CN105999402A - Preparation method of gadolinium-molybdenum-cobalt alloy and polyamide stent material - Google Patents

Preparation method of gadolinium-molybdenum-cobalt alloy and polyamide stent material Download PDF

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CN105999402A
CN105999402A CN201610447101.2A CN201610447101A CN105999402A CN 105999402 A CN105999402 A CN 105999402A CN 201610447101 A CN201610447101 A CN 201610447101A CN 105999402 A CN105999402 A CN 105999402A
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polyamide
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蓝碧健
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Taicang Biqi New Material Research Development Co Ltd
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L2430/28—Materials or treatment for tissue regeneration for liver reconstruction

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Abstract

The invention belongs to the technical field of biomedical materials, and relates to a preparation method of a gadolinium-molybdenum-cobalt alloy and polyamide stent material. The preparation method of the stent material comprises the steps of cleaning and surface modifying of a polyamide stent material, catalytic activating and chemical plating of a gadolinium-molybdenum-cobalt alloy. The preparation method has the advantages that the organic carbon overflow rate of the stent material is decreased by 99% or above, the Mohs hardness can reach 6.1, and according to a test which is used for simulating body fluid corrosion for 180 days, the metal ion overflow rate is smaller than 1 ppm, that is to say, the material has extremely high biological environment reliability. The gadolinium-molybdenum-cobalt alloy and polyamide material can be used for tissue engineering stent materials and is bright in application prospect and huge in market potential.

