CN114195962A - 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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- CN114195962A CN114195962A CN202111642468.7A CN202111642468A CN114195962A CN 114195962 A CN114195962 A CN 114195962A CN 202111642468 A CN202111642468 A CN 202111642468A CN 114195962 A CN114195962 A CN 114195962A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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]
Abstract
The invention discloses a synthetic method of an amphiphilic fluorine-containing block polymer, which comprises the following steps: adding a first fluorine-free solvent, an RAFT reagent and a first initiator, carrying out mixed polymerization reaction on styrene and maleic anhydride, adding a solvent after the reaction to dissolve a reaction product, adding an alcohol solvent for precipitation, filtering the precipitate, and drying to obtain a solid 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 fluorine-free solvent, and reacting to obtain a transparent solution containing the polymer. In the polymer, the repeatability of a styrene maleic anhydride macromolecule segment is an integer between 5 and 30, and the repeatability of a tridecyl acrylate unit is an integer between 5 and 30. The polymer of the invention has good solubility in fluorine-free solvent, high surface activity, few synthesis steps, low toxicity in environment, easy degradation and good application prospect.
Description
Technical Field
The invention relates to an amphiphilic fluorine-containing block polymer and a preparation method thereof, belonging to the field of novel fluorine-containing materials.
Background
Fluorosurfactants are usually composed of a fully or partially fluorinated fluorocarbon chain and hydrophilic groups and are characterized by high activity, high thermal stability and high chemical stability. Among the fluorosurfactants, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are the most widely used, but are difficult to degrade and toxic in the environment and are banned by the majority of the world.
Therefore, the development of a brand-new degradable fluorine surfactant to fully replace the prior PFOS/PFOA class fluorine-carbon surfactant is highly regarded by the scientific and industrial circles of various countries. The development orientations of alternatives can be roughly divided into two categories, (1) reduction of the length of the perfluorinated chains; (2) the fluorocarbon chain is introduced with a heteroatom such as N, O, methylene or methine. However, the above orientation has the following problems: when the length of the perfluoro chain is reduced, the surface activity thereof is not satisfactory in many fields; after the heteroatom is introduced into the fluorocarbon chain, the crystallinity of the fluorocarbon chain is obviously reduced, so that the surface activity of the fluorocarbon chain is reduced. Therefore, there is a need to develop new short carbon chain fluorosurfactants to meet the needs of the industry.
Gemini and Hetero-Gemini surfactants are surfactants obtained by linking a monomer of an active agent having two hydrophobic groups (or three hydrophobic groups) and two hydrophilic groups via a linker group near the hydrophilic group, and were first synthesized by Zana (Langmuir 1991,7,1072.) and Jaeger (Langmuir 1996,12,4314), respectively, in the 90 s of the 20 th century. Because two hydrophilic head groups in the gemini surfactant molecule are connected by chemical bonds, stronger hydrophobic interaction is easily generated between alkyl chains, and the repulsion between the hydrophilic head groups is greatly weakened due to the effect of the chemical bonds, so that the hydrophilic head groups can be arranged more closely. 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 complicated and complicated in synthesis steps during the preparation process, and are still far away from the application.
The polymerization of fluoropolymers, especially of tridecyl acrylate, usually requires synthesis in a special fluorine-containing solvent, such as trifluorotoluene, to obtain a clear solution. In common solvents, precipitation tends to occur, for example, Studies such as Yuanying et al show that (Macromolecular Rapid Communications,2018:1700840) polymerization of tridecafluorooctyl acrylate is initiated by using dimethylaminoethyl methacrylate as a Macromolecular chain transfer agent, and the obtained block is insoluble in isopropanol, toluene, dioxane, dimethylformamide and the like, which is not favorable for practical application.
Disclosure of Invention
The invention aims to solve the problem of replacing a fluorine-containing surfactant, and develops an environment-friendly fluorine-containing surfactant, namely a simple synthesis method of a gemini fluorine-containing surfactant.
Another object of the present invention is to invent a method for synthesizing a fluorine-containing block polymer having good solubility in an environmentally friendly solvent.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
An amphiphilic fluorine-containing block polymer, the structure of which is shown as a general formula (I):
in the general formula (I), R1Is a leaving group of RAFT agent, Z is a stabilizing group of RAFT agent, R2Is- (CF)2)5CF3Wherein 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 present invention, R is1is-C (CH)3)2-COOH, Z is CH3(CH2)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, an RAFT reagent and a first initiator at the temperature of-20-25 ℃, and mixing styrene and maleic anhydride according to the weight ratio of 1-1.2: 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 to be an oxygen-free environment, heating to 50-90 ℃, carrying out polymerization reaction for 8-24 hours, adding a solvent (such as butanone, methyl isobutyl ketone, propylene glycol methyl ether acetate and the like) to dissolve a reaction product after the reaction, adding another solvent (such as an alcohol solvent, methanol or a non-alcohol solvent, such as n-hexane, a solvent capable of precipitating a styrene-maleic anhydride macromolecular chain) to separate out a precipitate, filtering the precipitate, and drying to obtain a solid macromolecular chain transfer agent;
and B, adding the macromolecular chain transfer agent, the second initiator and the tridecafluorooctyl acrylate obtained in the step A into a second fluorine-free solvent, wherein the molar ratio of the tridecafluorooctyl acrylate to the macromolecular chain transfer agent to the second initiator is 5-30: 1: 0.1-0.5, reacting for 8-24h at the temperature of 60-100 ℃, and reacting 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) -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 preparation process of the amphiphilic fluorinated block polymer of the present invention, in step a, styrene and maleic anhydride are mixed according to a ratio of 1:1, were mixed.
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 tridecafluorooctyl acrylate to the macromolecular chain transfer agent is 10-20: 1.
The amphiphilic fluorine-containing block polymer can be applied to detergents and cosmetics by using the polymer as a surfactant.
The invention has the beneficial effects that: a simple synthesis method of gemini fluorine-containing surfactant is developed to obtain the environment-friendly amphiphilic fluorine-containing block polymer. In the polymer, the repetition degree (indicated by m and a hydrophilic group) of a styrene maleic anhydride macromolecule segment is an integer between 5 and 30, and the repetition degree (indicated by n and a hydrophobic group) of a tridecafluorooctyl acrylate unit is an integer between 5 and 30. During synthesis, with the increase of the chain length of the polystyrene maleic anhydride macromolecule transfer agent, the activity of the obtained polymer is gradually reduced, and the amphiphilic fluorine-containing block polymer has the property that a gemini fluorine-containing surfactant is transited to a macromolecule fluorine-containing surfactant. Meanwhile, the length of the macromolecular chain transfer agent has obvious influence on the dissolubility of the amphiphilic fluorine-containing block polymer, and when the number of monomer units in a molecule is less than 5, the dissolubility in a common solvent is obviously reduced. The amphiphilic fluorine-containing block polymer has the surface activity also related to the amount of fluorine-containing monomers, and when the content of the tridecyl octyl acrylate in the block polymer is less than 5, the property of reducing the surface tension is not obvious; when the content is more than 30, the resulting fluorine-containing block polymer is insoluble in a common solvent. The polymer of 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, easy degradation and good application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Hereinafter, the amphiphilic fluorine-containing block polymer of the present invention and the method for preparing the same will be described in detail.
The invention provides an amphiphilic fluorine-containing block polymer, which has a structure shown as a general formula (I):
R1is a leaving group of RAFT agent, Z is a stabilizing group of RAFT agent, R2Is- (CF)2)5CF3Wherein m is an integer between 5 and 30, and n is an integer between 5 and 30.
The RAFT reagent is a compound with reversible addition-fragmentation chain transfer characteristics, and has a chemical bond which is easy to generate addition reaction and fragmentation reaction in a molecular structure, and has a function of controlling the molecular weight of a polymer.
A preferred RAFT agent is 2- (dodecyl trithiocarbonate) -2-methylpropionic acid (DDMAT, CAS: 461642-78-4). R1 is-C (CH3)2-COOH, and Z is CH3(CH2)11-S- (C ═ S) -S-.
Common trithio and dithio esters are common RAFT agents, and reference is made to the structural formula and use thereof: macromolecules 2012,45,13, 5321-; compared with other RAFT reagents, DDMAT is easy to synthesize, good in regulation performance, and narrow in molecular weight distribution of the obtained polymer, so that the DDMAT is the best choice for regulating and preparing the block polymer.
