CN109943275A - A kind of preparation method of graphene oxide modified polyurethane material - Google Patents
A kind of preparation method of graphene oxide modified polyurethane material Download PDFInfo
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- CN109943275A CN109943275A CN201910220104.6A CN201910220104A CN109943275A CN 109943275 A CN109943275 A CN 109943275A CN 201910220104 A CN201910220104 A CN 201910220104A CN 109943275 A CN109943275 A CN 109943275A
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- graphene oxide
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Abstract
The invention belongs to polyurethane material technical fields, and in particular to a kind of preparation method of graphene oxide modified polyurethane material.It specifically includes: the graphene oxide of preparation is distributed to organic solvent, graphene oxide suspension is made, ionic liquid is then added, modified graphene oxide dispersion is made, is finally then added in adhesive for polyurethane and is mixed, obtains composite polyurethane material, carry out film, drying.The utility model has the advantages that the present invention solves the problems, such as the poor compatibility of graphene oxide and adhesive for polyurethane, the graphene oxide modified polyurethane of preparation has excellent heat resistance, it is higher at use temperature, the peel strength of adhesive for polyurethane is improved, without changing the structural behaviour of adhesive for polyurethane from the root, it is convenient and efficient, there is good application in fields such as building, woodenware.
Description
Technical field
The invention belongs to polyurethane material technical fields, and in particular to a kind of system of graphene oxide modified polyurethane material
Preparation Method.
Background technique
Adhesive for polyurethane has many advantages, such as that hardness is big, wear-resistant, adhesion property is excellent, is widely used in packaging, electricity
The fields such as device electronics, building, woodenware, health care, automobile and family life articles, play tie up, protect, sealing, insulating and
The various bonding effects such as fixed.But the thermal stability of adhesive for polyurethane, mechanical property are poor, and which also limits it in certain sides
The application in face.It can be improved peeling force at use temperature to meet adhesive for polyurethane higher, remain to it well
Adherend is clung, therefore adhesive for polyurethane is modified, the adhesive for polyurethane with different function is developed, expands it and answer
Use range.
In existing preparation method, in order to reach the performance of enhancing in a certain respect, otherwise defect is often brought,
The reagents such as organic silicone oil are added in order to improve the fast viscosity after adhesive solidifies, but reduce the temperature tolerance of adhesive；To improve
Temperature tolerance and peeling force use alkoxy alkane as crosslinking points, but reduce curing rate and stability etc..From research polyurethane adhesive
From the point of view of the status of glutinous agent (such as patent CN104130740 A, CN106978128A), typically by adjusting adhesive for polyurethane
Molecular structure, to adjust the peeling force size of adhesive film, and having ignored can be by outer doping answering in this respect
With process is complicated, increases manpower, material resources and financial resources.
Chinese patent CN108619921A discloses a kind of ion liquid modified graphene oxide/composite membrane of polymer, packet
Include 100 parts and ion liquid modified graphene oxide powder 0.1-2 parts of polymer membrane material；It is wherein ion liquid modified
Graphene powder is silanization graphene oxide interlayer to be connected to by way of bonding by ionic liquid and surface is prepared,
The temperature tolerance of graphene oxide is easily reduced in this method to the process that graphene oxide is alkylated, makes graphene oxide
Temperature tolerance is restricted, to influence the peel strength of polymer at high temperature.
Graphene oxide is a kind of new carbon haveing excellent performance, specific surface area with higher and surface official abundant
It can roll into a ball, be had a wide range of applications in field of compound material.But graphene oxide also has certain defect, is easy mutually absorption and rolls into a ball
Poly-, poor dispersion in a solvent influences compatibility and dispersibility in the polymer, and then can be to composite property
It has adverse effect on.
Summary of the invention
Graphene oxide existing in the prior art is easy to reunite and the poor defect of polyurethane temperature tolerance in order to solve, this hair
A kind of bright preparation method for being designed to provide graphene oxide modified polyurethane material.
Technical solution of the present invention is accomplished by the following way:
A kind of preparation method of graphene oxide modified polyurethane material, specifically comprises the following steps:
(1) graphene oxide of preparation is distributed in organic solvent, after ultrasonic treatment, obtains graphene oxide suspension
Liquid；
(2) ionic liquid is added in above-mentioned graphene oxide suspension, stirs, obtains the modified of stable dispersion
Graphene oxide dispersion；
(3) above-mentioned modified graphene oxide dispersion is added in adhesive for polyurethane, is mixed, is answered
Close polyurethane material；
(4) above-mentioned composite polyurethane material is uniformly applied on mylar, is dried.
