Medical polycarbonate and preparation method thereof

Abstract

The invention belongs to the field of medical engineering plastics, and particularly relates to medical polycarbonate and a preparation method thereof. The medical polycarbonate is prepared from the following components in parts by mass: 100 to 120 parts of polycarbonate, 10 to 20 parts of 4-nitro-2-(2-propynyloxy) aniline, 15 to 20 parts of 1, 3, 5-tri (p-formylphenyl) benzene, 0.5 to 2 parts of heparin and 0.1 to 0.2 part of a cross-linking agent. According to the invention, the framework material with a topological structure is used as an intermediate carrier, and the framework material can be stably matched with the polycarbonate, so that the heparin can be stably matched with the polycarbonate by virtue of the framework material, the heparin is prevented from falling off, and the anticoagulant stability of the polycarbonate is improved.

Description

Technical Field

[0001] The invention belongs to the field of medical engineering plastics, and in particular relates to medical polycarbonate and a preparation method thereof. Background Art

[0002] Polycarbonate is a common medical engineering plastic with good biocompatibility, mechanical properties and light transmittance, which are more compatible with the requirements of medical polymer materials. However, polycarbonate will stimulate the coagulation mechanism when it comes into contact with blood. Therefore, medical devices such as hemodialysis machines cannot be directly manufactured with polycarbonate, and the anti-coagulation properties of polycarbonate need to be modified.

[0003] At present, in order to improve the anticoagulant performance of polycarbonate, heparin is usually used to modify polycarbonate. Heparin is an effective anticoagulant. The common method of combining heparin and polycarbonate is to directly coat heparin on the surface of polycarbonate. However, the combination between heparin and polycarbonate using this method is not stable. After being stored for a long time, the heparin on the surface of polycarbonate may fall off. Summary of the invention

[0004] In order to solve the problems existing in the above-mentioned prior art, the present invention provides a medical polycarbonate and a preparation method thereof, which adopts a framework material with a topological structure as an intermediate carrier. The framework material can form a stable combination with the polycarbonate, so that heparin can form a stable combination with the polycarbonate with the help of the framework material, thereby avoiding the shedding of heparin and improving the anti-coagulation stability of the polycarbonate.

[0005] The specific technical solution adopted by the present invention is:

[0006] A medical polycarbonate comprises, by weight, 100-120 parts of polycarbonate, 10-20 parts of 4-nitro-2-(2-propynyloxy)aniline, 15-20 parts of 1,3,5-tri(p-formylphenyl)benzene, 0.5-2 parts of heparin and 0.1-0.2 parts of a crosslinking agent.

[0007] The cross-linking agent includes any one of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and dicyclohexylcarbodiimide.

[0008] A method for preparing medical polycarbonate comprises the following steps:

[0009] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and a reaction solvent into a reaction kettle, and heating the reaction to generate a framework material;

[0010] S2, then adding heparin and the framework material into an organic solvent, and then adding a cross-linking agent to react to generate an anticoagulant framework material;

[0011] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, and then dropping dilute hydrochloric acid solution to adjust the pH value to 8-9 to prepare a buffer solution;

[0012] S4. Add the anticoagulant framework material to the buffer solution, stir evenly to form a loading liquid, then put the polycarbonate into the loading liquid, react at room temperature for 8-12 hours, and obtain the medical polycarbonate after drying.

[0013] The reaction solvent includes any one of anhydrous tetrahydrofuran, ethanol, methanol and toluene, and the mass ratio of the reaction solvent to 4-nitro-2-(2-propynyloxy)aniline is 15-20:1.

[0014] The heating temperature in step S1 is 90-120° C., and the reaction time is 8-12 hours.

[0015] The organic solvent in step S2 includes any one of methanol, ethanol, benzene, toluene, cyclohexane, and methylcyclohexane.

[0016] The molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.03-0.06 mol / L.

[0017] The polycarbonate is subjected to an antioxidant treatment before being placed in the loading liquid, and the antioxidant treatment comprises the following steps:

[0018] A. dissolving polycarbonate in acetone to form a polycarbonate solution;

[0019] B. Put nano zinc oxide into acetone, then add antioxidant, stir evenly at a rate of 2000-3000r / min, and complete the antioxidant treatment of polycarbonate after drying.

