CN106084176A - A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof - Google Patents
A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of environment-friendly type antibiotic method for preparing thermoplastic polyurethane elastomer, it uses organic-inorganic nanocomposite antibacterial, it is dispersed in polyhydric alcohol first with mechanical dispersion method, pass through situ aggregation method again, realize the dispersed of nano material, use a step mass polymerization, by double screw extruder synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer simultaneously.The Polyurethane Thermoplastic Elastomer using the present invention to prepare has the antibiotic property of excellence, and more environmentally-friendly, can be widely applied to construction material, public place facility, medical facilities and the field such as medical apparatus and instruments or textile material.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer
And preparation method thereof.
Background technology
Anti-biotic material and goods still play irreplaceable work in reducing pathophoresis, reply public health emergency
With.From the point of view of anti-biotic material application performance, organic antibacterial (includes fragrant aldehydes, chlorophenols, quaternary ammonium salt and imidazoles etc.)
There is certain toxicity and volatility, easily human body is caused stimulation or corrosion, and its distinct issues are that temperature tolerance is poor, apply model
Enclose and be very limited.By contrast, inorganic antiseptic (such as silver system, zinc system and titanium dioxide series antibacterial agent) is more antibacterial than organic
Agent has that whiteness is high, heat-resist, stability is high, to human non-toxic or low toxicity, therefore has more preferably processing in processing and forming
Property and human body adaptability.But, from antibacterial effect, compare organic antibacterial, there is sterilization speed in mineral-type antibacterial
Degree is slow, efficiency is low, antibacterial range is narrow, antibacterial ability is low, high in cost of production is not enough.Therefore, how to make up mineral-type antibacterial and have
The deficiency of machine class antibacterial one-component, developing low-cost, high sterilizing ability, broad-spectrum antiseptic and the thermoplasticity of quick sterilization ability
Polyurethane elastomer has become current problem demanding prompt solution.
It addition, prominent along with problem of environmental pollution, the most also it is badly in need of a kind of environment-friendly type antibiotic thermoplastic polyurethane elastic
Body.
Summary of the invention
For solving above-mentioned technical problem, the invention provides a kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and system thereof
Preparation Method, the Polyurethane Thermoplastic Elastomer using the present invention to prepare has the antibiotic property of excellence, and more environmentally-friendly, can
It is widely used in construction material, public place facility, medical facilities and the field such as medical apparatus and instruments or textile material.
First aspect, the invention provides a kind of environment-friendly type antibiotic method for preparing thermoplastic polyurethane elastomer, described
Method uses organic-inorganic hybrid nanocomposite antibacterial, is dispersed in polyhydric alcohol first with mechanical dispersion method, then passes through in-situ polymerization
Method, it is achieved nano material dispersed, uses a step mass polymerization simultaneously, is resisted by double screw extruder synthetic environment-friendly
Bacterium Polyurethane Thermoplastic Elastomer.
According to the present invention, described environment-friendly type antibiotic method for preparing thermoplastic polyurethane elastomer comprises the following steps:
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
(2) utilize and the mixture of mechanical dispersion normal direction step (1) adds polyhydric alcohol, diisocyanate and chain extender, continue
Pouring in warmed-up mould after continuous stirring 3-5min, controlling temperature is 15-30 DEG C of curing molding 2-4h, then controls temperature and is
Vacuum solidification 3-4h at 60-90 DEG C, finally controlling temperature is 120-140 DEG C of vacuum solidification 15-24h, passes through double screw extruder
Synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer.
According to the present invention, step (1) described organic nano antibacterial is by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline three
Unit's coordination compound, Kathon, DCOIT and 1,2-benzo
The mass ratio that isothiazoline-3-ketone presses 1:1-3:3-5:2-5 is formulated.
According to the present invention, step (1) described inorganic nano antiseptic is pressed by amidatioon CNT and carbon fluoride nano-tube
Mass ratio according to 1-5:5-8 is formulated.
In the present invention, by using multiple organic and inorganic antiseptic, between each component, play synergistic function, from
And making preparation-obtained Polyurethane Thermoplastic Elastomer have the anti-microbial property of excellence, it is to escherichia coli and golden yellow Portugal
The antibiotic rate of grape coccus and Candida albicans is all higher than 99.5%.