Specifically, graphene oxide described in step (1) is prepared using Hummers method is improved.
Preferably, organic solvent described in step (1) is n,N-Dimethylformamide, the graphene oxide suspension
Concentration is that 0.1-2mg/mL is more preferably 1mg/mL.
Preferably, step (2) the intermediate ion liquid is the double trifluoro methylsulfonyl imonium salt of 1- butyl -3- methylimidazole, oxygen
The mass ratio of graphite alkene and ionic liquid is 1~5:1；The time of the stirring is 8-15h, mixing speed 800-2000r/
min。
Preferably, the frequency 40-150kHz of ultrasonic treatment described in step (1), ultrasonic time 1-4h.
Preferably, the mode of mixing described in step (3) is ultrasonic mixing, vibrates any 1 in mixing or being stirred
Kind or at least two kinds of combinations, incorporation time 2-5h.
Preferably, the solid content of the adhesive for polyurethane is 30-50%；The dosage of graphene oxide dispersion is poly- ammonia
The 0.05-1% of ester adhesive quality.
Preferably, the temperature of drying described in step (4) is 70-90 DEG C, drying time 24-48h.
The present invention carries out graphene oxide by the double trifluoro methylsulfonyl imonium salt of ionic liquid 1-butyl-3-methyl imidazolium
Non-covalent modification, ionic liquid is as a kind of green solvent, simultaneously, it is contemplated that partial ion liquid especially imidazole type ionic liquid
π-π effect between body and graphene oxide layer, helps to improve the dispersibility of graphene oxide layer, this ionic liquid
Since molecular volume is not that very greatly, preferably intercalation can enter between graphene layer and adsorb on the surface of graphene, increase graphene
Layer and interfloor distance, can effectively prevent the reunion of graphene, so that its dispersibility is improved.
On the other hand, the anion-exchange property for further utilizing ionic liquid is realized again by changing anion species
Condensation material provides more possibility in organic alternate transfer, for the application of graphene compound polyurethane material.In addition, ion
Liquid will be also dissolved in polyurethane material simultaneously, and the structure of ionic liquid can be dissolved in nonpolar solvent, be had to polyurethane material
Modifying function.
Beneficial effects of the present invention:
(1) present invention forms the good suspension of dispersion effect by being ultrasonically treated to graphene oxide, be added from
The double trifluoro methylsulfonyl imonium salt of sub- liquid 1- butyl -3- methylimidazole are modified graphene oxide, make it in the polymer
There is better dispersibility, graphene oxide is first subjected to alkyl in (publication number CN108619921A) compared with the prior art
Change, ion liquid modified, graphene oxide modified polyurethane prepared by the present invention then is carried out to alkylation graphene oxide again
With excellent heat resistance, and alkylated graphene oxide is unobvious to the heat resistance improvement effect of polyurethane.
(2) modified graphene oxide dispersion and adhesive for polyurethane are directly carried out at ultrasound, oscillation or stirring
Reason makes its mixed effect reach the polyurethane material for most preferably obtaining graphene oxide modification, and some are by powder in the prior art
The mode that the graphene oxide of shape is directly mixed with polymer causes graphene that cannot be completely dispersed in the polymer, dispersion
The uneven performance to influence polymer, and the present invention can overcome this disadvantage.
(3) graphene oxide dispersion is accounted for poly- ammonia by the characteristics of graphene oxide has bulk density small and large specific surface area
The mass percent of vinegar adhesive controls within 0.05%-1%, guarantees that the performance of graphene is effectively played.
(4) method provided by the invention is simple and easy, avoids heating during the preparation process, because graphene oxide is in temperature
In the case where excessively high, the oxygen-containing group chemical bond on surface is likely to be broken and is broken, to affect the knot of graphene oxide
Structure has certain defect to the modified aspect of graphene oxide；In addition, not having to heating, reaction temperature can be controlled, is reacted not acute
It is strong, reduce risk；Ionic liquid is stirred graphene oxide modification, does not change the size of graphene oxide, can
Ionic liquid is preferably effectively adsorbed on surface of graphene oxide, to effectively prevent the reunion of graphene oxide.
