CN106496782A - It is added with biomaterial of magnesium borate crystal whisker and preparation method thereof - Google Patents
It is added with biomaterial of magnesium borate crystal whisker and preparation method thereof Download PDFInfo
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- CN106496782A CN106496782A CN201610932792.5A CN201610932792A CN106496782A CN 106496782 A CN106496782 A CN 106496782A CN 201610932792 A CN201610932792 A CN 201610932792A CN 106496782 A CN106496782 A CN 106496782A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses being added with biomaterial of magnesium borate crystal whisker and preparation method thereof, which is with polypropylene, polyglycolic acid, methyl p-hydroxybenzoate is main component, by adding poly- 3 butyric ester, trishydroxymethylaminomethane, 2 mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, trimethyl ammonium iodide, epoxidized soybean oil, naphthalene sodium acetate, magnesium borate crystal whisker, montmorillonite powder, precipitated calcium carbonate, dispersant, stabilizer, it is aided with mixing, high temperature sintering, crush, high pressure calcination, acidleach, ultrasonic disperse, Screw Extrusion, the techniques such as injection process are prepared from.This is added with the biomaterial low-temperature impact resistance of magnesium borate crystal whisker and ageing-resistant performance is high, disclosure satisfy that the requirement of industry, with preferable application prospect.
Description
Technical field
The present invention relates to biology medical material technical field, be more particularly to added with magnesium borate crystal whisker biomaterial and its
Preparation method.
Background technology
Bio-medical material is for carrying out diagnosing, treat, repair or replacing its disease damage tissue, organ or increasing to organism
Enter the material of its function.It is the basis for studying artificial organs and medicine equipment, it has also become the important branch of contemporary material subject,
The application of bio-medical material has been greatly facilitated developing rapidly for medical consultations technology.So far, the life that was studied in detail
The existing kind more than 1,000 of thing material, widely used on clinical medicine also have tens kinds, is related to the every field of materialogy.At present
Bio-medical material research it is important that ensure security on the premise of find histocompatbility more preferable, degradable, corrosion-resistant,
Persistently, multiduty bio-medical material.Wherein macromolecular material is with its excellent property, reliable performance, convenient shaping
Technique is increasingly widely applied in medical field.Macromolecular material has good physical and mechanical property and change first
Stability is learned, is compared and is suitable for using in medical field；Secondly macromolecular material abundance, cheap, is suitable for making once
Property medical supplies, avoid sterilization and cross-infection caused by traditional material product has to be used for multiple times because price is high
Problem；And macromolecular material have or be easier to modification obtain good histocompatbility, blood compatibility product；Also high
Molecular material is easy to process, low manufacture cost, is suitable for multiple molding modes, is easy to be processed into the shape of complexity and the new doctor of exploitation
Treat product.
Polypropylene is a kind of obtained thermoplastic resin by propylene polymerization.It is divided into isotactic poly- third by methyl arrangement position
Three kinds of alkene, random polypropylene and syndiotactic polypropylene.Methyl is arranged in the same side of molecular backbone and claims isotactic polypropylene, if methyl without
The both sides for being arranged in molecular backbone of order claim random polypropylene, when rule are poly- between the both sides that methyl is arranged alternately in molecular backbone claim
Propylene.In the acrylic resin of general industry production, isotactic structural content is about 95%, and remaining is random or syndiotactic polypropylene.Work
Industry product is with isotactic thing as main component.Including polypropylene copolymer also including propylene with a small amount of ethene.Usually translucent
Colorless solid, odorless are nontoxic.The highly crystallized due to compound with regular structure, therefore fusing point may be up to 167 DEG C.Heat-resisting, corrosion-resistant, product
Available moise-heat sterilization is its outstanding advantages.Density is little, is most light general-purpose plastics.Have the disadvantage that low-temperature impact resistance is poor, be easier to old
Change.Therefore, one kind is developed with polypropylene as main component, be added with the novel biomaterial of other compositions, to improve material
Low-temperature impact resistance and ageing-resistant performance are just particularly important.
Content of the invention
For solving above-mentioned technical problem, the invention provides being added with biomaterial and its preparation side of magnesium borate crystal whisker
Method, its with polypropylene, polyglycolic acid, methyl p-hydroxybenzoate as main component, by add poly- 3-hydroxybutyrate ester, three
Hydroxymethyl aminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, trimethyl iodate
Ammonium, epoxidized soybean oil, naphthalene sodium acetate, magnesium borate crystal whisker, montmorillonite powder, precipitated calcium carbonate, dispersant, stabilizer, are aided with mixing
The techniques such as stirring, high temperature sintering, crushing, high pressure calcination, acidleach, ultrasonic disperse, Screw Extrusion, injection process are prepared from.Should
The biomaterial low-temperature impact resistance and ageing-resistant performance for being added with magnesium borate crystal whisker is high, disclosure satisfy that the requirement of industry, has
Preferable application prospect.
The purpose of the present invention can be achieved through the following technical solutions：
The biomaterial of magnesium borate crystal whisker is added with, is prepared by the raw materials in：Polypropylene 50-60 parts, polyglycolic acid
45-55 parts, methyl p-hydroxybenzoate 30-40 parts, poly- 3-hydroxybutyrate ester 15-20 parts, trishydroxymethylaminomethane 14-18
Part, 2- mercapto benzimidazole 10-12 parts, double maleamic acid 8-10 parts, ethylenediamine tetra-acetic acid 6-8 parts, dodecyl front three
Base ammonium iodide 5-9 parts, epoxidized soybean oil 4-6 parts, naphthalene sodium acetate 4-6 parts, magnesium borate crystal whisker 3-5 parts, montmorillonite powder 3-5 parts, light
Matter calcium carbonate 2-6 parts, dispersant 2-4 parts, stabilizer 2-4 parts.
Preferably, the dispersant is any in Tissuemat E, vinyl bis-stearamides, glyceryl tristearate
A kind of.
Preferably, the stabilizer appointing in ethylene bis stearamide, Phenyl Di-2-ethyl Hexyl Phosphite, aluminum stearate
Meaning is a kind of.
The preparation method of the described biomaterial for being added with magnesium borate crystal whisker, comprises the following steps：
（1）By polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, montmorillonite
Powder, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere, in
Sinter blocking at a temperature of 900-1000 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept pressure 0.8-1.0MPa, and reaction temperature is 650-
700 DEG C, react 25-35 minutes, obtain calcining mixt, question response terminate after by calcining mixt be immersed in concentration be 5% dilute
In acid solution, place 3 hours at a temperature of 85-95 DEG C, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally
Dry at a temperature of 110-120 DEG C, obtain intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Dispersant, stabilizer are added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as add, subsequently with 10% NaOH
Solution adjusts pH to 8.5, with the frequency ultrasound dispersion 1.5h of 35-45kHz, obtains ultrasonically treated mixture, subsequently by ultrasound
Reason mixture is placed in pyroreaction kettle and is stirred, and speed of agitator is 100rpm, and mixing time is 80 minutes, subsequently will mixing
Thing blowing is cooled to 60 DEG C to cold pot；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, material granule is obtained；
（5）By step（4）In material granule add injection machine in reacted, obtain finished product.
Preferably, the step（4）The screw speed of middle double screw extruder is 1200-1300 rev/min, extruder temperature
For 250 DEG C.
Preferably, the step（5）The reaction temperature of middle injection machine is controlled to 255 DEG C, injection time be the 3-5 seconds, pressurize
Time is 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80MPa.
Compared with prior art, its advantage is the present invention：
（1）The present invention the biomaterial for being added with magnesium borate crystal whisker with polypropylene, polyglycolic acid, methyl p-hydroxybenzoate be
Main component, by adding poly- 3-hydroxybutyrate ester, trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleic amides
Acid, ethylenediamine tetra-acetic acid, trimethyl ammonium iodide, epoxidized soybean oil, naphthalene sodium acetate, magnesium borate crystal whisker, montmorillonite powder,
Precipitated calcium carbonate, dispersant, stabilizer, are aided with mixing, high temperature sintering, crushing, high pressure calcination, acidleach, ultrasonic disperse, spiral shell
The techniques such as bar extrusion, injection process are prepared from.This is added with the biomaterial low-temperature impact resistance of magnesium borate crystal whisker and resistance to old
Change performance high, disclosure satisfy that the requirement of industry, with preferable application prospect.
