CN104004341B - A kind of graphene oxide sulfonate type Waterborne PU Composite and preparation method - Google Patents
A kind of graphene oxide sulfonate type Waterborne PU Composite and preparation method Download PDFInfo
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- CN104004341B CN104004341B CN201410222899.1A CN201410222899A CN104004341B CN 104004341 B CN104004341 B CN 104004341B CN 201410222899 A CN201410222899 A CN 201410222899A CN 104004341 B CN104004341 B CN 104004341B
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- graphene oxide
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Abstract
The invention discloses a kind of graphene oxide sulfonate type Waterborne PU Composite and preparation method, comprise the steps: that (1) uses the Hummers method improved to prepare graphite oxide (2) and is dispersed in water by the graphite oxide of preparation, prepare graphene oxide aqueous dispersions；(3) graphene oxide aqueous dispersions and sulfonate type water-based polyurethane emulsion are blended prepared graphene oxide sulfonate type Waterborne PU Composite.Two component compatibilities in the graphene oxide sulfonate type Waterborne PU Composite that the present invention prepares are preferable, and graphene oxide modification improves the heat stability of sulfonate type aqueous polyurethane.
Description
Technical field
The present invention relates to the preparation method of a kind of graphene oxide sulfonate type Waterborne PU Composite, belong to
In field of composite material preparation.
Background technology
Aqueous polyurethane refers to that polyurethane resin is dissolved in water or is dispersed in water the binary colloid system of formation.Water
Property polyurethane with water replace organic solvent as disperse medium, not only have nontoxic, do not fire, free from environmental pollution,
Save the advantage such as the energy and easy processing, and there is excellent mechanical performance, adhesive property, wear-resistant and resistance to
Ageing properties etc., are widely used in the industries such as building, automobile, shoemaking and packaging for foodstuff.
Generally, by introducing hydrophilic group in polyurethane molecular so that polyurethane molecular chain has certain
Hydrophilic such that it is able to be dispersed in water prepared aqueous pu dispersions.Current most of aqueous polyurethane
It is using anionic group as hydrophilic group, mainly includes carboxylate ion and sulfonate ion.Carboxylic acid type
Aqueous polyurethane is hydrophilic monomer frequently with dihydromethyl propionic acid (DMPA).Owing to DMPA is difficult to
Dissolving, reactivity is low, and needs to carry out amine neutralization, and therefore the existence of carboxylic acid type aqueous polyurethane contains
Machine solvent, response time length, amine nertralizer abnormal smells from the patient weight, solid content is relatively low, initial adhesive strength and glued membrane mechanics
The deficiencies such as poor-performing.And sulfonate type aqueous polyurethane frequently with ethylenediamine base ethyl sulfonic acid sodium (AAS) is
Hydrophilic monomer, its hydrophilic group is strong acid and strong base salt, and ionic strength is high, Coulomb repulsion between latex particle
Effect is relatively strong, easily prepares the aqueous polyurethane of high solids content.Due to without carrying out amine neutralization, sulfonate type water
Property the release of polyurethane non-irritating ammonia taste, and compared with carboxylic acid type aqueous polyurethane, it has higher
Adhesive strength, thermostability, resistance to water and solvent resistance etc..
Although sulfonate type aqueous polyurethane has better performance than carboxylic acid type aqueous polyurethane, but compares
In solvent borne polyurethane, its thermostability, solvent resistance and resistance to water etc. are the most relatively low.At present, aqueous polyurethane
Adhesive generally also exists the problem that thermostability is low.
Summary of the invention
It is an object of the invention to first prepare the preferable graphite oxide of water dispersible, and it is peeled off in water
Dispersion obtains stable graphene oxide aqueous dispersions, the graphene oxide aqueous dispersions pair that recycling is prepared
Sulfonate type aqueous polyurethane is modified, it is provided that a kind of graphene oxide sulfonate type aqueous polyurethane is combined
Material and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of graphene oxide sulfonate type Waterborne PU Composite, including following step
Rapid:
(1) in ice bath, graphite powder, sodium nitrate and concentrated sulphuric acid are mixed, and stir to mix homogeneously,
It is then slowly added into potassium permanganate, stirring reaction 2～2.5 hours under condition of ice bath；Then stir under room temperature
Mix 36～48 hours；After being slowly added to distilled water stirring 15min, add distilled water diluting, add double
The oxygen water remaining potassium permanganate of reduction and MnO2；Finally with the above-mentioned reactant liquor of deionized water cyclic washing, directly
To neutral, drying obtains graphite oxide；The mass ratio of described graphite powder, sodium nitrate and potassium permanganate is 1:
(0.8～1.2): (4～8), the addition of concentrated sulphuric acid is 40～50ml/g graphite powders；Distilled water for the first time
Addition is 80～100ml/g graphite powders；
(2) graphite oxide of preparation is dispersed in water, prepares graphene oxide aqueous dispersions；
(3) graphene oxide aqueous dispersions and sulfonate type water-based polyurethane emulsion are blended prepared oxidation stone
Ink alkene sulfonate type Waterborne PU Composite.
Step (2) described dispersion is by graphite oxide and water mixing and stirring, and ultrasonic stripping at 30 DEG C
From 1～2 hour, prepare graphene oxide aqueous dispersions.
The quality of step (2) described graphite oxide and the volume range of water are in the range of 1～5mg/ml.
Step (3) described blending condition is to stir 2～3 hours under the conditions of 50 DEG C.
In the composite that step (3) prepares, the content of graphene oxide is that sulfonate type aqueous polyurethane is solid
The 1.0～5.0wt% of body.
The addition of step (1) distilled water for the second time is 50～80ml/g graphite powders；Described hydrogen peroxide dense
Degree is 30wt%, and addition is 10～15ml/g graphite powders.
Reacting after step (1) described addition potassium permanganate, condition of ice bath controls below 5 DEG C.
The present invention compared with prior art has the following characteristics that
(1) the middle temperature response time that prepared by graphite oxide is longer, is 36～48 hours, is conducive to its oxidation
The raising of degree；
(2) graphene oxide has preferable water dispersible；
(3) graphene oxide dispersibility in sulfonate type aqueous polyurethane is preferable；
(4) Aqueous Polyurethane Adhesives that graphene oxide is modified has higher thermostability.
Accompanying drawing explanation
Fig. 1 is the XRD figure of graphite oxide in embodiment 1: the diffraction maximum at place about 2 θ=10.9 ° in figure
Diffraction maximum corresponding to graphite oxide.
Fig. 2 is the truncation surface SEM figure of graphene oxide aqueous polyurethane composite gel film in embodiment 1: figure
In have no block or laminated structure, show that graphene oxide is evenly dispersed in sulfonate type water polyurethane base
In matter.
Fig. 3, Fig. 4 and Fig. 5 are that in embodiment 1, embodiment 2 and embodiment 3, graphene oxide changes respectively
The thermogravimetric of property sulfonate type aqueous polyurethane and unmodified sulfonate type aqueous polyurethane (pure WPU) is divided
Analysis figure.From heat decomposition curve, the sulfonate type aqueous polyurethane of graphene oxide modification gathers than water-based
The thermostability of urethane is more preferable, i.e. graphene oxide modification improves the thermally-stabilised of sulfonate type aqueous polyurethane
Property.
Detailed description of the invention
Following example are used for the description of the invention, but the present invention is not restricted to this, and the present invention notes the most especially
Bright Parameter Conditions, can refer to routine techniques and carries out.
Embodiment 1
1, the preparation of graphite oxide: in ice bath, by 4g raw graphite powder, 4.8g sodium nitrate and 160ml
Concentrated sulphuric acid mixes, and stirs 15min to ensure to be sufficiently mixed uniformly, is then slowly added into 16g permanganic acid
Potassium, continues stirring reaction 2 hours under condition of ice bath.Then stir 36 hours under room temperature.It is slowly added to
320ml distilled water, stirs 15min, rear addition 320ml distilled water diluting, adds 40ml30wt%
Hydrogen peroxide reduce remaining potassium permanganate and MnO2, finally with the above-mentioned reactant liquor of deionized water cyclic washing,
Until neutral, drying obtains graphite oxide.
