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CN-121975064-A - Ultraviolet light cured polyethylene carbonate polyurethane resin and preparation method thereof

CN121975064ACN 121975064 ACN121975064 ACN 121975064ACN-121975064-A

Abstract

The invention relates to the technical field of photo-curing polyurethane materials, in particular to ultraviolet light curing polyethylene carbonate polyurethane resin and a preparation method thereof. The preparation method of the ultraviolet light solidified polyethylene carbonate polyurethane resin comprises the following steps of (1) reacting polyethylene carbonate dihydric alcohol and diisocyanate under the action of a catalyst to obtain a first precursor, (2) adding a reactive monomer into the first precursor until NCO groups disappear, then adding a metered polymerization inhibitor, cooling to obtain a second precursor, and (3) heating and stirring the second precursor, the phosphorus-containing olefine acid ester monomer, the reactive diluent and the photoinitiator to obtain the ultraviolet light solidified polyethylene carbonate polyurethane resin. The environment-friendly reactive phosphorus-containing flame retardant is used in the synthesis process of the patent, so that the problem of precipitation of the flame retardant can be effectively solved.

Inventors

  • SHENG WENQI
  • CAO HAO
  • ZHOU XINYI
  • Huang Caitong
  • LIU ZHU
  • LU MING
  • Zou jiao
  • ZHANG GUANGJI

Assignees

  • 惠州学院

Dates

Publication Date
20260505
Application Date
20260108

Claims (10)

  1. 1. The preparation method of the ultraviolet light curing polyethylene carbonate polyurethane resin is characterized by comprising the following steps of: (1) Reacting polyethylene carbonate dihydric alcohol and diisocyanate under the action of a catalyst to obtain a first precursor; (2) Adding a reactive monomer into the first precursor until NCO groups disappear, adding a metered polymerization inhibitor, and cooling to obtain a second precursor; (3) Heating and stirring the second precursor, the phosphoenolate-containing monomer, the reactive diluent and the photoinitiator to obtain the ultraviolet light cured polyethylene carbonate polyurethane resin; the preparation method of the phosphoenolate-containing monomer comprises the following steps: (A) Mixing a phosphorus-containing flame retardant OP 550, benzyl triethyl ammonium chloride, phosphite and 4-methoxyphenol in a protective gas atmosphere at 50-70 ℃ and dropwise adding glycidyl methacrylate within 20-40 minutes, and darkening the reaction mixture to obtain a third precursor; (B) And heating the third precursor to the temperature of not less than 80-100 ℃ for reaction for 7-9 hours to obtain the phosphoenolate monomer.
  2. 2. The method according to claim 1, wherein in the step (1), the catalyst comprises one or a mixture of several of organobismuth, stannous octoate, di-n-butyltin dilaurate and tin acetate.
  3. 3. The preparation method according to claim 1, wherein in the step (1), the reactants are added in an amount of 100 parts by weight of the polyethylene carbonate polyol, 20-30 parts by weight, 30-40 parts by weight or 40-50 parts by weight of the diisocyanate, and 0.12-0.36 parts by weight of the catalyst.
  4. 4. The method according to claim 1, wherein in the step (1), the molecular weight of the polyethylene carbonate polyol is 1000 to 3000, the hydroxyl functionality is 2 to 3, and the molar fraction of the carbonate groups in the molecule is 0.3 to 0.4.
  5. 5. The method according to claim 1, wherein in the step (2), the reactive monomer is an acrylic monomer capable of reacting with an end-NCO of the polyethylene carbonate based polyurethane prepolymer; the addition amount of the reactive monomer is 10-40 parts based on 100 parts by weight of the polyethylene carbonate polyol.
  6. 6. The method according to claim 5, wherein in the step (2), the reactive monomer is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and epoxy-modified acrylate.
  7. 7. The method according to claim 1, wherein in the step (2), the polymerization inhibitor is at least one of 2, 6-tetramethylpiperidine nitroxide radical (TEMPO), hydroquinone, 2, 6-di-t-butyl-4-methylphenol; The addition amount of the polymerization inhibitor is 0.1-0.5 part based on 100 parts by weight of the polyethylene carbonate polyol.
  8. 8. The method according to claim 1, wherein in the step (3), the reactive diluent is one or more of pentaerythritol triacrylate, tetrahydrofuranacrylate, glycidyl methacrylate, isobornyl acrylate, and acryloylmorpholine; The addition amount of the reactive diluent is 2-20 parts by weight based on 100 parts by weight of the polyethylene carbonate polyol.
  9. 9. The method according to claim 1, wherein in the step (3), the photoinitiator is a mixture of one or more of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropanone, and hydroxycyclohexyl phenyl ketone; The weight portion of the photoinitiator is 2-8 portions.
  10. 10. An ultraviolet light-curable polyethylene carbonate-based polyurethane resin, characterized in that the polyurethane resin is prepared by the preparation method of any one of claims 1-9.

