Synthesis and Application of New Fluoropolymer Gels

Synthesis and Application of New Fluorine-Containing Polymer Gels Alignment Arrangement of cyanoalkyl segments at the interface between gas and liquid (water) in an aqueous solution of a fluoroalkyl-terminated acrylic oligomer Indole Molecular Surfactants Incorporating Aromatic Alkyl Groups As shown, the fluoroalkyl segments in the fluorene molecular chain produce associations between the hydrazine molecules of the macromolecular surfactants, and thus the fluoroalkyl chain segments contained therein. The reason why it is difficult to align at the interface between gas/liquid (water) and why it is not effective to reduce the surface tension of water seems to be the reason.

1 The front-blind fluorinated alkyl hydrazine molecular compound shows a variety of unique properties that are different from those of the non-fluorinated polymer compound, which raises various concerns. However, most of these fluorine-containing polymer compounds are insoluble in common solvents, and there is an urgent need to develop fluorine-containing compounds that are soluble in various solvents. The idea of ​​introducing a strongly hydrophobic and strongly oleophobic fluoroalkyl chain moiety in the oxime molecular compound to increase the solubility of the fluorine-containing fluorene molecule compound has caused great interest. For the first time, a method for directly synthesizing fluorine-containing fluorene molecules dissolved in organic solvents by introducing an alkyl group into the carbon-carbon chain was introduced only at the two ends of the fluorene molecule. The specific method of synthesis is shown in the diagram. The fluoroperfluoroalkane is directly reacted with acrylic acid to pass through the first-order radical chain termination reaction and the chain transfer reaction caused by the peroxide chain growth reaction. In the research, it was found that the fluorine group was introduced only at the two ends of the fluorene molecule compound. The resulting oligomers are of even more interesting interest. Unlike molecular surfactants that introduce fluoroalkyl groups in polymers, which are generally different from the molecular surfactants that form molecular aggregates corresponding to micelles in water, Acrylic oligomers that incorporate a fluoroalkyl group at the end can form molecular complexes that are comparable to micelles. We have recently discovered that these terminals are introduced into fluoroalkyl oligomers because of the introduction of betaine into the primary bond or the introduction of a bond that can generate hydrogen bonds, which is due to ionic interactions or conduction under non-crosslinked conditions. Humans may form gels with the help of hydrogen bonding interactions. In the past, gelation of a polymer compound was generally performed by a method of adding a crosslinking agent, and a method of ion interaction or hydrogen bonding interaction was used. However, new fluoropolymer gels can also be synthesized using this fluorination. Accordingly, this review will explain the synthesis and application of this series of fluorene molecules.

2 Helping Ionic Interactions Synthesize fluorine-containing polymer gels. The fluoroalkyl-terminated acrylic oligomers can effectively aggregate to form molecular complexes between the terminal fluoroalkyl segments in the aqueous solution. We have conducted detailed studies on acrylic-trimethylvinylsilane oligomers with fluoroalkyl groups introduced at both ends. This oligomer-formed molecular assembly, as shown, can form a slender ellipsoid. Molecular assembly. Specifically, the electrostatic repulsion between the main chain hydrocarbons is shown, and the fluoroalkyl groups (-) agglomerate to one another due to van der Waals forces. In addition, the fluorene fluorescence test shows that these fluorinated oligomers are not molecular assemblies of the hydrophilic moiety and the hydrophobic moiety, but are two molecular assemblies that are present together.

Molecular polymer formed by acrylic acid-trimethylvinylsilane oligomer introduced into fluoroalkyl at the end of the male. Therefore, it can be expected that the fluoroalkyl-terminated oligomers introduced by these terminals are due to the introduction of ionic interactions in the new chain. The synergistic effect of coagulation with fluorine may form a gel. In fact, 2-acrylamido-2-methylpropane sulfonic acid (AMPS) reacts with the peroxyfluoride segments as shown schematically.

It is of great interest to indicate these synthetic betaine-type oligomers. Because they are soluble in dilute aqueous solutions, the molecular weight can be determined by gel permeation chromatography. The measured results showed that the number average molecular weight (W) was in the range of 1 to 20,000, but the dispersion ratio was 20 to 280, showing a polydispersed value. Its molecular weight is the value of the oligomer region. This clearly shows that these oligomers are oligomers that tend to agglomerate with each other. Compared to fluorinated oligomers, fluorine-free oligomers interact very little. In addition, the viscosity of the aqueous solution of the fluorine-containing AMPS oligomer significantly increased as the concentration increased, and the viscosity of oligomers at 0.5 g/dm 31.0 g/dm 3 or more drastically increased to finally form a gel. Therefore, it can be considered that when the concentration of the oligomer is thin, the solvent is preferentially different. The concentration range of 5 g/dm3 to 1.0 g/dm3, as shown, may form a gel due to the synergistic effect of the ionic interactions between the betaine segments and the aggregation of the fluoroalkyl groups at the terminal ends of the oligomers.

