Antibacterial Polyetheretherketone / Polyphenylsulfone Triple Shape Memory Composite Material

Abstract

The present invention relates to the technical field of shape memory composite materials, and particularly to an antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material, which comprises a resin and an antibacterial agent; the resin is composed of PEEK and PPSU in a mass ratio of 70:30 to 50:50; its preparation method comprises the following steps: mixing PEEK and PPSU evenly to form a melt blending system, adding an antibacterial agent thereto, first performing melt spinning, and then cooling and solidifying the filament to obtain a fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material; by designing and adjusting the proportions among PEEK, PPSU and the antibacterial agent, the prepared composite material has a good triple shape memory effect, and the proportions among the three can regulate the shape memory temperature and antibacterial effect, so that the composite material can respond to different temperature stimuli and return from multiple preset temporary shapes to the initial shape.

Description

Technical Field

[0001] The present invention relates to the technical field of shape memory composite materials, and particularly to an antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material. Background Art

[0002] Shape memory composite materials are intelligent materials that can change their shape under specific conditions and then return to their original shape. Such materials typically contain a fixed phase and a reversible phase, which crosslink to form an interpenetrating polymer network structure. The fixed phase is mainly responsible for memorizing the original shape of the material and can be chemical crosslinking points (thermosetting) or physical crosslinking points (thermoplastic). The reversible phase, on the other hand, has the ability to deform and can be in a crystalline state and an amorphous state, and its transition temperature (T trans ) can be the melting temperature (T m ) or the glass transition temperature (T g ), enabling the material to undergo a phase change at a specific temperature, thereby triggering the shape memory effect.

[0003] Shape memory composite materials are widely used in multiple fields, including aerospace, biomedicine, electronic devices, smart textiles, and self-assembly technology. For example, in the aerospace field, they are used to manufacture complex structural components; in the biomedicine field, they are used to manufacture surgical sutures and vascular stents; in electronic devices, they are used to manufacture flexible connection components.

[0004] Although shape memory composite materials have broad application potential, they also face some technical challenges. For example, shape memory alloys have limitations in biocompatibility, deformation recovery, driving speed, and fatigue life. In addition, existing shape memory materials often only have a single or dual shape memory effect, which limits their use in complex applications. Moreover, the demand for materials with antibacterial properties in the medical field is increasing to reduce the risk of postoperative infections. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides an antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material. The composite material of the present invention not only has good antibacterial properties but also has a good triple shape memory effect.

[0006] To achieve the above object, the present invention is realized through the following technical solutions:

[0007] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material comprises 100 parts by mass of resin and an antibacterial agent within the range of 0% - 30% of the mass of the resin;

[0008] The resin is composed of PEEK and PPSU in a mass ratio of 70:30 to 40:60. For example, typical ratios of PEEK and PPSU include the point values of 70:30, 60:40, 50:50, and 40:60.

[0009] Its preparation method includes the following steps:

[0010] Mix PEEK and PPSU evenly to form a melt blending system, add an antibacterial agent thereto, first perform melt spinning, and then cool and solidify the filament to obtain a fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material.

[0011] Furthermore, the antibacterial agent is carried on zeolite and loaded with antibacterial ions; the antibacterial ions are selected from one or more of silver ions, zinc ions, zirconium ions, and copper ions, the configuration of the zeolite is selected from clinoptilolite or type A zeolite, the particle size of the zeolite is 100 - 200 μm; the loading mass percentage of the antibacterial ions in the antibacterial agent is 0.5 - 1%.

[0012] Even further, the preparation method of the antibacterial agent includes the following steps: Place the zeolite in an aqueous solution of nitrate, carry out a heating and mixing reaction under dark conditions, maintain the pH value of the system between 6 - 8 during this period, perform solid-liquid separation, wash and dry multiple times, and then calcine.

