CN108641088A - A kind of preparation method and applications of high stability biomaterial for medical purpose - Google Patents
A kind of preparation method and applications of high stability biomaterial for medical purpose Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications of high stability biomaterial for medical purpose, this method, which uses, to obtain dry mixed powder after meteorological white carbon, aluminum fluoride progress wet ball grinding, drying；Polymethyl methacrylate, fatty acid polyethylene glycol ester are subjected to high-temperature stirring reaction in vacuum reaction kettle, addition methyl phenyl silicone oil carries out standing insulation reaction and obtains pyroreaction object after cooling, coconut monoethanolamide, sulfadimidine, naphthalene sodium acetate are added after cooling, compressive reaction obtains secondary response object in a nitrogen environment；Then it is mixed dry mixed powder, secondary response object and additive to obtain heat mixture, adds dimethyl sulfoxide (DMSO), finished product biomaterial for medical purpose is made in the techniques such as sonicated, extruding pelletization, injection molding, segmentation, packaging, sterilizing.The biomaterial for medical purpose being prepared, stability is strong, has a good application prospect on medical devices.
Description
Technical field
The present invention relates to medical biomaterial technical fields, and in particular to a kind of preparation of high stability biomaterial for medical purpose
Method and its application.
Background technology
Biomedical material refers to that one kind has property, features, for artificial organs, surgical repair, reason
Rehabilitation, diagnosis, treatment illness are treated, and not will produce dysgenic material to tissue.Present various synthetic materials and day
Right high molecular material, metal and alloy material, ceramics and carbon materials and various composite materials, it is wide to be made product
It is applied to clinical and scientific research generally.Biomaterial is widely used, various types, there is different sorting techniques.Typically press material
Attribute is divided into：Synthesize high molecular material（Polyurethane, polyester, polylactic acid, polyglycolic acid, lactic acid glycolate copolymer and other doctors
With synthetic plastic and rubber etc.）, natural macromolecular material（Such as collagen, silk-fibroin, cellulose, chitosan）, Metal and Alloy
Material（Such as admire metal and its alloy）, inorganic material（Bioactive ceramics, hydroxyapatite etc.）, composite material（Carbon fiber/
Polymer, glass fibre/polymer etc.）.
Medical macromolecular materials be develop earliest, most widely used, the maximum material of dosage in bio-medical material, and
One field rapidly developed.It has natural products and artificial synthesized two sources.The material, which removes, should meet general object
Reason, chemical property require outer, it is necessary to have biocompatibility good enough.It can be divided into non-drop by property medical macromolecular materials
Two class of solution type and biodegradation type.For the former, it is desirable that its in biotic environment can stable for extended periods of time, do not occur degradation,
Crosslinking or physical abrasion etc., and there is good physical mechanical property.Be not required for its absolute stability, but require itself and
A small amount of catabolite does not generate apparent toxic side effect to body, while catastrophic failure will not occur for material.Medical high score
Sub- material is mainly used for soft human body, hard tissue repair body, artificial organs, artificial blood vessel, contact lense, membrane material, bonding agent and tube chamber
Product etc..Ideal bioabsorbable polymer material should be stability it is strong, it is non-toxic to human body, without sensitization, it is nonirritant,
The adverse reactions such as hereditary-less toxicity and non-carcinogenesis.Therefore, current medical macromolecular materials and the real of people it is expected and want
Seek also a certain distance.
Invention content
In order to solve the above technical problems, the present invention provides a kind of preparation method of high stability biomaterial for medical purpose and its answers
With this method, which uses, to obtain dry mixed powder after meteorological white carbon, aluminum fluoride progress wet ball grinding, drying；By poly- methyl
Methyl acrylate, fatty acid polyethylene glycol ester carry out high-temperature stirring reaction in vacuum reaction kettle, and aminomethyl phenyl is added after cooling
Silicone oil, which carries out standing insulation reaction, obtains pyroreaction object, be added after cooling coconut monoethanolamide, sulfadimidine,
Naphthalene sodium acetate, in a nitrogen environment compressive reaction obtain secondary response object；Then by dry mixed powder, secondary response object and add
Add agent to be mixed to obtain heat mixture, add dimethyl sulfoxide (DMSO), sonicated, extruding pelletization, divides at injection molding
It the techniques such as cuts, pack, sterilizing and finished product biomaterial for medical purpose is made.The biomaterial for medical purpose being prepared, stability is strong,
It has a good application prospect on medical devices.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of high stability biomaterial for medical purpose, includes the following steps：
（1）By in 2-4 parts of meteorological white carbon 3-5 parts, aluminum fluoride input ball mills, then 2 times of matter of solid mixt are added thereto
A concentration of 95% ethanol solution of amount carries out wet ball grinding, and the mixed-powder that ball-milling treatment obtains then is placed in vacuum drying
It is 6-8 hours dry at a temperature of 60-70 DEG C in case, obtain dry mixed powder；
（2）35-45 parts of polymethyl methacrylate, 30-40 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, taken out true
Empty extremely -0.08 to -0.1 MPa, sets reactor temperature as 160-180 DEG C, under 150-160 revs/min of stir speed (S.S.)
