A polyacylthio carbamic acid ester compound, a preparation method and application thereof

Abstract

The application relates to the technical field of organic synthesis, in particular to a polyacyl thiourethane compound and a preparation method and application thereof. Potassium thiocyanate, a double acyl chloride compound and a polyhydric alcohol compound are reacted in an organic solvent to obtain the polyacyl thiourethane compound. The preparation method is characterized by that the raw materials can be commercially purchased, the cost is low, the method is simple, the atomic economy is high, and large-scale preparation can be carried out.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a polyacryl thiocarbamate compound, its preparation method, and its application. Background Technology

[0002] Sulfur, as a member of the chalcogen group, possesses advantages such as strong nucleophilicity, high molar refractive index, strong coordination ability, and multiple valence states. Therefore, introducing sulfur into polymers often brings unexpected functionalities to polymer materials. Studies have shown that sulfur-containing polymers constructed with sulfur atoms exhibit high refractive index, strong metal ion adsorption capacity, dielectric properties, and self-healing properties, showing broad application prospects in optoelectronic materials, industrial chemistry, and biomedical materials. Therefore, how to introduce sulfur atoms into polymers in a simple and environmentally friendly manner is gradually attracting attention.

[0003] Currently, the main methods for preparing sulfur-containing polymers include S8 vulcanization, desulfurization, copolymerization, copolymerization of COS and epoxides, coupling of CS2 and epoxides, ring-opening polymerization of sulfur-containing monomers, and multicomponent polymerization. Among these, multicomponent polymerization has proven to be a powerful tool for preparing sulfur-containing polymers, offering advantages such as high reaction efficiency, mild reaction conditions, simple operation, high atom economy, and diverse structures. In existing technologies, most multicomponent polymerizations of sulfur-containing polymers use elemental sulfur and carbon disulfide as sulfur sources. Elemental sulfur, as a byproduct of the chemical industry, is abundant, inexpensive, and readily available, and is often used in the preparation of polythioamides and polythioureas. However, elemental sulfur exhibits serious side reactions and low reactivity during reactions. Carbon disulfide is another abundant and sustainable sulfur-containing monomer, and is also frequently used as a sulfur source for preparing sulfur-containing polymers. However, carbon disulfide typically suffers from problems such as strong odor and toxicity. Summary of the Invention

[0004] The purpose of this invention is to provide a polyacryl thiocarbamate compound, its preparation method, and its application.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] A polyacryl thiocarbamate compound, characterized in that it has the structure shown in Formula I or the structural unit shown in any one of Formula II or Formula III:

[0007]

[0008]

[0009] Wherein, n = 2 to 2000, and n is an integer;

[0010] The R 1It is one of aryl, alkyl, or ether group;

[0011] The R 2 R 3 and R 4 It can be an alkyl or ether group independently.

[0012] Optionally, R 1 The aryl group is m-phenyl or p-phenyl;

[0013] R 1 The alkyl group is a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group with 1 to 80 carbon atoms;

[0014] R 1 The ether group is a straight-chain or branched ether group;

[0015] R 2 The alkyl group is a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group with 1 to 80 carbon atoms;

[0016] R 2 The ether group is a straight-chain or branched ether group;

[0017] R 3 The alkyl group is a branched alkyl group with 1 to 80 carbon atoms;

[0018] R 3 The ether group is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms;

[0019] R 4 The alkyl group is a branched alkyl group with 1 to 80 carbon atoms;

[0020] R 4 The ether group is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms.

[0021] Optionally, the polyacryl thiocarbamate compound comprises any one of the following structural formulas:

[0022]

[0023] Where n = 2 to 2000, and n is an integer; m = 1 to 20, and m is an integer; x = 2 to 100, and x is an integer.

[0024] This invention provides a method for preparing the polyacryl thiocarbamate compound, comprising the following steps:

[0025] 1) Under a protective atmosphere, potassium thiocyanate, a double-sided acyl chloride compound, a phase transfer catalyst and a first organic solvent are mixed and subjected to a substitution reaction to obtain an intermediate product;

[0026] 2) Under a protective atmosphere, the intermediate product, polyol compound, second organic solvent and catalyst are mixed and subjected to an addition reaction to obtain the polyacryl thiocarbamate compound.

[0027] Among them, when the bilateral acyl chloride compound is And the polyol compounds are HO-R 2 When -OH is present, formula I is obtained, wherein R 1 R is one of aryl, alkyl, or ether groups. 2 It is an alkyl or ether group;

[0028] When bilateral acyl chloride compounds are And polyol compounds are When formula II is obtained, the R... 3 It is an alkyl or ether group;

[0029] When bilateral acyl chloride compounds are And polyol compounds are When formula III is obtained, the R... 4 It is an alkyl or ether group.

[0030] Optionally, the bilateral acyl chloride compound is at least one of the following structures:

[0031]

[0032] Wherein, R in equation IV 5 It is an alkyl or ether group;

[0033] The molar ratio of potassium thiocyanate to the bismuth acyl chloride compound is 1–12:1–4.

[0034] Optionally, the phase transfer catalyst comprises one or more of polyethylene glycol, 18-crown ether-6, 15-crown ether-5, cyclodextrin, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, and tributylamine.

