Preparation method of amino-terminated hyperbranched polysulfide and internally cross-linked modified polyurethane prepared therefrom

Abstract

The present invention belongs to the technical field of polymer materials and relates to a method for preparing an amino-terminated hyperbranched polysulfide, comprising: stirring and dissolving a primary amine and 2,4-dinitrobenzenesulfonyl chloride in a solvent, heating, and keeping the temperature for 30 to 90 minutes; adjusting the temperature to 70 to 125° C., adding a primary alcohol, triphenylphosphine / diethyl azodicarboxylate as an initiator, adding thioglycolic acid, and keeping the temperature for 1 to 5 hours; removing the solvent to obtain a secondary amine and 2,4-dinitrobenzenesulfide; stirring and dissolving 2,4-dinitrobenzenesulfide in an acidic solvent, heating, adding iron powder, and keeping the temperature, removing the solid and solvent to obtain 2,4-diaminophenylenesulfide, stirring and dissolving 2,4-diaminophenylenesulfide in a solvent, heating, adding a catalyst, and keeping the temperature for 1 to 6 hours, and removing the solvent. The amino-terminated hyperbranched polysulfide obtained by the present invention is used to prepare hyperbranched internally cross-linked modified polyurethane.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, relates to the modification of hyperbranched polymers and polyurethanes, and in particular to a preparation method of amino-terminated hyperbranched polysulfide and an internally cross-linked modified polyurethane prepared therefrom. Background Art

[0002] As research on hyperbranched polymers deepens and their promising applications gradually unfold, numerous theories and research studies have emerged. Due to their significant structural differences from traditional linear polymers, hyperbranched polymers exhibit many unique physical properties, such as viscosity and rheological properties, that defy conventional polymer theory. Consequently, the emergence of hyperbranched polymers has challenged conventional polymer science theories based on linear polymers. Conventional polymer theory is no longer suitable for predicting the interactions between hyperbranched polymer chains. As research on hyperbranched polymers deepens, there is an urgent need to establish a corresponding theoretical framework. In fact, theoretical development of hyperbranched polymers predates experimental verification. The paper on hyperbranched polymers published by the renowned scholar Flory in 1952 has become the source of the theoretical foundation for hyperbranched polymers. In 1940, Flory used probabilistic statistical methods to calculate the relative molecular weight distribution, branching degree, and branching unit types of three-dimensional polymers containing trifunctional and tetrafunctional branching units in the gel state. However, the research objects at that time, whether experimental or computational methods, were based on the polymerization between two different monomers. Therefore, gelation would occur when the degree of polymerization approached a certain critical condition. It was not until 1952 that Flory theoretically predicted that AB b The possibility that type monomers can generate highly branched polymers through condensation reactions gives a complete concept of highly branched polymers. Since the system contains a large number of polymers of different sizes, statistical theory is the most appropriate theoretical tool. Therefore, the theoretical research on hyperbranched polymers can be roughly divided into several categories, such as statistical theory, molecular simulation, polymerization kinetics and thermodynamics. These theoretical methods complement each other with experimental work and jointly promote the development of hyperbranched polymers. In the 1950s and early 1960s, domestic scholars obtained the relative molecular weight and molecular weight distribution of high molecular weight polymers by solving differential kinetic equations, which laid the foundation for subsequent domestic research on hyperbranched polymers. Yan Deyue, Zhou Zhiping and others studied AB b The condensation reaction kinetics of the type monomers were studied, and the relative molecular weight distribution function as well as the number average and weight average molecular weight were derived. Some of the results were consistent with those obtained by Flory using statistical methods. The numerical calculation results showed that the more B functional groups on the monomer, the wider the relative molecular weight distribution of the polymer obtained by the reaction. The polydispersity increased with the increase of the conversion rate of the A group and increased rapidly when the reaction was close to completion.b Starting from the differential kinetic equation of the reaction system, we get AB b The number distribution function of the polycondensation reaction system was obtained, and the number average, weight average and Z average molecular weight as well as the radius of gyration of the reaction system were calculated based on this function. The kinetics and thermodynamics of the polymerization reaction were discussed, and the direct relationship between the reaction degree of the system and the external conditions was obtained. The influence of thermodynamic quantities on the average physical quantities of the system was discussed.

[0003] Currently, theoretical research on hyperbranched polymers focuses on the following areas: 1. Theoretical calculations of the radius of gyration and other characteristic dimensions of hyperbranched polymers; 2. Theoretical simulations of the flow and diffusion of hyperbranched polymers; 3. Calculations of the size distribution and various relative molecular weight distributions of hyperbranched polymers; and 3. Theoretical calculations of the kinetics and thermodynamics of hyperbranched polymers. These theoretical studies have guided experimental work on hyperbranched polymers and shaped the research direction. Summary of the Invention

[0004] In order to improve the problems of unstable or generally poor physical properties of traditional polyurethane dispersions, such as large particle size, high viscosity, poor wettability, and weak water resistance and corrosion resistance of the cured coating, the purpose of the present invention is to disclose a method for preparing amino-terminated hyperbranched polysulfide.

