CN108822527A - The modified aqueous polyurethane nano composite material and preparation method of carbon quantum dot - Google Patents
The modified aqueous polyurethane nano composite material and preparation method of carbon quantum dot Download PDFInfo
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- CN108822527A CN108822527A CN201810518889.0A CN201810518889A CN108822527A CN 108822527 A CN108822527 A CN 108822527A CN 201810518889 A CN201810518889 A CN 201810518889A CN 108822527 A CN108822527 A CN 108822527A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The present invention relates to the modified aqueous polyurethane nano composite material and preparation methods of carbon quantum dot, first prepare the carbon quantum dot that active group amino and hydroxyl are contained in surface, then amino is utilized, the reaction of isocyanate group in hydroxyl and Waterborne Polyurethane Prepolymer, finally use situ aggregation method, enable carbon quantum dot compound with aqueous polyurethane, to prepare the modified aqueous polyurethane fluorescence nano composite material of carbon quantum dot, easy to operate and safety and environmental protection, promote the development of sustainable and ecological friendly materials, the effectively application range of extension carbon quantum dot and water-base polyurethane material.
Description
Technical field
The invention belongs to functional nano-composite material production technical fields, and in particular to a kind of water that carbon quantum dot is modified
Property polyurethane nano composite material and preparation method thereof.
Background technique
Carbon quantum dot (Carbon dots or CQDs) is after graphene, carbon nanotube, fullerene emerging one
Kind of carbon nanomaterial, particle size is generally less than 10nm, since its synthesis cost is low, the carbon quantum dot optical stabilization prepared
Property is good, and toxicity is low, is easy to surface-functionalized, and compared with the inorganic-quantum-dot containing toxic heavy metal, carbon quantum dot has more environment
Friendly and biocompatibility.In addition, carbon quantum dot is mentioned by using nonpoisonous chemicla, environmentally friendly solvent and renewable precursor
Easy preparation route is supplied, this is consistent with the principle of Green Chemistry.So in bio-sensing and probe, bio-imaging, LED device
The fields such as part, photocatalysis and fluorescent ink all have received widespread attention.
The synthesis of carbon quantum dot and the preparation of functional polymer be modern material chemistry oneself through obtaining two of immense success
Field.In recent years, it is conceived to by carbon quantum dot in conjunction with the advantage of high polymer, the research for preparing new function composite material is got over
More to attract attention.Water-base polyurethane material be it is a kind of study more mature high polymer material, meet " before three of industrial development
Mention " (resource RESOURCE, energy ENERGY, pollution-free POLLUTION-FREE) and " 4E " principle (economic ECONOMY, efficiency
EFFICIENCY, ecology ECOLOGY, energy ENERGY), optical transparence is good, simple synthetic method and can pass through tune
The ratio of hard section and soft segment is saved to adjust the mechanical property of material.
Summary of the invention
The object of the present invention is to provide a kind of modified aqueous polyurethane nano composite material of carbon quantum dot and its preparation sides
Method, the material fluorescence property is good, can effectively extend the application range of carbon quantum dot and water-base polyurethane material.
The technical scheme adopted by the invention is as follows：
The preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot, it is characterised in that：
It is realized by following steps：
The carbon quantum dot that active group amino and hydroxyl are contained in surface is prepared first, then utilizes amino, hydroxyl and aqueous poly- ammonia
The reaction of isocyanate group in ester performed polymer finally uses situ aggregation method, enables carbon quantum dot compound with aqueous polyurethane, thus
Prepare the modified aqueous polyurethane fluorescence nano composite material of carbon quantum dot.