Furthermore, the amphiphilic fluorine-containing polymer has m being an integer between 10 and 25, and n being an integer between 10 and 20, and the fluorine-containing block polymer in the range has better solubility and surface activity compared with the fluorine-containing block polymer outside the range.
In the polymer, an internal group of a subscript m is a 1:1 alternating copolymerization chain formed by styrene and maleic anhydride, the length of the chain affects the surface activity of the final polymer, the activity of the obtained fluorine-containing surfactant is gradually reduced along with the increase of the chain length of a polystyrene maleic anhydride macromolecule transfer agent, and the nature of the amphiphilic fluorine-containing block polymer is that a gemini fluorine-containing surfactant is transited to a macromolecule fluorine-containing surfactant. Meanwhile, the length of the macromolecular chain transfer agent has obvious influence on the dissolubility of the amphiphilic fluorine-containing block polymer, and when the number of monomer units in a molecule is less than 5, the dissolubility in a common solvent is obviously reduced. The amphiphilic fluorinated block polymer of the present invention also has a correlation between surface activity and the amount of fluorinated monomer, and when the content of tridecyl octyl acrylate (group indicated by subscript n) in the block polymer is less than 5, the property of lowering surface tension is not significant; when the content 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, in an ice water bath at the temperature of-20-25 ℃, under the condition of adding an RAFT reagent and a free radical initiator, mixing styrene and maleic anhydride according to the weight ratio of 1-1.2: 1, and the molar 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 8-24h, adding acetone, butanone, methyl isobutyl ketone or propylene glycol methyl ether acetate, dissolving, precipitating in methanol or other alcohol solvents, filtering to obtain a precipitate, and drying to obtain a solid macromolecular chain transfer agent. The radical initiator may be azo type, such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, etc.; also, peroxides such as dibenzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, dilauroyl peroxide, and the like may be used. The preferred RAFT reagent is DDMAT ((2-dodecyl trithiocarbonate) -2-methylpropionic acid), which is easy to synthesize and has good regulation performance to the system. The preferred initiator is Azobisisobutyronitrile (AIBN), the molar ratio of styrene to maleic anhydride is 1:1, because maleic anhydride and styrene readily form electron-complex copolymers and maleic anhydride does not readily homopolymerize, and when in excess, only oligomers are obtained; although styrene can homopolymerize, the polymerization rate is slow, so that the molar ratio of styrene to maleic anhydride is selected to be 1:1 to synthesize the macromolecular chain transfer agent.
And B, adding the macromolecular chain transfer agent, the initiator and the tridecyl octyl acrylate obtained in the step A into a fluorine-free solvent, wherein the molar ratio of the tridecyl acrylate to the macromolecular chain transfer agent to the initiator is 5-30: 1: 0.1-0.5, reacting for 8-24h at 60-100 ℃, and obtaining a transparent polymer solution. The tridecyl acrylate monomer is soluble in common solvents such as acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, etc., but the polymer thereof is insoluble in common solvents, and usually requires special solvents such as fluorine-containing solvents, etc. Therefore, the invention improves the solubility of SMA copolymer (styrene maleic anhydride) which is easy to dissolve in common solvent by firstly introducing the SMA copolymer, and simultaneously introducing hydrophilic groups, and simultaneously controlling the chain length of tridecafluorooctyl acrylate by activity controlled polymerization, and the invention discovers that when the repeating unit of tridecafluorooctyl acrylate is controlled below 30, the polymer is dissolved in common solvent, and when the repeating unit is higher than 30, precipitation occurs.
In the preparation of SMA (styrene-maleic anhydride) macromolecular chain transfer agents, common solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol methyl ether acetate, or other solvents capable of dissolving SMA polymers may be used as the polymerization solvent. When the copolymer of the tridecyl octyl acrylate is prepared, a lipid solvent is required to improve the solubility of the copolymer, and butyl acetate is a good choice.
