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Photocurable polyester oligomer for 3D printing as well as preparation method and application thereof

A polyester oligomer and 3D printing technology, applied in the field of biomedical materials, can solve the problems of low printing efficiency and achieve the effect of excellent performance, broad application prospects and low viscosity

Pending Publication Date: 2020-05-19
BMF NANO MATERIAL TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004]The existing polyester biodegradable materials do not contain photocurable active groups. Ordinary printing methods such as film forming can only be used for printing models with low precision requirements, and the printing efficiency is low, so they cannot be used in finer light-curing 3D printing

Method used

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  • Photocurable polyester oligomer for 3D printing as well as preparation method and application thereof
  • Photocurable polyester oligomer for 3D printing as well as preparation method and application thereof
  • Photocurable polyester oligomer for 3D printing as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] (1) Preparation of photocurable polylactic acid PLA oligomer: Add 68g of L-lactic acid solution into a three-necked flask, gradually raise the temperature to 90°C under 20KPa, stir and dehydrate for 2 hours, then add 13.71g of 1,6 hexanedi Alcohol and 0.21g catalyst stannous octoate, continue to react at 10kPa, 130°C for 2h, then dehydrate at 1000Pa, 150°C for 1h, cool to 100°C under vacuum, add 0.4g polymerization inhibitor p-hydroxyanisole and 40g methacrylic acid Anhydride, and then heated to 120 ° C under normal pressure for 4 hours, heated to 140 ° C under reduced pressure to extract excess methacrylic anhydride, cooled to room temperature to obtain polylactic acid oligomers. Add 40g of tetrahydrofuran to the obtained product, stir and dissolve, then slowly add to a separatory funnel containing 400g of n-hexane, shake it several times and let it stand for a period of time, take out the lower layer of liquid; repeat three times; then put the lower layer of liquid int...

Embodiment 2

[0033](1) Preparation of photocurable polycaprolactone PCL oligomer: Add 86g of L-lactic acid solution into a three-necked flask, gradually raise the temperature to 90°C at 20KPa, stir and dehydrate for 2 hours, then add 13g of 1,2- Butanediol and 0.2g catalyst stannous octoate, continue to react at 10KPa, 130°C for 2h, then dehydrate at 1000Pa, 150°C for 1h, cool to 100°C under vacuum, add 0.4g polymerization inhibitor 2,6-di-tert-butyl p-cresol and 40g of methacrylic anhydride were heated to 120°C for 4 hours under normal pressure, and the excess methacrylic anhydride was extracted under reduced pressure at 140°C, and cooled to room temperature to obtain polylactic acid oligomers. Add 50g of tetrahydrofuran to the obtained product, stir and dissolve it, then slowly add it into a separatory funnel containing 500g of n-hexane, shake it several times and let it stand for a while, take out the lower layer of liquid; repeat three times; then put the lower layer of liquid into the ...

Embodiment 3

[0036] (1) Preparation of photocurable polylactic acid PLA oligomer: Add 68g of L-lactic acid solution into a three-necked flask, gradually raise the temperature to 90°C under 20KPa, stir and dehydrate for 2h, then add 10g of glycerin and 0.21g of catalyst Stannous chloride, continue to react at 10KPa, 130°C for 2h, then dehydrate at 1000Pa, 150°C for 1h, cool to 100°C under vacuum, add 0.4g of polymerization inhibitor p-hydroxyanisole and 40g of methacrylic anhydride, and then Raise the temperature to 120°C for 4 hours under normal pressure, raise the temperature to 140°C to extract excess methacrylic anhydride under reduced pressure, and cool to room temperature to obtain a star-shaped polylactic acid oligomer. Add 40g of tetrahydrofuran to the obtained product, stir and dissolve, then slowly add to a separatory funnel containing 400g of n-hexane, shake it several times and let it stand for a period of time, take out the lower layer of liquid; repeat three times; then put the...

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Abstract

The invention provides a photocurable polyester oligomer for 3D printing as well as a preparation method and application thereof. The preparation method comprises the following steps of: carrying outvacuum heating dehydration on an aliphatic hydroxyl acid monomer to prepare a polyester prepolymer, adding an initiator in the presence of polyol to prepare a hydroxyl-terminated prepolymer by a meltcopolymerization method, and finally adding acrylic acid anhydride to prepare the photocurable aliphatic polyester oligomer. The prepared photocurable aliphatic polyester oligomer can be directly combined with a photoinitiator, and is suitable for DLP type 3D printing. The photocurable aliphatic polyester resin material prepared by the method is high in purity, relatively low and adjustable in viscosity, can be used in the biomedical field, especially in the fields of drug sustained release, tissue engineering, bone fixation, repair materials and the like, a photocuring polyester degradation material is combined with a 3D printing technology, the printed material is non-toxic and has excellent biocompatibility and mechanical properties, the degradation rate is between 6 months and 36 months, and a new direction is provided for application of 3D printing.

Description

technical field [0001] The invention belongs to the technical field of biomedical materials, and in particular relates to a polyester oligomer capable of photocuring 3D printing and its preparation method and application. Background technique [0002] 3D printing technology based on digital projection technology (DLP) has strong advantages in the production of miniature and fine workpieces due to its high molding precision and short curing time of a single layer. In recent years, DLP 3D printing technology has developed rapidly, and people's requirements for 3D printing are also increasing. Many DLP functional materials have also emerged, including biodegradable materials, high temperature resistant materials, conductive materials and so on. Biodegradable materials are widely used in the field of biomedicine due to their excellent performance during use and the characteristics of rapid hydrolysis and degradation by enzymes or microorganisms after use. Synthetic biodegradabl...

Claims

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Application Information

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IPC IPC(8): C08G63/60C08F299/04B33Y70/10A61K47/34A61L27/18A61L27/50A61L31/06A61L31/14
CPCC08G63/60C08F299/04B33Y70/00A61K47/34A61L27/18A61L27/50A61L31/06A61L31/14A61L2430/02C08L67/06
Inventor 陈未凤黄立贺晓宁
Owner BMF NANO MATERIAL TECH CO LTD
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