CN104004341A - Graphene oxide sulfonate type waterborne polyurethane composite material and preparation method thereof - Google Patents
Graphene oxide sulfonate type waterborne polyurethane composite material and preparation method thereof Download PDFInfo
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- CN104004341A CN104004341A CN201410222899.1A CN201410222899A CN104004341A CN 104004341 A CN104004341 A CN 104004341A CN 201410222899 A CN201410222899 A CN 201410222899A CN 104004341 A CN104004341 A CN 104004341A
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Abstract
The invention discloses a graphene oxide sulfonate type waterborne polyurethane composite material and a preparation method thereof. The preparation method comprises the following steps of (1) preparing graphite oxide by using an improved Hummers method; (2) dispersing the prepared graphite oxide into water to prepare an aqueous dispersion solution of graphene oxide; and (3) blending the aqueous dispersion solution of graphene oxide and a sulfonate type waterborne polyurethane emulsion to prepare the graphene oxide sulfonate type waterborne polyurethane composite. The two components in the graphene oxide sulfonate type waterborne polyurethane composite material prepared by the invention are relatively good in compatibility; and in addition, the thermal stability of sulfonate type waterborne polyurethane is improved through graphene oxide modification.
Description
Technical field
The preparation method who the present invention relates to a kind of graphene oxide sulfonate type Waterborne PU Composite, belongs to matrix material preparation field.
Background technology
Aqueous polyurethane refers to that urethane resin is water-soluble or is scattered in the binary colloidal state system forming in water.Aqueous polyurethane be take water to replace organic solvent as dispersion medium, not only have nontoxic, do not fire, free from environmental pollution, save the energy and the easy advantage such as processing, and there is good mechanical property, adhesiveproperties, wear-resistant and ageing-resistant performance etc., be widely used in the industries such as building, automobile, shoemaking and food product pack.
Conventionally, by introduce hydrophilic radical in polyurethane molecular, make polyurethane molecular chain there is certain wetting ability, thereby can be dispersed in water, make aqueous polyurethane dispersion.Most aqueous polyurethane is to using anionic group as hydrophilic radical, mainly comprises carboxylate ion and sulfonate ion.It is hydrophilic monomer that carboxylic acid type aqueous polyurethane often adopts dimethylol propionic acid (DMPA).Because DMPA is not soluble, reactive behavior is low, and need to carry out amine neutralization, so carboxylic acid type aqueous polyurethane exists containing organic solvent, long reaction time, amine neutralizing agent smell is heavy, solid content is lower, initial adhesive strength and the deficiency such as mechanics performance of latex film is poor.And sulfonate type aqueous polyurethane often adopts quadrol base ethyl sulfonic acid sodium (AAS), be hydrophilic monomer, its hydrophilic radical is strong acid and strong base salt, and ionic strength is high, and between latex particle, electrostatic repulsion is stronger, easily makes the aqueous polyurethane of high solids content.Due to without carrying out amine neutralization, the non-irritating ammonia taste of sulfonate type aqueous polyurethane discharges, and compares with carboxylic acid type aqueous polyurethane, and it has higher bonding strength, thermotolerance, water tolerance and solvent resistance etc.
Although sulfonate type aqueous polyurethane has better properties than carboxylic acid type aqueous polyurethane, than solvent borne polyurethane, its thermotolerance, solvent resistance and water tolerance etc. are all lower.At present, Aqueous Polyurethane Adhesives ubiquity the problem that thermotolerance is low.
Summary of the invention
The object of the invention is to first prepare the good graphite oxide of water dispersible, and it is peeled off in water and disperse to obtain stable graphene oxide aqueous dispersions, the graphene oxide aqueous dispersions p-sulfonic acid salt type aqueous polyurethane that recycling is prepared carries out modification, and a kind of graphene oxide sulfonate type Waterborne PU Composite and preparation method thereof is provided.