The molar ratio of the styrene and the maleic anhydride to the RAFT agent determines the molecular weight of the macromolecular chain transfer agent, and in order to keep the obtained fluorine-containing block polymer to have better solubility and surface tension reducing performance, in the step A, the molar ratio of the styrene and the maleic anhydride is selected to be 1:1, and the molar ratio of the maleic anhydride and the RAFT agent is selected to be 10-25: 1, so that m is 10-25. In the step B, the molar ratio of the tridecafluorooctyl acrylate to the macromolecular chain transfer agent is 10-20: 1, so that n is 10-20. The macromolecular chain transfer agent increases in molecular weight and increases its solubility, but the resulting surface tension reducing properties decrease.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 5.58g (0.0153mol) of DDMAT and 0.251g (0.00153mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated by introducing nitrogen for 3 times, and then is subjected to temperature regulation to 70 ℃ for reaction for 12 hours. Dissolving butanone in the solution, precipitating in methanol to obtain macromolecular chain transfer agent, filtering to obtain precipitate, vacuum drying at 100 deg.C to obtain solid 35.6g with yield of 97.6%, wherein the macromolecular chain transfer agent (i.e. the precipitate) has chemical composition of DDMAT- (maleic anhydride-styrene macromolecular chain)m. GPC (gel permeation chromatography) measured the molecular weight of the macromolecular chain transfer agent, Mn 2400, MP2590, PDI 1.08. Wherein Mn is the number average molecular weight of the macromolecular chain transfer agent. MPIs the highest molecular weight of the macromolecular chain transfer agent. PDI is the dispersion coefficient of the macromolecular chain transfer agent, and the closer the PDI is to 1, the more uniform the molecular weight of the macromolecular chain transfer agent is. Wherein, the molecular weight Mr1 of maleic anhydride is 98, the molecular weight Mr2 of styrene is 104, and the molecular weight Mr3 of DDMAT is 365. From the structural formula (I), m ═ Mn-Mr3 ÷ (Mr1+ Mr2) ÷ (2400-.
B, adding 8g (0.0033mol) of the macromolecular chain transfer agent prepared in the step A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 14g (0.0335mol) of tridecyl acrylate, 20g of butyl acetate and 1.082g (0.00066mol) of azobisisobutyronitrile, reacting for 12 hours at 80 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Tridecafluorooctyl acrylate conversion of 95.2% was measured and the polymer molecular weight, Mn 6440, M, was determined by GPCP7400 and PDI 1.15. Wherein Mn is the number average molecular weight of the polymer. MPIs the highest molecular weight of the polymer. PDI is the dispersion coefficient of the polymer, and the closer the PDI is to 1, the more uniform the molecular weight of the polymer. The molecular weight Mr4 of tridecafluorooctyl acrylate is 418.From the structural formula (I), n ═ (6440-.
Example 2
The embodiment provides a preparation method of an amphiphilic fluorine-containing block polymer, which comprises the following steps A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of methyl isobutyl ketone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 5.58g (0.0153mol) of DDMAT and 0.251g (0.00153mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 75 ℃, and the reaction is carried out for 16 hours. Dissolving with methyl isobutyl ketone, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 35.1g with yield 96.2%, and molecular weight measured by GPC (Mn 2300, M)P＝2490，PDI＝1.08。m＝(Mn-Mr3)÷(Mr1+Mr2)＝(2300-365)÷(98+104)＝9.6。
B, adding 8g (0.0035mol) of the macromolecular chain transfer agent prepared in the step A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 14.84g (0.0355mol) of tridecyl acrylate, 20g of butyl acetate and 1.082g (0.00066mol) of azobisisobutyronitrile, reacting for 16h at 85 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Tridecafluorooctyl acrylate conversion was measured to be 95.6%, polymer molecular weight by GPC, Mn 6350, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of methyl isobutyl ketone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 2.79g (0.0077mol) of DDMAT and 0.126g (0.00077mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 90 ℃, and the reaction is carried out for 8 hours. Dissolving with methyl isobutyl ketone, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid(macromolecular chain transfer agent) 32.1g, yield 95.3%, molecular weight by GPC measurement, Mn 4280, MP＝4540，PDI＝1.06。m＝(4280-365)÷(98+104)＝19.4。
