Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof

A hyperbranched polyurethane and unsaturated technology, which is applied in the field of LED light-curing 3D printing resin materials and its preparation, can solve the problems of energy saving and environmental protection that are not as good as LED lights, high viscosity, and high energy consumption.

Inactive Publication Date: 2015-01-28
安徽思敬齐环保材料有限公司
View PDF5 Cites 33 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Its disadvantages: when curing, due to the interference of surface oxygen, the precision of the molded parts is low; when the resin is cured, the shrinkage is large, and the warpage of the molded parts is large; the reaction curing rate (curing degree) is lower than that of the epoxy system, and it takes two Secondary curing, large stress and deformation after reaction
Disadvantages: high viscosity, it needs to add a considerable amount of active monomer or low viscosity prepolymer to achieve satisfactory processing viscosity; cationic polymerization usually requires low temperature and anhydrous conditions, and the conditions are harsher than free radical polymerization
The material prepared by this method needs to be cured under the irradiation of a metal halide lamp, which is inferior to LED lamps in terms of energy saving and environmental protection, and the cationic photoinitiator is expensive, and the market is less industrialized, which is not conducive to the large-scale application of materials (Liu Haitao. Photocuring 3D Research and application of printing molding materials [D]. Huazhong University of Science and Technology, 2009)
Chinese Patent Publication No. CN 104004491 A, "A LED UV-curable Silicone Encapsulation Adhesive and Its Preparation Method" discloses a method for preparing LED UV-curable resin by using unsaturated silicone resin, which synthesizes unsaturated Silicone resin, and use it to prepare LED UV-curable resin. This invention uses a simple light-induced free radical polymerization method, and the curing speed is relatively slow (30s curing), which cannot be applied to the SLA process.
[0007]At present, the light source equipment for UV curing is mainly mercury lamp and xenon lamp. These two lamps are large in size, consume a lot of energy, and cause serious light pollution

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Unsaturated hyperbranched polyurethane prepolymer as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0048] The preparation method of LED photocurable 3D printing material is as follows:

[0049] (1) Preparation of unsaturated hyperbranched polyurethane prepolymer A1: Mix 3-4g of hydroxyl-terminated small molecule polyol and 10-30g of diisocyanate and heat to 80°C for 2-4 hours. After the reaction, cool down to 40°C and add 2.5 -8g end-capping agent, heat up to 80°C for 3-5 hours, cool down to 50°C and discharge to obtain unsaturated hyperbranched polyurethane prepolymer A1. The molecular weight of unsaturated hyperbranched polyurethane prepolymer is controlled within 3000g / mol;

[0050] (2) Put unsaturated hyperbranched polyurethane prepolymer A1, acrylate oligomer, epoxy resin, reactive diluent, photoinitiator, photosensitizer, epoxy latent curing agent and auxiliary agent in yellow Mix evenly under the light environment and store in the dark, and keep the mixing temperature at 20-30°C.

[0051] The molecular weight of the hydroxyl-terminated small molecule polyol is less...

Embodiment 1

[0059] The unsaturated hyperbranched polyurethane prepolymer A1 structural formula used in this embodiment is as follows:

[0060] ,

[0061] where R is , from the raw material ; R' is , from the raw material .

[0062] The preparation process of LED light-cured 3D printing materials is as follows:

[0063] Mix 30g of trimethylolpropane and 120g of hexamethylene diisocyanate and heat to 80°C for 2 hours. After the reaction, cool down to 40°C, add 80g of hydroxyethyl acrylate, heat up to 80°C for 4 hours, and cool down to 60°C °C discharging to obtain unsaturated hyperbranched polyurethane prepolymer A1. Mix 30gA1, 30g polyester acrylate (Shanghai Chunan Trading Co., Ltd., product grade 6325-100), hydrogenated bisphenol A epoxy resin 10g (Yantai Oliver Chemical Co., Ltd., grade AL-3040), two Trimethylolpropane tetraacrylate (DTEMPTTA) 20g, α,α-dimethoxy-α-dimethoxyphenylacetophenone (DMPA) 2g, camphorquinone 1g, 2-chlorothioxanthone (CTX) 2g, N.N-dimethylaniline 2...

Embodiment 2

[0065] The unsaturated hyperbranched polyurethane prepolymer A1 structural formula used in this embodiment is as follows:

[0066] ,

[0067] where R is , from the raw material ; R' is , from the raw material .

[0068] The preparation process of LED light-cured 3D printing materials is as follows:

[0069]Mix 30g of glycerin and 149g of isophorone diisocyanate and heat it to 80°C for 3 hours. After the reaction, cool down to 40°C and add 90g of hydroxyethyl methacrylate, raise the temperature to 80°C for 5 hours, then cool down to 50°C. Material obtains unsaturated hyperbranched polyurethane prepolymer A1. Mix 40g of A1, 20g of polyurethane acrylate (Tianjin Heinz Technology Development Co., Ltd., product grade 5349), 5g of epoxy resin (Changzhou Zhengfa Chemical Raw Materials Co., Ltd., grade E44), 1,6-hexanediol bis Acrylates (HDDA) 5g, Tripropylene glycol diacrylate (TPGDA) 5g, Trimethylolpropane triacrylate (TMPTA) 10g, Benzoin 2g, 2-Phenyl-2,2-Dimethylamino-...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

PropertyMeasurementUnit
strengthaaaaaaaaaa
strengthaaaaaaaaaa
strengthaaaaaaaaaa
Login to view more

Abstract

The invention discloses an unsaturated hyperbranched polyurethane prepolymer as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing hydroxyl-terminated small molecular polyol with diisocyanate, heating to 80 DEG C, reacting for 2-4 hours, cooling to 40 DEG C after the reaction is finished, adding an end-capping agent, heating to 80 DEG C, reacting for 3-5 hours, cooling to 50 DEG C, and discharging to obtain the unsaturated hyperbranched polyurethane prepolymer. The prepolymer can be used for preparing LED photocured three-dimensional printing resin; a hyperbranched technology is adopted for preparing the prepolymer, so that the photocuring time is shortened; moreover, a photo-initiated free radical polymerization and epoxy latent curing combined technology is adopted for quickly curing a material. The scheme has the advantages that the curing speed (curing by irradiating for 2 seconds by a 12 W lamp bead) is high, the curing shrinkage rate is low, the curing process cannot be influenced by moisture and oxygen in air, and the material obtained after the curing process is high strength (6-15 MPa) and small in curing shrinkage rate (not more than 3%).

Description

technical field [0001] The invention belongs to the technical field of LED photocurable polymer materials, and in particular relates to an LED photocurable three-dimensional printing resin material and a preparation method thereof. Background technique [0002] Three Dimensional Printing (Three Dimensional Printing), a type of rapid prototyping technology, is a technology based on digital model files, using bondable materials such as powdered metal or plastic, to construct objects by layer-by-layer printing. Therefore, 3D printing technology has the characteristics of low cost, short cycle, simple modification, and stable size. The consumables used in 3D printing are called 3D printing materials, or 3D printing materials for short. [0003] There are many kinds of 3D printing materials, and there are various classification methods, which can be classified according to physical state, chemical properties, and material forming methods. According to the materials used in the ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/67C08G18/32C08L51/08C08L51/00C08L63/00
CPCC08F290/06C08G18/3206C08G18/672
Inventor 王继印徐杰陶灿
Owner 安徽思敬齐环保材料有限公司
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap