CN103965639A - Antibacterial anticoagulant high polymer material, and preparation method and application thereof - Google Patents
Antibacterial anticoagulant high polymer material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103965639A CN103965639A CN201310028066.7A CN201310028066A CN103965639A CN 103965639 A CN103965639 A CN 103965639A CN 201310028066 A CN201310028066 A CN 201310028066A CN 103965639 A CN103965639 A CN 103965639A
- Authority
- CN
- China
- Prior art keywords
- weight part
- weight
- macromolecular material
- silicon rubber
- coagulant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to an antibacterial anticoagulant high polymer material, comprising medical silicone rubber. The material further comprises, on the basis of 100 parts by weight of the medical silicone rubber, A) 1 to 30 parts by weight of layered silicate, B) 1 to 30 parts by weight of a quaternary ammonium salt, C) 1 to 20 parts by weight of an anticoagulant, D) 1 to 30 parts by weight of a hydrophilic polymer and E) 1 to 20 parts by weight of an antibacterial agent. The antibacterial anticoagulant high polymer material provided by the invention has both anticoagulant and antibacterial functions and excellent comprehensive properties including mechanical properties and biological properties, is safer and more reliable due to breakthroughs of its mechanical properties and is especially applicable as a medical high polymer material. The invention further relates to preparation of the antibacterial anticoagulant high polymer material and application of the material as a medical antibacterial anticoagulant high polymer material.
Description
Technical field
The invention belongs to field of biomedical polymer materials, be specifically related to a kind of antibiosis anticoagulative blood macromolecular material and its preparation method and application, this macromolecular material can be used as medical macromolecular materials.
Background technology
Biomaterial is, the material with property or function compatible with animal organism of the class Clinics and Practices that can be used for the reparation of animal organ and tissue and replacement, disease.Antibiosis anticoagulative blood biomaterial is the important component part of biomaterial, on the medical material that is widely used in contacting with human blood and tissue, as hemodialysis system, extracorporeal circulation system, heart valve prosthesis, schrittmacher, artificial blood vessel, intravascular stent, surgical cable and conduit etc.In the time that exotic contacts with blood, can destroy erythrocyte, make platelet activation, gathering, and then form thrombus.At clinicing aspect, also do not have a kind of artificial biomaterial for medical purpose energy perfection to be applied in human body at present.In the time that anticoagulant biomaterial contacts with biological tissue, require material not only to there is histocompatibility, can not cause inflammation to bio-tissue, also should there is blood compatibility, can antithrombotic, can there is not blood coagulation phenomenon on the surface of material.
At present, the method for preparing anti-biotic material is mainly in body material, to add argent ionic compound, chitosan, titanium dioxide, diphenyl ether biocides and microbiotic etc.; The main method of preparing anticoagulant material is surface heparinization, is obtained polyoxy acetylene structure and obtained poly-Phosphorylcholine class material by modification by modification.
In the time that material carries out anticoagulation modification, key will consider aspect several in concentration of material surface etc. from the biological activity of the firm degree of anti-coagulant, anti-coagulant and anti-coagulant.In general, be divided into physical adsorption and the large class of Chemical bond two.The former is easy, but the quantification of anti-coagulant is difficult to control, and the anticoagulation time length is not long, easily runs off with blood dissolves; Latter can be taken into account utilization ratio and the stability of anti-coagulant, and can large-scale industrial production.
For applying anti-coagulant at material surface, its bonding force is mainly to rely on ionic linkage, on the one hand, very easily destroyed due to the fracture of ionic linkage, thereby cause the rate of release of anti-coagulant very fast, make this anticoagulant material generating in ionic bond mode to lose too quickly anticoagulation function, on the other hand, because the excessive wash-out of coating substance causes toxicity problem, therefore lose the object of application clinically.In Patent Application Publication CN1225281A, the people such as xuwei disclose material surface are applied and obtains anticoagulant effect, but its experimentation on animals has produced a small amount of thrombus after showing 18 days, and anticoagulation persistence is still inadequate.Patent Application Publication CN101156970A has disclosed a kind of coating of high stability, but it is mainly used in NiTi alloy, and well-known silastic surface inertia can be large, is difficult to obtain good persistence.
For at material surface chemical graft anti-coagulant, anti-coagulant multiple spot is bonded in securely material surface by covalent bonds, changed the normal conformation of anti-coagulant, and active part may be by embedding or destruction.Thereby reduced its biological activity, and making anticoagulant effect reduction in various degree, the even completely dissolve having, loses application value clinically.So far not having yet can be at the direct grafting anti-coagulant of silastic surface, and obtains the report of good anti-freezing blood.
Biostatic type elastomerics, under coenocorrelation, has good biologically inert and chemical stability, the reparation, the equivalent material etc. that are mainly used as external medical treatment product and implant for a long time.Heat-resisting owing to having, cold-resistant, nontoxic, corrosion-free, the resistance to biological aging of medical grade silicon rubber, can not cause the characteristics such as surrounding tissue inflammation and transformation reactions after using in human body, is a kind of desirable medical macromolecular materials.
But in clinical application, due to factors such as hospital's particular surroundingss, medical macromolecular materials easily cause infection, one reasons is that medical material can stimulate the streptococcus aureus propagation in body, and then the infection that causes inflammation; Be hospital infection on the other hand, in hospital environment, bacterium, by the propagation of the article in medical worker's clothing, gloves and hospital, easily causes and infects, and it is said that the U.S. approaches every year 100000 people and dies from this type of infection.Therefore, in preparing anticoagulant material, to take into account the anti-microbial property of considering material.
Summary of the invention
In view of above-mentioned prior art situation, the present inventor has carried out extensive and deep research for silicone rubber based medical material, to developing a kind of medical macromolecular materials that not only have antibacterial and anticoagulant functions concurrently, and the anticoagulant functions of this material is enhanced than the macromolecular material of prior art, the consistency of this material and blood is improved, and good mechanical properties.Found that, by comprise layered silicate, quaternary ammonium salt, anti-coagulant, hydrophilic polymer and antiseptic-germicide in medical grade silicon rubber body material, can realize aforementioned object, obtain a kind of antibiosis anticoagulative blood macromolecular material that has anticoagulation and antibacterial and excellent combination property concurrently.The inventor has completed the present invention based on aforementioned discovery just.
Therefore, an object of the present invention is to provide a kind of novel antibiosis anticoagulative blood macromolecular material, this material has good antibacterial, anticoagulant functions concurrently, and blood is had to good consistency, and good mechanical properties.
Another object of the present invention is to provide a kind of method of preparing antibiosis anticoagulative blood macromolecular material of the present invention.
A further object of the present invention is to provide the purposes of antibiosis anticoagulative blood macromolecular material of the present invention as antibiosis anticoagulative blood medical macromolecular materials.
The technical scheme that realizes above-mentioned purpose of the present invention can be summarized as follows:
1. an antibiosis anticoagulative blood macromolecular material, it comprises medical grade silicon rubber, and the medical grade silicon rubber that this material comprises based on every 100 weight parts also comprises following component:
A) layered silicate of 1-30 weight part;
B) quaternary ammonium salt of 1-30 weight part;
C) anti-coagulant of 1-20 weight part;
D) hydrophilic polymer of 1-30 weight part; With
E) antiseptic-germicide of 1-20 weight part.
2. according to the macromolecular material of the 1st, wherein said layered silicate is to be selected from one or more in lower group: the cured soil of leaf, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake stone flour, green mud stone flour, polynite and bentonite.
3. according to the 1st or the macromolecular material of 2, wherein said quaternary ammonium salt is to be selected from one or more in lower group: dodecyl trimethyl-ammonium halide, tetradecyl trimethyl-ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl-ammonium halide, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, cetyl dimethyl benzyl ammonium halide, aforementioned each ammonium halide compound is preferably quaternary ammonium chloride and/or Quaternary ammonium bromide.
4. according to the macromolecular material of any one in 1-3 item, wherein said anti-coagulant is to be selected from one or more in lower group: small molecules heparin sodium, unfractionated heparin sodium, temparin, Acenocoumarol, urokinase, warfarin, r-hirudin, argatroban, ximelagatran, acetylsalicylic acid, ticlopidine and chondroitin sulfate.
5. according to the macromolecular material of any one in 1-4 item, wherein said hydrophilic polymer is that weight-average molecular weight is the polymkeric substance that contains hydrophilic radical of 100-2000000, is preferably and is selected from one or more in lower group: polyoxyethylene glycol, polymine, sodium alginate, Hyaluronic Acid, polyvinylpyrrolidone and polymethyl acyl oxyethyl group Phosphorylcholine.
6. according to the macromolecular material of any one in 1-5 item, wherein said antiseptic-germicide is to be selected from one or more in lower group: any mixture of nano cupric oxide, nano zine oxide, nano titanium oxide, nano phase ag_2 o, Manganse Dioxide, Cadmium Sulfide, tungstic oxide, tindioxide, ferric oxide, chitosan, Cefuroxime sodium, Amikacin Sulphate, tetracycline hydrochloride, paraxin, erythromycin, ciprofloxacin HCl, metronidazole, Rifampin, lincomycin, nanometer silver or these antiseptic-germicides.
7. according to the macromolecular material of any one in 1-6 item, wherein said medical grade silicon rubber is bi-component addition type silicon rubber, for example ethylene methacrylic radical siloxane, preferred vinyl content is the silicon rubber of 0.001-5wt%, especially the methyl ethylene silicone rubber that contents of ethylene is 0.07-4wt%, the medical grade silicon rubber that particularly preferably weight-average molecular weight is 300000-900000.
8. according to the macromolecular material of any one in 1-7 item, based on every 100 weight part medical grade silicon rubbers, it also comprises following component:
A) 1-20 weight part, the preferably layered silicate of 1-8 weight part;
B) 1-20 weight part, the preferably quaternary ammonium salt of 1-10 weight part;
C) 1-10 weight part, the preferably anti-coagulant of 1-8 weight part;
D) 5-30 weight part, the preferably hydrophilic polymer of 5-20 weight part; With
E) antiseptic-germicide of 5-20 weight part.
9. a method of preparing the antibiosis anticoagulative blood macromolecular material as described in any one in 1-8 item, comprises the steps:
A) by layered silicate, quaternary ammonium salt and anti-coagulant, the solution using liquid solvent as dispersion medium or dispersion form mix, and obtain anticoagulation intermediate;
B) anticoagulation intermediate hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber a) being obtained with step mixes, and obtains blend glue; And
C) by blend glue vulcanization crosslinking.
10. according to the method for the 9th, wherein
Step a) in, layered silicate, quaternary ammonium salt and anti-coagulant are uniformly mixed to 0.5-10 hour with water as solvent at the temperature of 25-120 DEG C, then ultrasonic dispersion 0.5-10 hour, finally dries, pulverizes, and obtains anticoagulation intermediate; And/or
Step b) in, the anticoagulation intermediate that hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber and step a) are obtained in blending equipment at 25-120 DEG C blend 10min-2 hour, obtain blend glue; And/or
Step c) in, the blend glue that step b) is obtained thermal treatment 5 minutes to 4 hours and vulcanization crosslinking at the temperature of 100-180 DEG C.
11. according to the described antibiosis anticoagulative blood macromolecular material of any one in 1-8 item purposes, the especially purposes in medical catheter as medical macromolecular materials.
Brief description of the drawings
Fig. 1 is the external static platelet adhesion reaction scanning electron microscope (SEM) photograph of the silicone rubber material of use in specification sheets embodiment 1 of the present invention.
Fig. 2 is the external static platelet adhesion reaction scanning electron microscope (SEM) photograph of the antibiosis anticoagulative blood macromolecular material of preparation in specification sheets embodiment 1 of the present invention.
Embodiment
According to an aspect of the present invention, provide a kind of antibiosis anticoagulative blood macromolecular material, it comprises medical grade silicon rubber, and the medical grade silicon rubber that this material comprises based on every 100 weight parts also comprises following component:
A) layered silicate of 1-30 weight part;
B) quaternary ammonium salt of 1-30 weight part;
C) anti-coagulant of 1-20 weight part;
D) hydrophilic polymer of 1-30 weight part; With
E) antiseptic-germicide of 1-20 weight part.
In antibiosis anticoagulative blood macromolecular material of the present invention, anti-coagulant provides anticoagulant functions as anticoagulant composition.Preferably, anti-coagulant is small molecules heparin sodium, unfractionated heparin sodium, temparin, Acenocoumarol, urokinase, warfarin, r-hirudin, argatroban, ximelagatran, acetylsalicylic acid, ticlopidine, chondroitin sulfate or their any mixture.For the purpose of the present invention, the consumption of anti-coagulant should make, the medical grade silicon rubber comprising based on every this material of 100 weight parts, and macromolecular material of the present invention comprises the anti-coagulant of 1-20 weight part conventionally, the preferably anti-coagulant of 1-10 weight part, the more preferably anti-coagulant of 1-8 weight part.
An outstanding feature of macromolecular material of the present invention is to comprise layered silicate and quaternary ammonium salt.Quaternary ammonium salt has certain germ resistance, what is more important, due to the positively charged ion interchangeability of layered silicate, can there is ion-exchange in the positively charged ion of quaternary ammonium salt and layered silicate, the interlamellar spacing of layered silicate is expanded, thereby make anti-coagulant to enter interlayer and obtain certain nano effect, having controlled well the release of anti-coagulant by the from inside to outside migration of anti-coagulant, avoiding too early the losing of anticoagulation function of material.In addition, due to the provide protection of laminate structure, make the anti-coagulant that enters laminated silicate interlayer can tolerate better heating blend, anti-coagulant is reduced because of the loss of activity that causes of heating blend.And; due to the protection of layered silicate to anti-coagulant, make at higher temperature, to process, this has improved the workability of antibiosis anticoagulative blood macromolecular material of the present invention; can obtain difform goods, greatly shorten the time of machine-shaping simultaneously.Meanwhile, layered silicate can also play to silicon rubber the effect of reinforcement, makes up with this reduction to material mechanical performance that hydrophilic polymer and anti-coagulant cause.