High-temperature stirring reaction is carried out, the reaction time is 45-55 minutes, and reactor temperature is then down to 120 DEG C, aminomethyl phenyl is added
8-12 parts of silicone oil stands insulation reaction 30-40 minutes, obtains height after being stirred evenly under 150-160 revs/min of stir speed (S.S.)
Warm reactant；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide is then added thereto
12-16 parts, 6-8 parts of sulfadimidine, 2-4 parts of naphthalene sodium acetate, compressive reaction in a nitrogen environment, reaction pressure 2.5-
3.5 MPa, reaction temperature are 75-85 DEG C, and the reaction time is 80-120 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）It is obtained 1-3 parts of secondary response object and plasticizer, anti-
1-3 parts of oxidant is placed in mixing and blending machine, is stirred 15-25 minutes at 50-60 DEG C, heat mixture is obtained, by heat mixture
It is transferred in ultrasonic dispersers after cooling, the dimethyl sulfoxide (DMSO) with quality such as mixtures is added, then with the HCl of 0.1 mol/L
Solution regulation system pH to 6.0 disperses 40-60 minutes according to the frequency ultrasound of 20-22 kHz, obtains being ultrasonically treated mixture；
（5）By step（4）Extruding pelletization is carried out in obtained supersound process mixture injection double screw extruder, obtains particulate matter
Material；
（6）By step（5）Obtained granule materials are put into injection molding machine, obtain the biomaterial for medical purpose of injection molding, then pass through
Segmentation, packaging, sterilizing, are put in storage after cooling.
Further, the step（1）The ratio of grinding media to material of middle ball mill is 10:1, ball milling speed is 500 revolutions per seconds, when ball milling
Between be 60-90 minutes.
Further, the step（4）In plasticizer be selected from acetylation tri-n-butyl citrate, phthalic acid diformazan
Any one in ester, tirethylene glycol.
Further, the step（4）In antioxidant be selected from propylgallate, 2- tertiary butyl -4- methoxybenzenes
Any one in phenol, disodium ethylene diamine tetraacetate.
Further, the step（5）The driving screw rotating speed of middle double screw extruder is 600-700 revs/min, heating temperature
Degree is 190-210 DEG C, and head temperature is 195-200 DEG C.
Further, the step（6）The injection speed of middle injection molding machine is 60-80 mm/seconds, reaction temperature 200-
210 DEG C, injection time is 0.5-1.5 seconds, and injection pressure is 75 MPa, and the dwell time is 0.5 second
At the same time, the invention also discloses high stability biomaterial for medical purpose made from the preparation method on medical devices
Application.
Compared with prior art, the present invention advantage is：
（1）The preparation method of the high stability biomaterial for medical purpose of the present invention is used carries out wet method by meteorological white carbon, aluminum fluoride
Dry mixed powder is obtained after ball milling, drying；By polymethyl methacrylate, fatty acid polyethylene glycol ester in vacuum reaction kettle
High-temperature stirring reaction is carried out, addition methyl phenyl silicone oil carries out standing insulation reaction and obtains pyroreaction object after cooling, after cooling
Coconut monoethanolamide, sulfadimidine, naphthalene sodium acetate is added, compressive reaction obtains secondary response in a nitrogen environment
Object；Then it is mixed dry mixed powder, secondary response object and additive to obtain heat mixture, adds dimethyl
Finished product biomaterial for medical purpose is made in sulfoxide, the techniques such as sonicated, extruding pelletization, injection molding, segmentation, packaging, sterilizing.System
Biomaterial for medical purpose made of standby, stability is strong, has a good application prospect on medical devices.
