CN111825892A - Melanin and graphene composite material modified latex material and preparation method thereof - Google Patents
Melanin and graphene composite material modified latex material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a melanin and graphene composite material modified latex material, a preparation method and application thereof, wherein the melanin and graphene composite material modified latex material comprises the following components in parts by weight: 60-100 parts of latex, 1-6 parts of a composite material consisting of melanin and graphene, 0.1-0.5 part of a coupling agent, 0.2-1 part of a stabilizer and 0.1-0.8 part of a surfactant, wherein the mass ratio of the melanin to the graphene in the composite material consisting of the melanin and the graphene is 1: 1-10. The modified latex material modifies the latex by using the melanin and the graphene material, and has excellent mechanical property, tensile resistance and rebound resilience; meanwhile, the strength, the tearing resistance, the mite and bacteria prevention, the far infrared, the ultraviolet resistance, the oxidation resistance and other performances of the material are enhanced. And the preparation method of the invention has simple process and is easy for large-scale production.
Description
Technical Field
The invention relates to a latex material, in particular to a melanin and graphene modified latex material and a preparation method and application thereof.
Background
The latex product has excellent elasticity, touch, wearability, plasticity, biological property and other properties, and is widely applied to industry, agriculture, medical treatment and health, war industry, cultural sports and daily life. However, the common latex product is easy to be subjected to poor air oxidation durability and aging resistance, the damage rate is high, meanwhile, the latex product is often contacted with the skin of a human body, the latex product only has a barrier effect and cannot influence germs and bacteria, and therefore, the existing latex product cannot adapt to the increasingly developed steps of the modern society. Therefore, physical and mechanical properties such as hardness, tensile strength and the like of the pure latex cannot meet many actual requirements, and modification is urgently needed to improve the properties such as strength, wear resistance, ageing resistance and the like of the pure latex, so that the application field of the pure latex is further widened.
The nano material has special surface effect, small size effect, quantum size effect and quantum tunnel effect, and the composite material has unique mechanical, thermal, optical, electromagnetic and other performance. In the latex industry, compounding research on traditional nano reinforced particles such as carbon black, white carbon black, clay and the like is widely carried out, and a latex nano composite material with excellent performance is developed, so that the performances of various aspects of the latex nano composite material are improved to a certain degree of layering. Graphene is a two-dimensional carbon nanomaterial with a single atom thickness, has excellent optical, electrical, thermal and mechanical properties and a huge specific surface area, and is called as the king of a new material. Graphene and a polymer can be complexed by covalent or non-covalent interactions (hydrogen bonds, pi-pi interactions, electrostatic interactions, etc.). Patent publication No. CN105906854A discloses a method for modifying a graphene-modified natural latex polymer, wherein the mechanical property of the modified natural latex polymer is improved by 20-200%, the barrier property is improved, and various viruses can be blocked; patent publication No. CN106832453A discloses a graphene modified natural latex material, a preparation method and an application thereof, wherein the graphene modified latex shows that the graphene can enhance the strength, tear resistance, antibacterial property and the like of the latex material; chinese patent No. CN106947128A discloses a preparation method of graphene composite latex sponge, wherein the hardness of the product prepared by the method can reach 30-45 KPa, the rebound resilience is 90-95%, and the tensile strength is 150-200 KPa. Various patents show that both graphene and latex can be mixed together for use by a processing technique to achieve a reconstituted latex composite. And the direct interaction of the graphene and the polymer not only increases the solubility or the dispersibility of the graphene in the polymer, but also can improve the performance of the composite material or expand the function of the composite material, and the composite material can be prepared into various latex products, so that the use is comfortable and healthy.
In addition, melanin is a dark brown pigment present in animals and plants, and is produced by and stored in a special cell, i.e., melanocyte. Melanin has excellent functions of sun protection, aging protection, cancer protection and the like, and is applied to products such as glasses, films and the like at present.
