CN-117534837-B - Polythiourethane urea ketone polymer and synthetic method and application thereof

Abstract

The invention belongs to the fields of polymer synthesis and materialogy, and particularly discloses a polythiourethane uretdione polymer, a synthesis method and application thereof, wherein under the condition of base catalysis, the anionic copolymerization reaction of elemental sulfur and isocyanate is realized, and the prepared product is coated on a matrix material and can be cured and molded at room temperature to obtain a polythiourethane uretdione coating. The method has the advantages of small catalyst usage amount, mild reaction conditions, wide monomer adaptability, simple operation, lower monomer cost and the like. The polythiourethane uretdione prepared has better chemical stability and thermal stability, and simultaneously has excellent anti-ultraviolet capability and high refractive index, and can be applied to the fields of optical coatings, optical lenses and anti-ultraviolet coatings.

Inventors

• YANG HONGJUN
• ZHANG JIKAI
• JIANG LI
• HUANG WENYAN
• JIANG QIMIN
• JIANG BIBIAO

Assignees

• 常州大学

Dates

Publication Date

20260505

Application Date

20231109

Claims (7)

1. 1. The polythiourethane uretdione polymer is characterized by comprising, by mass, 83-95 wt% of isocyanate monomer, 3-15 wt% of elemental sulfur and 0.5-2.0 wt% of base catalyst; the isocyanate monomer is one or more of hexamethylene diisocyanate HDI, toluene diisocyanate MDI and isophorone diisocyanate IPDI.
2. 2. The polythiourethane urea ketone polymer of claim 1, wherein the base catalyst is 1, 8-diazabicyclo [5.4.0] undec-7-ene DBU or 1,5, 7-triazabicyclo (4.4.0) dec-5-ene TBD.
3. 3. A method for synthesizing polythiourethane uretdione polymers according to claim 1, wherein the method comprises the steps of reacting an isocyanate monomer and elemental sulfur in the presence of a base catalyst under a dry environment protected by inert gas to form polythiourethane uretdione prepolymers, and curing to obtain the polythiourethane uretdione polymers.
4. 4. Use of the polythiourethane uretdione polymer according to claim 1 for the preparation of optical coatings, optical lenses or anti-uv coatings.
5. 5. The use of the polythiourethane uretdione polymer according to claim 4, wherein the coating is prepared by casting a polythiourethane uretdione prepolymer onto a substrate material and curing the film.
6. 6. The use of polythiourethane urea ketone polymers according to claim 5, wherein the matrix material is a metallic material or a general purpose plastic.
7. 7. The use of polythiourethane urea ketone polymer according to claim 5, wherein the curing conditions are room temperature curing for 8-24 hours.

Description

Polythiourethane urea ketone polymer and synthetic method and application thereof Technical Field The invention belongs to the fields of polymer synthesis and materialics, and particularly discloses a polythiourethane urea ketone polymer and a synthesis method and application thereof. Background Polythiourethane is widely used as a traditional polymer material in the fields of high-performance adhesives, sealants, anticorrosive coatings and optical materials. The thioisocyanate structure in the structure provides better chain flexibility, so that the adhesiveness of the thioisocyanate structure to the surface of a substrate is obviously improved, and meanwhile, the introduction of sulfur element also enables the materials in the related coating and adhesive fields to show better optical performance. The traditional method for preparing polythiourethane material is mainly to gradually polymerize dimercapto monomer and diisocyanate monomer to form polythiourethane, and in addition, to carry out polycondensation by pentathiocarbonate and diamine monomer, ring-opening copolymerization of carbonyl sulfide and aziridine, and multi-component copolymerization of sulfur, diisonitrile and diol. However, the production cost of monomers such as dimercapto monomers, thiocarbonates, diisonitriles and the like used in the existing synthetic methods is high, and the problems of difficult operation of aziridine and carbonyl sulfide in the synthetic process exist, so that a novel method for synthesizing polythiourethane materials with high efficiency, simplicity, easy operation and low cost is needed at present. Disclosure of Invention In order to solve the defects of the existing polythiourethane synthetic route, the invention provides a method for synthesizing polythiourethane uretdione prepolymer by catalyzing direct reaction of elemental sulfur and isocyanate monomers and adopting an anionic copolymerization method under mild conditions, wherein the prepolymer can be directly solidified into a film and combined with a base material to form a novel functional coating with refractive property and ultraviolet resistance. The method has the advantages of using a small amount of catalyst, having mild reaction conditions, wide monomer adaptability, simple operation, lower monomer cost and the like. In order to achieve the above purpose, the invention is realized by the following technical scheme: The polythiourethane uretdione prepolymer comprises 83-95wt% of isocyanate, 3-15wt% of elemental sulfur and 0.5-2.0wt% of base catalyst according to mass percent. The isocyanate monomer is one or more of Benzyl Isocyanate (BI), n-butyl isocyanate (n-BIC), hexamethylene Diisocyanate (HDI), toluene diisocyanate (MDI) and isophorone diisocyanate (IPDI). The base catalyst is 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or 1-5-7-triazido bicyclo (4.4.0) dec-5-ene (TBD). The invention also provides a synthesis method of the polythiourethane uretdione polymer, which adopts anion copolymerization to prepare the polythiourethane uretdione prepolymer, specifically comprises the steps of reacting an isocyanate monomer and elemental sulfur in the presence of a base catalyst under a mild environment to obtain the prepolymer, and curing to obtain the polythiourethane uretdione polymer. The copolymerization reaction environment is a dry environment protected by inert gas, the copolymerization reaction temperature is 25 ℃, and the copolymerization reaction time is 6-24h. The polythiourethane uretdione prepolymer is used for preparing optical coatings, optical lenses and anti-ultraviolet coatings, and the specific preparation method of the coatings comprises the steps of casting and coating the polythiourethane uretdione prepolymer on a base material for curing. The matrix material is stainless steel, metal material, general plastic or organic glass. The curing condition is room temperature curing, and the curing time is 8-24h. The beneficial effects are that: The synthesis method of the polythiourethane urea ketone polymer provided by the invention is one-step synthesis, the reaction condition is mild, and the operation difficulty, time and economic cost of polymer synthesis are greatly reduced. And the range of optional monomers is wide, and the functionalized isocyanate can be used as a reaction monomer for copolymerization. The polythiourethane urea ketone coating prepared by the invention has better mechanical property, adhesion property and better thermal stability and chemical stability. Description of the drawings: FIG. 1 is a schematic diagram of an adhesion performance test. FIG. 2 is a graph showing the mass loss of the coating prepared in example 1 after seven days of immersion in an acidic and alkaline methanol solution and a dimethyl sulfoxide solution. FIG. 3 is an ultraviolet-visible spectrum of the polythiourethane uretdione prepared in example 2 compared with a general PET film in example 1. Fig. 4 is an XRD test of polythiourethane u