CN103965639B - Antibiosis anticoagulative blood high molecular material and its preparation method and application - Google Patents
Antibiosis anticoagulative blood high molecular material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of antibiosis anticoagulative blood high molecular material, and it includes medical grade silicon rubber, which is also included based on the medical grade silicon rubber that every 100 parts by weight are included：A) the phyllosilicate of 1 30 parts by weight；B) the quaternary ammonium salt of 1 30 parts by weight；C) the anticoagulant of 1 20 parts by weight；D) the hydrophilic polymer of 1 30 parts by weight；And E) 1 20 parts by weight antiseptic.The antibiosis anticoagulative blood high molecular material of the present invention has anticoagulation and antibacterial functions concurrently, and the excellent combination property including mechanical property and biological property, also it has breakthrough in mechanical property so that product safety and reliability, be especially suitable for medical macromolecular materials.Purposes the invention further relates to the preparation of antibiosis anticoagulative blood high molecular material and as medical antibacterial medical polymer material.
Description
Technical field
The invention belongs to field of biomedical polymer materials, and in particular to a kind of antibiosis anticoagulative blood high molecular material and its
Preparation method and application, the high molecular material can be used as medical macromolecular materials.
Background technology
Biomaterial be it is a kind of can be used for the reparation of animal organ and tissue and replacement, disease Clinics and Practices with moving
Thing bio-compatible, have the function of property or material.Antibiosis anticoagulative blood biomaterial is the important composition portion of biomaterial
Point, it is widely used in and human blood and organizes on the medical material that is in contact, such as hemodialysis system, extracorporal circulatory system system
System, heart valve prosthesis, pacemaker, artificial blood vessel, intravascular stent, surgical cable and conduit etc..When exotic and blood
When liquid contacts, erythrocyte can be destroyed, makes platelet activation, aggregation, and then form thrombus.At present in clinicing aspect, do not have also
A kind of manually biomaterial for medical purpose energy perfection is applied in human body., when anticoagulant biomaterial is in contact with living tissue
Ask material that not only there is histocompatbility, inflammation will not be caused to bio-tissue, should also have blood compatibility, blood can be resisted
Bolt, will not occur blood coagulation phenomenon on the surface of material.
At present, prepare anti-biotic material method mainly added in basis material metal silver iron compound, chitosan,
Titanium dioxide, diphenyl ether biocides and antibiotic etc.；The main method for preparing anticoagulant material is surface heparinization, leads to
Cross to be modified and obtain polyoxy acetylene structure and poly- Phosphorylcholine class material is obtained by modification.
When material carries out anticoagulation modification, it is critical to firmness from anticoagulant, the bioactivity of anticoagulant
And anticoagulant considers at several aspects such as the concentration of material surface.In general, it is divided into physical absorption and chemistry is tied
Close two major classes.The former is easy, but the quantization of anticoagulant is difficult to control, and the anticoagulation duration is not grown, and is easily dissolved with blood
And it is lost in；The latter can then take into account the utilization rate and stability of anticoagulant, and can be with large-scale industrial production.
For coating anticoagulant in material surface, advocate if it is combined by ionic bond, on the one hand, due to ionic bond
Fracture and easily destroyed, so as to cause the rate of release of anticoagulant very fast so that this to be given birth in a manner of ions binding
Into anticoagulant material can lose anticoagulation function too quickly, on the other hand, cause toxicity since coating substance excessively elutes
Problem, therefore lose the purpose clinically applied.In patent application publication CN1225281A, xuwei et al. is disclosed to material
Surface is coated acquisition anticoagulant effect, but its zoopery has generated a small amount of thrombus after showing 18 days, and anticoagulation is held
Long property is still inadequate.Patent application publication CN101156970A discloses a kind of coating of high stability, but it is mainly used in
NiTi alloys, it is known that silastic surface inertia can be big, it is difficult to obtain good persistence.
For anticoagulant multiple spot is bonded in material securely in material surface chemical graft anticoagulant, Covalent bonding together
Expect surface, change the normal conformation of anticoagulant, active part may be embedded or destroy.It is living thus to reduce its biology
Property so that the different degrees of reduction of anticoagulant effect, some even disappear completely, and lose application value clinically.So far still
Anticoagulant can be directly grafted in silastic surface by not having, and obtain the report of good anti-freezing blood.
Biostatic type elastomer has good biologically inert and chemical stability, is mainly used as under biotic environment
External medical supplies and it is chronically implanted internal reparation, alternative materials etc..Medical grade silicon rubber due to it is heat-resisting, cold-resistant, nontoxic,
Corrosion-free, resistance to biological aging, will not cause the characteristics such as surrounding tissue inflammation and allergy in human body after use, be a kind of reason
The medical macromolecular materials thought.
But in clinical practice, due to factors such as hospital's particular surroundings, medical macromolecular materials easily cause infection, its
On the one hand the reason is that medical material can stimulate internal staphylococcus aureus to breed, and then inflammation infection is caused；On the other hand
It is hospital infection, in hospital environment, the propagation of the article in clothing, gloves and hospital that bacterium passes through medical worker, easily draws
Hair infection, it is said that the U.S. has close to 100,000 people every year dies of such infection.Therefore, to be taken into account while anticoagulant material is prepared
Consider the anti-microbial property of material.
The content of the invention
In view of above-mentioned prior art situation, the present inventor for silicon rubber base medical material carried out extensively and
In-depth study, to develop a kind of medical macromolecular materials for not only having antibacterial functions and anticoagulant functions concurrently, but also the material
The high molecular material of the anticoagulant functions of material compared with the prior art is strengthened, and the compatibility of the material and blood is changed
It is kind, and good mechanical properties.It turns out that by medical grade silicon rubber basis material include phyllosilicate, quaternary ammonium salt,
Anticoagulant, hydrophilic polymer and antiseptic, you can realize object defined above, that is, obtain one kind have concurrently anticoagulation and antibacterial and
The antibiosis anticoagulative blood high molecular material of excellent combination property.The present inventor is based on foregoing discovery and completes the present invention.
Therefore, it is an object of the present invention to provide a kind of new antibiosis anticoagulative blood high molecular material, the material to have concurrently
Good antibacterial, anticoagulant functions, have blood good compatibility, and good mechanical properties.
It is a further object to provide a kind of method for preparing antibiosis anticoagulative blood high molecular material of the present invention.
Antibiosis anticoagulative blood high molecular material it is also another object of the present invention to provide the present invention is cured as antibiosis anticoagulative blood
With the purposes of high molecular material.