Disclosure of Invention
The invention aims to provide a composite material modified latex material consisting of melanin and graphene. In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a composite material modified latex material composed of melanin and graphene comprises the following components in parts by weight:
the mass ratio of the melanin to the graphene in the composite material consisting of the melanin and the graphene is 1: 1-10.
Preferably, in the composite material composed of melanin and graphene, the melanin and graphene are bonded together through a chemical bond formed by the graphene undergoing a reduction reaction on the surface of the melanin.
Preferably, the preparation method of the composite material composed of melanin and graphene comprises the following steps:
(1) dispersing graphene and a coupling agent into deionized water containing a dispersing agent, and performing one or more of shearing stirring, physical grinding, ultrasonic treatment, colloid mill treatment, sand mill treatment and high-pressure homogenization treatment to obtain a uniform graphene aqueous suspension; and
(2) adding melanin into the graphene water suspension, uniformly stirring, controlling the pH value of the system to be 6.5-12.5, heating to 50-80 ℃, continuously reacting for 1-8 hours, completing the grafting reaction of the melanin and graphene to obtain a dispersion liquid of a composite material consisting of the stably dispersed melanin and graphene, and performing spray drying to obtain the composite material consisting of the melanin and the graphene.
Preferably, in the step (1), the mass concentration of the graphene in the suspension formed by the graphene and the coupling agent is 2 g/L-20 g/L.
Preferably, the inorganic base solution is used to control the pH of the system in the step (2).
Preferably, the inorganic alkali solution is selected from one or more of ammonia water, sodium hydroxide solution and potassium hydroxide solution.
Preferably, the modified latex material further comprises the following components:
preferably, the graphene is selected from one or more of graphene and derivatives thereof, graphene oxide and derivatives thereof, or biomass graphene and derivatives thereof.
Preferably, the particle size of the melanin is 5 to 500 nm.
Preferably, the particle size of the graphene is 100 to 1000 nm.
More preferably, the graphene is selected from graphene oxide.
Preferably, the carbon-oxygen ratio of the graphene oxide is 3 to 7, and more preferably 5.
Preferably, the melanin is selected from plants, animals, microbial cultures or artificially synthesized melanin.
Preferably, the plant is selected from one or more of black rice, black bean and black sesame.
Preferably, the animal is selected from cuttlefish and/or cuttlefish bone.
Preferably, the melanin is selected from synthetic melanin.
Preferably, the artificial melanin is synthesized from one or more of cysteine, catechol, tyrosine, dopamine, 1, 8-dihydroxynaphthalene, 5, 6-dihydroxyindole, tryptophan, phenylalanine, serotonin and the like.
Preferably, the coupling agent is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, the dispersant is selected from one or more of polyvinylpyrrolidone, casein, sodium carboxymethylcellulose, casein, triethanolamine, sodium hexametaphosphate, dispersant NF, hexadecyl benzene sulfonic acid, sodium hexadecyl benzene sulfonate, sodium dodecyl benzene sulfonate, stabilizer LW, peregal 0, sodium isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
Preferably, the stabilizer is one or more selected from KOH, ammonia, stabilizer LW and casein.
Preferably, the above surfactant is selected from one or more of peregal O, sodium hexametaphosphate, dispersant NF, hexadecylbenzene sulfonic acid, sodium hexadecylbenzene sulfonate, sodium isopropyl naphthalene sulfonate and isobutyl naphthalene sulfonic acid.
Preferably, the above-mentioned accelerator is selected from one or more of zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, tetrabenzylthiuram disulfide, zinc dibenzyldithiocarbamate and 2-mercaptobenzothiazole.
Preferably, the antioxidant is selected from 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the vulcanizing agent is selected from sulfur.
Preferably, the vulcanization activator is selected from zinc oxide or magnesium oxide.
