CN111690133A - Polyalkenyl dithiocarbamate compound and preparation method thereof - Google Patents

Abstract

The invention discloses a polyalkenyl dithiocarbamate compound and a preparation method thereof. The preparation of the polyalkenyl dithiocarbamate compound comprises the following steps: (1) in nitrogen or air, the dibasic secondary amine and carbon disulfide are mixed and stirred in an organic solvent until the temperature is lowered to room temperature, and then the dibasic secondary amine is added. (2) After the reaction is completed, add water to quench the reaction, and extract with an organic solvent and then settle into a poor solvent, collect the precipitate, and dry to constant weight to obtain polyalkenyl dithiocarbamates. A compound whose structure is shown in formula (I). The method of the invention has mild conditions and simple process, no by-products, and conforms to atomic economy; the source of raw materials is wide, and the synthesis is simple; the introduction of carbon disulfide not only provides a way for the rational utilization of sulfur resources, but also the prepared polymer has good composition. Film properties and high refractive index have potential applications in the fields of optics and optoelectronics.

Description

A class of polyalkenyl dithiocarbamate compounds and preparation method thereof

technical field

The invention relates to the fields of polymer chemistry and materials science, in particular to a class of polyalkenyl dithiocarbamate compounds and a preparation method thereof.

Background technique

Sulfur resources are widely distributed and rich in reserves, but most of them have not been developed and utilized, but are piled up and idle in the form of simple substances, which is not only a waste of resources, but also puts pressure on environmental protection. As a common C1 resource, carbon disulfide prepared from sulfur and carbon is not only low-cost, but also can be widely used in industrial production, especially it has been used in the synthesis of polymers and makes polymers. It exhibits excellent mechanical properties and processability, and is of great development value in the fields of metal ion enrichment and optical materials. Alkynes are also one of the commonly used monomers for polymer synthesis. Unfortunately, the polymerization of alkynes involving carbon disulfide and triple bond monomers is rarely reported, and research and development are still needed.

The development of non-catalyzed and efficient polymer reactions involving alkynes has always been the goal of researchers. At present, various activated terminal alkynes have been reported to be able to produce high-efficiency spontaneous click polymerization reactions with amines under non-catalyzed room temperature conditions (J. Am. Chem. Soc., 2017, 139, 5437-5443; Macromolecules, 2019, 52, 4526-4533; Macromolecules, 2020, 53, 2516-2525.). However, in the polymerization of inner alkynes and amines, even if electron withdrawing groups such as carbonyl and ester groups are introduced to activate the triple bond, high temperature or the assistance of a catalyst is still required to complete the reaction (Polym.Chem., 2016,7,7375- 7382.).

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a class of polyalkenyl dithiocarbamate compounds and a preparation method thereof.

The invention provides a method for synthesizing polyalkenyl dithiocarbamate compounds without catalysis from activated internal acetylene compounds, secondary amine compounds and carbon disulfide. The method can be carried out at room temperature, and the conditions are mild and easy to implement. .

Another object of the present invention is to provide a class of polyalkenyl dithiocarbamate compounds obtained by the above method, the polymers have good processability and high refractive index, and can be used in the fields of optics and optoelectronics.

The object of the present invention is achieved by at least one of the following technical solutions.

A class of polyalkenyl dithiocarbamate compounds provided by the present invention, as shown in Figure 12, has the structure shown in the general formula (I):

Wherein, n is an integer of 2-1000, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are the same or different organic groups; R ₁ is selected from the following chemical structural formula 1 Any one of -15; R ₂ , R ₄ are selected from any one of the following structural formulas 19-25; R ₃ , R ₅ are selected from any one of the following structural formulas 1-18; R ₆ is selected from the following structural formula Any one of 19-25; R ₇ is selected from any one of the following structural formulas 16-18;

R ₈ is selected from any one of the following structural formulae 22-25;

Wherein, k, l, m are integers of 1-20; X is selected from O or S element; * represents the substitution position.

A method for preparing polyalkenyl dithiocarbamate compounds provided by the invention comprises the following steps:

(1) In nitrogen or air, the dibasic secondary amine compound and carbon disulfide are mixed and stirred in an organic solvent, and the mixture is uniform to generate dithiocarbamic acid intermediates. After cooling to room temperature, add binary activated internal alkynes The compound carries out spontaneous polymerization (catalyzed polymerization) to obtain a reaction solution;

(2) adding water to the reaction solution of step (1) to quench the reaction, and extracting it with an organic solvent and then sinking into a poor solvent, collecting the precipitate, and drying to constant weight to obtain the polyalkenyl dithiocarbamate class compounds.