[0035] The molar ratio of potassium thiocyanate to phase transfer catalyst is 1–30:0.05–2.

[0036] Optionally, the polyol compound is at least one of the following structural formulas:

[0037]

[0038] In formula V, R 6 It is an alkyl or ether group;

[0039] The molar ratio of the polyol compound to potassium thiocyanate is 1-2:1-16.

[0040] Optionally, the catalyst in step 2) comprises one or more of the following: potassium fluoride, potassium carbonate, cesium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, sodium hydride, triethylenediamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, bis(triphenylphosphine)ammonium chloride, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-tert-butyl, phosphazene ligand P2-tert-butyl, phosphazene ligand P4-tert-butyl, and triethylamine;

[0041] The molar ratio of the catalyst to potassium thiocyanate is 0.01–2:1–60.

[0042] Optionally, the temperature of the reaction in step 1) is 0–100°C, and the reaction time is 10–120 min;

[0043] The reaction temperature in step 2) is 0–130°C, and the reaction time is 1–72 h;

[0044] The protective atmosphere independently comprises one or more of air, nitrogen, argon, or rare gases;

[0045] The ratio of the first organic solvent to potassium thiocyanate is 8 mL: 1–10 mmol;

[0046] The ratio of potassium thiocyanate to the second organic solvent is 0.5–10 mmol: 2 mL;

[0047] The first organic solvent and the second organic solvent independently comprise one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone, and tetrahydrofuran.

[0048] The present invention also provides the application of the polyacryl thiocarbamate compounds in refractive materials.

[0049] The polyacryloyl thiocarbamate structure prepared in this invention contains acryloyl thiocarbamate groups. As a refractive material, it exhibits a higher refractive index and a higher Abbe number compared to general sulfur-containing polymers.

[0050] The polymerization method used in this invention is multi-component tandem polymerization, using potassium thiocyanate as the sulfur source monomer, which can generate polyacryl thiocarbamate with well-defined structure at high added value.

[0051] The beneficial effects of this invention are:

[0052] (1) The preparation method provided by the present invention uses potassium thiocyanate as a sulfur source monomer to react with bilateral acyl chloride compounds and polyol compounds to prepare polyacyl thiocarbamate compounds. The reaction raw materials used in this process are readily available, can be directly purchased commercially, are inexpensive, and the reaction conditions are mild and the process is simple, which can prepare polyacyl thiocarbamates with well-defined structures with high added value.

[0053] (2) The second step of the preparation method of the present invention can be carried out under air conditions and can be prepared on a large scale at the gram level.

[0054] (3) The preparation method of the present invention has good universality. Using this method, a variety of monomers can be made into polymers with different structures. Attached Figure Description

[0055] Figure 1 Comparison of the 1H NMR spectra of the polyacryl thiocarbamate compound prepared in Example 1, the acryl thiocarbamate model molecule, and 1,4-butanediol in deuterated dimethyl sulfoxide; wherein, A is the 1H NMR spectrum of 1,4-butanediol in deuterated dimethyl sulfoxide, B is the 1H NMR spectrum of the acryl thiocarbamate model molecule in deuterated dimethyl sulfoxide, and C is the 1H NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 1 in deuterated dimethyl sulfoxide;

[0056] Figure 2 Comparison of the carbon NMR spectra of the polyacryl thiocarbamate compound prepared in Example 1, the model small molecule of acryl thiocarbamate, and 1,4-butanediol in deuterated dimethyl sulfoxide; wherein, A is the carbon NMR spectrum of 1,4-butanediol in deuterated dimethyl sulfoxide, B is a comparison of the carbon NMR spectra of the model small molecule of acryl thiocarbamate in deuterated dimethyl sulfoxide, and C is the carbon NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 1 in deuterated dimethyl sulfoxide;

[0057] Figure 3 The infrared absorption spectra of the polyacryl thiocarbamate compound prepared in Example 1, 1,4-butanediol, terephthaloyl chloride, and the acryl thiocarbamate model molecule are shown below. In the image, A is the infrared absorption spectrum of 1,4-butanediol, B is the infrared absorption spectrum of terephthaloyl chloride, C is the infrared absorption spectrum of the acryl thiocarbamate model molecule, and D is the infrared absorption spectrum of the polyacryl thiocarbamate compound prepared in Example 1.

[0058] Figure 4 The following are the 1H NMR spectra of the polyacrylyl thiocarbamate compounds prepared in Examples 1-12 in deuterated dimethyl sulfoxide; wherein,

[0059] A is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 1 in deuterated dimethyl sulfoxide.

[0060] B is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 2 in deuterated dimethyl sulfoxide.

[0061] C is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 3 in deuterated dimethyl sulfoxide.

[0062] D is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 4 in deuterated dimethyl sulfoxide.

[0063] E is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 5 in deuterated dimethyl sulfoxide.

[0064] F is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 6 in deuterated dimethyl sulfoxide.

[0065] G is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 7 in deuterated dimethyl sulfoxide.

[0066] H is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 8 in deuterated dimethyl sulfoxide.

[0067] I is the 1H NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 9 in deuterated dimethyl sulfoxide.

