CN110183844A - A kind of amination graphene enhancing aqueous polyurethane and preparation method thereof - Google Patents
A kind of amination graphene enhancing aqueous polyurethane and preparation method thereof Download PDFInfo
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- 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
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- 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
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- 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 aqueous polyurethane technical field, a kind of amination graphene enhancing aqueous polyurethane and preparation method thereof is provided.The following steps are included: (1) mixes isophorone diisocyanate, polytetrahydrofuran diol and 1,4-butanediol, reaction obtains reaction mixture 1；(2) dihydromethyl propionic acid is added into reaction mixture 1, reaction obtains reaction mixture 2；(3) triethylamine is added into reaction mixture 2, reaction obtains reaction mixture 3；(4) add the aqueous dispersions of amination graphene to carry out secondary chain extension into reaction mixture 3, obtain amination graphene enhancing aqueous polyurethane.Amination graphene of the present invention enhances aqueous polyurethane, shows good mechanical property, hydrophobic performance and certain electric conductivity, can be used as functional coating material and membrane material, there is good application prospect.
Description
Technical field
The present invention relates to aqueous polyurethane technical field, in particular to a kind of amination graphene enhancing aqueous polyurethane and
Preparation method.
Background technique
With the raising of health of people and environmental consciousness, aqueous polyurethane (WPU) is due to its feature of environmental protection and good synthesis
Performance is increasingly becoming the important replacement of various solvent-based polyurethanes in industrial production.
Currently, outer emulsion process and the preparation of internal emulsification method can be used in aqueous polyurethane.Outer emulsion process is to add emulsifier outside
Under the conditions of by high shear force by polyurethane forced emulsification Yu Shuizhong, the WPU particle diameter of this method preparation is coarse, stability compared with
Difference seldom uses this preparation method at present both at home and abroad.Internal emulsification method refers to, will during this of performed polymer synthesis
Group with hydrophilic interaction is introduced on the main chain of PU, so that PU segment itself is had hydrophily using hydrophilic radical, is then existed
It shears under external force, is distributed to formation WPU lotion in water.The method of this internal emulsification method production WPU lotion, it is available steady
Qualitative good and excellent mechanical performance PU is the common method of current production WPU.
The characteristics of according to aqueous polyurethane synthetic method, internal emulsification method mainly include following several synthesis technologies.
(1) pre-polymer process
Pre-polymer process, which refers to, first introduces hydrophilic radical in synthesis of polyurethane performed polymer, in not solubilizer or is added very
Carry out neutralization emulsification under conditions of few solvent, emulsification while adds chain extension after chain extender carries out, and finally obtains WPU resin.
This synthesis technology has the advantages that the solvent used is few, can generate the macromolecular of branching.
(2) acetone method
Acetone method refers to during synthesizing performed polymer, dilutes polyurethane using more organic solvent, prevents viscosity
Cause very much emulsification difficult greatly, then plus water is emulsified, form WPU, finally again by the solvent in WPU lotion steam from.And acetone
As most common organic solvent, so also referred to as acetone method.The Property of Waterborne Polyurethane of method synthesis is stablized, reproducible, but
It is to have used a large amount of solvent, can cause environmental pollution.
(3) dispersion method is melted
Melting dispersion method refers to biuret groups of the synthesis containing hydrophilic group or end urea groups urethane oligomer, is then melted
Melt, be directly emulsifiable in water under mechanical stirring, carries out chain extending reaction with formaldehyde again while emulsification.Entire reaction is without molten
Agent, but maintain the temperature of synthetic reaction process higher, and obtained PU molecular weight is lower.
(4) ketimine
Ketimine refers to replaces binary primary amine to carry out in pre-polymer process with ketimide or ketazine
Chain extension afterwards.Ketimide/ketazine is a kind of Diamines chain extender of sealing end, and what diamines during the reaction can be stable unlocks
Come, chain extending reaction can be made smoothly to carry out.So having with aqueous polyurethane prepared by the method, functional, partial size is more equal
The high feature of uniform stability of emulsion.
(5) end group emulsion process is protected
Protection end group emulsion process refers to and is closed isocyanate groups in the prepress sealer of performed polymer emulsification, then into
Aqueous polyurethane is prepared in row emulsification.This aqueous polyurethane can make closed isocyanide in use, by heating
Acid esters group, which unlocks, to be come, these isocyanate groups can react with water or other crosslinking agents, and forming properties are excellent
Polyurethane material.The key of this preparation method is to select sealing effect good and the deblocking suitable sealer of temperature.
