CN115896971A - Fiber and preparation method thereof and artificial ligament/tendon - Google Patents
Fiber and preparation method thereof and artificial ligament/tendon Download PDFInfo
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- CN115896971A CN115896971A CN202111167711.4A CN202111167711A CN115896971A CN 115896971 A CN115896971 A CN 115896971A CN 202111167711 A CN202111167711 A CN 202111167711A CN 115896971 A CN115896971 A CN 115896971A
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Abstract
The preparation method of the fiber comprises the following steps: mixing biocompatible ceramic powder and first polyester to form a ceramic powder composition, wherein the weight ratio of the biocompatible ceramic powder to the first polyester is 10: 90 to 60: 40; mixing the ceramic powder composition with second polyester to form a composite material, wherein the weight ratio of the ceramic powder composition to the second polyester is 0.4: 99.6-40: 60; and spinning the composite to form fibers; wherein the first polyester has an Intrinsic viscosity (Intrinsic viscosensitivity) of 0.35dL/g to 0.55dL/g, and the second polyester has an Intrinsic viscosity (Intrinsic viscosensitivity) of 0.6dL/g to 0.8dL/g. The fibers can be woven into artificial ligaments/tendons.
Description
Technical Field
The present disclosure relates to the composition of fibers, and more particularly to artificial ligaments/tendons woven from fibers.
Background
The current clinical treatment surgery is performed with autologous ligament/tendon artificial ligament/tendon. However, autologous tissue repair has its inconvenience and negative impact on the patient. After long-term use, the current commercially available artificial ligament/tendon is implanted and repaired, and the tissue compatibility is poor, reactions such as inflammation, hydrops, swelling and the like occur, the regeneration and integration of autologous tissues cannot be effectively promoted, and even the situations of abrasion, looseness and fracture occur. Therefore, there is a need for tissue compatible artificial ligament/tendon materials to overcome the tissue regeneration and repair problems in clinical or market situations. In the prior art, in order to make the artificial fiber have good biocompatibility, a ceramic powder coating with biocompatibility is usually coated on the fiber by an infiltration coating method, but the ceramic powder with biocompatibility cannot be uniformly dispersed in the fiber by the method, the coating layer is easy to peel off, the biocompatibility function is reduced, and the peeled off fragments are more likely to cause side effects such as inflammation and the like. In order to uniformly disperse ceramic powder having biocompatibility in a fiber, a dispersant is generally added to reduce the interfacial energy between the ceramic powder and a carrier resin, so that the ceramic powder is uniformly dispersed in the carrier resin. However, the commercially available dispersants, due to their small molecular weight and high content of reactive functional groups, are not only prone to migrate to the surface of the fiber and cause cytotoxicity, but also do not meet the medical regulatory specifications. In other words, common small molecule dispersants cannot be used in biocompatible ceramic powder-carrier resin composites.
In view of the above, there is a need for a new technology to disperse biocompatible ceramic powder in carrier resin, and then spin into fiber and weave into artificial ligament/tendon, so as to meet clinical or market requirements.
Disclosure of Invention
An embodiment of the present disclosure provides a fiber comprising: 0.5 to 4 parts by weight of a biocompatible ceramic powder region; and 96 to 99.5 parts by weight of a polyester region, wherein the biocompatible ceramic powder regions are distributed in the polyester region, at least 90% of the biocompatible ceramic powder regions have a diameter of 300nm or less and greater than 0nm, and the cell survival rate of the fiber in a biotoxicity test is greater than 70%.
The artificial ligament/tendon provided by an embodiment of the present disclosure is woven by the above fibers.
An embodiment of the present disclosure provides a method of making a fiber, comprising: mixing biocompatible ceramic powder and first polyester to form a ceramic powder composition, wherein the weight ratio of the biocompatible ceramic powder to the first polyester is 10: 90 to 60: 40; mixing the ceramic powder composition with second polyester to form a composite material, wherein the weight ratio of the ceramic powder composition to the second polyester is 0.4: 99.6-40: 60; and spinning the composite to form fibers; wherein the first polyester has an Intrinsic viscosity (Intrinsic viscocity) of 0.35dL/g to 0.55dL/g and the second polyester has an Intrinsic viscosity (Intrinsic viscocity) of 0.6dL/g to 0.8dL/g.
An embodiment of the present disclosure provides an artificial ligament/tendon, including: a first fixed segment including warp yarns and first weft yarns; a telescoping section comprising warp yarns; the second fixing section comprises warp yarns and second weft yarns, and the telescopic section is positioned between the first fixing section and the second fixing section; wherein the warp yarns comprise polyester fibers; and the first weft yarns and the second weft yarns each comprise composite fibers, and the composite fibers comprise: 0.5 to 4 parts by weight of a biocompatible ceramic powder region; and 96 to 99,5 parts by weight of a polyester region, wherein the biocompatible ceramic powder regions are distributed in the polyester region, at least 90% of the biocompatible ceramic powder regions have a diameter of 300nm or less and greater than 0nm, and the fiber has a cell survival rate of greater than 70% in a biotoxicity test.