In the present invention, by the screening to organic antibacterial agent, use by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline three
Unit's coordination compound, Kathon, DCOIT and 1,2-benzo
Isothiazoline-3-ketone presses the organic antibacterial agent that the mass ratio of 1:1-3:3-5:2-5 is formulated, and it compares one-component, these
There is between component synergism；By the screening to inorganic antiseptic, use by amidatioon CNT and perfluorocarbon nanometer
Pipe is according to the formulated inorganic antiseptic of the mass ratio of 1-5:5-8, and it shows prominent anti-microbial property.
According to the present invention, the preparation of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex described in step (1)
Method comprises the following steps:
A () is by rare earth oxide (RE2O3) and hydrochloric acid reaction, prepare rare earth chloride (RECl3·6H2O)；
B (), to 50-100ml dissolved with in the ethanol water of 10-15mmol m-hydroxybenzoic acid sodium, dropping 40-100ml contains
There is the ethanol solution of 20-25mmol 8-hydroxyquinoline, stir under the conditions of 60-70 DEG C, drip 50-100ml after 1-2h containing 10-
The ethanol water of 15mmol rare earth chloride, continues to stir at 60-70 DEG C, controls pH to 6-7, ageing, sucking filtration, use secondary
Distilled water wash is to without chloride ion, then with absolute ethanol washing 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline
Ternary complex.
According to the present invention, described in step (1), the preparation method of amidatioon CNT comprises the following steps:
A () prepares carboxylic carbon nano-tube: being joined by CNT in Bronsted acid and mix, reaction temperature is 60-70 DEG C,
Ultrasonic power be 150-200W, supersonic frequency be 30-40KHz ultrasonic cleaner in condensing reflux 3-5h, ultrasonic after use
250-350ml deionized water dilutes, and then with the microporous filter membrane sucking filtration of a diameter of 0.1-0.2 μm, deionized water cyclic washing is straight
To neutral, at 70-80 DEG C, finally dry 10-12h, be ground to powder, obtain carboxylic carbon nano-tube；
Wherein, the CNT amount that every 100ml Bronsted acid adds is 0.1-0.5g；Described Bronsted acid be nitric acid, sulphuric acid or
A combination thereof；
B () prepares amidatioon CNT: carboxylic carbon nano-tube prepared for step (a) is joined 100-120ml
In DMF solvent, add acrylamide and dispersant, power be 100-200W, frequency be 30-40KHz under the conditions of ultrasonic disperse
10-20min, after being subsequently placed in 60-80 DEG C of water bath with thermostatic control reaction 48-72h, respectively with 25-50ml DMF solvent, 25-50ml
Deionized water wash, is vacuum dried 10-12h at 100-105 DEG C, obtains acrylic amide modified CNT after filtration；
Wherein, the usage ratio of described carboxylic carbon nano-tube, acrylamide and dispersant is following weight portion: carboxyl
Carbon nano tube 4-30 part, acrylamide 30-250 part, dispersant 15-30 part.
According to the present invention, carbon fluoride nano-tube described in step (1) is surface grafting polymethylacrylic acid perfluoroalkyl ester
Multi-walled carbon nano-tubes, its fluorine-contained surface amount is 1-5%.
According to the present invention, step (2) described polyhydric alcohol is by polytetramethylene adipate glycol, PTMG
Formulated according to the mass ratio of 1:3-7:5-7 with poly-1,2-oxygen trimethylene glycol.
According to the present invention, step (2) described diisocyanate is toluene di-isocyanate(TDI), diphenyl methane-4, and 4 '-two is different
In cyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4 '-dicyclohexyl methyl hydride diisocyanate extremely
Few one.
According to the present invention, step (2) described chain extender be BDO, 3,3 '-two chloro-4,4 '-diaminourea-diphenyl
At least one in methane, ethylenediamine, 1,2-propane diamine or 1,3-cyclohexanediamine.
Exemplarily, environment-friendly type antibiotic method for preparing thermoplastic polyurethane elastomer of the present invention, including following step
Rapid:
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
Organic nano antibacterial is different by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex, 2-n-octyl-4-
Thiazoline-3-ketone, DCOIT and 1,2-benzisothiazole-3-ketone press 1:1-3:
The mass ratio of 3-5:2-5 is formulated；Inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to 1-5:
The mass ratio of 5-8 is formulated；
Wherein, the preparation method of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex comprises the following steps:
A (), by rare earth oxide and hydrochloric acid reaction, prepares rare earth chloride；
B (), to 100ml dissolved with in the ethanol water of 12mmol m-hydroxybenzoic acid sodium, dropping 48ml contains 21mmol
The ethanol solution of 8-hydroxyquinoline, stirs under the conditions of 65 DEG C, drips the 100ml ethanol water containing 12mmol rare earth chloride after 1h
Solution, continues to stir at 61 DEG C, controls pH to 7, ageing, sucking filtration, wash without chloride ion with redistilled water, then with anhydrous
Washing with alcohol 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex.
