TWI382033B - Process for synthesizing poly(vinyl benzylamine) - Google Patents

Description

Method for synthesizing polymethylamine styrene compound

This invention relates to a process for the synthesis of polyamine compounds, and more particularly to a process for synthesizing homopolymers, agglomerates, and messy polymers of polymethylamine styrene compounds.

Polyamines, such as poly(vinyl benzyl amine); PVBAm, not only have physical properties similar to those of polystyrene (PS), but also have high activity of primary amine. The functional group is an effective cross-linking agent for a commercially available epoxy resin or polyurethane (PU), which can improve its mechanical properties. In addition, the polymethylamine styrene compound can also be applied to the adsorbed substance by using the primary amine, and can be used for the solid phase combined synthesis of the peptide and the nucleic acid. Agglomerates of polymethylamine styrene compounds (b-PS-PVBAm) can be used as a vesicle material for coating and transferring substances.

The conventional polymethylamine styrene compound is synthesized by radical polymerization of VBC monomer by using azoisobutyronitrile (AIBN) initiator as a vinyl benzyl chloride (VBC) monomer. After forming polychloromethylstyrene, it is reacted with Potassium phthalimide to carry out a Gabriel reaction, and then the protective group is removed to obtain polymethylamine styrene. However, when AIBN is used to initiate polymerization, the polymer has a wide polydispersity (PDI) and is difficult to control. The second stage of polymerization cannot be carried out after the reaction is completed.

Therefore, in recent years, the development of stable living radical polymerization has replaced traditional living ionic polymerization, and many homopolymers and block copolymers have been developed. Not only can a narrow molecular weight cloth polymer of less than 1.4 be obtained, but also a second stage polymerization can be carried out by controlling living radical polymerization, and a copolymer of chloromethylstyrene monomer can be polymerized as needed (block copolymer) Or a random copolymer, followed by a Gabriel reaction to remove the protecting group to obtain polymethylamine styrene.

Although the Gabriel reaction can directly produce polymethylamine styrene compounds, the details of the conversion rate and physical properties of the amine groups have not been clearly studied, and the progress of subsequent reactions is limited. In addition, although the Gabriel reaction is simple, the reaction process is not environmentally friendly, and the conversion rate cannot be completely converted.

Referring to Fig. 1, a radical polymerization, agglomerate copolymer or a chaotic copolymer of a narrowly distributed chloromethylstyrene monomer is obtained by radical polymerization, followed by azidation, phosphorization, and Hydrolysis, attempting to obtain polymethylamine styrene. However, in the process, a cross-linking reaction occurs, and when the homopolymer and the agglomerate copolymer are hydrolyzed and hydrolyzed, a cross-linked polymer having extremely poor solubility is produced.

Therefore, the traditional method has a low yield, so that polymethylamine styrene remains in the research field, and its applicability is not seen. This method cannot smoothly synthesize polymethylamine styrene or agglomerate copolymerized methylamine styrene, and also limits the subsequent application of polymethylamine styrene compounds.

The present invention provides a method for synthesizing a polyamine compound for improving the conventional synthesis of a polymethylamine styrene compound, which is difficult to control the PDI distribution of the polymer, the reaction process is not environmentally friendly, and the yield is poor.

The present invention provides a method for synthesizing a polymethylamine styrene compound for improving the synthesis method of the conventional polymethylamine styrene compound and the inability to synthesize a homopolymer and agglomerate copolymer.

According to the present invention, there is provided a method for synthesizing a polymethylamine styrene compound, which comprises providing a polymer having a plurality of repeating units as a starting material, and the polymer is poly(vinyl benzyl) (poly(vinyl benzyl) Halide)) or polystyrene-poly(vinyl benzyl halide), each of the above repeating units comprises a primary halogen compound, and the primary halogen compound is subjected to azide substitution reaction and phosphorization reaction. To form a high molecular polymer having a phosphorimine functional group. The high molecular weight polymer having a phosphorimine functional group is sequentially subjected to acidification reaction and alkalization reaction to form a homopolymer of polymethylamine styrene, agglomerate copolymer, and a disordered copolymer.