The invention further aims to provide a preparation method of the composite material modified latex material consisting of melanin and graphene, which comprises the following steps:
(1) dispersing graphene and a coupling agent into deionized water containing a dispersing agent to form a suspension, and performing one or more of shearing stirring, physical grinding, ultrasonic treatment, colloid mill treatment, sand mill treatment and high-pressure homogenization treatment to obtain a uniform graphene water suspension;
(2) adding melanin into the graphene water suspension, uniformly stirring, controlling the pH value of the system to be 6.5-12.5, heating to 50-80 ℃, continuously reacting for 1-8 hours, completing the grafting reaction of the melanin and graphene to obtain a composite material dispersion liquid consisting of stably dispersed melanin and graphene, and performing spray drying to obtain a composite material consisting of the melanin and the graphene;
(3) dissolving a composite material consisting of melanin and graphene in water to prepare a suspension liquid with the mass concentration of 0.1-3% so as to obtain a uniform and stable composite material dispersion liquid consisting of the melanin and the graphene;
(4) adding a stabilizer and a surfactant into the latex solution, and continuously stirring for 0.5-6 hours; slowly adding the composite material dispersion liquid composed of the melanin and the graphene, continuously stirring and grinding for 0.5-8 h, and adding an accelerator, an anti-aging agent, a vulcanizing agent and a vulcanization activator to obtain a latex mixed liquid; and
(5) and vulcanizing the latex mixed solution, dipping and molding by using a mold, and heating and drying to obtain the melanin and graphene composite modified latex material.
Preferably, in the step (1), the mass concentration of the graphene in the suspension formed by the graphene and the coupling agent is 2 g/L-20 g/L.
Preferably, the inorganic base solution is used to control the pH of the system in the step (2).
Preferably, the inorganic alkali solution is selected from one or more of ammonia water, sodium hydroxide solution and potassium hydroxide solution.
Preferably, in the step (2), the mixed solution is heated to 50-80 ℃.
More preferably, in the step (2), the mixture is heated to 60 ℃.
Preferably, the raw materials used in the preparation method are as follows in parts by weight:
preferably, the graphene is selected from one or more of graphene and derivatives thereof, graphene oxide and derivatives thereof, or biomass graphene and derivatives thereof.
Preferably, the particle size of the melanin is 5 to 500 nm.
Preferably, the particle size of the graphene is 100-1000 nm.
More preferably, the graphene is selected from graphene oxide.
Preferably, the carbon-oxygen ratio of the graphene oxide is 3 to 7, and more preferably 5.
Preferably, the melanin is selected from plants, animals, microbial cultures or artificially synthesized melanin.
Preferably, the plant is selected from one or more of black rice, black bean and black sesame.
Preferably, the animal is selected from cuttlefish and/or cuttlefish bone.
Preferably, the melanin is selected from synthetic melanin.
Preferably, the artificial melanin is synthesized from one or more of cysteine, catechol, tyrosine, dopamine, 1, 8-dihydroxynaphthalene, 5, 6-dihydroxyindole, tryptophan, phenylalanine, serotonin and the like.
Preferably, the coupling agent is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, the dispersant is selected from one or more of polyvinylpyrrolidone, casein, sodium carboxymethylcellulose, casein, triethanolamine, sodium hexametaphosphate, dispersant NF, hexadecyl benzene sulfonic acid, sodium hexadecyl benzene sulfonate, sodium dodecyl benzene sulfonate, stabilizer LW, peregal 0, sodium isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
Preferably, the stabilizer is selected from one or more of KOH, ammonia, stabilizer LW and casein.
Preferably, the above surfactant is selected from one or more of oleic acid, peregal O, sodium hexametaphosphate, dispersant NF, hexadecylbenzene sulfonic acid, sodium hexadecylbenzene sulfonate, sodium isopropyl naphthalene sulfonate and isobutyl naphthalene sulfonic acid.
Preferably, the above-mentioned accelerator is selected from one or more of zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, tetrabenzylthiuram disulfide, zinc dibenzyldithiocarbamate and 2-mercaptobenzothiazole.