Realizing the technical solution of above-mentioned purpose of the present invention can be summarized as follows：
1. a kind of antibiosis anticoagulative blood high molecular material, it includes medical grade silicon rubber, which is wrapped based on every 100 parts by weight
The medical grade silicon rubber contained also includes following component：
A) the phyllosilicate of 1-30 parts by weight；
B) the quaternary ammonium salt of 1-30 parts by weight；
C) the anticoagulant of 1-20 parts by weight；
D) the hydrophilic polymer of 1-30 parts by weight；With
E) the antiseptic of 1-20 parts by weight.
2. according to the high molecular material of the 1st, wherein layered silicate is the one or more in being selected from the group：Leaf
Cured soil, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake mountain flour, green mud mountain flour, montmorillonite and bentonite.
3. according to the high molecular material of the 1st or 2, wherein the quaternary ammonium salt is the one or more in being selected from the group：Ten
Dialkyl group trimethyl-ammonium halide, tetradecyltrimethylammonium ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl halogen
Change ammonium, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl Benzyl halides ammonium, myristyl benzyl dimethyl halogen
Change ammonium, cetyl dimethyl benzyl ammonium halide, foregoing each halogenated ammonium compound is preferably quaternary ammonium chloride and/or quaternary ammonium bromide
Salt.
4. according to the high molecular material of any one of 1-3, wherein the anticoagulant is one kind in being selected from the group
It is or a variety of：Low molecular weight sodium, unfractionated heparin sodium, bicoumarin, acenocoumarin, urokinase, warfarin, hirudin, A Jia
Qu Ban, ximelagatran, aspirin, ticlopidine and chondroitin sulfate.
5. according to the high molecular material of any one of 1-4, wherein the hydrophilic polymer is weight average molecular weight is
The polymer containing hydrophilic radical of 100-2000000, the one or more being preferably selected from the following group：Polyethylene glycol, poly- second
Alkene imines, sodium alginate, sodium hyaluronate, polyvinylpyrrolidone and polymethyl acyl ethyoxyl Phosphorylcholine.
6. according to the high molecular material of any one of 1-5, wherein the antiseptic be one kind in being selected from the group or
It is a variety of：Nano cupric oxide, nano zine oxide, nano-titanium dioxide, nano phase ag_2 o, manganese dioxide, cadmium sulfide, tungstic acid,
Stannic oxide, di-iron trioxide, chitosan, Cefuroxime Sodium, amikacin, quadracycline, chloramphenicol, erythromycin,
Ciprofloxacin Hydrochloride, metronidazole, rifampin, lincomycin, any mixture of nano silver or these antiseptics.
7. according to the high molecular material of any one of 1-6, wherein the medical grade silicon rubber is bi-component addition type silicon
Rubber, such as methyl vinyl silicone, preferred vinyl content are the silicon rubber of 0.001-5wt%, especially contents of ethylene
For the methyl vinyl silicone rubber of 0.07-4wt%, particularly preferred weight average molecular weight is the medical silicon rubber of 300000-900000
Glue.
8. according to the high molecular material of any one of 1-7, based on every 100 parts by weight medical grade silicon rubber, it is also included
Following component：
A the phyllosilicate of) 1-20 parts by weight, preferably 1-8 parts by weight；
B the quaternary ammonium salt of) 1-20 parts by weight, preferably 1-10 parts by weight；
C the anticoagulant of) 1-10 parts by weight, preferably 1-8 parts by weight；
D the hydrophilic polymer of) 5-30 parts by weight, preferably 5-20 parts by weight；With
E) the antiseptic of 5-20 parts by weight.
9. a kind of method of the antibiosis anticoagulative blood high molecular material prepared as any one of 1-8, including it is as follows
Step：
A) solution by phyllosilicate, quaternary ammonium salt and anticoagulant using liquid flux as decentralized medium or the scattered bodily form
Formula is uniformly mixed, and obtains anticoagulation intermediate；
B) hydrophilic polymer, antiseptic and medical grade silicon rubber are mixed with the anticoagulation intermediate that step a) is obtained
It is even, obtain Blend rubber；And
C) by Blend rubber vulcanization crosslinking.
10. according to the method for the 9th, wherein
In step a), by phyllosilicate, quaternary ammonium salt and anticoagulant with water as solvent at a temperature of 25-120 DEG C
Be stirred 0.5-10 it is small when, when then ultrasonic disperse 0.5-10 is small, finally dry, crush, obtain anticoagulation intermediate；With/
Or
In step b), among anticoagulation that hydrophilic polymer, antiseptic and medical grade silicon rubber and step a) are obtained
Body in blending equipment at 25-120 DEG C be blended 10min-2 it is small when, obtain Blend rubber；And/or
In step c), by the Blend rubber that step b) is obtained when being heat-treated 5 minutes small to 4 at a temperature of 100-180 DEG C
And vulcanization crosslinking.
11. according to the antibiosis anticoagulative blood high molecular material of any one of 1-8 as medical macromolecular materials
Purposes, the purposes especially in medical catheter.
Brief description of the drawings
Fig. 1 is the external static platelet adhesion reaction scanning electricity of description of the invention silicone rubber material used in embodiment 1
Mirror figure.
Fig. 2 is the external static blood platelet of the antibiosis anticoagulative blood high molecular material prepared in description of the invention embodiment 1
Adhere to scanning electron microscope (SEM) photograph.
Embodiment
According to an aspect of the invention, there is provided a kind of antibiosis anticoagulative blood high molecular material, it includes medical grade silicon rubber,
The material also includes following component based on the medical grade silicon rubber that every 100 parts by weight are included：
A) the phyllosilicate of 1-30 parts by weight；
B) the quaternary ammonium salt of 1-30 parts by weight；
C) the anticoagulant of 1-20 parts by weight；
D) the hydrophilic polymer of 1-30 parts by weight；With
E) the antiseptic of 1-20 parts by weight.
In the antibiosis anticoagulative blood high molecular material of the present invention, anticoagulant provides anticoagulation as anticoagulant composition
Function.Preferably, anticoagulant is low molecular weight sodium, unfractionated heparin sodium, bicoumarin, acenocoumarin, urokinase, China
Method woods, hirudin, argatroban, ximelagatran, aspirin, ticlopidine, chondroitin sulfate or their any mixing
Thing.For the purpose of the present invention, the dosage of anticoagulant should cause, the medical grade silicon rubber included based on every 100 parts by weight material,
High molecular material of the present invention generally comprises the anticoagulant of the anticoagulant of 1-20 parts by weight, preferably 1-10 parts by weight, more preferably
The anticoagulant of 1-8 parts by weight.