The preparation method of the modified aqueous polyurethane nano composite material of the carbon quantum dot, it is characterised in that：
Specific steps include：
Step 1：The preparation of carbon quantum dot：
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution；Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in baking oven and is stood hydro-thermal reaction, and room is naturally cooled to
Temperature obtains the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group, is then centrifuged dispersion liquid, dialyses
Processing, obtains the carbon quantum dot solution with good shelf-stability；Finally acquired solution is birdsed of the same feather flock together by freeze-drying
The dry-eye disease of polymers morphology；
Step 2：The preparation of carbon quantum dot-aqueous polyurethane nano composite material：
Isophorone diisocyanate, polypropylene glycol, dibutyl tin dilaurate, small molecule chain extender 1,4- butanediol are added
To being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, it is uniformly mixed, base polyurethane prepolymer for use as is made in temperature reaction；It is different
The molar ratio of isophorone diisocyanate and polypropylene glycol is 3 ~ 5, and dibutyl tin dilaurate amount is 2 ~ 4 drops, 1,4-butanediol
Amount be the 2% of isophorone diisocyanate and polypropylene glycol quality sum；
Then the double hydroxymethyl propionic acids heatings of hydrophilic chain extender are added and carry out chain extending reactions, be then added be scattered in solvent by step
The carbon quantum dot prepared in rapid 1, continues chain extending reaction；Finally product obtained is neutralized, emulsifies to obtain carbon quantum
Point-aqueous polyurethane fluorescent emulsion；The amount of double hydroxymethyl propionic acids is isophorone diisocyanate and polypropylene glycol quality sum
3% ~ 7%, the amount of carbon quantum dot is the 0.05% ~ 0.25% of isophorone diisocyanate and polypropylene glycol quality sum.
In step 1, mixed solution is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 in baking oven
DEG C stand hydro-thermal reaction 6 hours.
In step 2, prepolymerization reaction temperature, time are 50 DEG C and first react 20min, 60 ~ 70 DEG C of the reaction was continued 1 ~ 2h.
In step 2, the chain extending reaction temperature that the double hydroxymethyl propionic acids of hydrophilic chain extender are added is 80 DEG C, the reaction time is 1.5 ~
2.5h。
In step 2, the chain extending reaction temperature that carbon quantum dot is added is 80 DEG C, and the reaction time is 1 ~ 2h.
In step 2, the solvent for dispersing carbon quantum dot is dimethyl sub-maple, acetone or N-Methyl pyrrolidone.
The modified aqueous polyurethane nano composite material of carbon quantum dot made from preparation method as mentioned.
The present invention has the following advantages that：
1, the present invention successfully prepares the fluorescent carbon quantum dot that surface has amino and hydroxyl group using one step hydro thermal method, assigns it
As the active site amino and hydroxyl of multi-functional chain extender, operation route is easy, at low cost and environmentally protective, with Green Chemistry
Principle it is consistent.
2, carbon quantum dot is introduced into aqueous polyurethane matrix as multi-functional chain extender in a manner of chemical bonding, a side
Face, the fragrant carbonizing structure of the carbon quantum dot with high-polarity peripheral groups assign the strong physics with aqueous polyurethane matrix
Chemical interaction, to enhance the mechanical performance of aqueous polyurethane film.On the other hand, the quantum size of carbon quantum dot and and water
The good compatibility of property polyurethane substrates helps to maintain the transparency of original polyurethane film, this is other carbonaceous nanostructures
It is difficult to realize.
3, aqueous polyurethane is using water as dispersing agent, safety and environmental protection, promotes the development of sustainable and ecological friendly materials.
Detailed description of the invention
Fig. 1 is the synthesis process schematic diagram of carbon quantum dot-aqueous polyurethane of the present invention.
Fig. 2 is the synthesis mechanism schematic diagram of carbon quantum dot-aqueous polyurethane of the present invention.
Fig. 3 is the Waterborne Polyurethane Prepolymer that embodiment 2 obtains（PPU）With carbon quantum dot-Waterborne Polyurethane Prepolymer
（CQDs-PPU）Infrared figure.
Fig. 4 is carbon quantum dot-aqueous polyurethane that embodiment 2 obtains（CQDs-WPU）The transparent appearance photo of film.
Fig. 5 is the carbon quantum dot that embodiment 2 obtains（CQDs）With carbon quantum dot-aqueous polyurethane（CQDs-WPU）Film is certainly
Photo under right light and ultraviolet lamp.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
The present invention is directed to explore carbon quantum dot（CQDs）With aqueous polyurethane（WPU）Complex act, first pass through a step
Hydro-thermal method directly obtains the fluorescence CQDs that surface has amino and hydroxyl group, then as multi-functional chain extender, with
- the NH on the surface CQDs2It with-OH group as active site, is introduced into a manner of chemical bonding in WPU matrix, using in situ poly-
It is legal to prepare the modified WPU fluorescence nano composite material of CQDs, promote the development of sustainable and ecological friendly materials.