2, the preparation of 1mg/ml graphene oxide aqueous dispersions: take the graphite oxide addition that 0.25g prepares
Mixing and stirring in 250ml water, and ultrasonic stripping 1 hour at 30 DEG C, obtain 1mg/ml's
Graphene oxide aqueous dispersions.
3, graphene oxide content is the graphite oxide of the 1.0wt% that sulfonate type aqueous polyurethane solid divides
The preparation of alkene/Waterborne PU Composite: take the sulfonate type aqueous polyurethane that 50g solid content is 50%
In emulsion and step 2, the graphene oxide aqueous dispersions 250ml of preparation pours in four-hole boiling flask, at 50 DEG C
Under the conditions of stir 2 hours, obtain graphene oxide/sulfonate type aqueous polyurethane complex.By obtain
Graphene oxide sulfonate type aqueous polyurethane complex casting film-forming on polyfluortetraethylene plate, normal temperature drying
7 days, then it is dried 24 hours in 60 DEG C of vacuum drying ovens, standby.
Embodiment 2
1, the preparation of graphite oxide: in ice bath, by 5g raw graphite powder, 4g sodium nitrate and 225ml
Concentrated sulphuric acid mixes, and stirs 20min to ensure to be sufficiently mixed uniformly, is then slowly added into 30g permanganic acid
Potassium, continues stirring reaction 2.5 hours under condition of ice bath.Then stir 42 hours under room temperature.Slowly add
Enter 450ml distilled water, stir 15min, rear addition 350ml distilled water diluting, add 60ml30wt%
Hydrogen peroxide reduce remaining potassium permanganate and MnO2, finally with the above-mentioned reactant liquor of deionized water cyclic washing,
Until neutral, drying obtains graphite oxide.
2, the preparation of 3mg/ml graphene oxide aqueous dispersions: take the graphite oxide addition that 0.75g prepares
Mixing and stirring in 250ml water, at 30 DEG C, ultrasonic stripping 1.5 hours, obtain the oxygen of 3mg/ml
Functionalized graphene aqueous dispersions.
3, graphene oxide content is the graphite oxide of the 3.0wt% that sulfonate type aqueous polyurethane solid divides
The preparation of alkene/Waterborne PU Composite: take the sulfonate type aqueous polyurethane that 50g solid content is 50%
Pour in four-hole boiling flask, 50 DEG C of conditions with the graphene oxide aqueous dispersions 250ml of preparation in step 2
Lower stirring 2.5 hours, obtains graphene oxide/sulfonate type aqueous polyurethane complex.The oxidation that will obtain
Graphene sulfonate type aqueous polyurethane complex casting film-forming on polyfluortetraethylene plate, normal temperature drying 7
My god, then it is dried 24 hours in 60 DEG C of vacuum drying ovens, standby.
Embodiment 3
1, the preparation of graphite oxide: in ice bath, by 5g raw graphite powder, 5g sodium nitrate and 250ml
Concentrated sulphuric acid mixes, and stirs 30min to ensure to be sufficiently mixed uniformly, is then slowly added into 40g permanganic acid
Potassium, continues stirring reaction 2.5 hours under condition of ice bath.Then remove ice bath pot, under room temperature, stir 48
Hour.It is slowly added to 500ml distilled water, stirs 15min, add 250ml distilled water diluting afterwards, then
Add the hydrogen peroxide remaining potassium permanganate of reduction and the MnO of 75ml30wt%2, finally anti-with deionized water
Above-mentioned reactant liquor is washed in after backwashing, until neutral, drying prepares graphite oxide.
2, the preparation of 5mg/ml graphene oxide aqueous dispersions: take the graphite oxide addition that 1.25g prepares
Mixing and stirring in 250ml water, at 30 DEG C, ultrasonic stripping 2 hours, obtain the oxidation of 5mg/ml
Graphene acetone dispersion liquor.