Embodiments of the present invention utilize chloromethylstyrene homopolymer (homo-PVBC; h-PVBC), chloromethylstyrene agglomerate polymer (block-PSPVBC; b-PSPVBC), or chloromethylstyrene mess The polymer (random-PSPVBC; r-PSPVBC) is modified into a highly utilized and highly reactive azide functional group, which is then reacted with triphenyl phosphine (PPh ₃ ) to give a readily reformable The phosphine imine functional group is further modified into a highly polar primary amine functional group through acidification and alkalization steps, and can easily and rapidly synthesize different types of polyamines with high conversion rate (homopolymer) , agglomerates of copolymers and messy polymers). Among them, the reaction intermediates polyphosphine imine and polyazide are also valuable, not only can be easily converted into various functional groups, but also take into account environmental protection, simple synthesis, 100% conversion rate, each A high yield of at least 80% of the reaction yield.

The inventors of the present invention have found that the method shown in Fig. 1 is applied to a homopolymer and agglomerate copolymer to produce a crosslinked polymer having extremely poor solubility, so that homopolymeric methylamine styrene and agglomerate copolymerization cannot be smoothly obtained. Methylamine styrene, only the scrambled copolymer can smoothly obtain polymethylamine styrene due to the phosphoimine functional groups in the homopolymer (h-PVBAz) and the agglomerate polymer (b-PSPVBAz) system. Caused by high density.

Please refer to Fig. 2 for a schematic diagram of the main chain of different kinds of polymethylamine styrene, in which the black part is the part containing the phosphorous imine functional group. Wherein, the homopolymethylamine styrene or the agglomerate copolymerized methylamine styrene has a high density of the phosphorus imine functional group, and since the phosphorus imine has high reactivity, if the reaction is carried out in the method shown in FIG. 1, when added During the water reaction, the phosphoimine functional group that first hits the water reacts with the highly active amine functional group, and the amine functional group cross-links with the unhydrolyzed phosphoimine functional group, so it cannot be smoothly A homopolymethylamine styrene or agglomerate copolymerized methylamine styrene is obtained.

In the disordered copolymerization system, since the amount of styrene is more than that of chloromethylstyrene in the scrambled copolymer, when the phosphoimine functional group is reacted, the phosphoimine functional group is separated by styrene, and benzene is separated. Ethylene acts as a protecting group or a separating group, and can successfully separate the hydrolyzed amine functional groups without reacting the highly reactive amine functional groups with the adjacent unhydrolyzed phosphoimine functional groups. Interlocking structure.

Therefore, based on the above findings, a method for synthesizing a polyamine compound is proposed, which synthesizes a polymer containing a plurality of repeating units using a living polymerization method of a TEMPO system, wherein each of the above repeating units contains a primary halogen compound, and starts from the polymer The starting material further synthesizes a highly polar polyamine functional group on the polymer.

The above polymer containing a plurality of repeating units is a poly(vinyl benzyl halide) or a polystyrene-poly (vinyl benzyl halide), wherein the repeating unit is The one-level halogen compound may have the following formula: Wherein X is a halogen and comprises fluorine, chlorine, bromine and iodine.

The polymer may, for example, comprise a polymer of a vinyl benzyl chloride (VBC) monomer, comprising a homo-poly(vinyl benzyl chloride; h-PVBC), Block polystyrene-poly (vinyl benzyl chloride; b-PSPVBC), or polystyrene-chloromethylstyrene messy copolymer random polystyrene-poly ( Vinyl benzyl chloride; r-PSPVBC).

Here, the polymer containing the primary halogen compound is subjected to an azide substitution reaction, and the halogen is replaced by sodium azide (NaN ₃ ) to form an azide (R-CH ₂ N ₃ ) functional group. polymer. The azide-functional polyazide has high reactivity and high conversion and can be converted into various functional groups. For example, the azide group can be subjected to a bond chemistry, reacted with an alkyne to form a tetrazole functional group to form a molecular library, and can also be grafted with a carbon sphere (C60).

