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CN-121991340-A - Preparation method of non-isocyanate type photo-curing resin

CN121991340ACN 121991340 ACN121991340 ACN 121991340ACN-121991340-A

Abstract

The invention belongs to the technical field of 3D printing, and particularly relates to a preparation method of non-isocyanate type photo-curing resin, which comprises the steps of reacting cyclic carbonate with aliphatic primary amine under nitrogen, vacuum drying to obtain polyurethane prepolymer, reacting the polyurethane prepolymer with a chain extender under dibutyltin dilaurate and nitrogen, vacuum drying to obtain an intermediate product A, reacting a methacrylate monomer with a curing agent under a catalyst a and nitrogen to an amine value titration end point to obtain an intermediate product B, reacting the intermediate product A with the intermediate product B to obtain non-isocyanate type polyurethane acrylate C, and uniformly stirring the non-isocyanate type polyurethane acrylate C with a photoinitiator and a polymerization inhibitor to obtain liquid non-isocyanate type photo-curing resin D. The synthetic system of non-isocyanate is adopted, so that the toxicity and volatility of the traditional isocyanate are avoided, the production process is safer and more environment-friendly, and the multiple production requirements on the mechanical reliability, the curing efficiency and the safety of materials in a 3D printing use scene are met.

Inventors

  • SHI XINGHAO
  • ZHANG MINCONG
  • DENG QIJUN

Assignees

  • 广东云物未来科技有限公司

Dates

Publication Date
20260508
Application Date
20260318

Claims (10)

  1. 1. The preparation method of the non-isocyanate type photo-curing resin is characterized by comprising the following synthesis steps: Adding 180-210 parts of cyclic carbonate and 80-110 parts of aliphatic primary amine into a reaction kettle according to parts by weight, heating to 50-90 ℃ under the protection of nitrogen, stirring at a constant speed, performing polycondensation reaction for 4-48 hours, and performing post-treatment to obtain polyurethane prepolymer; Step two, adding 180-210 parts of polyurethane prepolymer and 80-110 parts of chain extender into a reaction kettle according to parts by weight, heating to 60-80 ℃, uniformly stirring, dropwise adding 0.1-1 part of dibutyltin dilaurate, reacting for 3-5 hours under the protection of nitrogen, and vacuum drying to obtain an intermediate product A; Adding 80-110 parts of methacrylate monomers and 80-110 parts of curing agent into a reaction kettle according to parts by weight, stirring at 60-100 ℃ under the protection of nitrogen, dropwise adding 0.1-1 part of catalyst a, reacting for 2-6 hours, and monitoring the reaction progress by an amine value titration method until the mass fraction of amino NH 2 in the system reaches 50.0% -50.2%, thus obtaining an intermediate product B; step four, adding 80-110 parts of intermediate product A and 180-210 parts of intermediate product B into a reaction kettle according to parts by weight, heating to 50-70 ℃, stirring at a constant speed, and reacting for 9-11 hours to obtain non-isocyanate polyurethane acrylic ester C; And fifthly, taking 80-110 parts by weight of non-isocyanate polyurethane acrylic ester C,0.8-1.2 parts by weight of photoinitiator, 0.1-1 part by weight of polymerization inhibitor, keeping the temperature at 50-70 ℃ and stirring uniformly at the rotating speed of 400-500r/min to obtain liquid non-isocyanate type photo-curing resin D.
  2. 2. The method for preparing a non-isocyanate type photocurable resin according to claim 1, wherein said synthesizing step comprises the steps of: Adding 180-210 parts of cyclic carbonate and 80-110 parts of trimethyl hexamethylenediamine into a reaction kettle according to parts by weight, heating to 50-90 ℃, stirring at a constant speed, adding 0.1-5 parts of catalyst triethylamine, carrying out polycondensation reaction for 4-48h under the protection of nitrogen, adding an stopping agent diethyl ether, filtering, washing and vacuum drying to obtain the polyurethane prepolymer.
  3. 3. The method for preparing a non-isocyanate type photocurable resin according to claim 2, wherein said synthesizing step comprises the steps of: adding 180-210 parts of cyclic carbonate and 80-110 parts of bis (4-aminocycloethyl) ether into a reaction kettle according to parts by weight, heating to 50-90 ℃, stirring at a constant speed, adding 0.1-5 parts of catalyst NaOH, carrying out polycondensation reaction for 4-48 hours under the protection of nitrogen, adding a stopping agent dilute hydrochloric acid, filtering, washing, and carrying out vacuum drying to obtain the polyurethane prepolymer.
  4. 4. The method for preparing a non-isocyanate type photocurable resin according to claim 1, wherein said synthesizing step comprises the steps of: 180-210 parts of cyclic carbonate, 80-110 parts of isophorone diamine and nitrogen are added into a reaction kettle according to parts by weight, the temperature is raised to 50-90 ℃ under the protection of nitrogen, the stirring is carried out at a constant speed for 0.5-2h, the temperature is raised to 90-140 ℃, the polycondensation reaction is carried out for 4-48h, and the polyurethane prepolymer is obtained after vacuum drying.
  5. 5. The method for producing a non-isocyanate type photocurable resin according to any one of claims 1 to 4, wherein the cyclic carbonate comprises any one of ethylene carbonate, propylene carbonate and 1, 2-glyceride carbonate, and the aliphatic primary amine comprises any one of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, isophoronediamine, trimethylhexamethylenediamine and bis (4-aminocycloethyl) ether.
  6. 6. The method of preparing a non-isocyanate type photocurable resin according to any one of claims 1-4, wherein the chain extender is any one of resorcinol bishydroxypropyl ether, hydroquinone bishydroxyethyl ether, bisphenol A bishydroxypropyl ether.
  7. 7. The method for preparing a non-isocyanate type photocurable resin according to any one of claims 1-4, wherein the catalyst a in the third step is titanium tetraisopropoxide, and the methacrylate monomer in the third step is any one of 2-hydroxyethyl methacrylate, methyl methacrylate, n-butyl methacrylate and isobutyl methacrylate.
  8. 8. The method for preparing a non-isocyanate type photocurable resin according to any one of claims 1-4, wherein the curing agent used in the third step is any one of 4, 4-diaminodiphenylmethane, 3, 5-dimethylthiotoluenediamine, 3, 5-diamino-4-chlorobenzoic acid isobutyl ester and 1, 4-di-sec-butylaminophenone.
  9. 9. The method for preparing a non-isocyanate type photocurable resin according to any one of claims 1-4, wherein the photoinitiator in the fifth step is any one or two of a photoinitiator 184, a photoinitiator TPO, a photoinitiator 819 and a photoinitiator 907.
  10. 10. The method for producing a non-isocyanate type photocurable resin according to any one of claims 1-4, wherein the polymerization inhibitor in the fifth step is any one of p-hydroxyanisole, hydroquinone, 2, 6-di-t-butyl-p-cresol.