Object of the present invention is achieved through the following technical solutions:
A preparation method for graphene oxide sulfonate type Waterborne PU Composite, comprises the steps:
(1) in ice bath, Graphite Powder 99, SODIUMNITRATE and the vitriol oil are mixed, and be stirred to and mix, then slowly add potassium permanganate, under condition of ice bath, stirring reaction is 2～2.5 hours; Then under normal temperature, stir 36～48 hours; Slowly add distilled water to stir after 15min, add distilled water diluting, then add hydrogen peroxide to reduce remaining potassium permanganate and MnO
2; Finally use the above-mentioned reaction solution of deionized water repetitive scrubbing, until neutral, drying obtains graphite oxide; The mass ratio of described Graphite Powder 99, SODIUMNITRATE and potassium permanganate is 1:(0.8～1.2): (4～8), the addition of the vitriol oil is 40～50ml/g Graphite Powder 99; The addition of distilled water is 80～100ml/g Graphite Powder 99 for the first time;
(2) graphite oxide of preparation is dispersed in water, makes graphene oxide aqueous dispersions;
(3) graphene oxide aqueous dispersions and the blend of sulfonate type aqueous polyurethane emulsion are made to graphene oxide sulfonate type Waterborne PU Composite.
The described dispersion of step (2) is by graphite oxide and water mixing and stirring, and at 30 ℃ ultrasonic peeling off 1～2 hour, make graphene oxide aqueous dispersions.
The quality of the described graphite oxide of step (2) and the volume ratio scope of water are within the scope of 1～5mg/ml.
The described blending condition of step (3) is to stir 2～3 hours under 50 ℃ of conditions.
In the matrix material that step (3) makes, the content of graphene oxide is 1.0～5.0wt% of sulfonate type aqueous polyurethane solid.
Step (1) for the second time addition of distilled water is 50～80ml/g Graphite Powder 99; The concentration of described hydrogen peroxide is 30wt%, and addition is 10～15ml/g Graphite Powder 99.
After adding potassium permanganate described in step (1), react, condition of ice bath is controlled at below 5 ℃.
The present invention compared with prior art has following characteristics:
(1) the middle temperature reaction times that prepared by graphite oxide is longer, is 36～48 hours, is conducive to the raising of its degree of oxidation;
(2) graphene oxide has good water dispersible;
(3) dispersiveness of graphene oxide in sulfonate type aqueous polyurethane is better;
(4) Aqueous Polyurethane Adhesives of graphene oxide modification has higher thermotolerance.
Accompanying drawing explanation
Fig. 1 is the XRD figure of graphite oxide in embodiment 1: in figure, the diffraction peak at ° place, left and right, 2 θ=10.9 is corresponding to the diffraction peak of graphite oxide.
Fig. 2 is the truncation surface SEM figure of graphene oxide aqueous polyurethane composite gel film in embodiment 1: in figure, have no bulk or sheet structure, show that graphene oxide is evenly dispersed in sulfonate type aqueous polyurethane matrix.
Fig. 3, Fig. 4 and Fig. 5 are respectively the thermogravimetric analysis figure of graphene oxide modified sulphonate type aqueous polyurethane and unmodified sulfonate type aqueous polyurethane (pure WPU) in embodiment 1, embodiment 2 and embodiment 3.From heat decomposition curve, the sulfonate type aqueous polyurethane of graphene oxide modification is better than the thermotolerance of water-based urethane, i.e. graphene oxide modification has improved the thermostability of sulfonate type aqueous polyurethane.
Embodiment
Following examples are used for explanation of the present invention, but the present invention is not restricted to this, and the Parameter Conditions that the present invention is not dated especially, can carry out with reference to routine techniques.
Embodiment 1
1, the preparation of graphite oxide: in ice bath, the primary Graphite Powder 99 of 4g, 4.8g SODIUMNITRATE and the 160ml vitriol oil are mixed, and stir 15min and fully mix guaranteeing, then slowly add 16g potassium permanganate, continue under condition of ice bath stirring reaction 2 hours.Then under normal temperature, stir 36 hours.Slowly add 320ml distilled water, stir 15min, after add 320ml distilled water diluting, then add the hydrogen peroxide of 40ml30wt% to reduce remaining potassium permanganate and MnO
2, finally use the above-mentioned reaction solution of deionized water repetitive scrubbing, until neutral, drying obtains graphite oxide.