The azide can be subjected to phosphine imination with triphenyl phosphine (PPh ₃ ), and a good reactivity with PPh ₃ and N ₃ can form a phosphorous imine. (phosphine imine; R-CH ₂ N = PPh ₃ ) high molecular weight polymer. The phosphorimine functional group polymer is easily modified. For example, the phosphorimide functional group can react with an isocyanate (R'-NCO) to form a carbodiimide (R-CH _{2 ).} A group of N=C=R') or reacted with acetaldehyde (aldehyde; R'-CO-H) to form an imine (R-CH ₂ N=CHR') group.

The polymer having a phosphorimine functional group is then subjected to acidation to form an Amine salt of the polymer. The acid subjected to the acidification reaction may contain hydrochloric acid (HCl), hydrofluoric acid (HF), bromic acid (HBr) or hydrogen iodide (HI).

The ammonium salt of the polymer is then subjected to alkalization to form a polyamine compound, including homopolymer, di-block and random type polymers, without causing a crosslinking reaction. The alkali to be subjected to the alkalization reaction may include sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), sodium hydrogencarbonate (NaHCO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydrogencarbonate ( KHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium borohydride (NaBH ₄ ), lithium aluminum hydride (LiAlH ₄ ).

Synthesis Example 1

Please refer to FIG. 3, which is a flow chart showing the reaction of a polyamine compound according to an embodiment of the present invention. Fig. 3 is a diagram showing the synthesis method of polymethylamine styrene compound by taking Polystyrene-poly (vinyl benzyl chloride); PS-PVBC as an example.

First, a polychloromethylstyrene (h-PVBC) is provided for azide substitution reaction (azidation).

Wherein, the synthesis step of polychloromethylstyrene can be carried out at about 80 ° C under the conditions of tetramethyl piperidine oxide (TEMPO), benzyl peroxide (BPO) and chloromethylstyrene (VBC) monomers. The reaction was carried out for 3 hours and then raised to about 130 ° C for living polymerization. After the completion of the reaction, the temperature was stopped, and the mixture was added dropwise to methanol for purification to remove unreacted VBC monomer, followed by drying at 70 ° C for 4 hours in a vacuum oven to obtain a homochloromethylstyrene having a narrow PDI containing TEMPO. (h-PVBC).

The azide substitution reaction treats PVBC with sodium azide (NaN ₃ ) to form PVBAz (polyazide) with azide functional groups on the PVBC.

Wherein, the synthesis step of PVBAz is to dissolve h-PVBC and excess NaN ₃ in tetrahydrofuran (THF), and react at about 70 ° C for 4 hours. After the reaction, THF is drained, and ethyl acetate and water are used. Extraction is carried out to obtain h-PVBAz.

h-PVBAz can synthesize h-PVBAS (amine salt) via phosphine imination and acidation.

The synthesis step of h-PVBAS is to dissolve h-PVBAz in THF, and add triphenyl phosphine (PPh ₃ ) to form a phosphine imine, and stir at room temperature for 8 hours. An excess of aqueous hydrochloric acid is added and the resulting h-PVBAS is dissolved in the aqueous phase and extracted with ethyl acetate and water.

Finally, alkalization is carried out, and the aqueous solution of h-PVBAS is added to NaOH for neutralization, at which time h-PVBAm (polyamine) precipitates due to insoluble water.

The above synthesis is based on the PVBC homopolymer (h-PVBC) as an example to illustrate the synthesis of its polyamine functional group (h-PVBAm), whereas the PVBC agglomerate copolymer (b-PSPVBC) and the messy copolymer. (r-PSPVBC) can also synthesize its polyamines (b-PSPVBAm and r-PSPVBAm) by the same principle. The side chain (R) of PVBC shown in Fig. 3 contains benzyl peroxide (BPO) and polystyrene, and different types of polymethyl groups can be synthesized according to the side chain (R). An amine styrene compound in which the homopolymer of polymethylamine styrene has a benzoic acid side chain (R) and the agglomerate copolymer has a polystyrene side chain (R).

Please refer to Fig. 4, which is a ¹ H-NMR chart of the synthesis process of polymethylamine styrene according to an embodiment of the present invention. Since the ¹ H-NMR results are consistent regardless of the homopolymer, the messy copolymer or the agglomerate copolymer, the functional group changes in the synthesis process of the method of the present invention are illustrated by using r-PVBC as an example. .