As layered silicate, the any mixture of the cured soil of leaf, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake stone flour, green mud stone flour, polynite, bentonite or these layered silicates be can use, polynite, talcum powder, mica, zeolite powder, attapulgite or its mixture preferably used.For the purpose of the present invention, the consumption of layered silicate should make, the medical grade silicon rubber comprising based on every 100 weight part macromolecular material of the present invention, macromolecular material of the present invention comprises the layered silicate of 1-30 weight part conventionally, the preferably layered silicate of 1-20 weight part, the more preferably layered silicate of 1-8 weight part.
As quaternary ammonium salt, can use any mixture of dodecyl trimethyl-ammonium halide, tetradecyl trimethyl-ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl-ammonium halide, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, cetyl dimethyl benzyl ammonium halide or aforementioned each ammonium halide.Preferably, quaternary ammonium salt is quaternary ammonium chloride and/or the Quaternary ammonium bromide in aforementioned each ammonium halide.For the purpose of the present invention, the consumption of quaternary ammonium salt should make, the medical grade silicon rubber comprising based on every 100 weight part macromolecular material of the present invention, and macromolecular material of the present invention comprises the quaternary ammonium salt of 1-30 weight part conventionally, the preferably quaternary ammonium salt of 1-20 weight part, the more preferably quaternary ammonium salt of 1-10 weight part.
Antibiosis anticoagulative blood macromolecular material of the present invention also comprises hydrophilic polymer, this polymkeric substance contains hydrophilic radical as hydroxyl, hydroxyl value is higher, adding of they improves the surface hydrophilicity of material, reduce the surface free energy between material and blood, increase blood compatibility, improved anticoagulant property.The weight-average molecular weight of hydrophilic polymer can be 100-2000000, preferably 400-600000.Further preferably, the molecular weight dispersion coefficient M of this polymkeric substance
w/ M
nfor 1-50, preferably 1-10.As hydrophilic polymer, preferably use any mixture of polyoxyethylene glycol, polymine, sodium alginate, Hyaluronic Acid, polyvinylpyrrolidone, polymethyl acyl oxyethyl group Phosphorylcholine or these hydrophilic polymers.Particularly preferably use polyoxyethylene glycol, sodium alginate, polymethyl acyl oxyethyl group Phosphorylcholine, polyvinylpyrrolidone and/or Hyaluronic Acid.For the purpose of the present invention, the consumption of hydrophilic polymer should make, the medical grade silicon rubber comprising based on every 100 weight part macromolecular material of the present invention, macromolecular material of the present invention comprises the hydrophilic polymer of 1-30 weight part conventionally, the preferably hydrophilic polymer of 5-30 weight part, the more preferably hydrophilic polymer of 5-20 weight part.
Another feature of macromolecular material of the present invention is to comprise antiseptic-germicide, thinks that macromolecular material of the present invention provides antibacterial.For the present invention, all antiseptic-germicides can be used in medical grade silicon rubber all can be used for the present invention.Preferably, antiseptic-germicide is any mixture of nano cupric oxide, nano zine oxide, nano titanium oxide, nano phase ag_2 o, Manganse Dioxide, Cadmium Sulfide, tungstic oxide, tindioxide, ferric oxide, chitosan, Cefuroxime sodium, Amikacin Sulphate, tetracycline hydrochloride, paraxin, erythromycin, ciprofloxacin HCl, metronidazole, Rifampin, lincomycin or these antiseptic-germicides.Particularly preferably use that titanium dioxide, chitosan, Cefuroxime sodium, ciprofloxacin HCl, welfare are flat, nanometer silver and/or zinc oxide.These antiseptic-germicides, for example nano titanium oxide can produce hydroxyl radical free radical in the situation that having illumination, makes bacterial oxidation be decomposed into carbonic acid gas and water, thereby gives material with anti-microbial property.Chitosan is crude substance, has the function of anti-inflammatory, pain relieving, promotion healing.For the purpose of the present invention, the consumption of antiseptic-germicide should make, the medical grade silicon rubber comprising based on every 100 weight part macromolecular material of the present invention, and macromolecular material of the present invention comprises the antiseptic-germicide of 1-20 weight part conventionally, preferably the antiseptic-germicide of 5-10 weight part.
As the matrix of macromolecular material of the present invention, use medical grade silicon rubber.For this reason, any can medically use silicon rubber all can be used for the present invention.Silicon rubber is the general name that molecular backbone chain only contains the specialty elastomer of silicon, Sauerstoffatom, can be represented by the formula:
In molecular formula, R is mainly methyl, and part is ethyl, vinyl, phenyl, itrile group and/or other extraordinary organic group.The present invention preferably, medical grade silicon rubber is dual composition addition type silicon rubber, and this can not produce hazardous and noxious substances because dual composition addition type silicon rubber has good processing characteristics and good mechanical property in the process of sulfuration, dimensional stability is very high, and job efficiency is high.As the example of silicon rubber, can mention ethylene methacrylic radical siloxane.The silicon rubber that particularly preferably contents of ethylene is 0.001-5wt%, especially contents of ethylene are the methyl ethylene silicone rubber of 0.07-4wt%.The weight-average molecular weight of especially preferred medical grade silicon rubber is 300000-900000.
In a preferred embodiment of the invention, every 100 weight part medical grade silicon rubbers that macromolecular material of the present invention comprises based on it also comprise following component:
A) layered silicate of 1-20 weight part;
B) quaternary ammonium salt of 1-20 weight part;
C) anti-coagulant of 1-10 weight part;
D) hydrophilic polymer of 5-30 weight part; With
E) antiseptic-germicide of 5-20 weight part.
According to another aspect of the present invention, provide a kind of method of preparing antibiosis anticoagulative blood macromolecular material of the present invention, the method comprises the steps:
A) by layered silicate, quaternary ammonium salt and anti-coagulant, the solution using liquid solvent as dispersion medium or dispersion form mix, and obtain anticoagulation intermediate;
B) anticoagulation intermediate hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber a) being obtained with step mixes, and obtains blend glue; And
C) by blend glue vulcanization crosslinking.
These three components of layered silicate, quaternary ammonium salt and anti-coagulant that in the step of the inventive method a), will form macromolecular material of the present invention are mixed.Solution or the dispersion form of the mixing of these three components using liquid solvent as dispersion medium carried out, make the positively charged ion generation ion-exchange in quaternary ammonium cation and layered silicate, thereby the interlamellar spacing that expands layered silicate, makes anti-coagulant can enter interlayer thus.As liquid solvent herein, be preferably water, for example distilled water, deionized water.
