Search

CN-122011953-A - CHDI type polyurethane film for laminated glass and preparation method and application thereof

CN122011953ACN 122011953 ACN122011953 ACN 122011953ACN-122011953-A

Abstract

The invention discloses a CHDI type polyurethane film for laminated glass, a preparation method and application thereof. The CHDI type polyurethane film is prepared from 1, 4-cyclohexane diisocyanate, polycaprolactone polyol, aliphatic dihydric alcohol chain extender, catalyst and silane coupling agent, wherein the cis-isomer content in the 1, 4-cyclohexane diisocyanate is 30-80%. The invention has simple production process, high transparency and excellent mechanical property, and has good adhesion to inorganic glass and PC plastic plates.

Inventors

  • ZHANG HAOTIAN
  • SHANG YONGHUA
  • SUN SHUCHANG
  • SUN LIDONG
  • CHEN RUI
  • YU YONG

Assignees

  • 万华化学集团股份有限公司

Dates

Publication Date
20260512
Application Date
20241108

Claims (10)

  1. 1. The CHDI type polyurethane film for laminated glass is characterized in that the preparation raw material comprises 1, 4-cyclohexane diisocyanate CHDI, wherein the cis-isomer content in the 1, 4-cyclohexane diisocyanate is 30-80 wt%, preferably 40-70 wt%.
  2. 2. The CHDI type polyurethane film for laminated glass according to claim 1, wherein the film is prepared from the following components, by weight, 10-28%, preferably 14-22% of 1, 4-cyclohexane diisocyanate; 60-85%, preferably 70-80% of polycaprolactone polyol; 2-8%, preferably 4-7% of aliphatic diol chain extender; 0.1-0.5%, preferably 0.12-0.2% of catalyst; 0.7-4%, preferably 1-2.5% of silane coupling agent.
  3. 3. CHDI polyurethane film for laminated glass according to claim 1 or 2, characterized in that the polycaprolactone polyol has a functionality of 2.0 to 2.5, preferably 2.0 to 2.1; Preferably, the polycaprolactone polyol has a molecular weight of 400-3000, preferably 800-2000.
  4. 4. A CHDI polyurethane film for laminated glass according to any one of claims 1 to 3, wherein the aliphatic diol chain extender is one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, methylpropylene glycol, hexylene glycol, or diethylene glycol.
  5. 5. CHDI polyurethane film for laminated glass according to any of claims 1 to 4, characterized in that the catalyst is one or more of an organotin salt and an organobismuth salt, preferably one or more of dibutyltin dilaurate, tin iso-octoate, bismuth iso-octoate, more preferably dibutyltin dilaurate.
  6. 6. The CHDI polyurethane film for laminated glass according to any one of claims 1 to 5, wherein the silane coupling agent is one or more of aminopropyl triethoxysilane, glycidol ether oxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane.
  7. 7. The process for producing a CHDI polyurethane film for laminated glass according to any one of claims 1 to 6, comprising the steps of: A, mixing polycaprolactone polyol, aliphatic diol chain extender and 1, 4-cyclohexane diisocyanate Adding (CHDI), catalyst and silane coupling agent into a screw extruder for mixing and reacting, and finally extruding, cooling and granulating to obtain transparent particles; b, casting the transparent particles obtained in the step A into a transparent film on a casting machine.
  8. 8. The method of claim 7, further comprising the step of vacuum dehydrating the polycaprolactone polyol and the aliphatic diol chain extender at 100-120 ℃ for at least 2 hours, respectively, to a moisture content of less than 0.08wt%, prior to step a.
  9. 9. The process according to claim 7 or 8, wherein the reaction conditions in step A are that the temperature in the feed zone of the extruder is from 90 to 150℃and the temperature in the reaction zone is from 150 to 220℃and the temperature in the extrusion zone is The temperature is 160-230 ℃ and the reaction time is 2-6 minutes.
  10. 10. Use of the CHDI-type polyurethane film for laminated glass according to any one of claims 1 to 6 or the special-purpose CHDI-type polyurethane film for laminated glass obtained by the production method according to any one of claims 7 to 9 for an intermediate adhesive layer of laminated glass.