[0020] The mass ratio of the polycarbonate, nano zinc oxide and antioxidant is 100:1-2:1-2.

[0021] The antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 10:1-3.

[0022] The beneficial effects of the present invention are:

[0023] 1. In order to improve the binding stability between heparin and polycarbonate, the present invention uses a framework material with a topological structure as an intermediate carrier. First, the hydroxyl group of heparin is cross-linked with the amino group of the framework material by chemical reaction to form a stable cross-linking bond between the two, and then the framework material is coated on the surface of the polycarbonate. Since the framework material has a hexahedral solid structure, the framework material will form a stable combination with the polycarbonate, so that the heparin forms a stable combination with the polycarbonate with the help of the framework material, avoiding the shedding of heparin and improving the anti-coagulation stability of the polycarbonate.

[0024] 2. The present invention also performs an antioxidant treatment on polycarbonate. The conventional antioxidant treatment of polycarbonate generally involves uniformly mixing polycarbonate powder and antioxidant powder and then re-forming polycarbonate using an extruder. However, this method causes uneven distribution of antioxidants in polycarbonate, resulting in the problem of local yellowing. In the present invention, polycarbonate is first dissolved into a liquid. The polycarbonate is dissolved in acetone, which causes the surface of polycarbonate molecules to become rough, thereby providing a place for nano zinc oxide to be embedded in the polycarbonate. On the one hand, nano zinc oxide can produce a composite synergistic effect with hindered phenol antioxidants and phosphite antioxidants, thereby improving the anti-yellowing performance of polycarbonate and preventing color change. In addition, the porous structure of nano zinc oxide can be more stably matched with the cage-like frame material, further improving the bonding stability between the frame material and polycarbonate, thereby preventing the shedding of heparin. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. 1. Specific embodiments

[0027] Example 1

[0028] S0, weigh 110 parts of polycarbonate, 15 parts of 4-nitro-2-(2-propynyloxy)aniline, 18 parts of 1,3,5-tri(p-formylphenyl)benzene, 1 part of heparin, and 0.15 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide;

[0029] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and anhydrous tetrahydrofuran into a reaction kettle, and reacting at 100° C. for 10 h to generate a framework material;

[0030] S2, then adding heparin and the framework material into methanol, and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide to react and generate an anticoagulant framework material;

[0031] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, then dropping a dilute hydrochloric acid solution to adjust the pH to 8.5 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.05 mol / L;

[0032] S4, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring evenly at a rate of 2500 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0033] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:1.5:1.5, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:2;

[0034] S5. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 10 hours, and obtain the medical polycarbonate after drying.

[0035] Example 2

[0036] S0, weigh 100 parts of polycarbonate, 10 parts of 4-nitro-2-(2-propynyloxy)aniline, 15 parts of 1,3,5-tri(p-formylphenyl)benzene, 0.5 parts of heparin, and 0.1 parts of dicyclohexylcarbodiimide;

[0037] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and anhydrous tetrahydrofuran into a reaction kettle, and reacting at 90° C. for 12 h to generate a framework material;

[0038] S2, then adding heparin and the framework material into methanol, and then adding dicyclohexylcarbodiimide to react to generate an anticoagulant framework material;

[0039] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, then dropping a dilute hydrochloric acid solution to adjust the pH to 8.0 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.03 mol / L;

[0040] S4, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring evenly at a rate of 2000 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0041] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:1:1, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:1;

[0042] S5. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, and then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 8 hours, and obtain the medical polycarbonate after drying.

[0043] Example 3

[0044] S0, weigh 120 parts of polycarbonate, 20 parts of 4-nitro-2-(2-propynyloxy)aniline, 20 parts of 1,3,5-tri(p-formylphenyl)benzene, 2 parts of heparin, and 0.2 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide;

[0045] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and anhydrous tetrahydrofuran into a reaction kettle, and reacting at 120° C. for 8 h to generate a framework material;

[0046] S2, then adding heparin and the framework material into methanol, and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide to react and generate an anticoagulant framework material;

[0047] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, then dropping a dilute hydrochloric acid solution to adjust the pH to 9.0 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.06 mol / L;

[0048] S4, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring evenly at a rate of 3000 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0049] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:2:2, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:3;

[0050] S5. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 12 hours, and obtain the medical polycarbonate after drying.