One outstanding feature of high molecular material of the present invention is to include phyllosilicate and quaternary ammonium salt.Quaternary ammonium salt has one
Fixed antibiotic property, it is even more important that due to the cation interchangeability of phyllosilicate, the sun of quaternary ammonium salt and phyllosilicate
Ion exchange can occur for ion so that the interlamellar spacing of phyllosilicate expands, so that anticoagulant can enter interlayer and obtain
Nano effect necessarily, the release of anticoagulant is controlled by migrating from inside to outside for anticoagulant well, avoids material
The anticoagulation function of material is premature to be lost.Further, since the protective effect of layer structure so that into laminated silicate interlayer
Anticoagulant can preferably be resistant to heating blending so that anticoagulant loss of activity caused by heating blending reduces.Moreover, by
In protection of the phyllosilicate to anticoagulant so that can also process at higher temperatures, this improves antibacterial of the present invention
The machinability of medical polymer material, can obtain product of different shapes, at the same substantially reduce machine-shaping when
Between.At the same time, phyllosilicate can also play the role of reinforcement to silicon rubber, and hydrophilic polymer and anti-freezing are made up with this
Reduction caused by blood agent to material mechanical performance.
As phyllosilicate, the cured soil of leaf, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake can be used
Mountain flour, green mud mountain flour, montmorillonite, any mixture of bentonite or these phyllosilicates, preferably using montmorillonite, talcum powder,
Mica, zeolite powder, attapulgite or its mixture.For the purpose of the present invention, the dosage of phyllosilicate should cause, based on every 100
The medical grade silicon rubber that parts by weight high molecular material of the present invention is included, high molecular material of the present invention generally comprise 1-30 parts by weight
The phyllosilicate of the phyllosilicate of phyllosilicate, preferably 1-20 parts by weight, more preferably 1-8 parts by weight.
As quaternary ammonium salt, trimethyl ammonium halide, tetradecyltrimethylammonium ammonium halide, cetyl can be used
Trimethyl-ammonium halide, octadecyl trimethyl ammonium halide, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl
Base ammonium halide, myristyl benzyl dimethyl ammonium halide, cetyl dimethyl benzyl ammonium halide or foregoing each ammonium halide are appointed
Meaning mixture.Preferably, quaternary ammonium salt is the quaternary ammonium chloride and/or Quaternary ammonium bromide in foregoing each ammonium halide.To the present invention
For, the dosage of quaternary ammonium salt should cause, the medical grade silicon rubber included based on every 100 parts by weight high molecular material of the present invention, this
Invention high molecular material generally comprises the quaternary ammonium salt of the quaternary ammonium salt of 1-30 parts by weight, preferably 1-20 parts by weight, more preferably 1-10 weights
Measure the quaternary ammonium salt of part.
The antibiosis anticoagulative blood high molecular material of the present invention also includes hydrophilic polymer, which contains hydrophilic radical
Such as hydroxyl, hydroxyl value is higher, their addition is so that the surface hydrophilicity raising of material, reduces the surface between material and blood
Free energy, adds blood compatibility, improves anticoagulant property.The weight average molecular weight of hydrophilic polymer can be 100-
2000000, preferably 400-600000.It is also preferred that the molecular weight dispersion coefficient M of the polymerw/MnFor 1-50, preferably 1-
10.As hydrophilic polymer, preferably using polyethylene glycol, polyethyleneimine, sodium alginate, sodium hyaluronate, polyvinylpyrrolidine
Any mixture of ketone, polymethyl acyl ethyoxyl Phosphorylcholine or these hydrophilic polymers.Particularly preferably use poly- second
Glycol, sodium alginate, polymethyl acyl ethyoxyl Phosphorylcholine, polyvinylpyrrolidone and/or sodium hyaluronate.To the present invention
Say, the dosage of hydrophilic polymer should cause, the medical silicon rubber included based on every 100 parts by weight high molecular material of the present invention
Glue, high molecular material of the present invention generally comprise the hydrophilic polymer of 1-30 parts by weight, and the hydrophily of preferably 5-30 parts by weight is gathered
The hydrophilic polymer of compound, more preferably 5-20 parts by weight.
Another feature of high molecular material of the present invention is to include antiseptic, anti-to be provided for high molecular material of the present invention
Bacterium function.For the present invention, all antiseptics that can be used in medical grade silicon rubber are used equally for the present invention.Preferably,
Antiseptic is nano cupric oxide, nano zine oxide, nano-titanium dioxide, nano phase ag_2 o, manganese dioxide, cadmium sulfide, three oxidations
It is tungsten, stannic oxide, di-iron trioxide, chitosan, Cefuroxime Sodium, amikacin, quadracycline, chloramphenicol, red mould
Element, Ciprofloxacin Hydrochloride, metronidazole, rifampin, any mixture of lincomycin or these antiseptics.Particularly preferably use two
Titanium oxide, chitosan, Cefuroxime Sodium, Ciprofloxacin Hydrochloride, welfare are put down, nano silver and/or zinc oxide.These antiseptics, example
As nano-titanium dioxide can produce hydroxyl radical free radical in the case where there is illumination so that bacterial oxidation be decomposed into carbon dioxide and
Water, so as to assign material with anti-microbial property.Chitosan is natural materials, has the function of anti-inflammatory, analgesic, promotes healing.To this
For invention, the dosage of antiseptic should cause, the medical silicon rubber included based on every 100 parts by weight high molecular material of the present invention
Glue, high molecular material of the present invention generally comprise the antiseptic of the antiseptic of 1-20 parts by weight, preferably 5-10 parts by weight.
As the matrix of high molecular material of the present invention, medical grade silicon rubber is used.Can medically it be used for this reason, any
Silicon rubber is used equally for the present invention.Silicon rubber for molecular backbone comprise only silicon, oxygen atom specific rubber general name, following formula can be used
Represent：
R is mainly methyl in molecular formula, is partly ethyl, vinyl, phenyl, itrile group and/or other extraordinary organic groups.
It is currently preferred that medical grade silicon rubber is dual composition addition type silicon rubber, this is because dual composition addition type silicon rubber has
Good processing performance and good mechanical performance, will not produce poisonous and harmful substance, dimensional stability during vulcanization
Very high, job efficiency is high.As the example of silicon rubber, methyl vinyl silicone can be mentioned that.Particularly preferred contents of ethylene
For the methyl vinyl silicone rubber that the silicon rubber of 0.001-5wt%, especially contents of ethylene are 0.07-4wt%.It is especially excellent
The weight average molecular weight of the medical grade silicon rubber of choosing is 300000-900000.
In a preferred embodiment of the invention, high molecular material of the present invention based on it includes every 100 parts by weight
Medical grade silicon rubber also includes following component：
A) the phyllosilicate of 1-20 parts by weight；
B) the quaternary ammonium salt of 1-20 parts by weight；
C) the anticoagulant of 1-10 parts by weight；
D) the hydrophilic polymer of 5-30 parts by weight；With
E) the antiseptic of 5-20 parts by weight.