Wherein, the preparation method of amidatioon CNT comprises the following steps:
The preparation of (a) carboxylic carbon nano-tube
Taking 1.2g CNT and the concentrated sulphuric acid that 300mL concentration is 90% joins in 500mL flask, reaction temperature is 70
DEG C, ultrasonic power be 100W, supersonic frequency be 30KHz ultrasonic cleaner in condensing reflux 5h；It is then transferred into beaker
Middle 350ml deionized water dilutes, and with the microporous filter membrane sucking filtration of a diameter of 0.2 μm, deionized water cyclic washing is until neutrality；?
After the CNT after sucking filtration is dried 10h at 80 DEG C, be ground to powder standby；Described CNT is chemical gaseous phase
The multi-walled carbon nano-tubes that sedimentation produces, caliber 35nm, pipe range 50 μm, purity 95 (wt) %, specific surface area 200m2/g；
The preparation of (b) amidatioon CNT
The carboxylated nanotube 0.300g taking step (a) prepared joins in 150ml DMF solvent, adds 2.480g propylene
Amide and 0.225g PEG-4000, power be 150W, supersonic frequency be 30KHz under conditions of ultrasonic disperse 10min,
Being subsequently placed in 80 DEG C of waters bath with thermostatic control reaction 72h, use 50ml DMF solvent, 50ml deionized water wash, after filtration at 105 DEG C
Vacuum drying 12h, obtains acrylic amide modified CNT.
(2) utilize the mixture of mechanical dispersion normal direction step (1) adds by polytetramethylene adipate glycol, poly-four
Hydrogen furan ether glycol and poly-1,2-oxygen trimethylene glycol are according to the formulated polyhydric alcohol of the mass ratio of 1:5:7, toluene diisocyanate
Acid esters and BDO, pour in warmed-up mould after continuing stirring 3min, and controlling temperature is 15 DEG C of curing molding 2h, so
Rear control temperature is vacuum solidification 4h at 60 DEG C, and finally controlling temperature is 140 DEG C of vacuum solidification 24h, passes through double screw extruder
Synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer.
Second aspect, present invention also offers the environment-friendly type antibiotic that method as described in the first aspect of the invention prepares
Polyurethane Thermoplastic Elastomer.
Environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer of the present invention has useful anti-microbial property, and it is to large intestine bar
The antibiotic rate of bacterium and staphylococcus aureus and Candida albicans is all higher than 99.5%, and more environmentally-friendly.
The third aspect, present invention also offers environment-friendly type antibiotic thermoplastic polyurethane bullet as described in respect of the second aspect of the invention
Gonosome is in construction material, public place facility, medical facilities and the application in medical apparatus and instruments or textile material.
Compared with prior art, the present invention at least has the advantages that
Use the Polyurethane Thermoplastic Elastomer for preparing of the present invention to have the antibiotic property of excellence, its to escherichia coli and
The antibiotic rate of staphylococcus aureus and Candida albicans is all higher than 99.5%, and more environmentally-friendly, can be widely applied to build
Build material, public place facility, medical facilities and the field such as medical apparatus and instruments or textile material.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example only help understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
Organic nano antibacterial is different by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex, 2-n-octyl-4-
Thiazoline-3-ketone, DCOIT and 1,2-benzisothiazole-3-ketone press 1:3:3:2
Mass ratio formulated；Inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to the mass ratio of 1:7
Formulated；
Wherein, the preparation method of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex comprises the following steps:
A () is by rare earth oxide (La2O3) and hydrochloric acid reaction, prepare rare earth chloride (LaCl3·6H2O)；
B (), to 100ml dissolved with in the ethanol water of 12mmol m-hydroxybenzoic acid sodium, dropping 48ml contains 21mmol
The ethanol solution of 8-hydroxyquinoline, stirs under the conditions of 65 DEG C, drips the 100ml ethanol water containing 12mmol rare earth chloride after 1h
Solution, continues to stir at 61 DEG C, controls pH to 7, ageing, sucking filtration, wash without chloride ion with redistilled water, then with anhydrous
Washing with alcohol 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex.
