CN104474592A - Medical organosilicone material for pancreas and intestine anastomosis instrument and preparation method thereof - Google Patents
Medical organosilicone material for pancreas and intestine anastomosis instrument and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a medical organosilicone material for a pancreas and intestine anastomosis instrument and a preparation method thereof. The medical organosilicone material is prepared from 60-80% of a silicone rubber matrix, 3-5% of a structure controlling agent, 2-4% of a vulcanizing agent, 0.5-1.5% of a crosslinking agent, 0.05-0.1% of a catalyst and 10-30% of a reinforcing agent. The preparation method of the medical organosilicone material comprises the following steps: (1) preparing rubber master batch; (2) mixing; (3) standing a rubber compound; (4) vulcanizing in two stages; and (5) increasing temperature gradually, and treating to obtain the medical organosilicone elastomer material. The invention further discloses the pancreas and intestine anastomosis instrument produced from the medical organosilicone elastomer material. The pancreas and intestine anastomosis instrument is in a strip shape, and titanium screws are uniformly distributed on the pancreas and intestine anastomosis instrument. The medical organosilicone elastomer material has the characteristics of high ductility, high tear strength, high flexibility and excellent medium resistance, is non-toxic physiologically and can be widely applied to the medical field.
Description
Technical field
The present invention relates to medical organic silicon elastomer pancreas intestine anastomat material, particularly a kind of elasticity better, medical organic silicon pancreas intestine anastomat material of excellent in mechanical performance and preparation method thereof.
Background technology
After nineteen thirty-five, Wipple initiated pancreaticoduodenectomy, through the development of nearly 80 years, the pancreas Surgical healing mode recorded with regard to document at present has just exceeded 50 kinds.And mainly adopting following three kinds of pancreas Surgical healing modes clinically: sleeve type end end Pancreaticoenterostomy, ductus pancreaticus are to mucosa side Pancreaticoenterostomy and Binding pancreatico-jejunostomy.
Binding pancreatico-jejunostomy is end end sleeve type anastomosis, for a kind of methods of anastomosis of improvement, but practical operation quite bothers, and when in the end using thick line binding anastomotic position, pancreas stump is easy to slippage from the jejunum broken ends of fractured bone, can not ensure that the jejunum broken ends of fractured bone and pancreas stump are firmly fixed together simultaneously.Based on this thought of performing the operation, use pancreas intestine anastomat instead and carry out pancreas Surgical healing, avoid using needlework to sew up, then can reach operation expected effect on the one hand, greatly will reduce the difficulty of operation on the other hand.
Pancreas intestine anastomat directly acts on human body pancreas intestinal surface, and the requirement of this type of material property is: the first, must safety, and this material should be nontoxic or side effect is minimum.The second, physics, chemistry and mechanical performance should meet functional requirement required in clinical practice.3rd, there is good adaptability.Silastic material have compared with common polyurethane material nontoxic, elasticity is high, high-low temperature resistant, protection against the tide, uvioresistant, resistance to chemical attack, aging resistance and the advantage such as morphotropism is little, emulation property is strong, sulfuration time do not release low molecule by-product, shrinkage factor is little, nontoxic, corrosion-free to ground, therefore, silicone rubber is selected to carry out the making of pancreas intestine anastomat.
Summary of the invention
An object of the present invention is to overcome the large and problem of postoperative easy generation pancreas fistula of medically Pancreas cancer patients pancreas intestinal engaging operation difficulty, providing the medical organic silicon pancreas intestine anastomat material of a kind of high resiliency and tearing toughness.
Another object of the present invention is to the preparation method that a kind of above-mentioned medical organic silicon pancreas intestine anastomat material is provided.
Another object of the present invention is to provide a kind of pancreas intestine anastomat utilizing above-mentioned medical organic silicon material to make.
The realization of the present invention first object, mainly improve elasticity and the tearing toughness of organosilicon material, make it have a kind of high density, high resiliency, high ductibility, high flexibility and be insoluble to the physicochemical properties such as solvent, and not by temperatures involved, can medical domain be widely used in.
The object of the invention is to be achieved through the following technical solutions.
As an embodiment of the invention, a kind of medical organic silicon pancreas intestine anastomat material, this medical organic silicon elastomer pancreas intestine anastomat material is prepared from by the raw material of following mass percentage content:
Further, described silicone rubber matrix is methyl phenyl vinyl silicone rubber, trifluoro propyl methyl vinyl silicone rubber, methyl vinyl silicone rubber or fluorosioloxane rubber.
Further, described constitution controller is α or alpha, omega-dihydroxy polydimethyl siloxane or Diphenylsilanediol.
Further, described vulcanizing agent is benzoyl peroxide, peroxidized t-butyl perbenzoate or platinum vulcanizing agent.
Further, described cross-linking agent is dimethylamino methyl-monosilane, methyl (hydrogen) dichlorosilane, trimethoxy hydrogen silane, chlorocarbon base modified polyorganosiloxane, polymethyl hydrogen siloxane or methylbenzene acetenyl polysiloxanes.
Further, described catalyst is Friedel-Crafts catalyst, Quaternary Ammonium Alkali Catalyst, colloid Raney nickel or dibutyltin dilaurate catalyst.
Further, described modification reinforcing agent is ultrafine mineral powder, fume colloidal silica or the nano-calcium carbonate powder body after modifier and dehydrated alcohol hybrid reaction are dried;
Described modifier is the linear polydimethysiloxane of silane resin acceptor kh-550 (gamma-aminopropyl-triethoxy-silane) or terminal hydroxy group.
Correspondingly, the present invention gives a kind of preparation method of medical organic silicon pancreas intestine anastomat material, comprises the steps:
(1) be, after the modifier of 1:1 mixes with dehydrated alcohol, together join mass ratio in flask with reinforcing agent, 70-80 DEG C of stirred in water bath evenly after, take out, be placed in vacuum drying oven and dry;
(2) modified 10-30% reinforcing agent, 3-5% constitution controller are successively evenly added in the silicone rubber matrix of 60-80% mixing, then add 2-4% vulcanizing agent, 0.5-1.5% cross-linking agent is evenly mixing;
(3) the matrix material mixed is placed more than 24h;
(4), after the matrix material after placement being carried out back mixing 10min, add the catalyst of 0.05-0.1% to evenly mixing;
(5) by matrix material step up cure good for back mixing, matrix material is loaded rapidly sulfuration in the mould having risen to one step cure temperature, then carry out post vulcanization, after two-stage reaction completes, carry out cooling and demolding, take out material;
(6) post processing is carried out to the sizing material vulcanizated, progressively slowly heat up four sections to heat up and dry, take out, be cooled to room temperature, obtain medical organic silicon elastomer pancreas intestine anastomat material.
Further, described one step cure temperature is 120 DEG C ~ 160 DEG C, and cure time is 6min ~ 10min; Post vulcanization temperature is 170 DEG C ~ 200 DEG C, and cure time is 5min ~ 10min;
Described four sections of intensifications are dried and are dried 0.5-1h for being first warming up to 90-120 DEG C, continue to be warming up to 140-160 DEG C and dry 0.5-1h, then continue to be warming up to 170-180 DEG C of oven dry 1-2h, finally continue to be warming up to 190-200 DEG C and dry 2-3h.
And then, The present invention gives a kind of pancreas intestine anastomat utilizing medical organic silicon material to prepare, comprise a strip sizing material sheet, a side surface along sizing material sheet is evenly equipped with vertically disposed titanium nail, titanium nail embeds in sizing material sheet, the head of a nail of titanium nail is placed in sizing material sheet, and the nail tip of titanium nail stretches out 0.30-0.50cm along sizing material sheet.
Further, medical organic silicon pancreas intestine anastomat material of the present invention, except the proportioning of system, this type of organosilicon is as the techniques such as mixing, sulfuration also can produce material impact to the performance of pancreas intestine anastomat in the course of processing, and therefore optimized fabrication technique is very necessary.Optimization Technology is as follows:
(1) the roll spacing of opening rubber mixing machine should be adjusted to and make silicone rubber bag roller and have necessarily to pile glue, and be suitable for adding of compounding ingredient like this, the rotating ratio of two rollers controls at 1:1.3, and mixing uniformity can be made to reach optimum degree.
(2) various auxiliary agent should fully grind, and particle diameter is less, and the degree of scatter in system is better.Experimental result shows, auxiliary agent such as the vulcanizing agent without grinding is added in elastomeric compound, can disperse uneven, and also has residual in silicone rubber after curing, and then affects the state of cure (vulcanization) of vulcanizate entirety.
(3) the elastomeric compound storage period preferably controlled in 6-24 hour, and the storage period is too short, and each component fully cannot be disperseed in system, and the storage period is long, compound viscosity can be made to increase excessive, affect the mixing uniformity of follow-up compounding ingredient.
(4) answer quiet run during thin-pass blanking, avoid being involved in the inconsistent of caused material physical property because of air.
(5) should guarantee during sulfuration that the temperature at each position of mould is homogeneous, controlled pressure, standardize solution is abundant.
(6), in last handling process, stable raised temperature, can make residue fully decompose.
The present invention is different from medical organic silicon elastomeric material in the past, and the present invention has following feature:
(1) the present invention is that one utilizes medical organic silicon material to prepare pancreas intestine anastomat, can wrap up pancreas and duodenum end, make it fit like a glove, and can not produce excessive pressure to more crisp pancreatic tissue, unlikely crushing pancreatic tissue and produce pancreas fistula.
(2) the medical organic silicon pancreas intestine anastomat that prepared by the present invention is embedded with four pieces of titanium nails, compares ligament strapping now medically used, effectively can fix pancreas and duodenum end, make its unlikely slippage, reach identical object.
(3) owing to have employed suitable silicone rubber matrix, impart the hot strength that medical organic silicon elastomeric material is good, elongation at break, tearing strength and resistance to medium.
(4) owing to have employed cross-linking agent, introduce cross-linking vulcanized mechanism, cross-linking agent and matrix are under the co-catalysis effect of catalyst and vulcanizing agent, matrix can be made while sulfuration again cross-linking reaction to occur, therefore improve rate of cure and state of cure (vulcanization), finally establish the full cross-linked structure of molecule level, this structure can ensure that material has good mechanical property; Especially the tear resistance of medical organic silicon elastomeric material excellence is imparted.
(5), owing to have employed catalyst, ensure that the completeness of reacting between cross-linking agent and matrix component one material, matrix component two material, be beneficial to the raising of medical organic silicon elastomeric material mechanical property.
Accompanying drawing explanation
Fig. 1 (a) and Fig. 1 (b) is anastomotic stoma tissue slice figure respectively.
Fig. 2 (a) and Fig. 2 (b) is anastomat side view and top view respectively.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.It should be noted that, following embodiment only for illustration of the present invention, but is not limited to practical range of the present invention.
Unless otherwise indicated, the raw material addition that the present invention is following adopted is mass percent.
The preparation method of medical organic silicon pancreas intestine anastomat material of the present invention, comprises the steps:
(1) be, after the modifier of 1:1 mixes with dehydrated alcohol, together join mass ratio in flask with reinforcing agent, 70-80 DEG C of stirred in water bath evenly after, take out, be placed in vacuum drying oven and dry;
Wherein, modification reinforcing agent is ultrafine mineral powder, fume colloidal silica or the nano-calcium carbonate powder body after modifier and dehydrated alcohol hybrid reaction are dried; Modifier is the linear polydimethysiloxane of silane resin acceptor kh-550 (gamma-aminopropyl-triethoxy-silane) or terminal hydroxy group.
(2) modified 10-30% reinforcing agent, 3-5% constitution controller are successively evenly added in the silicone rubber matrix of 60-80% mixing, add 2-4% vulcanizing agent again, 0.5-1.5% cross-linking agent is evenly mixing, ensure that mixing time, thin-pass number of times are to guarantee that in elastomeric compound, each component is in the base dispersed;
(3) the matrix material mixed is placed more than 24h;
(4), after the matrix material after placement being carried out back mixing 10min, add the catalyst of 0.05-0.1% to evenly mixing;
(5) by matrix material step up cure good for back mixing, matrix material is loaded rapidly to have risen to one step cure temperature be sulfuration in the mould of 120 DEG C ~ 160 DEG C, cure time is 6min ~ 10min; Carry out post vulcanization again, post vulcanization temperature is 170 DEG C ~ 200 DEG C, and cure time is 5min ~ 10min; Carry out cooling and demolding after two-stage reaction completes, take out material;
(6) post processing is carried out to the sizing material vulcanizated, progressively slowly heat up four sections to heat up and dry, first be warming up to 90-120 DEG C and dry 0.5-1h, continue to be warming up to 140-160 DEG C and dry 0.5-1h, continue to be warming up to 170-180 DEG C again and dry 1-2h, finally continue to be warming up to 190-200 DEG C and dry 2-3h, take out, be cooled to room temperature, obtain medical organic silicon elastomer pancreas intestine anastomat material.
Medical organic silicon pancreas intestine anastomat material, except the proportioning of system, this type of organosilicon is as the techniques such as mixing, sulfuration also can produce material impact to the performance of pancreas intestine anastomat in the course of processing, and therefore optimized fabrication technique is very necessary.As follows to Optimization Technology:
(1) the roll spacing of opening rubber mixing machine should be adjusted to and make silicone rubber bag roller and have necessarily to pile glue, and be suitable for adding of compounding ingredient like this, the rotating ratio of two rollers controls at 1:1.3, and mixing uniformity can be made to reach optimum degree.
(2) various auxiliary agent should fully grind, and particle diameter is less, and the degree of scatter in system is better.Experimental result shows, auxiliary agent such as the vulcanizing agent without grinding is added in elastomeric compound, can disperse uneven, and also has residual in silicone rubber after curing, and then affects the state of cure (vulcanization) of vulcanizate entirety.
(3) the elastomeric compound storage period preferably controlled in 6-24 hour, and the storage period is too short, and each component fully cannot be disperseed in system, and the storage period is long, compound viscosity can be made to increase excessive, affect the mixing uniformity of follow-up compounding ingredient.
(4) answer quiet run during thin-pass blanking, avoid being involved in the inconsistent of caused material physical property because of air.
(5) should guarantee during sulfuration that the temperature at each position of mould is homogeneous, controlled pressure, standardize solution is abundant.
(6), in last handling process, stable raised temperature, can make residue fully decompose.
Further illustrate preparation process of the present invention below in conjunction with concrete embodiment, specific embodiment is in table 1 (each component is according to mass percent):
Table 1 specific embodiment
Table 2 embodiment performance indications contrast
As known from Table 2, embodiment 3 is best, its elongation at break reaches 248.5%, the highest in all embodiments, hot strength reaches 2.35, although be not the highest, but the hot strength of this type of medical material requires general not high, comprehensive elongation at break, embodiment 3 combination property is better than other examples, simultaneously with reference to other examples, except embodiment 1, other embodiment elongation at breaks are all greater than 150%, can meet the needs of pancreas intestine anastomat the most completely, and this material meets medical material requirement on the whole.
Patience test is carried out to embodiment 3, the change occurred under this patience test simulation environment of silicone rubber pancreas intestine anastomat material each organ in human body and after disinfecting on the impact of goods, the solvent that silicone rubber pancreas intestine anastomat material obtained for embodiment 3 is placed in 75% ethanol, distilled water, hydrochloric acid (PH=0.8), 3% hydrogen peroxide and NaOH (PH=9) is respectively soaked, contrast is taken out after 14 days, observe its surface change and mass change, as shown in table 3.
Table 3 patience test result
In five kinds of solution, soak material after 14 days the phenomenon of xanthochromia or other surface breakdowns does not all occur, wherein, NaOH solution simulates the change of goods at the pH value of human pancreas and intestinal tube, the environment that HCl solution simulation human body inner acidic is maximum, tested by patience, goods are of poor quality very little in various solution, and explanation can grantee's internal milieu change, immersion through ethanol and hydrogen peroxide is also micro-and micro-to its general impacts, illustrates that goods can by using after routine disinfection.
The normal range of extracellular fluid pH value
Carry out pathological analysis to the good embodiment 3 of properties, result is as follows:
Fig. 1 (a) samples A tissue slice figure for pancreas intestine anastomat pancreas intestinal anastomotic stoma HE ╳ 100, and Fig. 1 (b) samples B tissue slice figure for pancreas intestine anastomat anastomotic stoma HE ╳ 100:
(1) phenomenon:
HE dyeing was carried out to anastomotic stoma tissue slice in postoperative 10th day, find a large amount of proliferation of fibrous tissue between pancreas and intestinal wall by microscopic examination, and have a small amount of inflammatory cell to invade profit and the formation of more blood capillary.
(2) pathological analysis:
Anastomotic stoma is recovered better, and in 10 days, capillary vascularization illustrates that duodenum and pancreas can carry out normal blood circulation, and turnaround time is fast.
(3) material property analysis:
Long strip type made by anastomat, because the own softness of methyl vinyl silicone rubber material after sulfuration is no lack of toughness and intensity, impel the pancreas intestine anastomat made with it to be wrapped in well outside pancreas intestinal, pancreas and jejunum can be combined closely, facilitate the reply of anastomotic stoma.
Each mechanical performance index of medical organic silicon elastomeric material of the present invention can be good at the problem solving elasticity and tearing toughness deficiency, makes operation connect the growth of pancreas Surgical healing smoothly.Therefore, material of this high resiliency and tearing toughness and preparation method thereof, and utilize this material to make this pancreas intestine anastomat can to solve this medical problem.
Medical organic silicon material of the present invention is utilized to prepare pancreas intestine anastomat structure as shown in Fig. 2 (a), (b), this pancreas intestine anastomat comprises a strip sizing material plate, sizing material is cut out the strip of growth 10-18cm, wide 0.5-2cm, thick 0.15-0.20cm, a side surface along sizing material plate is evenly equipped with vertically disposed titanium nail, and titanium nail is embedded in sizing material plate evenly distributedly, the head of a nail of titanium nail is placed in sizing material plate, the head of a nail can not expose sizing material surface, and the nail tip of titanium nail stretches out 0.30-0.50cm along sizing material plate.
This pancreas intestine anastomat can provide suitable resilient, more high anti-tearing strength, and respond well at treatment pancreas Surgical healing Post operation, what anastomat was followed closely by titanium fixes, and fits like a glove on pancreas intestinal, does not have the phenomenon that pancreatic juice leaks outside, and the growth of pancreas intestinal rapidly, coincide good.In addition, without any untoward reaction, all are normal for patient body function.
The above; it is only the embodiment of pin of the present invention; above-described embodiment not does any restriction to the present invention; every scope given by technical solution of the present invention and to any simple modification made for any of the above embodiments, change and equivalent structure change, all still belongs to the protection domain of technical solution of the present invention.
Claims (10)
1. a medical organic silicon pancreas intestine anastomat material, is characterized in that, this medical organic silicon elastomer pancreas intestine anastomat material is prepared from by the raw material of following mass percentage content:
2. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, is characterized in that, described silicone rubber matrix is methyl phenyl vinyl silicone rubber, trifluoro propyl methyl vinyl silicone rubber, methyl vinyl silicone rubber or fluorosioloxane rubber.
3. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, is characterized in that, described constitution controller is α or alpha, omega-dihydroxy polydimethyl siloxane or Diphenylsilanediol.
4. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, is characterized in that, described vulcanizing agent is benzoyl peroxide, peroxidized t-butyl perbenzoate or platinum vulcanizing agent.
5. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, it is characterized in that, described cross-linking agent is dimethylamino methyl-monosilane, methyl (hydrogen) dichlorosilane, trimethoxy hydrogen silane, chlorocarbon base modified polyorganosiloxane, polymethyl hydrogen siloxane or methylbenzene acetenyl polysiloxanes.
6. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, is characterized in that, described catalyst is Friedel-Crafts catalyst, Quaternary Ammonium Alkali Catalyst, colloid Raney nickel or dibutyltin dilaurate catalyst.
7. a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, is characterized in that, described modification reinforcing agent is ultrafine mineral powder, fume colloidal silica or the nano-calcium carbonate powder body after modifier and dehydrated alcohol hybrid reaction are dried;
Described modifier is the linear polydimethysiloxane of silane resin acceptor kh-550 (gamma-aminopropyl-triethoxy-silane) or terminal hydroxy group.
8., based on the preparation method of a kind of medical organic silicon pancreas intestine anastomat material according to claim 1, it is characterized in that, comprise the steps:
(1) be, after the modifier of 1:1 mixes with dehydrated alcohol, together join mass ratio in flask with reinforcing agent, 70-80 DEG C of stirred in water bath evenly after, take out, be placed in vacuum drying oven and dry;
(2) modified 10-30% reinforcing agent, 3-5% constitution controller are successively evenly added in the silicone rubber matrix of 60-80% mixing, then add 2-4% vulcanizing agent, 0.5-1.5% cross-linking agent is evenly mixing;
(3) the matrix material mixed is placed more than 24h;
(4), after the matrix material after placement being carried out back mixing 10min, add the catalyst of 0.05-0.1% to evenly mixing;
(5) by matrix material step up cure good for back mixing, matrix material is loaded rapidly sulfuration in the mould having risen to one step cure temperature, then carry out post vulcanization, after two-stage reaction completes, carry out cooling and demolding, take out material;
(6) post processing is carried out to the sizing material vulcanizated, progressively slowly heat up four sections to heat up and dry, take out, be cooled to room temperature, obtain medical organic silicon elastomer pancreas intestine anastomat material.