Preferably, the antioxidant is selected from 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the vulcanizing agent is selected from sulfur.
Preferably, the vulcanization activator is selected from zinc oxide or magnesium oxide.
The invention also provides the application of the composite material modified latex material consisting of the melanin and the graphene, and the composite material modified latex material consisting of the melanin and the graphene can be used for pillows, mattresses, cushions, back cushions, sofas, waist supports, insoles, bras, automobile seats, toilet seats, condoms, gloves, balloons, nipples, milk bottles, hand warmers and the like.
According to the invention, the melanin is grafted to the graphene through a physical bond or a chemical bond to form a composite material with the graphene, and then the composite material is added into the latex to form the modified latex, so that the adverse effect of aggregation of the graphene material in the latex is avoided, and the graphene material is better dispersed. The modified latex has the advantages of not reducing the performance of the latex, simultaneously having the excellent performances of graphene and melanin, more importantly realizing the synergistic enhancement of the performance of the composite material, and further widening the application field of the latex.
The beneficial effects of the composite material modified latex material consisting of melanin and graphene are as follows: the latex modified by the composite material consisting of the melanin and the graphene has excellent mechanical property, tensile resistance and rebound resilience; meanwhile, the strength, the tearing resistance, the mite and bacteria prevention, the far infrared, the ultraviolet resistance, the oxidation resistance, the barrier property, the moisture absorption and the air permeability and other performances of the material are enhanced.
The preparation method of the composite material modified latex material consisting of the melanin and the graphene has a simple process and is easy for large-scale production.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
fig. 1 is a scanning electron microscope image of a composite material composed of melanin and graphene prepared in example 1 of the present invention.
Fig. 2 shows composite dispersions of melanin and graphene with different concentrations in example 1 of the present invention.
Fig. 3 is a composite modified latex product composed of melanin and graphene, which is prepared in example 1 of the present invention.
Detailed Description
In the description of the present invention, "solution" generally refers to an aqueous solution unless otherwise specified.
In the description of the present invention, "plural" means two or more.
In the description of the present invention, the graphene includes, but is not limited to, graphene and its derivatives, graphene oxide and its derivatives, or biomass graphene and its derivatives.
In the description of the present invention, melanin includes, but is not limited to, plant, animal, microorganism culture or synthetic melanin, the surface of melanin contains active groups such as hydroxyl, amino, sulfhydryl and the like, and graphene can undergo a reduction reaction on the surface of melanin, so that melanin and graphene can be bonded together through a chemical bond.
In the description of the present invention, plants used as a melanin source include, but are not limited to, black rice, black beans, and black sesame.
In the context of the present invention, animals used as a source of melanin include, but are not limited to, cuttlefish and silky fowl bones.
In the description of the present invention, the synthetic melanin includes, but is not limited to, those synthesized from cysteine, catechol, tyrosine, dopamine, 1, 8-dihydroxynaphthalene, 5, 6-dihydroxyindole, tryptophan, phenylalanine, and serotonin.
In the description of the present invention, the coupling agent includes, but is not limited to, a mixture of one or more of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
In the description of the present invention, the dispersant includes, but is not limited to, one or more of polyvinylpyrrolidone, casein, sodium carboxymethylcellulose, casein, triethanolamine, sodium hexametaphosphate, dispersant NF, hexadecylbenzene sulfonic acid, sodium hexadecylbenzene sulfonate, sodium dodecylbenzene sulfonate, stabilizer LW, peregal 0, sodium isopropylnaphthalene sulfonate and sodium isobutylnaphthalene sulfonate.
In the description of the present invention, the stabilizer includes, but is not limited to, KOH, ammonia, stabilizer LW, or casein.
In the context of the present invention, surfactants include, but are not limited to, oleic acid, peregal O, sodium hexametaphosphate, dispersant NF, hexadecylbenzene sulfonic acid, sodium hexadecylbenzene sulfonate, sodium isopropyl naphthalene sulfonate, or isobutyl naphthalene sulfonic acid.