It can be seen from the NMR spectrum of Fig. 4 that the chemical shift of CH ₂ on the -CH ₂ -Cl functional group of r-PS-PVBC is 4.44 ppm, and the chemistry on the NMR spectrum proceeds with the azide substitution reaction. The shift was shifted from 4.44 ppm to 4.14 ppm, and its peak shape was bilaterally symmetric, so it had a high conversion rate, and NaN _{3 was} almost 100% converted into an azide functional group to form r-PS-PVBAz.

As the acidification reaction proceeds to form r-PS-PVBAS, the CH ₂ chemical shift shifts from 4.14 ppm to 3.87 ppm, while the quaternary ammonium salt signal (NH ₃ ⁺ ) appears at 8.43 ppm, and the integrated area of CH ₂ and NH ₃ The ratio is exactly 2:3.

After hydrolysis of the alkalized sodium hydroxide, CH ₂ was shifted from 3.87 ppm to 3.61 ppm to the right. At the same time, the original NH ₃ ⁺ signal is no longer appearing after being reduced to NH ₂ , and it can be determined that Polyamine is successfully synthesized.

NMR spectrum can be found from the application of the method according to the present invention, the h-PVBC variant h-PVBN yield of ₃ was 87%, h-PVBN ₃ variants of h-PVBAs yield of 83%, h-PVBAs variations of h-PVBAm The yield is 81%, the yield of all the steps is above 80%, and the conversion rate of each step from polyazide to polyamine is 100%, so there is no incomplete conversion and cross-linking to reduce the solubility of the compound. phenomenon.

Please refer to Fig. 5, which is an IR spectrum of the synthesis process of polymethylamine styrene according to an embodiment of the present invention. Since the IR results are consistent regardless of the homopolymer, the messy copolymer or the agglomerate, the r-PVBC is taken as an example.

Can be seen from FIG. 5 r-PVBC specific absorption peaks at 1266 cm ^-1, when the reaction of an azide formed PVBAz elapsed, there will be significant N ₃ functional groups on the IR spectrum (2100cm ^-1) absorption peaks, the substituted 1266 cm ^{-1 of} chlorine. After that, when the phosphoimine functional group reacts with the aqueous hydrochloric acid solution, the ammonium functional group is immediately generated, and TPPO is produced, and the originally strong azide functional group absorption peak of 2100 cm ^-1 on the IR spectrum disappears, which is caused by easy absorption of ammonium. There are no obvious absorption peaks on the IR spectrum. After alkalization, the absorption peaks of primary amines (3370 and 3460 cm ^-1 ) appeared on the map.

The method of the present invention reforms PVBC to have an N ₃ (azide) functional group, and then derives a primary amine functional group through an acidification and alkalization step. Although the step is more than the Gabriel reaction, the process is environmentally friendly and does not cause a cross-linking reaction. The homopolymer, the agglomerate copolymer and the disordered copolymer can be synthesized smoothly, and the intermediate product in the reaction process is easy to be functionalized and reacted, and has high application value.

Synthesis Example 2

Introduced into the r-PS-PVBAm of the present invention by mono-dione (N-phenyl-3,3-dimethyl-azetidine-2,4-dione), which can be ring-opened to form r-PS-PVBAM, since only the primary amine can have The ability to open the ring, generally aromatic amines or secondary amines, does not have this ability, and thus it can be demonstrated that the r-PS-PVBAm of the present invention is still active. Its reaction formula is as follows:

Please refer to Fig. 6 for the ¹ H-NMR spectrum of the r-PS-PVBAM synthesis process, wherein the above figure is a map of mono-dione, and the figure below is a map of r-PS-PVBAM. When r-PS-PVBAm was opened with mono-dione to form r-PS-PVBAM, the CH ₂ chemical shift was shifted from 3.61 ppm to 4.22 ppm.

Please refer to Figure 7 for the IR spectrum of the r-PS-PVBAM synthesis process. The absorption peaks of mono-dione at 1855 cm ^-1 and 1740 cm ^-1 were completely eliminated by ring opening of the amine functional group, and a specific absorption peak of 1678 cm ^{-1 of the} ring-opening amide was observed.

Synthesis Example 3

The polymethylamine styrene compound synthesized by the method of the present invention can be developed into a material having high practicability for application in various fields. For example, the polymethylamine styrene compound synthesized by the present invention can be applied to a polymer coated film via grafting.