[0068] J is the 1H NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 10 in deuterated dimethyl sulfoxide;

[0069] K is the 1H NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 11 in deuterated dimethyl sulfoxide;

[0070] L is the 1H NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 12 in deuterated dimethyl sulfoxide;

[0071] Figure 5 The following are carbon NMR spectra of the polyacrylyl thiocarbamate compounds prepared in Examples 1, 3-9 of this invention in deuterated dimethyl sulfoxide; wherein,

[0072] A is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 1 in deuterated dimethyl sulfoxide.

[0073] B is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 3 in deuterated dimethyl sulfoxide.

[0074] C is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 4 in deuterated dimethyl sulfoxide.

[0075] D is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 5 in deuterated dimethyl sulfoxide.

[0076] E is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 6 in deuterated dimethyl sulfoxide.

[0077] F is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 7 in deuterated dimethyl sulfoxide.

[0078] G is the carbon NMR spectrum of the polyacrylyl thiocarbamate compound prepared in Example 8 in deuterated dimethyl sulfoxide.

[0079] H is the carbon NMR spectrum of the polyacryl thiocarbamate compound prepared in Example 9 in deuterated dimethyl sulfoxide. Detailed Implementation

[0080] This invention provides a polyacryl thiocarbamate compound, comprising the structure shown in Formula I or any of the structural units shown in Formula II or Formula III:

[0081]

[0082]

[0083] Wherein, n = 2 to 2000, and n is an integer;

[0084] The R 1 It is aryl, alkyl, or ether group;

[0085] The R 2 R 3 and R 4 It can be an alkyl or ether group independently.

[0086] In this invention, n is preferably 8 to 1500, preferably 20 to 1000, preferably 22 to 500, preferably 30 to 300, preferably 31 to 200, preferably 54 to 150, preferably 82 to 130, more preferably 84 to 128, and even more preferably 123 to 126.

[0087] In this invention, R 1 The aryl group is preferably... m-phenyl or p-phenyl;

[0088] R 1 The alkyl group is preferably a straight-chain alkyl group, a branched alkyl group, or a cycloalkyl group with 1 to 80 carbon atoms.1 The alkane described herein preferably has 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0089] R 1 The ether group is a straight-chain or branched ether group.

[0090] R 2 The alkyl group is a straight-chain alkyl group, branched alkyl group, or cycloalkyl group with 1 to 80 carbon atoms, R 2 The alkane described herein preferably has 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0091] R 2 The ether group is a straight-chain or branched ether group, R 2 The ether group is preferably... Or polyethylene glycol.

[0092] R 3 The alkyl group is a branched alkyl group with 1 to 80 carbon atoms;

[0093] R 3 The ether group is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms;

[0094] R 3 The alkane described herein preferably has 4 to 60 carbon atoms, more preferably 6 to 50 carbon atoms, and may also preferably have 8 to 20 carbon atoms;

[0095] R 4 The alkyl group is a branched alkyl group with 1 to 80 carbon atoms;

[0096] R 4 The ether group is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms;

[0097] R 4 The carbon atoms described herein are preferably 4 to 60, more preferably 6 to 50, and even more preferably 8 to 20.

[0098] In this invention, the polyacryl thiocarbamate compound preferably comprises any one of the following structural formulas:

[0099]

[0100]

[0101] Where n = 2 to 2000, and n is an integer; m = 1 to 20, and m is an integer; x = 2 to 100, and x is an integer;

[0102] n is preferably 8 to 1500, preferably 20 to 1000, preferably 22 to 500, preferably 30 to 300, preferably 31 to 200, preferably 54 to 150, preferably 82 to 130, more preferably 84 to 128, and even more preferably 123 to 126;

[0103] m is preferably 1 to 15, more preferably 2 to 12, and even more preferably 5 to 10;

[0104] x is preferably 3 to 60, more preferably 4 to 55, and even more preferably 5 to 50.

[0105] This invention provides a method for preparing the polyacryl thiocarbamate compound, comprising the following steps:

[0106] 1) Under a protective atmosphere, potassium thiocyanate, a double-sided acyl chloride compound, a phase transfer catalyst and a first organic solvent are mixed and subjected to a substitution reaction to obtain an intermediate product;

[0107] 2) Under a protective atmosphere, the intermediate product, polyol compound, second organic solvent and catalyst are mixed and subjected to an addition reaction to obtain the polyacryl thiocarbamate compound.

[0108] Among them, when the bilateral acyl chloride compound is And the polyol compounds are HO-R 2 When -OH is present, formula I is obtained, wherein R 1 R is one of aryl, alkyl, or ether groups. 2 It is an alkyl or ether group;

[0109] When bilateral acyl chloride compounds are And polyol compounds are When formula II is obtained, the R... 3 It is an alkyl or ether group;

[0110] When bilateral acyl chloride compounds are And polyol compounds are When formula III is obtained, the R... 4 It is an alkyl or ether group.

[0111] In this invention, the bilateral acyl chloride compound is preferably at least one of the following structures:

[0112]

[0113] Wherein, R in equation IV 5The alkyl group is an alkyl or ether group, and the selected alkyl group is preferably one of methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, nonyl, dodecyl, hexadecyl or heptadecanyl; the selected ether group is preferably one of diethyl ether, butadiene ether, hexadecanyl ether, nontriether or polyethylene glycol.

[0114] In this invention, the molar ratio of potassium thiocyanate to the bismuth acyl chloride compound is preferably 1-12:1-4, preferably 2-10:1-3, more preferably 2-8:1-2, and even more preferably 2-6:1.

[0115] In this invention, the phase transfer catalyst preferably comprises one or more of polyethylene glycol, 18-crown ether-6, 15-crown ether-5, cyclodextrin, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, and tributylamine. When the phase transfer catalyst comprises two or more of the above, this invention does not have a special limitation on the ratio of different types of phase transfer catalysts, and any ratio is acceptable.

[0116] In this invention, the molar ratio of potassium thiocyanate to phase transfer catalyst is preferably 1-30:0.05-2, more preferably 10-25:0.06-1.5, further preferably 15-20:0.08-1.2, and even more preferably 17-18:1.

[0117] In this invention, the protective atmosphere in step (1) preferably includes nitrogen, argon or air;

[0118] The reaction temperature in step (1) is preferably 0 to 100°C, more preferably 10 to 70°C, even more preferably 15 to 60°C, and even more preferably 20 to 50°C;

[0119] The reaction time in step (1) is preferably 10 to 120 min, more preferably 12 to 100 min, and even more preferably 15 to 60 min;

[0120] The preferred ratio of the first organic solvent to potassium thiocyanate is 8 mL: 1-10 mmol, more preferably 8 mL: 1.1-9 mmol, even more preferably 8 mL: 1.2-7 mmol, and even more preferably 8 mL: 1.25-5 mmol.

[0121] The first organic solvent preferably comprises one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone, and tetrahydrofuran; when the organic solvent is two or more of the above, the present invention does not have a special limitation on the ratio of different kinds of organic solvents, and any ratio is acceptable.

[0122] In this invention, the reaction in step (1) is preferably carried out under stirring, with a stirring speed of 100-1000 r / min, preferably 200-900 r / min, more preferably 400-800 r / min, and even more preferably 500-600 r / min.

[0123] In this invention, the polyol compound is preferably at least one of the following structural formulas:

[0124]

[0125] R 6 The alcohol represented is preferably one of 1,2-propanediol, ethylene glycol, 1,3-propanediol, 1,3-butanediol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, or erythritol.

[0126] In this invention, the molar ratio of the polyol compound to potassium thiocyanate is preferably 1-2:1-16, more preferably 1-1.5:2-14, further preferably 1-1.2:2-10, and even more preferably 1:2.5-8.

[0127] In this invention, the catalyst in step 2) preferably comprises potassium fluoride, potassium carbonate, cesium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, sodium hydride, triethylenediamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, bis(triphenylphosphine)ammonium chloride, 1,5,7-triazidobicyclo(4.4.0)dec-5- The catalyst comprises one or more of the following: olefin, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-tert-butyl, phosphazene ligand P2-tert-butyl, phosphazene ligand P4-tert-butyl, and triethylamine; the molar ratio of the catalyst to potassium thiocyanate is 0.05–2:1–40, preferably 0.06–1.5:10–30, more preferably 0.08–1.2:15–28, and even more preferably 1:20–25.

[0128] In this invention, the temperature of the reaction in step 2) is preferably 0 to 130°C, more preferably 10 to 125°C, even more preferably 20 to 120°C, and even more preferably 30 to 120°C;

[0129] The reaction time in step (2) is preferably 1 to 72 hours, more preferably 2 to 60 hours, even more preferably 3 to 50 hours, and even more preferably 4 to 40 hours;

[0130] The protective atmosphere described in step (2) preferably includes nitrogen, argon, or air;

[0131] The preferred ratio of potassium thiocyanate to the second organic solvent is 0.5–10 mmol: 2 mL, more preferably 0.75–8 mmol: 2 mL, even more preferably 1–7 mmol: 2 mL, and even more preferably 1.2–6 mmol: 2 mL.

[0132] The second organic solvent is preferably one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone, and tetrahydrofuran; when the organic solvent is two or more of the above, the present invention does not have a special limitation on the ratio of different kinds of organic solvents, and any ratio is acceptable.

[0133] In this invention, the reaction described in step (2) is preferably carried out under stirring, with a stirring speed of 100-1000 r / min, preferably 200-900 r / min, more preferably 400-800 r / min, and even more preferably 500-600 r / min;

[0134] After the stirring reaction of the intermediate product, polyol compound, second organic solvent and catalyst in step (2) is completed, the product is preferably further subjected to filtration, washing, settling, filtration and drying in sequence.

[0135] The preferred reagent used for washing is water, and the amount of deionized water used in the washing process is adjusted according to actual needs;

[0136] The drying temperature is preferably 30-55°C, more preferably 35-50°C, and even more preferably 40-45°C;

[0137] The drying time is preferably 3 to 8 hours, more preferably 4 to 7 hours, and even more preferably 5 to 6 hours.

[0138] This invention also provides the application of polyacryl thiocarbamate compounds in refractive materials.

[0139] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0140] Example 1

[0141] The polyacryloyl thiocarbamate compound shown in P1 was prepared according to the reaction equation (I):

[0142]

[0143] Wherein, M1 is potassium thiocyanate, which is commercially available, and in this embodiment it was purchased from Amex Corporation; M2 is terephthaloyl chloride, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation; M3 is 1,4-butanediol, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation.

[0144] The preparation steps of the polyacryl thiocarbamate compound P1 are as follows:

[0145] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 r / min for 60 min to prepare terephthaloyl diisothiocyanate.

[0146] After the reaction was completed, 1,4-butanediol (45 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product system, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the precipitate was separated by filtration, washed with deionized water, allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the pale yellow solid P1 of the polyacryl thiocarbamate compound.

[0147] Analysis revealed that the final product, polyacryl thiocarbamate compound P1, had a yield of 67%, a weight-average molecular weight of 26,400 g / mol, a molecular weight distribution of 1.41, and a degree of polymerization n of 82.

[0148] The acyl thiocarbamate model molecule was prepared according to the above steps, wherein terephthaloyl chloride (101 mg, 0.5 mmol) was replaced with p-toluyl chloride (132 μL, 1 mmol), and ethanol (46 μL, 1 mmol) was replaced with 1,4-butanediol (45 μL, 0.5 mmol). The structure of the acyl thiocarbamate model molecule is as follows:

[0149] The 1,4-butanediol, acylthiocarbamate model molecule, and the prepared polyacylthiocarbamate compound P1 were characterized by nuclear magnetic resonance (NMR). The resulting 1H NMR spectra are shown below. Figure 1 As shown;

[0150] pass Figure 1 (* represents solvent peak) It can be observed that the monomer M31,4-butanediol ( Figure 1 A) contains hydroxyl hydrogen at 4.46 ppm. In the 1H NMR spectrum of polyacryl thiocarbamate compound P1 (… Figure 1 The chemical shift value of the hydrogen in the acylthiocarbamate group (-NH-) is located at a low field of 11.85 ppm, which is similar to that of the acylthiocarbamate model small molecule (C). Figure 1 The hydrogen chemical shift value of the -NH- group of the acyl thiocarbamate in compound B) is consistent with 12.18 ppm. The chemical shift value of the hydrogen on the -CH- ring of the polyacyl thiocarbamate compound P1 is 7.93 ppm, and the hydrogen on the alkyl chain is located at 4.53 ppm and 1.86 ppm, respectively.

[0151] The 1,4-butanediol used in Example 1, the prepared polyacryl thiocarbamate compound P1, and the acryl thiocarbamate model small molecule were characterized by nuclear magnetic resonance (NMR). The resulting carbon NMR spectra are shown below. Figure 2 As shown;

[0152] pass Figure 2 (* represents solvent peaks) It can be observed that in the carbon spectrum of polyacryl thiocarbamate compound P1 ( Figure 2 The chemical shifts of C=S and C=O in the model molecule are at 188.97 ppm and 163.73 ppm, respectively. Figure 2 The chemical shift values ​​of C=S and C=O in (B) are consistent, at 189.74 and 164.82 ppm respectively.

[0153] Infrared absorption spectroscopy was performed on 1,4-butanediol, terephthaloyl chloride, the prepared polyacryl thiocarbamate compound P1, and the acryl thiocarbamate model small molecule used in formula (I). The resulting infrared absorption spectra are shown below. Figure 3 As shown;

[0154] Wherein A is the infrared absorption spectrum of 1,4-butanediol, B is the infrared absorption spectrum of terephthaloyl chloride, C is the infrared absorption spectrum of the acyl thiocarbamate model small molecule, and D is the infrared absorption spectrum of the polyacyl thiocarbamate compound prepared in Example 1.

[0155] Depend on Figure 3It can be seen that the stretching vibration absorption peak of the C=S bond in polyacrylyl thiocarbamate compound P1 is located at 1520 cm⁻¹. -1 The stretching vibration peak of NH is located at 3240 cm⁻¹. -1 .

[0156] Example 2

[0157] A polyacryloyl thiocarbamate compound as shown in P2 was prepared according to the reaction equation (II):

[0158]

[0159] Wherein, M1 is potassium thiocyanate, which is commercially available, and in this embodiment it was purchased from Amex Corporation; M2 is terephthaloyl chloride, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation; M4 is 1,6-hexanediol, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation.

[0160] The preparation steps of the polyacryl thiocarbamate compound P2 are as follows:

[0161] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0162] After the reaction was completed, 1,6-hexanediol (62 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the precipitate was separated by filtration, washed with deionized water, allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the polyacryl thiocarbamate compound, a pale yellow solid P2. According to the analysis, the yield of the final product, polyacryl thiocarbamate compound P2, was 55%, the weight-average molecular weight was 46100 g / mol, the molecular weight distribution was 1.52, and the degree of polymerization n was 126.

[0163] Example 3

[0164] The polyacryloyl thiocarbamate compound shown in P3 was prepared according to the reaction equation (III):

[0165]

[0166] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Energie Company; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company; M5 is 1,4-cyclohexanediol, which can be purchased from the market, and in this embodiment it was purchased from THICA Company.