[0005] Technical solution:

[0006] A method for preparing an amino-terminated hyperbranched polysulfide comprises the following steps:

[0007] A. Stir and dissolve the primary amine and 2,4-dinitrobenzenesulfonyl chloride in a solvent, then heat to 56-98°C, preferably 74°C, and keep warm for 30-90 minutes, preferably 65 minutes; adjust the temperature to 70-125°C, preferably 93°C, add primary alcohol and triphenylphosphine / diethyl azodicarboxylate as initiators, and keep warm for 1-3 hours, preferably 2 hours; adjust the temperature to 40-85°C, preferably 67°C, add thioglycolic acid, and keep warm for 1-5 hours.

[0008] Preferably 2h; remove the solvent to obtain the secondary amine and 2,4-dinitrophenyl sulfide;

[0009] Among them, the primary amine is n-propylamine, 2-ethyl-1-hexylamine, n-butylamine, isononylamine, 1-amino-3-methylbutane, cycloheptylamine, 4-cyclohexyl-n-butylamine, 2-cyclopentyl-ethylamine, 2,6-dimethylaniline, 4-aminobiphenyl, o-methylaniline, 4-ethylaniline, etc., preferably n-butylamine; the solvent is acetone, benzene, chloroform, dichloromethane, carbon disulfide, dimethylformamide, pyridine, etc., preferably pyridine; the primary alcohol is 2-methylbenzyl alcohol, benzyl alcohol, 2-naphthalenemethanol, 4-biphenylmethanol, 2,4,6-trimethylbenzyl alcohol, 3-biphenylmethanol, p-ethylbenzyl alcohol, n-propanol, ethanol, 2-ethyl- 1-hexanol, 4-methyl-1-pentanol, 3,5,5-trimethyl-1-hexanol, etc., preferably 2-ethyl-1-hexanol; the ratio of primary amine, 2,4-dinitrobenzenesulfonyl chloride, solvent, primary alcohol, triphenylphosphine / diethyl azodicarboxylate, and thioglycolic acid is 1.0 mol: 0.95-1.22 mol: 30-120 mL: 0.9-1.1 mol: 25-40 mg: 1.0-1.6 mol; preferably 1.0 mol: 0.98 mol: 70 mL: 1.0 mol: 36 mg: 1.1 mol; the molar ratio of triphenylphosphine to diethyl azodicarboxylate is 1:1;

[0010] B. stirring and dissolving 2,4-dinitrophenylene sulfide in a solvent, and then heating to a temperature of 30 to 70° C., preferably 52° C., adding iron powder, and then keeping the temperature for 1 to 5 hours, preferably 3 hours; removing the solid and the solvent to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer;

[0011] The solvent is dioxane, petroleum ether, tert-butanol, acetone, n-butanol, etc., preferably tert-butanol, and the pH is adjusted to 4.5-5.5, preferably pH 4.7; the ratio of 2,4-dinitrophenyl sulfide, solvent, and iron powder is 1.0 mol:30-150 mL:0.2-0.6 g, preferably 1.0 mol:120 mL:0.4 g;

[0012] C. stirring and dissolving 2,4-diaminophenylene sulfide in a solvent, and then heating to a temperature of 80 to 140° C., preferably 121° C., adding a catalyst, and then maintaining the temperature for 1 to 6 hours, preferably 4 hours; and removing the solvent to obtain an amino-terminated hyperbranched polysulfide;

[0013] The solvent is dioxane, methyl tert-butyl ether, toluene, dimethylformamide, acetone, butanone, N-methylpyrrolidone, etc., preferably methyl tert-butyl ether; the catalyst is AlCl3, BF3, ZnCl2, SO3, FeBr2, etc., preferably AlCl3; the ratio of 2,4-diaminophenyl sulfide, solvent, and catalyst is 1.0~5.0mol:100mL:30~60mg, preferably 3.0mol:100mL:32mg.

[0014] The second purpose of the present invention is to disclose the application of the prepared amino-terminated hyperbranched polysulfide, that is, to prepare a hyperbranched internally cross-linked modified polyurethane using the prepared amino-terminated hyperbranched polysulfide.

[0015] A method for preparing a hyperbranched internally cross-linked modified polyurethane comprises: stirring and dissolving a polyether polyol and a diisocyanate in a solvent, and then heating the mixture to a temperature of 90 to 210° C., preferably 174° C.; adding a chain extender, the prepared amino-terminated hyperbranched polysulfide, and a catalyst, and then keeping the temperature for 2 to 10 hours, preferably 8 hours; adjusting the temperature to 75 to 125° C., preferably 114° C., adding the prepared secondary amine, and keeping the temperature for 1 to 4 hours, preferably 2 hours; obtaining a hyperbranched internally cross-linked modified polyurethane; and In the embodiment, the polyether polyol is NJ210, NJ220, NJ230, NJ207, NJ304T, N3063, NJ950, ​​etc., preferably NJ220; the diisocyanate is dimethyl diphenyl diisocyanate, methylene di-p-phenylene diisocyanate, p-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, 4,4-diisocyanate dicyclohexylmethane, etc., preferably 1,6 -hexamethylene diisocyanate; the solvent is dioxane, methyl tert-butyl ether, toluene, xylene, dimethylformamide, acetone, etc., preferably dimethylformamide; the chain extender is ethylene glycol, glycerol, trimethylolpropane, 1,4-cyclohexanediol, diethanolamine, triethanolamine, dimethylenephenyl glycol, preferably ethylene glycol; the catalyst is N-methylimidazole, 1,4-dimethylpiperazine, triethylenediamine, dibutyltin dilaurate, dibutyltin oxide, acetic acid Potassium, preferably dibutyltin dilaurate; the ratio of polyether polyol, diisocyanate, solvent, chain extender, amino-terminated hyperbranched polysulfide, catalyst, and secondary amine is 10g:3.0~9.0g:50~140mL:0.2~0.5mol:0.1~0.5g:10~20mg:0.05~0.12mol, preferably 10g:7.4g:110mL:0.3mol:0.2g:12mg:0.11mol.