Wherein, the preparation method of amidatioon CNT comprises the following steps:
The preparation of (a) carboxylic carbon nano-tube
Taking 1.2g CNT and the concentrated sulphuric acid that 300mL concentration is 90% joins in 500mL flask, reaction temperature is 70
DEG C, ultrasonic power be 100W, supersonic frequency be 30KHz ultrasonic cleaner in condensing reflux 5h；It is then transferred into beaker
Middle 350ml deionized water dilutes, and with the microporous filter membrane sucking filtration of a diameter of 0.2 μm, deionized water cyclic washing is until neutrality；?
After the CNT after sucking filtration is dried 10h at 80 DEG C, be ground to powder standby；Described CNT is chemical gaseous phase
The multi-walled carbon nano-tubes that sedimentation produces, caliber 35nm, pipe range 50 μm, purity 95 (wt) %, specific surface area 200m2/g；
The preparation of (b) amidatioon CNT
The carboxylated nanotube 0.300g taking step (a) prepared joins in 150ml DMF solvent, adds 2.480g propylene
Amide and 0.225g PEG-4000, power be 150W, supersonic frequency be 30KHz under conditions of ultrasonic disperse 10min,
Being subsequently placed in 80 DEG C of waters bath with thermostatic control reaction 72h, use 50ml DMF solvent, 50ml deionized water wash, after filtration at 105 DEG C
Vacuum drying 12h, obtains acrylic amide modified CNT.
(2) utilize the mixture of mechanical dispersion normal direction step (1) adds by polytetramethylene adipate glycol, poly-four
Hydrogen furan ether glycol and poly-1,2-oxygen trimethylene glycol are according to the formulated polyhydric alcohol of the mass ratio of 1:5:7, toluene diisocyanate
Acid esters and BDO, pour in warmed-up mould after continuing stirring 3min, and controlling temperature is 15 DEG C of curing molding 2h, so
Rear control temperature is vacuum solidification 4h at 60 DEG C, and finally controlling temperature is 140 DEG C of vacuum solidification 24h, passes through double screw extruder
Synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer.
Embodiment 2
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
Organic nano antibacterial is different by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex, 2-n-octyl-4-
Thiazoline-3-ketone, DCOIT and 1,2-benzisothiazole-3-ketone press 1:1:5:3
Mass ratio formulated；Inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to the mass ratio of 2:5
Formulated；
Wherein, the preparation method of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex comprises the following steps:
A () is by rare earth oxide (Ce2O3) and hydrochloric acid reaction, prepare rare earth chloride (Ce Cl3·6H2O)；
B (), to 50ml dissolved with in the ethanol water of 10mmol m-hydroxybenzoic acid sodium, dropping 48ml contains 21mmol 8-
The ethanol solution of hydroxyquinoline, stirs under the conditions of 65 DEG C, drips the 50ml ethanol containing 10mmol rare earth chloride water-soluble after 1h
Liquid, continues to stir at 65 DEG C, controls pH to 7, ageing, sucking filtration, wash without chloride ion with redistilled water, then use anhydrous second
Alcohol washs 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex.
Wherein, the preparation method of amidatioon CNT comprises the following steps:
The preparation of (a) carboxylic carbon nano-tube
Taking 1.2g CNT and the concentrated nitric acid that 300mL concentration is 90% joins in 500mL flask, reaction temperature is 70
DEG C, ultrasonic power be 100W, supersonic frequency be 40KHz ultrasonic cleaner in condensing reflux 5h；It is then transferred into beaker
Middle 350ml deionized water dilutes, and with the microporous filter membrane sucking filtration of a diameter of 0.2 μm, deionized water cyclic washing is until neutrality；?
After the CNT after sucking filtration is dried 10h at 80 DEG C, be ground to powder standby；Described CNT is chemical gaseous phase
The multi-walled carbon nano-tubes that sedimentation produces, caliber 35nm, pipe range 50 μm, purity 95 (wt) %, specific surface area 100m2/g；
The preparation of (b) amidatioon CNT
The carboxylated nanotube 0.300g taking step (a) prepared joins in 150ml DMF solvent, adds 2.480g propylene
Amide and 0.225g PEG-4000, power be 150W, supersonic frequency be 30KHz under conditions of ultrasonic disperse 10min,
Being subsequently placed in 80 DEG C of waters bath with thermostatic control reaction 72h, use 50ml DMF solvent, 50ml deionized water wash, after filtration at 115 DEG C
Vacuum drying 12h, obtains acrylic amide modified CNT.
