CN111218242A - High-thermal-conductivity and antistatic polymer/graphene oxide composite adhesive and preparation method thereof - Google Patents
High-thermal-conductivity and antistatic polymer/graphene oxide composite adhesive and preparation method thereof Download PDFInfo
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a high-thermal-conductivity antistatic polymer/graphene oxide composite adhesive and a preparation method thereof, wherein the polymer/graphene oxide composite adhesive is composite particles formed by combining graphene oxide nanosheets with the average transverse size within the range of 100-500 nm and a polymer in a chemical grafting manner; the composite adhesive can be prepared by the following method: mixing an oil phase dispersion liquid consisting of vinyl modified graphene oxide nanosheets, hydrophobic vinyl monomers, polar vinyl monomers and co-stabilizers with an aqueous solution of an emulsifier and/or a dispersant to obtain an oil-water mixed dispersion liquid; and shearing the oil-water mixed dispersion liquid at a high speed to obtain a monomer micro-suspension containing graphene oxide, and carrying out free radical copolymerization reaction to obtain the polymer/graphene oxide composite adhesive. The polymer/graphene oxide composite adhesive obtained by the invention has high heat conduction and antistatic performance, and the preparation method is simple and is easy for industrial implementation.
Description
(I) technical field
The invention relates to a functional polymer/graphene oxide composite adhesive and a preparation method thereof.
(II) background of the invention
With the rapid development of microelectronic integration and assembly technology and the use of high-power devices in large quantities, the heat productivity and the dissipation power density become larger and larger, which seriously affects the stability and the service life of electronic components, and the appearance of novel electronic products and functional devices such as flexible electronics, wearable electronics, transparent electronics and the like further improves the requirements on the heat conduction and antistatic performance of bonding materials.
In order to solve the above problems, it is necessary to develop a novel adhesive having excellent heat conductivity and antistatic property. Graphene has excellent heat conduction and resistance reduction capabilities, and has important application value [ ACS appl.mater.interface,2015,7,13685 & 13692 ] as a functional additive material in the construction of energy storage devices and efficient heat dissipation equipment. However, the graphene material with a single component has the problems of easy agglomeration, difficult processing and the like, and the wide application of graphene is limited to a certain extent. The functional modification of the graphene surface or the compounding of graphene and polymer materials is an important approach to improve the application performance of graphene and expand the application field of graphene [ chem.mater, 2016,28, 8082-containing 8118 ].
The invention provides an aqueous dispersion liquid of a polymer/graphene oxide composite binder, which is prepared by taking graphene oxide nanosheets as functional components and realizing in-situ compounding of graphene oxide and a binder polymer through micro-suspension copolymerization reaction. By means of hydrophobic modification of vinyl on the surface of the graphene oxide nanosheet, the dispersion uniformity of the graphene oxide nanosheet in a monomer and a polymer matrix is improved, and the graphene oxide participates in formation of a hybrid network of the adhesive through a grafting reaction, so that the composite adhesive is endowed with excellent heat conduction and antistatic performance.
Disclosure of the invention
The invention aims to provide the water dispersion of the high-thermal-conductivity and antistatic polymer/graphene oxide composite binder, which has the advantages of controllable particle size, good colloidal stability and high polymer and graphene oxide composite degree.
The second purpose of the invention is to provide a preparation method of the polymer/graphene oxide composite binder aqueous dispersion, which realizes in-situ coating of the graphene oxide nano-material by the polymer.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the invention provides a polymer/graphene oxide composite binder, wherein the polymer/graphene oxide composite binder is composite particles formed by combining graphene oxide nanosheets with an average transverse size within a range of 100-500 nm and a polymer in a chemical grafting manner;
the polymer/graphene oxide composite adhesive is prepared by the following method: mixing an oil phase dispersion liquid consisting of vinyl modified graphene oxide nanosheets, hydrophobic vinyl monomers, polar vinyl monomers and co-stabilizers with an aqueous solution of an emulsifier and/or a dispersant to obtain an oil-water mixed dispersion liquid; the oil-water mixed dispersion liquid is subjected to high-speed shearing to obtain monomer micro-suspension containing graphene oxide, and then the polymer/graphene oxide composite adhesive is prepared through free radical copolymerization reaction; wherein the mass usage of the vinyl modified graphene oxide nanosheets accounts for 0.1-20% of the total mass usage of the vinyl monomers (hydrophobic vinyl monomers and polar vinyl monomers), the mass usage of the hydrophobic vinyl monomers accounts for 80-99.9% of the total mass usage of the vinyl monomers, the mass usage of the polar vinyl monomers accounts for 0.1-20% of the total mass usage of the vinyl monomers, and the mass usage of the co-stabilizer accounts for 2-12% of the total mass usage of the vinyl monomers;
the hydrophobic vinyl monomer is selected from at least one of the following: acrylate or methacrylate monomer shown in formula (I), vinyl acetate and styrene;
in the formula (I), R1Is H or methyl; r2Is aliphatic linear chain, branched chain or cyclic alkyl of C1-C20;
the polar vinyl monomer is selected from at least one of the following: hydroxyalkyl methacrylate, hydroxyalkyl acrylate, acrylamide, N-hydroxyalkyl acrylamide, methacrylic acid, acrylic acid, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate;
the vinyl modified graphene oxide nanosheet is prepared by the following method: adding graphene oxide nanosheets into a modified solvent, carrying out ultrasonic treatment to obtain a uniform graphene oxide dispersion liquid, then adding a vinyl modifier, adjusting the temperature to 30-60 ℃, reacting for 0.5-72 h, drying and purifying to obtain vinyl-modified graphene oxide nanosheets; wherein the mass usage of the graphene oxide is 0.05-3.0% of that of the modified solvent, and the mass usage of the vinyl modifier is 0.1-30.0% of that of the graphene oxide;
the vinyl modifier is selected from at least one of the following: 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, a vinyl silane coupling agent, and an amino-terminated vinyl functional monomer;
wherein the amino-terminated vinyl functional monomer is at least one of amino acrylate hydrochloride and amino methacrylate hydrochloride shown in formula (II) and N- (aminoalkyl) acrylamide hydrochloride and N- (aminoalkyl) methacrylamide hydrochloride shown in formula (III);
in the formulae (II) and (III), R3、R5Each independently is H or methyl; r4、R6Each independently is a C1-C5 alkyl group.