[0051] Example 4

[0052] S0, weigh 105 parts of polycarbonate, 12 parts of 4-nitro-2-(2-propynyloxy)aniline, 16 parts of 1,3,5-tri(p-formylphenyl)benzene, 0.8 parts of heparin, and 0.12 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide;

[0053] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and anhydrous tetrahydrofuran into a reaction kettle, and reacting at 95° C. for 11 h to generate a framework material;

[0054] S2, then adding heparin and the framework material into methanol, and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide to react and generate an anticoagulant framework material;

[0055] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, then dropping a dilute hydrochloric acid solution to adjust the pH to 8.0 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.04 mol / L;

[0056] S4, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring evenly at a rate of 2500 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0057] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:1.2:1.2, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:1.5;

[0058] S5. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 10 hours, and obtain the medical polycarbonate after drying.

[0059] Example 5

[0060] S0, weigh 115 parts of polycarbonate, 18 parts of 4-nitro-2-(2-propynyloxy)aniline, 18 parts of 1,3,5-tri(p-formylphenyl)benzene, 1.8 parts of heparin, and 0.18 parts of 1-ethyl-(3-dimethylaminopropyl)carbodiimide;

[0061] S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and anhydrous tetrahydrofuran into a reaction kettle, and reacting at 110° C. for 9 hours to generate a framework material;

[0062] S2, then adding heparin and the framework material into methanol, and then adding 1-ethyl-(3-dimethylaminopropyl)carbodiimide to react and generate an anticoagulant framework material;

[0063] S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, then dropping a dilute hydrochloric acid solution to adjust the pH to 9.0 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.06 mol / L;

[0064] S4, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring evenly at a rate of 3000 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0065] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:1.8:1.8, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:2.5;

[0066] S5. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 10 hours, and obtain the medical polycarbonate after drying.

[0067] Comparative Example 1

[0068] The only difference between Comparative Example 1 and Example 1 is that no frame material is used as an intermediate carrier in Comparative Example 1. The specific steps of Comparative Example 1 are as follows:

[0069] S0, weigh 110 parts of polycarbonate and 1 part of heparin;

[0070] S1, dissolving tris(hydroxymethyl)aminomethane in water, dissolving it completely by ultrasonication, and then dropping dilute hydrochloric acid solution to adjust the pH to 8.5 to prepare a buffer solution, wherein the molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.05 mol / L;

[0071] S2, dissolving polycarbonate in acetone to form a polycarbonate solution, placing nano zinc oxide in the acetone, then adding an antioxidant, stirring at a rate of 2500 r / min, and completing the antioxidant treatment of the polycarbonate after drying;

[0072] The mass ratio of polycarbonate, nano zinc oxide and antioxidant is 100:1.5:1.5, and the antioxidant includes hindered phenol antioxidant 1010 and phosphite antioxidant 168 in a mass ratio of 10:2;

[0073] S3. Add heparin to the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate treated with antioxidants in the loading liquid, react at room temperature for 10 hours, and obtain medical polycarbonate after drying.

[0074] Comparative Example 2

[0075] The only difference between Comparative Example 2 and Example 1 is that nano zinc oxide is not added during the oxidation treatment process in Comparative Example 2.

[0076] Comparative Example 3

[0077] The only difference between Comparative Example 3 and Example 1 is that no antioxidant is added during the oxidation treatment process in Comparative Example 3.

[0078] 2. Performance Test

[0079] The surface heparin weight a1 of the medical polycarbonate prepared in the embodiment and the comparative example was measured, and then the surface heparin weight a2 was measured again after the medical polycarbonate was placed in an ultrasonic cleaning machine for 60 minutes. The heparin residual rate was a2 / a1, and the heparin content was determined by toluidine blue colorimetry; Antioxidant performance test The medical polycarbonate prepared in the embodiment and the comparative example was prepared into a 3mm thick test piece, and after irradiation with 30kGy dose of Co-60γ ray, it was placed under natural light for 15 days, and the yellow index before and after irradiation was determined according to the HG / T3862-2006 method. The results are shown in Table 1.