Description

The preparation method of gadolinium molybdenum cobalt alloy/polyamide timbering material
Technical field
The invention belongs to biology medical material technical field, relate to the preparation method of a kind of gadolinium molybdenum cobalt alloy/polyamide timbering material.
Background technology
Bio-medical material is the basis of artificial organ and medical apparatus and instruments, for interventional therapy field, being chosen to be preced with of support Cardiopathia cures the key link of success or failure.General clinical intravascular stent used is made up of metal material, and preferably internal metal rack must Must possess following physicochemical property: (1) has preferable biocompatibility, it is to avoid the generation of immunological rejection.Biocompatibility is Implant the most basic most important performance indications of medical-therapeutic treatment of human body apparatus；(2) there is X-ray opaque, in order to accurately fixed to intravascular stent Position, expansion effect are evaluated, and influence factor mainly has the composition of support own, the design of support, labelling point and face coat etc.； (3) there is preferable compliance.Compliance is the concentrated expression of support compliance and rigidity.Compliance is easy to intravascular stent well and is passed through Tortuous blood vessel and be successfully pushed to diseased region, but poor stability；The intravascular stent geometrical stability of good rigidly is good, but defeated Send difficulty；(4) good blood compatibility, is not susceptible to thrombosis and Coagulation test after implantation, the inflammation being difficult to cause blood vessel wall is anti- Should be with the neointimal hyperplasia of blood vessel.This with the roughness of rack surface, hydrophilic, surface can, surface charge relevant；(5) high expansion Property, can pass through with minimum diameter in induction system, again can high level expansion after arriving target；(6) radially support strength, has machinery Persistency, can firmly be attached at blood vessel wall and prevent vessel wall elasticity from bouncing back；(7) little blood vessel wall area coverage.The gold of support Belonging to thickness of pipe wall and surface area should be the least, mesh district reaches more than 80% and is more beneficial for endothelial cell growth.
Medical polyamide can be used for flexible pipe, adapter, adapter, piston.Feature is to have compliance, bending resistance, toughness Height not easy fracture, chemical resistance and wearability, do not discharge any harmful material, the most do not cause skin or tissue Inflammation.
In Medical rack material, metal rack density is big, retains human body burden in vivo big；Polymer support density is little, human body Bear little, but polymer is degradable, produce " organic carbon " and overflow, unfavorable to human body；Metal/polymer composite material type support Can be in conjunction with the advantage of the two, but the limitednumber of metal, how based on noble metal gold, silver, platinum etc., expensive.The present invention Being to be coated with gadolinium molybdenum cobalt alloy layer at polyamide surface, core process is under copper ferrum composite catalyzing activates, at chemical plating solution In, rare-earth element gadolinium enters in the lattice of molybdenum cobalt alloy, forms more form compact and stable alloy-layer, so effective by polyamides Amine is isolated with human body, makes polyamide organic carbon flood rate reduce by more than 99%, moreover, gadolinium molybdenum cobalt alloy/polyamide support The Mohs' hardness of material can reach 6.1, is best in current all metals/polyamide compound support frame material；Through simulation in 180 days Human body fluid corrosion test, the metal ion flood rate of gadolinium molybdenum cobalt alloy/polyamide timbering material is less than 1/1000000th (1ppm), illustrate that this material has high biotic environment reliability.In sum, the gadolinium molybdenum cobalt alloy that the present invention proposes/ The preparation method of polyamide timbering material has prominent substantive distinguishing features and significantly progress, i.e. possesses creativeness.
Summary of the invention
The invention belongs to biology medical material technical field, relate to the preparation method of a kind of gadolinium molybdenum cobalt alloy/polyamide timbering material. The step of this preparation method is as follows:
1) by polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go Ionized water is cleaned, is dried；
2) clean polyamide is propped up it is placed in modifier solution 30 minutes, take out, be placed in baking oven that to be dried 3 in 90 DEG C little Time, it is cooled to room temperature, obtains modified polyamide support；Wherein the formula of modifier solution be solvent be deionized water, each in solution Kind of solute concentration is respectively as follows: dimethylaminoethyl acrylate concentration 3～6g/L, 2-cyanoacrylate propyl propionate concentration 9～12g/L, Performic acid concentration 1～3g/L, acetone concentration 100～200g/L.
3) modified polyamide is propped up it is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then put In the sodium borohydride aqueous solution that weight percent concentration is 3% 10 minutes, take out, clean, polyamide support must be activated；Its The formula of middle activator solution be solvent be deionized water, in solution, various solute concentrations are respectively as follows: cuprous nitrate concentration 20～30g/L, ferrous chloride concentration 20～30g/L, sodium tartrate concentration 20～30g/L.
4) activation polyamide is propped up it is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry Dry, obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.Wherein the formula of gadolinium molybdenum cobalt electroless plating solution be solvent be deionized water, solution In various solute concentrations be respectively as follows: Gadolinium trinitrate concentration 20～30g/L；Cobalt nitrate concentration 20～30g/L；Nitric acid molybdenum concentration 40～60g/L；Disodiumedetate concentration 30～60g/L；Sodium tartrate concentration 60～90g/L；Dimethylamino borane concentration 3～6g/L；Sodium bicarbonate concentration 6～9g/L.