According to another aspect of the present invention, there is provided a kind of side for preparing antibiosis anticoagulative blood high molecular material of the present invention
Method, this method comprises the following steps：
A) solution by phyllosilicate, quaternary ammonium salt and anticoagulant using liquid flux as decentralized medium or the scattered bodily form
Formula is uniformly mixed, and obtains anticoagulation intermediate；
B) hydrophilic polymer, antiseptic and medical grade silicon rubber are mixed with the anticoagulation intermediate that step a) is obtained
It is even, obtain Blend rubber；And
C) by Blend rubber vulcanization crosslinking.
In the step a) of the method for the present invention, phyllosilicate, quaternary ammonium salt and the anti-freezing of high molecular material of the present invention will be formed
Blood agent these three components mixing.Solution of the mixing of these three components using liquid flux as decentralized medium or dispersion into
OK so that with the cation in phyllosilicate ion exchange occurs for quaternary ammonium cation, so as to expand the interlayer of phyllosilicate
Away from so that anticoagulant can enter interlayer.As liquid flux herein, preferably water, such as distilled water, deionization
Water.
In a preferred embodiment of the method for the present invention, in step a), by phyllosilicate, quaternary ammonium salt and anti-freezing
Blood agent with water as solvent be stirred at a temperature of 25-120 DEG C 0.5-10 it is small when, when then ultrasonic disperse 0.5-10 is small, most
Dry, crush afterwards, obtain anticoagulation intermediate.It is particularly preferred that phyllosilicate is first dissolved or dispersed in water, formed
The aqueous solution or aqueous dispersion of phyllosilicate；Quaternary ammonium salt and anticoagulant are dissolved in water, aqueous solution is formed, then by institute
Phyllosilicate aqueous solution or aqueous dispersion and mixed containing the aqueous solution of quaternary ammonium salt and anticoagulant, and ultrasonic disperse,
Obtain aqueous dispersion.Then the aqueous dispersion is filtered, water washing precipitation, dry, pulverize, anticoagulation intermediate is made.
After anticoagulation intermediate is obtained, remaining component of the intermediate and high molecular material of the present invention is mixed together,
Then vulcanization crosslinking.
In another preferred embodiment of the method for the present invention, in step b), by hydrophilic polymer, antiseptic and
The anticoagulation intermediate that medical grade silicon rubber and step a) are obtained be blended in blending equipment at 25-120 DEG C 10min to 2 it is small when,
Obtain Blend rubber.As blending equipment herein, mixer, open mill, double screw extruder etc. can be mentioned that.Blending temperature according to
Material makes choice, and is usually 25-60 DEG C.When being blended using mixer, the roll spacing of mixer is carried out also according to specific material
Selection, is usually 0.5-4mm.
For the Blend rubber vulcanization crosslinking for obtaining step b), the Blend rubber for preferably obtaining step b) is in 100-180 DEG C
At a temperature of be heat-treated 5 minutes to 4 it is small when.In order to carry out vulcanization crosslinking here, it usually needs add vulcanizing agent, such as platinum
Catalyst.The dosage of vulcanizing agent is conventional, as long as can be crosslinked Blend rubber.Typically, the dosage of vulcanizing agent is every
The medical grade silicon rubber that 100 parts by weight high molecular material of the present invention is included uses 1-2g.
The antibiosis anticoagulative blood high molecular material of the present invention has anticoagulation and antibacterial functions concurrently, and including mechanical property and life
Excellent combination property including physical performance, also has breakthrough in mechanical property so that product safety and reliability, is particularly suitable for using
Make medical macromolecular materials.
Therefore, according to the present invention in terms of last, there is provided antibiosis anticoagulative blood high molecular material conduct of the invention
The purposes of medical macromolecular materials, the purposes especially in medical catheter.
In the present invention, different from conventional coating and chemical grafting method, the acquisition of the courageous and upright energy of antibiosis anticoagulative comes
From mechanical blending physically, this greatly reduces cost and operation difficulty, and cost is reduced while performance is optimized.
In the high molecular material of the present invention, interlayer of the anticoagulant due to entering phyllosilicate, obtains certain
Nano effect, the release of anticoagulant is controlled by migrating from inside to outside for anticoagulant well, avoids the anti-of material
Coagulant property is premature to be lost.Further, since the protective effect of layer structure so that into the anticoagulation of laminated silicate interlayer
Agent can preferably be resistant to heating blending so that anticoagulant loss of activity caused by heating blending reduces.It is additionally, since stratiform
Protection of the silicate to anticoagulant so that can also process at higher temperatures, this improves high-molecular anti-bacteria of the present invention
The machinability of anticoagulant material, can obtain product of different shapes, while substantially reduce the time of machine-shaping.With this
Meanwhile phyllosilicate can also play the role of reinforcement to silicon rubber, and hydrophilic polymer and anticoagulant pair are made up with this
The reduction of material mechanical performance.
In addition, as phyllosilicate, part layer structure can be peeled off after curing, nano-dispersed be formed, to rubber-based
Body plays good humidification.
As quaternary ammonium salt, in the present invention, intercalator use is served not only as, and quaternary ammonium salt also plays antiseptic,
Further improve the anti-microbial property of material.
The antibiosis anticoagulative blood high molecular material of the present invention also includes hydrophilic polymer, their addition is so that the table of material
Face hydrophily improves, and reduces the surface free energy between material and blood, improves blood compatibility.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, it is noted that these embodiments are only pair
The present invention's is exemplary illustrated, and is not considered as limitation of the scope of the invention.
Embodiment 1
1) by 10g montmorillonites (by the acquisition purchased in market of Zhejiang Feng Hong clays Co., Ltd, cationic ion exchange capacity 90mmol/
100g) it is placed in 50ml deionized waters, and the dispersed 30min at a temperature of 30 DEG C, obtain montmorillonite suspension liquid.
2) by 10g unfractionated heparins sodium (by the acquisition purchased in market of Chinese medicines group chemical reagent Beijing Co., Ltd, potency 150u/mg)
Be dissolved in 10g dodecyl trimethyl ammonium chloride (by Tianjin recovery Fine Chemical Works company acquisition purchased in market, cp) 20ml go from
In sub- water, aqueous solution is obtained.