[0013] Preferably, the nitrate is selected from one or more of silver nitrate, zinc nitrate, zirconium nitrate, and copper nitrate, and the molar concentration range of the aqueous solution of the nitrate is 0.1 - 0.5 mol / L.

[0014] Preferably, the temperature of the heating and mixing reaction is 50 - 70 °C, the reaction time is 3 - 5 h; the temperature of the calcination is 350 - 420 °C, and the time is 40 - 80 min.

[0015] Furthermore, the antibacterial agent accounts for 5% - 25% of the mass of the resin.

[0016] Furthermore, the melt blending system is formed by a screw extruder, the temperature of the melt blending is 250 - 280 °C, and the antibacterial agent is added at the side feeding port of the screw extruder; the fiber diameter of the fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is 200 - 500 μm; the cooling and solidification of the filament is carried out by using multiple cooling rollers to cool the spinning, and the temperature of the cooling rollers is lower than the long-term use temperature of PPSU, such as the temperature of the cooling rollers is set between 180 °C - 200 °C.

[0017] Beneficial technical effects:

[0018] By adjusting the ratios among PEEK, PPSU, and zeolite antibacterial agent loaded with antibacterial ions, the prepared composite material has good triple shape memory effect. The ratios among the three can regulate the response temperature of the shape memory effect and the antibacterial effect, enabling the composite material to respond to different temperature stimuli and recover from multiple preset temporary shapes to the initial shape.

[0019] By selecting a corresponding zeolite with better heat resistance as the carrier of antibacterial ions, the antibacterial rate is as high as 96%, which is especially suitable for the medical field and can reduce the risk of infection. The composite material of the present invention greatly broadens its application potential in the fields of biomedicine, aerospace, intelligent wear, etc. The preparation method of the present invention is simple and easy to scale up production. Detailed implementation manners

[0020] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way constitutes a limitation on the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0021] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the said technologies and methods should be regarded as part of the specification. In all examples shown and discussed here, any specific value should be construed as merely exemplary, and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0022] For the experimental methods without specific conditions indicated in the following embodiments, they are usually determined according to national standards; if there are no corresponding national standards, they are carried out according to general standard requirements or general methods.

[0023] Example 1

[0024] Antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material, including 100 parts by mass of resin; the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30;

[0025] Its preparation method includes the following steps:

[0026] After mixing PEEK and PPSU evenly according to the ratio, they are added to a twin-screw extruder to form a molten blend system at 250 °C. After melt spinning and cooling and solidifying the filaments in sequence, a fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material with a fiber diameter of 200 - 500 μm is prepared.

[0027] Example 2

[0028] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material includes 100 parts by mass of resin and 5% by mass of silver-loaded clinoptilolite antibacterial agent based on the resin; the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30.

[0029] Its preparation method includes the following steps:

[0030] After mixing PEEK and PPSU evenly according to the ratio, they are added to a twin-screw extruder to form a molten blend system at 250 °C. At the same time, the silver-loaded clinoptilolite antibacterial agent is added to the side feeding port of the twin-screw extruder for co-melting and blending. After melt spinning and cooling and solidifying the filaments in sequence, a fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material with a fiber diameter of 200 - 500 μm is prepared.

[0031] The preparation method of the silver-loaded clinoptilolite antibacterial agent in this case is as follows: 10 g of clinoptilolite powder (powder particle size 100 - 200 μm) is added to 100 mL of 0.1 mol / L AgNO 3 solution, and a heating and mixing reaction is carried out under dark conditions. The temperature of the heating and mixing reaction is 60 °C, and the mixing time lasts for 4 h. During this period, dilute nitric acid (0.1 mol / L) is used to maintain the pH value of the solution between 6 and 8. After the reaction is completed, vacuum filtration is carried out for solid-liquid separation. The separated solid sample is redispersed in 100 mL of distilled water for washing to remove possible residues. After repeating the washing and filtration steps many times to ensure the sample is clean, it is dried at 90 °C for 12 h to remove moisture; the dried sample is then placed in a muffle furnace and heated from room temperature to 400 °C at a rate of 10 °C / min and calcined at the final temperature for 1 h, and then cooled naturally. Finally, silver-loaded clinoptilolite is obtained, and the mass percentage of silver loaded in the antibacterial agent is about 0.5 - 0.8%, and the silver content slightly decreases after calcination.