Description

Ultraviolet light cured polyethylene carbonate polyurethane resin and preparation method thereof Technical Field The invention relates to the technical field of photo-curing polyurethane materials, in particular to ultraviolet light curing polyethylene carbonate polyurethane resin and a preparation method thereof. Background The photocuring polyurethane material has very excellent performance and is widely applied, along with the continuous improvement of environmental protection consciousness and self-health protection consciousness of people, the polyurethane material is gradually changed from a solvent type system to an environment-friendly, safe and pollution-free system, the ordinary ultraviolet photocuring polyurethane has poor flame retardant effect, the limiting oxygen index is only about 18%, the photocuring polyurethane material belongs to inflammable materials, and the photocuring polyurethane material severely restricts the application of the photocuring polyurethane material in a plurality of fields with flame retardant requirements, such as home decoration, 3C, electronic and electric appliances, automobiles and the like, and has requirements on flame retardance. Traditional flame-retardant photo-curing polyurethane is prepared by introducing flame retardant into a photo-curing polyurethane system in a physical addition mode, so that flame-retardant performance is given to the photo-curing polyurethane. However, the addition of the flame retardant also causes the mechanical properties of the material to be reduced, the material becomes hard and brittle in the use process, and more serious, the externally added flame retardant and the photo-curing polyurethane material have no chemical structure linkage, and the flame retardant is inevitably separated out in the use process due to the undesirable compatibility, so that the performance of the flame retardant is reduced. Therefore, at present, the conventional externally added photo-curing polyurethane material cannot completely meet the requirements of the application scene. Disclosure of Invention In view of the above, the present invention provides an ultraviolet light cured polyethylene carbonate polyurethane resin and a preparation method thereof, which solves or alleviates the technical problems existing in the prior art, and at least provides a beneficial choice. The technical scheme of the embodiment of the invention is realized by providing a preparation method of ultraviolet light curing polyethylene carbonate polyurethane resin, which comprises the following steps: (1) Reacting polyethylene carbonate dihydric alcohol and diisocyanate under the action of a catalyst to obtain a first precursor; (2) Adding a reactive monomer into the first precursor until NCO groups disappear, adding a metered polymerization inhibitor, and cooling to obtain a second precursor; (3) Heating and stirring the second precursor, the phosphoenolate-containing monomer, the reactive diluent and the photoinitiator to obtain the ultraviolet light cured polyethylene carbonate polyurethane resin; the preparation method of the phosphoenolate-containing monomer comprises the following steps: (A) Mixing a phosphorus-containing flame retardant OP 550, benzyl triethyl ammonium chloride, phosphite and 4-methoxyphenol in a protective gas atmosphere at 50-70 ℃ and dropwise adding glycidyl methacrylate within 20-40 minutes, and darkening the reaction mixture to obtain a third precursor; (B) And heating the third precursor to the temperature of not less than 80-100 ℃ for reaction for 7-9 hours to obtain the phosphoenolate monomer. Further, in the step (1), the catalyst comprises one or a mixture of several of organic bismuth, stannous octoate, di-n-butyltin dilaurate and tin acetate. Further, in the step (1), the reactant is added in an amount of 100 parts by weight of the polyethylene carbonate polyol, 20-30 parts by weight, 30-40 parts by weight or 40-50 parts by weight of the diisocyanate and 0.12-0.36 parts by weight of the catalyst. Further, in the step (1), the molecular weight of the polyethylene carbonate polyol is 1000-3000, the hydroxyl functionality is 2-3, and the molar fraction of carbonate groups in the molecule is 0.3-0.4. Further, in the step (2), the reactive monomer is an acrylate monomer capable of reacting with an end group-NCO of the polyethylene carbonate polyurethane prepolymer. Further, the reactive monomer is added in an amount of 10 to 40 parts by weight based on 100 parts by weight of the polyethylene carbonate polyol. Further, in the step (2), the reactive monomer is at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylate. Further, in the step (2), the polymerization inhibitor is at least one of 2, 6-tetramethyl piperidine nitroxide radical (TEMPO), hydroquinone and 2, 6-di-tert-butyl-4-methylphenol. Further, the polymerizatio