The present invention relates to a kind of preparation methods of the modified aqueous polyurethane nano composite material of carbon quantum dot, first prepare table
The carbon quantum dot of active group amino and hydroxyl is contained in face, then utilizes isocyanide in amino, hydroxyl and Waterborne Polyurethane Prepolymer
The reaction of perester radical finally uses situ aggregation method, enables carbon quantum dot compound with aqueous polyurethane, change to prepare carbon quantum dot
The aqueous polyurethane fluorescence nano composite material of property.
Specific steps include：
Step 1：The preparation of carbon quantum dot：
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution；Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in baking oven and is stood hydro-thermal reaction, and room is naturally cooled to
Temperature obtains the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group, is then centrifuged dispersion liquid, dialyses
Processing, obtains the carbon quantum dot solution with good shelf-stability；Finally acquired solution is birdsed of the same feather flock together by freeze-drying
The dry-eye disease of polymers morphology；
Step 2：The preparation of carbon quantum dot-aqueous polyurethane nano composite material：
Isophorone diisocyanate, polypropylene glycol, dibutyl tin dilaurate, small molecule chain extender 1,4- butanediol are added
To being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, it is uniformly mixed, base polyurethane prepolymer for use as is made in temperature reaction；It is different
The molar ratio of isophorone diisocyanate and polypropylene glycol is 3 ~ 5, and the amount of dibutyl tin dilaurate is 2 ~ 4 drops, Isosorbide-5-Nitrae-fourth two
The amount of alcohol is the 2% of isophorone diisocyanate and polypropylene glycol quality sum；
Then the double hydroxymethyl propionic acids heatings of hydrophilic chain extender are added and carry out chain extending reactions, be then added be scattered in solvent by step
The carbon quantum dot prepared in rapid 1, continues chain extending reaction；Finally product obtained is neutralized, emulsifies to obtain carbon quantum
Point-aqueous polyurethane fluorescent emulsion；The amount of double hydroxymethyl propionic acids is isophorone diisocyanate and polypropylene glycol quality sum
3% ~ 7%, the amount of carbon quantum dot is the 0.05% ~ 0.25% of isophorone diisocyanate and polypropylene glycol quality sum.
In step 1, mixed solution is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 in baking oven
DEG C stand hydro-thermal reaction 6 hours.
In step 2, prepolymerization reaction temperature, time are 50 DEG C and first react 20min, 60 ~ 70 DEG C of the reaction was continued 1 ~ 2h.
In step 2, the chain extending reaction temperature that the double hydroxymethyl propionic acids of hydrophilic chain extender are added is 80 DEG C, the reaction time is 1.5 ~
2.5h。
In step 2, the chain extending reaction temperature that carbon quantum dot is added is 80 DEG C, and the reaction time is 1 ~ 2h.
In step 2, the solvent for dispersing carbon quantum dot is dimethyl sub-maple, acetone or N-Methyl pyrrolidone.
The modified aqueous polyurethane nano composite material of the carbon quantum dot as made from preparation method can be used for coating, anti-fake
The fields such as mark and Optical storage media.
Embodiment 1：
Step（1）：Carbon quantum dot（CQDs）Preparation
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution.Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 DEG C standing hydro-thermal reaction 6 hours in baking oven, from
It is so cooled to room temperature, the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group can be obtained, it then will dispersion
Liquid is centrifuged, dialysis treatment, obtains the carbon quantum dot with good shelf-stability（CQDs）Solution.Finally by acquired solution
The dry sample of similar polymer morphology can be obtained by freeze-drying.
Step（2）：Carbon quantum dot-aqueous polyurethane（CQDs-WPU）The preparation of nanocomposite
By 40mmol isophorone diisocyanate（IPDI）, 10mmol polypropylene glycol（PPG）, 2 drop dibutyl tin dilaurates
（DBTDL）, 4.22mmol small molecule chain extender 1,4- butanediol（BDO）It is added to equipped with thermometer, blender, glass bottle stopper
It in three-necked flask, is uniformly mixed, is warming up to 50 DEG C and first reacts 20min, then base polyurethane prepolymer for use as is made in 60 DEG C of the reaction was continued 2h.