Further, the binary activated internal alkyne compound described in step (1) has one of the structures shown in the following general formula (II):

Further, the dibasic secondary amine compound described in step (1) has the structure shown in the following general formula (III):

Further, the organic solvent in step (1) is at least one of dimethyl sulfoxide, N,N-dimethylformamide, chloroform, dichloromethane, and tetrahydrofuran. The preparation method described in step (1) can be carried out in various solvents.

Further, the molar ratio of the binary activated internal acetylene compound to the binary secondary amine compound described in step (1) is 1:0.01-0.01:1.

Preferably, the molar ratio of the binary activated internal acetylene compound to the binary secondary amine compound in step (1) is 1:(0.5-1.5).

Further, the molar concentration of the binary activated internal acetylene compound in the organic solvent in step (1) is 0.01-5 mol/L.

Further, in the organic solvent described in step (1), the molar concentration of carbon disulfide is greater than or equal to twice the concentration of the dibasic secondary amine compound; the temperature of the spontaneous polymerization reaction is 0-45 ° C, and the time of the spontaneous polymerization reaction is 1-72 hours.

Preferably, the temperature of the spontaneous polymerization reaction in step (1) is room temperature, and the time of the spontaneous polymerization reaction is 4-48 hours.

Further, the organic solvent for extraction described in step (2) is at least one of chloroform, dichloromethane and tetrahydrofuran.

Further, the poor solvent in step (2) is methanol, n-hexane or a mixed solution of n-hexane and chloroform.

A class of polyalkenyl dithiocarbamate compounds provided in the present invention can be obtained by the above-mentioned preparation method. Three monomers, realize the high-efficiency polymerization of secondary amine, carbon disulfide and activated internal alkyne under non-catalytic room temperature conditions, and develop the type of polymerization reaction involving carbon disulfide, and can obtain a kind of polyalkenyl disulfide with high sulfur content Substituted carbamate compounds. The polyalkenyl dithiocarbamate compound has high refractive index and excellent processability, which makes it have wide application prospects in the fields of optics and optoelectronics.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The preparation method of the present invention improves the polymerization reaction of the original activated internal alkyne and secondary amine, and introduces the third monomer carbon disulfide to first combine with the secondary amine, and then the reactivity is greatly improved when reacting with the activated internal alkyne, which can The conditions of the polymerization reaction are milder and the process is simpler, no heating or catalysis by an external catalyst is required, and additional energy consumption and catalyst residues are avoided;

(2) the synthesis method of activated internal alkyne used in the preparation method of the present invention is simple, and the yield is high; the secondary amine used can also be synthesized or directly purchased with common reagents and simple methods; at the same time, the third component carbon disulfide is low in cost, This method can not only introduce sulfur into polymers in a convenient way, but also provide a way to rationally exploit and utilize abundant sulfur resources;

(3) The polyalkenyl dithiocarbamate compounds obtained by the preparation method of the present invention have excellent regioselectivity, have no by-products in the reaction process, and are in line with atom economy;

(4) The polyalkenyl dithiocarbamate compounds obtained by the preparation method of the present invention have good film-forming properties, and the introduction of sulfur atoms enables them to have a higher refractive index, which is widely used in the fields of optics and optoelectronics. potential application value.

Description of drawings

Fig. 1 is the comparison diagram of H NMR spectra of monomers M1, M2 used in Example 1 of the present invention and the prepared polyalkenyl dithiocarbamate compound P1 in DMSO-d ₆ ;

Fig. 2 is the comparison chart of the carbon nuclear magnetic resonance spectrum of the monomers M1, M2 used in Example 1 and the prepared polyalkenyl dithiocarbamate compound P1 in DMSO-d ₆ ;

Fig. 3 is the infrared absorption spectrum comparison diagram of the monomers M1, M2 used in Example 1 and the prepared polyalkenyl dithiocarbamate compound P1;

4 is a graph of the refractive index of the film of the polyalkenyl dithiocarbamate compound P1 prepared in Example 1;