In the context of the present invention, accelerators include, but are not limited to, one or more of zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc tetrabenzylthiuram disulfide or dibenzyldithiocarbamate, or 2-mercaptobenzothiazole.
In the description of the present invention, the antioxidant includes, but is not limited to, 2, 6-di-tert-butyl-4-methylphenol.
In the description of the present invention, the vulcanizing agent includes, but is not limited to, sulfur.
In the context of the present invention, sulfidation activators include, but are not limited to, zinc oxide and magnesium oxide.
In the description of the present invention, graphene oxide may be manufactured by a conventional method well known in the art and may also be commercially available. For example, by using an improved Hummer method, 69ml of 98% concentrated sulfuric acid is taken, 1.5g of natural crystalline flake graphite and 1.5g of sodium nitrate are respectively added into the mixture during stirring, the temperature of the reaction solution is accurately controlled to be 0 +/-0.5 ℃, 9g of KMnO4 powder is slowly added into the mixture, the mixture is stirred and reacted for 1 hour, 100ml of deionized water is added, the temperature of the reactant is increased to 95 +/-1 ℃, and the reaction is carried out for 30 minutes. The reaction mixture was diluted with deionized water and 10ml of 30% H was added2O2Filtering while the solution is hot, and fully washing the solution by using ionized water until no SO is contained in the filtrate4 2-. And then centrifuging and drying to obtain graphene oxide powder. (see, Chinese patent publication No. CN 101993065A, title of invention: method for preparing graphene powder, Dingguqiao et al, published: 2011, 3/30/s).
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, for which specific conditions are not indicated in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. Percentages are by weight unless otherwise indicated.
The numbers of "parts" of the raw materials charged in the following examples are "parts by weight"
The "latex" used in the following examples was manufactured by Taber rubber (Thailand) group Co., Ltd, and the type was natural latex.
The graphene oxide used in the following examples was sold by Shanghai alkene Wang materials science and technology limited and had a particle size of 100nm to 1500 nm.
Example 1
The latex modified by the composite material composed of melanin and graphene in the embodiment comprises the following components:
the preparation method of the composite material modified latex composed of melanin and graphene in the embodiment is as follows:
1.1 the extraction method of melanin in cuttlefish ink sac comprises the following steps: see the section on the preparation method of Yang Wang, u et al, under the literature name: superior Performance of Polyurethane Based on Natural Melanin nanoparticles, Biomacromolecules,2016,17(11), 3782-.
1.2 preparation of composite Material composed of Melanin and graphene
0.5g of dispersant polyvinylpyrrolidone is dispersed into 1kg of deionized water, then about 1L of graphene oxide is added to prepare 3mg/ml graphene oxide aqueous suspension, wherein the carbon/oxygen ratio of the graphene oxide is 6, the sheet diameter is 800nm, and then silane coupling agent KH550 is added for sanding treatment; weighing 2g of melanin with the wavelength of 150nm extracted from a cuttlefish ink sac, dispersing the melanin into graphene oxide water suspension, uniformly stirring and dispersing, adding ammonia water, adjusting the pH to 10, and then carrying out high-pressure homogenization treatment for 2 hours under 240MPa to form physical surface modification, intercalation or chemical bonds between the melanin oxide and the graphene. And heating the mixed solution to 60 ℃, stirring, reducing graphene oxide under the action of melanin to obtain a composite material consisting of melanin and graphene, washing with water, spray-drying to obtain powder, and finally dispersing the powder for use.