Description

Preparation method of non-isocyanate type photo-curing resin Technical Field The invention belongs to the technical field of 3D printing, and particularly relates to a preparation method of non-isocyanate type photo-curing resin. Background The photocuring technology becomes a mainstream technology in the fields of 3D printing resin and the like due to the advantages of high curing efficiency, low VOC emission, low energy consumption and the like. The polyurethane acrylate oligomer is used as a core matrix material of the photo-curing resin, has polyurethane flexibility, wear resistance and acrylate photo-curing activity, and is widely used in the application fields of industrial anti-corrosion coatings, precise 3D printing parts, flexible electronic packaging materials and the like. In the preparation process of polyurethane acrylate oligomer in the prior art, for example, in the patent document with the patent number KR1020240103819A, isocyanate is taken as a core raw material, polyurethane prepolymer is generated through addition polymerization, and then acrylic acid double bond is introduced to prepare the product. The process has high maturity, and the prepared product has high crosslinking density and excellent mechanical strength and takes the dominant position in the market for a long time. However, isocyanate is extremely toxic, volatile and irritating, and can harm human health, and high-cost protection equipment and strict control are required for production, so that the labor cost of safety protection is greatly raised. The development of non-isocyanate polyurethane acrylate photo-curing resin of a cyanide-free system becomes an industry upgrading direction, the existing scheme adopts cyclic carbonate and amine ring-opening reaction to replace isocyanate addition reaction, but the acrylic double bond modification process is complex, and the contradiction that photo-curing activity and mechanical property are difficult to consider exists, namely, the photo-curing rate is slow, the conversion rate of the acrylic double bond is low, the requirement of 3D printing rapid prototyping cannot be met, or the attenuation of mechanical property (tensile strength and elongation at break) is obvious, the application requirement of the material toughness balance is difficult to adapt to the application scene, and the two are difficult to consider. Disclosure of Invention The invention aims to provide a preparation method of non-isocyanate type photo-curing resin, which aims to solve the technical problem that the photo-curing activity and mechanical property of the non-isocyanate type photo-curing resin are difficult to be compatible. In order to achieve the above object, the present invention provides a method for preparing a non-isocyanate type photocurable resin, comprising the following synthesis steps: Adding 180-210 parts of cyclic carbonate and 80-110 parts of aliphatic primary amine into a reaction kettle according to parts by weight, heating to 50-90 ℃ under the protection of nitrogen, stirring at a constant speed, performing polycondensation reaction for 4-48 hours, and performing post-treatment to obtain polyurethane prepolymer; Step two, adding 180-210 parts of polyurethane prepolymer and 80-110 parts of chain extender into a reaction kettle according to parts by weight, heating to 60-80 ℃, uniformly stirring, dropwise adding 0.1-1 part of dibutyltin dilaurate, reacting for 3-5 hours under the protection of nitrogen, and vacuum drying to obtain an intermediate product A; Adding 80-110 parts of methacrylate monomers and 80-110 parts of curing agent into a reaction kettle according to parts by weight, stirring at 60-100 ℃ under the protection of nitrogen, dropwise adding 0.1-1 part of catalyst a, reacting for 2-6 hours, and monitoring the reaction progress by an amine value titration method until the mass fraction of amino NH 2 in the system reaches 50.0% -50.2%, thus obtaining an intermediate product B; step four, adding 80-110 parts of intermediate product A and 180-210 parts of intermediate product B into a reaction kettle according to parts by weight, heating to 50-70 ℃, stirring at a constant speed, and reacting for 9-11 hours to obtain non-isocyanate polyurethane acrylic ester C; And fifthly, taking 80-110 parts by weight of non-isocyanate polyurethane acrylic ester C,0.8-1.2 parts by weight of photoinitiator, 0.1-1 part by weight of polymerization inhibitor, keeping the temperature at 50-70 ℃ and stirring uniformly at the rotating speed of 400-500r/min to obtain liquid non-isocyanate type photo-curing resin D. Further, step one of the synthesizing steps: Adding 180-210 parts of cyclic carbonate and 80-110 parts of trimethyl hexamethylenediamine into a reaction kettle according to parts by weight, heating to 50-90 ℃, stirring at a constant speed, adding 0.1-5 parts of catalyst triethylamine, carrying out polycondensation reaction for 4-48h under the protection of nitrogen, adding an stopping a