（2）The biomaterial raw material for being added with magnesium borate crystal whisker of the present invention is cheap, process is simple, is suitable to large-scale industry
Change and use, practical.
Specific embodiment
The technical scheme that invents is described in detail with reference to specific embodiment.
Embodiment 1
Weigh respectively 50 parts of polypropylene, 45 parts of polyglycolic acid, 30 parts of methyl p-hydroxybenzoate, 15 parts of poly- 3-hydroxybutyrate ester,
14 parts of trishydroxymethylaminomethane, 10 parts of 2- mercaptos benzimidazole, 8 parts of double maleamic acids, 6 parts of ethylenediamine tetra-acetic acid, ten
5 parts of dialkyl group trimethyl ammonium iodide, 4 parts of epoxidized soybean oil, 4 parts of naphthalene sodium acetate, 3 parts of magnesium borate crystal whisker, 3 parts of montmorillonite powder, light
2 parts of matter calcium carbonate, 2 parts of Tissuemat E, 2 parts of ethylene bis stearamide.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere,
Sinter blocking at a temperature of 900 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept 0.8 MPa of pressure, and reaction temperature is 650 DEG C, instead
Answer 25 minutes, obtain calcining mixt, question response after terminating is immersed in calcining mixt in the dilute acid soln that concentration is 5%,
Place at a temperature of 85 DEG C 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally in 110 DEG C of temperature
Lower drying, obtains intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Tissuemat E, ethylene bis stearamide are added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as add, subsequently with
10% NaOH solution adjusts pH to 8.5, with the frequency ultrasound dispersion 1.5h of 35 kHz, obtains ultrasonically treated mixture, subsequently will
Ultrasonically treated mixture is placed in pyroreaction kettle and is stirred, and speed of agitator is 100 rpm, and mixing time is 80 minutes, with
Afterwards by mixture blowing to cold pot, 60 DEG C are cooled to；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1200
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 3 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80 MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
Embodiment 2
Weigh respectively 55 parts of polypropylene, 50 parts of polyglycolic acid, 35 parts of methyl p-hydroxybenzoate, 17 parts of poly- 3-hydroxybutyrate ester,
16 parts of trishydroxymethylaminomethane, 11 parts of 2- mercaptos benzimidazole, 9 parts of double maleamic acids, 7 parts of ethylenediamine tetra-acetic acid, ten
7 parts of dialkyl group trimethyl ammonium iodide, 5 parts of epoxidized soybean oil, 5 parts of naphthalene sodium acetate, 4 parts of magnesium borate crystal whisker, 4 parts of montmorillonite powder, light
4 parts of matter calcium carbonate, 3 parts of vinyl bis-stearamides, 3 parts of Phenyl Di-2-ethyl Hexyl Phosphite.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere,
Sinter blocking at a temperature of 950 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept 0.9 MPa of pressure, and reaction temperature is 675 DEG C, instead
Answer 30 minutes, obtain calcining mixt, question response after terminating is immersed in calcining mixt in the dilute acid soln that concentration is 5%,
Place at a temperature of 90 DEG C 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally in 115 DEG C of temperature
Lower drying, obtains intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Vinyl bis-stearamides, Phenyl Di-2-ethyl Hexyl Phosphite are added in ultrasonic disperser jointly, the anhydrous of quality such as add
Ethanol, subsequently adjusts pH to 8.5 with 10% NaOH solution, disperses 1.5 h with the frequency ultrasound of 40 kHz, obtains ultrasonically treated
Mixture, is subsequently placed in ultrasonically treated mixture in pyroreaction kettle and is stirred, and speed of agitator is 100 rpm, during stirring
Between for 80 minutes, subsequently by mixture blowing to cold pot, be cooled to 60 DEG C；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1250
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 4 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80 MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
Embodiment 3
Weigh respectively 60 parts of polypropylene, 55 parts of polyglycolic acid, 40 parts of methyl p-hydroxybenzoate, 20 parts of poly- 3-hydroxybutyrate ester,