Then the bis- hydroxymethyl propionic acids of 8.42mmol are added（DMPA）The step of being warming up to 80 DEG C and carry out reaction 1.5h, be then added 0.05%
（1）The fluorescent carbon quantum dot of middle preparation（It is scattered in acetone）As chain extender, 80 DEG C continue chain extending reaction 1h.Finally will
Product obtained is neutralized, emulsifies to obtain carbon quantum dot-aqueous polyurethane（CQDs-WPU）Fluorescent emulsion.
Embodiment 2：
Step（1）：Carbon quantum dot（CQDs）Preparation
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution.Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in baking oven 160 DEG C after standing hydro-thermal reaction 6 hours,
The fluorescent carbon quantum dot dispersion liquid that surface has amino and hydroxyl group can be obtained in cooled to room temperature, then will dispersion
Liquid is centrifuged, dialysis treatment, obtains the carbon quantum dot with good shelf-stability（CQDs）Solution.Finally by acquired solution
The dry sample of similar polymer morphology can be obtained by freeze-drying.
Step（2）：Carbon quantum dot-aqueous polyurethane（CQDs-WPU）The preparation of nanocomposite
By 40mmol isophorone diisocyanate（IPDI）, 13mmol polypropylene glycol（PPG）, 2 drop dibutyl tin dilaurates
（DBTDL）, 3.28mmol small molecule chain extender 1,4- butanediol（BDO）It is added to equipped with thermometer, blender, glass bottle stopper
It in three-necked flask, is uniformly mixed, is warming up to 50 DEG C and first reacts 20min, then base polyurethane prepolymer for use as is made in 70 DEG C of the reaction was continued 1h.
Then the bis- hydroxymethyl propionic acids of 8.28mmol are added（DMPA）The step of being warming up to 80 DEG C and carry out reaction 2.5h, be then added 0.15%
（1）The fluorescent carbon quantum dot of middle preparation（It is scattered in dimethyl sulfoxide）As chain extender, 80 DEG C continue chain extending reaction
1.5h.Finally product obtained is neutralized, emulsifies to obtain carbon quantum dot-aqueous polyurethane（CQDs-WPU）Fluorescent emulsion.
Fig. 3 is the Waterborne Polyurethane Prepolymer that embodiment 2 obtains（PPU）With carbon quantum dot-Waterborne Polyurethane Prepolymer
（CQDs-PPU）Infrared figure, it can be seen that different quality containing carbon quantum dot be added after, be located at 2263cm-1Neighbouring isocyanic acid
The strong absworption peak of ester group obviously weakens, and illustrates remaining isocyanate functional group in amino group and hydroxyl group and performed polymer
Addition reaction has occurred.When the carbon quantum dot of addition is more, the absorption peak of isocyanate groups obviously weakens, this froms the perspective of from side
Amino existing for carbon quantum dot surface is illustrated and hydroxyl group takes part in reaction, it was confirmed that carbon quantum dot is the formation with chemical bond
It is combined to inside polyurethane matrix.
Fig. 4 is carbon quantum dot-aqueous polyurethane that embodiment 2 obtains（CQDs-WPU）The transparent appearance photo of film, explanation
Carbon quantum dot-aqueous polyurethane of this patent preparation（CQDs-WPU）Film remains the transparency of original aqueous polyurethane film, this
It is due to caused by the quantum size of carbon quantum dot and the good compatibility with polyurethane substrates.
Fig. 5 is the carbon quantum dot that embodiment 2 obtains（CQDs）With carbon quantum dot-aqueous polyurethane（CQDs-WPU）Film is certainly
Photo under right light and ultraviolet lamp, it can be seen that in the UV lamp, aqueous polyurethane film can also be observed that and carbon amounts for carbon quantum dot-
Son puts similar color change.