(2) utilize the mixture of mechanical dispersion normal direction step (1) adds by polytetramethylene adipate glycol, poly-four
Hydrogen furan ether glycol and poly-1,2-oxygen trimethylene glycol are according to the formulated polyhydric alcohol of the mass ratio of 1:3:5, isophorone two
Isocyanates and 1,3-cyclohexanediamine, to pour in warmed-up mould after continuing stirring 3min, control temperature is 15 DEG C and is solidified into
Type 2h, then controlling temperature is vacuum solidification 4h at 60 DEG C, and finally controlling temperature is 140 DEG C of vacuum solidification 24h, passes through twin screw
Extruder synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer.
Embodiment 3
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
Organic nano antibacterial is different by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex, 2-n-octyl-4-
Thiazoline-3-ketone, DCOIT and 1,2-benzisothiazole-3-ketone press 1:1:5:5
Mass ratio formulated；Inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to the mass ratio of 5:8
Formulated；
Wherein, the preparation method of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex comprises the following steps:
A () is by rare earth oxide (Nd2O3) and hydrochloric acid reaction, prepare rare earth chloride (NdCl3·6H2O)；
B (), to 100ml dissolved with in the ethanol water of 11mmol m-hydroxybenzoic acid sodium, dropping 48ml contains 21mmol
The ethanol solution of 8-hydroxyquinoline, stirs under the conditions of 65 DEG C, drips the 100ml ethanol water containing 12mmol rare earth chloride after 1h
Solution, continues to stir at 61 DEG C, controls pH to 7, ageing, sucking filtration, wash without chloride ion with redistilled water, then with anhydrous
Washing with alcohol 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex.
Wherein, the preparation method of amidatioon CNT comprises the following steps:
The preparation of (a) carboxylic carbon nano-tube
Taking 1.2g CNT and the concentrated sulphuric acid that 300mL concentration is 90% joins in 500mL flask, reaction temperature is 70
DEG C, ultrasonic power be 100W, supersonic frequency be 30KHz ultrasonic cleaner in condensing reflux 5h；It is then transferred into beaker
Middle 350ml deionized water dilutes, and with the microporous filter membrane sucking filtration of a diameter of 0.2 μm, deionized water cyclic washing is until neutrality；?
After the CNT after sucking filtration is dried 10h at 80 DEG C, be ground to powder standby；Described CNT is chemical gaseous phase
The multi-walled carbon nano-tubes that sedimentation produces, caliber 35nm, pipe range 50 μm, purity 95 (wt) %, specific surface area 200m2/g；
The preparation of (b) amidatioon CNT
The carboxylated nanotube 0.300g taking step (a) prepared joins in 150ml DMF solvent, adds 2.480g propylene
Amide and 0.225g PEG-4000, power be 150W, supersonic frequency be 30KHz under conditions of ultrasonic disperse 10min,
Being subsequently placed in 80 DEG C of waters bath with thermostatic control reaction 72h, use 50ml DMF solvent, 50ml deionized water wash, after filtration at 105 DEG C
Vacuum drying 12h, obtains acrylic amide modified CNT.
(2) utilize the mixture of mechanical dispersion normal direction step (1) adds by polytetramethylene adipate glycol, poly-four
Oneself is two different according to the formulated polyhydric alcohol of the mass ratio of 1:4:5,1,6-for hydrogen furan ether glycol and poly-1,2-oxygen trimethylene glycol
Cyanate and ethylenediamine, pour in warmed-up mould after continuing stirring 3min, and controlling temperature is 15 DEG C of curing molding 2h, then
Controlling temperature is vacuum solidification 4h at 60 DEG C, and finally controlling temperature is 140 DEG C of vacuum solidification 24h, is closed by double screw extruder
Become environment-friendly type Antibacterial thermoplastic polyurethane elastomer.
Embodiment 4
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
Organic nano antibacterial is different by rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex, 2-n-octyl-4-
Thiazoline-3-ketone, DCOIT and 1,2-benzisothiazole-3-ketone press 1:2:4:2
Mass ratio formulated；Inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to the mass ratio of 4:5
Formulated；
Wherein, the preparation method of rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex comprises the following steps:
A () is by rare earth oxide (Eu2O3) and hydrochloric acid reaction, prepare rare earth chloride (EuCl3·6H2O)；
B (), to 100ml dissolved with in the ethanol water of 12mmol m-hydroxybenzoic acid sodium, dropping 48ml contains 21mmol
The ethanol solution of 8-hydroxyquinoline, stirs under the conditions of 65 DEG C, drips the 100ml ethanol water containing 12mmol rare earth chloride after 1h
Solution, continues to stir at 61 DEG C, controls pH to 7, ageing, sucking filtration, wash without chloride ion with redistilled water, then with anhydrous
Washing with alcohol 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline ternary complex.