But thermal stability, water resistance and the mechanical property of WPU are still below solvent borne polyurethane, to be improved.Total comes
It says, the addition of nanoparticle is one of the effective ways for changing and improving WPU performance.In recent years, graphite nano plate is increasingly becoming
Prepare high intensity, hydrophobicity, electric conductivity WPU composite material research hotspot.But existing method is to pass through physical mixed
Mode graphite and WPU are carried out compound, the material mechanical performance and electric conductivity being mixed to get are unable to reach satisfied degree.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide a kind of amination graphene enhancing aqueous polyurethane and its
Preparation method, amination graphene enhancing aqueous polyurethane show good mechanical property, hydrophobic performance and certain conduction
Property.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of amination graphene enhancing aqueous polyurethane, comprising the following steps:
(1) isophorone diisocyanate, polytetrahydrofuran diol and 1,4-butanediol are mixed, it is mixed that reaction obtains reaction
Close object 1；
(2) dihydromethyl propionic acid is added into reaction mixture 1, reaction obtains reaction mixture 2；
(3) triethylamine is added into reaction mixture 2, reaction obtains reaction mixture 3；
(4) add the aqueous dispersions of amination graphene to carry out secondary chain extension into reaction mixture 3, obtain amino graphite
Alkene enhances aqueous polyurethane.
Preferably, according to mass fraction meter, each raw material dosage are as follows: 10~15 parts of isophorone diisocyanate, poly- tetrahydro
20~30 parts of furans glycol, 0.5~1 part of 1,4-butanediol, 1.5~2.5 parts of dihydromethyl propionic acid, 1~1.5 part of triethylamine, Gu
30~35 parts of aqueous dispersions of the amination graphene that content is 0.5%~1.5%.
Preferably, in step (1), reaction temperature is 75~95 DEG C, and the reaction time is 30~45min.
Preferably, in step (2), reaction temperature is 75~95 DEG C, and the reaction time is 20~30min.
Preferably, in step (3), reaction temperature is 50~60 DEG C, and the reaction time is 15~20min.
Preferably, in step (4), reaction temperature is 30~35 DEG C.
Preferably, amination graphene aqueous dispersions the preparation method is as follows:
1) it adds graphene oxide into water, ultrasonic disperse obtains graphene oxide water solution；
2) 1,10- diamino decane is dissolved in ethyl alcohol, addition graphene oxide water solution, back flow reaction 18~for 24 hours；
3) reaction mixture sat for obtaining step 2), the dispersion liquid for taking lower layer to contain solid component, centrifuge separation are washed
It washs, it is dry, product amination graphene is obtained, is diluted with water to obtain amination graphene aqueous dispersions.
Further, in terms of mass fraction, amination graphene aqueous dispersions prepare raw material dosage are as follows: graphene oxide
0.2~0.3 part, 1,10- 0.4~0.6 part of diamino decane.
Aqueous polyurethane is enhanced using the amination graphene that the preparation method obtains.
Preferably, the tensile strength and elongation at break to form a film is respectively 43.47MPa and 529.74%, water contact angle
It is 118.29 °, conductivity is 1.54 × 10-4S·m-1。
Compared with prior art, the invention has the following beneficial technical effects:
Amino fossil is prepared using amination graphene as secondary chain extension agent using pre-polymer process in the present invention
Black alkene enhances aqueous polyurethane.Amination graphene of the invention is connect in a manner of chemical bond in aqueous polyurethane amino
On, cross-linked structure is formed, graphene dispersion, relative to existing physical mixed, improves inside aqueous polyurethane network structure
The mechanical property of material, meanwhile, graphene specific surface area is bigger, and electric conductivity is more preferable.Gained amination graphene of the invention increases
The tensile strength and elongation at break of strong aqueous polyurethane film forming are respectively 43.47MPa and 529.74%, and water contact angle is
118.29 °, conductivity is 1.54 × 10-4S·m-1, show good mechanical property, hydrophobic performance and certain electric conductivity,
It can be used as functional coating material and membrane material, there is good application prospect.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 10~15 parts of different Buddhists are added into the three-necked flask equipped with mechanical agitator and condenser
That ketone diisocyanate (IPDI), 20~30 parts of polytetrahydrofuran diols (PTMG2000) and 0.5~1 part of 1,4- butanediol
(BDO), it is stirred to react 30~45min under conditions of 75 DEG C~95 DEG C, obtains reaction mixture 1；
(2) 1.5~2.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, in 75 DEG C~95 DEG C of condition
Under be stirred to react 20~30min, obtain reaction mixture 2；
(3) reaction mixture 2 is cooled to 50~60 DEG C, 1~1.5 part of triethylamine (TEA) is added, react 15~20min,
Obtain reaction mixture 3；
(4) reaction mixture 3 is cooled to 30~35 DEG C, adding 30~35 parts of solid contents is 0.5%~1.5% amination
The aqueous dispersions of graphene (AG) carry out secondary chain extension, and it is aqueous poly- to obtain the amination graphene enhancing that solid content is 25~35%
Urethane.