[0016] The polyurethane system prepared by the present invention introduces a hyperbranched structure, increases cross-linking sites within the molecule, significantly changes the physical properties of the dispersion, and significantly improves the water resistance and corrosion resistance of the coating after curing.

[0017] Experimental methods

[0018] (1) Infrared spectroscopy (FT-IR)

[0019] Using KBr as a control, first take an appropriate amount of KBr and place it in an agate mortar and grind it into extremely fine powder. After pressing it into a transparent thin sheet, it is scanned by infrared to form a background image. Then, take a trace amount of sample and mix it evenly with the aforementioned KBr extremely fine powder. After infrared scanning, a test image is formed. Finally, the KBr background value is deducted to obtain the infrared spectrum.

[0020] (2) Determination of particle size

[0021] An appropriate amount of sample was taken and diluted to a solid content of about 40%, and the particle size of the sample was measured using a laser particle size analyzer (BIC-9010, Brookhaven Instruments, USA).

[0022] (3) Determination of apparent viscosity

[0023] Take an appropriate amount of sample and dilute it to about 40% solid content. Use digital viscometer (NDJ-9S, Shanghai Precision Scientific Instrument Co., Ltd.) to measure the apparent viscosity of the sample. -1 ) can ensure high measurement accuracy.

[0024] (4) Determination of surface tension

[0025] An appropriate amount of sample was diluted to a solid content of about 40%, and the surface tension of the sample was measured using a surface / interface tensile testing machine (DCAT 11, Dataphysics Instrument Company, Germany). All measurements and data collection were automatically controlled by the software SCAT 31 at room temperature.

[0026] (5) Water absorption determination

[0027] An appropriate amount of polyurethane sample was weighed, and 2% reactive diluent (BA-TPGDA) and 0.1% photoinitiator (1173) were added. The mixture was evenly dispersed and coated onto a polytetrafluoroethylene plate. The film was air-dried at room temperature and then cured under UV light to produce a film approximately 3 mm thick. Approximately 2.0 g of the cured film was immersed in deionized water for 24 hours, removed, and wiped with filter paper to remove any excess water before weighing.

[0028] The water absorption rate can be calculated using the following formula:

[0029] W=(m1-m0) / m0×100%, wherein W represents the sample absorption rate, m0 represents the initial mass of the cured film, and m1 represents the mass of the cured film after absorption.

[0030] Beneficial effects

[0031] The present invention uses primary amine and 2,4-dinitrobenzenesulfonyl chloride as precursors to first form a dinitro-containing sulfonyl secondary amine intermediate, which then undergoes a transposition aromatic nucleophilic substitution reaction with thioglycolic acid. The obtained secondary amine can be used for polyurethane end-capping, and the obtained nitrophenyl sulfide is reduced to form a hyperbranched prepolymer monomer. Because the hyperbranched polyamide obtained by self-assembly contains a large number of active terminal amino groups, it can be used for polyurethane modification, increase the number of internal cross-linking sites in the system, and thus improve the physical properties of the polyurethane dispersion and the water resistance and corrosion resistance of the cured film. In addition, the hyperbranched polyamide prepared by the present invention has loose arrangement between molecular chain segments and a large number of gaps in the structure, which can accommodate small and medium molecular weight substances and form dynamic hydrogen bonding forces with them, and realize sustained release and fixed release of the contents under special environments. It is a highly promising pharmaceutical carrier. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Infrared spectrum of the hyperbranched prepolymer monomer of Example 1;

[0033] Figure 2 .The synthetic route of Example 1 includes the preparation of hyperbranched prepolymer monomer, the preparation of amino-terminated hyperbranched polysulfide and its internally cross-linked modified polyurethane. DETAILED DESCRIPTION

[0034] The present invention will be described in detail below with reference to the following examples so that those skilled in the art can better understand the present invention. However, the present invention is not limited to the following examples.

[0035] Control Example

[0036] 10 g of NJ220 and 7.4 g of 1,6-hexamethylene diisocyanate were stirred and dissolved in 110 mL of dimethylformamide, and then heated to 174°C. 0.3 mol of ethylene glycol and 12 mg of dibutyltin dilaurate were added, and the mixture was kept warm for 8 h. The temperature was adjusted to 114°C, 0.11 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 2 h to obtain a polyurethane.

