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CN-121990958-A - Stable selenol and polyseleno ammonia ester thereof, preparation and recovery method and application

CN121990958ACN 121990958 ACN121990958 ACN 121990958ACN-121990958-A

Abstract

The invention discloses stable selenol and polyseleno-ammonia ester thereof, a preparation method, a recovery method and an application, wherein selenol is a stable small molecule with at least two functionalities, and polyseleno-ammonia ester is prepared by directly participating in polymerization of selenol. The selenol overcomes the defect that small selenium-containing molecules are unstable in the environment, the selenol has rich and adjustable properties, stable structure, simple preparation method, high reaction speed, few side reactions in the polymerization process, higher molecular weight, proper polydispersion coefficient, excellent optical properties, good mechanical properties at room temperature and low temperature, and good thermal responsiveness and oxygen responsiveness, can realize chemical recovery of selenol under simple heating conditions, can react with oxygen, active oxygen and the like in the service environment to realize degradation of selenol, and simultaneously releases selenium-containing components which can be utilized biologically, thereby providing a new opportunity for development of organic selenium chemistry and selenium-containing polymers and internal and external application of organisms.

Inventors

  • GAO CHANGYOU
  • CHEN XIPING
  • LIU WENXING
  • DONG XIAOFEI
  • LIU YUNFAN
  • ZHONG ZILONG

Assignees

  • 浙江大学

Dates

Publication Date
20260508
Application Date
20260127

Claims (10)