An AMPS polymer has been synthesized in which the fluoroalkyl segment is not incorporated at both ends of the molecular chain but is introduced into the block inside the fluorene molecule main chain.

It is indicated that such a fluoropolymer may be soluble in water and solvents such as methanol, ethanol, dimethyl sulfoxide, n,rr dimethylformamide, etc. These do not gel. Therefore, in order to gel the hydrazine-containing compound in water or an organic solvent, the alkyl chain segment should not be introduced into the molecule but should be introduced at the end of the main chain of the molecular compound. This is very important. It can be considered that since the fluoroalkyl chain segments exhibiting strong hydrophobicity and oleophobicity to water and hydrocarbons can be stably present, only the fluoroalkyl segment is introduced at both ends of the fluorene molecule main chain, and the interaction between the macromolecular compound and the molecule is weak. The fluoroalkyl segments, in contrast, show "nucleophilic (pro-protonic)" properties and can cohere with one another.

On the other hand, the fluorine-containing alkyl sulfonic acid oligomer synthesized by the reaction of a fluorinated oxyalkanol with a sulfo-group-containing methacrylic ester monomer and fluoroalkyl alkane synthesizes trimethyl ammonium segment The aqueous solution of the fluoroalkyltrimethylammonium-based oligomer synthesized by the monomer reaction does not form a gel, and the viscosity of the aqueous solution greatly increases the viscosity as the concentration increases. From the results of these studies, it can be clearly seen that to achieve gelation of fluoroalkyl sulfonate oligomers and fluoroalkyltrimethylammonium oligomers, it is impossible to form coagulation by relying only on the interaction between anions or cations. Plastic.

In addition to water, the fluorine AMPS oligomer containing betaine segments in Shitongtong 4 can also gel organic solvents such as MeOH, EtOH, DMF, and DMSO, and can be used in hydrogels or lipogels.

The fluoroalkyl-based AMPS oligomer gel introduced at the 5th end of Shidanchuang, like the conventional polymer hydrogel, can capture heavy gold ions such as chromium and cobalt. In addition, as shown in Table 1, the AMPS oligomers are contained. The gel has the same value as an ordinary polymer thiocan that is considered to be an anti-AIDS drug. EC3 (concentration required for HIV suppression) has a small value, and CCM (concentration for inhibiting normal cells) has a large value. It is considered to be a compound that shows selective anti-HIV activity. In contrast, the fluorine-free AMPS oligomers have small CCM values, are toxic, and are not selective.

Table 1 Anti-HIV activity of cyano-containing AMPS oligomers Dextran sulfate (M=5000) Rr in oligomers inhibits HIV 50% concentration required inhibits normal cells 50% increase in concentration In particular, it is known that a part of the oligomers of these compounds not only have anti-HIV activity, but also have activity against Staphylococcus aureus. Therefore, the use of these compounds will produce physiologically active drugs. There is a great future for development.

We have noticed that the fluorinated betaine-type quinone molecule compound other than AMPS, 2-(3-acrylamido-propyl dimethyl ethanolate (APDMAE), which synthesizes oligomerization with a fluoroalkanol peroxide in a schematic manner The fluoroalkyl-terminated APPMAE oligomer was introduced at the end of the product.

1, 2, and 3 indicate that these fluorine-containing APDMAE oligomers are different from the corresponding fluorine-containing AMPS oligomers in that the ability to form gels is small, but long-chain fluoroalkyl groups indicate that these fluorine-containing trihydroxy oligomers are As expected, it is possible to gel a water-soluble polar solvent such as dimethyl ether and dimethylformamide. On the other hand, the corresponding fluorine-free NAT oligomers were soluble in these solvents and no gelation was observed. From this, it can be considered that the gelation of the fluorine-containing NAT oligomer is a result of the synergistic effect of the inter-condensation of the hydrogen bond within the trihydroxyl chain molecule with the fluoroalkyl chain terminal at the end of the oligomer.