Embodiment 3：
Step（1）：Carbon quantum dot（CQDs）Preparation
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution.Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 DEG C standing hydro-thermal reaction 6 hours in baking oven, from
It is so cooled to room temperature, the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group can be obtained, it then will dispersion
Liquid is centrifuged, dialysis treatment, obtains the carbon quantum dot with good shelf-stability（CQDs）Solution.Finally by acquired solution
The dry sample of similar polymer morphology can be obtained by freeze-drying.
Step（2）：Carbon quantum dot-aqueous polyurethane（CQDs-WPU）The preparation of nanocomposite
By 40mmol isophorone diisocyanate（IPDI）, 8mmol polypropylene glycol（PPG）, 3 drop dibutyl tin dilaurates
（DBTDL）, 3.75mmol small molecule chain extender 1,4- butanediol（BDO）It is added to equipped with thermometer, blender, glass bottle stopper
It in three-necked flask, is uniformly mixed, is warming up to 50 DEG C and first reacts 20min, then polyurethane prepolymer is made in 60 DEG C of the reaction was continued 1.5h
Body.Then the bis- hydroxymethyl propionic acids of 8.81mmol are added（DMPA）The step of being warming up to 80 DEG C and carry out reaction 2h, be then added 0.25%
（1）The fluorescent carbon quantum dot of middle preparation（It is scattered in N-Methyl pyrrolidone）As chain extender, 80 DEG C to continue chain extension anti-
Answer 2h.Finally product obtained is neutralized, emulsifies to obtain carbon quantum dot-aqueous polyurethane（CQDs-WPU）Fluorescent emulsion.
Embodiment 4：
Step（1）：Carbon quantum dot（CQDs）Preparation
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution.Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 DEG C standing hydro-thermal reaction 6 hours in baking oven, from
It is so cooled to room temperature, the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group can be obtained, it then will dispersion
Liquid is centrifuged, dialysis treatment, obtains the carbon quantum dot with good shelf-stability（CQDs）Solution.Finally by acquired solution
The dry sample of similar polymer morphology can be obtained by freeze-drying.
Step（2）：Carbon quantum dot-aqueous polyurethane（CQDs-WPU）The preparation of nanocomposite
By 40mmol isophorone diisocyanate（IPDI）, 11.4mmol polypropylene glycol（PPG）, 4 drop di lauric dibutyls
Tin（DBTDL）, 4.50mmol small molecule chain extender 1,4- butanediol（BDO）It is added to equipped with thermometer, blender, glass bottle stopper
Three-necked flask in, be uniformly mixed, be warming up to 50 DEG C and first react 20min, then it is pre- that polyurethane is made in 60 DEG C of the reaction was continued 1.5h
Aggressiveness.Then the bis- hydroxymethyl propionic acids of 9.08mmol are added（DMPA）It is warming up to 80 DEG C and carries out reaction 2.5h, be then added 0.15%
Step（1）The fluorescent carbon quantum dot of middle preparation（It is scattered in dimethyl sub-maple）As chain extender, 80 DEG C to continue chain extension anti-
Answer 1h.Finally product obtained is neutralized, emulsifies to obtain carbon quantum dot-aqueous polyurethane（CQDs-WPU）Fluorescent emulsion.
Embodiment 5：
Step（1）：Carbon quantum dot（CQDs）Preparation
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution.Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in 160 DEG C standing hydro-thermal reaction 6 hours in baking oven, from
It is so cooled to room temperature, the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group can be obtained, it then will dispersion
Liquid is centrifuged, dialysis treatment, obtains the carbon quantum dot with good shelf-stability（CQDs）Solution.Finally by acquired solution
The dry sample of similar polymer morphology can be obtained by freeze-drying.
Step（2）：Carbon quantum dot-aqueous polyurethane（CQDs-WPU）The preparation of nanocomposite
By 40mmol isophorone diisocyanate（IPDI）, 8.88mmol polypropylene glycol（PPG）, 2 drop di lauric dibutyls
Tin（DBTDL）, 3.94mmol small molecule chain extender 1,4- butanediol（BDO）It is added to equipped with thermometer, blender, glass bottle stopper
Three-necked flask in, be uniformly mixed, be warming up to 50 DEG C and first react 20min, then polyurethane prepolymer is made in 70 DEG C of the reaction was continued 1h
Body.Then the bis- hydroxymethyl propionic acids of 9.28mmol are added（DMPA）It is warming up to 80 DEG C and carries out reaction 2.5h, 0.25% step is then added
Suddenly（1）The fluorescent carbon quantum dot of middle preparation（It is scattered in acetone）As chain extender, 80 DEG C continue chain extending reaction 1.5h.Most
Product obtained is neutralized afterwards, emulsifies to obtain carbon quantum dot-aqueous polyurethane（CQDs-WPU）Fluorescent emulsion.