[0167] The preparation steps of the polyacryl thiocarbamate compound P3 are as follows:

[0168] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0169] After the reaction was completed, 1,4-cyclohexanediol (58 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the precipitate was separated by filtration, washed with deionized water, allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the polyacryl thiocarbamate compound, a pale yellow solid P3. According to the analysis, the yield of the final product, polyacryl thiocarbamate compound P3, was 47%, the weight-average molecular weight was 19700 g / mol, the molecular weight distribution was 1.37, and the degree of polymerization n was 54.

[0170] Example 4

[0171] The reaction equation for preparing compounds such as P4 polyacryloyl thiocarbamate is shown in equation (iv):

[0172]

[0173] Wherein, M1 is potassium thiocyanate, which is commercially available, and in this embodiment it was purchased from Amex Corporation; M6 is isophthaloyl chloride, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation; M3 is 1,4-butanediol, which is commercially available, and in this embodiment it was purchased from Aladdin Corporation.

[0174] The preparation steps of the polyacryl thiocarbamate compound P4 are as follows:

[0175] Potassium thiocyanate (121 mg, 1.25 mmol), isophthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 500 rpm at 25 °C for 60 min.

[0176] After the reaction was completed, 1,4-butanediol (45 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the precipitate was separated by filtration, washed with deionized water, allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the polyacryl thiocarbamate compound, a pale yellow solid P4. According to the analysis, the yield of the final product, polyacryl thiocarbamate compound P4, was 39%, the weight-average molecular weight was 39400 g / mol, the molecular weight distribution was 1.41, and the degree of polymerization n was 123.

[0177] Example 5

[0178] The polyacryloyl thiocarbamate compound shown in P5 was prepared by reaction equation (V):

[0179]

[0180] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Anaiji Company; M7 is 4,4-chloroformylphenyl ether, which can be purchased from the market, and in this embodiment it was purchased from Bidex Company; M3 is 1,4-butanediol, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company.

[0181] The preparation steps of the polyacryl thiocarbamate compound P5 are as follows:

[0182] Potassium thiocyanate (121 mg, 1.25 mmol), 4,4-chloroformylphenyl ether (148 mg, 0.5 mmol), and 18-crown ether-6 (0.07 mmol, 18 mg) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0183] After the reaction was completed, 1,4-butanediol (45 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the precipitate was separated by filtration, washed with deionized water, allowed to stand, filtered, and dried at 40 °C for 6 h to obtain the polyacryl thiocarbamate compound, a pale yellow solid P5. According to the analysis, the yield of the final product, polyacryl thiocarbamate compound P5, was 42%, the weight-average molecular weight was 36300 g / mol, the molecular weight distribution was 1.54, and the degree of polymerization n was 84.

[0184] Example 6

[0185] The polyacryloyl thiocarbamate compound shown on P6 was prepared by reaction equation (VI):

[0186]

[0187] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Amex Corporation; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Corporation; M8 is triethylene glycol diethylene glycol, which can be purchased from the market, and in this embodiment it was purchased from Amex Corporation.

[0188] The preparation steps of the polyacryl thiocarbamate compound P6 are as follows:

[0189] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0190] After the reaction was completed, triethylene glycol (67 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow liquid P6 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P6 was 70%, the weight average molecular weight was 12400 g / mol, the molecular weight distribution was 1.15, and the degree of polymerization n was 31.

[0191] Example 7

[0192] The polyacryloyl thiocarbamate compound shown in P7 was prepared by reaction equation (VII):

[0193]

[0194] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Energie Company; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company; M9 is tetraethylene glycol trioxide, which can be purchased from the market, and in this embodiment it was purchased from Sigma-Aldrich Company.

[0195] The preparation steps of the polyacryl thiocarbamate compound P6 are as follows:

[0196] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0197] After the reaction was completed, tetraethylene glycol (86 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow liquid P7 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P7 was 78%, the weight average molecular weight was 13200 g / mol, the molecular weight distribution was 1.14, and the degree of polymerization n was 30.

[0198] The refractive index and Abbe number of the polyacryl thiocarbamate compound P7 prepared in Example 7 were measured at 623.8 nm.

[0199] The polyacryl thiocarbamate compound P7 has a refractive index of 1.6500 and an Abbe number of 35.13 at 632.8 nm.

[0200] Example 8

[0201] The polyacryloyl thiocarbamate compound shown in P8 was prepared by reaction equation (eight):

[0202]

[0203] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Amex Corporation; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Corporation; M10 is polyethylene glycol-400, which can be purchased from the market, and in this embodiment it was purchased from Amex Corporation.

[0204] The preparation steps of the polyacryl thiocarbamate compound P8 are as follows:

[0205] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0206] After the reaction was completed, polyethylene glycol-400 (157 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the obtained product, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow liquid P8 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P8 was 76%, the weight average molecular weight was 14100 g / mol, the molecular weight distribution was 1.15, m=10, and the degree of polymerization n was 22.