[0080] Table 1

[0081]

[0082] It can be seen from Table 1 that the framework material used as the intermediate carrier in Examples 1-5 and Comparative Examples 2-3 can effectively increase the binding stability between heparin and polycarbonate. At the same time, it can be seen from Example 1 and Comparative Example 2 that the porous structure of nano zinc oxide can be more stably matched with the cage-like framework material, further improving the binding stability between the framework material and polycarbonate.

[0083] By comparing Example 1 with Comparative Examples 2-3, it can be seen that nano zinc oxide, hindered phenol antioxidants, and phosphite antioxidants together produce a complex synergistic effect, and the three together produce an unexpected antioxidant effect, which far exceeds the antioxidant effect of the combination of the two.

Claims

1. A medical polycarbonate, It is characterized in that The invention comprises, by weight, 100-120 parts of polycarbonate, 10-20 parts of 4-nitro-2-(2-propynyloxy)aniline, 15-20 parts of 1,3,5-tri(p-formylphenyl)benzene, 0.5-2 parts of heparin and 0.1-0.2 parts of a cross-linking agent.

2. A medical polycarbonate according to claim 1, It is characterized in that The cross-linking agent includes any one of 1-ethyl-(3-dimethylaminopropyl)carbodiimide and dicyclohexylcarbodiimide.

3. A method for preparing a medical polycarbonate according to claim 1, It is characterized in that The following steps are involved: S1, adding 4-nitro-2-(2-propynyloxy)aniline, 1,3,5-tri(p-formylphenyl)benzene and a reaction solvent into a reaction kettle to react and generate a framework material; S2, then adding heparin and the framework material into an organic solvent, and then adding a cross-linking agent to react to generate an anticoagulant framework material; S3, dissolving tris(hydroxymethyl)aminomethane in water, sonicating to completely dissolve it, and then dropping dilute hydrochloric acid solution to adjust the pH value to 8-9 to prepare a buffer solution; S4. Add the anticoagulant framework material into the buffer solution, stir evenly to form a loading liquid, then immerse the polycarbonate in the loading liquid, react at room temperature for 8-12 hours, and obtain the medical polycarbonate after drying.

4. A method for preparing a medical polycarbonate according to claim 3, It is characterized in that The reaction solvent includes any one of anhydrous tetrahydrofuran, ethanol, methanol and toluene, and the mass ratio of the reaction solvent to 4-nitro-2-(2-propynyloxy)aniline is 15-20:

1.

5. The method for preparing a medical polycarbonate according to claim 3, It is characterized in that The heating temperature in step S1 is 90-120° C., and the reaction time is 8-12 hours.

6. The method for preparing a medical polycarbonate according to claim 3, It is characterized in that The organic solvent in step S2 includes any one of methanol, ethanol, benzene, toluene, cyclohexane, and methylcyclohexane.

7. The method for preparing a medical polycarbonate according to claim 3, It is characterized in that The molar concentration of tris(hydroxymethyl)aminomethane in the buffer solution is 0.03-0.06 mol / L.

8. The method for preparing a medical polycarbonate according to claim 3, It is characterized in that The polycarbonate is subjected to an antioxidant treatment before being placed in the loading liquid, and the antioxidant treatment comprises the following steps: A. dissolving polycarbonate in acetone to form a polycarbonate solution; B. Put nano zinc oxide into acetone, then add antioxidant, stir evenly at a rate of 2000-3000r / min, and complete the antioxidant treatment of polycarbonate after drying.

9. The method for preparing a medical polycarbonate according to claim 8, It is characterized in that The mass ratio of the polycarbonate, nano zinc oxide and antioxidant is 100:1-2:1-2.

10. The method for preparing a medical polycarbonate according to claim 8, It is characterized in that The antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 10:1-3.

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