Drawings
Fig. 1 is a schematic view of an artificial ligament/tendon according to an embodiment of the present disclosure.
Description of reference numerals:
100: artificial ligament/tendon
110: first fixed section
130: expansion section
150: second fixed section
170: warp yarn
190: first weft yarn
190': the second weft yarn.
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure will be described in further detail with reference to specific embodiments.
One embodiment of the present disclosure provides a method of making a fiber. First, a biocompatible ceramic powder and a first polyester are mixed to form a ceramic powder composition. It will be appreciated that the method of blending the biocompatible ceramic powder with the first polyester may be any suitable blending method known in the art, such as melt blending. In one embodiment, the biocompatible ceramic powder includes hydroxyapatite, tricalcium phosphate, calcium sulfate, or a combination thereof, and has an average particle size of 20 nm to 100 nm, or 40 nm to 80 nm. If the particle size of the biocompatible ceramic powder is too large, breakage of the yarn or breakage of the fiber is likely to occur during spinning. The first polyester can be polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, and has an Intrinsic viscosity (Intrinsic viscosensitivity) of 0.35dL/g to 0.55dL/g, or 0.4dL/g to 0.55dL/g. If the intrinsic viscosity of the first polyester is too low, the mechanical strength of the finished fiber product is affected. If the intrinsic viscosity of the first polyester is too high, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed in the first polyester, i.e., the particle size of the biocompatible ceramic powder region in the final product is too large. In some embodiments, the weight ratio of the biocompatible ceramic powder to the first polyester is from 10: 90 to 60: 40, or from 20: 80 to 60: 40. If the amount of the biocompatible ceramic powder is too low, the biocompatibility of the ceramic powder composition with the fiber may be insufficient. If the amount of the biocompatible ceramic powder is too high, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed in the first polyester, i.e., the biocompatible ceramic powder region in the ceramic powder composition or the fiber has too large particle size, and is prone to breaking or fiber breakage during spinning.
Then, the ceramic powder composition and the second polyester are mixed to form the composite material. It is to be understood that the method of blending the ceramic powder composition with the second polyester may be any suitable blending method known in the art, such as melt blending. In some embodiments, the second polyester can be polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, and has an intrinsic viscosity (intrinsic viscosensitivity) of 0.6dL/g to 0.8dL/g, or 0.6dL/g to 0.7dL/g. If the intrinsic viscosity of the second polyester is too low, the mechanical strength of the finished fiber product will be affected. If the intrinsic viscosity of the second polyester is too high, spinning is not easily performed. In some embodiments, the intrinsic viscosity of the first polyester differs from the intrinsic viscosity of the second polyester by a difference (Δ IV) of greater than or equal to 0.1dL/g and less than or equal to 0.45dL/g. It is noted that the first polyester and the second polyester are of the same type, such as both polyethylene terephthalate. If the first polyester and the second polyester are different in kind, the ceramic powder composition may not be effectively dispersed in the second polyester. In some embodiments, the weight ratio of the ceramic powder composition to the second polyester is 0.4: 99.6 to 40: 60. If the amount of the ceramic powder composition used is too low, the biocompatibility of the ceramic powder composition with the fiber may be insufficient. If the amount of the ceramic powder composition is too high, the fiber tends to be broken during spinning or the fiber tends to be broken.
It is noted that if the first polyester, the second polyester, and the biocompatible ceramic powder are mixed together, the biocompatible ceramic powder is agglomerated and cannot be dispersed effectively. Similarly, if the first polyester and the second polyester are blended and then the biocompatible ceramic powder is blended, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed.
The composite is then spun to form fibers. It will be appreciated that the method of spinning the composite material may be any suitable spinning method known in the art, such as melt spinning. In some embodiments, the fiber comprises 0.5 to 4 parts by weight of the biocompatible ceramic powder region; and 96 to 99.5 parts by weight of a polyester region. In some embodiments, the fiber comprises 0.5 to 3 parts by weight of the biocompatible ceramic powder region; and 97 to 99.5 parts by weight of a polyester region. The biocompatible ceramic powder region is distributed in the polyester region. It is understood that the biocompatible ceramic powder region is from the biocompatible ceramic powder in the composite, and the polyester region is from the first polyester and the second polyester in the composite. In some embodiments, the region of the biocompatible ceramic powder is a region where the biocompatible ceramic powder is aggregated, and the polyester region is a region of the fiber excluding the biocompatible ceramic powder. At least 90% or even at least 95% of the biocompatible ceramic powder regions have a diameter of less than or equal to 300nm and greater than 0nm. If the diameter of the biocompatible ceramic powder region is too large, the composite material is prone to clogging the spinneret/filament breakage, and the mechanical strength of the fiber is weak. The cell viability of the composite material before spinning is more than 70% in the biotoxicity test, i.e. the composite material is not cytotoxic. The cell viability of the spun fibers as measured by the biotoxicity test is greater than 70% and even greater than 100%, i.e., in some embodiments, the fibers are not cytotoxic and can further promote cell growth.