In a preferred embodiment of the inventive method, step a) in, layered silicate, quaternary ammonium salt and anti-coagulant are uniformly mixed to 0.5-10 hour with water as solvent at the temperature of 25-120 DEG C, then ultrasonic dispersion 0.5-10 hour, finally dry, pulverize, obtain anticoagulation intermediate.Particularly preferably be, layered silicate is first dissolved or is dispersed in water, form the aqueous solution or the water dispersion of layered silicate; Quaternary ammonium salt and anti-coagulant are dissolved in water, form the aqueous solution, then by the aqueous solution of the layered silicate of gained or water dispersion with containing the aqueous solution of quaternary ammonium salt and anti-coagulant, and ultrasonic dispersion, obtain water dispersion.Then filter this water dispersion, water washing precipitation, dry, pulverize, and makes anticoagulation intermediate.
Obtaining after anticoagulation intermediate, all the other components of this intermediate and macromolecular material of the present invention are being mixed together to then vulcanization crosslinking.
In another preferred embodiment of the inventive method, step b) in, the anticoagulation intermediate that hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber and step a) are obtained is blend 10min to 2 hour at 25-120 DEG C in blending equipment, obtains blend glue.As blending equipment herein, can mention Banbury mixer, mill, twin screw extruder etc.Blending temperature is selected according to material, is generally 25-60 DEG C.In the time using Banbury mixer blend, the roll spacing of Banbury mixer is also selected according to concrete material, is generally 0.5-4mm.
For the blend glue vulcanization crosslinking that step b) is obtained, the blend glue preferably step b) being obtained thermal treatment 5 minutes to 4 hours at the temperature of 100-180 DEG C.In order to carry out the vulcanization crosslinking here, conventionally need to add vulcanizing agent, for example platinum catalyst.The consumption of vulcanizing agent is conventional, as long as can blend glue is crosslinked.Typically, the medical grade silicon rubber use 1-2g that the consumption of vulcanizing agent comprises for every 100 weight part macromolecular material of the present invention.
Antibiosis anticoagulative blood macromolecular material of the present invention has anticoagulation and antibacterial concurrently, and the excellent combination property including mechanical property and biological property, in mechanical property, also have breakthrough, make product safety and reliability, be especially suitable for use as medical macromolecular materials.
Therefore,, according to last aspect of the present invention, purposes, the especially purposes in medical catheter of antibiosis anticoagulative blood macromolecular material of the present invention as medical macromolecular materials are provided.
In the present invention, different from the method for coating in the past and chemical graft, antibiosis anticoagulative courageous and upright can acquisition all from mechanical blending physically, this greatly reduces cost and operation easier, has reduced cost in having optimized performance.
In macromolecular material of the present invention, anti-coagulant is owing to entering the interlayer of layered silicate, therefore obtain certain nano effect, controlled well the release of anti-coagulant by the from inside to outside migration of anti-coagulant, avoid too early the losing of anticoagulation function of material.In addition, due to the provide protection of laminate structure, make the anti-coagulant that enters laminated silicate interlayer can tolerate better heating blend, anti-coagulant is reduced because of the loss of activity that causes of heating blend.And; due to the protection of layered silicate to anti-coagulant, make at higher temperature, to process, this has improved the workability of high-molecular anti-bacteria anticoagulant material of the present invention; can obtain difform goods, greatly shorten the time of machine-shaping simultaneously.Meanwhile, layered silicate can also play to silicon rubber the effect of reinforcement, makes up hydrophilic polymer and the reduction of anti-coagulant to material mechanical performance with this.
In addition, as layered silicate, part laminate structure can be peeled off after sulfuration, forms nano-dispersed, and rubber matrix is played to good enhancement.
As quaternary ammonium salt, in the present invention, not only use as intercalator, and quaternary ammonium salt also plays antiseptic-germicide, further improve the anti-microbial property of material.
Antibiosis anticoagulative blood macromolecular material of the present invention also comprises hydrophilic polymer, and adding of they improves the surface hydrophilicity of material, reduced the surface free energy between material and blood, improved blood compatibility.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, it should be pointed out that these embodiment are only to exemplary illustrated of the present invention, and should not think limitation of the scope of the invention.
Embodiment 1
1) 10g polynite (by the commercial acquisition of Zhejiang Feng Hong clay company limited, cationic ion exchange capacity 90mmol/100g) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain montmorillonite suspension liquid.
2) by 10g unfractionated heparin sodium (by the commercial acquisition of traditional Chinese medicines group chemical reagent Beijing company limited, 150u/mg tires) and 10g Dodecyl trimethyl ammonium chloride (by the commercial acquisition of Tianjin recovery Fine Chemical Works company, cp) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) montmorillonite suspension liquid that obtains mixes, and fully stirs 30min at 40 DEG C, and then ultrasonic dispersion 30min, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 460,000, contents of ethylene 0.004wt%), 5g polyoxyethylene glycol is (by the commercial acquisition of Peking blue profit fine chemistry industry company, weight-average molecular weight is 400), 5g nano titanium oxide is (by the commercial acquisition of Hangzhou Wanjing New Material Co., Ltd., the trade mark is VK-TA18S) and 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 60 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
The external static platelet adhesion reaction scanning electron microscope (SEM) photograph of the silicone rubber material using in this embodiment is shown in Fig. 1, and the external static platelet adhesion reaction scanning electron microscope (SEM) photograph of antibiosis anticoagulative blood macromolecular material prepared by this embodiment is shown in Fig. 2.Scanning electron microscope used is the S-4700 type scanning electron microscope of Japanese HITACHI company.
As can be seen from Figure 1, have a large amount of platelet adhesion reactions on material surface, and distortion has occurred some of them thrombocyte, born pseudopodium, the anticoagulation function of illustrative material is not good.As can be seen from Figure 2, material surface does not almost have thrombocyte absorption, and surface clean is smooth, shows that material has good anticoagulation function.
Embodiment 2
1) 20g kaolin (Shanghai jump river titanium white heavy chemicals company limited, 300 orders, ion exchange capacity 100mg/100g) is placed in to 50ml deionized water, and at 60 DEG C of temperature dispersed 30min, obtain Kaolin clay suspension.
2) by 10g small molecules heparin sodium (Shanghai Al-Amin Biotech Co., Ltd., 120u/mg tires) and 20g dodecyl front three ammonium chloride/hexadecyl front three ammonium chloride/octadecyl trimethyl ammonium chloride mixture of 5/35/60 by weight (by the commercial acquisition of Tianjin recovery Fine Chemical Works company, cp) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) Kaolin clay suspension that obtains mixes, and fully stirs 70min at 30 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 370,000, contents of ethylene 0.06wt%), (traditional Chinese medicines group chemical reagent Beijing is limited for 20g polymine, weight-average molecular weight: 70000), 20g nano zine oxide (Hangzhou Wanjing New Material Co., Ltd., median size is 50nm), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, and banburying temperature is 30 DEG C, and the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.2g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 3
1) 10g talcum powder (Lingshou County Peng Xian talcum powder factory, food grade) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain talcum powder suspension.