3) aqueous solution that step 2) obtains is mixed with the montmorillonite suspension liquid that step 1) obtains, is sufficiently stirred at 40 DEG C
30min, then ultrasonic disperse 30min, obtains aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 460,000, contents of ethylene 0.004wt%), 5g polyethylene glycol (by the acquisition purchased in market of Peking blue profit fine chemistry industry company, is divided equally again
Son amount for 400), 5g nano-titanium dioxides (by Hangzhou Wanjing New Material Co., Ltd.'s acquisition purchased in market, trade mark VK-TA18S) and
Obtained anticoagulation intermediate mixing 30min in mixer, obtains Blend rubber in 5g steps 4), and wherein mixing rotating speed is
25rpm, mixing temperature are 60 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1g platinum catalysts (Kai Wote organosilicon materials Co., Ltd of Shenzhen)
In the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
The external static platelet adhesion reaction scanning electron microscope (SEM) photograph of the silicone rubber material used in the embodiment is shown in Fig. 1, the implementation
The external static platelet adhesion reaction scanning electron microscope (SEM) photograph of antibiosis anticoagulative blood high molecular material prepared by example is shown in Fig. 2.Scanning electron microscope used
For the S-4700 type scanning electron microscope of Japanese HITACHI companies.
From figure 1 it appears that have substantial amounts of platelet adhesion reaction on material surface, and some of blood platelets occur
Deformation, bears pseudopodium, illustrates that the anticoagulation function of material is bad.From figure 2 it can be seen that material surface is small almost without blood
Plate adsorbs, and surface is totally smooth, shows that material has preferable anticoagulation function.
Embodiment 2
1) by 20g kaolin (Shanghai jump river titanium white heavy chemicals Co., Ltd, 300 mesh, ion exchange capacity 100mg/
100g) it is placed in 50ml deionized waters, and the dispersed 30min at a temperature of 60 DEG C, obtain Kaolin clay suspension.
2) by 10g low molecular weights sodium (Shanghai Al-Amin Biotech Co., Ltd., potency 120u/mg) and 20g dodecanes
Base front three ammonium chloride/5/35/60 mixture of cetyl front three ammonium chloride/octadecyl trimethyl ammonium chloride by weight
(by the acquisition purchased in market of Tianjin recovery Fine Chemical Works company, cp) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the Kaolin clay suspension that step 1) obtains, is sufficiently stirred at 30 DEG C
70min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 370,000, contents of ethylene 0.06wt%), (Chinese medicines group chemical reagent Beijing is limited, Weight-average molecular for 20g polyethyleneimines
Amount：70000) system in, 20g nano zine oxides (Hangzhou Wanjing New Material Co., Ltd., average grain diameter 50nm), and 5g steps 4)
The anticoagulation intermediate obtained mixing 30min in mixer, obtains Blend rubber, wherein mixing rotating speed is 25rpm, and mixing temperature is
30 DEG C, the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.2g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 3
1) 10g talcum powder (Lingshou County Peng Xian talcum powder factory, food grade) is placed in 50ml deionized waters, and in 30 DEG C of temperature
Dispersed 30min under degree, obtains talcum powder suspension.
2) by 20g bicoumarins (Ti Xiai chemical engineering industries Development Co., Ltd, purity are more than 98.0 weight %) and 10g ten
Eight alkyl double hydroxyethyl ammonio methacrylates are dissolved in 20ml deionizations (by the acquisition purchased in market of Tianjin recovery Fine Chemical Works company, cp)
In water, aqueous solution is obtained.
3) aqueous solution that step 2) obtains is mixed with the talcum powder suspension that step 1) obtains, is sufficiently stirred at 40 DEG C
30min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 420,000, contents of ethylene 0.07wt%), (Chinese medicines group chemical reagent Beijing is limited, viscosity 0.45- for 5g sodium alginates
0.55PaS), 5g chitosans (Shanghai Bai Ao bio tech ltd, pale yellow powder, deacylation degree 90%), and 10g steps
4) obtained anticoagulation intermediate mixing 30min in mixer in, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, mixing
Temperature is 60 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.1g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 4
1) 10g bentonite (Shishewei Chemical Co., Ltd., Shanghai, CP) is placed in 50ml deionized waters, and in 30 DEG C of temperature
Dispersed 30min, obtains bentonite suspension under degree.
2) by 10g acenocoumarins (Chinese medicines group chemical reagent Beijing is limited, USP) and 30g dodecyl dimethyl benzyls
Ammonium chloride (Shandong long-chain Chemical Co., Ltd., 99 weight %) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the bentonite suspension that step 1) obtains, is sufficiently stirred at 40 DEG C
30min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 540,000, contents of ethylene 0.3wt%), 5g sodium hyaluronates (Furuida Biochemical Co., Ltd., Shandong), 5g Cefuroxime Sodiums
(Li Wei international corporation), and obtained anticoagulation intermediate mixing 30min in mixer in 15g steps 4), are total to
Mixed glue, wherein mixing rotating speed are 25rpm, and mixing temperature is 60 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.3g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 5
1) 10g micas (Ge Ruikuang Co., Ltds of Anhui Chuzhou, 1500 mesh) are placed in 50ml deionized waters, and in 30 DEG C
At a temperature of dispersed 30min, obtain mica suspension.
2) by 10g urokinases (Nanjing Nan great medicine companies biochemistry corporation,Ltd., potency 48kUmg-1) and 10g hexadecanes
Base dimethyl benzyl ammonium chloride (West Asia reagent, purity are more than 95 weight %) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the mica suspension that step 1) obtains, is sufficiently stirred at 40 DEG C
30min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 840,000, contents of ethylene 4wt%), 5g polyvinylpyrrolidones (Shanghai Yuan Ju bio tech ltd, Weight-average molecular
Amount：1200000), 5g Ciprofloxacin Hydrochlorides (the auspicious field biochemistry Co., Ltd in Shijiazhuang), and obtained anticoagulation in 20g steps 4)
Intermediate mixing 30min in mixer, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, and mixing temperature is 40 DEG C, mixing
The roll spacing of machine is 1mm.
6) by the Blend rubber that step 5) obtains in 1.5g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 6
1) 30g snakes mountain flour (serpentine mining industry Co., Ltd of Yiyang County, 200 mesh) is placed in 50ml deionized waters, and
The dispersed 30min at a temperature of 30 DEG C, obtains snake mountain flour suspension.
2) by 10g warfarins (ten thousand great achievement medication chemistry Co., Ltd of nation of Hubei) and 10g tetradecyl trimethyl ammonium chlorides
(by the acquisition purchased in market of Tianjin recovery Fine Chemical Works company, cp) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the snake mountain flour suspension that step 1) obtains, is fully stirred at 50 DEG C
30min, and then ultrasonic disperse 30min are mixed, obtains aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 600,000, contents of ethylene 5wt%), 30g polymethyl acyl ethyoxyls Phosphorylcholine (Nanjing Hui Zhe trade Co., Ltds,
Weight average molecular weight：100000), 5g rifampins (four medicine pharmaceutcal corporation, Ltd of Wuhan Zhong Lian groups), and made from 25g steps 4)
Anticoagulation intermediate mixing 30min in mixer, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, mixing temperature 40
DEG C, the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 2.0g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 100 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 7
1) 10g leaves cured native (Jiangxi Province Guangfeng County Qi Sen mineral products Co., Ltd, 800 mesh) are placed in 50ml deionizations
In water, and the dispersed 30min at a temperature of 30 DEG C, obtain the cured native suspension of leaf.