In some embodiments, at least 90% or even at least 95% of the biocompatible ceramic powder region has a diameter of less than or equal to 300nm and greater than 10nm.
In some embodiments, the fibers have a diameter of 2 to 150 microns or 10 to 110 microns. In some embodiments, the fibers have a diameter of 10 to 60 microns. In some embodiments, the fibers containing the biocompatible ceramic powder region and the polyester region do not need additional dispersant, such as dispersant with molecular weight of 5000 or less and greater than 0, or dispersant with molecular weight of 3000 or less and greater than 0. This is because generally common dispersants migrate easily to the surface of the fiber and are cytotoxic and not suitable for use in medical materials such as artificial ligaments/tendons.
In one embodiment, the fibers may be woven into an artificial ligament/tendon. It will be appreciated that the method of weaving the fibres may be any suitable weaving method known in the art. Since the fibers of the disclosed embodiments promote differentiation of cellular bone, they are more suitable for artificial ligament/tendon than fibers made of common biocompatible materials. Clinical animal experiments prove that after the fiber is woven into the artificial ligament, the fiber does not cause hepatotoxicity and renal toxicity after being implanted into animals through operation and has biocompatibility. After three months of implantation, the artificial ligament is successfully grown in the peripheral soft tissue to form the ligamentization phenomenon. A gap is formed between the ligament fastener and the bone, and the bone nail and the bone drill hole are healed. In addition, the artificial ligament of the present disclosure has a higher maximum tensile strength (ultimate tensile strength) for one month after surgical implantation in animals than commercially available artificial ligaments.
In some embodiments, an embodiment of the present disclosure provides an artificial ligament/tendon 100, as shown in fig. 1. The artificial ligament/tendon 100 includes a first fixing segment 110, a flexible segment 130, and a second fixing segment 150, and the flexible segment 130 is located between the first fixing segment 110 and the second fixing segment 150. The first fixed segment 110 includes warp yarns 170 and first weft yarns 190. The telescoping section 130 includes warp yarns 170. The second fixing segment 150 includes warp yarns 170 and second weft yarns 190'. It is understood that the warp yarn 170 of the first fixing segment 110, the warp yarn 170 of the expansion segment 130, and the warp yarn 170 of the second fixing segment 150 are continuous fibers, such as continuous polyester fibers. The first weft yarn 190 and the second weft yarn 190' each include composite fibers, i.e., the fibers containing 0.5 to 4 parts by weight of the biocompatible ceramic powder region and 96 to 99.5 parts by weight of the polyester region, and the details thereof are not described in detail herein for simplicity of explanation.
In some embodiments, the length ratio of the telescopic section 130 to the first fixing section 110 is 1: 1to 1: 5, and the length ratio of the telescopic section 130 to the second fixing section 150 is 1: 1to 1: 5. In some embodiments, the length ratio of the telescopic section 130 to the first fixing section 110 is 1: 1to 1: 3, and the length ratio of the telescopic section 130 to the second fixing section 150 is 1: 1to 1: 3. The lengths of the first and second stationary segments 110 and 150 may be the same or different depending on the desired application. In some embodiments, the composition of the first weft yarn 190 of the first fixed segment 110 and the second weft yarn 190' of the second fixed segment 150 may be the same or different (e.g., adjusting the ratio of the biocompatible ceramic powder region, the diameter of the composite fiber, or other parameters), depending on the desired application.
In some embodiments, the polyester fibers of warp yarn 170 comprise polyethylene terephthalate, polybutylene terephthalate, or a combination thereof. In some embodiments, the Intrinsic viscosity (Intrinsic viscocity) of the polyester fibers of the warp yarn 170 is 0.50 to 0.80dL/g, and the diameter of the polyester fibers is 10 to 50 microns. If the intrinsic viscosity of the polyester fiber is too low, the fiber strength is low, and yarn breakage is likely to occur. If the intrinsic viscosity of the polyester fiber is too high, it is difficult to melt-spin the polyester fiber into a fiber. If the diameter of the polyester fiber is too small, the fiber strength is low, and yarn breakage is likely to occur. If the diameter of the polyester fiber is too large, knitting is not easy. Compared to the artificial fiber/ligament composed of all composite fibers, the artificial fiber ligament 100 has a lower cost and has the effects of osseointegration (provided by the biocompatible ceramic powder region in the composite fibers of the first weft yarn 190 and the second weft yarn 190') and mechanical strength (provided by the polyester fibers of the warp yarns 110).
