WO2017148199A1 - Composite de polyuréthane modifié par du graphène, adhésif en polyuréthane préparé à partir de celui-ci, procédé de préparation d'un adhésif, et aérostat - Google Patents

Composite de polyuréthane modifié par du graphène, adhésif en polyuréthane préparé à partir de celui-ci, procédé de préparation d'un adhésif, et aérostat Download PDF

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Publication number
WO2017148199A1
WO2017148199A1 PCT/CN2016/109114 CN2016109114W WO2017148199A1 WO 2017148199 A1 WO2017148199 A1 WO 2017148199A1 CN 2016109114 W CN2016109114 W CN 2016109114W WO 2017148199 A1 WO2017148199 A1 WO 2017148199A1
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Prior art keywords
graphene
toluene diisocyanate
graphene oxide
component
modified
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PCT/CN2016/109114
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English (en)
Chinese (zh)
Inventor
刘若鹏
赵治亚
李雪
冯玉林
石玉元
刘列
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洛阳尖端技术研究院
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Publication of WO2017148199A1 publication Critical patent/WO2017148199A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64B—LIGHTER-THAN AIR AIRCRAFT
    • B64B1/00—Lighter-than-air aircraft
    • B64B1/58—Arrangements or construction of gas-bags; Filling arrangements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic

Definitions

  • the present invention relates to the field of polyurethane materials, and in particular to a graphene-modified polyurethane composition, a polyurethane adhesive prepared therefrom, a method of preparing the polyurethane adhesive, and a float having a polyurethane adhesive Empty.
  • Graphite thin is a two-dimensional sheet-like material composed of a single layer of sp2 hybridized carbon atoms. Its special structure determines its peculiar electrical properties, excellent physical and mechanical properties, thermal properties and gases. Barrier performance is an ideal filler for electromagnetic shielding, antistatic, high strength and gas barrier polymer composites, and has broad application potential in the preparation of lightweight, low cost, high performance composite materials.
  • Two-dimensional sheet-like defect-free graphene and graphene oxide have impermeable properties to gas molecules, and when graphene or graphene oxide is uniformly dispersed in a permeable polymer matrix, gas molecules can be added.
  • the length of the diffusion path reduces the gas permeability of the polymer.
  • the aspect ratio, dispersibility, orientation of the graphite sheet, interfacial bonding and crystallization of the polymer matrix of graphene or graphene oxide have a great influence on the gas barrier properties of the composite material.
  • Polyurethane is the abbreviation of polyurethane, which is formed by the reaction of alcohol and isocyanate. Due to the influence of reaction raw materials and process factors on the morphology of polyurethane materials, polyurethane polymers can be made into plastics, rubber, fibers and coatings. , adhesives, etc. At present, in order to integrate the excellent properties of polyurethane and graphene, the prior art has also conducted a lot of research on the performance of the composite materials, and mainly focuses on the application of coatings. Due to the excellent bonding advantage of polyurethane-based polymers as binders, The combination of polyurethane and graphene to form a binder is also an important research direction for the composite.
  • the dispersion of graphene or graphene oxide in the polymer matrix has the advantage of lowering the gas permeability of the polymer, it is difficult to form a polyurethane-based binder because the surface thereof is hydrophilic. Dispersion in organic solvents, and thus it is difficult to form a solution to the problem of composite materials with both gas permeability and cohesiveness
  • a main object of the present invention is to provide a graphene-modified polyurethane composition, a polyurethane adhesive prepared therefrom, a method of preparing the polyurethane adhesive, and a floater having the polyurethane adhesive, The problem that the graphene in the prior art is difficult to disperse in the organic solvent forming the polyurethane binder is solved.
  • a graphene-modified polyurethane composition comprising, by weight percentage, a composition, component A, 10 to 85%; component B, 10 ⁇ 85%; thinner, 1 ⁇ 30 ⁇ 3 ⁇ 4; and modified graphene, 1 ⁇ 5%, modified graphene is toluene diisocyanate surface modified graphene oxide or toluene diisocyanate surface modified graphene.
  • the above composition comprises: component A, 20 to 70%; component B, 20 to 70%; diluent, 5 to 25% ; and modified graphene, 3 ⁇ 5%.