2) by 10g hirudins (Guangzhou Ai Bao bio tech ltd, content are more than 99 weight %) and 10g cetyls
Trimethyl ammonium chloride (Fine Chemical Works, cp are recovered in Tianjin) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) the cured native suspension of leaf obtained the aqueous solution that step 2) obtains with step 1) mixes, and is sufficiently stirred at 60 DEG C
30min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 700,000, contents of ethylene 0.25wt%), 5g polyethylene glycol (Peking blue profit fine chemistry industry, weight average molecular weight：400), 5g gathers
(Chinese medicines group chemical reagent Beijing is limited, weight average molecular weight for aziridine：70000), 5g nano phase ag_2 os (Beijing Deco island gold
Science and Technology Ltd., average grain diameter 50nm, 99.95 weight % of purity), and in 5g steps 4) obtained anticoagulation intermediate close
Mixing 30min in mill, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, and mixing temperature is 40 DEG C, and the roll spacing of mixer is
1mm。
6) by the Blend rubber that step 5) obtains in 1.8g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 100 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 8
1) 10g green muds mountain flour (Ninghai County praises and Chemical Co., Ltd., 500 mesh) is placed in 50ml deionized waters, and in
Dispersed 180min at a temperature of 50 DEG C, obtains chlorite suspension.
2) by 20g argatrobans (Jinan Nuo Kang Pharmaceutical Technology Co., Ltd) and 10g octadecyltrimethylammonium chloride (my god
Fine Chemical Works, cp recover in Jinshi City) it is dissolved in 20ml deionized waters, obtain aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the green mud mountain flour suspension that step 1) obtains, is fully stirred at 30 DEG C
100min, and then ultrasonic disperse 30min are mixed, obtains aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 800,000, contents of ethylene 2wt%), (Chinese medicines group chemical reagent Beijing is limited, weight average molecular weight for 5g polyethyleneimines：
70000), 5g sodium alginates (Chinese medicines group chemical reagent Beijing is limited, viscosity 0.45-0.55PaS), 20g hydrochloric acid Fourth Ring
Plain (Shanghai Jingchun Industrial Co., Ltd.), and obtained anticoagulation intermediate mixing 30min in mixer in 5g steps 4), obtain
To Blend rubber, wherein mixing rotating speed is 45rpm, and mixing temperature is 30 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.2g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 9
1) by 10g leaves cured native (Jiangxi Province Guangfeng County Qi Sen mineral products Co., Ltd, 800 mesh) and (spirit of 10g talcum powder
Shou County Peng Xian talcum powder factory, food grade) it is placed in 50ml deionized waters, and the dispersed 30min at a temperature of 30 DEG C, obtain leaf
The mixing suspension of cured soil and talcum powder.
2) by 20g ximelagatrans (Shanghai Yi Fei Bioisystech Co., Ltd) and 10g myristyl benzyl dimethyl chlorinations
Ammonium (Shandong long-chain Chemical Co., Ltd., 99%) is dissolved in 20ml deionized waters, obtains aqueous solution.
3) the cured soil of leaf and the suspension of talcum powder obtained the aqueous solution that step 2) obtains with step 1) mixes, at 20 DEG C
Under be sufficiently stirred 70min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, weight average molecular weight 460,000, vinyl contains
Measure 3.8wt%), 10g sodium alginates (Chinese medicines group chemical reagent Beijing is limited, viscosity 0.45-0.55PaS), 10g glass urine
Sour (Furuida Biochemical Co., Ltd., Shandong), 20g di-iron trioxides (Shanghai Pu Zhen bio tech ltd, CP), and
Obtained anticoagulation intermediate mixing 30min in mixer, obtains Blend rubber, wherein rotating speed 25rpm, temperature in 5g steps 4)
30 DEG C, roll spacing 2mm.
6) by the Blend rubber that step 5) obtains in 1.3g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 10
1) by 10g zeolite powders (Faku County Bao Jiatun townshiies Zeolite mineral, 200 mesh, SiO2>67 weight %) it is placed in 50ml deionizations
In water, and the dispersed 30min at a temperature of 30 DEG C, obtain the suspension of zeolite powder.
2) by 10g sodium chondroitin sulfates (Shandong Hai Yu Bioisystech Co., Ltd) and 10g trimethyl chlorine
(Tianjin recovery becomes more meticulous for change ammonium (Fine Chemical Works, cp are recovered in Tianjin) and 10g octadecyl double hydroxyethyls ammonio methacrylate
Factory, cp) it is dissolved in 20ml deionized waters, obtain aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the zeolite powder suspension that step 1) obtains, is sufficiently stirred at 40 DEG C
30min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 900,000, contents of ethylene 0.18wt%), 2.5g sodium hyaluronates (Furuida Biochemical Co., Ltd., Shandong), 2.5g polyethylene
Pyrrolidones (Shanghai Yuan Ju bio tech ltd, weight average molecular weight：80000), 5g manganese dioxide (the big prosperous manganese product in Xiang Tan
Co., Ltd, 800 mesh), and obtained anticoagulation intermediate mixing 30min in mixer in 5g steps 4), Blend rubber is obtained,
Wherein mixing rotating speed is 25rpm, and mixing temperature is 60 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.0g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 11
1) 20g attapulgites (Ming Mei mineral Chemical Co., Ltd. of Anhui Province, 200 mesh) are placed in 50ml deionized waters,
And the dispersed 30min at a temperature of 60 DEG C, obtain attapulgite suspension.
2) by 10g low molecular weights sodium (Shanghai Al-Amin Biotech Co., Ltd., weight average molecular weight：And 10g ten 5000)
Dialkyl group trimethyl ammonium chloride/cetyl front three ammonium chloride/octadecyl trimethyl ammonium chloride by weight 5/35/60 it is mixed
Compound is dissolved in 20ml deionized waters, obtains aqueous solution.
