CN108659472B - Method for regulating PPDO mechanical property and degradation rate based on crystallization temperature - Google Patents

Method for regulating PPDO mechanical property and degradation rate based on crystallization temperature Download PDF

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CN108659472B
CN108659472B CN201810428180.1A CN201810428180A CN108659472B CN 108659472 B CN108659472 B CN 108659472B CN 201810428180 A CN201810428180 A CN 201810428180A CN 108659472 B CN108659472 B CN 108659472B
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ppdo
degradation rate
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polydioxanone
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潘鹏举
郑映
单国荣
包永忠
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Zhejiang University ZJU
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Abstract

The invention relates to a biodegradable high polymer material technology, and aims to provide a method for regulating and controlling PPDO mechanical property and degradation rate based on crystallization temperature. The method comprises the following steps: melting the PPDO material at 140 ℃ for 3min by using a hot press, and then carrying out hot pressing on the material to form a film; crystallizing the membrane material at 0-90 ℃ for 0.5-40 h to obtain the PPDO membrane material crystallized at different temperatures. The invention can effectively and simply regulate and control the mechanical property and the degradation property of the material by changing the crystallization temperature of the PPDO material, thereby preparing the high-strength rapidly degradable PPDO material. In addition, the material can meet the actual application requirements by comprehensively regulating and controlling the performance of the PPDO material, thereby expanding the application range of the PPDO material. The method is simple and convenient, does not need to additionally add an auxiliary agent or a solvent, and has low production cost and little pollution.

Description

Method for regulating PPDO mechanical property and degradation rate based on crystallization temperature
Technical Field
The invention relates to a biodegradable high polymer material technology, in particular to a method for regulating and controlling PPDO mechanical property and degradation rate based on crystallization temperature.
Background
In recent years, biodegradable aliphatic polyesters have unique biodegradability, biocompatibility and bioabsorbability, and have been widely used in the field of biomedical degradable materials. The excellent biodegradability of the biodegradable polyester resin is mainly benefited by ester bonds in molecular chains, and the biodegradable polyester resin is easily attacked and broken under natural conditions, so that the biodegradable polyester resin is degraded. Currently, the most widely used aliphatic polyesters include polyglycolic acid (PGA), polylactic acid (PLA), Polycaprolactone (PCL), polydioxanone (PPDO), and the like.
PPDO is a typical thermoplastic aliphatic polyether ester material, has good biodegradability, biocompatibility and bioabsorbability, and is easy to process and form. PPDO has excellent flexibility compared with common aliphatic polyesters (such as PGA, PLA and the like) due to the ether bond contained in the molecular chain. Due to the excellent performance of PPDO, PPDO has wide application in the field of biomedical materials, such as surgical sutures, tissue engineering, plastic surgery, drug carriers, orthopedic repair materials and the like. Among them, surgical sutures are the main application field of the polymer material.
Surgical sutures can be classified into absorbable surgical sutures and non-absorbable surgical sutures according to their degradability, and among the absorbable artificial sutures, PGA (Dexon, Syneture corporation), PPDO (PDS, Ethicon corporation), and copolyester suture of glycolide and L-lactide (PLGA) (trade name vcyrol) are mainly used. An ideal surgical suture should satisfy the following conditions: the material has certain mechanical properties (such as proper mechanical strength), about 20 percent of extensibility, certain flexibility, certain wet strength and friction coefficient; the operation is convenient when sewing and knotting, and the knot holding performance is good after the knot is made; the suture line can keep certain strength in the body for a certain time; has adaptability to organism tissues, stable and reliable product quality, safety and the like. The PGA and PLGA suture has a braided multifilament structure in physical form, has a high friction coefficient and is vulnerable to wound injury. Compared with the polymers, PPDO has higher initial strength, better comprehensive performance and flexibility, can be prepared into a monofilament suture line, has high strength retention rate in a human body, and is particularly useful for suturing wounds with longer healing time. For faster healing wounds, however, the suture becomes a tissue drag when the support is lost. Various documents or patents report that the mechanical property and the degradation property of PPDO are regulated and controlled by blending or copolymerizing modified PPDO. The Duek research group has reported that the Young's modulus of PPDO/PLLA blends increases significantly with the addition of PLLA, but the rate of PPDO degradation in vitro decreases, prolonging their degradation time (J.Appl.Polym.Sci.2003,88,2744; J.Appl.Polym.Sci.2006,101, 1899). Patent US 5714551 reports that PLLA-PPDO block copolymers of different PLA contents have higher mechanical strength and toughness. Patents US 4653497 and US 5403347 report that in block copolymer sutures of dioxanone (PDO) and Glycolide (GA), the addition of GA shortens the suture absorption period, with the degradation rate increasing with the GA content. In general, solution blending is not beneficial to environmental protection, and the prepared product is difficult to remove the solvent and cannot be applied to the field of medicines; the block copolymerization operation has great difficulty and complex process, and is not easy to realize industrial production. Aiming at the defects, a suitable and convenient method is sought for regulating and controlling the mechanical property and the degradation property of the PPDO material, so that the property of the PPDO material meets the required requirements, and the PPDO material has more important significance for the practical application of PPDO.