2) by 20g temparin (Ti Xiai chemical engineering industry Development Co., Ltd, purity is greater than 98.0 % by weight) and 10g octadecyl double hydroxyethyl ammonio methacrylate (by the commercial acquisition of Tianjin recovery Fine Chemical Works company, cp) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the talcum powder suspension that obtains mixes, and fully stirs 30min at 40 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 420,000, contents of ethylene 0.07wt%), (traditional Chinese medicines group chemical reagent Beijing is limited for 5g sodium alginate, viscosity is 0.45-0.55PaS), 5g chitosan (Bai Ao bio tech ltd, Shanghai, pale yellow powder, deacylated tRNA degree 90%), with 10g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 60 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.1g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 4
1) 10g bentonite (Shishewei Chemical Co., Ltd., Shanghai, CP) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain bentonite suspension.
2) 10g Acenocoumarol (traditional Chinese medicines group chemical reagent Beijing is limited, USP) and 30g dodecyl benzyl dimethyl ammonium chloride (Shandong long-chain Chemical Co., Ltd., 99 % by weight) are dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) bentonite suspension that obtains mixes, and fully stirs 30min at 40 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 540,000, contents of ethylene 0.3wt%), 5g Hyaluronic Acid (Furuida Biochemical Co., Ltd., Shandong), 5g Cefuroxime sodium (Li Wei international corporation), with 15g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 60 DEG C, and the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.3g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 5
1) 10g mica (Ge Ruikuang company limited of Anhui Chuzhou, 1500 orders) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain mica suspension.
2) by 10g urokinase (Nanjing Nan great medicine company biochemistry corporation,Ltd., 48kUmg-1 tires) and 10g cetalkonium chloride (West Asia reagent, purity is greater than 95 % by weight) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the mica suspension that obtains mixes, and fully stirs 30min at 40 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 840,000, contents of ethylene 4wt%), 5g polyvinylpyrrolidone (Yuan Ju bio tech ltd, Shanghai, weight-average molecular weight: 1200000), 5g ciprofloxacin HCl (the biochemical company limited in auspicious field, Shijiazhuang), with 20g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 40 DEG C, and the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.5g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 6
1) 30g snake stone flour (serpentine mining industry company limited of Yiyang County, 200 orders) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain snake stone flour suspension.
2) 10g warfarin (Hubei ten thousand great achievement medication chemistry company limiteds of nation) and 10g tetradecyl trimethyl ammonium chloride (are recovered to the commercial acquisition of Fine Chemical Works company by Tianjin, cp) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the snake stone flour suspension that obtains mixes, and fully stirs 30min at 50 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 600,000, contents of ethylene 5wt%), 30g polymethyl acyl oxyethyl group Phosphorylcholine (Nanjing Hui Zhe trade Co., Ltd, weight-average molecular weight: 100000), 5g Rifampin (four medicine pharmaceutcal corporation, Ltds of Wuhan Zhong Lian group), with 25g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 40 DEG C, and the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 2.0g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 100 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 7
1) cured 10g leaf soil (Guangfeng County, Jiangxi Province Qi Sen mineral products limited liability company, 800 orders) is placed in to 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain the cured native suspension of leaf.
2) 10g r-hirudin (Ai Bao bio tech ltd, Guangzhou, content is greater than 99 % by weight) and 10g palmityl trimethyl ammonium chloride (Tianjin recovery Fine Chemical Works, cp) are dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the cured native suspension of leaf that obtains mixes, and fully stirs 30min at 60 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 700,000, contents of ethylene 0.25wt%), 5g polyoxyethylene glycol (Peking blue profit fine chemistry industry, weight-average molecular weight: 400), (traditional Chinese medicines group chemical reagent Beijing is limited for 5g polymine, weight-average molecular weight: 70000), 5g nano phase ag_2 o (Beijing Deco Dao Jin Science and Technology Ltd., median size 50nm, purity 99.95 % by weight), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 40 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.8g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 100 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 8
1) 10g green mud stone flour (good and Chemical Co., Ltd. of Ninghai County, 500 orders) is placed in to 50ml deionized water, and at 50 DEG C of temperature dispersed 180min, obtain chlorite suspension.
2) 20g argatroban (Jinan Nuo Kang Pharmaceutical Technology Co., Ltd) and 10g octadecyl trimethyl ammonium chloride (Tianjin recovery Fine Chemical Works, cp) are dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the green mud stone flour suspension that obtains mixes, and fully stirs 100min at 30 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 800,000, contents of ethylene 2wt%), (traditional Chinese medicines group chemical reagent Beijing is limited for 5g polymine, weight-average molecular weight: 70000), (traditional Chinese medicines group chemical reagent Beijing is limited for 5g sodium alginate, viscosity is 0.45-0.55PaS), 20g tetracycline hydrochloride (Shanghai Jingchun Industrial Co., Ltd.), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 45rpm, banburying temperature is 30 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.2g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 9
1) by cured 10g leaf soil (Guangfeng County, Jiangxi Province Qi Sen mineral products limited liability company, 800 orders) and 10g talcum powder (Lingshou County Peng Xian talcum powder factory, food grade) be placed in 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain the cured soil of leaf and talcous mixing suspension.
2) 20g ximelagatran (Shanghai Yi Fei Bioisystech Co., Ltd) and 10g tetradecyl dimethyl benzyl ammonium chloride (Shandong long-chain Chemical Co., Ltd., 99%) are dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the cured soil of leaf and the talcous suspension that obtain mixes, and fully stirs 70min at 20 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 460,000, contents of ethylene 3.8wt%), (traditional Chinese medicines group chemical reagent Beijing is limited for 10g sodium alginate, viscosity is 0.45-0.55PaS), 10g Hyaluronic Acid (Furuida Biochemical Co., Ltd., Shandong), 20g ferric oxide (Pu Zhen bio tech ltd, Shanghai, CP), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, its medium speed 25rpm, 30 DEG C of temperature, roll spacing 2mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.3g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 10
1) by 10g zeolite powder (zeolite ore deposit, Bao Jiatun township, Faku County, 200 orders, SiO
2>67 % by weight) be placed in 50ml deionized water, and at 30 DEG C of temperature dispersed 30min, obtain the suspension of zeolite powder.
2) by 10g sodium chondroitin sulfate (Shandong Hai Yu Bioisystech Co., Ltd) and 10g Dodecyl trimethyl ammonium chloride (Tianjin recovery Fine Chemical Works, and 10g octadecyl double hydroxyethyl ammonio methacrylate (Tianjin recovery Fine Chemical Works cp), cp) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the zeolite powder suspension that obtains mixes, and fully stirs 30min at 40 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 900,000, contents of ethylene 0.18wt%), 2.5g Hyaluronic Acid (Furuida Biochemical Co., Ltd., Shandong), 2.5g polyvinylpyrrolidone (Yuan Ju bio tech ltd, Shanghai, weight-average molecular weight: 80000), 5g Manganse Dioxide (Xiang Tan Wei Xinmeng Products Co., Ltd, 800 orders), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 60 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.0g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 11
1) 20g attapulgite (Ming Mei mineral Chemical Co., Ltd. of Anhui Province, 200 orders) is placed in to 50ml deionized water, and at 60 DEG C of temperature dispersed 30min, obtain attapulgite suspension.