18 parts of trishydroxymethylaminomethane, 12 parts of 2- mercaptos benzimidazole, 10 parts of double maleamic acids, 8 parts of ethylenediamine tetra-acetic acid, ten
9 parts of dialkyl group trimethyl ammonium iodide, 6 parts of epoxidized soybean oil, 6 parts of naphthalene sodium acetate, 5 parts of magnesium borate crystal whisker, 5 parts of montmorillonite powder, light
6 parts of matter calcium carbonate, 4 parts of glyceryl tristearate, 4 parts of aluminum stearate.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere,
Sinter blocking at a temperature of 1000 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept 1.0 MPa of pressure, and reaction temperature is 700 DEG C, instead
Answer 35 minutes, obtain calcining mixt, question response after terminating is immersed in calcining mixt in the dilute acid soln that concentration is 5%,
Place at a temperature of 95 DEG C 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally in 120 DEG C of temperature
Lower drying, obtains intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Glyceryl tristearate, aluminum stearate are added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as add, subsequently with
10% NaOH solution adjusts pH to 8.5, disperses 1.5 h with the frequency ultrasound of 45 kHz, obtains ultrasonically treated mixture, subsequently
Ultrasonically treated mixture is placed in pyroreaction kettle and is stirred, speed of agitator is 100 rpm, and mixing time is 80 minutes,
Mixture blowing is cooled to 60 DEG C to cold pot subsequently；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1300
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 5 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
Embodiment 4
Weigh respectively 50 parts of polypropylene, 55 parts of polyglycolic acid, 30 parts of methyl p-hydroxybenzoate, 20 parts of poly- 3-hydroxybutyrate ester,
14 parts of trishydroxymethylaminomethane, 12 parts of 2- mercaptos benzimidazole, 8 parts of double maleamic acids, 8 parts of ethylenediamine tetra-acetic acid, ten
5 parts of dialkyl group trimethyl ammonium iodide, 6 parts of epoxidized soybean oil, 4 parts of naphthalene sodium acetate, 5 parts of magnesium borate crystal whisker, 3 parts of montmorillonite powder, light
6 parts of matter calcium carbonate, 2 parts of Tissuemat E, 4 parts of aluminum stearate.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere,
Sinter blocking at a temperature of 900 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept 1.0 MPa of pressure, and reaction temperature is 650 DEG C, instead
Answer 35 minutes, obtain calcining mixt, question response after terminating is immersed in calcining mixt in the dilute acid soln that concentration is 5%,
Place at a temperature of 85 DEG C 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally in 120 DEG C of temperature
Lower drying, obtains intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Tissuemat E, aluminum stearate are added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as add, subsequently with 10%
NaOH solution adjusts pH to 8.5, disperses 1.5 h with the frequency ultrasound of 35 kHz, obtains ultrasonically treated mixture, subsequently by ultrasound
Process mixture is placed in pyroreaction kettle and is stirred, and speed of agitator is 100 rpm, and mixing time is 80 minutes, subsequently will
Mixture blowing is cooled to 60 DEG C to cold pot；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1300
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 3 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
Comparative example 1
Weigh respectively 50 parts of polypropylene, 45 parts of polyglycolic acid, 30 parts of methyl p-hydroxybenzoate, 15 parts of poly- 3-hydroxybutyrate ester,
14 parts of trishydroxymethylaminomethane, 10 parts of 2- mercaptos benzimidazole, 6 parts of ethylenediamine tetra-acetic acid, trimethyl iodate
5 parts of ammonium, 4 parts of epoxidized soybean oil, 4 parts of naphthalene sodium acetate, 3 parts of magnesium borate crystal whisker, 3 parts of montmorillonite powder, 2 parts of Tissuemat E, ethylene are double
2 parts of stearmide.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour mixes, and adds the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere, in 900 DEG C of temperature