In order to make the aforementioned and other objects, features and advantages of the present disclosure more comprehensible, preferred embodiments accompanied with figures are described in detail below:
[ examples ]
Intrinsic Viscosity (IV) of the polyesters of the following examples was measured according to ASTM D4603.
Example 1
194.18 weight portions of dimethyl terephthalate, 173.79 weight portions of ethylene glycol and 0.01 weight portion of n-butyl titanate are taken to react for about 2 hours at the temperature of about 200 ℃, then the temperature is increased to about 260 ℃, the pressure is reduced to about 4torr for about 1 hour, then the temperature is increased to about 270 ℃, and the pressure is reduced to about 0.1torr for reaction until the intrinsic viscosity is 0.433dL/g. The polyethylene terephthalate (PET, with an intrinsic viscosity of 0.433 dL/g) was used as the first polyester, placed in a vacuum oven, heated to about 120 ℃ and dewatered under reduced pressure. Hydroxyapatite (hydroxyapatite) powder (original average particle diameter of about 60nm, available from Yuqing industries) was used as the biocompatible ceramic powder. 60 parts by weight of the dehydrated PET and 40 parts by weight of the hydroxyapatite powder were fed into a twin-screw extruder, and melt-blended and dispersed at a screw temperature of about 265 ℃ and a rotational speed of 40rpm to prepare a ceramic powder composition. The ceramic powder composition has cytotoxicity (MTT) measured according to ISO10993-1 standard, and cell survival rate of 70% or more, i.e., no cytotoxicity.
Example 2
Similar to example 1, the difference is that the weight ratio of the first polyester to the hydroxyapatite is changed from 60: 40 to 40: 60. The remaining processes and the property measurement methods are the same as those of example 1.
Example 3
194.18 parts by weight of dimethyl terephthalate, 173.79 parts by weight of ethylene glycol and 0.01 part by weight of n-butyl titanate are taken to react for about 2 hours under about 200 eta, then the temperature is increased to about 260 ℃, the pressure is reduced to about 4torr for about 1 hour, then the temperature is increased to about 270 eta, and the pressure is reduced to about 0.1torr for reaction until the intrinsic viscosity is 0.502dL/g. The PET (with the intrinsic viscosity of 0.502 dL/g) is taken as the first polyester, placed in a vacuum oven, heated to 120 ℃ and subjected to reduced pressure for water removal. Hydroxyapatite powder (original average particle size 60 nm) is used as biocompatible ceramic powder. 60 parts by weight of the dehydrated PET and 40 parts by weight of the hydroxyapatite powder are fed into a twin-screw extruder, and are melted, mixed and dispersed at a screw temperature of 265 ℃ and a rotation speed of 40rpm to prepare the ceramic powder composition. The ceramic powder composition has cytotoxicity (MTT) measured according to ISO10993-1 standard, and cell survival rate of 70% or more, i.e., no cytotoxicity.
Example 4
Similar to example 3, the difference is that the weight ratio of the first polyester to the hydroxyapatite is changed from 60: 40 to 40: 60. The rest of the process and the property measurement method are the same as those of example 3.
Example 5
Commercially available PET (T-2150T from New optical fiber, intrinsic viscosity 0.535 dL/g) was used as the first polyester, placed in a vacuum oven, heated to 120 ℃ and water was removed under reduced pressure. Hydroxyapatite powder (original average particle size 60 nm) is used as biocompatible ceramic powder. 60 parts by weight of the dehydrated PET and 40 parts by weight of the hydroxyapatite powder are fed into a twin-screw extruder, and are melted, mixed and dispersed at a screw temperature of 265 ℃ and a rotation speed of 40rpm to prepare the ceramic powder composition. The ceramic powder composition has cytotoxicity (MTT) measured according to ISO10993-1, and cell survival rate of 70% or more, i.e., no cytotoxicity.
Example 6
Similar to example 5, the difference is that the weight ratio of the first polyester to the hydroxyapatite is changed from 60: 40 to 40: 60. The remaining processes and property measurements were performed in the same manner as in example 5.
TABLE 1
* Cytotoxicity test pass criteria: the cell survival rate is more than or equal to 70 percent
Example 7
Commercially available PET (C-0226C from New optical fiber, intrinsic viscosity 0.66 dL/g) was used as the second polyester, placed in a vacuum oven, heated to 120 ℃ and dewatered under reduced pressure. 98.33 parts by weight of the dewatered second Polyester (PET) and 1.67 parts by weight of the ceramic powder composition of example 4 were fed to a twin-screw extruder, and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotational speed of 40rpm to prepare a composite material. Intrinsic viscosity of the composite was measured by ASTM D4603. The cytotoxicity (MTT) of the composite material is measured according to the ISO10993-1 specification, and the cell survival rate is more than or equal to 70 percent, namely the composite material has no cytotoxicity.