Preferably, the average lateral dimension of the vinyl-modified graphene oxide is between 100nm and 300 nm.
Preferably, the reaction conditions of the radical copolymerization are as follows: under the action of oil-soluble initiator or water-soluble initiator, reacting for 0.5-24 h at 50-95 ℃ under the protection of nitrogen.
Preferably, the hydrophobic vinyl monomer is at least one of: isooctyl acrylate, butyl acrylate, methyl methacrylate, methyl acrylate, vinyl acetate, styrene.
Preferably, the polar vinyl monomer is at least one of: hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, glycidyl acrylate, N-methylolacrylamide, acrylamide.
Preferably, the emulsifier is selected from at least one of the following: tween series emulsifiers, OP series emulsifiers, MOA series emulsifiers, alkyl sulfonate emulsifiers, alkyl benzene sulfonate emulsifiers, alkyl sulfate emulsifiers, alkyl trimethyl ammonium halide emulsifiers, betaine emulsifiers.
Preferably, the dispersant is selected from at least one of the following: polyvinyl alcohol, sodium lignosulfonate, maleic anhydride-styrene copolymer, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, gelatin and sodium alginate.
Preferably, the co-stabilizer is selected from at least one of the following: aliphatic straight chain or branched chain alkane of C14-C22 and aliphatic alcohol of C14-C22.
Further preferably, the aqueous solution contains an emulsifier and a dispersant.
In a second aspect, the present invention provides a method for preparing an aqueous dispersion of a polymer/graphene oxide composite binder, the method comprising the following steps:
(1) adding graphene oxide nanosheets into a modified solvent, carrying out ultrasonic treatment to obtain a uniform graphene oxide dispersion solution, then adding a vinyl modifier, adjusting the temperature to 30-60 ℃, reacting for 0.5-72 h, purifying, and drying to obtain vinyl-modified graphene oxide nanosheets; wherein the mass usage of the graphene oxide is 0.05-3.0% of that of the modified solvent, and the mass usage of the vinyl modifier is 0.1-30.0% of that of the graphene oxide;
the vinyl modifier is selected from at least one of the following: 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, a vinyl silane coupling agent, and an amino-terminated vinyl functional monomer;
wherein the amino-terminated vinyl functional monomer is at least one of amino acrylate hydrochloride and amino methacrylate hydrochloride shown in formula (II) and N- (aminoalkyl) acrylamide hydrochloride and N- (aminoalkyl) methacrylamide hydrochloride shown in formula (III);
in the formulae (II) and (III), R3、R5Each independently is H or methyl; r4、R6Each independently is C1-C5 alkyl;
(2) dissolving an emulsifier and/or a dispersant in water to prepare an aqueous solution of the emulsifier and/or the dispersant; mixing the graphene oxide nanosheet with the surface vinyl modified, the hydrophobic vinyl monomer, the polar vinyl monomer and the co-stabilizer, placing the container in an ice water bath, and treating for 1-60 min under the ultrasonic power of 50-500W to prepare an oil-phase dispersion liquid of the modified graphene oxide; mixing an aqueous solution of an emulsifier and/or a dispersant with an oil phase dispersion liquid of modified graphene oxide, and processing for 0.5-200 min under a high-speed shearing condition of 3000-30000 rpm to obtain a monomer micro-suspension containing graphene oxide, wherein the mass usage of water is 80-1700% of the total mass usage of vinyl monomers (hydrophobic vinyl monomers + polar vinyl monomers), the mass usage of vinyl modified graphene oxide nanosheets accounts for 0.1-20% of the total mass usage of vinyl monomers (hydrophobic vinyl monomers + polar vinyl monomers), the mass usage of the emulsifier is 0-8% of the mass of water, the mass usage of the dispersant is 0-8% of the mass of water, the mass usage of the emulsifier and the dispersant is not 0, the mass usage of the hydrophobic vinyl monomers is 80-99.9% of the total mass usage of the vinyl monomers, and the mass usage of the polar vinyl monomers is 0.1-20% of the total mass usage of the vinyl monomers, the mass usage of the co-stabilizer is 2-12% of the total mass usage of the vinyl monomer; after nitrogen is introduced and oxygen is removed, the temperature is adjusted to 50-95 ℃, and the mixture reacts for 0.5-24 hours under the protection of nitrogen, so that the polymer/graphene oxide composite adhesive water dispersion is prepared;
and the initiator is introduced by the following means a or b:
in the step (2), adding an oil-soluble initiator into the monomer mixed solution, wherein the mass usage of the oil-soluble initiator is 0.05-5% of the total mass usage of the vinyl monomer;
mode b: in the step (2), a water-soluble initiator is added into the monomer micro-suspension containing graphene, wherein the mass usage of the water-soluble initiator is 0.05-5% of the total mass usage of the vinyl monomer.
In the invention, the graphene oxide can be obtained by the existing method, (1) the graphene oxide with the average transverse size of 100 nm-500 nm is synthesized by a modified Hummers method (Ceramics International,2020,46, 2392-2402); (2) commercially available graphene oxide aqueous dispersions in this size range are purchased directly. In consideration of the coating rate of the polymer to the graphene oxide nanoplatelets in the microsuspension polymerization system of step (2), graphene oxide nanoplatelets having an average transverse dimension in the range of 100nm to 300nm are preferred.
In step (1) of the present invention, the modifying solvent is preferably at least one of: ethanol, dimethylformamide, dimethyl sulfoxide.
In step (1) of the present invention, the vinyl modifier is preferably at least one of: 2-isocyanoethyl methacrylate, 3-trimethoxysilylpropyl methacrylate, 2-aminoethyl methacrylate hydrochloride.
In step (1) of the present invention, the ultrasonic treatment conditions are preferably: ultrasonic treatment is carried out for 0.5min to 60min under the power of 50W to 600W.
In the step (1) of the present invention, in consideration of the dispersibility and modification efficiency of graphene oxide in the modification solvent, the mass usage amount of the graphene oxide nanosheet is preferably 0.1% to 2.5% of the mass usage amount of the modification solvent.
In the step (1) of the present invention, in consideration of the graphene oxide surface modification effect and oil-water amphipathy, the mass usage amount of the vinyl modifier is preferably 0.5% to 20.0% of the mass usage amount of the graphene oxide.
In step (2) of the present invention, the emulsifier is selected from at least one of the following: tween series emulsifiers, OP series emulsifiers, MOA series emulsifiers, alkyl sulfonate emulsifiers, alkyl benzene sulfonate emulsifiers, alkyl sulfate emulsifiers, alkyl trimethyl ammonium halide emulsifiers, betaine emulsifiers. The Tween series emulsifier can be one or more of Tween-20, Tween-40, Tween-60 or Tween-80; the OP series emulsifier can be one or a combination of more than one of OP-7, OP-10, OP-15 or OP-20; the MOA series emulsifier can be one or a combination of more of MOA-3, MOA-7 and MOA-9. The alkyl sulfonate emulsifier may be R7-SO3M, wherein R7Is a fatty chain of C12-C20, M is Na+Or K+(ii) a The alkylbenzene sulfonate emulsifier may be R8-C6H4-SO3M, wherein R8Is a fatty chain of C10-C18, M is Na+Or K+(ii) a The alkyl trimethyl ammonium halide emulsifier may be R9N+(CH3)3X-Wherein R is9Is a C12-C20 fatty chain, and X is Cl and Br; the betaine emulsifier may be a carboxylic betaine (R)10N+(CH3)2CH2COO-Wherein R is10Fatty chain of C12-C18), sulfobetaine (R)11N+(CH3)2CH2CH2SO3 -Or R12N+(CH3)2CH2CH2CH2SO3 -Wherein R is11And R12Fatty chain of C12-C18). Preferred emulsifiers are MOA-9, Tween-20, sodium lauryl sulfate, cetyltrimethylammonium bromide, OP-10 and dodecyldimethylhydroxypropylsulfobetaine.
In step (2) of the present invention, the dispersant is selected from at least one of: polyvinyl alcohol, sodium lignosulfonate, maleic anhydride-styrene copolymer, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, gelatin and sodium alginate. Preferably the dispersing agent is polyvinyl alcohol, sodium lignosulfonate, methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose or hydroxypropylmethylcellulose.
Preferably, the aqueous solution in the step (2) contains an emulsifier and a dispersant simultaneously, the mass consumption of the emulsifier is 0.01-8% of the mass of the water, and the mass consumption of the dispersant is 0.01-8% of the mass of the water.
In the step (2), the dispersing capacity of the modified graphene oxide in the polymer matrix, the adhesive property of the adhesive and the heat conduction and antistatic properties of the adhesive are comprehensively considered, and the mass usage of the vinyl modified graphene nanosheets is preferably 0.5-16% of the mass usage of the monomer.
In step (2) of the present invention, in consideration of the adhesive property of the adhesive, the hydrophobic vinyl monomer is preferably at least one of the following: isooctyl acrylate, butyl acrylate, methyl methacrylate, methyl acrylate, vinyl acetate, styrene; the polar vinyl group is preferably at least one of: hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, glycidyl acrylate, N-methylolacrylamide, acrylamide.
In step (2) of the present invention, the co-stabilizer is selected from at least one of the following: aliphatic straight chain or branched chain alkane of C14-C22 and aliphatic alcohol of C14-C22. The co-stabilizer is preferably an aliphatic linear or branched alkane of C16 to C22, more preferably n-hexadecane, in view of the stability of the droplets.
In step (2) of the present invention, the oil-soluble initiator is selected from at least one of: azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dibenzoyl peroxide, dilauroyl peroxide. The water-soluble initiator is selected from at least one of the following: 2, 2' -azobisbutylamidine dihydrochloride, persulfate; the persulfate is generally ammonium persulfate or potassium persulfate.
In the step (2) of the present invention, the polymerization reaction temperature is preferably 50 to 85 ℃ in consideration of the initiation temperature of the initiator; the reaction time is preferably 1-24 h; in order to achieve a superior homogenization effect, the rotation speed of the high-speed shearing disperser is preferably 5000 to 26000rpm, and the shearing time is preferably 5 to 60 min.
In the invention, active groups such as epoxy, carboxyl and hydroxyl of graphene oxide are utilized, and the graphene surface is chemically modified by a vinyl monomer containing a reactive group, so that not only can the dispersibility of graphene nanosheets in the monomer be improved, but also the graphene oxide can be endowed with the capability of participating in free radical polymerization, the graphene is further bonded into a hybrid network of a binder through a chemical bond, and the interface bonding strength between a polymer matrix and the graphene oxide nanosheets is improved.
The inventor finds that under the synergistic stabilization effect of the dispersing agent, the emulsifying agent and the co-stabilizer, the coalescence among monomer droplets and the monomer diffusion can be inhibited, and the stability of the monomer droplets and a particle phase in the polymerization process can be improved. The combination and proportion of the hydrophobic vinyl monomer/polar vinyl monomer, the amount of graphene oxide and the degree of vinyl modification and other reaction parameters have important influences on the stability of the micro-suspension polymerization system, the size and distribution of the adhesive, the bonding performance of the adhesive, the heat conduction performance and the antistatic performance of the adhesive and other aspects. The vinyl modified graphene oxide nanosheets are connected with the polymer matrix through chemical bonds, so that the vinyl modified graphene oxide nanosheets can be distributed in the polymer matrix more uniformly. The graphene oxide nanosheets are uniformly dispersed, so that the overlapping of heat conduction and electric conduction paths is facilitated, the interlayer combination is more sufficient along with the increase of the content of the graphene oxide, and the heat conduction and antistatic performance are obviously improved. Meanwhile, the chemical bonding between the graphene oxide and the polymer matrix improves the compatibility of two-phase interfaces, so that the cohesive force of the adhesive film is improved. However, it should be noted that too high graphene usage will result in a decrease in the adhesive properties of the adhesive, and thus a decrease in the overall adhesive properties of the composite adhesive.
Compared with the prior art, the invention has the following beneficial effects: surface vinyl modification is carried out on the graphene oxide by utilizing reactive functional groups on the surface of the graphene oxide, oil-water amphipathy of the graphene oxide is regulated and controlled, and reactive capability is endowed to the graphene oxide. In the framework of a micro-suspension polymerization technology, vinyl monomers participate in free radical copolymerization reaction, the vinyl modified graphene nanosheets are coated in situ, and the polymer/graphene oxide composite adhesive with heat conduction and antistatic performance is efficiently prepared. The method has the advantages that: (1) the surface functionalization modification of the graphene oxide can improve the dispersion uniformity of the graphene oxide in a monomer and endow the graphene oxide with the capability of participating in a grafting reaction; (2) the formula design of the polymer/graphene oxide adhesive is various, the preparation process is simple, and the industrial implementation is easy; (3) through effective compounding between the polymer and the graphene oxide nanosheets, the material is endowed with excellent heat conduction and antistatic properties on the basis of not reducing the adhesive property of the adhesive, so that the material has higher application value in high-end fields such as military industry, electronic components, automobiles and the like.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
adding 5g of graphene oxide nanosheet (with the average transverse size of 200nm) into 495g of ethanol, carrying out ultrasonic treatment for 20min under the power of 300W to prepare graphene oxide dispersion liquid, adjusting the temperature to 30 ℃, adding 0.2g of 2-isocyanoethyl methacrylate, reacting for 24h to prepare graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 0.5g of MOA-9 and 1.5g of polyvinyl alcohol in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; then mixing 1.25g of vinyl modified graphene oxide nanosheet, 6.4g of isooctyl acrylate, 2.3g of styrene, 1.5g of methyl methacrylate, 1.9g of 2-hydroxyethyl methacrylate, 0.4g of glycidyl acrylate and 0.84g of n-hexadecane, placing the container in an ice-water bath, and treating for 10min under 200W of ultrasonic power to prepare the oil-phase dispersion liquid of the modified graphene oxide. And finally, mixing the aqueous solution of the emulsifier and the dispersant with the oil-phase dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and carrying out high-speed shearing dispersion for 10min under the condition of 20000rpm to obtain the monomer micro-suspension containing the graphene. And then adding 0.17g of water-soluble initiator potassium persulfate into the monomer micro-suspension, introducing nitrogen to remove oxygen, adjusting the reaction temperature to 70 ℃, and reacting for 6 hours under the protection of nitrogen to obtain the polymer/graphene oxide adhesive water dispersion.
The Z-average particle size of the polymer/graphene oxide binder particles was 889nm as measured by a dynamic light scattering nano-particle sizer. After the solid content of the aqueous dispersion was adjusted to 10 wt%, 6g of the aqueous dispersion was added with 1.5g of PTE thickener (san Shui Datang resin Co., Ltd., Fushan City) having a solid content of 3.0 wt% to prepare an adhesive working solution. Cutting polyethylene terephthalate (PET) film into 20cm × 26cm sample, placing in plasma processing equipment (HD-1B, Heitai plasma technology Co., Ltd. of Zhongzhou), and processing under oxygen atmosphere and 200W power for 5min to obtain PET hydrophilic film. The hydrophilic PET film was placed on an automatic Coater (K control Coater model 202, R K Print Coat Instruments Ltd), and a number 3 roller was selected at 100 mm. min-1Applying a working solution of the binder, and then baking at 100 ℃ for 2 min. The sized PET film was cut into 2.5cm X26 cm strips, and butt-jointed at a straight angle of 2.5cm X25 cm. Determination of glue by universal drawing machineThe shear strength of the film was 100 mm. min-1The shear strength of the adhesive film was 23.9MPa at the stretching rate of (1). Cutting the PET film after glue application into 2.5cm multiplied by 12.5cm strip-shaped samples, keeping the side with glue of the adhesive tape outward, making into standard annular samples with the circumference of 98mm, contacting with a test steel plate specified in GB/T3280 plus 2007, and measuring at 300 mm.min-1The initial adhesion of the sample was measured to be 0.65N by pulling it upward. Cutting the PET adhesive film into strip-shaped samples of 2.5cm multiplied by 26cm, and stretching at a rate of 300mm min-1The T-peel strength test was conducted under the conditions of (1), and the peel strength of the sample was measured to be 5.2N · cm-1。
Weighing 10g of the adhesive aqueous dispersion, placing the adhesive aqueous dispersion in a tetrafluoroethylene mold with a groove, and placing the adhesive aqueous dispersion in a constant temperature and humidity box with 70 ℃ and 60% RH for one week to obtain a complete adhesive film. Under the conditions of the ambient temperature of 23 +/-2 ℃ and the humidity of 50 +/-5 percent R.H, according to GB/T1410-2006, the surface resistivity of the adhesive film is measured to be 6.4 multiplied by 10 by an SLD-699 type surface resistance tester8Omega, antistatic effect is good.
Measuring the specific heat capacity of the adhesive film according to GB/T19466.4-2016; the density of the adhesive film is determined according to GB/T24542-; the thermal conductivity was measured according to GB/T22588-. The diameter of the sample is 20mm, the thickness of the sample is 0.5mm, and the heat conductivity coefficient of the product is 3.1 W.m measured by adopting a German xenon-lamp LFA447 heat conductivity meter-1·K-1And the heat conduction effect is good.
Comparative example 1:
dissolving 0.5g of MOA-9 and 1.5g of polyvinyl alcohol in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; then, 6.4g of isooctyl acrylate, 2.3g of styrene, 1.5g of methyl methacrylate, 1.9g of 2-hydroxyethyl methacrylate, 0.4g of glycidyl acrylate and 0.84g of n-hexadecane were mixed to obtain an oil phase solution. Then, mixing the water solution of the emulsifier and the dispersant with the oil phase solution to obtain an oil-water mixed solution, and carrying out high-speed shearing dispersion for 10min under the condition of 20000rpm to obtain the monomer micro-suspension. And then 0.17g of water-soluble initiator potassium persulfate is added into the monomer micro-suspension, after nitrogen is introduced and oxygen is removed, the reaction temperature is adjusted to 70 ℃, and the mixture is reacted for 6 hours under the protection of nitrogen, so as to prepare the adhesive aqueous dispersion.
The particle size of the binder particles was 752nm as measured by a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, and the adhesive film had a shear strength of 20.1MPa, an initial tack of 0.69N, and a peel strength of 5.3N cm-1The surface resistivity of the sample was 2.6X 1013Omega, heat transfer coefficient of 0.05 W.m-1·K-1Almost no antistatic effect and poor heat conduction effect.
Example 2:
adding 10g of graphene oxide nanosheet (with the average transverse size of 150nm) into 490g of dimethylformamide, carrying out ultrasonic treatment for 10min under the power of 500W to prepare graphene oxide dispersion liquid, adjusting the temperature to 30 ℃, adding 1.0g of 2-isocyanoethyl methacrylate, reacting for 24h to prepare graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 1.0g of Tween 20 and 2.4g of hydroxypropyl methylcellulose in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; then 3.3g of vinyl modified graphene oxide nanosheet, 12.9g of isooctyl acrylate, 4.1g of vinyl acetate, 3.0g of methyl methacrylate, 1.8g N-hydroxymethyl acrylamide, 1.3g of n-hexadecane and 0.2g of azobisisobutyronitrile are mixed, the container is placed in an ice-water bath, and the mixture is treated for 15min under the ultrasonic power of 300W, so that the oil-phase dispersion liquid of the modified graphene oxide is prepared. Then, mixing the aqueous solution of the emulsifier and the dispersant with the oily dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and carrying out high-speed shearing dispersion for 25min under the condition of 15000rpm to obtain the monomer micro-suspension containing graphene. And after nitrogen is introduced to remove oxygen, adjusting the reaction temperature to 65 ℃, and reacting for 20 hours under the protection of nitrogen to obtain the polymer/graphene oxide adhesive aqueous dispersion.
The Z-average particle size of the polymer/graphene oxide binder particles was 970nm as measured with a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, the adhesive film had a shear strength of 23.0MPa, and the initial tack and peel strengths of the samples were 0.70N and 5.8N-cm, respectively-1The surface resistivity of the sample was 3.7X 107Omega, thermal conductivity of 3.8 W.m-1·K-1And the antistatic and heat-conducting effects are excellent.
Example 3:
adding 2.5g of graphene oxide nanosheet (with the transverse dimension of 280nm) into 497.5g of dimethyl sulfoxide, carrying out ultrasonic treatment for 10min under the power of 450W to obtain a graphene oxide dispersion liquid, adjusting the temperature to 30 ℃, adding 0.375g of 3-trimethoxysilylpropyl methacrylate, reacting for 24h to obtain graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 0.2g of sodium dodecyl sulfate and 3.6g of hydroxymethyl cellulose in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; and mixing 2.4g of vinyl modified graphene oxide nanosheet, 10.8g of butyl acrylate, 9.3g of methyl methacrylate, 6.0g of methyl acrylate, 3.5g of methacrylic acid, 1.8g of n-hexadecane and 0.6g of dibenzoyl peroxide, placing the container in an ice-water bath, and treating for 20min under the ultrasonic power of 200W to prepare the oily dispersion liquid of the modified graphene oxide. Then, mixing the aqueous solution of the emulsifier and the dispersant with the oily dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and shearing and dispersing at a high speed of 25000rpm for 8min to obtain the monomer micro-suspension containing graphene. And after nitrogen is introduced to remove oxygen, adjusting the reaction temperature to 80 ℃, and reacting for 8 hours under the protection of nitrogen to obtain the polymer/graphene oxide adhesive aqueous dispersion.
The Z-average particle size of the polymer/graphene oxide binder particles was 920nm as measured with a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, the adhesive film had a shear strength of 25.6MPa, and the initial tack and peel strengths of the samples were 0.63N and 6.5N-cm, respectively-1The surface resistivity of the sample was 1.8X 108Omega, thermal conductivity of 2.9 W.m-1·K-1And the antistatic and heat-conducting effects are good.
Example 4:
adding 10g of graphene oxide nanosheets (with the average transverse size of 150nm) into 490g of dimethylformamide, carrying out ultrasonic treatment for 10min under the power of 500W to prepare graphene oxide dispersion liquid, adjusting the temperature to 40 ℃, adding 1.0g of 2-aminoethyl methacrylate hydrochloride, reacting for 24h to prepare graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 0.3g of cetyltrimethylammonium bromide and 5.0g of methylcellulose in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; then 1.6g of vinyl modified graphene oxide nanosheet, 11.6g of butyl acrylate, 11.5g of vinyl acetate, 7.0g of methyl methacrylate, 0.9g of acrylamide, 0.6g of 2-hydroxyethyl acrylate, 2.0g of n-hexadecane and 0.4g of azobisisobutyronitrile are mixed, and the container is placed in an ice-water bath and treated under 200W of ultrasonic power for 15min to prepare the oily dispersion liquid of modified graphene oxide. Then, mixing the aqueous solution of the emulsifier and the dispersant with the oily dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and performing high-speed shearing dispersion for 20min under the condition of 20000rpm to obtain the monomer micro-suspension containing graphene. And after nitrogen is introduced to remove oxygen, adjusting the reaction temperature to 65 ℃, and reacting for 15 hours under the protection of nitrogen to obtain the polymer/graphene oxide adhesive aqueous dispersion.
The Z-average particle size of the polymer/graphene oxide binder particles was 860nm as measured by a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, the adhesive film had a shear strength of 24.8MPa, and the initial tack and peel strengths of the samples were 0.64N and 6.3N-cm, respectively-1The surface resistivity of the sample was 7.6X 109Omega, thermal conductivity of 2.4 W.m-1·K-1And the antistatic and heat-conducting effects are good.
Example 5:
adding 10g of graphene oxide nanosheet (with the average transverse size of 150nm) into 490g of dimethylformamide, carrying out ultrasonic treatment for 10min under the power of 500W to prepare graphene oxide dispersion liquid, adjusting the temperature to 30 ℃, adding 1.0g of 2-isocyanoethyl methacrylate, reacting for 24h to prepare graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 1.2g of OP-10 and 3.3g of hydroxypropyl cellulose in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; and mixing 2.4g of vinyl modified graphene oxide nanosheet, 15.0g of vinyl acetate, 6.3g of methyl methacrylate, 7.2g of isooctyl acrylate, 2.5g of 2-hydroxyethyl methacrylate and 2.0g of n-hexadecane, placing the container in an ice-water bath, and treating for 10min under 200W of ultrasonic power to prepare the oily dispersion liquid of the modified graphene oxide. Then, mixing the aqueous solution of the emulsifier and the dispersant with the oily dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and performing shearing treatment for 15min under a high-speed shearing disperser with 20000rpm to obtain the monomer micro-suspension containing graphene. And then 0.18g of potassium persulfate is added into the monomer micro-suspension, after nitrogen is introduced and oxygen is removed, the reaction temperature is adjusted to 70 ℃, and the mixture reacts for 8 hours under the protection of nitrogen, so that the polymer/graphene oxide adhesive water dispersion is prepared.
The Z-average particle size of the polymer/graphene oxide binder particles was 990nm as measured by a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, the adhesive film had a shear strength of 24.4MPa, and the initial tack and peel strengths of the samples were 0.68N and 6.2N cm, respectively-1The surface resistivity of the sample was 1.5X 108Omega, thermal conductivity of 2.8 W.m-1·K-1And the antistatic and heat-conducting effects are good.
Example 6:
adding 10g of graphene oxide nanosheet (with the average transverse size of 150nm) into 490g of dimethylformamide, carrying out ultrasonic treatment for 10min under the power of 500W to prepare graphene oxide dispersion liquid, adjusting the temperature to 30 ℃, adding 1.0g of 2-isocyanoethyl methacrylate, reacting for 24h to prepare graphene oxide with surface vinyl modified, and purifying and drying the product for later use.
Dissolving 0.5g of dodecyl dimethyl hydroxypropyl sulfobetaine and 2.3g of sodium lignosulfonate in 100g of water to obtain an aqueous solution of an emulsifier and a dispersant; and mixing 2.4g of vinyl modified graphene oxide nanosheet, 11.2g of methyl methacrylate, 11.7g of butyl acrylate, 5.0g of methyl acrylate, 1.7g of glycidyl methacrylate and 1.9g of n-hexadecane, placing the container in an ice-water bath, and treating for 10min under the ultrasonic power of 200W to prepare the oily dispersion liquid of the modified graphene oxide. Then, mixing the aqueous solution of the emulsifier and the dispersant with the oily dispersion liquid of the modified graphene oxide to obtain an oil-water mixed solution, and shearing the oil-water mixed solution for 30min by using a high-speed shearing disperser with 12000rpm to obtain the monomer micro-suspension containing the graphene. And then adding 0.2g of water-soluble initiator potassium persulfate into the monomer micro-suspension, introducing nitrogen to remove oxygen, adjusting the reaction temperature to 70 ℃, and reacting for 12 hours under the protection of nitrogen to obtain the polymer/graphene oxide adhesive water dispersion.
The Z-average particle size of the polymer/graphene oxide binder particles was 980nm as measured by a dynamic light scattering nano-particle sizer. The same sizing process and test method as in example 1 were used, the adhesive film had a shear strength of 24.2MPa, and the initial tack and peel strengths of the samples were 0.67N and 6.0N cm, respectively-1The surface resistivity of the sample was 1.9X 108Omega, thermal conductivity of 3.0 W.m-1·K-1And the antistatic and heat-conducting effects are good.
The above-described embodiments of the invention are intended to be illustrative of the invention and are not to be construed as limiting the invention, and any variations that fall within the meaning and scope of the invention equivalent to the claims are intended to be embraced therein.
Claims (10)
1. A polymer/graphene oxide composite adhesive is characterized in that: the polymer/graphene oxide composite binder is a composite particle formed by combining a graphene oxide nanosheet with a transverse average size within a range of 100-500 nm and a polymer in a chemical grafting manner;
the polymer/graphene oxide composite adhesive can be prepared by the following method: mixing an oil phase dispersion liquid consisting of vinyl modified graphene oxide nanosheets, hydrophobic vinyl monomers, polar vinyl monomers and co-stabilizers with an aqueous solution of an emulsifier and/or a dispersant to obtain an oil-water mixed dispersion liquid; the oil-water mixed dispersion liquid is subjected to high-speed shearing to obtain monomer micro-suspension containing graphene oxide, and then the polymer/graphene oxide composite adhesive is prepared through free radical copolymerization reaction; wherein the mass usage of the vinyl modified graphene oxide nanosheet accounts for 0.1-20% of the total mass usage of the vinyl monomer, the mass usage of the hydrophobic vinyl monomer accounts for 80-99.9% of the total mass usage of the vinyl monomer, the mass usage of the polar vinyl monomer accounts for 0.1-20% of the total mass usage of the vinyl monomer, and the mass usage of the co-stabilizer accounts for 2-12% of the total mass usage of the vinyl monomer;
the hydrophobic vinyl monomer is selected from at least one of the following: acrylate or methacrylate monomer shown in formula (I), vinyl acetate and styrene;
in the formula (I), R1Is H or methyl; r2Is aliphatic linear chain, branched chain or cyclic alkyl of C1-C20;
the polar vinyl monomer is selected from at least one of the following: hydroxyalkyl methacrylate, hydroxyalkyl acrylate, acrylamide, N-hydroxyalkyl acrylamide, methacrylic acid, acrylic acid, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate;
the vinyl modified graphene oxide nanosheet is prepared by the following method: adding graphene oxide nanosheets into a modified solvent, carrying out ultrasonic treatment to obtain a uniform graphene oxide dispersion liquid, then adding a vinyl modifier, adjusting the temperature to 30-60 ℃, reacting for 0.5-72 h, drying and purifying to obtain vinyl-modified graphene oxide nanosheets; wherein the mass usage of the graphene oxide is 0.05-3.0% of that of the modified solvent, and the mass usage of the vinyl modifier is 0.1-30.0% of that of the graphene oxide;
the vinyl modifier is selected from at least one of the following: 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, a vinyl silane coupling agent, and an amino-terminated vinyl functional monomer;
wherein the amino-terminated vinyl functional monomer is at least one of amino acrylate hydrochloride and amino methacrylate hydrochloride shown in formula (II) and N- (aminoalkyl) acrylamide hydrochloride and N- (aminoalkyl) methacrylamide hydrochloride shown in formula (III);
in the formulae (II) and (III), R3、R5Each independently is H or methyl; r4、R6Each independently is a C1-C5 alkyl group.
2. A method for preparing the aqueous dispersion of the polymer/graphene oxide composite binder of claim 1, the method comprising the following steps:
(1) adding graphene oxide nanosheets into a modified solvent, carrying out ultrasonic treatment to obtain a uniform graphene oxide dispersion solution, then adding a vinyl modifier, adjusting the temperature to 30-60 ℃, reacting for 0.5-72 h, purifying, and drying to obtain vinyl-modified graphene oxide nanosheets; wherein the mass usage of the graphene oxide is 0.05-3.0% of that of the modified solvent, and the mass usage of the vinyl modifier is 0.1-30.0% of that of the graphene oxide;
the vinyl modifier is selected from at least one of the following: 2-isocyanoethyl methacrylate, 2-isocyanoethyl acrylate, a vinyl silane coupling agent, and an amino-terminated vinyl functional monomer;
wherein the amino-terminated vinyl functional monomer is at least one of amino acrylate hydrochloride and amino methacrylate hydrochloride shown in formula (II) and N- (aminoalkyl) acrylamide hydrochloride and N- (aminoalkyl) methacrylamide hydrochloride shown in formula (III);
in the formulae (II) and (III), R3、R5Each independently is H or methyl; r4、R6Each independently is C1-C5 alkyl;
(2) dissolving an emulsifier and/or a dispersant in water to prepare an aqueous solution of the emulsifier and/or the dispersant; mixing the graphene oxide nanosheet with the surface vinyl modified, the hydrophobic vinyl monomer, the polar vinyl monomer and the co-stabilizer, placing the container in an ice water bath, and treating for 1-60 min under the ultrasonic power of 50-500W to prepare an oil-phase dispersion liquid of the modified graphene oxide; mixing the aqueous solution of the emulsifier and/or the dispersant with the oil phase dispersion liquid of the modified graphene oxide, processing for 0.5min to 200min under the high-speed shearing condition of 3000rpm to 30000rpm to obtain monomer micro-suspension containing graphene oxide, wherein the mass usage of the water is 80-1700% of the total mass usage of the vinyl monomer, the mass usage of the vinyl modified graphene oxide nano sheet accounts for 0.1-20% of the total mass usage of the vinyl monomer, the mass usage of the emulsifier accounts for 0-8% of the mass of the water, the mass usage of the dispersant accounts for 0-8% of the mass of the water, the mass usage of the emulsifier and the dispersant is not 0, the mass usage of the hydrophobic vinyl monomer is 80-99.9% of the total mass usage of the vinyl monomer, the mass usage of the polar vinyl monomer is 0.1-20% of the total mass usage of the vinyl monomer, and the mass usage of the co-stabilizer is 2-12% of the total mass usage of the vinyl monomer; after nitrogen is introduced and oxygen is removed, the temperature is adjusted to 50-95 ℃, and the mixture reacts for 0.5-24 hours under the protection of nitrogen, so that the polymer/graphene oxide composite adhesive water dispersion is prepared;
and the initiator is introduced by the following means a or b:
in the step (2), adding an oil-soluble initiator into the monomer mixed solution, wherein the mass usage of the oil-soluble initiator is 0.05-5% of the total mass usage of the vinyl monomer;
mode b: in the step (2), a water-soluble initiator is added into the monomer micro-suspension containing graphene, wherein the mass usage of the water-soluble initiator is 0.05-5% of the total mass usage of the vinyl monomer.
3. The method of claim 2, wherein: in the step (1), the modifying solvent is selected from at least one of the following: ethanol, dimethylformamide, dimethyl sulfoxide.
4. The method of claim 2, wherein: in the step (1), the graphene oxide nanosheet is a graphene oxide nanosheet with a transverse average size within a range of 100 nm-300 nm; the vinyl modifier is selected from at least one of the following: 2-isocyanoethyl methacrylate, 3-trimethoxysilylpropyl methacrylate, 2-aminoethyl methacrylate hydrochloride.
5. The method of claim 2, wherein: in the step (1), the mass usage of the graphene oxide nanosheet is 0.1-2.5% of the mass usage of the modification solvent, and the mass usage of the vinyl modifier is 0.5-20.0% of the mass usage of the graphene oxide.
6. The method of claim 2, wherein: in the step (2), the emulsifier is selected from at least one of the following: tween series emulsifier, OP series emulsifier, MOA series emulsifier, alkyl sulfonate emulsifier, alkyl benzene sulfonate emulsifier, alkyl sulfate emulsifier, alkyl trimethyl ammonium halide emulsifier, betaine emulsifier;
the dispersant is selected from at least one of the following: polyvinyl alcohol, sodium lignosulfonate, maleic anhydride-styrene copolymer, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, gelatin and sodium alginate;
the co-stabilizer is selected from at least one of the following: aliphatic straight chain or branched chain alkane of C14-C22 and aliphatic alcohol of C14-C22.
7. The method of claim 6, wherein: the emulsifier is MOA-9, tween-20, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, OP-10 and dodecyl dimethyl hydroxypropyl sulfobetaine; the dispersing agent is polyvinyl alcohol, sodium lignosulfonate, methylcellulose, hydroxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose; the hydrophobic vinyl monomer is at least one of the following: isooctyl acrylate, butyl acrylate, methyl methacrylate, methyl acrylate, vinyl acetate, styrene; the polar vinyl group is at least one of: hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, glycidyl acrylate, N-methylolacrylamide, acrylamide; the co-stabilizer is aliphatic straight chain or branched chain alkane of C16-C22.
8. The method of claim 2, wherein: the aqueous solution in the step (2) simultaneously contains an emulsifier and a dispersant, wherein the mass consumption of the emulsifier is 0.01-8% of the mass of the water, and the mass consumption of the dispersant is 0.01-8% of the mass of the water.
9. The method of claim 2, wherein: in the step (2), the mass usage of the vinyl modified graphene nanosheets is preferably 0.5-16% of the mass usage of the monomers.
10. The method of claim 6, wherein: in the step (2), the polymerization reaction temperature is 50-85 ℃; the reaction time is 1-24 h; the high-speed shearing dispersion machine has the rotating speed of 5000-26000 rpm and the shearing time of 5-60 min.
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