The lower sintering of degree is blocking, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, ethylenediamine tetra-acetic acid, trimethyl ammonium iodide
Add in sealing calcining furnace, be filled with argon gas, stove and keep 0.8 MPa of pressure, reaction temperature is 650 DEG C, reacts 25 minutes, obtains
Calcining mixt, question response after terminating are immersed in calcining mixt in the dilute acid soln that concentration is 5%, at a temperature of 85 DEG C
Place 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally dry at a temperature of 110 DEG C, obtain middle
Mixture；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate,
Tissuemat E, ethylene bis stearamide are added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as add, subsequently with
10% NaOH solution adjusts pH to 8.5, with the frequency ultrasound dispersion 1.5h of 35 kHz, obtains ultrasonically treated mixture, subsequently will
Ultrasonically treated mixture is placed in pyroreaction kettle and is stirred, and speed of agitator is 100 rpm, and mixing time is 80 minutes, with
Afterwards by mixture blowing to cold pot, 60 DEG C are cooled to；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1200
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 3 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80 MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
Comparative example 2
Weigh respectively 60 parts of polypropylene, 55 parts of polyglycolic acid, 40 parts of methyl p-hydroxybenzoate, 20 parts of poly- 3-hydroxybutyrate ester,
18 parts of trishydroxymethylaminomethane, 12 parts of 2- mercaptos benzimidazole, 10 parts of double maleamic acids, 8 parts of ethylenediamine tetra-acetic acid, ten
9 parts of dialkyl group trimethyl ammonium iodide, 5 parts of magnesium borate crystal whisker, 5 parts of montmorillonite powder, 6 parts of precipitated calcium carbonate, glyceryl tristearate 4
Part, 4 parts of aluminum stearate.
（1）Will be de- to polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, magnesium borate crystal whisker, illiteracy
Stone flour, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxidizing atmosphere,
Sinter blocking at a temperature of 1000 DEG C, then block is put in pulverizer the powdery product for being ground into 100 mesh；
（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, dodecyl
Trimethyl ammonium iodide is added in sealing calcining furnace, is filled with argon gas, stove and is kept 1.0 MPa of pressure, and reaction temperature is 700 DEG C, instead
Answer 35 minutes, obtain calcining mixt, question response after terminating is immersed in calcining mixt in the dilute acid soln that concentration is 5%,
Place at a temperature of 95 DEG C 3 hours, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times, finally in 120 DEG C of temperature
Lower drying, obtains intermediate blend；
（3）By step（1）The powdery product that obtains, step（2）The intermediate blend that obtains, glyceryl tristearate, tristearin
Sour aluminium is added in ultrasonic disperser jointly, the absolute ethyl alcohol of quality such as adds, and subsequently adjusts pH with 10% NaOH solution
To 8.5,1.5 h are disperseed with the frequency ultrasound of 45 kHz, ultrasonically treated mixture is obtained, subsequently ultrasonically treated mixture is placed in
It is stirred in pyroreaction kettle, speed of agitator is 100 rpm, and mixing time is 80 minutes, subsequently by mixture blowing to cold
Pot, is cooled to 60 DEG C；
（4）By step（3）In mixture injection double screw extruder after cooling, extruding pelletization is carried out, screw speed is 1300
Rev/min, extruder temperature is 250 DEG C, obtains material granule；
（5）By step（4）In material granule add injection machine in reacted, reaction temperature is controlled to 255 DEG C, injection time
For 5 seconds, the dwell time was 0.4 second, and screw speed is 270 revs/min, and injection pressure is 80MPa, obtains finished product.
The performance test results of the obtained biomaterial for being added with magnesium borate crystal whisker are as shown in table 1.
The biomaterial for being added with magnesium borate crystal whisker obtained in embodiment 1-4 and comparative example 1-2 is carried out -30 DEG C respectively
Notch impact strength, 23 DEG C of notch impact strengths, heat distortion temperature, this several performance tests of high temperature ageing degree.