9. the preparation method of a kind of medical organic silicon pancreas intestine anastomat material according to claim 8, is characterized in that, described one step cure temperature is 120 DEG C ~ 160 DEG C, and cure time is 6min ~ 10min; Post vulcanization temperature is 170 DEG C ~ 200 DEG C, and cure time is 5min ~ 10min;
Described four sections of intensifications are dried and are dried 0.5-1h for being first warming up to 90-120 DEG C, continue to be warming up to 140-160 DEG C and dry 0.5-1h, then continue to be warming up to 170-180 DEG C of oven dry 1-2h, finally continue to be warming up to 190-200 DEG C and dry 2-3h.
10. based on pancreas intestine anastomat prepared by a kind of medical organic silicon material according to claim 1, it is characterized in that, comprise a strip sizing material sheet, a side surface along sizing material plate is evenly equipped with vertically disposed titanium nail, titanium nail embeds in sizing material sheet, the head of a nail of titanium nail is placed in sizing material sheet, and the nail tip of titanium nail stretches out 0.30-0.50cm along sizing material sheet.
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| CN108434521A (en) * | 2018-06-14 | 2018-08-24 | 中国人民解放军陆军军医大学第附属医院 | A kind of implantation material and preparation method thereof promoting bone wound healing |
| CN109486195A (en) * | 2018-10-24 | 2019-03-19 | 常州工程职业技术学院 | A kind of puncture outfit valve material and its preparation method and application |
| CN110600167A (en) * | 2019-08-05 | 2019-12-20 | 东莞福川精密工业股份有限公司 | Special cable for high-flexibility robot and manufacturing process |
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| CN101617949A (en) * | 2009-06-19 | 2010-01-06 | 刘忠臣 | Pancreatoduodenal-binding and sleeving matching device |
| CN102648863A (en) * | 2012-05-10 | 2012-08-29 | 西安交通大学 | Anastomat device applicable for pancreaticojejunostomy |
| CN102746674A (en) * | 2012-07-31 | 2012-10-24 | 西安科技大学 | High heat-resistant porous organic silicon alloy elastomer material and method for preparing same |
| CN103536345A (en) * | 2012-07-17 | 2014-01-29 | 上海微创骨科医疗科技有限公司 | Dynamic stabilization implanting unit for spine |
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| CN101617949A (en) * | 2009-06-19 | 2010-01-06 | 刘忠臣 | Pancreatoduodenal-binding and sleeving matching device |
| CN102648863A (en) * | 2012-05-10 | 2012-08-29 | 西安交通大学 | Anastomat device applicable for pancreaticojejunostomy |
| CN103536345A (en) * | 2012-07-17 | 2014-01-29 | 上海微创骨科医疗科技有限公司 | Dynamic stabilization implanting unit for spine |
| CN102746674A (en) * | 2012-07-31 | 2012-10-24 | 西安科技大学 | High heat-resistant porous organic silicon alloy elastomer material and method for preparing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108434521A (en) * | 2018-06-14 | 2018-08-24 | 中国人民解放军陆军军医大学第附属医院 | A kind of implantation material and preparation method thereof promoting bone wound healing |
| CN109486195A (en) * | 2018-10-24 | 2019-03-19 | 常州工程职业技术学院 | A kind of puncture outfit valve material and its preparation method and application |
| CN109486195B (en) * | 2018-10-24 | 2021-01-08 | 常州工程职业技术学院 | Puncture device valve material and preparation method and application thereof |
| CN110600167A (en) * | 2019-08-05 | 2019-12-20 | 东莞福川精密工业股份有限公司 | Special cable for high-flexibility robot and manufacturing process |
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| CN104474592B (en) | 2017-04-19 |
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