1.3 preparation of modified latex materials
Adding a stabilizer KOH and a surfactant hexadecylbenzene sulfonic acid into the latex solution, and continuously stirring for 1h at 40 ℃; then dispersing the composite material consisting of melanin and graphene in water to prepare a suspension with the mass concentration of 1%, slowly adding the suspension into the latex solution, and continuously stirring for 2 hours; then adding accelerating agent zinc diethyldithiocarbamate, anti-aging agent 2, 6-di-tert-butyl-4-methylphenol, vulcanizing agent sulfur and vulcanizing activator zinc oxide to obtain composite material modified latex mixed solution consisting of melanin and graphene, and finally processing to obtain composite material modified latex material consisting of melanin and graphene.
Comparative examples 1 to 1
The modified latex in this example was composed of the following components:
the preparation method of the graphene oxide modified latex material of the embodiment is as follows:
in this comparative example, the preparation method of the graphene oxide modified latex material is the same as that of the 1.3 part of example 1, except that the composite material of melanin and graphene in the 1.3 part of example 1 is replaced by graphene oxide (the amount of graphene oxide in the two examples is the same).
Comparative examples 1 to 2
The modified latex in this example was composed of the following components:
the preparation method of the melanin-modified latex material of this example is as follows:
in this comparative example, the preparation method of the melanin-modified latex material was the same as that of the 1.3 part of example 1, except that the composite material of the melanin and graphene in the 1.3 part of example 1 was replaced with sepia melanin (the amount of melanin used was the same in both examples).
Example 2
The latex modified by the composite material composed of melanin and graphene in the embodiment comprises the following components:
the preparation method of the composite material modified latex composed of melanin and graphene in the embodiment is as follows:
2.1 extraction of Black Rice Melanin
The extraction method comprises the following steps: (1) and (3) extraction of a melanin crude product: weighing a proper amount of black rice, cleaning with clear water, and placing into a round-bottom flask; adding appropriate amount of ethanol as extractant, adjusting pH of the extractive solution to 2-3 with diluted hydrochloric acid, and reflux-extracting in water bath at 60 deg.C (please supplement) for 2 hr each time. Extracting twice according to the conditions, combining leaching liquor obtained in twice, filtering, adjusting the pH value of the leaching liquor to 10 by using a dilute NaOH solution, standing for 24 hours to fully precipitate, distilling and concentrating under reduced pressure, adding hot water to wash off starch and salts, filtering under reduced pressure, and drying melanin at 60 ℃ in vacuum to constant weight to obtain a solid crude product. (2) Refining: dissolving the crude product in hot sodium hydroxide solution (pH 10), filtering, regulating to neutral, precipitating, filtering, and drying to obtain solid refined product. (see, Zaizao et al, extraction and refining of black rice melanin, food science and technology, 2006, (27), No.12-305)
2.2 preparation of composite Material composed of Melanin and graphene
0.5g of dispersant polyvinylpyrrolidone is dispersed into 1kg of deionized water, then about 1L of 2m g/ml graphene oxide aqueous suspension is prepared by adding graphene oxide, wherein the carbon/oxygen ratio of the graphene oxide is 6, the sheet diameter is 800nm, and then silane coupling agent KH550 is added for sanding treatment; weighing 2g of melanin with the wavelength of 200nm extracted from black rice, dispersing the melanin into graphene oxide water suspension, uniformly stirring and dispersing, adding ammonia water, adjusting the pH to 11, and then performing sanding treatment at the rotating speed of 2300rpm for 2 hours to form physical surface modification, intercalation or chemical bonds between the melanin oxide and the graphene. And heating the mixed solution to 60 ℃, stirring, reducing graphene oxide under the action of melanin to obtain a melanin-modified graphene composite material, washing with water, spray-drying to obtain powder, and finally dispersing the powder for use.
2.3 preparation of composite modified latex Material consisting of Melanin and graphene
Adding a stabilizer KOH and a surfactant sodium hexadecylbenzene sulfonate into the latex solution, and continuously stirring for 1h at 40 ℃; then dispersing the composite material consisting of melanin and graphene in water to prepare a suspension with the mass concentration of 1%, slowly adding the suspension into the latex solution, and continuously stirring for 2 hours; then adding accelerating agent zinc diethyldithiocarbamate, anti-aging agent 2, 6-di-tert-butyl-4-methylphenol, vulcanizing agent sulfur and vulcanizing activator zinc oxide to obtain composite material modified latex mixed liquor consisting of melanin and graphene, and finally processing to obtain the composite material of the composite material modified latex consisting of the melanin and the graphene.