[0032] Example 3

[0033] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material includes 100 parts by mass of resin and 10% by mass of silver-loaded clinoptilolite (the same as in Example 2) based on the resin; the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30.

[0034] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2.

[0035] Example 4

[0036] The composite material in this example has the same preparation process as that in Example 2, except that the resin composition: the mass ratio of PEEK to PPSU is 60:40.

[0037] Example 5

[0038] The composite material in this example has the same preparation process as that in Example 2, except that the resin composition: the mass ratio of PEEK to PPSU is 50:50.

[0039] Example 6

[0040] The composite material in this example has the same preparation process as that in Example 2, except that the resin composition: the mass ratio of PEEK to PPSU is 40:60.

[0041] Example 7

[0042] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material includes 100 parts by mass of resin and silver-loaded clinoptilolite accounting for 15% of the mass of the resin (the same as in Example 2); the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30;

[0043] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2.

[0044] Example 8

[0045] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material includes 100 parts by mass of resin and silver-loaded clinoptilolite accounting for 20% of the mass of the resin (the same as in Example 2); the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30;

[0046] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2.

[0047] Example 9

[0048] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material includes 100 parts by mass of resin and silver-loaded clinoptilolite accounting for 25% of the mass of the resin (the same as in Example 2); the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 70:30;

[0049] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2.

[0050] Example 10

[0051] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material comprises 100 parts by mass of resin and silver-loaded clinoptilolite accounting for 20% of the mass of the resin (the same as in Example 2); the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 60:40.

[0052] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2, except that the temperature of melt blending is 280°C.

[0053] Example 11

[0054] The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material comprises 100 parts by mass of resin and silver-loaded clinoptilolite accounting for 20% of the mass of the resin (the same as in Example 2); the resin is composed of PEEK and PPSU, and the mass ratio of PEEK to PPSU is 50:50.

[0055] The preparation of the antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is the same as that in Example 2, except that the temperature of melt blending is 280°C.

[0056] Comparative Example 1

[0057] The composite material in this case has the same preparation process as that in Example 2, except that the resin is only PEEK.

[0058] Comparative Example 2

[0059] The composite material in this case has the same preparation process as that in Example 2, except that the resin is only PPSU.

[0060] Comparative Example 3

[0061] The composite material in this case has the same preparation process as that in Example 2, except that the resin composition: the mass ratio of PEEK to PPSU is 80:20.

[0062] Comparative Example 4

[0063] The composite material in this case has the same preparation process as that in Example 2, except that zeolite loading is not adopted, and nano-silver is directly added at the side feeding port, and other operations are the same as in Example 2. The proportion of nano-silver in the composite material is 1%.

[0064] Test Example

[0065] The composite material in the above case was compression molded (molding temperature: 400 - 420 °C, molding pressure: 100 - 150 MPa, molding time: 1 min) to obtain a spline (spline size: 50 mm × 3 mm × 1 mm), and its shape memory was tested. The test method is as follows:

[0066] First, prepare two "straight bar" samples (this is the permanent shape S 0 ). Deform them under the programming temperature T prog1 (240 °C) and an external force, and cool them down to T prog2 (150 °C). Remove the external force to obtain a "JL" shape (this is the first temporary shape S 1 );

[0067] Then, further deform them under the external force at 150 °C and cool them down to 25 °C. Remove the external force to obtain a "70" shape (this is the second temporary shape S 2 );

[0068] Finally, heat the sample to 150 °C and 240 °C in sequence, and examine the shape recovery time of the spline from the second temporary shape "70" to the first temporary shape "JL" and the permanent shape "straight bar". The driving force for the shape recovery of the spline is provided by the entropy elasticity of the molecular chain segments.