Example 8
Similar to example 7, the difference is that the weight ratio of the second polyester to the ceramic powder composition is changed from 98.33: 1.67 to 96.67: 3.33. The remaining processes and the property measurement methods are the same as those of example 7.
Example 9
Similar to example 7, the difference is that the weight ratio of the second polyester to the ceramic powder composition was changed from 98.3: 1.67 to 93.34: 6.66. The remaining processes and the property measurement methods are the same as those of example 7.
TABLE 2
* Cytotoxicity test pass criteria: the cell survival rate is more than or equal to 70 percent
Example 10
Commercially available PET (C-0226C from New optical fiber, intrinsic viscosity 0.66 dL/g) was used as the second polyester, placed in a vacuum oven, heated to 120 ℃ and dewatered under reduced pressure. 97.5 parts by weight of the dewatered second Polyester (PET) and 2.5 parts by weight of the ceramic powder composition of example 1 were fed to a twin-screw extruder, and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotational speed of 40rpm to prepare a composite material. Intrinsic viscosity of the composite was measured by ASTM D4603. The cytotoxicity (MTT) of the composite material is measured according to the ISO10993-1 specification, and the cell survival rate is more than or equal to 70 percent, namely the composite material has no cytotoxicity.
Example 11
Similar to example 10, the difference is that the ceramic powder composition of example 1 was changed to the ceramic powder composition of example 3. The remaining processes and the property measurement methods are the same as those of example 10.
Example 12
Similar to example 10, the difference is that the ceramic powder composition of example 1 was changed to the ceramic powder composition of example 5. The remaining processes and the property measurement methods are the same as those of example 10.
TABLE 3
* Cytotoxicity test pass criteria: the cell survival rate is more than or equal to 70 percent
Example 13
The composite material of example 8 was taken and spun by the melt spinning method. The composite material is added into a screw extruder, is conveyed to a heating zone by a rotating screw, is conveyed to a metering pump by extrusion and melting, is spun at a spinning temperature of 290 ℃ and a spinning speed of 64m/min, and is extended at 110 ℃ to form fibers, and the extension ratio is 3.4%. The fiber had a fineness of 8.1den, a strength of 3.4 + -0.5 g/den and an elongation of 20.6%. The cytotoxicity (MTT) of the fiber is measured according to the ISO10993-1 specification, and the cell survival rate is more than or equal to 70 percent, namely the fiber has no cytotoxicity. In addition, the cell viability of the composite material after being made into fiber is more than 100%, which indicates that the fibrous composite material can promote cell growth.
Example 14
Similar to example 13, the difference is that the draw ratio of the fiber increased from 3.4% to 3.8%. The remaining processes and the property measurement method are the same as those of example 14.
TABLE 4
* Cytotoxicity test pass criteria: the cell survival rate is more than or equal to 70 percent
As can be seen from Table 4, in some embodiments, the fibers have a tensile strength of between about 2.5g/den and about 5.5 g/den.
Comparative example 1
Similar to example 13, the difference is that PET (C-0226C from New optical fiber) is used instead of the composite. After melt spinning to form PET fibers, cell culture adhesion and bone differentiation tests were performed with cells T2B 004P 5 to measure the expression of important differentiation markers (RUNX 2). However, pure PET fibers (without biocompatible ceramic powder dispersed therein) have no effect of promoting differentiation of cell bones.
Example 15
The fibers of example 13 were used for cell culture attachment and bone differentiation assays using cell T2B 004P 5, and the expression of important differentiation markers (RUNX 2) was measured. The fibers of the composite material are 5 times faster in bone differentiation and also have good cell adhesion properties.
TABLE 5
Comparative example 2
Commercially available PET (C-0226C from New optical fiber, intrinsic viscosity 0.66 dL/g) was used as the polyester, placed in a vacuum oven, heated to 120 ℃ and dewatered under reduced pressure. Hydroxyapatite powder (original average particle size 60 nm) is used as biocompatible ceramic powder. 98 parts by weight of the dewatered polyester and 2 parts by weight of the hydroxyapatite powder were fed into a twin-screw extruder, and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotational speed of 40rpm to prepare a composite material. The composite material is fed into a screw extruder, conveyed to a heating zone by a rotating screw, extruded and melted and conveyed forward to a metering pump, spun at a spinning temperature of 290 ℃, a spinning speed of 64m/min and extended at 110 ℃ to form fibers. However, the ceramic powder in the composite material is seriously agglomerated and blocks the spinning nozzle to cause filament breakage. Scanning Electron Microscopy (SEM) confirmed that the diameters of the biocompatible ceramic powder regions in the fibers of comparative example 1 and example 8 were distributed as follows:
TABLE 6
As can be seen from table 6, comparative example 2 does not pre-disperse the biocompatible ceramic powder with the first polyester, and the method of directly dispersing the biocompatible ceramic powder in the second polyester causes powder agglomeration. The method comprises the steps of dispersing biocompatible ceramic powder by using the first polyester with lower characteristic viscosity to form a ceramic powder composition, and then dispersing the ceramic powder composition in the second polyester with higher characteristic viscosity to reduce the agglomeration degree of the biocompatible ceramic powder. For example, more than 90% or even more than 95% of the biocompatible ceramic powder region has a particle size of less than or equal to 300nm.