Fig. 5 is the infrared absorption spectrogram of polyalkenyl dithiocarbamate compounds P2, P3, P4 and P5 prepared by embodiment 2-5;

Fig. 6 is the hydrogen nuclear magnetic resonance spectra of polyalkenyl dithiocarbamate compounds P2, P3, P4 and P5 prepared in Example 2-5 in DMSO-d ₆ ;

Fig. 7 is the carbon nuclear magnetic resonance spectra of polyalkenyl dithiocarbamate compounds P2, P3, P4 and P5 prepared in Example 2-5 in DMSO-d ₆ ;

8 is a graph of the refractive index of the film of the polyalkenyl dithiocarbamate compound P2 prepared in Example 2;

9 is a graph of the refractive index of the film of the polyalkenyl dithiocarbamate compound P3 prepared in Example 3;

10 is a graph of the refractive index of the film of the polyalkenyl dithiocarbamate compound P4 prepared in Example 4;

11 is a graph of the refractive index of the film of the polyalkenyl dithiocarbamate compound P5 prepared in Example 5;

Figure 12 is a schematic diagram of the general structural formula of polyalkenyl dithiocarbamate compounds.

Detailed ways

The specific implementation of the present invention will be further described below with reference to examples, but the implementation and protection of the present invention are not limited thereto. It should be pointed out that, if there are any processes that are not described in detail below, those skilled in the art can realize or understand them with reference to the prior art. If the reagents or instruments used do not indicate the manufacturer, they are regarded as conventional products that can be purchased in the market.

Example 1

A polyalkenyl dithiocarbamate compound, its structural formula is shown in P1:

The activated internal alkyne monomers are prepared by the Sonogashira reaction of acid chlorides and alkynes, and the reaction equation is as formula (1):

Wherein, compound 1 is 4,4'-oxybis(benzoyl chloride), and compound 2 is phenylacetylene, both of which can be purchased from the market. In this example, they were purchased from TCI Company.

The synthetic steps of the monomer M2 are as follows:

In a 250mL two-necked flask, 2.95g (10mmol) of compound 1, 140mg (0.2mmol) of bis(triphenylphosphine)palladium dichloride, 76.2mg (0.4mmol) of cuprous iodide, and 76.2mg (0.4mmol) of cuprous iodide were successively added, and the nitrogen was purged for three times. Add 100 mL of redistilled tetrahydrofuran, 3.47 mL (25 mmol) of triethylamine and 2.75 mL (25 mmol) of phenylacetylene, stir at room temperature for 6 hours, filter out insoluble matter, and concentrate the filtrate on a rotary evaporator and then purify it with a silica gel column. The eluent is Petroleum ether/ethyl acetate (v/v=10:1), after removing the eluent, the beige solid powder obtained is the monomer M2.

The polyalkenyl dithiocarbamate compounds are prepared by the spontaneous reaction of activated internal alkynes, secondary secondary amines and carbon disulfide, and the reaction equation is as formula (2):

Wherein M1 is N,N'-diethylethylenediamine, and M1 and carbon disulfide can be purchased from the market, and in this example, they were purchased from Merrill Chemical Technology Co., Ltd.

The preparation steps of described polyalkenyl dithiocarbamate compound are as follows:

Add 21.5 μL (0.15 mmol) of monomer M1 to a 25 mL polymerization tube, dissolve in 0.2 mL of dimethyl sulfoxide, add 27.2 μL (0.45 mmol) of carbon disulfide, stir until the temperature drops to room temperature, and then add dissolved in 0.2 mL of dimethyl sulfoxide. 63.9 mg (0.15 mmol) of monomer M2 in sulfoxide, rinse the tube wall with 0.1 mL of dimethyl sulfoxide, and react at room temperature for 8 hours; after the reaction is over, add 20 mL of water to stop the reaction, and then add saturated saline and two Methyl chloride extraction; the obtained organic phase is dried with anhydrous sodium sulfate and then immersed in 120 mL of n-hexane stirred at 600 rpm, then the precipitate is left to stand, filtered, and dried to constant weight to obtain polyalkenyl disulfide Substituted carbamate compound P1.

After measurement and analysis, the yield of the final product polyalkenyl dithiocarbamate compound P1 was 76%, the weight average molecular weight was 31600, and the molecular weight distribution was 2.13.