3) aqueous solution that step 2) obtains is mixed with the attapulgite suspension that step 1) obtains, is fully stirred at 80 DEG C
70min, and then ultrasonic disperse 30min are mixed, obtains aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 420,000, contents of ethylene 0.45wt%), (Shanghai Yuan Ju bio tech ltd, divides equally 15g polyvinylpyrrolidones again
Son amount：650000), 15g methacryloyloxyethyls Phosphorylcholine (Nanjing Hui Zhe trade Co., Ltds, weight average molecular weight：
100000), 20g stannic oxides (Shanghai height into Trade Co., Ltd., 99 weight % of content), and obtained anti-freezing in 5g steps 4)
Blood intermediate mixing 30min in mixer, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, and mixing temperature is 30 DEG C, close
The roll spacing of mill is 1mm.
6) by the Blend rubber that step 5) obtains in 1.2g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
Embodiment 12
1) by 10g montmorillonites (Zhejiang Feng Hong clays Co., Ltd, cationic ion exchange capacity 90mmol/100g) and 10g
Bentonite (Shishewei Chemical Co., Ltd., Shanghai, CP) is placed in 50ml deionized waters, and dispersed at a temperature of 60 DEG C
30min, obtains the mixing suspension of montmorillonite and bentonite.
2) by 20g aspirin (Shanghai Pu Zhen bio tech ltd, GR) and 10g dodecyl dimethyl benzyl chlorides
Change ammonium/5/35/60 mixture of myristyl benzyl dimethyl ammonium chloride/hexadecane dimethyl benzyl ammonium chloride by weight
(Shandong long-chain Chemical Co., Ltd., 99 weight %) are dissolved in 20ml deionized waters, obtain aqueous solution.
3) montmorillonite obtained the aqueous solution that step 2) obtains with step 1) and the suspension of bentonite mix, at 110 DEG C
Under be sufficiently stirred 70min, and then ultrasonic disperse 30min, obtain aqueous dispersion.
4) aqueous dispersion for obtaining step 3) filters, and precipitation is fully washed with distilled water 3 times, is dried under vacuum to constant weight,
After grinding, anticoagulation intermediate is obtained.
5) by 100g methyl vinyl silicones silicon rubber, (Kai Wote organosilicon materials Co., Ltd of Shenzhen, divides equally again
Son amount 600,000, contents of ethylene 0.55wt%), 10g polyethylene glycol (Peking blue profit fine chemistry industry, weight average molecular weight：400), 20g
Sodium alginate (Chinese medicines group chemical reagent Beijing is limited, viscosity 0.45-0.55PaS), 10g nano-titanium dioxides are (by Hangzhoupro
The acquisition purchased in market of ten thousand scape new material Co., Ltds of state, trade mark VK-TA18S), (Beijing Deco island gold science and technology has 10g nano phase ag_2 os
Limit company, average grain diameter 50nm, 99.95 weight % of purity), and in 5g steps 4) obtained anticoagulation intermediate in mixer
Mixing 30min, obtains Blend rubber, and wherein mixing rotating speed is 25rpm, and mixing temperature is 30 DEG C, and the roll spacing of mixer is 1mm.
6) by the Blend rubber that step 5) obtains in 1.3g platinum catalysts (the limited public affairs of Shenzhen's Kai Wote organosilicon materials
Department) in the presence of vulcanize 4h at 120 DEG C in compression molding instrument, being made has the function of the silastic material of antibiosis anticoagulative blood.
The silastic material that the silicone rubber material and each embodiment used the various embodiments described above is prepared carries out mechanics
Performance test, hemolysis rate, antibiotic rate and recalcification time test.
In Mechanics Performance Testing, device therefor sets for the LR30K types of LIOYD companies of electronic universal material testing machine Britain
Standby, test condition is draw speed 500mm/min, and test bars size is (115*6*2) mm.
In hemolysis rate test, using YBB0003-2003 standards.
In antibiotic rate test, using QB/T2591-2003 standards.
Recalcification time test method is as follows：
The trisodium citrate aqueous solution of the 3.8wt% of rabbit blood 5mL and anti-freezing by volume 9 is extracted using cardiac puncher method：1
Ratio is configured to fresh anticoagulation.Take the NaCl aqueous solutions of above-mentioned fresh anticoagulation and 0.9wt% by volume 1:1.25 ratio
Example is configured to dilution rabbit blood, then centrifuges 10min with 1000r/min rotating speeds, takes supernatant spare as blood plasma.By each reality
The composite silicone rubber material for applying example preparation is cut into the small bar of 0.2cm × 0.2cm, inserts in the NaCl aqueous solutions of 0.9wt% and soaks
24h, then moves in the test tube of Φ 1x7.5cm.Every group of three Duplicate Samples, be separately added into 0.2mL blood plasma and
The CaCl of 0.2mL0.025mol/L2Aqueous solution, is placed in 37 DEG C of waters bath with thermostatic control, manual time-keeping, jiggling test tube makes CaCl2Water
Solution is uniformly mixed with supernatant.When occurring a white fibre shape thing in test tube, i.e., by second hand stop table, recalcification time can be obtained.It is multiple
Calcium time can reflect anticoagulant property, and recalcification time is longer, and anticoagulant property is better.
For the silicone rubber material used in the various embodiments described above, its fracture tensile strength is 9.21MPa, elongation at break
For 1220.87%, shore hardness 46.3, hemolysis rate 4.02%, recalcification time 122s, antibiotic rate (staphylococcus aureus)
For 0%, and the test result for the silastic material that each embodiment is prepared see the table below 1.
Table 1
Above-mentioned experiment embodiment does not limit the present invention in any way, all to be obtained in the form of equivalent substitution or equivalent transformation
The technical solution obtained, is within the scope of the present invention.
Claims (28)
1. a kind of antibiosis anticoagulative blood high molecular material, it includes medical grade silicon rubber, which is included based on every 100 parts by weight
Medical grade silicon rubber also includes following component：
A) the phyllosilicate of 1-30 parts by weight；
B) the quaternary ammonium salt of 1-30 parts by weight；
C) the anticoagulant of 1-20 parts by weight；
D) the hydrophilic polymer of 1-30 parts by weight；With
E) the antiseptic of 1-20 parts by weight,
Wherein hydrophilic polymer is the one or more in being selected from the group：Polyethylene glycol, polyethyleneimine, sodium alginate, glass
Uric acid and polymethyl acyl ethyoxyl Phosphorylcholine.
2. high molecular material according to claim 1, wherein layered silicate is the one or more in being selected from the group：Leaf
Cured soil, zeolite powder, attapulgite, talcum powder, mica, kaolin, snake mountain flour, green mud mountain flour, montmorillonite and bentonite.
3. high molecular material according to claim 1, wherein the quaternary ammonium salt is the one or more in being selected from the group：Dodecane
Base trimethyl-ammonium halide, tetradecyltrimethylammonium ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl halogenation
Ammonium, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl Benzyl halides ammonium, myristyl benzyl dimethyl halogenation
Ammonium, cetyl dimethyl benzyl ammonium halide.