[0069] The shape fixation rate and shape recovery rate of the material were tested using a Q800 dynamic thermomechanical analyzer from TA Instruments, USA.

[0070] The triple shape memory test method is as follows: (i) The sample is stretched from the initial shape (ε prog1 (T g1 + 10 °C)) to a 5% deformation (ε S0 ) under the first programming temperature T S1,load and an external force; (ii) Cool it down to the second programming temperature T prog2 (T g2 + 10 °C), remove the force, and obtain the first temporary shape (ε S1 ); (iii) Under T prog2 and an external force, stretch the sample to a 10% deformation (ε S2,load ); (iv) Cool it down to 25 °C, remove the force, and obtain the second temporary shape (ε S2 ); (v) In the shape recovery stage, heat it up to T prog2 , and the shape recovers to ε S1,rec ; (vi) Heat it up to T prog1 , and the deformation recovers to ε S0,rec . The R f and R r of the triple shape memory are calculated from formulas (1 - 1), (1 - 2), (1 - 3), and (1 - 4).

[0071]

[0072] The data are shown in Table 1 and Table 2.

[0073] Performance of each embodiment in Table 1

[0074]

[0075]

[0076] Performance of the embodiment and its comparative example in Table 2

[0077]

[0078] As can be seen from Table 1 and Table 2, the antibacterial composite material of the present invention has a good triple shape memory effect by designing and adjusting the ratio among PEEK, PPSU and the antibacterial agent. Both the shape fixing effect and the shape recovery effect are good, and the shape recovery time is also short. However, the antibacterial composite material made only of polyetheretherketone or polyphenylsulfone does not have the triple shape memory effect.

[0079] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. Antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material, characterized in that: The invention comprises 100 parts by weight of a resin and an antibacterial agent, wherein the antibacterial agent accounts for 5% to 10% of the weight of the resin; The resin is composed of PEEK and PPSU in a mass ratio of 70:30 to 40:60; The antibacterial agent uses zeolite as a carrier and carries antibacterial ions, wherein the antibacterial ions are silver ions, the configuration of the zeolite is clinoptilolite, and the particle size of the zeolite is 100-200 μm; the loading mass percentage of the antibacterial ions in the antibacterial agent is 0.5-1%; The method for preparing the composite material comprises the following steps: PEEK and PPSU are uniformly mixed to form a melt blend system, an antibacterial agent is added thereto, and the mixture is first melt-spun and then cooled and solidified to obtain a fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material.

2. The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material according to claim 1, characterized in that: The preparation method of the antibacterial agent comprises the following steps: The zeolite is placed in an aqueous solution of silver nitrate, and heated and mixed to react in the dark, during which the pH value of the system is maintained between 6 and 8, and the solid and liquid are separated, and after multiple washing and drying, the zeolite is calcined.

3. The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material according to claim 2, characterized in that: The molar concentration of the aqueous solution of silver nitrate is in the range of 0.1-0.5 mol / L.

4. The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material according to claim 2, characterized in that: The temperature of the heating mixing reaction is 50-70° C. and the reaction time is 3-5 hours; the temperature of the roasting is 350-420° C. and the time is 40-80 minutes.

5. The antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material according to claim 1, characterized in that: The melt blending system is formed by a screw extruder, the melt blending temperature is 250-280° C., and the antibacterial agent is added at the side feeding port of the screw extruder; The fiber diameter of the fibrous antibacterial polyetheretherketone / polyphenylsulfone triple shape memory composite material is 200-500 μm; The filaments are cooled and solidified by using a plurality of cooling rollers for spinning cooling, and the temperature of the cooling rollers is lower than the long-term use temperature of PPSU.

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