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 PDF

Info

Publication number
CN106084176A
CN106084176A CN201610608208.0A CN201610608208A CN106084176A CN 106084176 A CN106084176 A CN 106084176A CN 201610608208 A CN201610608208 A CN 201610608208A CN 106084176 A CN106084176 A CN 106084176A
Authority
CN
China
Prior art keywords
cnt
nano
rare earth
environment
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610608208.0A
Other languages
Chinese (zh)
Inventor
何建雄
王良
王一良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Xionglin New Materials Technology Co Ltd
Original Assignee
Dongguan Xionglin New Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Xionglin New Materials Technology Co Ltd filed Critical Dongguan Xionglin New Materials Technology Co Ltd
Priority to CN201610608208.0A priority Critical patent/CN106084176A/en
Publication of CN106084176A publication Critical patent/CN106084176A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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

A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof
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.
CN201610608208.0A 2016-07-28 2016-07-28 A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof Pending CN106084176A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610608208.0A CN106084176A (en) 2016-07-28 2016-07-28 A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610608208.0A CN106084176A (en) 2016-07-28 2016-07-28 A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN106084176A true CN106084176A (en) 2016-11-09

Family

ID=57479209

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610608208.0A Pending CN106084176A (en) 2016-07-28 2016-07-28 A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106084176A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
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
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

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
CN106084176A (en) A kind of environment-friendly type antibiotic Polyurethane Thermoplastic Elastomer and preparation method thereof
Pant et al. Characterization and antibacterial properties of Ag NPs loaded nylon-6 nanocomposite prepared by one-step electrospinning process
CN101787101B (en) Preparation method of nanometer resin with high hygroscopy
CN104145993B (en) A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials
CN106479303A (en) A kind of water-proof antibiotic coating
CN104558323B (en) A kind of highly-water-soluble nano-hexagonal boron nitride and the preparation method of polymer composite aquogel thereof
Seshadri et al. Use of polyaniline as an antimicrobial agent in textiles
CN102492090B (en) Preparation method for montmorillonite intercalation cation flocculating agent emulsion
CN102787497A (en) Method for preparing novel quaternary ammonium salt copolymer/nanometer ZnO composite antimicrobial for fabric
CN102125055A (en) Sliver-carried nano-montmorillonite antibacterial agent and preparation method thereof
CN111849282B (en) Monoatomic antibacterial and disinfectant interior wall coating and preparation method thereof
CN104289181A (en) Preparation and application of magnetic hydroxyapatite/graphene oxide adsorbent
CN103739786A (en) High polymer quaternary phosphonium salt antibacterial material and preparation method thereof
CN105199541B (en) A kind of preparation method of water-based anticorrosive paint
CN108219212A (en) A kind of preparation method of modified chitosan anti-bacteria compounded latex
CN103360679A (en) High-efficient reinforced anti-agglomeration antibacterial filler masterbatch for non-woven fabric and preparation process thereof
CN106188471A (en) A kind of nano composite material and preparation method thereof
CN105327683A (en) Carbon nanotube printing and dyeing wastewater treatment complexing agent based on SiO<2>/TiO<2> mesoporous composite microsphere carrier and preparation method
CN110407982A (en) A kind of antibacterial hydrogel material and preparation method thereof
Wang et al. Superelastic three-dimensional nanofiber-reconfigured spongy hydrogels with superior adsorption of lanthanide ions and photoluminescence
CN103554367A (en) Beta-cyclodextrin containing halogen amine antimicrobial agent copolymer as well as preparation method and application of copolymer
CN105199112A (en) Preparation method of high-strength gamma-polyglutamic acid hydrogel
CN103172092B (en) A kind of Nanometer magnesia-triclosan composite nanometer antimicrobial agent
CN103881151B (en) A kind of preparation method of marine alga acidic group-conducting polymer composite material
CN107244667A (en) A kind of amphipathic aeroge and preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20161109

RJ01 Rejection of invention patent application after publication