[0037] Example 1

[0038] 1.0 mol of n-butylamine and 0.98 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 70 mL of pyridine, and then heated to 74°C for 65 minutes. The temperature was adjusted to 93°C, and 1.0 mol of 2-ethyl-1-hexanol and 36 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators and the temperature was kept for 2 hours. The temperature was adjusted to 67°C, and 1.1 mol of thioglycolic acid was added and the temperature was kept for 2 hours. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0039] 1.0 mol of the above 2,4-dinitrophenyl sulfide was dissolved in 120 mL of acidic tert-butyl alcohol at pH 4.7 with stirring, and then heated to 52° C. 0.4 g of iron powder was added, and the temperature was kept for 3 hours. The solid and solvent were removed to obtain 2,4-diaminophenyl sulfide, which is a hyperbranched prepolymer monomer;

[0040] 3.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of methyl tert-butyl ether with stirring, and then heated to 121°C. 32 mg of AlCl3 was added and kept warm for 4 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0041] 10 g of NJ220 and 7.4 g of 1,6-hexamethylene diisocyanate were stirred and dissolved in 110 mL of dimethylformamide and heated to 174° C.; 0.3 mol of ethylene glycol, 0.2 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 12 mg of dibutyltin dilaurate were added and the mixture was kept warm for 8 h; the temperature was adjusted to 114° C., 0.11 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 2 h to obtain a hyperbranched internally cross-linked modified polyurethane.

[0042] Example 2

[0043] 1.0 mol of n-butylamine and 0.95 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 30 mL of pyridine, and then heated to 56°C for 30 minutes. The temperature was adjusted to 70°C, 0.9 mol of 2-ethyl-1-hexanol and 25 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was kept for 1 hour. The temperature was adjusted to 40°C, 1.0 mol of thioglycolic acid was added, and the temperature was kept for 1 hour. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0044] 1.0 mol of the above 2,4-dinitrophenyl sulfide was dissolved in 30 mL of acidic tert-butyl alcohol at pH 4.5 by stirring, and then heated to 30°C. 0.2 g of iron powder was added and the mixture was kept warm for 1 hour. The solid and solvent were removed to obtain 2,4-diaminophenyl sulfide, which was the hyperbranched prepolymer monomer.

[0045] 1.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of methyl tert-butyl ether with stirring, and then heated to 80°C, 30 mg of AlCl3 was added, and the temperature was kept for 1 hour; the solvent was removed to obtain an amino-terminated hyperbranched polysulfide;

[0046] 10 g of NJ220 and 3.0 g of 1,6-hexamethylene diisocyanate were stirred and dissolved in 50 mL of dimethylformamide, and then heated to 90° C. 0.2 mol of ethylene glycol, 0.1 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 10 mg of dibutyltin dilaurate were added, and the mixture was kept warm for 2 h. The temperature was adjusted to 75° C., 0.05 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 1 h to obtain a hyperbranched internally cross-linked modified polyurethane.

[0047] Example 3

[0048] 1.0 mol of n-butylamine and 1.22 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 120 mL of pyridine, and then heated to 98°C for 90 minutes. The temperature was adjusted to 125°C, and 1.1 mol of 2-ethyl-1-hexanol and 40 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators and the temperature was kept for 3 hours. The temperature was adjusted to 85°C, and 1.6 mol of thioglycolic acid was added and the temperature was kept for 5 hours. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0049] 1.0 mol of the above 2,4-dinitrophenyl sulfide was dissolved in 150 mL of acidic tert-butyl alcohol with a pH of 5.5 by stirring, and then heated to 70°C. 0.6 g of iron powder was added and the temperature was kept for 5 hours. The solid and solvent were removed to obtain 2,4-diaminophenyl sulfide, which is a hyperbranched prepolymer monomer.

[0050] 5.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of methyl tert-butyl ether with stirring, and then heated to 140°C, 60 mg of AlCl3 was added, and the temperature was kept for 6 hours; the solvent was removed to obtain an amino-terminated hyperbranched polysulfide;

[0051] 10 g of NJ220 and 9.0 g of 1,6-hexamethylene diisocyanate were stirred and dissolved in 140 mL of dimethylformamide, and then heated to 210° C. 0.5 mol of ethylene glycol, 0.5 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 20 mg of dibutyltin dilaurate were added, and the mixture was kept warm for 10 hours. The temperature was adjusted to 125° C., 0.12 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 4 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0052] Example 4

[0053] 1.0 mol of n-propylamine and 0.96 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 40 mL of acetone, and then heated to 59° C. for 32 minutes; the temperature was adjusted to 88° C., 0.9 mol of 2-methylbenzyl alcohol and 26 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was kept for 1.5 hours; the temperature was adjusted to 42° C., 1.2 mol of thioglycolic acid was added, and the temperature was kept for 3 hours; the solvent was removed to obtain a secondary amine and 2,4-dinitrophenylene sulfide; 1.0 mol of the above 2,4-dinitrophenylene sulfide was stirred and dissolved in 37 mL of acidic dioxane with a pH of 4.6, and then heated to 44° C., 0.3 g of iron powder was added, and the temperature was kept for 2 hours; the solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which is the hyperbranched prepolymer monomer;

[0054] 1.2 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of toluene with stirring and then heated to 82°C. 34 mg of BF3 was added and kept warm for 2 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0055] 10 g of NJ210 and 3.1 g of dimethylbiphenyl diisocyanate were stirred and dissolved in 54 mL of dioxane and heated to 93° C.; 0.4 mol of propylene glycol, 0.3 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 18 mg of N-methylimidazole were added and kept warm for 7 hours; the temperature was adjusted to 102° C., 0.06 mol of the above-mentioned secondary amine was added, and the temperature was kept warm for 2 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0056] Example 5

[0057] 1.0 mol of 2-ethyl-1-hexylamine and 1.04 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 89 mL of chloroform, then heated to 87°C for 52 minutes. The temperature was adjusted to 112°C, 1.0 mol of 2-naphthylmethanol and 28 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was maintained for 2 hours. The temperature was adjusted to 43°C, 1.5 mol of thioglycolic acid was added, and the temperature was maintained for 4 hours. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0058] 1.0 mol of the above 2,4-dinitrophenylene sulfide was dissolved in 112 mL of acidic petroleum ether at pH 4.8, and then heated to 45°C. 0.5 g of iron powder was added and the temperature was kept for 2 h. The solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which was the hyperbranched prepolymer monomer.

[0059] 4.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of dimethylformamide with stirring, and then heated to 82°C. 50 mg of ZnCl2 was added and kept warm for 3 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0060] 10 g of NJ230 and 8.3 g of p-phenylene diisocyanate were stirred and dissolved in 54 mL of toluene, and then heated to 201° C.; 0.4 mol of 1,4-cyclohexanediol, 0.4 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 17 mg of triethylenediamine were added, and the mixture was kept warm for 4 hours. The temperature was adjusted to 92° C., 0.10 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 3 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0061] Example 6

[0062] 1.0 mol of isononylamine and 1.21 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 87 mL of carbon disulfide, and then heated to 91°C for 33 minutes. The temperature was adjusted to 78°C, and 0.9 mol of 3-biphenylmethanol and 29 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators and the temperature was kept for 2 hours. The temperature was adjusted to 62°C, and 1.4 mol of thioglycolic acid was added and the temperature was kept for 2 hours. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0063] 1.0 mol of the above 2,4-dinitrophenylene sulfide was dissolved in 97 mL of acidic acetone at pH 5.0 with stirring, and then heated to 32°C. 0.3 g of iron powder was added, and the temperature was kept for 3 hours. The solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer;

[0064] 4.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of butanone with stirring, and then heated to 135°C, 37 mg of SO3 was added, and the temperature was kept for 5 hours; the solvent was removed to obtain an amino-terminated hyperbranched polysulfide;

[0065] 10 g of NJ304T and 6.5 g of 1,5-naphthalene diisocyanate were stirred and dissolved in 87 mL of acetone, and then heated to 183° C. 0.4 mol of diethanolamine, 0.3 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 17 mg of dibutyltin oxide were added, and the mixture was kept warm for 4 hours. The temperature was adjusted to 112° C., 0.06 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 2 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0066] Example 7

[0067] 1.0 mol of 1-amino-3-methylbutane and 0.99 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 80 mL of dimethylformamide, then heated to 59°C for 62 minutes. The temperature was adjusted to 82°C, 1.0 mol of p-ethylbenzyl alcohol and 39 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was maintained for 2 hours. The temperature was adjusted to 80°C, 1.4 mol of thioglycolic acid was added, and the temperature was maintained for 1 to 5 hours. The solvent was removed to obtain a secondary amine and 2,4-dinitrobenzene sulfide.

[0068] 1.0 mol of the above 2,4-dinitrophenylene sulfide was dissolved in 94 mL of acidic acetone at pH 5.2 with stirring, and then heated to 34°C. 0.3 g of iron powder was added, and the temperature was kept for 4 hours. The solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer;

[0069] 4.0 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of N-methylpyrrolidone with stirring and then heated to 82°C, 58 mg of SO3 was added and kept warm for 5 h; the solvent was removed to obtain an amino-terminated hyperbranched polysulfide;

[0070] 10 g of N3063 and 4.3 g of isophorone diisocyanate were stirred and dissolved in 80 mL of xylene and then heated to 124° C.; 0.2 mol of triethanolamine, 0.4 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 17 mg of dibutyltin oxide were added and kept warm for 3 hours; the temperature was adjusted to 121° C., 0.10 mol of the above-mentioned secondary amine was added, and the temperature was kept warm for 3 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0071] Example 8

[0072] 1.0 mol of 2,6-dimethylaniline and 1.04 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 86 mL of chloroform, then heated to 59°C for 66 min. The temperature was adjusted to 71°C, 0.9 mol of n-propanol and 39 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was maintained for 2 h. The temperature was adjusted to 64°C, 1.4 mol of thioglycolic acid was added, and the temperature was maintained for 2 h. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0073] 1.0 mol of the above 2,4-dinitrophenyl sulfide was dissolved in 140 mL of acidic dioxane at pH 5.4 by stirring, and then heated to 38°C. 0.5 g of iron powder was added and the mixture was kept warm for 2 h. The solid and solvent were removed to obtain 2,4-diaminophenyl sulfide, which was the hyperbranched prepolymer monomer.

[0074] 2.5 mol of the above 2,4-diaminophenylene sulfide was dissolved in 100 mL of dimethylformamide with stirring, and then heated to 86°C. 58 mg of FeBr2 was added and kept warm for 3 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0075] 10 g of NJ950 and 8.1 g of 4,4-diisocyanate dicyclohexylmethane were stirred and dissolved in 105 mL of acetone, and then heated to 92° C.; 0.2 mol of triethanolamine, 0.4 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 11 mg of potassium acetate were added, and the mixture was kept warm for 5 hours. The temperature was adjusted to 114° C., 0.12 mol of the above-mentioned secondary amine was added, and the mixture was kept warm for 1 hour to obtain a hyperbranched internally cross-linked modified polyurethane.