2) by 10g small molecules heparin sodium (Shanghai Al-Amin Biotech Co., Ltd., weight-average molecular weight: 5000) and 10g Dodecyl trimethyl ammonium chloride/hexadecyl front three ammonium chloride/octadecyl trimethyl ammonium chloride mixture of 5/35/60 be by weight dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) the attapulgite suspension that obtains mixes, and fully stirs 70min at 80 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 420,000, contents of ethylene 0.45wt%), 15g polyvinylpyrrolidone (Yuan Ju bio tech ltd, Shanghai, weight-average molecular weight: 650000), 15g methacryloyl oxyethyl group Phosphorylcholine (Nanjing Hui Zhe trade Co., Ltd, weight-average molecular weight: 100000), 20g tindioxide (Shanghai Gao Cheng Trade Co., Ltd., content 99 % by weight), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 30 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.2g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
Embodiment 12
1) by 10g polynite (Zhejiang Feng Hong clay company limited, cationic ion exchange capacity 90mmol/100g) and 10g bentonite (Shishewei Chemical Co., Ltd., Shanghai, CP) be placed in 50ml deionized water, and at 60 DEG C of temperature dispersed 30min, obtain the mixing suspension of polynite and bentonite.
2) by 20g acetylsalicylic acid (Pu Zhen bio tech ltd, Shanghai, and 10g dodecyl benzyl dimethyl ammonium chloride/tetradecyl dimethyl benzyl ammonium chloride/n-Hexadecane dimethyl benzyl ammonium chloride mixture (Shandong long-chain Chemical Co., Ltd. of 5/35/60 by weight GR), 99 % by weight) be dissolved in 20ml deionized water, obtain the aqueous solution.
3) by step 2) aqueous solution and the step 1 that obtain) polynite obtaining and the suspension of bentonite mixes, and fully stirs 70min at 110 DEG C, and ultrasonic dispersion 30min then, obtains water dispersion.
4) by step 3) water dispersion that obtains filters, and with the abundant washing precipitation of distilled water 3 times, vacuum-drying, to constant weight, after grinding, obtains anticoagulation intermediate.
5) by 100g ethylene methacrylic radical siloxane silicon rubber (Kai Wote organosilicon material company limited of Shenzhen, weight-average molecular weight 600,000, contents of ethylene 0.55wt%), 10g polyoxyethylene glycol (Peking blue profit fine chemistry industry, weight-average molecular weight: 400), (traditional Chinese medicines group chemical reagent Beijing is limited for 20g sodium alginate, viscosity is 0.45-0.55PaS), 10g nano titanium oxide is (by the commercial acquisition of Hangzhou Wanjing New Material Co., Ltd., the trade mark is VK-TA18S), 10g nano phase ag_2 o (Beijing Deco Dao Jin Science and Technology Ltd., median size 50nm, purity 99.95 % by weight), with 5g step 4) in anticoagulation intermediate banburying 30min in Banbury mixer of making, obtain blend glue, wherein banburying rotating speed is 25rpm, banburying temperature is 30 DEG C, the roll spacing of Banbury mixer is 1mm.
6) by step 5) the blend glue that obtains vulcanizes 4h under 1.3g platinum catalyst (Kai Wote organosilicon material company limited of Shenzhen) exists in compression molding instrument at 120 DEG C, makes the silastic material with antibiosis anticoagulative blood function.
The silastic material that the silicone rubber material that the various embodiments described above are used and each embodiment prepare carries out Mechanics Performance Testing, hemolysis rate, antibiotic rate and recalcification time test.
In Mechanics Performance Testing, equipment used is the LR30K type equipment of LIOYD company of electronic universal material testing machine Britain, and test condition is draw speed 500mm/min, and test bars is of a size of (115*6*2) mm.
In hemolysis rate test, adopt YBB0003-2003 standard.
In antibiotic rate test, adopt QB/T2591-2003 standard.
Recalcification time testing method is as follows:
The trisodium citrate aqueous solution of the 3.8wt% of employing cardiac puncture method extraction rabbit blood 5mL and anti-freezing by volume 9:1 ratio is mixed with fresh anticoagulation.The NaCl aqueous solution of getting above-mentioned fresh anticoagulation and the 0.9wt% by volume ratio of 1:1.25 is mixed with dilution rabbit blood, then, with 1000r/min rotating speed centrifugation 10min, gets supernatant liquor for subsequent use as blood plasma.Composite silicone rubber material prepared by each embodiment is cut into little of 0.2cm × 0.2cm, inserts in the NaCl aqueous solution of 0.9wt% and soaks 24h, then moves to Φ 1x7.5cm in vitro.Every group of three Duplicate Samples, add respectively the CaCl of 0.2mL blood plasma and 0.2mL0.025mol/L
2the aqueous solution, is placed in 37 DEG C of waters bath with thermostatic control, and manual time-keeping, jiggles test tube and make CaCl
2the aqueous solution mixes with supernatant.In the time there is a fine shape thing of white in test tube, press second hand stop table, can obtain recalcification time.Recalcification time can reflect anticoagulant property, and recalcification time is longer, and anticoagulant property is better.
For the silicone rubber material adopting in the various embodiments described above, its fracture tensile strength is 9.21MPa, elongation at break is 1220.87%, shore hardness is 46.3, hemolysis rate is 4.02%, recalcification time 122s, antibiotic rate (streptococcus aureus) is 0%, and the test result of the silastic material that each embodiment prepares sees the following form 1.
Table 1
Above-mentioned experiment embodiment limits the present invention never in any form, and all employings are equal to the technical scheme of the form acquisition of replacement or equivalent transformation, within all dropping on protection scope of the present invention.
Claims (11)
1. an antibiosis anticoagulative blood macromolecular material, it comprises medical grade silicon rubber, and the medical grade silicon rubber that this material comprises based on every 100 weight parts also comprises following component:
A) layered silicate of 1-30 weight part;
B) quaternary ammonium salt of 1-30 weight part;
C) anti-coagulant of 1-20 weight part;
D) hydrophilic polymer of 1-30 weight part; With
E) antiseptic-germicide of 1-20 weight part.
2. according to the macromolecular material of claim 1, wherein said layered silicate is to be selected from one or more in lower group: the cured soil of leaf, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake stone flour, green mud stone flour, polynite and bentonite.
3. according to the macromolecular material of claim 1 or 2, wherein said quaternary ammonium salt is to be selected from one or more in lower group: dodecyl trimethyl-ammonium halide, tetradecyl trimethyl-ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl-ammonium halide, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, cetyl dimethyl benzyl ammonium halide, aforementioned each ammonium halide compound is preferably quaternary ammonium chloride and/or Quaternary ammonium bromide.
4. according to the macromolecular material of any one in claim 1-3, wherein said anti-coagulant is to be selected from one or more in lower group: small molecules heparin sodium, unfractionated heparin sodium, temparin, Acenocoumarol, urokinase, warfarin, r-hirudin, argatroban, ximelagatran, acetylsalicylic acid, ticlopidine and chondroitin sulfate.
5. according to the macromolecular material of any one in claim 1-4, wherein said hydrophilic polymer is that weight-average molecular weight is the polymkeric substance that contains hydrophilic radical of 100-2000000, is preferably and is selected from one or more in lower group: polyoxyethylene glycol, polymine, sodium alginate, Hyaluronic Acid, polyvinylpyrrolidone and polymethyl acyl oxyethyl group Phosphorylcholine.