According to previous researches, the crystallization or processing conditions of the biodegradable polyester material can influence the crystallization structure or the crystallinity of the biodegradable polyester material, so that the final properties of the product are changed. Therefore, it is one of the most convenient and effective methods to control the final properties of degradable polyester materials by changing their crystallization or processing conditions. In biodegradable polyesters such as PLA, Polybutyleneadipate (PBA), etc., it has been reported in the literature to change the final properties by changing the crystallization or processing conditions of the material. For PLA materials, solid state extrusion conditions have a significant impact on the mechanical properties of PLLA, where an increase in the extrusion draw ratio significantly increases the tensile strength and modulus of the material (macromol. symp.2006,242, 93). For PBA materials, changing the crystallization temperature can significantly affect the degradation properties of the material. The crystal structure and the crystallinity of the polymer can change remarkably at different crystallization temperatures, and the degradation rate of the alpha crystal form is obviously faster than that of the beta crystal form (Polym. Degrad. Stab.2005,87,191). At present, no patent or literature reports that the final performance of the PPDO material is regulated by changing the crystallization condition or the processing condition of the PPDO material.
Therefore, the invention changes the crystallization condition of the PPDO material to change the crystallization structure of the PPDO material, so as to regulate and control the mechanical property and the degradation property of the PPDO material, and ensure that the final property of the product meets the actual application requirement.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for regulating and controlling the mechanical property and the degradation rate of PPDO based on the crystallization temperature.
In order to solve the technical problem, the solution of the invention is as follows:
the method for regulating and controlling the mechanical property and the degradation rate of PPDO based on the crystallization temperature comprises the following steps:
(1) melting the PPDO material at 140 ℃ for 3min by using a hot press, and then carrying out hot pressing on the material to form a film; the structural formula of the polydioxanone is as follows:
Figure BDA0001652699360000021
(2) crystallizing the membrane material at 0-90 ℃ for 0.5-40 h to obtain a PPDO membrane material crystallized at different temperatures;
in the invention, when the film material is crystallized at 0-10 ℃, the yield strength of the finally obtained PPDO film material is 18.2-19.9 MPa, the Young modulus is 124.8-138.2 MPa, the elongation at break is 853.3-872.3%, and the degradation rate is 0.0009-0.0011 h-1In the meantime.
In the invention, when the membrane material is crystallized at 50-90 ℃, the yield strength of the finally obtained PPDO membrane material is 34.2-37.8 MPa, the Young modulus is 258.0-334.3 MPa, the elongation at break is 230.6-504.7%, and the degradation rate is 0.0021-0.0026 h-1In the meantime.
In the invention, the thickness of the membrane material obtained by hot-pressing membrane formation is 0.4 mm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention can effectively and simply regulate and control the mechanical property and the degradation property of the material by changing the crystallization temperature of the PPDO material, thereby preparing the high-strength rapidly degradable PPDO material. In addition, the material can meet the actual application requirements by comprehensively regulating and controlling the performance of the PPDO material, thereby expanding the application range of the PPDO material.