[0207] Example 9

[0208] The polyacryloyl thiocarbamate compound shown on page 9 was prepared by reaction equation (IX):

[0209]

[0210] Wherein, M1 is potassium thiocyanate, which is commercially available, and in this embodiment it was purchased from Anaiji Company; M7 is 4,4-chloroformylphenyl ether, which is commercially available, and in this embodiment it was purchased from Bidex Company; M10 is polyethylene glycol-400, which is commercially available, and in this embodiment it was purchased from Anaiji Company; and the degree of polymerization n is 20.

[0211] The preparation steps of the polyacryl thiocarbamate compound P9 are as follows:

[0212] Potassium thiocyanate (121 mg, 1.25 mmol), 4,4-chloroformylphenyl ether (148 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0213] After the reaction was completed, polyethylene glycol-400 (157 μL, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the reaction system, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow liquid P9 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P9 was 72%, the weight average molecular weight was 14600 g / mol, the molecular weight distribution was 1.22, m=10, and the degree of polymerization n was 20.

[0214] Example 10

[0215] The polyacryloyl thiocarbamate compound shown in P10 was prepared by reaction equation (x):

[0216]

[0217] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Anaiji Company; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company; M11 is polyethylene glycol-2000, which can be purchased from the market, and in this embodiment it was purchased from Anaiji Company.

[0218] The preparation steps of the polyacryl thiocarbamate compound P10 are as follows:

[0219] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0220] After the reaction was completed, polyethylene glycol-400 (1 g, 0.5 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the reaction system, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow liquid P10 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P10 was 76%, the weight-average molecular weight was 15900 g / mol, the molecular weight distribution was 1.34, x=50, and the degree of polymerization n was 8.

[0221] Example 11

[0222] The polyacryloyl thiocarbamate compound shown in P11 was prepared by reaction equation (XI):

[0223]

[0224] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Anaiji Company; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company; M12 is glycerol, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company.

[0225] The preparation steps of the polyacryl thiocarbamate compound P11 are as follows:

[0226] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0227] After the reaction was completed, glycerol (25 μL, 0.33 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the reaction system, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow solid P11 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P11 was 66%, the weight average molecular weight was 16400 g / mol, and the molecular weight distribution was 1.78.

[0228] Example 12

[0229] The polyacryloyl thiocarbamate compound shown in P12 was prepared by reaction equation (XII):

[0230]

[0231] Wherein, M1 is potassium thiocyanate, which can be purchased from the market, and in this embodiment it was purchased from Anaiji Company; M2 is terephthaloyl chloride, which can be purchased from the market, and in this embodiment it was purchased from Aladdin Company; M13 is erythritol, which can be purchased from the market, and in this embodiment it was purchased from Bailingwei Company.

[0232] The preparation steps of the polyacryl thiocarbamate compound P12 are as follows:

[0233] Potassium thiocyanate (121 mg, 1.25 mmol), terephthaloyl chloride (101 mg, 0.5 mmol), and 18-crown ether-6 (18 mg, 0.07 mmol) were added sequentially to a 25 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 8 mL of 1,2-dichloroethane was added using a syringe, and the mixture was stirred at 25 °C and 500 rpm for 60 min.

[0234] After the reaction was completed, erythritol (31 mg, 0.25 mmol), 1,2-dichloroethane (2 mL), and sodium hydride (0.05 mmol) were added to the reaction system, and the mixture was stirred at 120 °C and 500 r / min for 24 h. After the reaction was completed, the solid in the obtained solution was removed by filtration, and then the reaction solution was added dropwise to n-hexane solution to settle. Finally, the mixture was allowed to stand, separated, and dried at 40 °C for 6 h to obtain the yellow solid P12 of the polyacryl thiocarbamate compound. According to the analysis, the yield of the final product polyacryl thiocarbamate compound P11 was 70%, the weight average molecular weight was 18000 g / mol, and the molecular weight distribution was 1.85.

[0235] The polyacryloyl thiocarbamate compounds prepared in Examples 1-12 were characterized by nuclear magnetic resonance (NMR), and the resulting 1H NMR spectra are shown below. Figure 4 As shown.

[0236] The polyacryloyl thiocarbamate compounds prepared in Examples 1, 3-9 were characterized by nuclear magnetic resonance (NMR), and the resulting carbon NMR spectra are shown below. Figure 5 As shown.

[0237] Depend on Figures 4-5 It can be seen that the present invention has successfully synthesized polyacryl thiocarbamate compounds.

[0238] As can be seen from the above embodiments, the present invention provides a polyacrylated thiocarbamate compound and its preparation method. The present invention involves a stepwise heating and stirring reaction of potassium thiocyanate, a bi-acrylamide compound, and a polyol compound in an organic solvent to obtain the polyacrylated thiocarbamate compound. All raw materials used in the present invention are commercially available, resulting in low cost, a simple method, high atom economy, and the ability to be prepared on a large scale.