4. high molecular material according to claim 2, wherein the quaternary ammonium salt is the one or more in being selected from the group：Dodecane
Base trimethyl-ammonium halide, tetradecyltrimethylammonium ammonium halide, cetyl trimethyl ammonium halide, octadecyl trimethyl halogenation
Ammonium, octadecyl double hydroxyethyl methyl ammonium halide, dodecyl dimethyl Benzyl halides ammonium, myristyl benzyl dimethyl halogenation
Ammonium, cetyl dimethyl benzyl ammonium halide.
5. high molecular material according to claim 3, wherein the quaternary ammonium salt is the one or more in being selected from the group：Dodecane
Base trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl chlorination
Ammonium, octadecyl double hydroxyethyl ammonio methacrylate, dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl chlorination
Ammonium, cetalkonium chloride, dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, hexadecane
Base trimethylammonium bromide, Cetyltrimethylammonium bromide, octadecyl double hydroxyethyl methyl bromide ammonium, dodecyl dimethyl
Benzylphosphonium Bromide ammonium, tetradecyl dimethyl benzyl ammonium and/or cetyl dimethyl benzyl ammonium bromide.
6. high molecular material according to claim 4, wherein the quaternary ammonium salt is the one or more in being selected from the group：Dodecane
Base trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl chlorination
Ammonium, octadecyl double hydroxyethyl ammonio methacrylate, dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl chlorination
Ammonium, cetalkonium chloride, dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, hexadecane
Base trimethylammonium bromide, Cetyltrimethylammonium bromide, octadecyl double hydroxyethyl methyl bromide ammonium, dodecyl dimethyl
Benzylphosphonium Bromide ammonium, tetradecyl dimethyl benzyl ammonium and/or cetyl dimethyl benzyl ammonium bromide.
7. high molecular material according to claim 1, wherein the anticoagulant is the one or more in being selected from the group：Small point
Sub- heparin sodium, unfractionated heparin sodium, bicoumarin, acenocoumarin, urokinase, warfarin, hirudin, argatroban, Xi Meijia
Group, aspirin, ticlopidine and chondroitin sulfate.
8. high molecular material according to claim 2, wherein the anticoagulant is the one or more in being selected from the group：Small point
Sub- heparin sodium, unfractionated heparin sodium, bicoumarin, acenocoumarin, urokinase, warfarin, hirudin, argatroban, Xi Meijia
Group, aspirin, ticlopidine and chondroitin sulfate.
9. high molecular material according to claim 1, wherein it is 100-2000000 that the hydrophilic polymer, which is weight average molecular weight,
The polymer containing hydrophilic radical.
10. high molecular material according to claim 2, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
11. high molecular material according to claim 3, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
12. high molecular material according to claim 4, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
13. high molecular material according to claim 5, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
14. high molecular material according to claim 6, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
15. high molecular material according to claim 7, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
16. high molecular material according to claim 8, wherein it is 100- that the hydrophilic polymer, which is weight average molecular weight,
2000000 polymer containing hydrophilic radical.
17. according to the high molecular material of any one of claim 1-16, wherein the antiseptic is one kind in being selected from the group
It is or a variety of：Nano cupric oxide, nano zine oxide, nano-titanium dioxide, nano phase ag_2 o, manganese dioxide, cadmium sulfide, three oxidations
It is tungsten, stannic oxide, di-iron trioxide, chitosan, Cefuroxime Sodium, amikacin, quadracycline, chloramphenicol, red mould
Element, Ciprofloxacin Hydrochloride, metronidazole, rifampin, lincomycin, any mixture of nano silver or these antiseptics.
18. according to the high molecular material of any one of claim 1-16, wherein the medical grade silicon rubber is bi-component addition type
Silicon rubber.
19. high molecular material according to claim 18, wherein the medical grade silicon rubber is methyl vinyl silicone.
20. high molecular material according to claim 18, wherein it is 0.001-5wt% that the medical grade silicon rubber, which is contents of ethylene,
Methyl vinyl silicone rubber.
21. high molecular material according to claim 18, wherein it is 0.07-4wt% that the medical grade silicon rubber, which is contents of ethylene,
Methyl vinyl silicone rubber.
22. high molecular material according to claim 18, wherein the weight average molecular weight of the medical grade silicon rubber is 300000-
900000。
23. according to the high molecular material of any one of claim 1-16, based on every 100 parts by weight medical grade silicon rubber, it is also wrapped
Containing following component：
A) 1-20 weight parts layered silicates；
B) 1-20 parts by weight quaternary ammonium salt；
C) 1-10 parts by weight anticoagulant；
D) 5-30 part by weight of hydrophilic polymer；With
E) the antiseptic of 5-20 parts by weight.
24. according to the high molecular material of any one of claim 1-16, based on every 100 parts by weight medical grade silicon rubber, it is also wrapped
Containing following component：
A) 1-8 weight parts layered silicates；
B) 1-10 parts by weight quaternary ammonium salt；
C) 1-8 parts by weight anticoagulant；
D) 5-20 part by weight of hydrophilic polymer；With
E) 5-20 parts by weight antiseptic.
25. a kind of method of the antibiosis anticoagulative blood high molecular material prepared as any one of claim 1-24, including such as
Lower step：
A) solution by phyllosilicate, quaternary ammonium salt and anticoagulant using liquid flux as decentralized medium or dispersion mix
Close uniformly, obtain anticoagulation intermediate；
B) hydrophilic polymer, antiseptic and medical grade silicon rubber are uniformly mixed with the anticoagulation intermediate that step a) is obtained, obtained
To Blend rubber；And
C) by Blend rubber vulcanization crosslinking.
26. method according to claim 25, wherein
In step a), phyllosilicate, quaternary ammonium salt and anticoagulant are stirred with water as solvent at a temperature of 25-120 DEG C
When mixing 0.5-10 is small, when then ultrasonic disperse 0.5-10 is small, finally dries, crush, obtain anticoagulation intermediate；And/or
In step b), the obtained anticoagulation intermediate of hydrophilic polymer, antiseptic and medical grade silicon rubber and step a) is existed
When blending 10min-2 is small at 25-120 DEG C in blending equipment, Blend rubber is obtained；And/or
In step c), by the Blend rubber that step b) is obtained when being heat-treated 5 minutes small to 4 at a temperature of 100-180 DEG C sulphur
Change crosslinking.
27. according to the antibiosis anticoagulative blood high molecular material of any one of claim 1-24 as medical macromolecular materials
Purposes.
28. purposes according to claim 27, wherein the antibiosis anticoagulative blood high molecular material is used for medical catheter.
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