6. according to the macromolecular material of any one in claim 1-5, wherein said antiseptic-germicide is to be selected from one or more in lower group: any mixture of nano cupric oxide, nano zine oxide, nano titanium oxide, nano phase ag_2 o, Manganse Dioxide, Cadmium Sulfide, tungstic oxide, tindioxide, ferric oxide, chitosan, Cefuroxime sodium, Amikacin Sulphate, tetracycline hydrochloride, paraxin, erythromycin, ciprofloxacin HCl, metronidazole, Rifampin, lincomycin, nanometer silver or these antiseptic-germicides.
7. according to the macromolecular material of any one in claim 1-6, wherein said medical grade silicon rubber is bi-component addition type silicon rubber, for example ethylene methacrylic radical siloxane, preferred vinyl content is the silicon rubber of 0.001-5wt%, especially the methyl ethylene silicone rubber that contents of ethylene is 0.07-4wt%, the medical grade silicon rubber that particularly preferably weight-average molecular weight is 300000-900000.
8. according to the macromolecular material of any one in claim 1-7, based on every 100 weight part medical grade silicon rubbers, it also comprises following component:
A) layered silicate of 1-20 weight part, preferred 1-8 weight part;
B) 1-20 weight part, the preferably quaternary ammonium salt of 1-10 weight part;
C) 1-10 weight part, the preferably anti-coagulant of 1-8 weight part;
D) 5-30 weight part, the preferably hydrophilic polymer of 5-20 weight part; With
E) antiseptic-germicide of 5-20 weight part.
9. a method of preparing the antibiosis anticoagulative blood macromolecular material as described in any one in claim 1-8, comprises the steps:
A) by layered silicate, quaternary ammonium salt and anti-coagulant, the solution using liquid solvent as dispersion medium or dispersion form mix, and obtain anticoagulation intermediate;
B) anticoagulation intermediate hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber a) being obtained with step mixes, and obtains blend glue; And
C) by blend glue vulcanization crosslinking.
10. according to the method for claim 9, wherein
Step a) in, layered silicate, quaternary ammonium salt and anti-coagulant are uniformly mixed to 0.5-10 hour with water as solvent at the temperature of 25-120 DEG C, then ultrasonic dispersion 0.5-10 hour, finally dries, pulverizes, and obtains anticoagulation intermediate; And/or
Step b) in, the anticoagulation intermediate that hydrophilic polymer, antiseptic-germicide and medical grade silicon rubber and step a) are obtained in blending equipment at 25-120 DEG C blend 10min-2 hour, obtain blend glue; And/or
Step c) in, the blend glue that step b) is obtained thermal treatment 5 minutes to 4 hours and vulcanization crosslinking at the temperature of 100-180 DEG C.
11. according to the described antibiosis anticoagulative blood macromolecular material of any one in claim 1-8 purposes, the especially purposes in medical catheter as medical macromolecular materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028066.7A CN103965639B (en) | 2013-01-25 | 2013-01-25 | Antibiosis anticoagulative blood high molecular material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028066.7A CN103965639B (en) | 2013-01-25 | 2013-01-25 | Antibiosis anticoagulative blood high molecular material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103965639A true CN103965639A (en) | 2014-08-06 |
| CN103965639B CN103965639B (en) | 2018-05-01 |
Family
ID=51235662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310028066.7A Active CN103965639B (en) | 2013-01-25 | 2013-01-25 | Antibiosis anticoagulative blood high molecular material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965639B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367957A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Nano silver modified fluororubber composite material |
| CN105367958A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Antibacterial modified fluororubber composite material |
| CN105367956A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Antibacterial aging-resistant modified fluororubber composite material |
| CN106178144A (en) * | 2016-07-07 | 2016-12-07 | 腾科宝迪（厦门）生物科技有限公司 | Single use incision protective sleeve and preparation method thereof |
| CN107041582A (en) * | 2016-11-17 | 2017-08-15 | 无锡市长安曙光手套厂 | A kind of wear-resisting anti-cutting gloves |
| CN107569735A (en) * | 2017-10-26 | 2018-01-12 | 徐州诺克非医药科技有限公司 | A kind of convenient use vagina cleaner |
| CN108114309A (en) * | 2018-01-02 | 2018-06-05 | 大连理工大学 | A kind of aldehydedodextrans/montmorillonite Composite rapid hemostatic material and preparation method thereof |
| CN110292653A (en) * | 2019-07-09 | 2019-10-01 | 洛阳理工学院 | A kind of Collagon base nanometer compound hemostatic material and preparation method thereof with bacteriostasis efficacy |
| CN110448735A (en) * | 2019-07-04 | 2019-11-15 | 郑州欧姆康生物材料有限公司 | A kind of amphiphilic biology carbon complex and its preparation method and purposes with antibiosis anticoagulative |
| CN110694118A (en) * | 2019-09-23 | 2020-01-17 | 江苏理工学院 | Antibacterial and anticoagulant ventricles and abdominocentesis shunt tube silica gel tube body and preparation method and application thereof |
| CN111298202A (en) * | 2020-03-04 | 2020-06-19 | 四川大学 | Long-acting anticoagulant antibacterial coating for extracorporeal membrane oxygenation device (ECMO) and preparation method thereof |
| CN111418607A (en) * | 2020-03-30 | 2020-07-17 | 北京机科国创轻量化科学研究院有限公司 | Composite nano-silver antiviral agent and preparation method and application thereof |
| CN111635549A (en) * | 2020-06-12 | 2020-09-08 | 中国科学院长春应用化学研究所 | Surface anticoagulation modification method for high polymer material |
| CN113881161A (en) * | 2021-10-20 | 2022-01-04 | 台湾塑胶工业股份有限公司 | Anti-sticking material, medical catheter contacting human tissue containing same and manufacturing method thereof |
| CN114106565A (en) * | 2021-11-19 | 2022-03-01 | 广州市瑞合新材料科技有限公司 | Hydrophilic antibacterial silicone rubber and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780883A (en) * | 2003-03-07 | 2006-05-31 | 庄臣及庄臣视力保护公司 | Diluents for forming clear,wettable silicone hydrogel articles |
| CN1943804A (en) * | 2006-10-23 | 2007-04-11 | 南方医科大学 | The medical use anti-infection polymeric material and its preparation method |
-
2013
- 2013-01-25 CN CN201310028066.7A patent/CN103965639B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780883A (en) * | 2003-03-07 | 2006-05-31 | 庄臣及庄臣视力保护公司 | Diluents for forming clear,wettable silicone hydrogel articles |
| CN1943804A (en) * | 2006-10-23 | 2007-04-11 | 南方医科大学 | The medical use anti-infection polymeric material and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 陈亚红 等: "蒙脱土/聚合物纳米复合抗凝血膜的制备及其性能研究", 《功能材料》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367958A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Antibacterial modified fluororubber composite material |