（2）Present invention employs polymethyl methacrylate, fatty acid polyethylene glycol ester, coconut monoethanolamide,
The raw materials such as sulfadimidine, naphthalene sodium acetate participate in preparing high stability biomaterial for medical purpose, are carried out to biomaterial for medical purpose
Effective performance boost, although these materials are not first Application in biomaterial for medical purpose, amount combination according to a certain ratio
Afterwards, it is aided with corresponding processing mode, significantly carrying in performance is brought to the biomaterial for medical purpose being finally prepared
Height, this is never to report in previous research, for realizing that it is conclusive that the technique effect of the present invention plays the role of.
Specific implementation mode
The technical solution of invention is described in detail with reference to specific embodiment.
Embodiment 1
（1）By in 2 parts of 3 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 60 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 6 at a temperature of 60 DEG C
Hour, obtain dry mixed powder；
（2）35 parts of polymethyl methacrylate, 30 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.08 MPa sets reactor temperature as 160 DEG C, high-temperature stirring reaction is carried out under 150 revs/min of stir speed (S.S.), instead
It is 45 minutes between seasonable, reactor temperature is then down to 120 DEG C, 8 parts of methyl phenyl silicone oil is added, at 150 revs/min
Insulation reaction 30 minutes are stood after being stirred evenly under stir speed (S.S.), obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 12 is then added thereto
Part, 6 parts of sulfadimidine, 2 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 2.5 MPa, reaction temperature in a nitrogen environment
Degree is 75 DEG C, and the reaction time is 80 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and acetylation citric acid is just
1 part of butyl ester, 1 part of propylgallate are placed in mixing and blending machine, are stirred 15 minutes at 50 DEG C, are obtained heat mixture, will be hot
It is transferred in ultrasonic dispersers after mixture cooling, the dimethyl sulfoxide (DMSO) with quality such as mixtures is added, then with 0.1 mol/L
HCl solution regulation system pH to 6.0, according to 20 kHz frequency ultrasound disperse 40 minutes, obtain be ultrasonically treated mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 600 revs/min, and heating temperature is 190 DEG C, and head temperature is 195 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 60 mm/seconds,
Reaction temperature is 200 DEG C, and injection time is 0.5 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Embodiment 2
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）40 parts of polymethyl methacrylate, 35 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.09 MPa sets reactor temperature as 170 DEG C, high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), instead
It is 50 minutes between seasonable, reactor temperature is then down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, at 155 revs/min
Stir speed (S.S.) under stir evenly after stand insulation reaction 35 minutes, obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 14 is then added thereto
Part, 7 parts of sulfadimidine, 3 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 3.0 MPa, reaction temperature in a nitrogen environment
Degree is 80 DEG C, and the reaction time is 100 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Embodiment 3
（1）By in 4 parts of 5 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 90 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 8 at a temperature of 70 DEG C
Hour, obtain dry mixed powder；
（2）45 parts of polymethyl methacrylate, 40 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.1 MPa sets reactor temperature as 180 DEG C, and high-temperature stirring reaction, reaction are carried out under 160 revs/min of stir speed (S.S.)
Time is 55 minutes, and reactor temperature is then down to 120 DEG C, 12 parts of methyl phenyl silicone oil is added, at 160 revs/min
Insulation reaction 40 minutes are stood after being stirred evenly under stir speed (S.S.), obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 16 is then added thereto
Part, 8 parts of sulfadimidine, 4 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 3.5 MPa, reaction temperature in a nitrogen environment
Degree is 85 DEG C, and the reaction time is 120 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained 3 parts of secondary response object and tirethylene glycol,
3 parts of disodium ethylene diamine tetraacetate is placed in mixing and blending machine, is stirred 25 minutes at 60 DEG C, heat mixture is obtained, by hot mixing
It is transferred in ultrasonic dispersers after material is cooling, the dimethyl sulfoxide (DMSO) with quality such as mixtures is added, then with 0.1 mol/L's
HCl solution regulation system pH to 6.0 disperses 40-60 minutes according to the frequency ultrasound of 22 kHz, obtains being ultrasonically treated mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 700 revs/min, and heating temperature is 210 DEG C, and head temperature is 200 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 80 mm/seconds,
Reaction temperature is 210 DEG C, and injection time is 1.5 seconds, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Comparative example 1
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）Fatty acid polyethylene glycol ester is added in vacuum reaction kettle for 35 parts, -0.09 MPa is evacuated to, sets in reaction kettle
Temperature is 170 DEG C, and high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), and the reaction time is 50 minutes, then will
Reactor temperature is down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, after being stirred evenly under 155 revs/min of stir speed (S.S.)