Description

CHDI type polyurethane film for laminated glass and preparation method and application thereof Technical Field The invention relates to a CHDI type polyurethane film with good adhesion to organic or inorganic glass plates, and a preparation method and application thereof, and belongs to the field of laminated glass. Background The laminated glass is a high-end glass product integrating decoration and safety, and is widely applied to the bulletproof fields of automobiles, glass curtain walls, aviation and military industry. For laminated glass, the middle adhesive layer plays a vital role in the impact resistance and optical performance of the laminated glass, the common adhesive layer materials at present mainly comprise PVB, PU, EVA and SGP, wherein the polyurethane material has a wider temperature application range and excellent mechanical properties, has good adhesive force on inorganic glass, organic PC and PMMA materials, and is widely applied to the production of organic-inorganic composite laminated glass. Because the requirements on weather resistance, transparency, impact resistance and adhesive force of the laminated adhesive layer are high, the diisocyanate monomer used for preparing the polyurethane laminated adhesive layer basically adopts all aliphatic isocyanate products, wherein the HMDI type polyurethane film has the largest quantity of products and the largest application. At present, related reports of preparing glass laminated layers by CHDI are fresh, and commercial CHDI in the market in the prior art is a product with trans isomer of more than 99%. Disclosure of Invention The invention aims to provide a CHDI type polyurethane film for laminated glass, a preparation method and application thereof, wherein the polyurethane film creatively adopts CHDI matched with polycaprolactone polyol as a raw material, the production process is simple, and the prepared polyurethane film has transparency and excellent mechanical properties. According to a first aspect of the present invention, a CHDI type polyurethane film for laminated glass is prepared from 1, 4-Cyclohexanediisocyanate (CHDI) in which the cis isomer content in 1, 4-cyclohexanediisocyanate is 30 to 80wt%, for example 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, etc., preferably 40 to 70wt%. According to the invention, CHDI with different cis-isomer contents can be prepared by phosgenation of CHDA products with different isomers, and the main synthesis steps comprise 1) carrying out phosgenation reaction on the CHDA and phosgene to obtain a reaction solution containing a solvent, isocyanate and phosgene, 2) carrying out phosgene and solvent removal treatment on the reaction solution obtained in the step 1) and separating to obtain a CHDI crude product composition, and 3) refining the CHDI crude product composition obtained in the step 2) to obtain CHDI products with different isomer contents. The process for preparing CHDI by phosgenation of CHDA and the purification of CHDI as described above are referred to in the art and will not be described in detail herein. In a preferred embodiment, a CHDI polyurethane film for laminated glass is prepared from the following components in weight percent: 10-28%, for example 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc., preferably 14-22%, more preferably 18-22%, of 1, 4-cyclohexane diisocyanate; 60-85%, such as 60%, 65%, 70%, 75%, 80%, 85%, etc., preferably 70-80%, more preferably 70-74% of polycaprolactone polyol; 2-8%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8% and the like, preferably 4-7%, more preferably 5-7% of an aliphatic diol chain extender; 0.1 to 0.5%, for example, 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5% and the like, preferably 0.12 to 0.2%; the silane coupling agent is 0.7 to 4%, for example, 0.7%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc., preferably 1 to 2.5%. Further, the polycaprolactone polyols of the present invention have a functionality of 2.0 to 2.5, for example 2, 2.1, 2.2, 2.3, 2.4, 2.5, Etc., preferably 2.0 to 2.1; preferably, the polycaprolactone polyol has a molecular weight of 400 to 3000, for example 400, 500, 600, 800, 1000, 1200, 1500, 1800, 2000, 2500, 2800, 3000, etc., preferably 800 to 2000. Further, the polyurethane film of the invention, wherein the aliphatic diol chain extender is one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, methyl propylene glycol, hexanediol or diethylene glycol. Further, the catalyst is one or more of organic tin salt and organic bismuth salt, preferably one or more of dibutyl tin dilaurate, tin isooctanoate and bismuth isooctanoate, more preferably dibutyl tin dilaurate. Further, the method comprises the steps of, the silane coupling agent is one or the combination of any ratio of more of aminopropyl triethoxysilane, glycidol ether oxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, mercaptopropyl triethoxysilane, ethylenediamine pr