The contents of the present invention are not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, all are covered by the claims of the invention.
Claims (8)
1. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot, it is characterised in that：
It is realized by following steps：
The carbon quantum dot that active group amino and hydroxyl are contained in surface is prepared first, then utilizes amino, hydroxyl and aqueous poly- ammonia
The reaction of isocyanate group in ester performed polymer finally uses situ aggregation method, enables carbon quantum dot compound with aqueous polyurethane, thus
Prepare the modified aqueous polyurethane fluorescence nano composite material of carbon quantum dot.
2. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 1, special
Sign is：
Specific steps include：
Step 1：The preparation of carbon quantum dot：
2g citric acid and 1g urea are added in 50mL distilled water, obtain clear solution after completely dissolution；Then it will mix molten
Liquid is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, is placed in baking oven and is stood hydro-thermal reaction, and room is naturally cooled to
Temperature obtains the Water-soluble carbon quantum dot dispersion liquid that surface has amino and hydroxyl group, is then centrifuged dispersion liquid, dialyses
Processing, obtains the carbon quantum dot solution with good shelf-stability；Finally acquired solution is birdsed of the same feather flock together by freeze-drying
The dry-eye disease of polymers morphology；
Step 2：The preparation of carbon quantum dot-aqueous polyurethane nano composite material：
Isophorone diisocyanate, polypropylene glycol, dibutyl tin dilaurate, small molecule chain extender 1,4- butanediol are added
To being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, it is uniformly mixed, base polyurethane prepolymer for use as is made in temperature reaction；It is different
The molar ratio of isophorone diisocyanate and polypropylene glycol is 3 ~ 5, and dibutyl tin dilaurate amount is 2 ~ 4 drops, 1,4-butanediol
Amount be the 2% of isophorone diisocyanate and polypropylene glycol quality sum；
Then the double hydroxymethyl propionic acids heatings of hydrophilic chain extender are added and carry out chain extending reactions, be then added be scattered in solvent by step
The carbon quantum dot prepared in rapid 1, continues chain extending reaction；Finally product obtained is neutralized, emulsifies to obtain carbon quantum
Point-aqueous polyurethane fluorescent emulsion；The amount of double hydroxymethyl propionic acids is isophorone diisocyanate and polypropylene glycol quality sum
3% ~ 7%, the amount of carbon quantum dot is the 0.05% ~ 0.25% of isophorone diisocyanate and polypropylene glycol quality sum.
3. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 2, special
Sign is：
In step 1, mixed solution is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, be placed in baking oven 160 DEG C it is quiet
Set hydro-thermal reaction 6 hours.
4. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 2, special
Sign is：
In step 2, prepolymerization reaction temperature, time are 50 DEG C and first react 20min, 60 ~ 70 DEG C of the reaction was continued 1 ~ 2h.
5. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 2, special
Sign is：
In step 2, the chain extending reaction temperature that the double hydroxymethyl propionic acids of hydrophilic chain extender are added is 80 DEG C, the reaction time is 1.5 ~
2.5h。
6. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 2, special
Sign is：
In step 2, the chain extending reaction temperature that carbon quantum dot is added is 80 DEG C, and the reaction time is 1 ~ 2h.
7. the preparation method of the modified aqueous polyurethane nano composite material of carbon quantum dot according to claim 2, special
Sign is：
In step 2, the solvent for dispersing carbon quantum dot is dimethyl sub-maple, acetone or N-Methyl pyrrolidone.
8. the modified aqueous polyurethane nano composite material of carbon quantum dot made from preparation method as claimed in claim 1 or 2.
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Application publication date: 20181116 |