The amination graphene (AG) the preparation method is as follows: (1) in terms of mass fraction, by 100~150 parts of deionizations
Water is put into the three-neck flask equipped with condenser, adds 0.2~0.3 part of graphene oxide, then is surpassed under conditions of 20~25 DEG C
20~30min of sonication；(2) 0.4~0.6 part of 1,10- diamino decane (DMDC) is dissolved in 100~150 parts of ethanol solutions,
Above-mentioned reactant is added, the back flow reaction 18~for 24 hours under the conditions of 90 DEG C；(3) above-mentioned reactant is poured into and stands 1~2 in beaker
It, takes lower layer to contain the dispersion liquid of solid part, is centrifugated and with ethyl alcohol lotion 20 times；(4) after being centrifugated again, acquisition
Solid is 3 hours dry under vacuum under conditions of 80 DEG C, obtains product AG, being diluted with water as solid content is 0.5%~1.5%
The aqueous dispersions of AG.
Embodiment 1
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 100 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.2 part of graphene oxide is added, is ultrasonically treated 20min under conditions of 20 DEG C；(2) by 0.4 part
1,10- diamino decane (DMDC) is dissolved in 100 parts of ethanol solutions, and above-mentioned reactant is added, back flow reaction under the conditions of 90 DEG C
18h；(3) above-mentioned reactant is poured into beaker and stands 1 day, taken lower layer to contain the dispersion liquid of solid part, be centrifugated and use second
Alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, obtains product
AG is diluted with water the aqueous dispersions for the AG for being 0.5% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 10 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 20 parts of polytetrahydrofuran diols (PTMG2000) and 0.5 part of 1,4-butanediol (BDO), at 75 DEG C
Under the conditions of be stirred to react 30min, obtain reaction mixture 1；
(2) 1.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 75 DEG C
20min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 50 DEG C, 1 part of triethylamine (TEA) is added, react 15min, obtain reaction mixing
Object 3；
(4) reaction mixture 3 is cooled to 30 DEG C, adding 30 parts of solid contents is the water of 0.5% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 25% enhances aqueous polyurethane.
Embodiment 2
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 130 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.25 part of graphene oxide is added, is ultrasonically treated 22min under conditions of 25 DEG C；(2) by 0.45
Part 1,10- diamino decane (DMDC) is dissolved in 110 parts of ethanol solutions, and above-mentioned reactant is added, and is flowed back under the conditions of 90 DEG C anti-
Answer 20h；(3) above-mentioned reactant is poured into beaker and stands 2 days, lower layer is taken to contain the dispersion liquid of solid part, centrifuge separation is used in combination
Ethyl alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, is produced
Object AG is diluted with water the aqueous dispersions for the AG for being 0.8% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 12 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 22 parts of polytetrahydrofuran diols (PTMG2000) and 0.6 part of 1,4-butanediol (BDO), at 80 DEG C
Under the conditions of be stirred to react 35min, obtain reaction mixture 1；
(2) 2 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 80 DEG C
25min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 55 DEG C, 1 part of triethylamine (TEA) is added, react 18min, obtain reaction mixing
Object 3；
(4) reaction mixture 3 is cooled to 35 DEG C, adding 30 parts of solid contents is the water of 0.8% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 30% enhances aqueous polyurethane.
Embodiment 3
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 140 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.3 part of graphene oxide is added, is ultrasonically treated 25min under conditions of 20 DEG C；(2) by 0.7 part
1,10- diamino decane (DMDC) is dissolved in 120 parts of ethanol solutions, and above-mentioned reactant is added, back flow reaction under the conditions of 90 DEG C
22h；(3) above-mentioned reactant is poured into beaker and stands 2 days, taken lower layer to contain the dispersion liquid of solid part, be centrifugated and use second
Alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, obtains product
AG is diluted with water the aqueous dispersions for the AG for being 1% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 13 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 24 parts of polytetrahydrofuran diols (PTMG2000) and 0.5 part of 1,4-butanediol (BDO), at 85 DEG C
Under the conditions of be stirred to react 30min, obtain reaction mixture 1；
(2) 1.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 85 DEG C
20min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 50 DEG C, 1.5 parts of triethylamines (TEA) is added, react 15min, it is mixed to obtain reaction
Close object 3；
(4) reaction mixture 3 is cooled to 37 DEG C, adding 35 parts of solid contents is the moisture of 1% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 30% enhances aqueous polyurethane.