Insulation reaction 35 minutes are stood, pyroreaction object is obtained；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 14 is then added thereto
Part, 7 parts of sulfadimidine, 3 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 3.0 MPa, reaction temperature in a nitrogen environment
Degree is 80 DEG C, and the reaction time is 100 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Comparative example 2
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）Polymethyl methacrylate is added in vacuum reaction kettle for 40 parts, -0.09 MPa is evacuated to, sets in reaction kettle
Temperature is 170 DEG C, and high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), and the reaction time is 50 minutes, then will
Reactor temperature is down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, after being stirred evenly under 155 revs/min of stir speed (S.S.)
Insulation reaction 35 minutes are stood, pyroreaction object is obtained；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 14 is then added thereto
Part, 7 parts of sulfadimidine, 3 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 3.0 MPa, reaction temperature in a nitrogen environment
Degree is 80 DEG C, and the reaction time is 100 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Comparative example 3
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）40 parts of polymethyl methacrylate, 35 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.09 MPa sets reactor temperature as 170 DEG C, high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), instead
It is 50 minutes between seasonable, reactor temperature is then down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, at 155 revs/min
Stir speed (S.S.) under stir evenly after stand insulation reaction 35 minutes, obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and 7 parts of sulfadimidine, naphthalene vinegar are then added thereto
3 parts of sour sodium, compressive reaction, reaction pressure are 3.0 MPa in a nitrogen environment, and reaction temperature is 80 DEG C, and the reaction time is 100 points
Clock obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Comparative example 4
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）40 parts of polymethyl methacrylate, 35 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.09 MPa sets reactor temperature as 170 DEG C, high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), instead
It is 50 minutes between seasonable, reactor temperature is then down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, at 155 revs/min
Stir speed (S.S.) under stir evenly after stand insulation reaction 35 minutes, obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 14 is then added thereto
Part, 3 parts of naphthalene sodium acetate, compressive reaction, reaction pressure are 3.0 MPa in a nitrogen environment, and reaction temperature is 80 DEG C, the reaction time
It is 100 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Comparative example 5
（1）By in 3 parts of 4 parts of meteorological white carbon, aluminum fluoride input ball mills, then 2 times of quality of solid mixt are added thereto
A concentration of 95% ethanol solution carries out wet ball grinding, and the ratio of grinding media to material of ball mill is 10:1, ball milling speed is 500 revolutions per seconds, ball milling
Time is 75 minutes, and then the mixed-powder that ball-milling treatment obtains is placed in vacuum drying chamber dry 7 at a temperature of 65 DEG C
Hour, obtain dry mixed powder；
（2）40 parts of polymethyl methacrylate, 35 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, be evacuated to-
0.09 MPa sets reactor temperature as 170 DEG C, high-temperature stirring reaction is carried out under 155 revs/min of stir speed (S.S.), instead
It is 50 minutes between seasonable, reactor temperature is then down to 120 DEG C, 10 parts of methyl phenyl silicone oil is added, at 155 revs/min
Stir speed (S.S.) under stir evenly after stand insulation reaction 35 minutes, obtain pyroreaction object；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide 14 is then added thereto
Part, 7 parts of sulfadimidine, compressive reaction, reaction pressure are 3.0 MPa in a nitrogen environment, and reaction temperature is 80 DEG C, reaction
Time is 100 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）Obtained secondary response object and phthalic acid diformazan
2 parts of ester, 2 parts of 2- tertiary butyl -4- metoxyphenols are placed in mixing and blending machine, are stirred 20 minutes at 55 DEG C, are obtained hot mixing
Material, is transferred to after heat mixture is cooled down in ultrasonic dispersers, and the dimethyl sulfoxide (DMSO) with the quality such as mixture is added, then with
The HCl solution regulation system pH to 6.0 of 0.1 mol/L disperses 50 minutes according to the frequency ultrasound of 21 kHz, is ultrasonically treated
Mixture；
（5）By step（4）Extruding pelletization, twin-screw extrusion are carried out in obtained supersound process mixture injection double screw extruder
The driving screw rotating speed of machine is 650 revs/min, and heating temperature is 200 DEG C, and head temperature is 197.5 DEG C, obtains granule materials；
（6）By step（5）Obtained granule materials are put into injection molding machine, set the injection speed of injection molding machine as 70 mm/seconds,
Reaction temperature is 205 DEG C, and injection time is 1 second, and injection pressure is 75 MPa, and the dwell time is 0.5 second, obtains injection molding
Biomaterial for medical purpose, then segmented, packaging, sterilizing, are put in storage after cooling.
The performance test results of biomaterial for medical purpose obtained are as shown in table 1.
Test side during the biomaterial for medical purpose obtained of embodiment 1-3 and comparative example 1-5 is distinguished according to national standards
Method carries out this several ultraviolet absorptivity, heat distortion temperature, elongation at break performance tests.
Table 1
| Ultraviolet absorptivity | Heat distortion temperature（℃） | Elongation at break（%） | |
| Embodiment 1 | 0.04 | 89 | 470 |
| Embodiment 2 | 0.03 | 93 | 480 |
| Embodiment 3 | 0.03 | 91 | 470 |
| Comparative example 1 | 0.04 | 78 | 360 |
| Comparative example 2 | 0.03 | 82 | 350 |
| Comparative example 3 | 0.05 | 84 | 370 |
| Comparative example 4 | 0.03 | 80 | 350 |
| Comparative example 5 | 0.04 | 79 | 370 |
The preparation method of the high stability biomaterial for medical purpose of the present invention is used carries out wet method ball by meteorological white carbon, aluminum fluoride
Dry mixed powder is obtained after mill, drying；By polymethyl methacrylate, fatty acid polyethylene glycol ester in vacuum reaction kettle into
Row high-temperature stirring is reacted, and addition methyl phenyl silicone oil carries out standing insulation reaction and obtains pyroreaction object after cooling, adds after cooling
Enter coconut monoethanolamide, sulfadimidine, naphthalene sodium acetate, compressive reaction obtains secondary response in a nitrogen environment
Object；Then it is mixed dry mixed powder, secondary response object and additive to obtain heat mixture, adds dimethyl
Finished product biomaterial for medical purpose is made in sulfoxide, the techniques such as sonicated, extruding pelletization, injection molding, segmentation, packaging, sterilizing.System
Biomaterial for medical purpose made of standby, stability is strong, has a good application prospect on medical devices.Also, this hair
It is bright to use polymethyl methacrylate, fatty acid polyethylene glycol ester, coconut monoethanolamide, sulfadimidine, naphthalene
The raw materials such as sodium acetate participate in preparing high stability biomaterial for medical purpose, and effective performance boost has been carried out to biomaterial for medical purpose,
Although these materials are not first Application in biomaterial for medical purpose, according to a certain ratio after amount combination, it is aided with corresponding place
Reason mode brings increasing substantially in performance to the biomaterial for medical purpose being finally prepared, this grinds in previous
It is never to report in studying carefully, for realizing that it is conclusive that the technique effect of the present invention plays the role of.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of high stability biomaterial for medical purpose, which is characterized in that include the following steps：
（1）By in 2-4 parts of meteorological white carbon 3-5 parts, aluminum fluoride input ball mills, then 2 times of matter of solid mixt are added thereto
A concentration of 95% ethanol solution of amount carries out wet ball grinding, and the mixed-powder that ball-milling treatment obtains then is placed in vacuum drying
It is 6-8 hours dry at a temperature of 60-70 DEG C in case, obtain dry mixed powder；
（2）35-45 parts of polymethyl methacrylate, 30-40 parts of fatty acid polyethylene glycol ester are added in vacuum reaction kettle, taken out true
Empty extremely -0.08 to -0.1 MPa, sets reactor temperature as 160-180 DEG C, under 150-160 revs/min of stir speed (S.S.)
High-temperature stirring reaction is carried out, the reaction time is 45-55 minutes, and reactor temperature is then down to 120 DEG C, aminomethyl phenyl is added
8-12 parts of silicone oil stands insulation reaction 30-40 minutes, obtains height after being stirred evenly under 150-160 revs/min of stir speed (S.S.)
Warm reactant；
（3）By step（2）Obtained pyroreaction object is cooled to room temperature, and coconut monoethanolamide is then added thereto
12-16 parts, 6-8 parts of sulfadimidine, 2-4 parts of naphthalene sodium acetate, compressive reaction in a nitrogen environment, reaction pressure 2.5-
3.5 MPa, reaction temperature are 75-85 DEG C, and the reaction time is 80-120 minutes, obtains secondary response object；
（4）By step（1）Obtained dry mixed powder, step（3）It is obtained 1-3 parts of secondary response object and plasticizer, anti-
1-3 parts of oxidant is placed in mixing and blending machine, is stirred 15-25 minutes at 50-60 DEG C, heat mixture is obtained, by heat mixture
It is transferred in ultrasonic dispersers after cooling, the dimethyl sulfoxide (DMSO) with quality such as mixtures is added, then with the HCl of 0.1 mol/L
Solution regulation system pH to 6.0 disperses 40-60 minutes according to the frequency ultrasound of 20-22 kHz, obtains being ultrasonically treated mixture；
（5）By step（4）Extruding pelletization is carried out in obtained supersound process mixture injection double screw extruder, obtains particulate matter
Material；
（6）By step（5）Obtained granule materials are put into injection molding machine, obtain the biomaterial for medical purpose of injection molding, then pass through
Segmentation, packaging, sterilizing, are put in storage after cooling.
2. the preparation method of high stability biomaterial for medical purpose according to claim 1, which is characterized in that the step
（1）The ratio of grinding media to material of middle ball mill is 10:1, ball milling speed is 500 revolutions per seconds, and Ball-milling Time is 60-90 minutes.
3. the preparation method of high stability biomaterial for medical purpose according to claim 1, which is characterized in that the step
（4）In any one in acetylation tri-n-butyl citrate, repefral, tirethylene glycol of plasticizer.
4. the preparation method of high stability biomaterial for medical purpose according to claim 1, which is characterized in that the step
（4）In antioxidant in propylgallate, 2- tertiary butyl -4- metoxyphenols, disodium ethylene diamine tetraacetate appoint
Meaning is a kind of.
5. the preparation method of high stability biomaterial for medical purpose according to claim 1, which is characterized in that the step
（5）The driving screw rotating speed of middle double screw extruder is 600-700 revs/min, and heating temperature is 190-210 DEG C, and head temperature is
195-200℃。
6. the preparation method of high stability biomaterial for medical purpose according to claim 1, which is characterized in that the step
（6）The injection speed of middle injection molding machine is 60-80 mm/seconds, and reaction temperature is 200-210 DEG C, and injection time is 0.5-1.5 seconds,
Injection pressure is 75 MPa, and the dwell time is 0.5 second.
7. according to high stability biomaterial for medical purpose made from any one of the claim 1-6 preparation methods on medical devices
Application.
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| JP2002037745A (en) * | 2000-07-25 | 2002-02-06 | ▲高▼田 ▲寛▼治 | Technique for ameliorating bioavailability of water- soluble hardly resorptive/low resorptive drug |
| CN104941006A (en) * | 2015-06-30 | 2015-09-30 | 苏州佑君环境科技有限公司 | Preparation method of composite material for joint prosthesis |
| CN106188907A (en) * | 2016-08-30 | 2016-12-07 | 何仁英 | A kind of biological material being applicable to flexible pipe for medical purpose and preparation method thereof |
| CN106366524A (en) * | 2016-08-30 | 2017-02-01 | 胡何辉 | Medicinal polyvinyl alcohol material and preparation method thereof |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037745A (en) * | 2000-07-25 | 2002-02-06 | ▲高▼田 ▲寛▼治 | Technique for ameliorating bioavailability of water- soluble hardly resorptive/low resorptive drug |
| CN104941006A (en) * | 2015-06-30 | 2015-09-30 | 苏州佑君环境科技有限公司 | Preparation method of composite material for joint prosthesis |
| CN106188907A (en) * | 2016-08-30 | 2016-12-07 | 何仁英 | A kind of biological material being applicable to flexible pipe for medical purpose and preparation method thereof |
| CN106366524A (en) * | 2016-08-30 | 2017-02-01 | 胡何辉 | Medicinal polyvinyl alcohol material and preparation method thereof |
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