。
Example 7
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of acetone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 1.86g (0.0051 mol) of DDMAT and 0.167g (0.00102 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 50 ℃ for reaction for 24 hours. Dissolving in acetone, precipitating in methanol, filtering to obtain precipitate, and vacuum drying at 100deg.C to obtain solid (macromolecular chain transfer agent) 30.89g, yield 94.3%, GPC test molecular weight, mn=6360, M P ＝6870，PDI＝1.08。m＝(6360-365)÷(98+104)＝29.7。
And B, adding 8g (0.0013 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 15.1g (0.037 mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048 mol) of azodiisobutyronitrile, and reacting the mixture at 80 ℃ for 16 hours to obtain a pale yellow transparent solution, wherein the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 96.2%, GPC test Polymer molecular weight, mn=18690, M P ＝22050，PDI＝1.18。n＝(18690-6360)÷418＝29.5。
Example 8
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 1.90g (0.0052 mol) of DDMAT and 0.167g (0.00102 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 60 ℃ for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 31.2g of solid (macromolecular chain transfer agent) with the yield of 95.0%, GPC test molecular weight, mn=6080, M P ＝6750，PDI＝1.11。m＝(6080-365)÷(98+104)＝28.3。
A100 ml single-port bottle is added with 8g (0.0013 mol) of macromolecular chain transfer agent prepared in the part A, dissolved by 20g butanone, then 3.0g (0.0072 mol) of tridecafluorooctyl acrylate, 10g of butyl acetate and 0.0213g (0.00013 mol) of azodiisobutyronitrile are added, and the mixture is reacted for 16 hours at 80 ℃ to obtain a pale yellow transparent solution, and the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 93.9%, GPC test Polymer molecular weight, mn=8250, M P ＝9900，PDI＝1.20。n＝(8250-6080)÷418＝5.2。
Example 9
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps of A and B, wherein the amphiphilic fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 10.22g (0.028 mol) of DDMAT and 0.046g (0.00028 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then the mixture is heated to 60 ℃ for reaction for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 39.1g of solid (macromolecular chain transfer agent) with the yield of 95.1%, GPC test molecular weight, mn=1480, M P ＝1610，PDI＝1.09。m＝(1480-365)÷(98+104)＝5.5。
A100 ml single-port bottle is added with 8g (0.0054 mol) of macromolecular chain transfer agent prepared in the part A, dissolved by 20g butanone, 67.8g (0.162 mol) of tridecyl fluoride acrylate, 40g of butyl acetate and 0.4433g (0.0027 mol) of azodiisobutyronitrile, and the mixture is reacted for 16 hours at 80 ℃ to obtain a pale yellow transparent solution, and the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Test of the conversion of tridecafluorooctyl acrylate to 97.3%, GPC test Polymer molecular weight, mn=13680, M P ＝16560，PDI＝1.21。n＝(13680-1480)÷418＝29.2。
Comparative example 1
The comparative example provides a preparation method of a fluorine-containing block polymer with a long hydrophobic fluorine chain, which comprises the following steps of A and B, and the fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 10.22g (0.028 mol) of DDMAT and 0.046g (0.00028 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then the mixture is heated to 60 ℃ for reaction for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 39.1g of solid (macromolecular chain transfer agent) with the yield of 95.1%, GPC test molecular weight, mn=1480, M P ＝1610，PDI＝1.09。m＝(1480-365)÷(98+104)＝5.5。
And B, adding 8g (0.0054 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, then adding 93.97g (0.2248 mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.4433g (0.0027 mol) of azodiisobutyronitrile, and reacting the mixture at 80 ℃ for 16 hours to obtain a turbid yellow solution, wherein gel is separated from the bottle wall. Test of tridecafluorooctyl acrylate conversion 96.8%, GPC test Polymer molecular weight, mn=18330, M P ＝24400，PDI＝1.33。n＝(18330-1480)÷418＝40.3。
Comparative example 2
The comparative example provides a preparation method of a fluorine-containing block polymer with a hydrophilic macromolecule chain segment which is overlong, comprising the following steps of A and B, and the fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 1.387g (0.0038 mol) of DDMAT and 0.046g (0.00028 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then the mixture is heated to 60 ℃ for reaction for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 30.6g of solid (macromolecular chain transfer agent) with 94.6% yield, GPC test molecular weight, mn=8550, M P ＝10100，PDI＝1.18。m＝(8550-365)÷(98+104)＝40.5。
B to a 100ml single-necked flask, 8g (0.0009 mol) of the macromolecular chain transfer agent prepared in part A was added, and the mixture was dissolved in 20g of butanone, followed by addition of 4.055g (0.0097 mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.0657g (0.0004 mol) of azobisisobutyronitrileThe reaction was carried out at 80℃for 16h to give a pale yellow transparent solution. The conversion of tridecafluorooctyl acrylate was 95.1%, the molecular weight of the polymer was determined by GPC, mn=12850, M P ＝16580，PDI＝1.29。n＝(12850-8550)÷418＝10.3。
Comparative example 3
The comparative example provides a preparation method of a fluorine-containing block polymer with too short hydrophilic macromolecule chain segments and too short hydrophobic fluorine chains, which comprises the following steps of A and B, and the fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 14.6g (0.040 mol) of DDMAT and 1.3136g (0.008 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the vacuum pumping and nitrogen circulating are carried out for 3 times, and then the temperature is regulated to 60 ℃ for 24 hours. Butanone is added for dissolution, then the precipitate is precipitated in methanol, the precipitate is filtered and dried in vacuum at 100 ℃ to obtain 42.4g of solid (macromolecular chain transfer agent) with 93.2 percent yield, GPC test molecular weight, mn=1070, M P ＝1240，PDI＝1.16。m＝(1070-365)÷(98+104)＝3.5。
A100 ml single-port bottle is added with 8g (0.0075 mol) of the macromolecular chain transfer agent prepared in the part A, dissolved by 20g butanone, then added with 10.95g (0.0262 mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.4433g (0.0027 mol) of azodiisobutyronitrile, and reacted for 16 hours at 80 ℃ to obtain a turbid yellow solution, and gel is separated out from the bottle wall. Test of 94.5% conversion of tridecafluorooctyl acrylate, GPC test Polymer molecular weight, mn=2450, M P ＝3280，PDI＝1.34。n＝(2450-1070)÷418＝3.3。
Comparative example 4
The comparative example provides a preparation method of a fluorine-containing block polymer with long hydrophilic macromolecule chain segments and long hydrophobic fluorine chains, which comprises the following steps of A and B, and the fluorine-containing block polymer is prepared:
under the ice water bath condition, 30g of butanone, 15g (0.153 mol) of maleic anhydride, 15.9g (0.153 mol) of styrene, 1.387g (0.0038 mol) of DDMAT and 0.046g (0.00028 mol) of azodiisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then the mixture is heated to 60 ℃ for reaction for 24 hours. Adding butanone for dissolution,then precipitating in methanol, filtering to obtain precipitate, and vacuum drying at 100deg.C to obtain solid (macromolecular chain transfer agent) 30.14g, yield 93.3%, GPC test molecular weight, mn=8750, M P ＝10850，PDI＝1.24。m＝(8750-365)÷(98+104)＝41.5。
And B, adding 8g (0.0009 mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-port bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, then adding 16.72g (0.040 mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.0657g (0.0004 mol) of azodiisobutyronitrile, and reacting the mixture at 80 ℃ for 16 hours to obtain a turbid yellow solution, wherein gel is separated from the bottle wall. Test of tridecafluorooctyl acrylate conversion 96.3%, GPC test Polymer molecular weight, mn=26650, M P ＝37580，PDI＝1.41。n＝(26650-8750)÷418＝42.8。
Comparative example 5
This comparative example first synthesized tridecafluorooctyl acrylate macromolecular chain transfer agent.
A, adding 15g of butanone, 1.31g of DDMAT (0.00036 mol) into a 100ml single-port bottle, then adding 15.1g (0.036 mol) of trideoxyfluoride acrylate, 15g of butyl acetate and 0.0787g (0.00048 mol) of azodiisobutyronitrile, reacting for 16 hours at 80 ℃ to obtain a pale yellow turbid solution, standing, layering, filtering to obtain a precipitate, drying the precipitate, and then using common solvents such as acetone, butanone, ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol methyl ether acetate, butanone and butyl acetate according to a mass ratio of 1:0.5-2, and the like, wherein the common solvents cannot be dissolved.
Test example 1
The interfacial tension between the two liquids was obtained by using a surface tensiometer (model HTYZL-H, electric power in wuhua days), referring to standard GB11985-1989, each of the polymer products of examples 1 to 9 and comparative examples 1 to 5 described above was an organic phase, injecting pure water into the organic phase through a capillary, measuring the volume of water droplets formed at the end of the upright capillary when the water droplets were detached from the pipe section by contact with the organic phase, balancing the weight of the droplets with a force supporting the interfacial tension thereof, and adding a correction factor. Interfacial tension was calculated from drop volume, capillary radius, density difference between two liquid phases, and gravitational acceleration. The surface tension was measured as shown in table 1 below.
Table 1 results of cross-section tension of polymer and water for each example and comparative example
| Interfacial tension mN/m | |
| Example 1 | 18.5 |
| Example 2 | 18.2 |
| Example 3 | 12.6 |
| Example 4 | 8.8 |
| Example 5 | 20.7 |
| Example 6 | 28.1 |
| Example 7 | 21.4 |
| Example 8 | 30.3 |
| Example 9 | 23.5 |
| ComparisonExample 1 | 37.4 |
| Comparative example 2 | 44.2 |
| Comparative example 3 | 50.9 |
| Comparative example 4 | 34.8 |
| Comparative example 5 | —— |
As can be seen from table 1 above, the effect of the polymers of examples 1 to 9 on lowering the surface tension is significantly better than that of comparative examples 1 to 4. Among them, example 4 achieves the best effect of reducing the surface tension.