Wherein, the preparation method of amidatioon CNT comprises the following steps:
The preparation of (a) carboxylic carbon nano-tube
Taking 1.2g CNT and the concentrated sulphuric acid that 300mL concentration is 90% joins in 500mL flask, reaction temperature is 70
DEG C, ultrasonic power be 100W, supersonic frequency be 30KHz ultrasonic cleaner in condensing reflux 5h；It is then transferred into beaker
Middle 350ml deionized water dilutes, and with the microporous filter membrane sucking filtration of a diameter of 0.2 μm, deionized water cyclic washing is until neutrality；?
After the CNT after sucking filtration is dried 10h at 80 DEG C, be ground to powder standby；Described CNT is chemical gaseous phase
The multi-walled carbon nano-tubes that sedimentation produces, caliber 35nm, pipe range 50 μm, purity 95 (wt) %, specific surface area 200m2/g；
The preparation of (b) amidatioon CNT
The carboxylated nanotube 0.300g taking step (a) prepared joins in 150ml DMF solvent, adds 2.480g propylene
Amide and 0.225g PEG-4000, power be 150W, supersonic frequency be 30KHz under conditions of ultrasonic disperse 10min,
Being subsequently placed in 80 DEG C of waters bath with thermostatic control reaction 72h, use 50ml DMF solvent, 50ml deionized water wash, after filtration at 105 DEG C
Vacuum drying 12h, obtains acrylic amide modified CNT.
(2) utilize the mixture of mechanical dispersion normal direction step (1) adds by polytetramethylene adipate glycol, poly-four
Hydrogen furan ether glycol and poly-1,2-oxygen trimethylene glycol are according to the formulated polyhydric alcohol of the mass ratio of 1:5:5, toluene diisocyanate
Acid esters and 1,2-propane diamine, pour in warmed-up mould after continuing stirring 3min, controlling temperature is 15 DEG C of curing molding 2h, so
Rear control temperature is vacuum solidification 4h at 60 DEG C, and finally controlling temperature is 140 DEG C of vacuum solidification 24h, passes through double screw extruder
Synthetic environment-friendly Antibacterial thermoplastic polyurethane elastomer.
Comparative example 1
Compared with Example 1, in addition to being not added with any organic nano antibacterial, other is same as in Example 1.
Comparative example 2
Compared with Example 1, in addition to being not added with any inorganic nano antiseptic, other is same as in Example 1.
Comparative example 3
Compared with Example 1, except the rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline being not added with in organic nano antibacterial
Outside ternary complex, other is same as in Example 1.
Comparative example 4
Compared with Example 1, in addition to the amidatioon CNT being not added with in inorganic nano antiseptic, other and embodiment
1 is identical.
Comparative example 5
Compared with Example 1, in addition to the carbon fluoride nano-tube being not added with in inorganic nano antiseptic, other and embodiment 1
Identical.
Comparative example 6
Compared with Example 1, except polyhydric alcohol is by polytetramethylene adipate glycol, PTMG and poly-1,
2-oxygen trimethylene glycol according to the mass ratio of 5:1:1 formulated outside, other is same as in Example 1.
Table 1 shows the anti-microbial property of the Polyurethane Thermoplastic Elastomer prepared by embodiment 1-4 and comparative example 1-6.
Table 1
In summary it can be seen, the present invention, by the screening to organic antibacterial agent, uses by rare earth-m-hydroxybenzoic acid-8-
Hydroxyquinoline ternary complex, Kathon, DCOIT
Pressing, with BIT, the organic antibacterial agent that the mass ratio of 1:1-3:3-5:2-5 is formulated, it compares single
Component, has synergism between these components；By the screening to inorganic antiseptic, use by amidatioon CNT and fluorine
Carbon nano tube is according to the formulated inorganic antiseptic of the mass ratio of 1-5:5-8, and it shows prominent anti-microbial property；Pass through
Comprehensive organic-inorganic nano antibacterial, its Polyurethane Thermoplastic Elastomer prepared is to escherichia coli and golden yellow Fructus Vitis viniferae
The antibiotic rate of coccus and Candida albicans is all higher than 99.5%, and more environmentally-friendly, can be widely applied to construction material, public
Place facility, medical facilities and the field such as medical apparatus and instruments or textile material.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention have to rely on above-mentioned in detail
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's
Within the scope of protection domain and disclosure.
