Degradable bio-based medical polymer composite material and preparation method thereof

Abstract

The invention discloses a degradable bio-based medical polymer composite material and a preparation method thereof in the technical field of medical materials. The degradable bio-based medical polymer composite material is prepared from the following raw materials in parts by weight: 80 to 100 parts of polylactic acid, 30 to 70 parts of polycaprolactone, 10 to 15 parts of hydrophilic modifier, 30 to 50 parts of flexibilizer, 3 to 5 parts of functional filler and 0.1 to 0.3 part of antioxidant. Polylactic acid is used as a matrix, polycaprolactone and a hydrophilic modifier are added for blending modification, the mechanical property and biocompatibility of the polylactic acid can be improved by introducing the polycaprolactone, the hydrophilicity of the polylactic acid can be remarkably improved by adding hydrophilic modification, the use space of a polylactic acid material in the medical field is widened, and a bio-based material is explaining and has a good application prospect. According to the invention, the silane coupling agent is used for modifying the nano silicon dioxide, so that the compatibility of the nano silicon dioxide and the polylactic acid matrix can be improved, and the mechanical property of the composite material is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of medical materials, and in particular to a degradable bio-based medical polymer composite material and a preparation method thereof. Background Art

[0002] Currently, disposable syringes are commonly made of materials such as polypropylene. These syringes do not biodegrade upon disposal, polluting the environment and endangering human health. Conventional centralized incineration not only fails to achieve resource recycling but also worsens environmental pollution. Driven by profit, discarded syringes are illegally reused by criminals, creating medical risks such as cross-infection. Therefore, the development of fully biodegradable, disposable medical infusion devices is urgent.

[0003] Polylactic acid (PLA) has a high melting point (175°C) and physical properties between those of PET (polyethylene terephthalate) and PA-6 (nylon). It exhibits high crystallinity, excellent transparency, and good resistance to solvents, moisture, oil, and grease, as well as breathability. It also possesses some bacterial resistance, flame retardancy, and UV resistance. Polylactic acid (PLA) exhibits excellent biocompatibility and biodegradability. It also has good processability, making it suitable for traditional processing methods such as extrusion, injection molding, and blow molding. However, PLA does have limitations in terms of material properties and processing performance. These limitations are primarily: 1. Material properties: While PLA's mechanical properties are similar to those of PS, it is brittle and has poor impact resistance. 2. Processing performance: PLA suffers from poor thermal stability, and its molecular weight decreases significantly when processed below its melting temperature or thermal decomposition temperature.

[0004] Currently, researchers have made significant progress in modifying PLA, using methods such as plasticization, blending, grafting, copolymerization, and composite modification. However, research on polylactic acid (PLA) in the field of disposable medical devices remains elusive. Existing PLA raw materials, due to their poor toughness and heat resistance, limit their application in disposable medical devices. For example, syringes are fragile at room and low temperatures, and deform when sterilized with ethylene oxide at 50-60°C. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a degradable bio-based medical polymer composite material and a preparation method thereof.

[0006] The object of the present invention is achieved like this: A biodegradable bio-based medical polymer composite material, characterized by comprising the following raw materials in parts by weight: 80-100 parts of polylactic acid, 30-70 parts of polycaprolactone, 10-15 parts of a hydrophilic modifier, 30-50 parts of a toughening agent, 3-5 parts of a functional filler, and 0.1-0.3 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

[0007] Furthermore, the hydrophilic modifier is HL560.

[0008] Furthermore, the toughening agent is polybutylene adipate-terephthalate or polybutylene succinate.

[0009] Furthermore, the antioxidant is antioxidant 1010 or antioxidant 168.

[0010] Furthermore, the functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to 4-5, and the mixture was stirred at a constant speed for 30 minutes. Nano-silica was added, and the temperature was raised to 65-70°C. The mixture was stirred at a constant speed and reacted for 4-6 hours. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol and deionized water for 3 times respectively, and then dried in a vacuum at 85°C to obtain a functional filler.

[0011] Furthermore, the weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution is controlled to be 10:3-5:50.

[0012] The preparation method of the biodegradable bio-based medical polymer composite material comprises the following steps: After drying, polylactic acid, polycaprolactone, hydrophilic modifier and toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded and granulated to produce a degradable bio-based medical polymer composite material.

[0013] Furthermore, the processing temperature of the extruder and the die head temperature were controlled to be 120-150° C., 160-165° C., 170-175° C., and 180-185° C., and the rotation speed of the extruder was 120 r / min.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The present invention prepares a biodegradable bio-based medical polymer composite material, which uses polylactic acid as a matrix and is blended and modified by adding polycaprolactone and a hydrophilic modifier. The introduction of polycaprolactone can improve the mechanical properties and biocompatibility of polylactic acid, while the addition of a hydrophilic modifier can significantly improve the hydrophilicity of polylactic acid, broadening the application space of polylactic acid materials in the medical field. Moreover, the bio-based material is degradable and meets environmental protection requirements. The present invention also modifies nano-silica with a silane coupling agent, which can improve the compatibility of nano-silica with the polylactic acid matrix and further improve the mechanical properties of the composite material. DETAILED DESCRIPTION

[0015] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0016] Example 1: A biodegradable bio-based medical polymer composite material, characterized by comprising the following raw materials in parts by weight: 80 parts of polylactic acid, 30 parts of polycaprolactone, 10 parts of a hydrophilic modifier, 30 parts of a toughening agent, 3 parts of a functional filler, and 0.1 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

[0017] The hydrophilic modifier is HL560.

[0018] The toughening agent is polybutylene adipate-terephthalate.

[0019] The antioxidant is antioxidant 1010.

[0020] The functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to pH=4, and the mixture was stirred at a constant speed for 30 minutes. Nano-silica was added, the temperature was raised to 65°C, and the mixture was stirred at a constant speed and reacted for 4 hours. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol and deionized water for 3 times, respectively. The mixture was vacuum-dried at 85°C to obtain a functional filler. The weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution was controlled to be 10:3:50.

[0021] The preparation method of the biodegradable bio-based medical polymer composite material comprises the following steps: After drying, polylactic acid, polycaprolactone, a hydrophilic modifier, and a toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded, and granulated to produce a biodegradable bio-based medical polymer composite material. The extruder processing temperature and die head temperature are controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed is 120 r / min.

[0022] Example 2: A biodegradable bio-based medical polymer composite material, characterized by comprising the following raw materials in parts by weight: 85 parts of polylactic acid, 40 parts of polycaprolactone, 12 parts of a hydrophilic modifier, 40 parts of a toughening agent, 4 parts of a functional filler, and 0.2 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

[0023] The hydrophilic modifier is HL560.

[0024] The toughening agent is polybutylene adipate-terephthalate.

[0025] The antioxidant is antioxidant 1010.

[0026] The functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to pH=4, and the mixture was stirred at a constant speed for 30 minutes. Nano-silica was added, the temperature was raised to 65°C, and the mixture was stirred at a constant speed and reacted for 4-6 hours. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol and deionized water for 3 times respectively, and vacuum-dried at 85°C to obtain a functional filler. The weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution was controlled to be 10:3:50.

[0027] The preparation method of the biodegradable bio-based medical polymer composite material comprises the following steps: After drying, polylactic acid, polycaprolactone, a hydrophilic modifier, and a toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded, and granulated to produce a biodegradable bio-based medical polymer composite material. The extruder processing temperature and die head temperature are controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed is 120 r / min.

[0028] Example 3: A biodegradable bio-based medical polymer composite material, characterized by comprising the following raw materials in parts by weight: 90 parts of polylactic acid, 50 parts of polycaprolactone, 14 parts of a hydrophilic modifier, 45 parts of a toughening agent, 4 parts of a functional filler, and 0.2 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

[0029] The hydrophilic modifier is HL560.

[0030] The toughening agent is polybutylene succinate.

[0031] The antioxidant is antioxidant 168.

[0032] The functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to pH=5, the mixture was stirred at a constant speed for 30 minutes, nano-silica was added, the temperature was raised to 65-70°C, the mixture was stirred at a constant speed and reacted for 6 hours, and the mixture was centrifuged after the reaction was completed. The mixture was washed three times with anhydrous ethanol and deionized water respectively, and vacuum dried at 85°C to obtain a functional filler. The weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution was controlled to be 10:5:50.

[0033] The preparation method of the biodegradable bio-based medical polymer composite material comprises the following steps: After drying, polylactic acid, polycaprolactone, a hydrophilic modifier, and a toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded, and granulated to produce a biodegradable bio-based medical polymer composite material. The extruder processing temperature and die head temperature are controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed is 120 r / min.

[0034] Example 4: A biodegradable bio-based medical polymer composite material, characterized by comprising the following raw materials in parts by weight: 100 parts of polylactic acid, 70 parts of polycaprolactone, 15 parts of a hydrophilic modifier, 50 parts of a toughening agent, 5 parts of a functional filler, and 0.3 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

[0035] The hydrophilic modifier is HL560.