The fluorine-containing NAT oligomer hydrogel can effectively trap ions D as shown in the curve above. On the other hand, the fluorine oligomer gel that once trapped the metal ions is easily trapped as shown in the curve shown in C. The metal ions are released into the water system. In contrast, after the aforementioned fluorine-containing AMPS hydrogel captures metal ions once, the once-captured metal ions are not released into the water system. This is because the metal ions trapped in the fluorine-containing NAT hydrogel are coordinately associated ions, not the metal ions captured by the fluorine-containing AMPS oligomers are ion-absorptive. This series shows that the series has hydroxyl groups in the terminal groups. Fluorine-containing oligomers, unlike the corresponding non-fluorine-containing oligomers, do not gel, and both oligomers can hydrogelize. This is considered to be due to the fact that the terminal introduces a synergistic effect of the mutual condensation action of the fluoroalkyl group with the molecular hydrogen bonding of the hydroxyl group and the carboxyl group segment to form a gel.

Hydroxy-group-containing fluorooligomer hydrogels have the ability to capture metal ions, as well as fluorine-containing AMPS and NAT oligomer hydrogels, especially in the presence of trimethyl ammonium fluoropolymer oligomers and antimicrobial activity. .

The fluoroalkyl oligomer containing a phosphate chain can be synthesized using a fluorinated alkanol, as schematically shown.

The fluoroalkyl group-containing oligomer having a phosphate chain is shown to gel the hydrogel. This is believed to be due to the synergistic effect of the synergistic effect of the molecular hydrogen bond between the phosphate chain and the fluoroalkyl chain terminal at the end of the oligomer. Of particular interest is the fact that fluorinated oligomers with these phosphate chains can impart excellent oleophobicity. It has also been found that these fluorinated oligomers having a phosphate chain have a very selective anti-HIV activity in vitro and can therefore be used as new functional materials.

4 Synthesis and Gelation of Perfluorocyclohexyl-Containing Oligomers A number of reports have been made on low-molecular-weight synthetic pyrene molecular compounds using linear alkyl groups and their applications, but concerning the use of perfluoroalkylhexyl groups and other perfluorocarbons. Cyclohexyl introduced some of the hydrocarbon compounds reported very little. Therefore, research on the introduction of a cyclic fluoroalkyl group has attracted great interest. In addition, we conducted a detailed study of the introduction of the full-cycle hexyl.

As shown in illustration 0, the perfluorocyclohexyl group introduction bis(hexacyclohexylcarbonyl) peroxide can be synthesized using perfluorocyclohexylcarbonyl fluoride and hydrogen peroxide under basic conditions.

It is indicated that the peroxide has the same properties as the corresponding perfluorocyclohexyl peroxide, and the perfluorocyclohexyl radical is easily generated, and in addition, the LUM0 (lowest unoccupied molecular orbital) energy level is also the same, which suggests that it can be used. The radical process for perfluorocyclohexyl radicalization transfers electrons from the HOMO (lowest occupied molecular orbital) to the peroxide by the more rudimentary matrix.

In fact, as shown in Scheme 1, peroxidation (cyclohexane) reacts with 1 acrylic acid, 2 benzene, and 3 polystyrene, respectively, to generate an oligomer with a perfluorocyclohexyl-based acrylic perfluorinated ring at both ends. Hexyl oligomers, phenyl perfluorocyclohexyl oligomers with perfluorocyclohexyl groups introduced at both ends of the 2 oligomers, and polycyclohexyl oligomers with perfluorocyclohexyl groups introduced at both ends of the 3 oligomers Things.

It is shown that the perfluorocyclohexyl-derived acrylic oligomer at the 1st end can reduce the surface tension of water to the level of the fluorine-based surface polyactive agent as does the acrylic oligomer into which the linear perfluoroalkyl group is introduced.

This hydroxy perfluorocyclohexyl-containing oligomer, like the corresponding linear perfluoroalkoxy-containing oligomer, can hydrogelize. However, this gelling ability was found to be much greater than that of the linear oligomers. It is believed that this is because, as shown, the hydrogen bonding between the hydroxyl groups, the condensation of perfluorocyclohexyl groups, and the hydrogen bonding between the fluorine atoms on the perfluorocyclohexyl group and the hydroxyl groups Can easily cause three-dimensional effects.

Schematic illustration of the use of fluoroalkyl chain aggregation in the establishment of molecular aggregates and the use of this molecular assembly As mentioned earlier, the aggregation of compounds with fluoroalkyl groups introduced at the end of oligomers is generally easy to form molecular bodies. It has been specifically mentioned that these fluorine-containing oligomers introduce new hydrogen-bonding segments in addition to the betaine chain. These interactions assist the coagulation of fluorine and form gels. These ends lead to The fluoroalkyl-based low copolymer can prevent gelation by moderately suppressing the interaction of the lower copolymer main chain, but it can be expected to be a fluorine molecule assembly capable of sufficiently exhibiting the aggregation of fluorine.