2, the preparation of 1mg/ml graphene oxide aqueous dispersions: get the graphite oxide that 0.25g makes and join mixing and stirring in 250ml water, and at 30 ℃ ultrasonic peeling off 1 hour, obtain the graphene oxide aqueous dispersions of 1mg/ml.
3, graphene oxide content is the preparation of graphene oxide/Waterborne PU Composite of the 1.0wt% that divides of sulfonate type aqueous polyurethane solid: the graphene oxide aqueous dispersions 250ml that gets 50g solid content and be preparation in 50% sulfonate type aqueous polyurethane emulsion and step 2 pours in four-hole boiling flask, under 50 ℃ of conditions, stir 2 hours, obtain graphene oxide/sulfonate type aqueous polyurethane mixture.By the graphene oxide sulfonate type aqueous polyurethane mixture casting film-forming on polyfluortetraethylene plate obtaining, Air drying 7 days is then dried 24 hours in 60 ℃ of vacuum drying ovens, standby.
Embodiment 2
1, the preparation of graphite oxide: in ice bath, the primary Graphite Powder 99 of 5g, 4g SODIUMNITRATE and the 225ml vitriol oil are mixed, and stir 20min and fully mix guaranteeing, then slowly add 30g potassium permanganate, continue under condition of ice bath stirring reaction 2.5 hours.Then under normal temperature, stir 42 hours.Slowly add 450ml distilled water, stir 15min, after add 350ml distilled water diluting, then add the hydrogen peroxide of 60ml30wt% to reduce remaining potassium permanganate and MnO
2, finally use the above-mentioned reaction solution of deionized water repetitive scrubbing, until neutral, drying obtains graphite oxide.
2, the preparation of 3mg/ml graphene oxide aqueous dispersions: get the graphite oxide that 0.75g makes and join mixing and stirring in 250ml water, ultrasonic peeling off 1.5 hours at 30 ℃, obtains the graphene oxide aqueous dispersions of 3mg/ml.
3, graphene oxide content is the preparation of graphene oxide/Waterborne PU Composite of the 3.0wt% that divides of sulfonate type aqueous polyurethane solid: the graphene oxide aqueous dispersions 250ml that gets 50g solid content and be preparation in 50% sulfonate type aqueous polyurethane and step 2 pours in four-hole boiling flask, under 50 ℃ of conditions, stir 2.5 hours, obtain graphene oxide/sulfonate type aqueous polyurethane mixture.By the graphene oxide sulfonate type aqueous polyurethane mixture casting film-forming on polyfluortetraethylene plate obtaining, Air drying 7 days is then dried 24 hours in 60 ℃ of vacuum drying ovens, standby.
Embodiment 3
1, the preparation of graphite oxide: in ice bath, the primary Graphite Powder 99 of 5g, 5g SODIUMNITRATE and the 250ml vitriol oil are mixed, and stir 30min and fully mix guaranteeing, then slowly add 40g potassium permanganate, continue under condition of ice bath stirring reaction 2.5 hours.Then remove ice bath pot, under normal temperature, stir 48 hours.Slowly add 500ml distilled water, stir 15min, after add 250ml distilled water diluting, then add the hydrogen peroxide of 75ml30wt% to reduce remaining potassium permanganate and MnO
2, finally use the above-mentioned reaction solution of deionized water repetitive scrubbing, until neutral, drying makes graphite oxide.
2, the preparation of 5mg/ml graphene oxide aqueous dispersions: get the graphite oxide that 1.25g makes and join mixing and stirring in 250ml water, ultrasonic peeling off 2 hours at 30 ℃, obtains the graphene oxide acetone dispersion liquor of 5mg/ml.