  • the content of the toluene diisocyanate in the modified graphene is 1 to 10 in terms of weight percentage.
  • the content of the toluene diisocyanate in the modified graphene is 3 to 10 in terms of weight percentage.
  • the above A component includes a polyester polyol and a first solvent, and the above component A has a solid content of 70 to 80 wt ⁇ 3 ⁇ 4.
  • the above component B comprises a TDI-TMP polymer and a second solvent, and the component B has a solid content of 70 to 80 wt ⁇ 3 ⁇ 4.
  • the first solvent is ethyl acetate or xylene
  • the second solvent is ethyl acetate or xylene
  • the above diluent is ethyl acetate or xylene.
  • a method of preparing a polyurethane adhesive using the above composition comprises the following steps: Step S1, mixing the modified graphene and the diluent to obtain a dispersion; Step S2, mixing the dispersion with the component A to obtain a first mixture; and Step S3, The mixed solution was mixed with the component B to obtain a polyurethane binder.
  • step S1 the modified graphene and the diluent are mixed by high-speed shear stirring and ultrasonic, the stirring speed of the high-speed shear stirring is 5000-15000 rpm, and the ultrasonic working frequency is 20-50 KHz.
  • step S2 includes: adding a dispersion to the component A to form a mixture;
  • the first mixed solution is formed by stirring at a temperature of 0 to 5 ° C at a rate of 15,000 to 25,000 rpm for 20 to 40 minutes; and ultrasonic treatment of the primary mixed solution with a frequency of 20 to 50 KHz for 20 to 40 minutes to obtain a first mixed liquid.
  • the first mixed liquid and the B component are mixed by stirring, and the stirring speed of the stirring is 5000 to 15000 rpm.
  • the above method further includes a process of preparing the modified graphene, and the preparation process comprises the following steps: Step S01
  • step S02 Dispersing graphene oxide or graphene in an organic solvent to form a mixed solution; and in step S02, reacting the toluene diisocyanate with the mixed solution under nitrogen or an inert gas at 25 to 50 ° C for 12 to 24 hours.
  • Graphene Dispersing graphene oxide or graphene in an organic solvent to form a mixed solution; and in step S02, reacting the toluene diisocyanate with the mixed solution under nitrogen or an inert gas at 25 to 50 ° C for 12 to 24 hours.
  • the weight ratio of the above graphene oxide or graphene to tolylene diisocyanate is 1:10 to 1:100, and the organic solvent is selected from one of acetone, ethyl acetate, xylene and dimethylformamide. kind or more.
  • step S02 includes: Step S021, adding toluene diisocyanate to the mixed solution under nitrogen or an inert gas to form a reaction system; Step S022, controlling the temperature of the reaction system at 25 to 50 ° C Between the reaction system and the ultrasonic reaction and stirring at a stirring speed of 500 to 2000 rpm for 12 to 24 hours, to obtain a product system; step S023, using a alcohol solution to precipitate the product system to form a suspension; and step S024, hanging The turbid liquid is filtered, and the filtered cake is dried to obtain a modified graphene.
  • step S02 includes: Step S021', adding toluene diisocyanate to the mixed solution under nitrogen or an inert gas to form a first reaction system; Step S022', controlling the temperature of the first reaction system at Between 25 and 50 ° C, the first reaction system is continuously reacted for 12 to 24 hours under ultrasonication and a stirring speed of 500 to 2000 rpm to obtain a first product system; step S023', after cooling the first product system to room temperature, Adding a reducing agent to the first product system to form a second reaction system, and continuously stirring the second reaction system at a stirring speed of 500 to 2000 rpm for 10 to 60 minutes to form a second product system; Step S024', The second product system is precipitated with an alcohol solution to form a suspension; and in step S025', the suspension is filtered, and the filtered cake is dried to obtain a modified graphene.
  • the frequency of the above ultrasonic waves is 20 to 50 KHz
  • the alcohol liquid is ethanol
  • the weight ratio of the above alcohol liquid to toluene diisocyanate is from 1:1-1:10.
  • the above reducing agent is sodium borohydride.
  • the weight ratio of the above sodium borohydride to toluene diisocyanate is from 1:10 to 1:100.
  • the graphene oxide is a graphene oxide powder dried in a vacuum environment of 80 to 100 ° C for 12 to 24 hours, and the graphene is dried in a vacuum environment of 80 to 100 ° C. Graphene powder after 24h.
  • an aerostat having an adhesive, the adhesive being the polyurethane adhesive described above.
  • the aerostat has a skin material comprising a weathering layer, a fiber layer and a gas barrier layer which are bonded by a polyurethane adhesive.
  • the toluene diisocyanate group in the modified graphene in the above composition is grafted to the surface of graphene oxide or graphene, so that the surface properties of graphene oxide or graphene are changed from hydrophilic to hydrophobic, and thus stable Dispersed in a diluent, and further mixed with component A and component B, capable of being sufficiently dispersed, thereby ensuring uniform dispersion of graphene oxide or graphene in the formed composition, such that graphene oxide or The gas barrier properties of graphene and the bonding properties of polyurethanes formed by other components are fully exerted.
  • the above weight percentage can achieve a sufficient dispersion of the modified graphene by the diluent, and a mutual matching of the gas barrier properties of the graphene oxide or graphene and the binding property of the polyurethane.
  • components A and B described below in the present application are all understood to be polyurethanes as understood by those skilled in the art.
  • a conventional component of the composition such as component A is a polyol component and component B is a curing component.
  • a graphene-modified polyurethane composition which comprises, by weight percent, a component, 10 to 85%; component B, 10 ⁇ 85%; Diluent, 1 ⁇ 3 0%; and modified graphene, 1 ⁇ 5%, the modified graphene is a surface modified graphene or toluene diisocyanate surface-modified graphene of toluene diisocyanate.
  • the toluene diisocyanate group in the modified graphene in the above composition is grafted to the surface of graphene oxide or graphene, so that the surface properties of graphene oxide or graphene are changed from hydrophilic to hydrophobic, and thus stable Dispersed in a diluent, and further mixed with component A and component B, capable of being sufficiently dispersed, thereby ensuring uniform dispersion of graphene oxide or graphene in the formed composition, such that graphene oxide or The gas barrier properties of graphene and the bonding properties of polyurethanes formed by other components are fully exerted.
  • the above weight percentage can achieve a sufficient dispersion of the modified graphene by the diluent, and a mutual matching of the gas barrier properties of the graphene oxide or graphene and the binding property of the polyurethane.
  • the above composition comprises: component A, 20 ⁇ 70 ⁇ 3 ⁇ 4; component B, 20 ⁇ 70 ⁇ 3 ⁇ 4; diluent, 5 ⁇ 25 ⁇ 3 ⁇ 4; and modified graphene, 3 ⁇ 5 ⁇ 3 ⁇ 4.
  • the above composition is based on the mutual matching of the gas barrier properties of graphene oxide or graphene and the binding properties of the polyurethane, so that the raw material interaction of each part is more sufficient, and the economical efficiency of the composition is improved.
  • the graft ratio of toluene diisocyanate in the modified graphene used in the present application has an effect on the dispersion effect of graphene oxide or graphene in a diluent.
  • the higher the graft ratio the higher the dispersibility.
  • the better, but the excessive grafting rate has an effect on the structure and properties of graphene oxide or graphene. Therefore, in the present application, the content of toluene diisocyanate in the modified graphene is preferably 1 to 10% by weight. , preferably 3 ⁇ 10 ⁇ 3 ⁇ 4.
  • the components A and B forming the graphene-modified polyurethane composition of the present application can be referred to the conventional components for forming a polyurethane-based binder in the prior art, and the present application is to further improve the surface modification of toluene diisocyanate.
  • the dispersion effect of graphene oxide or tolylene diisocyanate surface-modified graphene preferably component A comprises polyester polyol and first solvent, and component A has a solid content of 70-80 wt%; preferably component B includes TDI-TMP polymer And the second solvent, the solid content of component B is 70-80 wt%; further preferably, the first solvent is ethyl acetate or xylene, the second solvent is ethyl acetate or xylene; and the diluent is ethyl acetate or xylene .
  • a polyester polyol as an example, a conventional polyester polyol used in the art for synthesizing a polyurethane-based binder can be used in the present application.
  • a method of preparing a polyurethane adhesive using the above composition comprising: Step S1, mixing the modified graphene and a diluent, A dispersion is obtained; in step S2, the dispersion is mixed with the component A to obtain a first mixture; and in step S3, the first mixture is mixed with the component B to obtain a polyurethane binder.
  • the above method firstly mixes the modified graphene with a diluent, and uses the solubility of toluene diisocyanate on the modified graphene in a diluent to sufficiently disperse the graphene oxide or graphene in a diluent.
  • Dispersing solution then mixing the dispersion with component A, pre-polymerizing the toluene diisocyanate therein with the active component in component A to form a first mixture comprising the prepolymer, thereby making graphene oxide or graphite
  • the olefin is dispersed in the prepolymer; the first mixture is further mixed with the component B, and the formed prepolymer is cross-linked and solidified to form a polyurethane binder in which graphene oxide or graphene is dispersed.
  • the method provided by the present application is simple, and the in-situ polymerization method for forming a graphene oxide composite material in the prior art is not only simple, but also can improve the dispersibility of graphene oxide or graphene.
  • the above step S1 uses high-speed shear stirring and ultrasonic to mix the modified graphene and the diluent, and the stirring speed of the high-speed shear stirring is 5000-15.
  • the operating frequency of ultrasound is 20 ⁇ 50KHz.
  • the step S2 includes: adding a dispersion to the component A to form a mixture; and mixing the mixture at a temperature of 0 to 5 ° C at 15000 to 25000 rpm.
  • the initial mixed solution is formed after stirring at a speed of 20 to 40 minutes.
  • the first mixed liquid is obtained by ultrasonic treatment of the primary mixed liquid for 20 to 40 minutes using ultrasonic with a frequency of 20 to 50 KHz.
  • adding the dispersion to the component A, the graphene oxide or graphene entering the component A can be quickly dispersed in the component A to form a mixture; then mixing at the above specific temperature and stirring speed Stirring of the body not only promotes the occurrence of the prepolymerization reaction, but also prevents the formed prepolymer from sticking to each other.
  • the prepolymer is further dispersed in the primary mixed liquid by ultrasonic treatment, and the next step is Joint Create an evenly dispersed environment.
  • the first step and the component B are mixed by stirring in the above step S3, and the stirring speed of the stirring is 5000 to 15000 rpm.
  • the modified graphene of the present application may be a prior art material prepared by the prior art method, but the modification method of the modified graphene in the prior art is cumbersome and difficult to be widely applied, in order to further The method is widely used.
  • the method further includes a process for preparing the modified graphene, the preparation process comprising: step S01, dispersing graphene oxide or graphene in an organic solvent, Forming a mixed solution; and in step S02, reacting the toluene diisocyanate with the mixed solution under nitrogen or an inert gas at 25 to 50 ° C for 12 to 24 hours to obtain modified graphene oxide.
  • the above-mentioned toluene diisocyanate surface-modified graphene oxide has a simple preparation process and can be widely applied. And by controlling the reaction conditions, the reaction conversion ratio of toluene diisocyanate to graphene oxide or graphene is increased, and as much as possible toluene diisocyanate is grafted onto the surface of graphene oxide or graphene, and the modification is formed.
  • the dispersibility of graphene in an organic solvent is relatively stable.
  • the above graphene oxide or graphene is preferably used.
  • the weight ratio of toluene diisocyanate is from 1:10 to 1:100.
  • organic solvents that can be used in the present application.
  • the organic solvent is one or more selected from the group consisting of acetone, ethyl acetate, xylene and dimethylformamide.
  • the toluene diisocyanate can be uniformly dispersed as much as possible in an organic solvent, thereby facilitating graft modification on the surface of the graphene oxide.
  • the step S02 includes the following steps: Step S021, adding toluene diisocyanate to the mixed solution under nitrogen or an inert gas to form a reaction system; Step S022, controlling the reaction system The temperature is between 25 and 50 ° C, and the reaction system is continuously reacted for 12 to 24 hours under ultrasonication and a stirring speed of 500 to 2000 rpm to obtain a product system; step S023, the product system is precipitated by an alcohol solution to form a suspension. And step S024, filtering the suspension, and drying the filter cake obtained by filtration to obtain modified graphene.
  • step S22 Due to the poor solubility of graphene oxide and graphene in an organic solvent, toluene diisocyanate and graphene oxide or graphene can be maintained throughout the reaction process by the above-mentioned ultrasonic accompanying stirring method.
  • the high-efficiency contact ensures a higher grafting rate.
  • the step S02 includes: Step S021', adding toluene diisocyanate to the mixed solution under nitrogen or an inert gas to form a first reaction system; Step S02 2 ', controlling the temperature of the first reaction system between 25 and 50 ° C, and allowing the first reaction system to continue to react for 12 to 24 hours under ultrasonication and a stirring speed of 500 to 2000 rpm to obtain a first product system; step S023', After cooling the first product system to room temperature, a reducing agent is added to the first product system to form a second reaction system, and the second reaction system is continuously stirred at a stirring speed of 500 to 2000 rpm for 10 to 60 minutes to form a second product system; Step S024', the second product system is precipitated by an alcohol solution to form a suspension; and in step S02 5', the suspension is filtered, and the filtered cake is dried to obtain a modified graphene.
  • This embodiment further increases the hydrophobicity of the modified graphene because the same effect as the above embodiment can be obtained, because the reduction ij is further used.
  • the frequency of the ultrasound used in the above embodiments can be adjusted according to the progress of the test, because the ultrasound also generates heat, and if the temperature of the reaction environment is found to be increased, the ultrasonic frequency can be appropriately lowered, and the ultrasonic frequency is increased, preferably ultrasonic.
  • the frequency is 20 ⁇ 50KHz, which can keep the temperature of the reaction process within a stable range.
  • the alcohol liquid in the above embodiment utilizes the alcohol precipitation principle to precipitate the modified graphene oxide from the product system, and thus the alcohol liquid capable of achieving the above functions can be used in the present application, for example.
  • the addition of hydrazine can stop the addition of the alcohol liquid. After extensive testing, it has been found that when the weight ratio of the alcohol liquid to the toluene diisocyanate is 1:1-1:10 ⁇ , not only can the purpose of completely precipitating the target be achieved, but also Excessive waste of alcohol.
  • the reducing agent used in the above embodiments of the present application is intended to further improve the hydrophobic properties of the finally obtained modified graphene, and therefore, a reducing agent capable of achieving the above object, such as hydrazine hydrate, can be used in the present application.
  • a reducing agent capable of achieving the above object such as hydrazine hydrate
  • the reducing agent is preferably sodium borohydride, and further preferably sodium borohydride and toluene.
  • the weight ratio of isocyanate is 1:10-1:100.
  • the above graphene oxide or graphene is preferably a graphene oxide powder or a graphene powder which is dried in a vacuum environment of 80 to 100 ° C for 12 to 24 hours. Since the current graphene oxide or graphene is present in the form of being dispersed in ethanol or water, the graphene oxide or graphene is dried to remove the ethanol solvent or water solvent entrained in the graphene oxide or graphene itself. Drop it.
  • a polyurethane adhesive is provided which is prepared by the method described above.
  • the polyurethane binder prepared by the above method has better dispersibility of graphene oxide or graphene therein, thereby fully utilizing the gas barrier properties of graphene oxide or graphene and ensuring the inherentity of the polyurethane binder. Bonding properties expand the range of applications for polyurethane adhesives.
  • an aerostat having an adhesive, the adhesive being the polyurethane adhesive described above. Applying the polyurethane adhesive provided by the present application to the air damper further improves the barrier performance of the aerostat to the helium gas while achieving the same bonding requirements.
  • the aerostat has a skin material comprising a weathering layer, a fiber layer and a gas barrier layer which are sequentially bonded by a polyurethane adhesive, or comprises sequentially bonding with a polyurethane adhesive.
  • Weathering layer, gas barrier layer and fiber layer Improves the barrier properties of the binder to helium and reduces the helium permeability of the skin material.
  • the aerostat may be an airship or a high air ball or the like.
  • composition raw materials were taken according to the weight percentage in Table 1, wherein the toluene diisocyanate surface-modified graphene oxide was obtained from the zirconium nano new material Co., Ltd., wherein toluene diisocyanate surface-modified toluene diisocyanate in the graphene oxide The weight percentage is 3%.
  • the toluene diisocyanate surface-modified graphene oxide and the diluent are mixed under high-speed shear stirring at a stirring speed of 15000 rpm and an operating frequency of 20 KHz to form a graphene oxide dispersion; (including polyester polyol and dimethylbenzene of HT218, solid content of 70wt%), adding the graphene oxide dispersion to form a mixture, placing the mixture in a stirred vessel, and placing the stirred vessel in an ice water cooling device In the middle, the ⁇ ⁇ homogenizer is stirred, and stirred at a stirring speed of 15000 rpm for 40 minutes to form an initial mixed liquid; then the initial mixed liquid is placed in an ultrasonic bath, and the first mixed liquid is formed by ultrasonication at 50 kHz for 20 minutes; the first mixed liquid is added.
  • Component B (including TDI-TMP polymer and ethyl acetate, having a solid content of 80% by weight) was stirred at a stirring speed of 5000 rpm for 30 minutes to obtain a graphene-dispersed polyurethane binder of Example 2.
  • the toluene diisocyanate surface-modified graphene oxide and the diluent (ethyl acetate) are mixed under high-speed shear stirring at a stirring speed of 5000 rpm and an operating frequency of 50 KHz to form a graphene oxide dispersion; (including polyester polyol and ethyl acetate of HT218, solid content of 80wt%), adding the graphene oxide dispersion to form a mixture, placing the mixture in a stirred vessel, and placing the stirred vessel in ice water for cooling
  • the ⁇ ⁇ homogenizer is stirred, and stirred at a stirring speed of 25000 rpm for 20 minutes to form an initial mixed liquid; then the primary mixed liquid is placed in an ultrasonic bath, and the first mixed liquid is formed by ultrasonication at 20 kHz for 40 minutes; to the first mixed liquid
  • the component B including TDI-TMP polymer and xylene, solid content of 75 wt%) was added, and
  • the toluene diisocyanate surface-modified graphene oxide and the diluent (ethyl acetate) are mixed at a stirring speed of 18000 rpm and a working frequency of 20 KHz to form a graphene oxide dispersion; (including polyester polyol and ethyl acetate of HT218, solid content of 75wt%), adding the graphene oxide dispersion to form a mixture, placing the mixture in a stirred vessel, and placing the stirred vessel in ice water for cooling
  • the ⁇ ⁇ homogenizer is stirred, stirred at a stirring speed of 100 rpm for 50 min to form an initial mixed liquid; then the primary mixed liquid is placed in an ultrasonic bath, and the first mixed liquid is formed by ultrasonication at 50 kHz for 20 minutes; to the first mixed liquid Component B (including TDI-TMP polymer and ethyl acetate, solid content of 80% by weight) was added, and stirred at a stirring speed of 18
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:10) under nitrogen atmosphere, ultrasonic at 35 ° C at 35 ° C and lOOOr / min Stirring at a stirring speed for 18 h, then adding 200 ml of ethanol to precipitate, and the obtained filter cake was filtered, dried, and ground to obtain a toluene diisocyanate surface-modified graphene oxide powder of Example 10, toluene diisocyanate surface-modified graphene oxide toluene diisocyanate.
  • the weight percentage is 3%.
  • the corresponding composition materials were taken according to the weight percentages in Table 1. The other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate 40ml (corresponding to the weight of graphene oxide with toluene diisocyanate is about 1: 10), 25 ° C for at a frequency of 50KHz ultrasound and 500r / mi n
  • the stirring speed was stirred for 24 hours, and then 200 ml of ethanol was added to precipitate.
  • the obtained filter cake was filtered, dried, and ground to obtain the toluene diisocyanate surface-modified graphene oxide powder of Example 11, and the toluene diisocyanate surface-modified graphene oxide toluene.
  • the isocyanate is present in an amount of 3% by weight.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution. To the mixed solution was added 32.8 ml of toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:10) under nitrogen atmosphere, ultrasonic at 500 Hz at 50 ° C and 200 r/mi.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 100 ° C for 12 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:10) under nitrogen atmosphere, ultrasonic at 35 ° C at 35 ° C and lOOOr / min Stirring at a stirring speed for 18 h, then adding 200 ml of ethanol to precipitate, and the obtained filter cake was filtered, dried, and ground.
  • the toluene diisocyanate surface-modified graphene oxide powder of Example 13 was obtained, and the toluene diisocyanate surface-modified graphene oxide had a weight percentage of toluene diisocyanate of 3%.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 80 ° C for 24 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:10) under nitrogen atmosphere, ultrasonic at 35 ° C at 35 ° C and lOOOr / min Stirring at a stirring speed for 18 h, then adding 200 ml of propanol precipitate, the obtained filter cake was filtered, dried, and ground to obtain the toluene diisocyanate surface-modified graphene oxide powder of Example 14, and the toluene diisocyanate surface-modified graphene oxide toluene The isocyanate is present in an amount of 3% by weight.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of toluene, and a magnetic stirring device was used for 2000 r. The stirring was carried out at a stirring speed of /min to form a mixed solution.
  • toluene diisocyanate was added, stirred at 35 ° C for 15 h at a frequency of 35 kHz and at a stirring speed of 1000 r/min, cooled to room temperature, and then 5 g of sodium borohydride (corresponding to the weight of sodium borohydride and toluene diisocyanate) The ratio is about 1:10), then 200 ml of ethanol is added to precipitate, and the obtained filter cake is filtered, dried, and ground to obtain the toluene diisocyanate surface-modified graphene oxide powder of Example 16, and the toluene diisocyanate surface-modified toluene in the graphene oxide.
  • the diisocyanate is present in an amount of 3% by weight.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of xylene, and magnetic stirring device was used. Stirring was carried out at a stirring speed of 2000 r/min to form a mixed solution. To the mixed solution, 40 ml of toluene diisocyanate was added under a nitrogen atmosphere, and the mixture was stirred at 35 ° C for 15 hours at a frequency of 35 kHz and at a stirring speed of 1000 r/min, cooled to room temperature, and then 0.5 g of sodium borohydride was added.
  • the toluene diisocyanate surface-modified graphene oxide has a weight percentage of toluene diisocyanate of 3%.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution. To the mixed solution was added 15 ml of toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:4) under nitrogen atmosphere, ultrasonic at 35 Hz at 35 ° C and lOOOr/min.
  • the mixture was stirred at a stirring speed for 18 hours, and then precipitated by adding 200 ml of ethanol.
  • the obtained cake was filtered, dried, and ground to obtain a toluene diisocyanate surface-modified graphene oxide powder of Example 18.
  • the toluene diisocyanate surface was modified to 1% by weight of toluene diisocyanate in the graphene oxide.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • Example 19 The graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution. To the mixed solution was added 400 ml of toluene diisocyanate (corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:100) under nitrogen atmosphere, ultrasonic at 35 Hz at 35 ° C and lOOOr/min.
  • toluene diisocyanate corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:100
  • the mixture was stirred at a stirring speed for 18 hours, and then precipitated by adding 200 ml of ethanol.
  • the obtained cake was filtered, dried, and ground to obtain a toluene diisocyanate surface-modified graphene oxide powder of Example 19.
  • the toluene diisocyanate surface-modified graphene oxide has a weight percentage of toluene diisocyanate of 13%.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:50
  • ultrasonic 35 ° C at 35 ° C and lOOOr / min
  • the mixture was stirred at a stirring speed for 18 hours, and then precipitated by adding 200 ml of ethanol.
  • the obtained cake was filtered, dried, and ground to obtain a toluene diisocyanate surface-modified graphene oxide powder of Example 20.
  • Toluene diisocyanate surface modification The weight percentage of toluene diisocyanate in the graphene oxide was 10%.
  • composition materials were taken in accordance with the weight percentages in Table 1.
  • the other processes are the same as in the first embodiment.
  • the graphene oxide powder was dried in a vacuum oven at 90 ° C for 18 h, and 5000 mg of the dried graphene oxide powder was weighed and added to 1000 ml of a one-neck round bottom flask containing 500 ml of anhydrous dimethylformamide. The mixture was stirred with a magnetic stirring device at a stirring speed of 2000 r/min to form a mixed solution.
  • toluene diisocyanate corresponding to a weight ratio of graphene oxide to toluene diisocyanate of about 1:75
  • ultrasonic 35 Hz and lOOOr/min at 35 ° C
  • the mixture was stirred at a stirring speed for 18 hours, and then precipitated by adding 200 ml of ethanol.
  • the obtained cake was filtered, dried, and ground to obtain a toluene diisocyanate surface-modified graphene oxide powder of Example 21.
  • the toluene diisocyanate surface-modified graphene oxide has a weight percentage of toluene diisocyanate of 12%.
  • the corresponding composition materials were taken according to the weight percentages in Table 1. The other processes are the same as in the first embodiment.
  • the toluene diisocyanate surface-modified graphene oxide of Examples 1 to 9 was replaced with toluene diisocyanate surface-modified graphene, wherein the content of toluene diisocyanate in the toluene diisocyanate surface-modified graphene was equivalent to that of the above respective examples.
  • the specific method repeats the above embodiments in order.
  • the weight percentage in Table 1 the corresponding composition raw materials were obtained, and the toluene diisocyanate surface-modified graphene oxide was obtained from the excellent zirconium nano new material Co., Ltd., wherein the weight of the toluene diisocyanate in the toluene diisocyanate surface-modified graphene oxide The percentage is 3%.
  • composition raw materials were taken according to the weight percentage in Table 1, wherein the toluene diisocyanate surface-modified graphene oxide was obtained from the zirconium nano new material Co., Ltd., wherein toluene diisocyanate surface-modified toluene diisocyanate in the graphene oxide The weight percentage is 3%.
  • the toluene diisocyanate surface-modified graphene oxide and the diluent (ethyl acetate) were mixed under high-speed shear stirring at a stirring speed of 2000 rpm and an operating frequency of 20 KHz to form a graphene oxide dispersion; (including polyester polyol and xylene with HT218, solid content of 70wt%) and component B (including TDI-TMP polymer and ethyl acetate, solid content of 80wt%) mixed in a stirred tank, will be stirred
  • the container is placed in an ice water cooling device, stirred by a homogenizer, and stirred at a stirring speed of 15000 rpm for 40 minutes to form a mixed liquid; the mixed solution is added to the graphene oxide dispersion to form a mixture, followed by The mixture was stirred for 40 min at a stirring speed of 15,000 rpm in an ice water cooling apparatus to obtain a graphene-dispersed graphene-containing polyurethan
  • the polyurethane binder of Comparative Example 4 was prepared by taking the component A, the component B and the diluent of the corresponding composition in the weight percentages in Table 1.
  • the polyurethane adhesive obtained in each of the above examples and the comparative examples was uniformly coated on a P ⁇ ( ⁇ 2 ⁇ ) film by a film stick (12 ⁇ ), placed in an oven, and cured at 60 ° C for 24 hours.
  • the polyurethane adhesive prepared by the composition of the present application has a significantly reduced helium permeability, and the polyurethane adhesive formed by the preparation method of the present application is used.
  • the helium permeability is further reduced, and it can be seen from the comparison of Examples 1 to 9 that the higher the content of graphene or graphene oxide in the polyurethane binder, the lower the helium permeability; It can be seen from the comparison of Examples 18 to 21 that the more the content of toluene diisocyanate in the modified graphene used, the more favorable the dispersion of the modified graphene in the polyurethane binder, and thus the helium exhibited.

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Abstract

La présente invention concerne composite de polyuréthane modifié par du graphène, un adhésif de polyuréthane préparé à partir de celui-ci, un procédé de préparation de l'adhésif de polyuréthane, et un aérostat comportant l'adhésif de polyuréthane. Le composite comprend, en pourcentage en poids : un composant A : 10 à 85 %; un composant B : 10 à 85 %; un diluant : 1 à 30 %; et du graphène modifié : 1 à 5 %, le graphène modifié étant un oxyde de graphène modifié en surface par du diisocyanate de toluène ou un graphène modifié en surface par du diisocyanate de toluène. Un groupe diisocyanate de toluène dans le graphène modifié du composite permet à la surface d'oxyde de graphène ou de graphène de passer du statut d'hydrophile à hydrophobe, de telle sorte que l'oxyde de graphène ou le graphène peut se disperser de manière stable dans un diluant, et se disperser totalement lors du mélange avec le composant A et le composant B, ce qui assure une dispersion uniforme de l'oxyde de graphène ou du graphène dans le composite formé.
PCT/CN2016/109114 2016-02-29 2016-12-09 Composite de polyuréthane modifié par du graphène, adhésif en polyuréthane préparé à partir de celui-ci, procédé de préparation d'un adhésif, et aérostat WO2017148199A1 (fr)

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