Poly(N-vinylpyrrolidone) Aqueous Solution As shown, it is a known fact that the amide bond of the polymer through the intermediary hydrogen bonding of water can enhance the interaction between the polymers.

Therefore, research on the formation of molecular assemblies of acrylonitrile-oligo-low molecular weight acrylamide low copolymers and the applications of these molecular assemblies have attracted great interest.

The intermolecular phase interaction in the aqueous solution of vinyl-pyrrolidone) Actually, as shown in Scheme 3, we react fluoroalkanol peroxide with acryloyl morpholine to synthesize an acryloyl morpholine with an end-capping alkyl group. Low copolymer.

These acrylamide low copolymers can reduce the surface tension of water to the level of low molecular fluorine-based surfactants. In addition, these low copolymers also exhibit a clear breakpoint corresponding to CMC (Critical Micelle Concentration), suggesting the formation of molecular assemblies. In addition, the alkyl-containing acryloylmorpholine copolymers are also effective in lowering the surface tension of xylenes, forming molecular assemblies in xylene. In other words, these low copolymers are capable of effectively utilizing intermolecular hydrogen bonding in addition to fluoroalkyl coacervation and amide-based chain additions through the intermediary of water, exhibiting similar molecular assemblies as previously described.

In fact, these molecular assemblies, as shown, effectively trap as much calcium ions as possible that cannot be explained with normal quinones. In addition, as can be seen from the graph, the horizontal axis indicates the calcium ion concentration, and in addition, as shown in the diagram 4, the peroxymonoalkane is reacted with N-(vinylpyrrolidone) and acrylic acid to make them co-oligomerized and synthesized. A fluoroalkyl-terminated N-vinylpyrrolidone-acrylic acid low copolymer was introduced at the end.

CF (CF3) can be directly linked from the hydrogen-bonded carboxyl segment low copolymer to the oligomer straight chain, and the intermolecular hydrogen bonding interaction between the molecules is weak, and the ability to form a molecular assembly from agglomeration is lower than that of the corresponding N - Low vinylpyrrolidone copolymers.

There is also a general large capacity for trapping calcium ions in propyl morpholine low copolymers containing fluoroalkane S. The amount of calcium ion trapped in this way is involved in the intermolecular hydrogen bonding between the amide segments in the molecular assembly of the low molecular weight copolymer of fluorine-containing acrylamide low copolymer and N-vinyl pyrrolidone. In other words, a part of the interior of the fluorine-containing molecular assembly has an influence, and it is considered that these fluorine-containing molecular assemblies can effectively trap calcium ions.

The end of the introduction of fluoroalkyl acrylamide low copolymer, as shown in Table 2, with liquid-liquid extraction of kalasseine (N-methyl -2-propyryl pyrrolidine) assay found, and the corresponding fluorine-free Low acrylamide copolymers do not extract metal ions at all. In addition to calcium ions, low-fluorinated acrylamide copolymers can extract potassium ions, cobalt ions, antimony ions, lead ions, and other metal ions, making them even more interesting. However, these low-fluorinated copolymers can even be extracted from organic molecules of gudouine.

Conclusion In this article, we introduced a method for synthesizing fluoroalkyl-terminated indole molecular compounds with fluoroalkanol peroxide as the basic raw material. In particular, it is known that these fluorine-containing macromolecular compounds are due to the interaction of ions and the introduction of intermolecular hydrogen bonding-bonded segments, and these interactions are coupled with the synergistic effect of mutual cohesion of the fluoroalkyl segments introduced at the terminal ends of the hydrazone molecules. The effect can form a gel. Organic fluorine compounds have always been weakly intermolecularly intermolecular. However, we found that the fluoroalkyl group in the low fluoroalkyl-containing copolymer was conversely capable of agglomeration, that is, it was found to exhibit "pro-fluorine" properties. It is of particular interest that new fluorine-containing low copolymers made using this fluorine coagulation can cause gel sheets under non-crosslinking conditions. In addition, in addition to the commonly known functions of fluorine oleophobicity and other general functions, we discovered that fluoroalkyl-based organic compounds exhibit anti-HIV activity, anti-herpetic and anti-bacterial properties, and these compounds can exhibit new functional properties of Bin as functionalities. Material will have great potential for development in the future. Flexible and effective use of fluoroalkyl chain aggregation to produce the extraction rate Table 2 fluoroalkyl-containing acrylamide low copolymer extracted metal ion oligomers Fluorine-containing molecular aggregates Capturing with conventional chelation Impossible to explain There are so many metal ions such as calcium ions that may even capture organic molecules such as gudouine. Therefore, these fluorine-containing molecular assemblies are also very effective as a functional fluorine-based functional material.

Huang Hansheng 1Haodou