[0036] The toughening agent is polybutylene succinate.

[0037] The antioxidant is antioxidant 168.

[0038] The functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to pH=5, and the mixture was stirred at a constant speed for 30 minutes. Nano-silica was added, the temperature was raised to 70°C, and the mixture was stirred at a constant speed and reacted for 6 hours. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol and deionized water for 3 times, respectively. The mixture was vacuum-dried at 85°C to obtain a functional filler. The weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution was controlled to be 10:5:50.

[0039] A method for preparing a biodegradable bio-based medical polymer composite material comprises the following steps: After drying, polylactic acid, polycaprolactone, a hydrophilic modifier, and a toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded, and granulated to produce a biodegradable bio-based medical polymer composite material. The extruder processing temperature and die head temperature are controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed is 120 r / min.

[0040] Comparative Example 1: Compared with Example 1, this comparative example uses nano-silica as the functional filler. The rest is the same as Example 1. The preparation method is as follows: Weigh the following raw materials in parts by weight: 80 parts of polylactic acid, 30 parts of polycaprolactone, 10 parts of hydrophilic modifier, 30 parts of toughening agent, 3 parts of nano-silica, and 0.1 parts of antioxidant; The hydrophilic modifier is HL560.

[0041] The toughening agent is polybutylene adipate-terephthalate.

[0042] The antioxidant is antioxidant 1010.

[0043] After drying, polylactic acid, polycaprolactone, a hydrophilic modifier, and a toughening agent are fed into a twin-screw extruder, nano-silica and an antioxidant are added, melt-extruded, and granulated to produce a biodegradable bio-based medical polymer composite material. The extruder processing temperature and die head temperature are controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed is 120 r / min.

[0044] The properties of the composite materials prepared in Examples 1-4 and Comparative Example 1 were tested, and the results are shown in Table 1 below: Table 1 It can be seen from Table 1 above that the composite materials prepared in Examples 1-4 of the present invention have excellent mechanical properties, and after hydrophilic modification, the contact angle is reduced by 5-6° compared with pure polylactic acid, indicating that the hydrophilic modifier has undergone hydrophilic modification.

[0045] The above embodiments are only intended to help understand the method and core concept of the present invention. It should be noted that, without departing from the principles of the present invention, a number of improvements and modifications may be made to the present invention by those skilled in the art, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A biodegradable bio-based medical polymer composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of polylactic acid, 30-70 parts of polycaprolactone, 10-15 parts of a hydrophilic modifier, 30-50 parts of a toughening agent, 3-5 parts of a functional filler, and 0.1-0.3 parts of an antioxidant; The functional filler is nano silicon dioxide grafted with a silane coupling agent.

2. The biodegradable bio-based medical polymer composite material according to claim 1, characterized in that: The hydrophilic modifier is HL560.

3. The biodegradable bio-based medical polymer composite material according to claim 1, characterized in that: The toughening agent is polybutylene adipate-terephthalate or polybutylene succinate.

4. The degradable bio-based medical polymer composite material according to claim 1, characterized in that: The antioxidant is antioxidant 1010 or antioxidant 168.

5. The degradable bio-based medical polymer composite material according to claim 1, characterized in that: The functional filler is prepared by the following steps: Octadecyltrimethoxysilane was added to a 25% ethanol aqueous solution, the pH was adjusted to 4-5, and the mixture was stirred at a constant speed for 30 minutes. Nano-silica was added, and the temperature was raised to 65-70°C. The mixture was stirred at a constant speed and reacted for 4-6 hours. After the reaction, the mixture was centrifuged and washed with anhydrous ethanol and deionized water for 3 times respectively, and then dried in a vacuum at 85°C to obtain a functional filler.

6. The degradable bio-based medical polymer composite material according to claim 5, characterized in that: The weight ratio of octadecyltrimethoxysilane, nano-alumina powder and ethanol aqueous solution is controlled to be 10:3-5:

50.

7. The method for preparing the degradable bio-based medical polymer composite material according to claim 1, characterized in that: The steps include: After drying, polylactic acid, polycaprolactone, hydrophilic modifier and toughening agent are fed into a twin-screw extruder, functional fillers and antioxidants are added, melt-extruded and granulated to produce a degradable bio-based medical polymer composite material.

8. The method for preparing the degradable bio-based medical polymer composite material according to claim 7, characterized in that: The extruder processing temperature and die head temperature were controlled at 120-150°C, 160-165°C, 170-175°C, and 180-185°C, and the extruder speed was 120 r / min.

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