TWI708797B - Method for preparing photopolymerized polyglyceryl sebacate copolymerized lignin elastomer - Google Patents

Abstract

A photopolymerized polyglyceryl sebacate copolymerized lignin elastomer, which comprises the use of glyceryl methacrylate with C=C double bond to synthesize a biodegradable material polyglyceryl sebacate and a water-soluble lignin , Through the lignin, the biological properties of the polyglyceryl sebacate have photopolymerization properties and tensile strength, and the mechanical properties of the photopolymerized polyglyceryl sebacate are enhanced.

Description

Preparation method of photopolymerized polyglyceryl sebacate copolymerized lignin elastomer

The present invention relates to the use of lignin to improve the mechanical properties of polyglyceryl sebacate, especially the synthesis of a photopolymerized polyglyceryl sebacate copolymerized lignin elastomer from glyceryl methacrylate with C=C double bonds .

Installing a stent in the heart artery or performing vascularization surgery is now a common treatment. These all use biodegradable materials, including: polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), etc. The above biodegradable materials and composite materials can be made An alternative stent, and the alternative stent has the functions of soft tissue repair, tissue regeneration stent, drug carrier, and surgical sealant. However, after such an alternative material is implanted in the body, due to the long-term circulation in the body and the strain environment, its mechanical The nature will be limited, such as the inability to withstand multiple strains and other characteristics, will cause the replacement stent to lose its function.

Poly-glycerol sebacate (hereinafter referred to as PGS) is a biodegradable chemical polymer with biocompatible properties. The products decomposed in the body can be metabolized naturally. The cost is low, and the process is simple, so that it has been widely used in biomedicine in recent years. In order to respond to the mechanical properties or repair characteristics of different tissues in the human body, materials of different properties are added during the process and related functions are prepared. Sex polymers to achieve better results.

Lignin has various functional groups, namely hydroxyl, methoxy, carbonyl and carboxyl. Due to its structural complexity, and the aromatic structure of lignin, most materials based on simple addition or incorporation of lignin are fragile, making it difficult to realize lignin for higher-end applications. In order to solve this limitation, lignin needs to be modified to increase its application range. Different types of modifications increase the chemical-chemical reactivity of lignin, reduce the brittleness of its derived polymers, increase its solubility in organic solvents, and improve the ease of processing of lignin.

The versatility of lignin and its multiple applications have great potential. Therefore, the application of lignin needs to be chemically modified and synthesized with other polymers to obtain materials with advanced properties.

Glycidyl methacrylate (Glycidyl methacrylate, GMA for short) is a monomer commonly used in the production of epoxy resin. The GMA molecule contains two active vinyl groups and ionic reactive epoxy groups. Functional group, GMA can polymerize with other substances in a functional group-to-functional group, and can also polymerize in an ionic reaction. Please refer to Figure 1. Natural lignin contains a large number of OH functional groups. Therefore, the OH functional groups of lignin react with the epoxy groups of GMA to produce lignin containing double bonds that can be photopolymerized.

For this reason, in view of the lack of conventional technology, the applicant invented a photopolymerizable "elastomer" that can improve the mechanical properties of polyglyceryl sebacate and has elasticity to improve the above-mentioned conventional defects.

The object of the present invention is to provide a method for preparing a photopolymerizable elastomer, which comprises mixing a biodegradable material of polyglyceryl sebacate and lignin that has been reacted with 2,3-dihydroxypropyl methacrylate, A polyglyceryl sebacate copolymerized lignin elastomer is produced, and the mechanical properties of the elastomer are increased. And the elastic body is a biodegradable material. When the elastic body is organized to repair membranes and regenerate supports When the drug carrier or drug carrier enters the body, it will not be affected by the human environment, and will damage its mechanical properties or rapidly degrade, resulting in the loss of its original function.

A: Lignin

B: Polyglyceryl sebacate (PGS)

C: Polyglyceryl sebacate (PGS) of lignin and glyceryl methacrylate (GMA) mixture PGS-g-GMA

D: Polyglycerol sebacate copolymerized lignin elastomer (PGS-co-Lignin-g-GMA)

E: The product of the invention incorporating 0.2g of lignin

F: The product of the invention incorporating 0.4g of lignin

Figure 1 is a schematic diagram of the polymerization of lignin and 2,3-dihydroxypropyl methacrylate functional groups.

Figure 2 is the FTIR synthesis analysis diagram. (This picture needs to be in color)

Figure 3 shows the stress-strain comparison of adding lignin with different weight ratios. (This picture needs to be in color)

Figure 4 is the tensile analysis table of adding lignin with different weight ratios.

In order to facilitate your reviewer to have a further understanding and understanding of this case, the following examples are provided in conjunction with the scheme.

The present invention provides a poly-glycerol sebacate (PGS-co-Lignin-g-GMA) via a biodegradable material poly-glycerol sebacate (hereinafter referred to as PGS). ) Is mixed with lignin (Lignin) which has been reacted with Glycidyl methacrylate (GMA).

The steps are as follows: first make polyglyceryl sebacate copolymerized lignin elastomer (PGS-co-Lignin-g-GMA), and then polyglyceryl sebacate copolymerized lignin elastomer (PGS-co-Lignin-g -GMA) for photopolymerization, detailed steps are as follows:

Step 1. Put sebacic acid (10.1g) and glycerol (4.6g) with a molar ratio of 1:1 into a double-necked flask, and add lignin with a weight percentage of 1% to 3%. ₂ Mix evenly under the environment. In this embodiment, 0.2g (1.34wt%) and 0.4g (2.65wt%) of lignin are added.