[0076] Example 9

[0077] 1.0 mol of o-methylaniline and 1.22 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 78 mL of dimethylformamide, then heated to 56°C for 65 min. The temperature was adjusted to 84°C, 1.1 mol of ethanol and 33 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was maintained for 2 h. The temperature was adjusted to 67°C, 1.6 mol of thioglycolic acid was added, and the temperature was maintained for 4 h. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0078] 1.0 mol of the above 2,4-dinitrophenylene sulfide was dissolved in 95 mL of acidic acetone at pH 5.2 with stirring, and then heated to 54°C. 0.3 g of iron powder was added and the temperature was kept for 3 hours. The solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which was the hyperbranched prepolymer monomer.

[0079] 2.0 mol of the above 2,4-diaminophenyl sulfide was dissolved in 100 mL of dioxane with stirring, and then heated to 105°C. 37 mg of FeBr2 was added and kept warm for 5 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0080] 10 g of NJ304T and 3.1 g of 4,4-diisocyanate dicyclohexylmethane were stirred and dissolved in 80 mL of acetone, followed by heating to 91° C. 0.4 mol of diethanolamine, 0.1 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 20 mg of N-methylimidazole were added, followed by incubation for 3 h. The temperature was adjusted to 114° C., 0.12 mol of the above-mentioned secondary amine was added, and the mixture was incubated for 1 h to obtain a hyperbranched internally cross-linked modified polyurethane.

[0081] Example 10

[0082] 1.0 mol of n-propylamine and 1.21 mol of 2,4-dinitrobenzenesulfonyl chloride were stirred and dissolved in 115 mL of dichloromethane, then heated to 58°C for 65 minutes. The temperature was adjusted to 73°C, 1.1 mol of 4-biphenylmethanol and 31 mg of triphenylphosphine / diethyl azodicarboxylate were added as initiators, and the temperature was kept for 2 hours. The temperature was adjusted to 62°C, 1.6 mol of thioglycolic acid was added, and the temperature was kept for 5 hours. The solvent was removed to obtain the secondary amine and 2,4-dinitrobenzenesulfide.

[0083] 1.0 mol of the above 2,4-dinitrophenylene sulfide was dissolved in 115 mL of acidic acetone at pH 5.5 with stirring, and then heated to 42°C. 0.6 g of iron powder was added and the temperature was kept for 3 hours. The solid and solvent were removed to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer.

[0084] 3.2 mol of the above 2,4-diaminophenyl sulfide was dissolved in 100 mL of dioxane with stirring, and then heated to 114°C. 58 mg of AlCl3 was added and kept warm for 3 h. The solvent was removed to obtain an amino-terminated hyperbranched polysulfide.

[0085] 10 g of NJ950 and 5.6 g of p-phenylene diisocyanate were stirred and dissolved in 50 mL of xylene and heated to 175° C.; 0.5 mol of trimethylolpropane, 0.5 g of the above-mentioned amino-terminated hyperbranched polysulfide, and 14 mg of N-methylimidazole were added and kept warm for 3 hours; the temperature was adjusted to 114° C., 0.12 mol of the above-mentioned secondary amine was added, and the temperature was kept warm for 3 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

[0086] Test results and analysis

[0087] The infrared spectrum test results of the hyperbranched prepolymer monomer of Example 1 are as follows: Figure 1 As shown. Generally, 3204cm -1 、1387cm -1 The absorption peaks are generated by the stretching vibration and bending vibration of OH in the carboxyl group, 1631 cm -1 The absorption peak usually originates from the stretching vibration of C=O in the carboxyl group, 1252 cm -1 The absorption peak is usually derived from the stretching vibration of CO in the carboxyl group, which indicates that the hyperbranched prepolymer contains -COOH; usually 2880 cm -1 、1312cm -1 The absorption peaks are generated by the stretching vibration and bending vibration of NH in the amino group, which indicates that the hyperbranched prepolymer contains -NH2; 1235 cm -1 , 870cm -1 The absorption peaks are generated by the stretching vibration and bending vibration of CN in amine; 704cm -1 The absorption peak is mainly caused by the CS stretching vibration in sulfide, 3103 cm -1 、1012cm -1 The absorption peaks are generated by CH stretching vibration and orientation bending vibration, 1194 cm -1 The absorption peak mainly comes from the conjugated CC structure; comprehensive judgment shows that the functional groups contained in the molecular structure match the hyperbranched prepolymer monomer in the synthesis route.