[0239] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polyacryl thiocarbamate compound, characterized in that, It has the structure shown in Equation I or the structural unit shown in any one of Equations II or III: Formula I Formula II Formula III; Wherein, n = 2~2000, and n is an integer; The R 1 It is one of aryl, alkyl, or ether groups; The R 2 R 3 and R 4 It can be alkyl or ether group independently; When R 1 When it is aryl, it is m-phenyl or p-phenyl; When R 1 When it is an alkyl group, it is a straight-chain alkyl group, branched alkyl group, or cycloalkyl group with 1 to 80 carbon atoms; When R 1 When it is an ether group, it is a straight-chain or branched ether group; When R 2 When it is an alkyl group, it is a straight-chain alkyl group, branched alkyl group, or cycloalkyl group with 1 to 80 carbon atoms; When R 2 When it is an ether group, it is a straight-chain or branched ether group; When R 3 When it is an alkyl group, it is a branched alkyl group with 1 to 80 carbon atoms; When R 3 When it is an ether group, it is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms; When R 4 When it is an alkyl group, it is a branched alkyl group with 1 to 80 carbon atoms; When R 4 When it is an ether group, it is a branched ether group or a cycloalkoxy group with 1 to 80 carbon atoms; The preparation method of the polyacryl thiocarbamate compound includes the following steps: 1) Under a protective atmosphere, potassium thiocyanate, a double-sided acyl chloride compound, a phase transfer catalyst, and a first organic solvent are mixed and subjected to a substitution reaction to obtain an intermediate product; 2) Under a protective atmosphere, the intermediate product, polyol compound, second organic solvent and catalyst are mixed and subjected to an addition reaction to obtain the polyacryl thiocarbamate compound; Among them, when the bilateral acyl chloride compound is And polyol compounds are At that time, Formula I is obtained; When bilateral acyl chloride compounds are And polyol compounds are At that time, Formula II is obtained; When bilateral acyl chloride compounds are And polyol compounds are At that time, Formula III was obtained.

2. The polyacryl thiocarbamate compound according to claim 1, characterized in that, The polyacylthiocarbamate compound comprises any one of the following structural formulas: 、 、 、 、 、 、 or ； Where n = 2 ~ 2000, and n is an integer; m = 1 ~ 20, and m is an integer; x = 2 ~ 100, and x is an integer.

3. A method for preparing the polyacrylyl thiocarbamate compound according to any one of claims 1 to 2, characterized in that, Includes the following steps: 1) Under a protective atmosphere, potassium thiocyanate, a double-sided acyl chloride compound, a phase transfer catalyst, and a first organic solvent are mixed and subjected to a substitution reaction to obtain an intermediate product; 2) Under a protective atmosphere, the intermediate product, polyol compound, second organic solvent and catalyst are mixed and subjected to an addition reaction to obtain the polyacryl thiocarbamate compound; Among them, when the bilateral acyl chloride compound is And polyol compounds are At that time, Formula I is obtained; When bilateral acyl chloride compounds are And polyol compounds are At that time, Formula II is obtained; When bilateral acyl chloride compounds are And polyol compounds are At that time, Formula III was obtained.

4. The preparation method according to claim 3, characterized in that, The bilateral acyl chloride compound has at least one of the following structures: 、 、 、 、 Formula IV; Wherein, R in equation IV 5 It is an alkyl or ether group; The molar ratio of potassium thiocyanate to the bismuth acyl chloride compound is 1~12:1~4.

5. The preparation method according to claim 3, characterized in that, The phase transfer catalyst comprises one or more of polyethylene glycol, 18-crown ether-6, 15-crown ether-5, cyclodextrin, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, pyridine, and tributylamine. The molar ratio of potassium thiocyanate to phase transfer catalyst is 1~30:0.05~2.

6. The preparation method according to claim 3 or 4, characterized in that, The polyol compound is at least one of the following structural formulas: 、 、 、 、 、 、 Formula V; In formula V, R 6 It is an alkyl or ether group; The molar ratio of the polyol compound to potassium thiocyanate is 1~2:1~16.

7. The preparation method according to claim 3 or 4, characterized in that, Step 2) The catalyst comprises one or more of the following: potassium fluoride, potassium carbonate, cesium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide, sodium hydride, triethylenediamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, bis(triphenylphosphine)ammonium chloride, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, potassium tert-butoxide, 1,4-diazabicyclo, 4-dimethylaminopyridine, phosphazene ligand P1-tert-butyl, phosphazene ligand P2-tert-butyl, phosphazene ligand P4-tert-butyl, and triethylamine; The molar ratio of the catalyst to potassium thiocyanate is 0.01~2:1~60.

8. The preparation method according to claim 3 or 4, characterized in that, The reaction temperature in step 1) is 0~100℃, and the reaction time is 10~120min; Step 2) The reaction temperature is 0~130℃, and the reaction time is 1~72h; The protective atmosphere independently comprises one of nitrogen and argon; The ratio of the first organic solvent to potassium thiocyanate is 8 mL: 1~10 mmol; The ratio of potassium thiocyanate to the second organic solvent is 0.5~10 mmol: 2 mL; The first organic solvent and the second organic solvent independently comprise one or more of chloroform, n-hexane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,4-dioxane, toluene, acetonitrile, dichloromethane, 1,2-dichloroethane, acetone, and tetrahydrofuran.

9. The application of the polyacryl thiocarbamate compound according to any one of claims 1 to 2 or the polyacryl thiocarbamate compound prepared by the preparation method according to any one of claims 3 to 8 in the field of refractive materials.

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