Comparative example 3
Commercially available PET (PCG 60 from SABIC, having an intrinsic viscosity of 0.60 dL/g) was used as the first polyester, placed in a vacuum oven and heated to 120 ℃ and water was removed under reduced pressure. Hydroxyapatite powder (original average particle size 60 nm) is used as biocompatible ceramic powder. 60 parts by weight of the dehydrated PET and 40 parts by weight of the hydroxyapatite powder are fed into a twin-screw extruder, and are melted, mixed and dispersed at a screw temperature of 265 ℃ and a rotation speed of 40rpm to prepare the ceramic powder composition. Taking commercially available PET (C-0226C available from New optical fiber and having an intrinsic viscosity of 0.66 dL/g) as a second polyester, placing the second polyester in a vacuum oven, heating to 120 ℃, decompressing and removing water, feeding 97.5 parts by weight of the second polyester after water removal and 2.5 parts by weight of the ceramic powder composition into a double-screw extruder, and carrying out melt blending dispersion at a screw temperature of 270 ℃ and a rotating speed of 40rpm to prepare the composite material. The composite material is fed into a screw extruder, conveyed to a heating zone by a rotating screw, extruded and melted and conveyed forward to a metering pump, spun at a spinning temperature of 290 ℃, a spinning speed of 64m/min and extended at 110 ℃ to form fibers. However, the ceramic powder in the composite material is seriously agglomerated and blocks the spinning nozzle to cause filament breakage.
Example 16
The composite material of example 11 was spun by the melt spinning method. The composite material is added into a screw extruder, is sent to a heating zone by a rotating screw, is sent to a metering pump by extrusion and melting, is spun at a spinning temperature of 290 ℃ and a spinning speed of 64m/min, and is extended at 110 ℃ to form fibers, and the extension ratio is 3.4%.
Example 17
The composite material of example 12 was spun in a melt spinning process. The composite material is added into a screw extruder, is sent to a heating zone by a rotating screw, is sent to a metering pump by extrusion and melting, is spun at a spinning temperature of 290 ℃ and a spinning speed of 64m/min, and is extended at 110 ℃ to form fibers, and the extension ratio is 3.4%.
TABLE 7
As is clear from Table 7, in comparative example 3, when the Δ IV is less than 0.1dL/g, the powder was not dispersed well, and the nozzle was clogged, resulting in yarn breakage. The method comprises the steps of dispersing biocompatible ceramic powder by using first polyester with low characteristic viscosity to form a ceramic powder composition, and then dispersing the ceramic powder composition in second polyester with high characteristic viscosity, wherein delta IV of the two polyesters is more than or equal to 0.1, so that the agglomeration degree of the biocompatible ceramic powder can be reduced.
Comparative example 4
1 part by weight of hydroxyapatite powder (original average particle diameter 60 nm) as a biocompatible ceramic powder, 0.67 part by weight of a dispersant A (LuboluSolplus DP 320) and a commercially available PET (C-0226C available from New optical fiber, intrinsic viscosity of which is 0.66 dL/g) as a second polyester were fed to a twin-screw extruder and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotational speed of 40rpm to prepare a composite material. The cytotoxicity (MTT) of the composite material is measured according to the ISO10993-1 specification, and the cell survival rate is less than 70 percent, namely the composite material is cytotoxic.
Comparative example 5
Similar to comparative example 4, the difference is that dispersant A was changed to dispersant B (Pico chemical BYK P4102). The remaining processes and the property measurement methods are the same as those of comparative example 4.
Comparative example 6
Similar to comparative example 4, the difference is that dispersant A is changed to dispersant C (Bicke chemical DISPERPLAST-1018). The remaining processes and the property measurement methods are the same as those of comparative example 4.
TABLE 8
* Cytotoxicity test pass criteria: the cell survival rate is more than or equal to 70 percent
As can be seen from table 8, the composite material using the small molecule dispersant has cytotoxicity, and is not suitable for medical materials such as artificial ligament/tendon.