Step 2: Place the product of Step 1 in an oil bath, and heat and stir for 24 hours after it is completely dissolved. The temperature of the oil bath is 110°C to 130°C, and 120°C is used in this embodiment.

Step 3. After the product of Step 2 is lowered to room temperature, add 3.2 g of Glycidyl methacrylate (GMA), 0.06 g of benzyl dimethylamine (BDMA) and 4-methoxyphenol ( 4-Methoxyphenol (MEHQ for short) 0.06g, put in an oil bath and stirred for 24 hours. The temperature of the oil bath is 50°C to 70°C, and 60°C is used in this embodiment.

Step 4: Add the product of Step 3 to 10wt% hydroxyethyl methacrylate and stir for 10 minutes.

Step 5. Add 2wt% brightener (Irgacure 819, brand BASF) and stir for 10 minutes.

Step 6. Drop the solution of Step 5 into the mold, irradiate it with UV light for 10 minutes and then take it off to produce the polyglyceryl sebacate copolymer lignin elastomer (PGS-co-Lignin-g-GMA) of the present invention .

The control group of this embodiment are respectively lignin (Lignin), polyglyceryl sebacate (PGS) and the mixture of polyglyceryl sebacate (PGS) and glyceryl methacrylate (GMA) without lignin. PGS -g-GMA, the step is to copolymerize lignin elastomer (PGS-co-Lignin-g-GMA) with polyglyceryl sebacate, which will not be repeated here.

FTIR analysis

The functional group identification of polyglyceryl sebacate co-lignin elastomer (PGS-co-Lignin-g-GMA) was analyzed by FTIR. Please refer to Figure 2, PGS-g-GMA and polyglyceryl sebacate co-polymerized lignin elastomer (PGS-co-Lignin-g-GMA) at 1638cm ^-1 , obvious glyceryl methacrylate ( GMA) C=C absorption peak, pure polyglyceryl sebacate (PGS) does not have this absorption peak, it is known that polyglyceryl sebacate copolymerized lignin elastomer (PGS-co-Lignin-g-GMA ) The grafting reaction is successful.

Pull analysis

Cut different proportions of the elastomer (PGS-co-Lignin-g-GMA) and polyglyceryl sebacate (PGS) into a standard test shape with a film knife, and measure the thickness of each test piece with a film thickness meter. 1 to 1.5mm, and then clamp the test piece, use a load cell of 50N, stretch at a rate of 20mm/min ^-1 , and finally discuss the stress and strain of different ratios of elastomer (PGS-co-Lignin-g-GMA) relationship.

The results are shown in Table 1. Polyglycerol sebacate (PGS) mixed with 0.2g (1.34wt%) of lignin, the tensile strength is from 0.09MPa (s= 0.03) increased to 0.18MPa (s=0.06), the tensile strength increased by 2 times, and the strain of ductility increased from 19.17% (s=3.9%) to 24.22% (s=4.5%). After increasing the proportion of lignin to 0.4g (2.65wt%), the elastic modulus of rigidity (15% secant modulus) increased from 0.7MPa (s=0.2) to 1.07MPa (s=0.1), please refer to Figure 3 It is shown that lignin helps to strengthen the mechanical strength of polyglyceryl sebacate copolymerized lignin elastomer (PGS-co-Lignin-g-GMA).

It can be seen from the above experiments that the addition of lignin can improve the elasticity of polyglyceryl sebacate (PGS) and enhance its mechanical properties, so that the polyglyceryl sebacate copolymerized lignin elastomer has a wider range of applications, including In the field of biomedicine, it includes artificial blood vessels, artificial organs, orthopedic fillers, contact lenses and wound dressings, etc.

B: Polyglyceryl sebacate (PGS)

E: The product of the invention incorporating 0.2g of lignin

F: The product of the invention incorporating 0.4g of lignin

Claims (4)

A preparation method of photopolymerized polyglyceryl sebacate copolymerized lignin elastomer includes the following steps: Step 1. Put sebacic acid and glycerin into a double-necked flask, and then add 1% to 3% by weight. % Lignin, mixed uniformly under N ₂ environment; Step 2. Place the product of Step 1 in an oil bath, and heat and stir for 24 hours after it is completely dissolved; Step 3. Wait for the product of Step 2 to drop to room temperature and add methyl Glycidyl methacrylate (GMA for short), Benzylidimethylamine (BDMA for short) and 4-Methoxyphenol (MEHQ for short) are placed in an oil bath and stirred for 24 hours; Step 4. Add the product from step 3 to 10wt% hydroxyethyl methacrylate and stir for 10 minutes; step 5, add 2wt% brightener, and stir for 10 minutes; and step 6, drop the solution from step 5 into the mold, and use UV light After being irradiated for 10 minutes, it is removed to produce the polyglyceryl sebacate copolymer lignin elastomer of the present invention. The preparation method of the photopolymerized polyglyceryl sebacate copolymerized lignin elastomer as described in item 1 of the scope of patent application, wherein the sebacic acid and glycerin in step 1 are mixed with a molar ratio of 1:1. The method for preparing the photopolymerized polyglyceryl sebacate copolymerized lignin elastomer as described in item 1 of the scope of patent application, wherein the temperature of the oil bath in step 1 is 110°C to 130°C. The preparation method of the photopolymerized polyglyceryl sebacate copolymerized lignin elastomer as described in item 1 of the scope of patent application, wherein the temperature of the oil bath in step 3 is 50°C to 70°C.

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