B, adding 8g (0.0018mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, then adding 14.38g (0.0188mol) of tridecyl acrylate, 20g of butyl acetate and 1.082g (0.00066mol) of azobisisobutyronitrile, reacting for 24 hours at 100 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization into the solution. Tridecafluorooctyl acrylate conversion 95.9% was measured and the polymer molecular weight, Mn 8450, M, was determined by GPCP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 3.71g (0.0102mol) of DDMAT and 0.167g (0.00102mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated for 3 times by introducing nitrogen, and then is subjected to reaction for 24 hours at the temperature of 60 ℃. Dissolving butanone in the solvent, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 32.5g, yield 93.9%, molecular weight determined by GPC, Mn 3380, MP＝3620，PDI＝1.07。m＝(3380-365)÷(98+104)＝14.9。
B, adding 8g (0.0024mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, adding 15.1g (0.037mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048mol) of azobisisobutyronitrile, reacting for 8 hours at 60 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization into the solution. Tridecafluorooctyl acrylate conversion was found to be 97.6%, polymer molecular weight by GPC, Mn 9660, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of ice-water bath, 30g of propylene glycol monomethyl ether acetate, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 2.23g (0.0061mol) of DDMAT and 0.167g (0.00102mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 80 ℃, and the reaction is carried out for 24 hours. Dissolving propylene glycol methyl ether acetate, precipitating in methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 31.4g, yield 94.8%, molecular weight measured by GPC, Mn 5350, MP＝5830，PDI＝1.09。m＝(5350-365)÷(98+104)＝24.7。
B, adding 8g (0.0015mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, adding 12.65g (0.0303mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048mol) of azobisisobutyronitrile, reacting for 16h at 70 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization into the solution. Tridecafluorooctyl acrylate conversion of 98.3% was measured and the polymer molecular weight was determined by GPC, Mn 13660, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 11.3g (0.031mol) of DDMAT and 0.167g (0.00102mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for circulation for 3 times, the temperature is adjusted to 60 ℃, and the reaction is carried out for 24 hours. Dissolving butanone in ethanol, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain 39.83g solid (macromolecular chain transfer agent), yield 94.4%, molecular weight measured by GPC, Mn 1350, MP＝1480，PDI＝1.1。m＝(1350-365)÷(98+104)＝4.9。
B, adding 8g (0.0059mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, then adding 12.89g (0.0308mol) of tridecyl acrylate, 20g of butyl acetate and 0.0969g (0.00059mol) of azobisisobutyronitrile, reacting for 16h at 80 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization in the solution. Tridecafluorooctyl acrylate conversion was determined to be 96.6%, polymer molecular weight by GPC, Mn 3460, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of ice-water bath, 30g of acetone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 1.86g (0.0051mol) of DDMAT and 0.167g (0.00102mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated by nitrogen for 3 times, and then is adjusted to 50 ℃ for reaction for 24 hours. Dissolving in acetone, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 30.89g with yield of 94.3%, and molecular weight determined by GPC (Mn 6360, M)P＝6870，PDI＝1.08。m＝(6360-365)÷(98+104)＝29.7。
B, adding 8g (0.0013mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent by using 20g of butanone, adding 15.1g (0.037mol) of tridecafluorooctyl acrylate, 20g of butyl acetate and 0.0787g (0.00048mol) of azobisisobutyronitrile, reacting for 16h at 80 ℃ to obtain a light yellow transparent solution, and dissolving the amphiphilic fluorine-containing block polymer obtained by polymerization into the solution. Tridecafluorooctyl acrylate conversion was determined to be 96.2%, polymer molecular weight by GPC, Mn 18690, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 1.90g (0.0052mol) of DDMAT and 0.167g (0.00102mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, circulated by introducing nitrogen for 3 times, and then is subjected to temperature regulation to 60 ℃ for reaction for 24 hours. Dissolving butanone in the solvent, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 31.2g with yield 95.0%, and measuring molecular weight by GPC (Mn 6080, M)P＝6750，PDI＝1.11。m＝(6080-365)÷(98+104)＝28.3。
B, in a 100ml single-neck bottle, 8g (0.0013mol) of the macromolecular chain transfer agent prepared in the part A is added, dissolved by 20g of butanone, and then 3.0g (0.0072mol) of tridecyl octyl acrylate, 10g of butyl acetate and 0.0213g (0.00013mol) of azobisisobutyronitrile are added, and reacted at 80 ℃ for 16 hours to obtain a light yellow transparent solution, and the amphiphilic fluorine-containing block polymer obtained by polymerization is dissolved in the solution. Tridecafluorooctyl acrylate conversion was measured to be 93.9%, polymer molecular weight by GPC, Mn 8250, MP＝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 A and B to prepare the amphiphilic fluorine-containing block polymer:
a, under the condition of ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 10.22g (0.028mol) of DDMAT and 0.046g (0.00028mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 60 ℃, and the reaction is carried out for 24 hours. Dissolving butanone in ethanol, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 39.1g with yield of 95.1%, and molecular weight determined by GPC (Mn: 1480, M)P＝1610，PDI＝1.09。m＝(1480-365)÷(98+104)＝5.5。
B in a 100ml single-neck flask, 8g (0.0054mol) of the macromolecular chain transfer agent prepared in part A was added, dissolved in 20g of methyl ethyl ketone, and then 67.8g (0.162mol) of tridecyl octyl acrylate, 40g of butyl acetate, and azo octyl acrylate were addedDiisobutyronitrile 0.4433g (0.0027mol), reacted at 80 ℃ for 16 hours to give a pale yellow transparent solution in which the amphiphilic fluorine-containing block polymer obtained by polymerization was dissolved. Tridecafluorooctyl acrylate conversion was found to be 97.3%, polymer molecular weight by GPC, Mn 13680, MP＝16560，PDI＝1.21。n＝(13680-1480)÷418＝29.2。
Comparative example 1
The comparative example provides a method for preparing a fluorine-containing block polymer with an excessively long hydrophobic fluorine chain, which comprises the following steps A and B to prepare a fluorine-containing block polymer:
a, under the condition of ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 10.22g (0.028mol) of DDMAT and 0.046g (0.00028mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 60 ℃, and the reaction is carried out for 24 hours. Dissolving butanone in ethanol, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 39.1g with yield of 95.1%, and molecular weight determined by GPC (Mn: 1480, M)P＝1610，PDI＝1.09。m＝(1480-365)÷(98+104)＝5.5。
B, adding 8g (0.0054mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, adding 93.97g (0.2248mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.4433g (0.0027mol) of azobisisobutyronitrile, and reacting at 80 ℃ for 16h to obtain a turbid yellow solution, wherein gel is precipitated on the bottle wall. Tridecafluorooctyl acrylate conversion was measured to be 96.8%, polymer molecular weight by GPC, Mn 18330, MP＝24400，PDI＝1.33。n＝(18330-1480)÷418＝40.3。
Comparative example 2
The comparative example provides a method for preparing a fluorine-containing block polymer with an excessively long hydrophilic macromolecular segment, which comprises the following steps A and B:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 1.387g (0.0038mol) of DDMAT and 0.046g (0.00028mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, and the mixture is vacuumized and nitrogen is introducedThe gas is circulated for 3 times, and then the temperature is adjusted to 60 ℃ to react for 24 hours. Dissolving butanone in the solvent, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 30.6g with yield of 94.6%, and measuring molecular weight by GPC (Mn is 8550, M)P＝10100，PDI＝1.18。m＝(8550-365)÷(98+104)＝40.5。
B, in a 100ml single-neck bottle, 8g (0.0009mol) of the macromolecular chain transfer agent prepared in the part A is added, dissolved by 20g of butanone, and then 4.055g (0.0097mol) of tridecyl acrylate, 40g of butyl acetate and 0.0657g (0.0004mol) of azobisisobutyronitrile are added, and the mixture is reacted for 16 hours at 80 ℃ to obtain a light yellow transparent solution. Tridecafluorooctyl acrylate conversion 95.1% was measured, polymer molecular weight was determined by GPC, Mn 12850, MP＝16580，PDI＝1.29。n＝(12850-8550)÷418＝10.3。
Comparative example 3
The comparative example provides a method for preparing a fluorine-containing block polymer with an excessively long hydrophobic fluorine chain, which comprises the following steps A and B to prepare a fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 14.6g (0.040mol) of DDMAT and 1.3136g (0.008mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times of circulation, the temperature is adjusted to 60 ℃, and the reaction is carried out for 24 hours. Dissolving butanone in the solvent, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 42.4g, yield 93.2%, molecular weight by GPC, Mn 1070, MP＝1240，PDI＝1.16。m＝(1070-365)÷(98+104)＝3.5。
B, adding 8g (0.0075mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 10.95g (0.0262mol) of tridecyl acrylate, 40g of butyl acetate and 0.4433g (0.0027mol) of azobisisobutyronitrile, and reacting for 16h at 80 ℃ to obtain a turbid yellow solution, wherein gel is precipitated on the bottle wall. Tridecafluorooctyl acrylate conversion of 94.5%, polymer molecular weight by GPC, Mn 2450, MP＝3280，PDI＝1.34。n＝(2450-1070)÷418＝3.3。
Comparative example 4
The comparative example provides a method for preparing a fluorine-containing block polymer with an excessively long hydrophobic fluorine chain, which comprises the following steps A and B to prepare a fluorine-containing block polymer:
a, under the condition of an ice-water bath, 30g of butanone, 15g (0.153mol) of maleic anhydride, 15.9g (0.153mol) of styrene, 1.387g (0.0038mol) of DDMAT and 0.046g (0.00028mol) of azobisisobutyronitrile are added into a 100ml single-neck flask, the mixture is vacuumized, nitrogen is introduced for 3 times, the temperature is adjusted to 60 ℃, and the reaction is carried out for 24 hours. Dissolving butanone in the solvent, precipitating with methanol, filtering to obtain precipitate, and vacuum drying at 100 deg.C to obtain solid (macromolecular chain transfer agent) 30.14g with yield 93.3%, and molecular weight measured by GPC (Mn: 8750, M)P＝10850，PDI＝1.24。m＝(8750-365)÷(98+104)＝41.5。
B, adding 8g (0.0009mol) of the macromolecular chain transfer agent prepared in the part A into a 100ml single-neck bottle, dissolving the macromolecular chain transfer agent with 20g of butanone, then adding 16.72g (0.040mol) of tridecafluorooctyl acrylate, 40g of butyl acetate and 0.0657g (0.0004mol) of azobisisobutyronitrile, and reacting for 16h at 80 ℃ to obtain a turbid yellow solution, wherein gel is precipitated on the bottle wall. Tridecafluorooctyl acrylate conversion of 96.3% was measured and the polymer molecular weight was determined by GPC, Mn 26650, MP＝37580，PDI＝1.41。n＝(26650-8750)÷418＝42.8。
Comparative example 5
The comparative example synthesizes tridecafluorooctyl acrylate macromolecular chain transfer agent.
A, adding 15g of butanone and 1.31g (0.00036mol) of DDMAT into a 100ml single-neck bottle, then adding 15.1g (0.036mol) of tridecyl acrylate, 15g of butyl acetate and 0.0787g (0.00048mol) of azobisisobutyronitrile, reacting for 16h at 80 ℃ to obtain a light yellow turbid solution, standing, demixing, filtering to obtain a precipitate, drying the precipitate, and then using acetone, butanone, ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol methyl ether acetate, butanone and butyl acetate to obtain a mixed solvent with the mass ratio of 1: 0.5-2, wherein the mixed solvent can not be dissolved.
Test example 1
The interfacial tension between two liquid phases can be obtained by using a surface tension meter (wuhan huatian power, model number HTYZL-H), reference standard GB11985-1989, the above-mentioned polymer products of examples 1 to 9 and comparative examples 1 to 5 being organic phases, injecting pure water into the organic phases through capillaries, measuring the volume of water droplets formed at the ends of the upright capillaries falling off the pipe section through contact with the organic phase, balancing the weight of the droplets with the force supporting its interfacial tension, and adding a correction factor. The interfacial tension is calculated from the drop volume, the capillary radius, the density difference between the two liquid phases and the gravitational acceleration. The surface tension was measured as in table 1 below.
TABLE 1 examples and comparative examples the results of polymer and water cross-sectional tension testing are shown
| 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 |
| Comparative example 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 surface tension-reducing effects of the polymers of examples 1 to 9 are significantly superior to those of comparative examples 1 to 4. Among them, example 4 achieved the best surface tension reducing effect.