The nuclear magnetic resonance spectra of the polyalkenyl dithiocarbamate compound P1 and its corresponding monomer are shown in Figures 1 and 2 (* represents the solvent peak), and A, B, and C in Figure 1 represent the monomer M1, respectively. , M2 and the prepared polyalkenyl dithiocarbamate compound P1 in DMSO-d ₆ NMR spectra. A, B and C of FIG. 2 represent the carbon nuclear magnetic resonance spectra of monomers M1, M2 and the prepared polyalkenyl dithiocarbamate compound P1 in DMSO-d ₆ , respectively. From the generation of characteristic peaks corresponding to the hydrogen atoms on the double bond (cis/trans) of the polyalkenyl dithiocarbamate compounds at the chemical shifts of 7.37 ppm and 7.17 ppm in Figure 1, it shows that the polymerization method has indeed prepared polyalkenyl dithiocarbamate compounds; in the C NMR spectrum of Figure 2, the characteristic peaks of alkynyl carbon with chemical shifts at 93.32 ppm and 86.86 ppm disappear, and the characteristic peak of carbon atom on the carbon-sulfur double bond appears at 194 ppm Nearby, it can also be shown that the activated internal acetylene monomers have been completely converted into polyalkenyl dithiocarbamates.

At the same time, the infrared absorption spectra of the polyalkenyl dithiocarbamate compound P1 and its corresponding monomers (M1, M2) prepared in this example are shown in Figure 3, which further shows that the polymerization method has indeed prepared Polyalkenyl dithiocarbamate compounds. A, B, and C in FIG. 3 represent the infrared absorption spectra of the monomers M1, M2 and the prepared polyalkenyl dithiocarbamate compound P1, respectively.

The polyalkenyl dithiocarbamate compounds are easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide, dimethyl sulfoxide and the like at room temperature, indicating that their Has excellent solubility and processability.

Based on the good film-forming properties and high sulfur content of the polyalkenyl dithiocarbamate compound, the polyalkenyl dithiocarbamate compound P1 prepared in this example was dissolved in dichloride After benzene, a polymer film was prepared on a silicon wafer by spin coating, and its refractive index was tested with an ellipsometer. The results are shown in Figure 4. It can be seen from the figure that the polymer has a refractive index of 632.8 nm. It is 1.70, which is much higher than that of common polymers, and has potential applications in the fields of optics and optoelectronics.

Example 2

A kind of polyalkenyl dithiocarbamate compound, its structural formula is shown as P2:

The synthesis method of monomer M3 in this example can be synthesized according to the synthesis method of the applicant in the published literature (Macromolecules, 2017, 50, 5719-5728.).

The polyalkenyl dithiocarbamate compound is prepared by the spontaneous reaction of activated internal alkyne, secondary secondary amine and carbon disulfide, and the reaction equation is as formula (3):

Wherein, the synthesis method of M2 monomer is the same as that of embodiment 1, and carbon disulfide can be purchased from the market, and the source in this embodiment is the same as that of embodiment 1.

Add 76.3 mg (0.15 mmol) of monomer M3 to a 25 mL polymerization tube, dissolve it in 0.2 mL of dimethyl sulfoxide, add 27.2 μL (0.45 mmol) of carbon disulfide, stir until the temperature drops to room temperature, and add dissolved in 0.2 mL of dimethyl sulfoxide. 63.9 mg (0.15 mmol) of monomer M2 in sulfoxide, rinse the tube wall with 0.1 mL of dimethyl sulfoxide, and react at room temperature for 8 hours; after the reaction is over, add 20 mL of water to stop the reaction, and then add saturated saline and two Extraction with methyl chloride (3 mL×4); the obtained organic phase was dried with anhydrous sodium sulfate and then immersed in 120 mL of n-hexane stirred at 600 rpm, and then the precipitate was allowed to stand, filtered, and dried to constant weight to obtain a polymer. Alkenyl dithiocarbamate compound P2.

After measurement and analysis, the yield of the final product polyalkenyl dithiocarbamate compound P2 was 92%, the weight average molecular weight was 21200, and the molecular weight distribution was 1.81.

The infrared absorption spectrum of the polyalkenyl dithiocarbamate compound P2 is shown in Part A of FIG. 5 , and the nuclear magnetic resonance spectrum (* represents the solvent peak) is shown in Part A of FIG. 6 and Part A of FIG. 7 . The positions of the characteristic peaks are similar to those of the polymer P1 in Example 1, which proves the formation of polyalkenyl dithiocarbamate compounds.