(5) present invention is using solving the problems, such as the poor compatibility of graphene oxide and adhesive for polyurethane, higher
At use temperature, the peel strength of adhesive for polyurethane is improved, without changing the knot of adhesive for polyurethane from the root
Structure performance, it is convenient and efficient, there is good application in fields such as building, woodenware.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, in following embodiment party of the invention
Specific embodiment described in formula is only used as the exemplary illustration of a specific embodiment of the invention, it is intended to for explaining this hair
It is bright, it is not intended to restrict the invention.
Embodiment 1
(1) graphene oxide is prepared with improvement Hummers method: the concentrated sulfuric acid (98%) of 23mL being added in 250mL flask,
It is cooled to 0 DEG C with ice-water bath, 1g graphite powder is added under magnetic stirring, is slow added into 3g KMnO4, control reacting liquid temperature
At 10~15 DEG C, it is stirred to react 2h.Then by the flask 30min that is placed in 35 DEG C of waters bath with thermostatic control that the reaction was continued, it is slowly added to 46mL
Deionized water controls 90~95 DEG C of reaction temperature, continues to be stirred to react 15min, sequentially add 140mL deionized water and 10mL
30%H2O2Aqueous solution filters while hot, and filter cake obtains graphite oxide after being dried in vacuo at 40 DEG C after sufficiently being washed with 5%HCl
Alkene, it is spare.
(2) graphene oxide for weighing 100mg step (1) preparation is added in the DMF solution of 100mL, ultrasonic reaction 2h,
The frequency of ultrasonic reaction is configured to the graphene oxide suspension of 1mg/mL so that graphene oxide is uniformly dissolved for 50kHz.
(3) the double trifluoro methylsulfonyl imonium ionic liquids of 100mg 1- butyl -3- methylimidazole is taken to be added to above-mentioned oxidation
In graphene suspension, magnetic agitation 8h, mixing speed 1000r/min obtain the modified graphite oxide of stable dispersion
Alkene dispersion liquid.
(4) taking solid content is 30% adhesive for polyurethane 20g, and above-mentioned modified graphene oxide solution is added
12mg carries out ultrasonic mixing 2h, obtains the modified compound polyurethane material of graphene oxide.
(5) silk thread stick is used on polyester film, to be placed in above-mentioned compound polyurethane material even application in 80 DEG C of baking oven
Drying for 24 hours, obtains polyurethane composite membrane.
Embodiment 2
(1) graphene oxide is prepared with improvement Hummers method: preparing graphene oxide with Hummers method is improved:
The concentrated sulfuric acid (98%) of 23mL is added in 250mL flask, is cooled to 0 DEG C with ice-water bath, 1g graphite powder is added under magnetic stirring,
It is slow added into 3g KMnO4, reacting liquid temperature is controlled at 10~15 DEG C, is stirred to react 2h.Then flask is placed in 35 DEG C of constant temperature
The reaction was continued in water-bath 30min is slowly added to 46mL deionized water, controls 90~95 DEG C of reaction temperature, continues to be stirred to react
15min sequentially adds 140mL deionized water and 10mL 30%H2O2Aqueous solution filters while hot, and filter cake is sufficiently washed with 5%HCl
Graphene oxide is obtained after being dried in vacuo at 40 DEG C after washing, it is spare.
(2) graphene oxide for weighing 100mg step (1) preparation is added in the DMF solution of 100mL, ultrasonic reaction 3h,
The frequency of ultrasonic reaction is configured to the graphene oxide suspension of 1mg/mL so that graphene oxide is uniformly dissolved for 56kHz.
(3) the double trifluoro methylsulfonyl imonium ionic liquids of 120mg 1- butyl -3- methylimidazole is taken to be added to above-mentioned oxidation
In graphene suspension, magnetic agitation 10h, mixing speed 1200r/min obtain the modified graphite oxide of stable dispersion
Alkene dispersion liquid.
(4) taking solid content is 40% adhesive for polyurethane 30g, and above-mentioned modified graphene oxide solution is added
48mg, ultrasonic 1h stir 1.5h, obtain the modified compound polyurethane material of graphene oxide.
(5) silk thread stick is used on polyester film, to be placed in above-mentioned compound polyurethane material even application in 70 DEG C of baking oven
Dry 36h, obtains polyurethane composite membrane.