It can be seen that the length of the macromolecular chain transfer agent has a significant influence on the solvent property of the amphiphilic fluorine-containing block polymer, and when the number of styrene-maleic anhydride macromolecular chain units in the molecule is significantly less than 5, the solubility in a common solvent is significantly reduced, such as comparative example 3, and a turbidity phenomenon occurs. When the number of units of the styrene-maleic anhydride macromolecular chain in the molecule is significantly more than 30, the surface tension-reducing property is lowered, as in comparative examples 2 and 4.
The amphiphilic fluorinated block polymer also has a correlation between surface activity and the amount of fluorinated monomer (tridecafluorooctyl acrylate polymer chain), and when the amount of tridecafluorooctyl acrylate (indicated by subscript n) in the block polymer is significantly less than 5, the surface tension lowering properties are not significant, as in comparative example 3. And when the content of tridecyl octyl acrylate is more than 30, the resulting 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 m being an integer between 10 and 25 and n being an integer between 10 and 20, and the fluorine-containing block polymer in the range has better solubility and surface activity compared with the fluorine-containing block polymer in the range, such as examples 1 to 5, which are superior to examples 7 to 9.
The polymer of the invention has good solubility in fluorine-free solvent, high surface activity, few synthesis steps, low toxicity in environment, easy 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 present 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. An amphiphilic fluorine-containing block polymer, which is characterized in that the structure of the polymer is shown as a general formula (I):
in the general formula (I), R1Is a leaving group of RAFT agent, Z is a stabilizing group of RAFT agent, R2Is- (CF)2)5CF3Wherein m is an integer between 5 and 30, and n is an integer between 5 and 30.
2. The amphiphilic fluorinated block polymer of claim 1, wherein R is1is-C (CH)3)2-COOH, Z is CH3(CH2)11-S-(C＝S)-S-。
3. The amphiphilic fluorinated block polymer of claim 1, wherein m is an integer from 10 to 25, and n is an integer from 10 to 20.
4. A method for preparing the amphiphilic fluorine-containing block polymer according to any one of claims 1 to 3, comprising the steps of:
adding a first fluorine-free solvent, an RAFT reagent and a first initiator at the temperature of-20-25 ℃, and mixing styrene and maleic anhydride according to the weight ratio of 1-1.2: 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 to be an oxygen-free environment, heating to 50-90 ℃, carrying out polymerization reaction for 8-24 hours, adding a solvent after the reaction to dissolve a reaction product, then adding another solvent to separate out a precipitate, filtering the precipitate, and drying to obtain a solid macromolecular chain transfer agent;
and B, adding the macromolecular chain transfer agent, the second initiator and the tridecafluorooctyl acrylate obtained in the step A into a second fluorine-free solvent, wherein the molar ratio of the tridecafluorooctyl acrylate to the macromolecular chain transfer agent to the second initiator is 5-30: 1: 0.1-0.5, reacting for 8-24h at the temperature of 60-100 ℃, and reacting to obtain a transparent solution containing the polymer.
5. The method of claim 4, wherein the RAFT agent is 2- (dodecyl trithiocarbonate) -2-methylpropionic acid; the first initiator and the second initiator are both azobisisobutyronitrile.
6. The method of claim 4, wherein in step A, the first non-fluorinated solvent is one of methyl ethyl ketone, acetone, methyl isobutyl ketone, and propylene glycol methyl ether acetate.
7. The method for preparing an amphiphilic fluorine-containing block polymer according to claim 4, wherein in the step B, the second fluorine-free solvent is a mixed solvent of butanone and butyl acetate in a mass ratio of 1: 0.5-2.
8. The method for producing an amphiphilic fluorine-containing block polymer according to claim 4, characterized in that: in step a, styrene and maleic anhydride were mixed according to a 1:1, were mixed.
9. The method for producing an amphiphilic fluorine-containing block polymer according to claim 4 or 8, 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 tridecafluorooctyl acrylate to the macromolecular chain transfer agent is 10-20: 1.
10. Use of amphiphilic fluorinated block polymers according to any of claims 1 to 3 as surfactants in detergents and cosmetics.
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