The polyalkenyl dithiocarbamate compound P2 is easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide, and dimethyl sulfoxide at room temperature, indicating that It has excellent solubility and processability. After dissolving the polyalkenyl dithiocarbamate compound P2 prepared in this example in dichlorobenzene, a polymer film was prepared on a silicon wafer by spin coating, and its refractive index was tested with an ellipsometer. , the results are shown in Figure 8, it can be seen from Figure 8 that the refractive index of the polymer at 632.8 nm is 1.66, which is much higher than that of common polymers.

Example 3

A kind of polyalkenyl dithiocarbamate compound, its structural formula is shown as P3:

The synthesis method of the dibasic secondary amine monomer M4 can be synthesized according to the synthesis method of the applicant in the published literature (J.Am.Chem.Soc.2017,139,5437-5443.).

The polyalkenyl dithiocarbamate compounds are prepared by the spontaneous reaction of activated internal alkynes, secondary secondary amines and carbon disulfide, and the reaction equation is as formula (4):

The sources of M2 monomer and carbon disulfide are the same as those in Example 1.

Add 84.4 mg (0.15 mmol) of monomer M4 to a 25 mL polymerization tube, dissolve it in 0.2 mL of dimethyl sulfoxide, add 27.2 μL (0.45 mmol) of carbon disulfide, stir until the temperature drops to room temperature, and add dissolved in 0.2 mL of dimethyl sulfoxide. 63.9 mg (0.15 mmol) of monomer M2 in sulfoxide, rinse the tube wall with 0.1 mL of dimethyl sulfoxide, and react at room temperature for 8 hours; after the reaction is over, add 20 mL of water to stop the reaction, and then add saturated saline and two Chloromethane (3mL×4) extraction; the obtained organic phase is dried with anhydrous sodium sulfate and then immersed in 120mL and added to n-hexane stirred at 600 rpm, then the precipitate is left to stand, filtered, and dried to constant weight to obtain Polyalkenyl dithiocarbamate compound P3.

After measurement and analysis, the yield of the final product polyalkenyl dithiocarbamate compound P3 was 55%, the weight average molecular weight was 7100, and the molecular weight distribution was 1.39.

The infrared absorption spectrum of the polyalkenyl dithiocarbamate compound P3 is shown in Part B of Fig. 5 , and the nuclear magnetic resonance spectrum (* represents the solvent peak) is shown in Part B of Fig. 6 and Part B of Fig. 7, the above-mentioned spectrum The positions of the characteristic peaks are similar to those of the polymer P1 in Example 1, which proves the formation of polyalkenyl dithiocarbamate compounds.

The polyalkenyl dithiocarbamate compounds are easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide, dimethyl sulfoxide and the like at room temperature, indicating that their Has excellent solubility and processability. After dissolving the polyalkenyl dithiocarbamate compound P3 prepared in this example in dichlorobenzene, a polymer film was prepared on a silicon wafer by spin coating, and its refractive index was tested with an ellipsometer. , the results are shown in Figure 9, it can be seen from the figure that the refractive index of the polymer at 632.8 nm is 1.66, which is much higher than that of common polymers.

Example 4

A kind of polyalkenyl dithiocarbamate compound, its structural formula is shown as P4:

The activated endoacetylene monomer M5 was synthesized with reference to the synthetic method of the applicant in the published literature (Polym.Chem., 2016, 7, 7375-7382.). The reaction equation is as formula (5):

Wherein, compound 11 is 4,4'-dihydroxydiphenyl ether, and compound 12 is phenylpropynoic acid, both of which can be purchased from the market. In this example, the above-mentioned compounds were purchased from Annagy Chemical.

The polyalkenyl dithiocarbamate compound is prepared by the spontaneous reaction of activated internal alkyne, dibasic secondary amine and carbon disulfide, and the reaction equation is as formula (6):

Wherein the monomer M1 and carbon disulfide can be purchased from the market, and the sources in this example are the same as those in Example 1.

Add 21.5 μL (0.15 mmol) of monomer M1 to a 25 mL polymerization tube, dissolve in 0.2 mL of dimethyl sulfoxide, add 27.2 μL (0.45 mmol) of carbon disulfide, stir until the temperature drops to room temperature, and then add dissolved in 0.2 mL of dimethyl sulfoxide. 68.8 mg (0.15 mmol) of monomer M5 in sulfoxide, rinse the tube wall with 0.1 mL of dimethyl sulfoxide, and react at room temperature for 8 hours; after the reaction, add 20 mL of water to stop the reaction, and then add saturated saline and two Chloromethane (3mL×4) extraction; the obtained organic phase is dried with anhydrous sodium sulfate and then immersed in 120mL and added to n-hexane stirred at 600 rpm, then the precipitate is left to stand, filtered, and dried to constant weight to obtain Polyalkenyl dithiocarbamate compound P4.

After measurement and analysis, the yield of the final product polyalkenyl dithiocarbamate compound P4 was 55%, the weight average molecular weight was 11200, and the molecular weight distribution was 1.59.

The infrared absorption spectrum of the polyalkenyl dithiocarbamate compound P4 is shown in Part C of Figure 5, and the nuclear magnetic resonance spectrum (* represents the solvent peak) is shown in Part C of Figure 6 and Part C of Figure 7, and the above-mentioned spectrum The positions of the characteristic peaks are similar to those of the polymer P1 in Example 1, which proves the formation of polyalkenyl dithiocarbamate compounds.

The polyalkenyl dithiocarbamate compounds are easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide, dimethyl sulfoxide and the like at room temperature, indicating that their Has excellent solubility and processability. After dissolving the polyalkenyl dithiocarbamate compound P4 prepared in this example in dichlorobenzene, a polymer film was prepared on a silicon wafer by spin coating, and its refractive index was tested with an ellipsometer. , the results are shown in Figure 10. It can be seen from the figure that the refractive index of the polymer at 632.8 nm is 1.67, which is much higher than that of common polymers.

Example 5

A polyalkenyl dithiocarbamate compound, its structural formula is shown in P5:

The activated internal alkyne monomer M6 is prepared by the Sonogashira reaction of acid chlorides and alkynes, and the reaction equation is such as formula (VII):

Among them, intermediate 15 was synthesized with reference to the method in the published literature (Macromolecules, 2017, 51, 42-48.) of the applicant; compound 13 was 4,4'-dibromodiphenyl ether, and compound 14 was trimethylsilicon Acetylene, compound 16 is 2-thiophenecarbonyl chloride, which can be purchased from the market. In this example, the above-mentioned compounds 13 and 14 were purchased from AlfaAesar (China) Chemical Co., Ltd., and compound 16 was purchased from Anaiji Chemical 3.

Weigh 218mg (1mmol) of above-mentioned compound 15, 14.0mg (0.02mmol) of bis(triphenylphosphine) palladium dichloride and 7.6mg (0.04mmol) of cuprous iodide into the two-necked flask of 50mL, and then add 10mL of re-distilled of tetrahydrofuran, 346 μL (2.5 mmol) of triethylamine and 268 μL (2.5 mmol) of compound 16, the insolubles were filtered off after stirring at room temperature for 6 hours, and the filtrate was concentrated by a rotary evaporator and purified with a silica gel column. The eluent was petroleum ether/acetic acid. Ethyl ester (v/v=10:1), after removing the eluent, the beige solid powder obtained is the monomer M6.

The polyalkenyl dithiocarbamate compound is prepared by the spontaneous reaction of activated internal alkyne, secondary secondary amine and carbon disulfide, and the reaction equation is as formula (VIII):

The monomer M1 and carbon disulfide can be purchased from the market, and the sources in this example are the same as those in Example 1.

Add 21.5 μL (0.15 mmol) of monomer M1 to a 25 mL polymerization tube, dissolve in 0.2 mL of dimethyl sulfoxide, add 27.2 μL (0.45 mmol) of carbon disulfide, stir until the temperature drops to room temperature, and then add dissolved in 0.2 mL of dimethyl sulfoxide. 65.8 mg (0.15 mmol) of monomer M6 in sulfoxide, rinsed the tube wall with 0.1 mL of dimethyl sulfoxide, and reacted at room temperature for 8 hours; after the reaction was completed, 20 mL of water was added to stop the reaction, and then saturated saline and two Chloromethane (3mL×4) extraction; the obtained organic phase is dried with anhydrous sodium sulfate and then immersed in 120mL and added to n-hexane stirred at 600 rpm, then the precipitate is left to stand, filtered, and dried to constant weight to obtain Polyalkenyl dithiocarbamate compound P5.