Comparative example 7
98.98 parts by weight of dehydrated PET (first polyester, C-0226C available from New optical fiber, having an intrinsic viscosity of 0.66 dL/g) and 1.02 parts by weight of hydroxyapatite powder (original average particle diameter 60nm, biocompatible ceramic powder) were fed to a twin-screw extruder, and melt-blended and dispersed at a screw temperature of about 265 ℃ and a rotation speed of 40rpm to prepare a ceramic powder composition. 1.96 parts by weight of dehydrated PET (second polyester, T-2150T from New optical fiber, intrinsic viscosity of 0.535 dL/g) and 98.04 parts by weight of the above ceramic powder composition were fed to a twin-screw extruder, and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotation speed of 40rpm to prepare a composite material. The composite material was fed into a screw extruder, fed by a rotating screw to a heating zone, extruded, melted and fed forward to a metering pump, spun at a spinning temperature of 290 ℃ and a spinning speed of 64m/min, and extended at 110 ℃ to form fibers. However, the ceramic powder in the composite material is seriously agglomerated and blocks the spinning nozzle to cause filament breakage.
TABLE 9
As is clear from Table 9, the reverse addition (high IV polyester first and high IV polyester second) of comparative example 7 resulted in poor powder dispersion and clogging of the nozzle, resulting in yarn breakage. The method comprises the steps of dispersing biocompatible ceramic powder by using the first polyester with lower characteristic viscosity to form a ceramic powder composition, and then dispersing the ceramic powder composition in the second polyester with higher characteristic viscosity to reduce the agglomeration degree of the biocompatible ceramic powder.
Comparative example 8
97.5 parts by weight of dehydrated PET (C-0226C available from a new optical fiber and having an intrinsic viscosity of 0.66 dL/g) and 1.5 parts by weight of dehydrated PET (T-2150T available from a new optical fiber and having an intrinsic viscosity of 0.535 dL/g) and 1 part by weight of hydroxyapatite powder (original average particle size of 60 nm) were simultaneously fed into a twin-screw extruder, and melt-blended and dispersed at a screw temperature of 270 ℃ and a rotational speed of 40rpm, to prepare a composite material. The composite material is added into a screw extruder, is conveyed to a heating zone by a rotating screw, is conveyed to a metering pump by extrusion and melting, and is spun at the spinning temperature of 290 ℃ and the spinning speed of 64m/min, however, the ceramic powder in the composite material is seriously agglomerated and blocks a spinning nozzle to cause yarn breakage.
Artificial ligament: clinical animal efficacy validation
Ligament reconstruction surgery was performed using a new zealand white rabbit (weighing about 3 kg) as a model of experimental animals, hindlimb Medial Collateral Ligament (MCL), and the experiments were divided into two groups: (1) comparative example 9: the Orthomed commercially available artificial ligament material is pure PET; example 18: the artificial ligament is woven by taking the fiber of the example 8 and weaving the artificial ligament in a plane weaving method. Before surgery, anaesthesia is carried out by using anaesthetics (Sutai 50: locapone 20= 1: 1,0.5 ml/kg), and the knee joint of the hind limb is opened by surgery: making skin incision along the straight line of the anterior lateral side of the knee joint and the lateral side of the patella, opening the synovial capsule of the knee joint through the incision, respectively implanting two groups of artificial ligaments beside an autologous MCL (small wound) in an operation mode and sewing the artificial ligaments together with the autologous MCL, after the operation is finished, sewing the pulled tissues and the skin of each layer to finish the operation, and performing animal care after the operation. The medial collateral ligament reconstruction surgery was performed on 9 hind limbs for each group, followed by 1, 3, and 6 months.
Serum amino propionic acid transaminase (ALT), creatinine (Creatinine) and Blood urea nitrogen value (Blood urea nitrogen) in the range of normal reference values (ALT: 22-80iu/lit, BUN:17-24mg/dl and Creatinine:0.8-1.8 mg/dl) after the artificial ligament is implanted into the animal by the operation at 0, 1 and 3 months after the artificial ligament is implanted into the animal by the operation.
Each group of artificial ligaments is respectively sampled one month and three months after being implanted into animals through operations, the artificial ligaments and the bone tissues connected in front and back are taken down, and the results are observed by naked eyes: the artificial ligaments and the bone nails in the example 18 and the comparative example 9 which were observed one month after the operation were all clearly visible, but the artificial ligaments and the bone nails which were observed three months after the operation were all covered by soft tissues and could not be seen, and after the artificial ligaments were removed, the ligamentization phenomenon that the peripheral soft tissues successfully grow into the artificial ligaments was also found.
According to the X-ray image display of one month and three months after each group of artificial ligaments was surgically implanted into animals, in example 18 and comparative example 9, it was found that a part of the artificial ligament was loosened, and a gap was generated between the ligament buckle and the bone. After three months of operation, the healing phenomenon of the bone nail and the bone drill hole is found.