5) gadolinium molybdenum cobalt alloy/polyamide timbering material test characterizes.Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulation human body In body fluid, place 180 days in 37 DEG C, take out, organic carbon spill-out in test solution, and compared with polyamide timbering material, Calculate organic carbon and overflow reduction rate；With the constituent content of Energy Dispersive X-ray detector (EDX) test bracket material, meter Calculate gadolinium, molybdenum, the flood rate of cobalt ion；With the bending modulus of universal testing machine test bracket material, measure with Mohs' hardness The case hardness of examination timbering material.The wherein each component content of simulated body fluid: NaCl 8g/L, KCl 0.4g/L, NaHCO3 0.35g/L, CaCl20.14g/L, Na2HPO40.06g/L, KH2PO40.06g/L, MgSO4.7H2O 0.2g/L, glucose 1g/L.
The gadolinium molybdenum cobalt alloy/polyamide timbering material prepared with the preparation method of the present invention can be used for tissue engineering bracket material and includes: Bone, cartilage, blood vessel, nerve, skin and artificial organ, such as the tissue stent material of liver,spleen,kidney, bladder etc..
Detailed description of the invention
The invention is further illustrated by the following examples
Embodiment 1
By polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go from Sub-water is cleaned, is dried.
By 5.3g dimethylaminoethyl acrylate, 9.9g 2-cyanoacrylate propyl propionate, 2.8g performic acid is dissolved in 156g acetone, Add deionized water, be made into the modifier solution that volume is 1L.
Clean polyamide is propped up and is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, It is cooled to room temperature, obtains modified polyamide support.
By 25.4g cuprous nitrate, 24.2g ferrous chloride, 21.36g sodium tartrate is dissolved in 500mL deionized water, then dilutes Becoming volume is the activator solution of 1L.
Modified polyamide is propped up and is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in weight Amount percent concentration be 3% sodium borohydride aqueous solution in 10 minutes, take out, clean, polyamide support must be activated.
By 26.6g Gadolinium trinitrate, 23.2g cobalt nitrate, 48.9g nitric acid molybdenum, 56.7g disodiumedetate, 81.2g tartaric acid Sodium, 3.1g dimethylamino borine, 6.6g sodium bicarbonate is dissolved in 500mL deionized water, then is diluted to the gadolinium molybdenum that volume is 1L Cobalt electroless plating solution.
Activation polyamide is propped up and is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, Obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose is dissolved in 500mL deionized water, then is diluted to the simulated body fluid that volume is 1L.
Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulated body fluid, places 180 days in 37 DEG C, take out, test molten Organic carbon spill-out in liquid, and compared with polyamide timbering material, calculate organic carbon overflowing reduction rate is 99.1%；With energy The constituent content of Dispersive X-ray detector (EDX) test bracket material, calculates the flood rate difference of gadolinium, molybdenum, cobalt ion For 0.56ppm, 0.88ppm, 0.77ppm；With the bending modulus of universal testing machine test bracket material as 0.08GPa, with The case hardness of Moh's hardness scale test bracket material is 6.1.
Embodiment 2
By polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go from Sub-water is cleaned, is dried.
By 4.3g dimethylaminoethyl acrylate, 9.6g 2-cyanoacrylate propyl propionate, 1.1g performic acid is dissolved in 145g acetone, Add deionized water, be made into the modifier solution that volume is 1L.
Clean polyamide is propped up and is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, It is cooled to room temperature, obtains modified polyamide support.
By 25.6g cuprous nitrate, 24.1g ferrous chloride, 23.7g sodium tartrate is dissolved in 500mL deionized water, then is diluted to Volume is the activator solution of 1L.
Modified polyamide is propped up and is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in weight Amount percent concentration be 3% sodium borohydride aqueous solution in 10 minutes, take out, clean, polyamide support must be activated.
By 27.3g Gadolinium trinitrate, 21.6g cobalt nitrate, 50.9g nitric acid molybdenum, 50.1g disodiumedetate, 70.6g tartaric acid Sodium, 3.8g dimethylamino borine, 6.1g sodium bicarbonate is dissolved in 500mL deionized water, then is diluted to the gadolinium molybdenum that volume is 1L Cobalt electroless plating solution.
Activation polyamide is propped up and is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, Obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose is dissolved in 500mL deionized water, then is diluted to the simulated body fluid that volume is 1L.
Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulated body fluid, places 180 days in 37 DEG C, take out, test molten Organic carbon spill-out in liquid, and compared with polyamide timbering material, calculate organic carbon overflowing reduction rate is 99.4%；With energy The constituent content of Dispersive X-ray detector (EDX) test bracket material, calculates the flood rate difference of gadolinium, molybdenum, cobalt ion For 0.44ppm, 0.34ppm, 0.23ppm；With the bending modulus of universal testing machine test bracket material as 0.06GPa, with The case hardness of Moh's hardness scale test bracket material is 6.2.
Embodiment 3
By polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go from Sub-water is cleaned, is dried.
By 6g dimethylaminoethyl acrylate, 12g 2-cyanoacrylate propyl propionate, 3g performic acid is dissolved in 200g acetone, adds Add deionized water, be made into the modifier solution that volume is 1L.
Clean polyamide is propped up and is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, It is cooled to room temperature, obtains modified polyamide support.
By 30g cuprous nitrate, 30g ferrous chloride, 30g sodium tartrate is dissolved in 500mL deionized water, then is diluted to volume Activator solution for 1L.
Modified polyamide is propped up and is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in weight Amount percent concentration be 3% sodium borohydride aqueous solution in 10 minutes, take out, clean, polyamide support must be activated.
By 30g Gadolinium trinitrate, 30g cobalt nitrate, 60g nitric acid molybdenum, 60g disodiumedetate, 90g sodium tartrate, 6g bis- Methylamino borine, 9g sodium bicarbonate is dissolved in 500mL deionized water, then is diluted to the gadolinium molybdenum cobalt electroless plating solution that volume is 1L.
Activation polyamide is propped up and is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, Obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose is dissolved in 500mL deionized water, then is diluted to the simulated body fluid that volume is 1L.
Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulated body fluid, places 180 days in 37 DEG C, take out, test molten Organic carbon spill-out in liquid, and compared with polyamide timbering material, calculate organic carbon overflowing reduction rate is 99.1%；With energy The constituent content of Dispersive X-ray detector (EDX) test bracket material, calculates the flood rate difference of gadolinium, molybdenum, cobalt ion For 0.13ppm, 0.13ppm, 0.18ppm；With the bending modulus of universal testing machine test bracket material as 3.03GPa, with The case hardness of Moh's hardness scale test bracket material is 6.1.
Embodiment 4
By polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go from Sub-water is cleaned, is dried.
By 4.9g dimethylaminoethyl acrylate, 11.1g 2-cyanoacrylate propyl propionate, 2.1g performic acid is dissolved in 171g acetone, Add deionized water, be made into the modifier solution that volume is 1L.
Clean polyamide is propped up and is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, It is cooled to room temperature, obtains modified polyamide support.
By 23.1g cuprous nitrate, 21.2g ferrous chloride, 21.5g sodium tartrate is dissolved in 500mL deionized water, then is diluted to Volume is the activator solution of 1L.
Modified polyamide is propped up and is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in weight Amount percent concentration be 3% sodium borohydride aqueous solution in 10 minutes, take out, clean, polyamide support must be activated.
By 22.1g Gadolinium trinitrate, 21.2g cobalt nitrate, 41.6g nitric acid molybdenum, 53.8g disodiumedetate, 71.2g tartaric acid Sodium, 4.3g dimethylamino borine, 8.1g sodium bicarbonate is dissolved in 500mL deionized water, then is diluted to the gadolinium molybdenum that volume is 1L Cobalt electroless plating solution.
Activation polyamide is propped up and is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, Obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose is dissolved in 500mL deionized water, then is diluted to the simulated body fluid that volume is 1L.
Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulated body fluid, places 180 days in 37 DEG C, take out, test molten Organic carbon spill-out in liquid, and compared with polyamide timbering material, calculate organic carbon overflowing reduction rate is 99.8%；With energy The constituent content of Dispersive X-ray detector (EDX) test bracket material, calculates the flood rate difference of gadolinium, molybdenum, cobalt ion For 0.46ppm, 0.14ppm, 0.24ppm；With the bending modulus of universal testing machine test bracket material as 2.51GPa, with The case hardness of Moh's hardness scale test bracket material is 6.1.
Embodiment 5
By polyamide support successively with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, go from Sub-water is cleaned, is dried.
By 3g dimethylaminoethyl acrylate, 9g 2-cyanoacrylate propyl propionate, 1g performic acid is dissolved in 100g acetone, adds Deionized water, is made into the modifier solution that volume is 1L.
Clean polyamide is propped up and is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, It is cooled to room temperature, obtains modified polyamide support.
By 20g cuprous nitrate, 20g ferrous chloride, 20g sodium tartrate is dissolved in 500mL deionized water, then is diluted to volume Activator solution for 1L.
Modified polyamide is propped up and is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in weight Amount percent concentration be 3% sodium borohydride aqueous solution in 10 minutes, take out, clean, polyamide support must be activated.
By 20g Gadolinium trinitrate, 20g cobalt nitrate, 40g nitric acid molybdenum, 30g disodiumedetate, 60g sodium tartrate, 3g bis- Methylamino borine, 6g sodium bicarbonate is dissolved in 500mL deionized water, then is diluted to the gadolinium molybdenum cobalt electroless plating solution that volume is 1L.
Activation polyamide is propped up and is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, Obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
By 8g NaCl, 0.4g KCl, 0.35g NaHCO3, 0.14g CaCl2, 0.06g Na2HPO4, 0.06g KH2PO4, 0.2g MgSO4.7H2O, 1g glucose is dissolved in 500mL deionized water, then is diluted to the simulated body fluid that volume is 1L.
Gadolinium molybdenum cobalt alloy/polyamide timbering material is placed in simulated body fluid, places 180 days in 37 DEG C, take out, test molten Organic carbon spill-out in liquid, and compared with polyamide timbering material, calculate organic carbon overflowing reduction rate is 99.1%；With energy The constituent content of Dispersive X-ray detector (EDX) test bracket material, calculates the flood rate difference of gadolinium, molybdenum, cobalt ion For 0.55ppm, 0.16ppm, 0.34ppm；With the bending modulus of universal testing machine test bracket material as 2.41GPa, with The case hardness of Moh's hardness scale test bracket material is 6.1.

Claims (4)

1. the preparation method of gadolinium molybdenum cobalt alloy/polyamide timbering material, it is characterised in that:
1) polyamide support is cleaned with the aqueous sodium carbonate that weight percent concentration is 10%, the hydrogen peroxide solution of 5%, deionized water, dried successively；
2) clean polyamide is propped up it is placed in modifier solution 30 minutes, take out, be placed in baking oven and be dried 3 hours in 90 DEG C, be cooled to room temperature, obtain modified polyamide support；
3) modified polyamide is propped up it is placed in activator solution 30 minutes, take out, be washed with deionized water clean, dry, then be placed in the sodium borohydride aqueous solution that weight percent concentration is 3% 10 minutes, take out, be washed with deionized water clean, polyamide support must be activated；
4) activation polyamide is propped up it is placed in gadolinium molybdenum cobalt electroless plating solution, in 60 DEG C of chemical platings 3 hours, take out and clean, dry, obtain gadolinium molybdenum cobalt alloy/polyamide timbering material.
2. the preparation method of gadolinium molybdenum cobalt alloy/polyamide timbering material as claimed in claim 1, it is characterised in that the formula of described modifier solution be solvent be deionized water, in solution, various solute concentrations are respectively as follows:
Dimethylaminoethyl acrylate concentration 3~6 g/L；
2-cyanoacrylate propyl propionate concentration 9 ~ 12 g/L；
Performic acid concentration 1 ~ 3 g/L；
Acetone concentration 100 ~ 200 g/L。
3. the preparation method of gadolinium molybdenum cobalt alloy/polyamide timbering material as claimed in claim 1, it is characterised in that the formula of described activator solution be solvent be deionized water, in solution, various solute concentrations are respectively as follows:
Cuprous nitrate concentration 20~30g/L；
Ferrous chloride concentration 20~30g/L；
Sodium tartrate concentration 20 ~ 30g/L.
4. the preparation method of gadolinium molybdenum cobalt alloy/polyamide timbering material as claimed in claim 1, it is characterised in that the formula of described gadolinium molybdenum cobalt electroless plating solution be solvent be deionized water, in solution, various solute concentrations are respectively as follows:
Gadolinium trinitrate concentration 20 ~ 30g/L；
Cobalt nitrate concentration 20 ~ 30g/L；
Nitric acid molybdenum concentration 40 ~ 60g/L；
Disodiumedetate concentration 30~60g/L；
Sodium tartrate concentration 60 ~ 90g/L；
Dimethylamino borane concentration 3~6g/L；
Sodium bicarbonate concentration 6 ~ 9g/L.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1793008A1 (en) * 2005-12-02 2007-06-06 Siemens Aktiengesellschaft Alloy, protective coating for protecting a structural member against corrosion and oxidation at high temperatures and structural member
CN102046214A (en) * 2008-01-04 2011-05-04 史密夫和内修有限公司 Surface alloyed medical implant
CN102400115A (en) * 2011-10-20 2012-04-04 复旦大学 Preparation method of flexible copper electrode pattern in micron level wire width
WO2012167063A1 (en) * 2011-06-03 2012-12-06 Synthes Usa, Llc Surgical implant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1793008A1 (en) * 2005-12-02 2007-06-06 Siemens Aktiengesellschaft Alloy, protective coating for protecting a structural member against corrosion and oxidation at high temperatures and structural member
CN102046214A (en) * 2008-01-04 2011-05-04 史密夫和内修有限公司 Surface alloyed medical implant
WO2012167063A1 (en) * 2011-06-03 2012-12-06 Synthes Usa, Llc Surgical implant
CN102400115A (en) * 2011-10-20 2012-04-04 复旦大学 Preparation method of flexible copper electrode pattern in micron level wire width

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