In view of the island-type climate with high humidity in Taiwan, the design of clothes is constantly improving. In addition to comfort, it requires high functionality. Therefore, in windbreaker or jacket design, it is required to be able to prevent moisture and breathe, and even further prevent water splashing. Therefore, the longer the hydrophobic chain is, the more obvious the hydrophobic property is, and the grafting is applied to r-PSPVBAm under the bionic design, resulting in a lotus effect, which will increase the contact angle and achieve a water repellent effect.

Please refer to Fig. 8 for a schematic diagram of the application results of the r-PSPVBAm grafted according to the present invention. The hydrophobic effect is best expressed by the contact angle. Generally, the PS is about 41.8 degrees. After grafting 18 carbon long alkyl chains, the contact angle is raised to 112 degrees, which is increased by 70 degrees. After the grafting, the polymer has good solubility, and can be easily applied to various substrates at different angles, so that the substrate not only has hydrophobic ability, but also is less likely to absorb water, thereby achieving the best polymer coating film for preserving articles.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.

Figure 1 is a conventional method for producing a polymethylamine styrene compound.

Figure 2 is a schematic diagram showing the main chain of different kinds of polymethylamine styrene.

Figure 3 is a flow chart showing the reaction of a polymethylamine styrene compound in accordance with one embodiment of the present invention.

Fig. 4 is a ¹ H-NMR chart of the synthesis process of polymethylamine styrene according to an embodiment of the present invention.

Figure 5 is a graph showing the synthesis of polymethylamine styrene according to an embodiment of the present invention. The IR spectrum of the process.

Fig. 6 is a ¹ H-NMR chart of the synthesis process of r-PS-PVBAM according to another embodiment of the present invention.

Figure 7 is an IR spectrum of the r-PS-PVBAM synthesis process in accordance with another embodiment of the present invention.

Fig. 8 is a schematic view showing the application results of grafting of r-PSPVBAm of the present invention.

Claims (7)

A method for synthesizing a polymethylamine styrene compound, comprising: providing a polymer having a plurality of repeating units, wherein the polymer is poly(vinyl benzyl halide) or polystyrene-polyhalogen Polystyrene-poly(vinyl benzyl halide), each of the repeating units comprising a primary halogen compound, and the primary halogen compound has the following formula: Wherein the X is a halogen; performing an azide substitution reaction on the primary halogen compound, and substituting the halogen with sodium azide (NaN ₃ ) to form a polymer having an azide functional group; The phosphine imination is carried out on the polymer having an azide functional group, and triphenyl phosphine is reacted with the azide functional group to form a phosphine imine (phosphine imine) a polymer of -P=N-)) functional group; performing an acidation reaction on the polymer having a phosphorimine functional group to form a quaternary ammonium salt, wherein the acidification reaction is hydrochloric acid or hydrofluoric acid And bromic acid or hydrogen iodide; and alkalization of the quaternary ammonium salt to form a polymethylamine styrene compound, wherein the alkalization reaction uses sodium hydroxide, potassium hydroxide, hydrogen It is carried out with lithium oxide, sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium borohydride or lithium aluminum hydride. The method for synthesizing a polymethylamine styrene compound according to claim 1, wherein the polymer comprises poly(vinyl benzyl chloride). The method for synthesizing a polymethylamine styrene compound according to claim 2, wherein the synthesized polymethylamine styrene compound comprises homo-poly(vinyl benzyl amine). The method for synthesizing a polymethylamine styrene compound according to claim 1, wherein the polymer comprises polystyrene-poly(vinyl benzyl chloride). The method for synthesizing a polymethylamine styrene compound according to claim 4, wherein the synthesized polymethylamine styrene compound comprises a block co-polystyrene-poly (vinyl benzyl) Amine)). The method for synthesizing a polymethylamine styrene compound according to claim 4, wherein the synthesized polymethylamine styrene compound comprises random polystyrene-poly(vinyl benzyl amine) . The method for synthesizing a polymethylamine styrene compound according to claim 1, wherein the X is selected from the group consisting of fluorine, chlorine, bromine and iodine. Become a group of people.