Table 1
| Notch impact strength, -30 DEG C（kJ/m2） | Notch impact strength, 23 DEG C（kJ/m2） | Heat distortion temperature（℃） | High temperature ageing degree | |
| Embodiment 1 | 6.7 | 51.3 | 89 | Slightly |
| Embodiment 2 | 7.1 | 55.0 | 97 | Slightly |
| Embodiment 3 | 6.9 | 53.9 | 95 | Slightly |
| Embodiment 4 | 6.7 | 52.4 | 93 | Slightly |
| Comparative example 1 | 3.9 | 31.7 | 74 | Typically |
| Comparative example 2 | 3.5 | 30.2 | 71 | Typically |
The biomaterial for being added with magnesium borate crystal whisker of the present invention is based on polypropylene, polyglycolic acid, methyl p-hydroxybenzoate
Composition is wanted, by adding poly- 3-hydroxybutyrate ester, trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleic amides
Acid, ethylenediamine tetra-acetic acid, trimethyl ammonium iodide, epoxidized soybean oil, naphthalene sodium acetate, magnesium borate crystal whisker, montmorillonite powder,
Precipitated calcium carbonate, dispersant, stabilizer, are aided with mixing, high temperature sintering, crushing, high pressure calcination, acidleach, ultrasonic disperse, spiral shell
The techniques such as bar extrusion, injection process are prepared from.This is added with the biomaterial low-temperature impact resistance of magnesium borate crystal whisker and resistance to old
Change performance high, disclosure satisfy that the requirement of industry, with preferable application prospect.Meanwhile, the present invention is added with magnesium borate crystal whisker
Biomaterial raw material is cheap, process is simple, be suitable to heavy industrialization utilization, practical.
Embodiments of the invention are the foregoing is only, the scope of the claims of the present invention is not thereby limited, every using this
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (6)
1. the biomaterial of magnesium borate crystal whisker is added with, it is characterised in that：It is prepared by the raw materials in：Polypropylene 50-
60 parts, polyglycolic acid 45-55 parts, methyl p-hydroxybenzoate 30-40 parts, poly- 3-hydroxybutyrate ester 15-20 parts, trihydroxy methyl
Aminomethane 14-18 parts, 2- mercapto benzimidazole 10-12 parts, double maleamic acid 8-10 parts, ethylenediamine tetra-acetic acid 6-8 parts,
Trimethyl ammonium iodide 5-9 parts, epoxidized soybean oil 4-6 parts, naphthalene sodium acetate 4-6 parts, magnesium borate crystal whisker 3-5 parts, illiteracy are de-
Stone flour 3-5 parts, precipitated calcium carbonate 2-6 parts, dispersant 2-4 parts, stabilizer 2-4 parts.
2. the biomaterial for being added with magnesium borate crystal whisker according to claim 1, it is characterised in that：The dispersant is selected from
Any one in Tissuemat E, vinyl bis-stearamides, glyceryl tristearate.
3. the biomaterial for being added with magnesium borate crystal whisker according to claim 1, it is characterised in that：The stabilizer is selected from
Any one in ethylene bis stearamide, Phenyl Di-2-ethyl Hexyl Phosphite, aluminum stearate.
4., according to the preparation method of the arbitrary described biomaterial for being added with magnesium borate crystal whisker of claim 1-3, its feature exists
In comprising the following steps：（1）By polypropylene, polyglycolic acid, methyl p-hydroxybenzoate, poly- 3-hydroxybutyrate ester, antifungin
Whisker, montmorillonite powder, precipitated calcium carbonate mixing, add the deionized water of 15 times of quality, and stirring obtains mixed slurry, subsequently in oxygen
Change in atmosphere, sinter blocking at a temperature of 900-1000 DEG C, then block is put in pulverizer the powder for being ground into 100 mesh
Shape product；（2）By trishydroxymethylaminomethane, 2- mercapto benzimidazoles, double maleamic acids, ethylenediamine tetra-acetic acid, 12
Alkyl trimethyl ammonium iodide is added in sealing calcining furnace, is filled with holding pressure 0.8-1.0MPa in argon gas, stove, and reaction temperature is
650-700 DEG C, 25-35 minutes are reacted, obtain calcining mixt, calcining mixt is immersed in concentration for 5% after terminating by question response
Dilute acid soln in, place 3 hours at a temperature of 85-95 DEG C, subsequently filter, with 85 DEG C of deionized water washing copolymers 3 times,
Last dry at a temperature of 110-120 DEG C, obtain intermediate blend；（3）By step（1）The powdery product that obtains, step（2）
The intermediate blend that obtains, epoxidized soybean oil, naphthalene sodium acetate, dispersant, stabilizer are added in ultrasonic disperser jointly, then
The absolute ethyl alcohol of the quality such as addition, subsequently adjusts pH to 8.5 with 10% NaOH solution, is disperseed with the frequency ultrasound of 35-45kHz
1.5h, obtains ultrasonically treated mixture, subsequently ultrasonically treated mixture is placed in pyroreaction kettle and is stirred, speed of agitator
For 100rpm, mixing time is 80 minutes, subsequently by mixture blowing to cold pot, is cooled to 60 DEG C；（4）By step（3）Cooling
In mixture injection double screw extruder afterwards, extruding pelletization is carried out, material granule is obtained；（5）By step（4）In material granule
Add and reacted in injection machine, obtain finished product.