Claims (8)
1. an environment-friendly type antibiotic method for preparing thermoplastic polyurethane elastomer, it is characterised in that described method use organic-
Inorganic nano composite antimicrobial agent, is dispersed in polyhydric alcohol first with mechanical dispersion method, then passes through situ aggregation method, it is achieved nanometer material
That expects is dispersed, uses a step mass polymerization, by double screw extruder synthetic environment-friendly antibacterial thermoplastic poly ammonia simultaneously
Ester elastomer.
2. the method for claim 1, it is characterised in that said method comprising the steps of:
(1) organic nano antibacterial and inorganic nano antiseptic are mixed；
(2) utilize and the mixture of mechanical dispersion normal direction step (1) adds polyhydric alcohol, diisocyanate and chain extender, continue to stir
Pouring into after mixing 3-5min in warmed-up mould, controlling temperature is 15-30 DEG C of curing molding 2-4h, and then controlling temperature is 60-
Vacuum solidification 3-4h at 90 DEG C, finally controlling temperature is 120-140 DEG C of vacuum solidification 15-24h, is synthesized by double screw extruder
Environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer.
3. method as claimed in claim 2, it is characterised in that step (1) described organic nano antibacterial is by a rare earth-hydroxyl
Benzoic acid-8-hydroxyquinoline ternary complex, Kathon, the 4,5-bis-chloro-2-different thiophene of n-octyl-4-
The mass ratio that oxazoline-3-ketone and 1,2-benzisothiazole-3-ketone press 1:1-3:3-5:2-5 is formulated；
Preferably, step (1) described inorganic nano antiseptic by amidatioon CNT and carbon fluoride nano-tube according to 1-5:5-8
Mass ratio formulated.
4. method as claimed in claim 3, it is characterised in that rare earth described in step (1)-m-hydroxybenzoic acid-8-hydroxyl
The preparation method of quinoline ternary complex comprises the following steps:
A () is by rare earth oxide (RE2O3) and hydrochloric acid reaction, prepare rare earth chloride (RECl3·6H2O)；
B (), to 50-100ml dissolved with in the ethanol water of 10-15mmol m-hydroxybenzoic acid sodium, dropping 40-100ml contains
The ethanol solution of 20-25mmol 8-hydroxyquinoline, stirs under the conditions of 60-70 DEG C, drips 50-100ml containing 10-after 1-2h
The ethanol water of 15mmol rare earth chloride, continues to stir at 60-70 DEG C, controls pH to 6-7, ageing, sucking filtration, use secondary
Distilled water wash is to without chloride ion, then with absolute ethanol washing 3 times, obtains described rare earth-m-hydroxybenzoic acid-8-hydroxyquinoline
Ternary complex.
5. method as claimed in claim 3, it is characterised in that the preparation method of amidatioon CNT described in step (1)
Comprise the following steps:
A () prepares carboxylic carbon nano-tube: being joined by CNT in Bronsted acid and mix, reaction temperature is 60-70 DEG C, super
Acoustical power is 150-200W, supersonic frequency be 30-40KHz ultrasonic cleaner in condensing reflux 3-5h, ultrasonic after use 250-
350ml deionized water dilute, then with the microporous filter membrane sucking filtration of a diameter of 0.1-0.2 μm, deionized water cyclic washing until in
Property, at 70-80 DEG C, finally dry 10-12h, be ground to powder, obtain carboxylic carbon nano-tube；
Wherein, the CNT amount that every 100ml Bronsted acid adds is 0.1-0.5g；Described Bronsted acid is nitric acid, sulphuric acid or its group
Close；
B () prepares amidatioon CNT: carboxylic carbon nano-tube prepared for step (a) is joined 100-120ml DMF molten
In agent, add acrylamide and dispersant, power be 100-200W, frequency be 30-40KHz under the conditions of ultrasonic disperse 10-
20min, be subsequently placed in 60-80 DEG C of water bath with thermostatic control reaction 48-72h after, respectively with 25-50ml DMF solvent, 25-50ml go from
Sub-water washs, and is vacuum dried 10-12h, obtains acrylic amide modified CNT after filtration at 100-105 DEG C；
Wherein, the usage ratio of described carboxylic carbon nano-tube, acrylamide and dispersant is following weight portion: carboxylated carbon
Nanotube 4-30 part, acrylamide 30-250 part, dispersant 15-30 part；
Preferably, carbon fluoride nano-tube described in step (1) is many walls carbon of surface grafting polymethylacrylic acid perfluoroalkyl ester
Nanotube, its fluorine-contained surface amount is 1-5%.