[0088] The polyurethane prepared in the control example was compared with the hyperbranched internal cross-linked modified polyurethane prepared in some examples, and the apparent viscosity, surface tension and absorption rate of the cured film were tested respectively. The results are shown in Table 1. It can be found that: (1) The particle size of the polyurethane modified by the hyperbranched polymer is generally smaller, and the particle size of the unmodified polyurethane is 45.3nm. When the branched structure is introduced into the system, the particle size of the emulsion is significantly reduced. This is because the cross-linking sites on the polyurethane molecular chain increase, and the linear polyurethane structures of different lengths are connected to the surface of the branched structure. The molecules are arranged relatively compactly, which reduces the molecular particle size; (2) The viscosity of the hyperbranched modified series polyurethane dispersion is generally lower than that before modification. This is because the introduction of the cross-linked structure and the branched structure leads to a decrease in the particle size of the polyurethane aqueous dispersion, an increase in the distance between particles, a weakening of the interaction between particles, and a decrease in the viscosity of the system; (3) The surface tension of the polyurethane dispersion is a very important physical parameter during its use, and its size depends on the size of the polyurethane dispersion. The size, number and volume of the polar groups on the molecular chain, the smaller the surface tension, the better the wetting performance to the substrate and the better its film-forming property; It can be seen from the table that the surface tension of all hyperbranched modified polyurethane dispersions is lower than that of ordinary polyurethane. This is because the network structure makes the hydrophilic -NH2 groups more evenly distributed on the surface of the macromolecular chain, making the surface tension smaller and the surface-modified polyurethane material improve the wetting performance to the substrate; (4) Compared with the unmodified polyurethane film after hyperbranched modification, the water absorption rate of the modified film is greatly reduced. This is mainly due to the increase of intramolecular cross-linking after hyperbranched modification, which helps to form a dense network structure. After curing, the body structure hinders the movement of the macromolecular chain, the molecular bonds are more tightly combined, and it is difficult for water molecules to penetrate, so the water absorption rate is reduced.

[0089] Table 1. Comparison of physical properties of polyurethane and its cured film

[0090]

[0091] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the description of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A method for preparing an amino-terminated hyperbranched polysulfide, characterized in that: The steps include: A. A primary amine and 2,4-dinitrobenzenesulfonyl chloride are stirred and dissolved in a solvent, then heated to 56-98°C and kept warm for 30-90 minutes. The temperature is then adjusted to 70-125°C, and a primary alcohol, triphenylphosphine, and diethyl azodicarboxylate are added as initiators, and the temperature is kept warm for 1-3 hours. The temperature is then adjusted to 40-85°C, and thioglycolic acid is added, and the temperature is kept warm for 1-5 hours. The solvent is then removed to obtain a secondary amine and 2,4-dinitrobenzenesulfide. B. stirring and dissolving 2,4-dinitrophenylene sulfide in a solvent, heating to 30-70° C., adding iron powder, and maintaining the temperature for 1-5 hours, removing the solid and the solvent to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer; C. 2,4-diaminophenylene sulfide is stirred and dissolved in a solvent and then heated to 80-140° C. After adding a catalyst, the temperature is kept at 1-6 hours, and the solvent is removed to obtain an amino-terminated hyperbranched polysulfide.

2. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step A, a primary amine and 2,4-dinitrobenzenesulfonyl chloride are stirred and dissolved in a solvent, then heated to 74°C and kept warm for 65 minutes; the temperature is then adjusted to 93°C, and a primary alcohol, triphenylphosphine, and diethyl azodicarboxylate are added as initiators, and the temperature is kept warm for 2 hours; the temperature is adjusted to 67°C, and thioglycolic acid is added, and the temperature is kept warm for 2 hours; the solvent is removed to obtain a secondary amine and 2,4-dinitrobenzenesulfide.

3. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step A, the primary amine is n-propylamine, 2-ethyl-1-hexylamine, n-butylamine, isononylamine, 1-amino-3-methylbutane, cycloheptylmethylamine, 4-cyclohexyl-n-butylamine, 2-cyclopentyl-ethylamine, 2,6-dimethylaniline, 4-aminobiphenyl, o-methylaniline or 4-ethylaniline.

4. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 3, wherein: In step A, the primary amine is n-butylamine.

5. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step A, the solvent is acetone, benzene, chloroform, dichloromethane, carbon disulfide, dimethylformamide or pyridine.

6. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 5, wherein: In step A, the solvent is pyridine.

7. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step A, the primary alcohol is 2-methylbenzyl alcohol, benzyl alcohol, 2-naphthalene methanol, 4-biphenylmethanol, 2,4,6-trimethylbenzyl alcohol, 3-biphenylmethanol, p-ethylbenzyl alcohol, n-propanol, ethanol, 2-ethyl-1-hexanol, 4-methyl-1-pentanol or 3,5,5-trimethyl-1-hexanol.

8. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 7, wherein: In step A, the primary alcohol is 2-ethyl-1-hexanol.

9. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step A, the ratio of primary amine, 2,4-dinitrobenzenesulfonyl chloride, solvent, primary alcohol, triphenylphosphine, diethyl azodicarboxylate, and thioglycolic acid is 1.0 mol: 0.95-1.22 mol: 30-120 mL: 0.9-1.1 mol: 25-40 mg: 1.0-1.6 mol, and the molar ratio of triphenylphosphine to diethyl azodicarboxylate is 1:

1.

10. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 9, wherein: In step A, the ratio of the primary amine, 2,4-dinitrobenzenesulfonyl chloride, solvent, primary alcohol, triphenylphosphine, diethyl azodicarboxylate, and thioglycolic acid is 1.0 mol: 0.98 mol: 70 mL: 1.0 mol: 36 mg: 1.1 mol.

11. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step B, 2,4-dinitrophenylene sulfide is stirred and dissolved in an acidic solvent, and then heated to 52° C., iron powder is added and kept warm for 3 hours, and the solid and solvent are removed to obtain 2,4-diaminophenylene sulfide, which is a hyperbranched prepolymer monomer.

12. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step B, the solvent is dioxane, petroleum ether, tert-butanol, acetone or n-butanol, and the pH is adjusted to 4.5-5.

5.

13. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 12, wherein: In step B, the solvent is tert-butanol, and the pH is adjusted to 4.

7.

14. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step B, the ratio of 2,4-dinitrophenyl sulfide, solvent, and iron powder is 1.0 mol: 30-150 mL: 0.2-0.6 g.

15. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 14, wherein: In step B, the ratio of 2,4-dinitrophenyl sulfide, solvent, and iron powder is 1.0 mol:120 mL:0.4 g.

16. The method for preparing amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step C, 2,4-diaminophenylene sulfide is stirred and dissolved in a solvent and then heated to 121° C., a catalyst is added and the temperature is kept for 4 hours, and the solvent is removed to obtain an amino-terminated hyperbranched polysulfide.

17. The method for preparing amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step C, the solvent is dioxane, methyl tert-butyl ether, toluene, dimethylformamide, acetone, butanone or N-methylpyrrolidone.

18. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 17, wherein: In step C, the solvent is methyl tert-butyl ether.

19. The method for preparing amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step C, the catalyst is AlCl3, BF3, ZnCl2, SO3 or FeBr2.

20. The method for preparing amino-terminated hyperbranched polysulfide according to claim 19, wherein: In step C, the catalyst is AlCl3.

21. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 1, wherein: In step C, the ratio of 2,4-diaminophenylene sulfide, solvent and catalyst is 1.0-5.0 mol:100 mL:30-60 mg.

22. The method for preparing an amino-terminated hyperbranched polysulfide according to claim 21, wherein: In step C, the ratio of 2,4-diaminophenylene sulfide, solvent and catalyst is 3.0 mol:100 mL:32 mg.

23. An amino-terminated hyperbranched polysulfide prepared according to any one of claims 1 to 22.

24. A use of the amino-terminated hyperbranched polysulfide according to claim 23, characterized in that: It is applied to the preparation of hyperbranched internally cross-linked modified polyurethane.

25. The use of the amino-terminated hyperbranched polysulfide according to claim 24, characterized in that: include: The polyether polyol and diisocyanate are stirred and dissolved in a solvent and then heated to a temperature of 90-210°C; a chain extender, the amino-terminated hyperbranched polysulfide according to claim 23, and a catalyst are added and kept warm for 2-10 hours; the temperature is adjusted to 75-125°C, the secondary amine prepared in step A of claim 1 is added, and the temperature is kept warm for 1-4 hours to obtain a hyperbranched internally cross-linked modified polyurethane.

26. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that include: Stir and dissolve the polyether polyol and diisocyanate in a solvent and heat to 174° C.; add a chain extender, the amino-terminated hyperbranched polysulfide according to claim 23, and a catalyst and keep the temperature for 8 hours; The temperature was adjusted to 114° C., the secondary amine prepared in step A of claim 1 was added, and the mixture was kept warm for 2 h to obtain a hyperbranched internally cross-linked modified polyurethane.

27. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The polyether polyol is NJ210, NJ220, NJ230, NJ207, NJ304T, N3063 or NJ950.

28. The use of the amino-terminated hyperbranched polysulfide according to claim 27, characterized in that: The polyether polyol is NJ220.

29. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The diisocyanate is dimethyldiphenyl diisocyanate, methylene diparaphenylene diisocyanate, paraphenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate or 4,4-diisocyanate dicyclohexylmethane.

30. The use of the amino-terminated hyperbranched polysulfide according to claim 29, characterized in that: The diisocyanate is hexamethylene diisocyanate.

31. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The solvent is dioxane, methyl tert-butyl ether, toluene, xylene, dimethylformamide or acetone.

32. The use of the amino-terminated hyperbranched polysulfide according to claim 31, characterized in that: The solvent is dimethylformamide.

33. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The chain extender is ethylene glycol, glycerol, trimethylolpropane, 1,4-cyclohexanediol, diethanolamine, triethanolamine or dimethylenephenyl glycol.

34. The use of the amino-terminated hyperbranched polysulfide according to claim 33, characterized in that: The chain extender is ethylene glycol.

35. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The catalyst is N-methylimidazole, 1,4-dimethylpiperazine, triethylenediamine, dibutyltin dilaurate, dibutyltin oxide or potassium acetate.

36. The use of the amino-terminated hyperbranched polysulfide according to claim 35, characterized in that: The catalyst is dibutyltin dilaurate.

37. The use of the amino-terminated hyperbranched polysulfide according to claim 25, characterized in that: The ratio of polyether polyol, diisocyanate, solvent, chain extender, amino-terminated hyperbranched polysulfide, catalyst and secondary amine is 10g:3.0-9.0g:50-140mL:0.2-0.5mol:0.1-0.5g:10-20mg:0.05-0.12mol.

38. The use of the amino-terminated hyperbranched polysulfide according to claim 37, characterized in that: The ratio of the polyether polyol, diisocyanate, solvent, chain extender, amino-terminated hyperbranched polysulfide, catalyst, and secondary amine is 10 g:7.4 g:110 mL:0.3 mol:0.2 g:12 mg:0.11 mol.

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