  1. 1. The stable selenol is characterized in that the stable selenol is a selenol small molecule with a beta-site oxygen structure, the molecular chain of the stable selenol contains at least 6 carbons and has at least two functionalities, and the synthesis method of the selenol comprises the following steps: Under ice bath, adding simple substance selenium, sodium borohydride and ethanol into N, N-dimethylformamide according to the mol ratio of 1:2:8, after the reaction system turns from dark brown to colorless, adding formic acid equivalent to sodium borohydride to form seleno reagent, then heating the reaction system to room temperature, adding brominated molecules with at least two functionalities, reacting to obtain stable polyfunctional selenol, and purifying the obtained stable polyfunctional selenol by adopting diethyl ether extraction, wherein the brominated molecules with at least two functionalities are prepared by nucleophilic substitution reaction of alcohol with corresponding functionalities and the brominated reagent.
  2. 2. The stabilized selenol of claim 1, wherein the selenol is capable of reacting directly with diisocyanate monomers, dihalogen monomers, diepoxy monomers, diene monomers, diacetylene monomers, dithiol monomers to obtain a seleno polymer.
  3. 3. A polyseleno urethane based on stable selenol, wherein the stable selenol is as defined in claim 1, and wherein the polyseleno urethane is prepared by directly participating in a reaction from the selenol, and has the following structural formula: Wherein R 1 is a part of diisocyanate for removing two isocyanate groups, R 2 is an intermediate segment of selenol for removing two selenol, R 3 is a part of long-chain diol for removing two hydroxyl groups, the molar quantity of R 1 is the sum of the molar quantities of R 2 and R 3 , x is any integer between 9 and 46, m is any integer between 20 and 100, n is any integer between 0 and 100, when n=0, the two-component selenoamine is formed by isocyanate and selenol, and when n=1 to 100, the three-component selenoamine is formed by isocyanate, selenol and long-chain diol.
  4. 4. The polyseleno-urethane of claim 3 wherein said selenol molecule contains 8 carbons.
  5. 5. A polyselenamide according to claim 3 wherein R 1 is selected from the group consisting of 、 、 、 At least one of (a) and (b); R 2 is selected from , , , , , Wherein y=0 or a positive integer; r 3 is selected from 、 、 、 At least one of them.
  6. 6. The method for preparing the diselenide according to claim 3, wherein the preparation method of the diselenide comprises the steps of controlling the reaction temperature to be 0-20 ℃, dissolving a compound I in a solvent I, adding a compound II, stirring until a reaction system is sticky, precipitating, washing and vacuumizing the reaction system in methanol to obtain a diselenide elastomer, wherein the molar ratio of the compound I to the compound II is 1:1, wherein the compound I is a difunctional selenol compound, and the compound II is a difunctional isocyanate compound; the preparation method of the three-component polyseleno-methyl ester comprises the steps of mixing a compound III with a compound II, adding a catalyst I, heating and stirring to perform a prepolymerization reaction, controlling the temperature of the prepolymerization reaction to be 40-90 ℃, controlling the prepolymerization reaction time to be 2-12 hours, adding a solvent I after the reaction is finished, adding the compound I, stirring to react until a reaction system is sticky, precipitating, washing and vacuumizing the reaction system in methanol to obtain the three-component polyseleno-methyl ester elastomer, wherein the molar ratio of the sum of the compound I and the compound III to the compound II is 1:1, the compound III is polyalcohol, and the catalyst I is nucleophilic polyaddition catalyst.
  7. 7. The preparation method of claim 6, wherein the solvent I is one or more of isopentane, pentane, petroleum ether, hexane, cyclohexane, cyclopentane, ethyl acetate, diethyl ether, isopropyl ether, tetrahydrofuran, chloroform, dioxane, benzene, toluene, methylene chloride, acetone, acetonitrile, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; The difunctional selenol compound is one or a mixture of more of tri-polyethylene glycol diselenol, tetra-polyethylene glycol diselenol, penta-polyethylene glycol diselenol, hexa-polyethylene glycol diselenol, hepta-polyethylene glycol diselenol and 1, 1-diselenol-p-phenethyl diethyl ether; The difunctional isocyanate compound is at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 1, 3-phenylene diisocyanate, dimethylbiphenyl diisocyanate (TODI), polymethylene polyphenyl isocyanate (PAPI), 1, 6-Hexamethylene Diisocyanate (HDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), trimethylhexamethylene diisocyanate, xylylene isocyanate (XDI), tetramethyl m-xylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), 1, 4-cyclohexane diisocyanate (CHDI), hydrogenated Methylene Diphenyl Isocyanate (HMDI), L-lysine diisocyanate, hydrogenated toluene diisocyanate, cyclohexane dimethylene diisocyanate (HXDI), norbornane diisocyanate (NBDI); The polyol is one or more of polyester polyol, polyether polyol or other polyols, wherein the polyester polyol is an ester substance containing two or more than two-OH groups in the structure, the number average molecular weight is 500-10000, the polyether polyol is an ether substance containing two or more than two-OH groups in the structure, the number average molecular weight is 500-10000, and the other polyol is at least one of glycerol, pentaerythritol, sorbitol, castor oil, soybean oil polyol, palm oil polyol, rosin ester polyol, trimethylolpropane, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polybutadiene-acrylonitrile, hydroxyl-terminated butylbenzene liquid rubber, hydroxyl-terminated polyisoprene, hydroxyl-terminated hydrogenated polyisoprene, polystyrene-allyl alcohol copolymer polyol, polydimethylsiloxane polyol and tetrahydrofuran-propylene oxide copolymer glycol; The nucleophilic polyaddition reaction catalyst is at least one of dibutyl tin dilaurate, stannous octoate, dibutyl tin diacetate, triphenylbismuth, triethylenediamine, bis (dimethylaminoethyl) ether, dimethylethanolamine, trimethylhydroxyethyl propylene diamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N, N, N '-trimethyl-N' -hydroxyethyl-diaminoethyl ether, N, N-dimethylcyclohexylamine, N-ethylmorpholine, N, N-dimethylbenzylamine and N, N-dimethylhexadecylamine.
  8. 8. The polyseleno-mate of claim 3, wherein the polyseleno-mate is thermally and oxygen responsive.
  9. 9. The degradation recovery method of the polyseleno-ammonia ester according to claim 3, wherein the thermal responsiveness of the polyseleno-ammonia ester is utilized to realize degradation recovery of selenium-containing components, the polyseleno-ammonia ester is placed in a solvent I and heated for 0.01-2 days at 40-100 ℃ to finish degradation, and then the selenium-containing monomers are separated out at the bottom of a container after deionized water is added, and the selenium-containing components are recovered, wherein the volume ratio of the deionized water to the solvent I is (0.5-10): 1.
  10. 10. The use of the polyseleno-urethane of claim 3 in the preparation of a selenium releasing medicament, wherein the polyseleno-urethane is reactive with oxygen in a service environment or with active oxygen to effect degradation of the polyseleno-urethane and release selenium containing components for use by organisms.