6. the method as described in one of claim 2-5, it is characterised in that step (2) described polyhydric alcohol is own by polytetramethylene
Diacid esterdiol, PTMG and poly-1,2-oxygen trimethylene glycol are formulated according to the mass ratio of 1:3-7:5-7；
Preferably, step (2) described diisocyanate is toluene di-isocyanate(TDI), diphenyl methane-4,4 '-diisocyanate,
At least one in hexamethylene diisocyanate, isophorone diisocyanate or 4,4 '-dicyclohexyl methyl hydride diisocyanate；
Preferably, step (2) described chain extender be BDO, 3,3 '-two chloro-4,4 '-diaminourea-diphenyl methane, second
At least one in diamidogen, 1,2-propane diamine or 1,3-cyclohexanediamine.
7. the environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer that the method as described in one of claim 1-6 prepares.
8. environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer as claimed in claim 7 is construction material, public place facility, doctor
Treat facility and the application in medical apparatus and instruments or textile material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233128A (en) * | 2018-08-28 | 2019-01-18 | 安徽江淮汽车集团股份有限公司 | A kind of antibacterial antistatic PS composite material and preparation method |
| CN109294061A (en) * | 2018-09-20 | 2019-02-01 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method of antibacterial agent |
| CN110903470A (en) * | 2019-12-10 | 2020-03-24 | 东莞市道尔新材料科技有限公司 | Novel PET material, preparation method thereof, granules and fiber product |
| CN112708256A (en) * | 2020-12-27 | 2021-04-27 | 宁波长阳科技股份有限公司 | Ultraviolet light aging resistant fluorescent TPU (thermoplastic polyurethane) film material as well as preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191471A (en) * | 1995-06-07 | 1998-08-26 | 耐克国际有限公司 | Membranes of polyurethane based on materials including polyester polyols |
| CN104193949A (en) * | 2014-07-30 | 2014-12-10 | 苏州市雄林新材料科技有限公司 | Nano-antibacterial TPU (Thermoplastic Polyurethane) material and preparation method thereof |
| CN104193950A (en) * | 2014-07-30 | 2014-12-10 | 东莞市吉鑫高分子科技有限公司 | Nano antibacterial polyurethane composition and preparation method thereof |
-
2016
- 2016-07-28 CN CN201610608208.0A patent/CN106084176A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1191471A (en) * | 1995-06-07 | 1998-08-26 | 耐克国际有限公司 | Membranes of polyurethane based on materials including polyester polyols |
| CN104193949A (en) * | 2014-07-30 | 2014-12-10 | 苏州市雄林新材料科技有限公司 | Nano-antibacterial TPU (Thermoplastic Polyurethane) material and preparation method thereof |
| CN104193950A (en) * | 2014-07-30 | 2014-12-10 | 东莞市吉鑫高分子科技有限公司 | Nano antibacterial polyurethane composition and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233128A (en) * | 2018-08-28 | 2019-01-18 | 安徽江淮汽车集团股份有限公司 | A kind of antibacterial antistatic PS composite material and preparation method |
| CN109294061A (en) * | 2018-09-20 | 2019-02-01 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method of antibacterial agent |
| CN110903470A (en) * | 2019-12-10 | 2020-03-24 | 东莞市道尔新材料科技有限公司 | Novel PET material, preparation method thereof, granules and fiber product |
| CN110903470B (en) * | 2019-12-10 | 2022-05-03 | 东莞市道尔新材料科技有限公司 | PET material and preparation method thereof, and granular material and fiber product |
| CN112708256A (en) * | 2020-12-27 | 2021-04-27 | 宁波长阳科技股份有限公司 | Ultraviolet light aging resistant fluorescent TPU (thermoplastic polyurethane) film material as well as preparation method and application thereof |
| CN112961491A (en) * | 2021-01-25 | 2021-06-15 | 上海大学 | Antibacterial polyurethane foam material and preparation method thereof |
| CN114055799A (en) * | 2021-12-13 | 2022-02-18 | 福建恩迈特新材料有限公司 | Material for isolation cabin and preparation method thereof |
| CN114055799B (en) * | 2021-12-13 | 2024-04-12 | 福建恩迈特新材料有限公司 | Material for isolation cabin and preparation method thereof |
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