Embodiment 3
(1) graphene oxide is prepared with improvement Hummers method: preparing graphene oxide with Hummers method is improved:
The concentrated sulfuric acid (98%) of 23mL is added in 250mL flask, is cooled to 0 DEG C with ice-water bath, 1g graphite powder is added under magnetic stirring,
It is slow added into 3gKMnO4, reacting liquid temperature is controlled at 10~15 DEG C, is stirred to react 2h.Then flask is placed in 35 DEG C of constant temperature
The reaction was continued in water-bath 30min is slowly added to 46mL deionized water, controls 90~95 DEG C of reaction temperature, continues to be stirred to react
15min sequentially adds 140mL deionized water and 10mL 30%H2O2Aqueous solution filters while hot, and filter cake is sufficiently washed with 5%HCl
Graphene oxide is obtained after being dried in vacuo at 40 DEG C after washing, it is spare.
(2) graphene oxide for weighing 100mg step (1) preparation is added in the DMF solution of 100mL, ultrasonic reaction
The frequency of 2.5h, ultrasonic reaction are 40kHz, so that graphene oxide is uniformly dissolved, the graphene oxide for being configured to 1mg/mL is outstanding
Supernatant liquid.
(3) the double trifluoro methylsulfonyl imonium ionic liquids of 150mg 1- butyl -3- methylimidazole is taken to be added to above-mentioned oxidation
In graphene suspension, magnetic agitation 12h, mixing speed 1200r/min obtain the modified graphite oxide of stable dispersion
Alkene dispersion liquid.
(4) taking solid content is 45% adhesive for polyurethane 30g, and above-mentioned modified graphene oxide solution is added
81mg, ultrasonic 1.5h stir 1.5h, obtain the modified compound polyurethane material of graphene oxide.
(5) silk thread stick is used on polyester film, to be placed in above-mentioned compound polyurethane material even application in 85 DEG C of baking oven
Dry 30h, obtains polyurethane composite membrane.
Embodiment 4
(1) graphene oxide is prepared with improvement Hummers method: preparing graphene oxide with Hummers method is improved: with improvement
Hummers method prepares graphene oxide: the concentrated sulfuric acid (98%) of 23mL being added in 250mL flask, is cooled to 0 with ice-water bath
DEG C, 1g graphite powder is added under magnetic stirring, is slow added into 3g KMnO4, reacting liquid temperature is controlled at 10~15 DEG C, is stirred
React 2h.Then by the flask 30min that is placed in 35 DEG C of waters bath with thermostatic control that the reaction was continued, it is slowly added to 46mL deionized water, control is anti-
90~95 DEG C of temperature are answered, continues to be stirred to react 15min, sequentially adds 140mL deionized water and 10mL 30%H2O2Aqueous solution,
It filters while hot, filter cake obtains graphene oxide after being dried in vacuo at 40 DEG C after sufficiently being washed with 5%HCl, spare.
(2) graphene oxide for weighing 100mg step (1) preparation is added in the DMF solution of 100mL, ultrasonic reaction 3h,
The frequency of ultrasonic reaction is configured to the graphene oxide suspension of 1mg/mL so that graphene oxide is uniformly dissolved for 55kHz.
(3) the double trifluoro methylsulfonyl imonium ionic liquids of 200mg 1- butyl -3- methylimidazole is taken to be added to above-mentioned oxidation
In graphene suspension, magnetic agitation 15h, mixing speed 1500r/min obtain the modified graphite oxide of stable dispersion
Alkene dispersion liquid.
(4) taking solid content is 50% adhesive for polyurethane 40g, and above-mentioned modified graphene oxide solution is added
200mg, ultrasonic 1h stir 2h, obtain the modified compound polyurethane material of graphene oxide.
(5) silk thread stick is used on polyester film, to be placed in above-mentioned compound polyurethane material even application in 80 DEG C of baking oven
Dry 48h, obtains polyurethane composite membrane.
Embodiment 5
(1) graphene oxide is prepared with improvement Hummers method: preparing graphene oxide with Hummers method is improved: with improvement
Hummers method prepares graphene oxide: the concentrated sulfuric acid (98%) of 23mL being added in 250mL flask, is cooled to 0 with ice-water bath
DEG C, 1g graphite powder is added under magnetic stirring, is slow added into 3g KMnO4, reacting liquid temperature is controlled at 10~15 DEG C, is stirred
React 2h.Then by the flask 30min that is placed in 35 DEG C of waters bath with thermostatic control that the reaction was continued, it is slowly added to 46mL deionized water, control is anti-
90~95 DEG C of temperature are answered, continues to be stirred to react 15min, sequentially adds 140mL deionized water and 10mL 30%H2O2Aqueous solution,
It filters while hot, filter cake obtains graphene oxide after being dried in vacuo at 40 DEG C after sufficiently being washed with 5%HCl, spare.
(2) graphene oxide for weighing 100mg is added in the DMF solution of 100mL, ultrasonic reaction 3h, ultrasonic reaction
Frequency is 150kHz, so that graphene oxide is uniformly dissolved, is configured to the graphene oxide suspension of 1mg/mL.
(3) the double trifluoro methylsulfonyl imonium ionic liquids of 500mg 1- butyl -3- methylimidazole is taken to be added to above-mentioned oxidation
In graphene suspension, magnetic agitation 15h, mixing speed 2000r/min obtain the modified graphite oxide of stable dispersion
Alkene dispersion liquid.
(4) taking solid content is 50% adhesive for polyurethane 40g, and above-mentioned modified graphene oxide solution is added
200mg, ultrasonic 2h stir 3h, obtain the modified compound polyurethane material of graphene oxide.
(5) silk thread stick is used on polyester film, to be placed in above-mentioned compound polyurethane material even application in 80 DEG C of baking oven
Dry 48h, obtains polyurethane composite membrane.
Comparative example 1
Taking solid content is 50% adhesive for polyurethane 20g, with silk thread stick by above-mentioned polyurethane material even application poly-
On ester film, dry 48h is placed in 80 DEG C of baking oven.
The polyurethane composite membrane that Examples 1 to 5 and comparative example 1 obtain is placed in baking oven to heat and is carried out after a certain period of time
The results are shown in Table 1 for the test of peel strength, test condition and peel strength test:
As shown in Table 1, under normal temperature state, in the modified polyurethane material of graphene oxide, graphene oxide is to oxidation
The peel strength of the modified polyurethane of graphene influences little；But at high temperature, graphene oxide prepared by the present invention is modified
Polyurethane is obvious to the promotion of peel strength, it may be possible to because stannic oxide/graphene nano material possessed by structure feature and
Performance, the effective heat resistance for enhancing polymer so that the heat resistance of polymer enhances, improve it at high operating temperatures
Peel strength.In addition, the strength of glass of modified polyurethane is with increase with the increase of graphene oxide amount.
Claims (8)
1. a kind of preparation method of graphene oxide modified polyurethane material, which comprises the steps of:
(1) graphene oxide of preparation is distributed in organic solvent, after ultrasonic treatment, obtains graphene oxide suspension；
(2) ionic liquid is added in above-mentioned graphene oxide suspension, stirs, obtains the modified oxidation of stable dispersion
Graphene dispersing solution；
(3) above-mentioned modified graphene oxide dispersion is added in adhesive for polyurethane, is mixed, obtained compound poly-
Urethane material；
(4) above-mentioned composite polyurethane material is uniformly applied on mylar, is dried.
2. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that step
Suddenly organic solvent described in (1) is n,N-Dimethylformamide, and the concentration of the graphene oxide suspension is 0.1-2mg/mL.
3. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that institute
The concentration for stating graphene oxide suspension is 1mg/mL.
4. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that institute
Stating step (2) intermediate ion liquid is the double trifluoro methylsulfonyl imonium salt of 1- butyl -3- methylimidazole, graphene oxide suspension with from
The mass ratio of sub- liquid is 1~5:1；The time of the stirring is 8-15h, mixing speed 800-2000r/min.
5. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that step
Suddenly the frequency 40-150kHz of ultrasonic treatment described in (1), ultrasonic time 1-4h.
6. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that step
Suddenly the mode of mixing described in (3) is ultrasonic mixing, vibrates any a kind or at least two kinds of of combination in mixing or being stirred,
Incorporation time is 2-5h.
7. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that institute
The solid content for stating adhesive for polyurethane is 30-50%；The dosage of graphene oxide dispersion is adhesive for polyurethane quality
0.05-1%.
8. a kind of preparation method of graphene oxide modified polyurethane material according to claim 1, which is characterized in that step
Suddenly the temperature of drying described in (4) is 70-90 DEG C, drying time 24-48h.
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| CN108099322A (en) * | 2017-12-14 | 2018-06-01 | 安徽大学 | A kind of graphite oxide alkenyl high-barrier nano laminated film and preparation method thereof |
| CN108619921A (en) * | 2017-03-16 | 2018-10-09 | 同济大学 | Ion liquid modified graphene oxide/composite membrane of polymer and its preparation and application |
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