It can be seen that the length of the macromolecular chain transfer agent has a significant effect on the solvent properties of the amphiphilic fluorine-containing block polymer, and when the number of the macromolecular chain units of the styrene-maleic anhydride in the molecule is significantly less than 5, the solubility in a common solvent is significantly reduced, as in comparative example 3, and a turbidity phenomenon occurs. When the number of styrene-maleic anhydride macromolecular chain units in the molecule is significantly more than 30, the surface tension lowering property is lowered as in comparative examples 2 and 4.
The surface activity of the amphiphilic fluorine-containing block polymer is also related to the amount of fluorine-containing monomer (tridecyl acrylate polymer chain), and when the content of tridecyl acrylate (the group indicated by the subscript n) in the block polymer is obviously less than 5, the property of reducing the surface tension is not obvious, as in comparative example 3. And when the content of tridecyl acrylate is more than 30, the obtained fluorine-containing block polymer is insoluble in a common solvent, as in comparative example 1 and comparative example 4.
The amphiphilic fluorine-containing polymer has better solubility and surface activity than fluorine-containing block polymers in the range, wherein m is an integer between 10 and 25, n is an integer between 10 and 20, and the fluorine-containing block polymers in the range have better solubility and surface activity than the fluorine-containing block polymers in the range, such as examples 1 to 5 and are better than examples 7 to 9.
The polymer disclosed by the invention has the advantages of good solubility in a fluorine-free solvent, high surface activity, few synthesis steps, low toxicity in the environment, easiness in degradation and good application prospect.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (9)
1. An amphiphilic fluorine-containing block polymer is characterized in that the structure of the polymer is shown as a general formula (I):
（Ⅰ）
in the general formula (I), R 1 Z is a stable group of the RAFT reagent, R is a leaving group of the RAFT reagent 2 Is- (CF) 2 ) 5 CF 3 Wherein m is an integer of 5 to 30, and n is an integer of 5 to 30; wherein the R is 1 is-C (CH) 3 ) 2 -COOH, Z is CH 3 (CH 2 ) 11 -S-(C=S)-S-。
2. The amphiphilic fluorine-containing block polymer of claim 1, wherein m is an integer between 10 and 25 and n is an integer between 10 and 20.
3. A method for preparing the amphiphilic fluorine-containing block polymer according to any one of claims 1 to 2, comprising the steps of:
adding a first fluorine-free solvent, a RAFT reagent and a first initiator at the temperature of-20 ℃ to 25 ℃, and mixing styrene and maleic anhydride according to the proportion of 1 to 1.2:1, and the molar ratio of the maleic anhydride, the RAFT agent and the first initiator is 5-30: 1: 0.01-0.2, setting a reaction environment as an anaerobic environment, heating to 50-90 ℃ to perform polymerization reaction 8-24h, adding a solvent to dissolve a reaction product after the reaction, adding another solvent to separate out a precipitate, filtering the precipitate and drying to obtain a solid macromolecular chain transfer agent;
b, adding the macromolecular chain transfer agent, the second initiator and the tridecyl acrylate into a second fluorine-free solvent, wherein the molar ratio of the tridecyl acrylate to the macromolecular chain transfer agent to the second initiator is 5-30:1:0.1-0.5, and reacting at 60-100 ℃ for 8-24 hours to obtain a transparent solution containing the polymer.
4. The method of preparing an amphiphilic fluorine-containing block polymer according to claim 3, wherein the RAFT agent is 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid; the first initiator and the second initiator are both azobisisobutyronitrile.
5. The method of preparing an amphiphilic fluorine-containing block polymer according to claim 3, wherein in the step a, the first fluorine-free solvent is one of butanone, acetone, methyl isobutyl ketone and propylene glycol methyl ether acetate.
6. The method for preparing an amphiphilic fluorine-containing block polymer according to claim 3, wherein in the step B, the second fluorine-free solvent is a mixed solvent of butanone and butyl acetate according to a mass ratio of 1:0.5-2.
7. The method for preparing an amphiphilic fluorine-containing block polymer according to claim 3, wherein: in step a, styrene and maleic anhydride are reacted according to 1:1 in a molar ratio of 1.
8. The method for preparing an amphiphilic fluorine-containing block polymer according to claim 3 or 7, characterized in that: in the step A, the molar ratio of maleic anhydride to RAFT reagent is 10-25:1; in the step B, the molar ratio of the tridecyl acrylate to the macromolecular chain transfer agent is 10-20:1.
9. The use of an amphiphilic fluorine-containing block polymer according to any of claims 1-2, wherein the polymer is used as a surfactant in detergents and cosmetics.
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| JP2009520074A (en) * | 2005-12-16 | 2009-05-21 | アーケマ・インコーポレイテッド | Production method and use of low surface energy block copolymer |
| FR2935000B1 (en) * | 2008-08-12 | 2011-07-01 | Arkema France | PROCESS FOR THE SYNTHESIS OF AMPHIPHILIC COPOLYMERS WITH A GRADIENT OF COMPOSITON AND SOLUBLES IN ALKALI |
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