Embodiment 4
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 150 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.2 part of graphene oxide is added, is ultrasonically treated 25min under conditions of 25 DEG C；(2) by 0.6 part
1,10- diamino decane (DMDC) is dissolved in 140 parts of ethanol solutions, and above-mentioned reactant is added, back flow reaction under the conditions of 90 DEG C
23h；(3) above-mentioned reactant is poured into beaker and stands 1 day, taken lower layer to contain the dispersion liquid of solid part, be centrifugated and use second
Alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, obtains product
AG is diluted with water the aqueous dispersions for the AG for being 0.5% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 14 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 26 parts of polytetrahydrofuran diols (PTMG2000) and 0.8 part of 1,4-butanediol (BDO), at 90 DEG C
Under the conditions of be stirred to react 40min, obtain reaction mixture 1；
(2) 2.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 90 DEG C
20min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 50 DEG C, 1.2 parts of triethylamines (TEA) is added, react 20min, it is mixed to obtain reaction
Close object 3；
(4) reaction mixture 3 is cooled to 35 DEG C, adding 33 parts of solid contents is the water of 0.5% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 28% enhances aqueous polyurethane.
Embodiment 5
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 120 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.3 part of graphene oxide is added, is ultrasonically treated 30min under conditions of 23 DEG C；(2) by 0.55
Part 1,10- diamino decane (DMDC) is dissolved in 150 parts of ethanol solutions, and above-mentioned reactant is added, and is flowed back under the conditions of 90 DEG C anti-
It should for 24 hours；(3) above-mentioned reactant is poured into and stands 15h in beaker, lower layer is taken to contain the dispersion liquid of solid part, centrifuge separation is used in combination
Ethyl alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, is produced
Object AG is diluted with water the aqueous dispersions for the AG for being 1.5% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 15 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 28 parts of polytetrahydrofuran diols (PTMG2000) and 1 part of 1,4-butanediol (BDO), in 95 DEG C of item
It is stirred to react 30min under part, obtains reaction mixture 1；
(2) 1.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 75 DEG C
30min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 60 DEG C, 1 part of triethylamine (TEA) is added, react 15min, obtain reaction mixing
Object 3；
(4) reaction mixture 3 is cooled to 30 DEG C, adding 32 parts of solid contents is the water of 1.5% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 27% enhances aqueous polyurethane.
Embodiment 6
Amination graphene the preparation method is as follows: (1) in terms of mass fraction, 100 parts of deionized waters are put into equipped with cold
In the three-neck flask of condenser, 0.2 part of graphene oxide is added, is ultrasonically treated 20min under conditions of 20 DEG C；(2) by 0.4 part
1,10- diamino decane (DMDC) is dissolved in 100 parts of ethanol solutions, and above-mentioned reactant is added, back flow reaction under the conditions of 90 DEG C
18h；(3) above-mentioned reactant is poured into beaker and stands 1 day, taken lower layer to contain the dispersion liquid of solid part, be centrifugated and use second
Alcohol lotion 20 times；(4) after being centrifugated again, the solid of acquisition is 3 hours dry under vacuum under conditions of 80 DEG C, obtains product
AG is diluted with water the aqueous dispersions for the AG for being 0.5% for solid content.
The preparation method of amination graphene enhancing aqueous polyurethane of the present invention, comprising the following steps:
(1) based on parts by weight, 10 parts of isophorones are added into the three-necked flask equipped with mechanical agitator and condenser
Diisocyanate (IPDI), 30 parts of polytetrahydrofuran diols (PTMG2000) and 0.5 part of 1,4-butanediol (BDO), at 75 DEG C
Under the conditions of be stirred to react 45min, obtain reaction mixture 1；
(2) 1.5 parts of dihydromethyl propionic acids (DMPA) are added into reaction mixture 1, are stirred to react under conditions of 75 DEG C
20min obtains reaction mixture 2；
(3) reaction mixture 2 is cooled to 50 DEG C, 1 part of triethylamine (TEA) is added, react 15min, obtain reaction mixing
Object 3；
(4) reaction mixture 3 is cooled to 30 DEG C, adding 30 parts of solid contents is the water of 0.5% amination graphene (AG)
Dispersion liquid carries out secondary chain extension, and obtaining the amination graphene that solid content is 32% enhances aqueous polyurethane.
The product of embodiment 1 is tested for the property, the results show that the tensile strength of its film forming and elongation at break difference
For 43.47MPa and 529.74%, water contact angle is 118.29 °, and conductivity is 1.54 × 10-4S·m-1.Illustrate preparation of the present invention
Amination graphene enhancing aqueous polyurethane have good mechanical property, hydrophobic performance and certain electric conductivity.
Claims (10)
1. a kind of preparation method of amination graphene enhancing aqueous polyurethane, which comprises the following steps:
(1) isophorone diisocyanate, polytetrahydrofuran diol and 1,4-butanediol are mixed, reaction obtains reaction mixture
1；
(2) dihydromethyl propionic acid is added into reaction mixture 1, reaction obtains reaction mixture 2；
(3) triethylamine is added into reaction mixture 2, reaction obtains reaction mixture 3；
(4) add the aqueous dispersions of amination graphene to carry out secondary chain extension into reaction mixture 3, obtain amination graphene increasing
Strong aqueous polyurethane.
2. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 1, which is characterized in that according to
Mass fraction meter, each raw material dosage are as follows: 10~15 parts of isophorone diisocyanate, 20~30 parts of polytetrahydrofuran diol, 1,
0.5~1 part of 4- butanediol, 1.5~2.5 parts of dihydromethyl propionic acid, 1~1.5 part of triethylamine, solid content is 0.5%~1.5%
30~35 parts of the aqueous dispersions of amination graphene.
3. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 1, which is characterized in that step
(1) in, reaction temperature is 75~95 DEG C, and the reaction time is 30~45min.
4. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 1, which is characterized in that step
(2) in, reaction temperature is 75~95 DEG C, and the reaction time is 20~30min.
5. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 1, which is characterized in that step
(3) in, reaction temperature is 50~60 DEG C, and the reaction time is 15~20min.
6. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 1, which is characterized in that step
(4) in, reaction temperature is 30~35 DEG C.
7. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 3, which is characterized in that amino
Graphite alkene aqueous dispersions the preparation method is as follows:
1) it adds graphene oxide into water, ultrasonic disperse obtains graphene oxide water solution；
2) 1,10- diamino decane is dissolved in ethyl alcohol, addition graphene oxide water solution, back flow reaction 18~for 24 hours；
3) reaction mixture sat for obtaining step 2), the dispersion liquid for taking lower layer to contain solid component are centrifugated, washing,
It is dry, product amination graphene is obtained, is diluted with water to obtain amination graphene aqueous dispersions.
8. the preparation method of amination graphene enhancing aqueous polyurethane according to claim 7, which is characterized in that with matter
Number meter is measured, amination graphene aqueous dispersions prepare raw material dosage are as follows: 0.2~0.3 part of graphene oxide, 1,10- diamino
0.4~0.6 part of decane.
9. the amination graphene enhancing aqueous polyurethane obtained using the described in any item preparation methods of claim 1-8.
10. amination graphene according to claim 9 enhances aqueous polyurethane, which is characterized in that its stretching to form a film
Intensity and elongation at break are respectively 43.47MPa and 529.74%, and water contact angle is 118.29 °, and conductivity is 1.54 × 10- 4S·m-1。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643272A (en) * | 2019-11-08 | 2020-01-03 | 陕西科技大学 | Graphene oxide modified waterborne polyurethane heat-conducting flame-retardant antistatic coating film-forming agent and preparation method thereof |
| CN113736053A (en) * | 2021-08-24 | 2021-12-03 | 华南理工大学 | Functional waterborne polyurethane material and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2362459A1 (en) * | 2010-02-24 | 2011-08-31 | University College Cork-National University of Ireland, Cork | Modified graphene structure and method of manufacture thereof |
| CN102304274A (en) * | 2011-06-22 | 2012-01-04 | 同济大学 | Preparation method of multidimensional hybrid composite of glass fibre/ grapheme- carbon nano tube/ epoxy resin |
| CN103466610A (en) * | 2013-09-25 | 2013-12-25 | 中国科学院理化技术研究所 | Graphene chemical modification method |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN103861472A (en) * | 2014-03-28 | 2014-06-18 | 东华大学 | Preparation method of amino-modified graphene oxide composite positive permeable film |
| CN104368384A (en) * | 2014-09-29 | 2015-02-25 | 常州大学 | Preparation method of organic diamine-modified graphene oxide solid catalyst |
| CN104497385A (en) * | 2014-11-05 | 2015-04-08 | 中国石油天然气集团公司 | Aminated graphene oxide/high-density polyethylane nano composite membrane and preparation method thereof |
| CN104650322A (en) * | 2015-02-18 | 2015-05-27 | 中国科学院长春应用化学研究所 | Preparation method of carbon-dioxide-base polyurea high polymer material |
| CN105019052A (en) * | 2015-06-29 | 2015-11-04 | 浙江华峰氨纶股份有限公司 | Preparation method of high performance polyurethane elastic fiber |
| CN106120375A (en) * | 2016-06-27 | 2016-11-16 | 苏州聚福环保科技有限公司 | A kind of environment-friendlytype type fabric printing and dyeing ink and preparation method thereof |
| CN108178827A (en) * | 2017-12-28 | 2018-06-19 | 山东诺威聚氨酯股份有限公司 | Antistatic urethane elastomer and preparation method thereof |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
| CN108587437A (en) * | 2018-05-11 | 2018-09-28 | 嘉兴烯成新材料有限公司 | A kind of graphene and organic fluorinated silicone aqueous polyurethane complex emulsions and preparation method thereof |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
-
2019
- 2019-05-30 CN CN201910464777.6A patent/CN110183844A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2362459A1 (en) * | 2010-02-24 | 2011-08-31 | University College Cork-National University of Ireland, Cork | Modified graphene structure and method of manufacture thereof |
| CN102304274A (en) * | 2011-06-22 | 2012-01-04 | 同济大学 | Preparation method of multidimensional hybrid composite of glass fibre/ grapheme- carbon nano tube/ epoxy resin |
| CN103466610A (en) * | 2013-09-25 | 2013-12-25 | 中国科学院理化技术研究所 | Graphene chemical modification method |
| CN103805046A (en) * | 2014-01-26 | 2014-05-21 | 陕西科技大学 | Graphene-containing waterborne polyurethane composite conductive coating prepared in situ and preparation method thereof |
| CN103861472A (en) * | 2014-03-28 | 2014-06-18 | 东华大学 | Preparation method of amino-modified graphene oxide composite positive permeable film |
| CN104368384A (en) * | 2014-09-29 | 2015-02-25 | 常州大学 | Preparation method of organic diamine-modified graphene oxide solid catalyst |
| CN104497385A (en) * | 2014-11-05 | 2015-04-08 | 中国石油天然气集团公司 | Aminated graphene oxide/high-density polyethylane nano composite membrane and preparation method thereof |
| CN104650322A (en) * | 2015-02-18 | 2015-05-27 | 中国科学院长春应用化学研究所 | Preparation method of carbon-dioxide-base polyurea high polymer material |
| CN105019052A (en) * | 2015-06-29 | 2015-11-04 | 浙江华峰氨纶股份有限公司 | Preparation method of high performance polyurethane elastic fiber |
| CN106120375A (en) * | 2016-06-27 | 2016-11-16 | 苏州聚福环保科技有限公司 | A kind of environment-friendlytype type fabric printing and dyeing ink and preparation method thereof |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
| CN108178827A (en) * | 2017-12-28 | 2018-06-19 | 山东诺威聚氨酯股份有限公司 | Antistatic urethane elastomer and preparation method thereof |
| CN108373149A (en) * | 2018-03-15 | 2018-08-07 | 常州恒利宝纳米新材料科技有限公司 | The preparation method of industrial amination graphene |
| CN108587437A (en) * | 2018-05-11 | 2018-09-28 | 嘉兴烯成新材料有限公司 | A kind of graphene and organic fluorinated silicone aqueous polyurethane complex emulsions and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李晓萱等: "氨基功能化石墨烯／水性聚氨酯", 《合肥工业大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110643272A (en) * | 2019-11-08 | 2020-01-03 | 陕西科技大学 | Graphene oxide modified waterborne polyurethane heat-conducting flame-retardant antistatic coating film-forming agent and preparation method thereof |
| CN110643272B (en) * | 2019-11-08 | 2022-03-01 | 陕西科技大学 | Graphene oxide modified waterborne polyurethane heat-conducting flame-retardant antistatic coating film-forming agent and preparation method thereof |
| CN113736053A (en) * | 2021-08-24 | 2021-12-03 | 华南理工大学 | Functional waterborne polyurethane material and preparation method thereof |
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