3, graphene oxide content is the preparation of graphene oxide/Waterborne PU Composite of the 5.0wt% that divides of sulfonate type aqueous polyurethane solid: the graphene oxide aqueous dispersions 250ml that gets 50g solid content and be preparation in 50% sulfonate type aqueous polyurethane and step 2 pours in four-hole boiling flask, under 50 ℃ of conditions, stir 3 hours, obtain graphene oxide/sulfonate type aqueous polyurethane mixture.By the graphene oxide sulfonate type aqueous polyurethane mixture casting film-forming on polyfluortetraethylene plate obtaining, Air drying 7 days is then dried 24 hours in 60 ℃ of vacuum drying ovens, standby.
Claims (8)
1. a preparation method for graphene oxide sulfonate type Waterborne PU Composite, is characterized in that, comprises the steps:
(1) in ice bath, Graphite Powder 99, SODIUMNITRATE and the vitriol oil are mixed, and be stirred to and mix, then slowly add potassium permanganate, under condition of ice bath, stirring reaction is 2～2.5 hours; Then under normal temperature, stir 36～48 hours; Slowly add distilled water to stir after 15min, add distilled water diluting, then add hydrogen peroxide to reduce remaining potassium permanganate and MnO
2; Finally use the above-mentioned reaction solution of deionized water repetitive scrubbing, until neutral, drying obtains graphite oxide; The mass ratio of described Graphite Powder 99, SODIUMNITRATE and potassium permanganate is 1:(0.8～1.2): (4～8), the addition of the vitriol oil is 40～50ml/g Graphite Powder 99; The addition of distilled water is 80～100ml/g Graphite Powder 99 for the first time;
(2) graphite oxide of preparation is dispersed in water, makes graphene oxide aqueous dispersions;
(3) graphene oxide aqueous dispersions and the blend of sulfonate type aqueous polyurethane emulsion are made to graphene oxide sulfonate type Waterborne PU Composite.
2. preparation method according to claim 1, is characterized in that, the described dispersion of step (2) is by graphite oxide and water mixing and stirring, and at 30 ℃ ultrasonic peeling off 1～2 hour, make graphene oxide aqueous dispersions.
3. preparation method according to claim 1 and 2, is characterized in that, the quality of the described graphite oxide of step (2) and the volume ratio scope of water are within the scope of 1～5mg/ml.
4. preparation method according to claim 1 and 2, is characterized in that, the described blending condition of step (3) is to stir 2～3 hours under 50 ℃ of conditions.
5. preparation method according to claim 1 and 2, is characterized in that, in the matrix material that step (3) makes, the content of graphene oxide is 1.0～5.0wt% of sulfonate type aqueous polyurethane solid.
6. preparation method according to claim 1 and 2, is characterized in that, step (1) for the second time addition of distilled water is 50～80ml/g Graphite Powder 99; The concentration of described hydrogen peroxide is 30wt%, and addition is 10～15ml/g Graphite Powder 99.
7. preparation method according to claim 1 and 2, is characterized in that, reacts after adding potassium permanganate described in step (1), and condition of ice bath is controlled at below 5 ℃.
8. the graphene oxide sulfonate type Waterborne PU Composite of preparing according to method described in claim 1～7 any one.
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| CN104761882A (en) * | 2015-04-24 | 2015-07-08 | 青岛墨烯产业科技有限公司 | Preparation method for oxidized graphene/water-soluble polyurethane composite material |
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| CN106400506A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Waterborne polyurethane textile size based on graphene modification and preparation method thereof |
| CN106832883A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Aqueous PU composite mortars of Graphene and its production and use |
| CN108659199A (en) * | 2018-04-13 | 2018-10-16 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and vamp finishing agent |
| CN109943275A (en) * | 2019-03-22 | 2019-06-28 | 江苏理工学院 | A kind of preparation method of graphene oxide modified polyurethane material |
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| CN106832883A (en) * | 2017-01-17 | 2017-06-13 | 南通强生安全防护科技股份有限公司 | Aqueous PU composite mortars of Graphene and its production and use |
| CN108659199A (en) * | 2018-04-13 | 2018-10-16 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Modified aqueous polyurethane dispersoid and preparation method thereof and vamp finishing agent |
| CN109943275A (en) * | 2019-03-22 | 2019-06-28 | 江苏理工学院 | A kind of preparation method of graphene oxide modified polyurethane material |
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