3, graphene oxide content is the graphite oxide of the 5.0wt% that sulfonate type aqueous polyurethane solid divides
The preparation of alkene/Waterborne PU Composite: take the sulfonate type aqueous polyurethane that 50g solid content is 50%
Pour in four-hole boiling flask, 50 DEG C of conditions with the graphene oxide aqueous dispersions 250ml of preparation in step 2
Lower stirring 3 hours, obtains graphene oxide/sulfonate type aqueous polyurethane complex.The oxidation that will obtain
Graphene sulfonate type aqueous polyurethane complex casting film-forming on polyfluortetraethylene plate, normal temperature drying 7
My god, then it is dried 24 hours in 60 DEG C of vacuum drying ovens, standby.
Claims (6)
1. a preparation method for graphene oxide sulfonate type Waterborne PU Composite, its feature exists
In, comprise the steps:
(1) in ice bath, graphite powder, sodium nitrate and concentrated sulphuric acid are mixed, and stir to mix homogeneously,
It is then slowly added into potassium permanganate, stirring reaction 2～2.5 hours under condition of ice bath；Then stir under room temperature
Mix 36～48 hours；After being slowly added to distilled water stirring 15min, add distilled water diluting, add double
The oxygen water remaining potassium permanganate of reduction and MnO2；Finally with the above-mentioned reactant liquor of deionized water cyclic washing, directly
To neutral, drying obtains graphite oxide；The mass ratio of described graphite powder, sodium nitrate and potassium permanganate is 1:
(0.8～1.2): (4～8), the addition of concentrated sulphuric acid is 40～50ml/g graphite powders；Distilled water for the first time
Addition is 80～100ml/g graphite powders；The addition of distilled water is 50～80ml/g graphite powders for the second time；
(2) graphite oxide of preparation is dispersed in water, prepares graphene oxide aqueous dispersions；Described oxygen
The quality of graphite and the volume ratio of water are in the range of 1～5mg/ml；
(3) graphene oxide aqueous dispersions and sulfonate type water-based polyurethane emulsion are blended prepared oxidation stone
Ink alkene sulfonate type Waterborne PU Composite；In the composite prepared, the content of graphene oxide is sulphur
The 1.0～5.0wt% of hydrochlorate type aqueous polyurethane solid.
Preparation method the most according to claim 1, it is characterised in that step (2) described dispersion is
By graphite oxide and water mixing and stirring, and ultrasonic stripping 1～2 hours at 30 DEG C, prepare oxidation stone
Ink alkene aqueous dispersions.
Preparation method the most according to claim 1 and 2, it is characterised in that step (3) is described common
Silver mixing part is to stir 2～3 hours under the conditions of 50 DEG C.
Preparation method the most according to claim 1 and 2, it is characterised in that step (1) is described double
The concentration of oxygen water is 30wt%, and addition is 10～15ml/g graphite powders.
Preparation method the most according to claim 1 and 2, it is characterised in that step adds described in (1)
Reacting after entering potassium permanganate, condition of ice bath controls below 5 DEG C.
6. the graphene oxide sulfonate type aqueous prepared according to method described in Claims 1 to 5 any one
Compound polyurethane material.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761882B (en) * | 2015-04-24 | 2017-07-14 | 青岛墨烯产业科技有限公司 | A kind of preparation method of graphene oxide/water-soluble polyurethane composite material |
| CN105385148B (en) * | 2015-12-04 | 2018-08-28 | 浙江华峰合成树脂有限公司 | Sulfonated graphene modified aqueous polyurethane resin and preparation method |
| CN106400506B (en) * | 2016-09-21 | 2018-06-19 | 江西省高精科技有限公司 | A kind of aqueous polyurethane spinning sizing agent being modified based on graphene 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 |
| CN108659199B (en) * | 2018-04-13 | 2021-08-20 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Modified aqueous polyurethane dispersion, 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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| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
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