2. The method for regulating the PPDO material performance is simple and convenient, does not need to add an auxiliary agent or a solvent additionally, and is low in generation cost and less in pollution.
Drawings
FIG. 1 is a WAXD chart of examples 3 and 6.
FIG. 2 is a stress-strain curve for examples 3, 4, and 6.
FIG. 3 is a graph of the degradation kinetics of examples 3, 4, 6.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments below:
the raw materials used in the present invention are described belowPPDO is provided by Henan Hospital science and technology Limited, Tianjin, and has a viscosity average molecular weight of 1.2 × 105g/mol; sodium hydroxide was purchased from Shanghai Aladdin Biotechnology Ltd.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
In the following examples 1 to 6, a PPDO film was obtained in a crystalline state as follows:
(1) melting the PPDO material at 140 ℃ for 3min by using a hot press, and then carrying out hot pressing on the material to form a film; the structural formula of the polydioxanone is as follows:
Figure BDA0001652699360000031
(2) crystallizing the membrane material at 0-90 ℃ for 0.5-40 h to obtain a PPDO membrane material crystallized at different temperatures;
the specific crystallization temperatures in the examples are shown in Table 1.
TABLE 1 preparation conditions and methods of examples 1-6
Figure BDA0001652699360000041
Testing and analysis of sample Performance in the examples:
1. the crystal structure and crystal form of PPDO are analyzed by wide-angle X-ray diffractometer (WAXD). Melting PPDO in a hot press at 140 ℃ for 3min to eliminate heat history, pressing into slices with the thickness of about 0.4mm, quickly transferring to a 90 ℃ oven or a 10 ℃ low-temperature circulating water bath for isothermal crystallization for a certain time to ensure that the slices are completely crystallized, and carrying out WAXD analysis on the crystallized slices.
2. And (3) testing mechanical properties: the PPDO films crystallized at different temperatures were cut into standard dumbbell-shaped specimens with a length of about 35mm, a cross-sectional width of about 3.0mm and a thickness of about 0.4 mm. And (4) performing unidirectional tensile test by using a universal material testing machine, wherein the tensile rate is 20.0 mm/min. Each sample was tested in parallel at least five times and averaged.
3. And (3) testing the degradation performance: the PPDO films crystallized at different temperatures are cut into block-shaped samples with similar quality and size. Putting the block sample into a test tube containing 10mL of 0.02mol/L sodium hydroxide solution, degrading for a certain time in a constant-temperature oscillating water bath at 37 ℃, taking out, washing with deionized water for three times, drying in a vacuum oven to constant weight, weighing the mass, and calculating the degradation rate. Each sample was tested in triplicate and the average was taken.
As can be seen from fig. 1, the crystal structure of PPDO is significantly affected by the crystallization temperature. According to literature report, PPDO shows three diffraction peaks in 2 theta, 17.8 degrees, 19.2 degrees and 23.4 degrees
Figure BDA0001652699360000042
The crystal structures corresponding to the crystal planes of (210), (020) and (310) (macro mol. Rapid Commun.2004,25,1943), respectively, PPDO crystallized at 90 ℃ are consistent with the literature reports and show three obvious diffraction peaks, while no obvious (020) diffraction peak is observed for PPDO crystallized at low temperature (10 ℃), which indicates that PPDO crystallized at high temperature (90 ℃) and low temperature (10 ℃) has different crystal structures, therefore, the crystal structure formed by PPDO at high temperature is defined as α crystal form, and the crystal structure formed at low temperature is defined as α' crystal form.
From the stress-strain curve of the PPDO material of fig. 2, the yield strength, young's modulus and elongation at break of examples 1 to 6 were calculated, and the results are shown in table 2. As can be seen from Table 2, when PPDO is crystallized at a higher temperature, the yield strength and Young's modulus of the resulting material are higher, and the elongation at break is lower; when PPDO is crystallized at a lower temperature, the yield strength and Young modulus of the obtained material are lower, and the elongation at break is higher. As the crystallization temperature increases, the yield strength and Young's modulus of the PPDO material gradually increase, while the elongation at break gradually decreases. In examples 1-6, the yield strength of the PPDO material increased from 18.2MPa to 37.8MPa, the Young's modulus increased from 124.8MPa to 334.3MPa, and the elongation at break decreased from 872.3% to 230.6% as the crystallization temperature increased from 0 ℃ to 90 ℃. Therefore, the crystallization temperature of the PPDO material is increased, and the strength and the plasticity of the material can be obviously improved.
TABLE 2 mechanical Property parameter results of examples 1 to 6
Figure BDA0001652699360000051
As can be seen from FIG. 3, the degradation rate of PPDO is linear with time, so the slope of the degradation rate with time is used to represent the rate of degradation, as shown in Table 3. As can be seen from Table 3, the degradation rate increased from 0.0009h when the crystallization temperature was increased from 0 ℃ to 90 ℃-1Quickening to 0.0026h-1This indicates that increasing the crystallization temperature of the PPDO material can significantly increase the degradation rate of the material, that is, the α -form possesses a faster degradation rate.
TABLE 3 degradation Performance parameter results of examples 1-6
Degradation Rate (h)-1)
Example 1 0.0009
Example 2 0.0010
Example 3 0.0011
Example 4 0.0021
Example 5 0.0024
Example 6 0.0026
Based on the above results, it can be seen that when PPDO is crystallized at a lower temperature, the resulting material has a higher elongation at break, a lower yield strength and young's modulus, and a slower degradation rate. When PPDO is crystallized at a higher temperature, the elongation at break of the obtained material is lower, the yield strength and Young modulus are higher, and the degradation rate is faster. Therefore, the crystallization temperature can be changed, so that the crystal structure of the PPDO material is changed, and the PPDO material with controllable mechanical property and degradation rate is prepared.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (1)

1. A method for regulating and controlling mechanical properties and degradation rate of polydioxanone based on crystallization temperature is characterized by comprising the following steps:
(1) melting the polydioxanone material at 140 ℃ for 3min by using a hot press, and then carrying out hot pressing on the film-forming material; the structure of the repeating unit of the polydioxanone is as follows:
Figure DEST_PATH_IMAGE002
(2) crystallizing the membrane material at 0-90 ℃ for 0.5-40 h to obtain poly (p-dioxanone) membrane material crystallized at different temperatures;
when the membrane material is crystallized at the temperature of 0-10 ℃, the yield strength of the finally obtained poly (p-dioxanone) membrane material is 18.2-19.9 MPa, and poplarThe modulus of the material is 124.8 to 138.2MPa, the elongation at break is 853.3 to 872.3 percent, and the degradation rate is 0.0009 to 0.0011h-1To (c) to (d);
when the membrane material is crystallized at the temperature of 50-90 ℃, the yield strength of the finally obtained poly (p-dioxanone) membrane material is 34.2-37.8 MPa, the Young modulus is 258.0-334.3 MPa, the elongation at break is 230.6-504.7%, and the degradation rate is 0.0021-0.0026 h-1To (c) to (d);
the mechanical property data are obtained by the following method: cutting the poly (p-dioxanone) films crystallized at different temperatures into standard dumbbell-shaped sample strips, wherein the length of the sample strips is 35mm, the width of the cross section is 3.0mm, and the thickness is 0.4 mm; performing unidirectional tensile test by using a universal material testing machine, wherein the tensile rate is 20.0 mm/min; each sample was tested in parallel at least five times, and the mean value was taken; calculating the yield strength, Young modulus and elongation at break according to the stress-strain curve of the polydioxanone material;
the degradation rate data is obtained by: cutting poly (p-dioxanone) films crystallized at different temperatures into block-shaped samples, and ensuring the quality and the size to be similar; putting the block sample into a test tube containing 10mL of 0.02mol/L sodium hydroxide solution, degrading in a constant-temperature oscillating water bath at 37 ℃ for a certain time, taking out, washing with deionized water for three times, drying in a vacuum oven to constant weight, weighing the mass, and calculating the degradation rate; testing each sample in parallel for three times, and taking an average value; the degradation rate of the polydioxanone is in a linear relation with time, so the slope of the degradation rate and the time is used for expressing the speed of the degradation rate.
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