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Photo-thermal double-curing 3D printing method by using ring-opening metathesis polymerization (ROMP) and product thereof

A ring-opening metathesis polymerization and 3D printing technology, applied in the field of 3D printing, can solve the problems of ROMP light-dark dual-cured products becoming brittle and losing toughness, achieving good toughness, improving elongation at break, and broadening the application range Effect

Inactive Publication Date: 2020-03-31
HANGZHOU LEYI NEW MATERIAL TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] If the ROMP thermal curing system is used as the dark curing system in the light-dark dual curing system in 3D printing, the ROMP thermal curing temperature will generally be higher than the glass transition temperature of the first-stage light-curing polymer (the glass transition temperature of this product higher than room temperature), so the light-cured polymer product becomes brittle after returning to room temperature, resulting in ROMP light-dark dual-cure products are easy to become brittle and lose basic toughness

Method used

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  • Photo-thermal double-curing 3D printing method by using ring-opening metathesis polymerization (ROMP) and product thereof
  • Photo-thermal double-curing 3D printing method by using ring-opening metathesis polymerization (ROMP) and product thereof
  • Photo-thermal double-curing 3D printing method by using ring-opening metathesis polymerization (ROMP) and product thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0027] (1) Preparation of polyurethane polyacrylate: Mix 1 mol of PPG-1000 with 0.5% of the weight of PPG-1000 of DBT and add dropwise to 2 mol of HDI, react at 60°C for 1 hour, then add 2 mol of HEA, and react at 60°C for 3 hours. To obtain polyether urethane acrylate;

[0028] (2) Light-heat dual curing 3D printing: The polyether urethane acrylate obtained in step (1) is mixed with ACMO and TPO according to the following mass percentages first, and then 3D printing is performed using a light curing printer to obtain a photopolymer, and testing The glass transition temperature of the photopolymer is -15°C, which is lower than room temperature; then according to the following mass percentages, the polyether urethane acrylate, ACMO, TPO, Umicore 22 catalyst and dicyclopentadiene are mixed and photocured for printing, and then heated to After curing at 100°C for 2 hours, a 3D printed product was obtained; the catalyst was Umicore brand Umicore 22, specifically (1,3-bis(2,4,6-trimet...

Embodiment 2

[0032] (1) Preparation of polyurethane polyacrylate: Mix 1mol PCDL-1000 with 0.5% of the weight of PCDL-1000 DBT and add dropwise to 2mol HDI, react at 60℃ for 1h, then add 2mol HEMA, react at 60℃ for 3h, Obtain polyester polyurethane acrylate;

[0033] (2) Light-heat dual curing 3D printing: The polyester polyurethane acrylate obtained in step (1) is mixed uniformly with HEMA and TPO according to the following mass percentages, and 3D printing is performed using a light curing printer to obtain a polymer. Test the polymer The glass transition temperature is -9℃, which is lower than room temperature; then according to the following mass percentages, mix the polyester urethane acrylate, HEMA, TPO, catalyst and cyclopentadiene uniformly, then light-curing and printing, then heat to 90℃ and cure for 2h , To obtain 3D printed products; wherein the catalyst is Umicore brand Umicore 22, specifically (1,3-bis(2,4,6-trimethylphenyl) 2-imidazolidinyl subunit) dichloro (3 -Phenyl-1H-inden...

Embodiment 3

[0036] (1) Preparation of polyurethane polyacrylate: mix 1 mol of PCDL-1000 with 0.5% of the weight of PCDL-1000 of DBT and add dropwise to 2 mol of HDI, react at 60°C for 1 hour, then add 2 mol of HEA, and react at 60°C for 3 hours. Obtain polyester polyurethane acrylate;

[0037] (2) Light-heat dual curing 3D printing: The polyester polyurethane acrylate obtained in step (1) is mixed uniformly with ACMO, TPO and dicyclopentadiene acrylate according to the following mass percentages, and 3D printing is performed using a light curing printer to obtain Polymer, the glass transition temperature of the tested polymer is 6℃, which is lower than room temperature; then according to the following mass percentages, the polyester urethane acrylate, ACMO, TPO, Umicore 22 catalyst and dicyclopentadiene are mixed uniformly and then light-cured 3D printing , And then heated to 60°C and cured for 6 hours to obtain 3D printed products. The acrylate group of dicyclopentadiene acrylate undergoes...

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Abstract

The invention discloses a photo-thermal double-curing 3D printing method by using ROMP and a product thereof. The method includes: mixing raw materials and performing photo-curing 3D printing and performing thermal-curing to obtain the 3D printing product. The raw materials comprise: polyurethane (meth)acrylate, a diluent, an initiator, cyclic olefin monomer, and a thermally induced ROMP catalyst,wherein the polyurethane (meth)acrylate is obtained through a reaction of isocyanate and polyol and termination by (meth)acrylate containing hydroxyl; the polyol is polyester polyol or polyether polyol with molecular being not less than 1,000. The method avoids the problem of brittleness of the photo-cured product due to the thermal-curing of the ROMP and achieves the ROMP in a dark reaction during light-dark dual curing. The product has basic toughness and satisfies industrial manufacturing application.

Description

Technical field [0001] The invention relates to the field of 3D printing, in particular to a photo-thermal dual-curing 3D printing method using ring-opening metathesis polymerization and its products. Background technique [0002] Light-curing 3D printing products are thermosetting resins. Thermosetting materials are a kind of cross-linked polymer materials with a network structure. The biggest weakness of the cross-linked structure of thermosetting resins is the brittleness after curing, the poor resistance to impact and stress cracking. , Plastic deformation is constrained, which limits their application in certain fields. In addition, limited by the photocurable printing technology, photosensitive resins with low molecular weight and low viscosity are generally used, and the polymerization degree of the photosensitive resin monomers is not high during the printing process, so the mechanical properties of the resulting 3D printed products are insufficient. The introduction of ...

Claims

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Application Information

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IPC IPC(8): C08F283/00C08G61/08C08L51/08C08L65/00B33Y70/00
CPCC08F283/008C08G61/08C08L51/08B33Y70/00C08G2261/11C08G2261/418C08L65/00
Inventor 刘丹丹陈遒张小敏
Owner HANGZHOU LEYI NEW MATERIAL TECH CO LTD
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