After measurement and analysis, the yield of the final product polyalkenyl dithiocarbamate compound P5 was 65%, the weight average molecular weight was 10600, and the molecular weight distribution was 1.52.

The infrared absorption spectrum of the polyalkenyl dithiocarbamate compound P2 is shown in Part D of Fig. 5, and the nuclear magnetic resonance spectrum (* represents the solvent peak) is shown in Part D of Fig. 6 and Part D of Fig. 7, the above-mentioned spectrum The positions of the characteristic peaks are similar to those of the polymer P1 in Example 1, which proves the formation of polyalkenyl dithiocarbamate compounds.

The polyalkenyl dithiocarbamate compounds are easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene, N,N-dimethylformamide, dimethyl sulfoxide and the like at room temperature, indicating that their Has excellent solubility and processability. After dissolving the polyalkenyl dithiocarbamate compound P5 prepared in this example in dichlorobenzene, a polymer film was prepared on a silicon wafer by spin coating, and its refractive index was tested with an ellipsometer. , the result is shown in Figure 11, it can be seen from the figure that the refractive index of the polymer at 632.8 nm is 1.75, which is a high refractive index polymer.

The above examples are only preferred embodiments of the present invention, and are only used to explain the present invention, but not to limit the present invention. Changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention shall belong to the present invention. The scope of protection of the invention.

Claims (10)

1. A polyalkenyl dithiocarbamate compound is characterized by having a structure represented by the following general formula (I):

wherein n is an integer of 2 to 1000, R₁，R₂，R₃，R₄，R₅，R₆，R₇，R₈Are identical or different organic radicals; r₁Selected from any one of the following chemical structural formulas 1 to 15; r₂，R₄Selected from any one of the following structural formulas 19 to 25; r₃，R₅Selected from any one of the following structural formulas 1 to 18; r₆Selected from any one of the following structural formulas 19 to 25; r₇Selected from any one of the following structural formulas 16 to 18; r₈Selected from any one of the following structural formulas 22 to 25;

wherein k, l and m are integers of 1-20; x is selected from O or S elements; indicates the substitution position.

2. A process for preparing the polyalkenyl dithiocarbamate compound of claim 1, which comprises the steps of:

(1) in nitrogen or air, mixing and stirring a secondary diamine compound and carbon disulfide in an organic solvent to generate a dithiocarbamic acid intermediate, cooling to room temperature, adding a binary activated internal alkyne compound to perform a non-catalytic polymerization reaction to obtain a reaction liquid;

(2) and (2) adding water into the reaction liquid obtained in the step (1) to quench the reaction, extracting with an organic solvent, settling into a poor solvent, collecting precipitates, and drying to constant weight to obtain the polyalkenyl dithiocarbamate compound.

3. The method for preparing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the dually activated internal acetylene compound of step (1) has one of the structures represented by the following general formula (II):

4. the method for producing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the secondary diamine compound of step (1) has a structure represented by the following general formula (III):

5. the method for preparing polyalkenyl dithiocarbamate compound according to claim 2, wherein the organic solvent in step (1) is at least one of dimethyl sulfoxide, N-dimethylformamide, chloroform, dichloromethane and tetrahydrofuran.

6. The method for preparing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the molar ratio of the di-activated internal acetylene compound to the di-secondary amine compound in step (1) is 1:0.01-0.01: 1.

7. The method for preparing polyalkenyl dithiocarbamate compound according to claim 2, wherein the molar concentration of the binary activated internal acetylene compound in step (1) in the organic solvent is 0.01-5 mol/L.

8. The method for preparing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the molar concentration of carbon disulfide in the organic solvent of step (1) is not less than twice the concentration of secondary amines, the temperature of the spontaneous polymerization is 0-45 ℃, and the time of the spontaneous polymerization is 1-72 hours.

9. The method for preparing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the organic solvent used in the extraction in step (2) is at least one of chloroform, dichloromethane and tetrahydrofuran.

10. The method for preparing polyalkenyl dithiocarbamate compounds according to claim 2, wherein the poor solvent in step (2) is methanol, n-hexane or a mixed solution of n-hexane and chloroform.

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