The maximum tensile strength (ultimate tensile strength) of each group of artificial ligaments one month after surgical implantation into animals was about 100 newtons (N) for example 18 and about 60N for comparative example 9. The fiber of example 9, which promotes cell bone differentiation better than pure PET, is one of the factors affecting the maximum tensile strength of example 18 better than that of comparative example 9.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (19)
1. A fiber, comprising:
0.5 to 4 parts by weight of a biocompatible ceramic powder region; and
96 to 99.5 parts by weight of a polyester region,
wherein the biocompatible ceramic powder regions are distributed in the polyester region, at least 90% of the biocompatible ceramic powder regions have a diameter of less than or equal to 300nm and greater than 0nm, and the cell survival rate of the fiber in a biotoxicity test is greater than 70%.
2. The fiber of claim 1, having a diameter of 2 to 150 microns.
3. The fiber of claim 1, wherein the polyester region comprises polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, and the biocompatible ceramic powder region comprises hydroxyapatite, tricalcium phosphate, calcium sulfate, or a combination thereof.
4. The fiber of claim 1, wherein no dispersant is added.
5. The fiber of claim 1, wherein the fiber has a cell viability in a biotoxicity test of greater than 100%.
6. An artificial ligament/tendon characterized by being woven from the fiber of claim 1.
7. A method of making a fiber, comprising:
mixing biocompatible ceramic powder and first polyester to form a ceramic powder composition, wherein the weight ratio of the biocompatible ceramic powder to the first polyester is 10: 90 to 60: 40;
mixing the ceramic powder composition with a second polyester to form a composite material, wherein the weight ratio of the ceramic powder composition to the second polyester is 0.83: 99.17-40: 60; and
spinning the composite material to form a fiber;
wherein the intrinsic viscosity of the first polyester is 0.35dL/g to 0.55dL/g, and the intrinsic viscosity of the second polyester is 0.6dL/g to 0.8dL/g.
8. The method of claim 7, wherein the fiber comprises:
0.5 to 4 parts by weight of a biocompatible ceramic powder region; and
96 to 99.5 parts by weight of a polyester region,
wherein the biocompatible ceramic powder regions are distributed in the polyester region, at least 90% of the biocompatible ceramic powder regions have a diameter of 300nm or less and greater than 0nm, and the cell survival rate of the fiber in a biotoxicity test is greater than 70%.
9. The method of claim 7, wherein the diameter of the fiber is 2 to 150 microns.
10. The method of claim 7, wherein the first polyester and the second polyester comprise polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, and the biocompatible ceramic powder comprises hydroxyapatite, tricalcium phosphate, calcium sulfate, or a combination thereof.
11. The method of claim 7, wherein the fiber is free of added dispersant.
12. The method of claim 7, wherein the intrinsic viscosity of the first polyester differs from the intrinsic viscosity of the second polyester by a value greater than or equal to 0.1dL/g and less than or equal to 0.45dL/g.
13. An artificial ligament/tendon comprising:
a first fixed section including a warp yarn and a first weft yarn;
a stretch section including the warp; and
a second fixed segment including the warp and a second weft,
wherein the telescopic section is positioned between the first fixed section and the second fixed section;
wherein the warp yarn comprises a polyester fiber; and
the first weft yarn and the second weft yarn each comprise a composite fiber, and the composite fiber comprises:
0.5 to 4 parts by weight of a biocompatible ceramic powder region; and
96 to 99.5 parts by weight of a polyester region,
wherein the biocompatible ceramic powder regions are distributed in the polyester region, at least 90% of the biocompatible ceramic powder regions have a diameter of less than or equal to 300nm and greater than 0nm, and the cell survival rate of the fiber in a biotoxicity test is greater than 70%.
14. The artificial ligament/tendon according to claim 13, wherein the composite fiber has a diameter of 2-150 microns.
15. The artificial ligament/tendon of claim 13, wherein the polyester region comprises polyethylene terephthalate, polybutylene terephthalate, or a combination thereof, and the biocompatible ceramic powder region comprises hydroxyapatite, tricalcium phosphate, calcium sulfate, or a combination thereof.
16. The artificial ligament/tendon according to claim 13, wherein the composite fiber is free of additional dispersant.
17. The artificial ligament/tendon according to claim 13, wherein the composite fiber has a cell viability of greater than 100% in a biotoxicity test.
18. The artificial ligament/tendon according to claim 13, wherein the length ratio of the expansion section to the first fixing section is 1: 1to 1: 5, and the length ratio of the expansion section to the second fixing section is 1: 1to 1: 5.
19. The artificial ligament/tendon of claim 13, wherein the polyester fibers comprise polyethylene terephthalate, polybutylene terephthalate, or a combination thereof.
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| CN202111167711.4A CN115896971A (en) | 2021-09-30 | 2021-09-30 | Fiber and preparation method thereof and artificial ligament/tendon |
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| CN202111167711.4A CN115896971A (en) | 2021-09-30 | 2021-09-30 | Fiber and preparation method thereof and artificial ligament/tendon |
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