5. the preparation method of the biomaterial for being added with magnesium borate crystal whisker according to claim 4, it is characterised in that：Described
Step（4）The screw speed of middle double screw extruder is 1200-1300 rev/min, and extruder temperature is 250 DEG C.
6. the preparation method of the biomaterial for being added with magnesium borate crystal whisker according to claim 4, it is characterised in that：Described
Step（5）The reaction temperature of middle injection machine is controlled to 255 DEG C, and injection time is the 3-5 seconds, and the dwell time is 0.4 second, screw speed
For 270 revs/min, injection pressure is 80MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107648675A (en) * | 2017-09-16 | 2018-02-02 | 常州富思通管道有限公司 | A kind of preparation method of high-strength bone internal fixation material |
| CN107855096A (en) * | 2017-11-20 | 2018-03-30 | 陕西师范大学 | A kind of double salt inversion of phases prepares multi-stage porous flower ball-shaped nanostructured 7MgO2B2O3·7H2O method |
| CN108424637A (en) * | 2018-03-21 | 2018-08-21 | 苏州凌科特新材料有限公司 | The preparation method of biomaterial with optical activation |
| CN112646307A (en) * | 2020-12-23 | 2021-04-13 | 上海普利特复合材料股份有限公司 | Low-density, high-rigidity, high-toughness and high-flame-retardance polypropylene composite material for automobile hard-plastic instrument board and preparation method thereof |
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| CN103509242A (en) * | 2012-06-29 | 2014-01-15 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene/inorganic whisker composite with enhanced flame resistance and preparation method thereof |
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| CN102504414A (en) * | 2011-11-28 | 2012-06-20 | 成都理工大学 | Preparation method of modified magnesium borate whisker/PP (propene polymer) composite material |
| CN103509242A (en) * | 2012-06-29 | 2014-01-15 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene/inorganic whisker composite with enhanced flame resistance and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107648675A (en) * | 2017-09-16 | 2018-02-02 | 常州富思通管道有限公司 | A kind of preparation method of high-strength bone internal fixation material |
| CN107855096A (en) * | 2017-11-20 | 2018-03-30 | 陕西师范大学 | A kind of double salt inversion of phases prepares multi-stage porous flower ball-shaped nanostructured 7MgO2B2O3·7H2O method |
| CN107855096B (en) * | 2017-11-20 | 2020-07-28 | 陕西师范大学 | Preparation of hierarchical porous flower spherical nanostructure 7 MgO.2B by double salt phase inversion2O3·7H2Method of O |
| CN108424637A (en) * | 2018-03-21 | 2018-08-21 | 苏州凌科特新材料有限公司 | The preparation method of biomaterial with optical activation |
| CN112646307A (en) * | 2020-12-23 | 2021-04-13 | 上海普利特复合材料股份有限公司 | Low-density, high-rigidity, high-toughness and high-flame-retardance polypropylene composite material for automobile hard-plastic instrument board and preparation method thereof |
| CN112646307B (en) * | 2020-12-23 | 2024-02-20 | 上海普利特复合材料股份有限公司 | Low-density, high-rigidity and high-toughness and high-flame-retardance polypropylene composite material for automobile hard plastic instrument board and preparation method thereof |
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