| CN105367956A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Antibacterial aging-resistant modified fluororubber composite material |
| CN105367957A (en) * | 2015-11-27 | 2016-03-02 | 安徽锦洋氟化学有限公司 | Nano silver modified fluororubber composite material |
| CN106178144A (en) * | 2016-07-07 | 2016-12-07 | 腾科宝迪（厦门）生物科技有限公司 | Single use incision protective sleeve and preparation method thereof |
| CN107041582A (en) * | 2016-11-17 | 2017-08-15 | 无锡市长安曙光手套厂 | A kind of wear-resisting anti-cutting gloves |
| CN107569735B (en) * | 2017-10-26 | 2020-11-10 | 沈阳菁华医院有限公司 | Vagina purger of facilitating use |
| CN107569735A (en) * | 2017-10-26 | 2018-01-12 | 徐州诺克非医药科技有限公司 | A kind of convenient use vagina cleaner |
| CN108114309A (en) * | 2018-01-02 | 2018-06-05 | 大连理工大学 | A kind of aldehydedodextrans/montmorillonite Composite rapid hemostatic material and preparation method thereof |
| CN110448735A (en) * | 2019-07-04 | 2019-11-15 | 郑州欧姆康生物材料有限公司 | A kind of amphiphilic biology carbon complex and its preparation method and purposes with antibiosis anticoagulative |
| CN110292653A (en) * | 2019-07-09 | 2019-10-01 | 洛阳理工学院 | A kind of Collagon base nanometer compound hemostatic material and preparation method thereof with bacteriostasis efficacy |
| CN110292653B (en) * | 2019-07-09 | 2021-11-26 | 洛阳理工学院 | Collagen-based nano composite hemostatic material with antibacterial effect and preparation method thereof |
| CN110694118A (en) * | 2019-09-23 | 2020-01-17 | 江苏理工学院 | Antibacterial and anticoagulant ventricles and abdominocentesis shunt tube silica gel tube body and preparation method and application thereof |
| CN111298202A (en) * | 2020-03-04 | 2020-06-19 | 四川大学 | Long-acting anticoagulant antibacterial coating for extracorporeal membrane oxygenation device (ECMO) and preparation method thereof |
| CN111298202B (en) * | 2020-03-04 | 2021-03-30 | 四川大学 | Long-acting anticoagulant antibacterial coating for extracorporeal membrane oxygenation device (ECMO) and preparation method thereof |
| CN111418607A (en) * | 2020-03-30 | 2020-07-17 | 北京机科国创轻量化科学研究院有限公司 | Composite nano-silver antiviral agent and preparation method and application thereof |
| CN111635549A (en) * | 2020-06-12 | 2020-09-08 | 中国科学院长春应用化学研究所 | Surface anticoagulation modification method for high polymer material |
| CN111635549B (en) * | 2020-06-12 | 2021-09-21 | 中国科学院长春应用化学研究所 | Surface anticoagulation modification method for high polymer material |
| CN113881161A (en) * | 2021-10-20 | 2022-01-04 | 台湾塑胶工业股份有限公司 | Anti-sticking material, medical catheter contacting human tissue containing same and manufacturing method thereof |
| CN113881161B (en) * | 2021-10-20 | 2022-09-23 | 台湾塑胶工业股份有限公司 | Anti-sticking material, medical catheter contacting human tissue containing same and manufacturing method thereof |
| CN114106565A (en) * | 2021-11-19 | 2022-03-01 | 广州市瑞合新材料科技有限公司 | Hydrophilic antibacterial silicone rubber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103965639B (en) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103965639A (en) | Antibacterial anticoagulant high polymer material, and preparation method and application thereof | |
| Qi et al. | Salecan polysaccharide-based hydrogels and their applications: a review | |
| Yan et al. | Thermoresponsive in situ forming hydrogel with sol–gel irreversibility for effective methicillin-resistant Staphylococcus aureus infected wound healing | |
| Qi et al. | Macroporous hydrogel scaffolds with tunable physicochemical properties for tissue engineering constructed using renewable polysaccharides | |
| Hu et al. | Formation of self-assembled polyelectrolyte complex hydrogel derived from salecan and chitosan for sustained release of Vitamin C | |
| Zheng et al. | Bioactive anti-inflammatory, antibacterial, conductive multifunctional scaffold based on MXene@ CeO2 nanocomposites for infection-impaired skin multimodal therapy | |
| Song et al. | A natural cordycepin/chitosan complex hydrogel with outstanding self-healable and wound healing properties | |
| Shin et al. | Hemostatic swabs containing polydopamine-like catecholamine chitosan-catechol for normal and coagulopathic animal models | |
| CN104927348A (en) | Antibacterial and anticoagulant polymer material, preparation method and application thereof | |
| CN106492279A (en) | A kind of fast preparation method of fibroin albumen hyaluronic acid pluralgel | |
| KR20080073419A (en) | Microbead of hyaluronic acid derivatives for medical purpose and process for preparing the same | |
| CN104829843B (en) | A kind of citric acid and chitin modified Biocompatible Polyurethane and preparation method thereof | |
| Zheng et al. | A novel pullulan oxidation approach to preparing a shape memory sponge with rapid reaction capability for massive hemorrhage | |
| Wang et al. | Mussel-inspired multifunctional hydrogels with adhesive, self-healing, antioxidative, and antibacterial activity for wound healing | |
| Zheng et al. | An antibacterial hemostatic AuNPs@ corn stalk/chitin composite sponge with shape recovery for promoting wound healing | |
| CN1481907A (en) | Carboxymethyl chitosan / carboxymethyl cellulose operative antiblocking film and method for making the same | |
| CN1810298A (en) | Bacteriostatic porous polyelectrolyte material and its prepn process | |
| CN105713106A (en) | Double-crosslinked sodium alginate hydrogel and preparation method and application thereof | |
| Singh et al. | Application of tragacanth gum and alginate in hydrogel wound dressing's formation using gamma radiation | |
| CN109568643A (en) | A kind of preparation method and applications of the antibacterial anti hemorrhagic microballoon containing jamaicin | |
| CN106866996A (en) | A kind of fast preparation method of silk fibroin matter gel | |
| Zhang et al. | Antimicrobial cellulose hydrogels preparation with RIF loading from bamboo parenchyma cells: A green approach towards wound healing | |
| Tashakkorian et al. | Transparent chitosan based nanobiocomposite hydrogel: Synthesis, thermophysical characterization, cell adhesion and viability assay | |
| CN201669064U (en) | Anti-coagulation composite ultrafiltration membrane | |
| Jayabal et al. | Fabrication of a chitosan-based wound dressing patch for enhanced antimicrobial, hemostatic, and wound healing application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 467000. East section of Longshan Road, Chengguan Town, Pingdingshan City, Henan, Jiaxian Co-patentee after: Beijing University of Chemical Technology Patentee after: Holy light medical products, Limited by Share Ltd Address before: 467000. East section of Longshan Road, Chengguan Town, Pingdingshan City, Henan, Jiaxian Co-patentee before: Beijing University of Chemical Technology Patentee before: Shengguang Medical Instrument Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |