Medical nylon composite pipe material and preparation method thereof
Technical field
The invention belongs to medicine equipment catheter arts, specifically, the present invention relates to medical nylon composite pipe material of a kind of novel polycomponent and preparation method thereof.
Background technology
Nylon (Nylon, Polyamide are called for short PA) refers to the plastics be made up of polyamide-based resin.This resinoid can be obtained by polycondensation by diamine and diprotic acid, also the lactan formed after can being dewatered by amino acid is obtained by ring-opening polymerization, different from PS, PE, PP etc., PA does not soften gradually with the rising of heating temperature, but it is softening in the narrow temperature range of fusing point at one, clearly, just there is flowing once reach in temperature to fusing point.
The kind of PA is a lot, mainly contains PA6, PA66, PA610, PA11, PA12, PA1010, PA612, PA46, PA6T, PA9T etc.The most conventional with PA6, PA66, PA610, PA11, PA12.Normally, nylon material physical strength is high, and softening temperature is high, heat-resisting, and coefficient of friction is low, wear-resistant, self lubricity, oil resistant, weak acid resistant, alkaline-resisting and common solvent, and electrical insulating property is good, has self-extinguishing, nontoxic, odorless, good weatherability.Wherein, the water-intake rate of nylon 12 is minimum in nylon series of products, and water-intake rate is very micro-on the impact of its mechanical property.Therefore, more external enterprises extensively adopt nylon 12 to prepare foley's tube, for the preparation of lower limb foley's tube, as pushed dry, interior pipe in the DEEP foley's tube of NVATEC, the BANTAM α foley's tube of CLEARSTREAM and CORDIS, ABBOTT, EV3 Medical lower limb foley's tube and sacculus all adopts nylon material, be widely used in medical instruments field.
But because the concentration of the polyamide-based in nylon 12 molecular structure is lower, thus its physical strength and rigidity are lower than nylon 6 and nylon66 fiber.Comparatively speaking, the hardness of nylon material is PA66 > PA66/6 > PA6 > PA610 > PA1010 > PA11 > PA12.Therefore, the hardness that single component nylon 12 material prepares minor diameter thin wall tubing is poor, and rigidity is lower, obtained push rod propelling movement property is poor, and mechanics transitivity is poor, is unfavorable for the propelling movement of the lower limb foley's tube in surgical procedure, add to operation, add the misery of patient.
Therefore, minimum at the water-intake rate giving full play to nylon 12, water-intake rate, under the prerequisite of the very micro-advantage of the impact of its mechanical property, improves hardness and the rigidity of Pa 12 Tube, and then expand its application at medical instruments field, be the current technical issues that need to address of those skilled in the art.
Many nylon composite materials have been prepared in prior art.Such as CN101200587 discloses a kind of preparation method of novel nylon 12 composite material, and the polyolefine of 20 ~ 40wt% is added in nylon 12 monomer of melting, disperses by stirring; The polynite of 0.5 ~ 2wt% is dispersed in nylon 12 monomer of melting; After both mixing above-mentioned, add 0.5 ~ 2wt% initiator and 0.5 ~ 2wt% promotor, carry out the anionic ring-opening polymerization of monomer, obtain matrix material.But nylon 12 matrix material is not owing to being suitable for medical instruments field containing multiple auxiliary agent disclosed in this patent application.
Summary of the invention
In view of the defect of above-mentioned prior art, the technical problem to be solved in the present invention is to provide a kind of new medical nylon composite conduit material that can be used for medical instruments field, and described new medical nylon composite conduit material can solve the problems such as single component nylon 12 material hardness is low, water-intake rate is high, poor rigidity.And many components nylon composite pipe material prepared by the present invention does not add any auxiliary agent, to human body fanout free region, there is good biocompatibility, therefore can be used for medical field; And the present invention has technique simply, the features such as flow process is short, and efficiency is high, pollution-free.
Therefore, first object of the present invention is to provide a kind of medical nylon composite pipe material, it is characterized in that it contains at least one in nylon 6, nylon66 fiber, NYLON610, nylon 1010, nylon 11 or aromatic nylon, its total mass percent is less than or equal to 50%, and nylon 12, its mass percent is for being more than or equal to 50%.
According to an embodiment of the invention, the number-average molecular weight of described nylon 6, nylon66 fiber, NYLON610, nylon 1010, nylon 11, aromatic nylon and nylon 12 can be 10000-40000, preferred 10000-20000.
According to another implementation of the invention, described aromatic nylon can be selected from MXD6 or PA9T.
According to a particularly preferred embodiment of the present invention, medical nylon composite pipe material of the present invention is less than or equal to nylon 6, nylon66 fiber, NYLON610, nylon 1010, at least one in nylon 11 or aromatic nylon of 50% by total mass per-cent, and mass percent is that the nylon 12 being more than or equal to 50% forms.Such as, but medical nylon composite pipe material of the present invention optionally can also add other components, PET, polyethylene terephthalate.
According to an embodiment of the invention, the internal diameter of described medical nylon composite pipe material can be 0.2mm-7.5mm.
According to an embodiment of the invention, the external diameter of described medical nylon composite pipe material can be 0.4mm-8.0mm.
According to another implementation of the invention, the wall thickness of described medical nylon composite pipe material can be 0.2mm-2.0mm.
Second object of the present invention is to provide the method preparing above-mentioned medical nylon composite pipe material, said method comprising the steps of:
A) at least one in nylon 6, nylon66 fiber, NYLON610, nylon 1010, nylon 11 or aromatic nylon and nylon 12 are added melting mixing in forcing machine and extruding pelletization to obtain medical nylon composite granule; With
B) above-mentioned medical nylon composite granule is added in forcing machine melt extrude, cooling and shaping, dry obtain medical nylon composite pipe material.
According to an embodiment of the invention, described forcing machine can be screw extrusion press.
According to another implementation of the invention, carrying out a) before step, individual hour of described nylon 6, nylon66 fiber, NYLON610, nylon 1010, nylon 11, aromatic nylon and nylon 12 vacuum-drying 4-24 at 60-120 DEG C can be made in advance, preferably 12 hours.
According to an embodiment of the invention, melting mixing in described a) step the temperature of extruding pelletization can be 180-350 DEG C.
According to another implementation of the invention, the median size of the nylon composite granule obtained in described a) step can be 1mm-5mm.
According to an embodiment of the invention, the temperature melt extruded in described b) step can be 180-300 DEG C.
The present invention prepares in the method for medical nylon composite pipe material and does not add any auxiliary agent, and therefore obtained medical nylon composite pipe material, to human body fanout free region, has good biocompatibility, can be used for medical field.And described new medical nylon composite pipe material hardness is higher, water-intake rate is lower and rigidity is better.
Embodiment
Embodiment 1
The nylon 12 (BASF, 111104) of to be the nylon66 fiber (BASF, 110921-02) of 1.5w and molecular weight by molecular weight be 1.5w is placed in the vacuum drying oven vacuum-drying 24 hours of 60 DEG C respectively, the systemic moisture of removing nylon material.Take the nylon66 fiber of 500 grams and the nylon 12 of 4500 grams, join dual-screw-stem machine forcing machine (SHJ-20C), by twin screw blending extrusion, granulation, drying, obtained a kind of particle diameter is the two-pack nylon composite granule of 1mm.Take the two-pack nylon composite granule of a certain amount of 3000 grams, join single-screw machine forcing machine, by melt extruding, to prepare internal diameter be 1.3mm for cooling and shaping, drying, external diameter is 1.5mm, wall thickness is the two-pack nylon composite pipe material of 0.20mm, and this tubing may be used for the medical instruments fields such as foley's tube.Medical nylon composite pipe material performance prepared by this embodiment is in table 1.
Wherein tension strain and ultimate load are the obtained composite pipe of 70mm embodiment 1 by intercepted length, is clamped in Instron5543 universal testing machine obtains with the test of the draw speed of 300mm/min; Water-intake rate is the composite pipe that the embodiment 1 taking 100 grams by electronic analytical balance BS124S (Shanghai Jie Sheng scientific instrument company limited) obtains, then the electric heating constant-temperature blowing drying box DZF-6050 (Shanghai Jie Sheng scientific instrument company limited) putting into 100 DEG C heats 30 minutes, take the weight of tubing again, can water-intake rate be calculated according to the weight that twice takes.
Embodiment 2
It is the nylon 6 (BASF of 1.5w by molecular weight, 110921-01), molecular weight is the nylon66 fiber (BASF of 1.5w, 110921-02) and molecular weight be the nylon 12 (BASF of 1.5w, 111104) the vacuum drying oven vacuum-drying 4 hours of 70 DEG C is placed in respectively, the systemic moisture of removing nylon material.Take the nylon66 fiber of nylon 6,250 grams and the nylon 12 of 4500 grams of 250 grams, join dual-screw-stem machine forcing machine (SHJ-20C), by twin screw blending extrusion, granulation, drying, obtained a kind of three components nylon composite granule.Take the three components nylon composite granule of 4000 grams, join single-screw machine forcing machine, by melt extruding, to prepare internal diameter be 1.5mm for cooling and shaping, drying, external diameter is 1.75mm, wall thickness is the three components nylon composite pipe material of 0.25mm, and this tubing may be used for the medical instruments fields such as foley's tube.Medical nylon composite pipe material performance prepared by this embodiment is in table 1.
Wherein tension strain and ultimate load are the obtained composite pipe of 70mm embodiment 2 by intercepted length, is clamped in Instron5543 universal testing machine obtains with the test of the draw speed of 300mm/min; Water-intake rate is the composite pipe that the embodiment 2 taking 100 grams by electronic analytical balance BS124S (Shanghai Jie Sheng scientific instrument company limited) obtains, then the electric heating constant-temperature blowing drying box DZF-6050 (Shanghai Jie Sheng scientific instrument company limited) putting into 100 DEG C heats 30 minutes, take the weight of tubing again, can water-intake rate be calculated according to the weight that twice takes.
Embodiment 3
The nylon 12 (BASF, 111104) of to be the nylon 11 (BASF, 110921-03) of 2w and molecular weight by molecular weight be 1.5w is placed in the vacuum drying oven vacuum-drying 10 hours of 120 DEG C respectively, the systemic moisture of removing nylon material.Take the nylon 11 of 2000 grams and the nylon 12 of 3000 grams, join dual-screw-stem machine forcing machine (SHJ-20C), by twin screw blending extrusion, granulation, drying, obtained a kind of two-pack nylon composite granule.Take the two-pack nylon composite granule of 1000 grams, join single-screw machine forcing machine, by melt extruding, to prepare internal diameter be 0.25mm for cooling and shaping, drying, external diameter is 0.5mm, wall thickness is the two-pack nylon composite pipe material of 0.25mm, and this tubing may be used for the medical instruments fields such as foley's tube.Medical nylon composite pipe material performance prepared by this embodiment is in table 1.
Wherein tension strain and ultimate load are the obtained composite pipe of 70mm embodiment 3 by intercepted length, is clamped in Instron5543 universal testing machine obtains with the test of the draw speed of 300mm/min; Water-intake rate is the composite pipe that the embodiment 3 taking 100 grams by electronic analytical balance BS124S (Shanghai Jie Sheng scientific instrument company limited) obtains, then the electric heating constant-temperature blowing drying box DZF-6050 (Shanghai Jie Sheng scientific instrument company limited) putting into 100 DEG C heats 30 minutes, take the weight of tubing again, can water-intake rate be calculated according to the weight that twice takes.
Embodiment 4
The nylon 12 (BASF, 111104) of to be the nylon 6 (BASF, 110921-01) of 1.5w and molecular weight by molecular weight be 1.5w is placed in the vacuum drying oven vacuum-drying 12 hours of 110 DEG C respectively, the systemic moisture of removing nylon material.Take the nylon 6 of 1000 grams and the nylon 12 of 4000 grams, join dual-screw-stem machine forcing machine (SHJ-20C), by twin screw blending extrusion, granulation, drying, obtained a kind of two-pack nylon composite granule.Take the two-pack nylon composite granule of 2000 grams, join single-screw machine forcing machine, by melt extruding, to prepare internal diameter be 1.75mm for cooling and shaping, drying, external diameter is 2mm, wall thickness is the two-pack nylon composite pipe material of 0.25mm, and this tubing may be used for the medical instruments fields such as foley's tube.Medical nylon composite pipe material performance prepared by this embodiment is in table 1.
Wherein tension strain and ultimate load are the obtained composite pipe of 70mm embodiment 4 by intercepted length, is clamped in Instron5543 universal testing machine obtains with the test of the draw speed of 300mm/min; Water-intake rate is the composite pipe that the embodiment 4 taking 100 grams by electronic analytical balance BS124S (Shanghai Jie Sheng scientific instrument company limited) obtains, then the electric heating constant-temperature blowing drying box DZF-6050 (Shanghai Jie Sheng scientific instrument company limited) putting into 100 DEG C heats 30 minutes, take the weight of tubing again, can water-intake rate be calculated according to the weight that twice takes.
Embodiment 5
It is nylon 9 T (the PA9T) (BASF of 1w by molecular weight, 110921-04), molecular weight is the nylon 12 (BASF of 1.5w, 111104), the vacuum drying oven vacuum-drying 24 hours of 70 DEG C is placed in respectively, the systemic moisture of removing material.Take nylon 9 T (the PA9T) (BASF that 150 gram molecular weights are 1w, 110921-04) He 4850 gram molecular weights are the nylon 12 (BASF of 1.5w, 111104), join dual-screw-stem machine forcing machine (SHJ-20C), by twin screw blending extrusion, granulation, drying, obtained a kind of two-pack nylon composite granule.Take the two-pack nylon composite granule of 5000 grams, join dual-screw-stem machine forcing machine (SHJ-20C), by melt extruding, to prepare internal diameter be 6.0mm for cooling and shaping, drying, external diameter is 8.0mm, wall thickness is the two-pack nylon composite pipe material of 2.0mm, and this tubing may be used for the medical instruments fields such as foley's tube.Medical nylon composite pipe material performance prepared by this embodiment is in table 1.
Wherein tension strain and ultimate load are the obtained composite pipe of 70mm embodiment 6 by intercepted length, is clamped in Instron5543 universal testing machine obtains with the test of the draw speed of 300mm/min; Water-intake rate is the composite pipe that the embodiment 6 taking 100 grams by electronic analytical balance BS124S (Shanghai Jie Sheng scientific instrument company limited) obtains, then the electric heating constant-temperature blowing drying box DZF-6050 (Shanghai Jie Sheng scientific instrument company limited) putting into 100 DEG C heats 30 minutes, take the weight of tubing again, can water-intake rate be calculated according to the weight that twice takes.
Table 1: the tension strain of the composite pipe that each embodiment obtains, ultimate load and water-intake rate