Description

Stable selenol and polyseleno ammonia ester thereof, preparation and recovery method and application Technical Field The invention relates to stable selenol and polyseleno-methyl ester thereof, and a preparation and recovery method and application thereof, wherein the polyseleno-methyl ester is a novel dynamic selenium-containing polymer, has good thermal responsiveness and oxygen responsiveness, and belongs to the field of selenium-containing polymers. Background Selenium-containing polymers are receiving wide attention due to their excellent stimulus response characteristics and bioactivity, which makes them have wide application prospects in the fields of biological medicine, high refractive index materials, and degradable and recyclable materials. However, despite the many selenium containing structures reported, the structural diversity of selenium containing polymers is primarily limited to the selenoether (R-Se-R) and diselenide (R-Se-R) linkages. Because the selenium-containing functional groups with reactivity are unstable, the traditional method for constructing the selenium-containing polymer generally adopts traditional polymerization (such as free radical polymerization, gradual polymerization and ring-opening polymerization), namely Se-Se bonds and the like are introduced into the reaction monomers, and the polymerization reaction is participated by the rest functional groups (hydroxyl, amino, double bonds and the like) in the reaction monomers, so that the polymer has single type, limited functions and no universality. Polymerization by using selenol (R-SeH) is a more efficient and simpler method for preparing selenium-containing polymer, and the lower bond energy (276 kJ mol -1) of Se-H ensures high reactivity and wide reaction range. However, the extremely oxidative nature of selenol prevents isolation, purification and manipulation under atmospheric conditions, making it unusable directly for polymerization reactions. Although Pan Xiangjiang et al developed a method for in-situ ring-opening selenolactone to obtain selenol for polymerization reaction, the method took a long time (24 hours), the obtained selenol was extremely easy to oxidize and limited in application, xu Hua et al synthesized some series of selenium-containing polymers containing diselenide bonds and selenoether bonds, and had a single structure and no thermal responsiveness, and could not recover selenium-containing components. In general, the existing selenium-containing polymer has the problems of single structure, difficult recovery, poor responsiveness and the like. Disclosure of Invention Based on the analysis, the invention provides stable selenol, and a polyseleno urethane based on stable selenol with thermal and oxygen responsiveness, and a preparation method, a recovery method and application thereof. The technical scheme adopted by the invention is as follows: The stable selenol is a selenol small molecule with a beta-site oxygen structure, and the polyseleno ammonia ester is prepared by directly participating in a reaction of the selenol, and has the following structural general formula: Wherein R 1 is a part of diisocyanate for removing two isocyanate groups, R 2 is an intermediate segment of selenol for removing two selenol, R 3 is a part of long-chain diol for removing two hydroxyl groups, the molar quantity of R 1 is the sum of the molar quantities of R 2 and R 3, x=any integer between 9 and 46, m=any integer between 20 and 100, n=any integer between 0 and 100, when n=0, the two-component selenoamine composed of isocyanate and selenol, and when n=1 to 100, the three-component selenoamine composed of isocyanate, selenol and long-chain diol. Further, the molecular chain of the selenol contains at least 6 carbons, preferably 8 carbons, and is a small molecule with at least two functionalities. Further, R 1 is 、、、Wherein the wavy line represents the portion attached to the molecular chain. Further, R 2 is Wherein y=0 or a positive integer,,,,,At least one of them. Further, R 3 is 、、、. Wherein the wavy line represents the portion attached to the molecular chain. The invention relates to a preparation method of stable selenol and polyseleno-ammonia ester based on stable selenol, which comprises the following steps: The preparation method of the stable selenol comprises the following steps: Under ice bath, adding simple substance selenium, sodium borohydride and ethanol into N, N-dimethylformamide according to the mol ratio of 1:2:8, after the reaction system turns from dark brown to colorless, adding formic acid equivalent to sodium borohydride to form seleno reagent, then heating the reaction system to room temperature, adding brominated molecules with at least two functionalities, reacting to obtain stable multifunctional selenol, and then adopting diethyl ether extraction to purify the obtained stable multifunctional selenol. The brominated molecule with at least two functionalities is prepared by nucleophilic