Comparative example 2-1
The preparation method of the graphene oxide modified latex material of the embodiment is as follows:
in this comparative example, the preparation method of the graphene oxide modified latex material is the same as that of the 2.3 part of example 2, except that the composite material of melanin and graphene in the 2.3 part of example 2 is replaced by graphene oxide (the same applies to the amount of graphene oxide in the two examples).
Comparative examples 2 to 2
The preparation method of the melanin-modified latex material of this example is as follows:
in this comparative example, the preparation method of the melanin-modified latex material was the same as that of the 2.3 part of example 2, except that the composite material of the melanin and graphene in the 2.3 part of example 2 was replaced with sepia melanin (the amount of melanin used was the same in both examples).
Example 3
The latex modified by the composite material composed of melanin and graphene in the embodiment comprises the following components:
the preparation method of the composite material modified latex composed of melanin and graphene in the embodiment is as follows:
3.3 preparation of Polydopamine Black pigment
Adopting theophylline as a pH regulator for the poly-hemiamine hydrochloride solution (2g/L), regulating the pH value to be 8-9, heating to 60-80 ℃, reacting for 8h, cooling to obtain brown yellow particle precipitate, centrifuging, washing with water, and vacuum drying to obtain the poly-hemiamine melanin.
3.2 preparation of composite Material composed of Melanin and graphene
0.5g of dispersant polyvinylpyrrolidone is dispersed into 1kg of deionized water, then graphene oxide is added to prepare about 1L of 2.5mg/ml graphene oxide aqueous suspension, wherein the carbon/oxygen ratio of the graphene oxide is 6, the sheet diameter is 500nm, and then silane coupling agent KH550 is added for sanding treatment; weighing 1g of dopamine black pigment with the particle size of 100nm obtained by oxidative polymerization of dopamine, dispersing the dopamine black pigment into graphene oxide aqueous suspension, uniformly stirring and dispersing the dopamine black pigment, adding ammonia water, adjusting the pH value to 8.5, and then carrying out physical grinding treatment for 2 hours to form physical surface modification, intercalation or chemical bonds between the dopamine black pigment and graphene. And heating the mixed solution to 60 ℃, stirring, reducing graphene oxide under the action of melanin to obtain a melanin-modified graphene composite material, washing with water, spray-drying to obtain powder, and finally dispersing the powder for use.
3.3 preparation of composite modified latex Material consisting of Melanin and graphene
Adding a stabilizer KOH and a surfactant sodium dodecyl benzene sulfonate into the latex solution, and continuously stirring for 1h at 40 ℃; then dispersing the composite material consisting of melanin and graphene in water to prepare a suspension with the mass concentration of 1%, slowly adding the suspension into the latex solution, and continuously stirring for 2 hours; then adding accelerating agent zinc diethyldithiocarbamate, anti-aging agent 2, 6-di-tert-butyl-4-methylphenol, vulcanizing agent sulfur and vulcanizing activator zinc oxide to obtain composite material modified latex mixed solution consisting of melanin and graphene, and finally processing to obtain the melanin and graphene composite material modified latex material.
Example 4
The latex modified by the composite material composed of melanin and graphene in the embodiment comprises the following components:
the preparation method of the composite material modified latex composed of melanin and graphene in the embodiment is as follows:
4.1 preparation of tyrosine Melanin
139g/L of tyrosine and 500g/L of sodium persulfate were fed at a rate of 2.7ml/min to a 1L reactor equipped with a stirrer and a pilot port, respectively, and the pH of the mixture was adjusted to about 9.5 with sodium hydroxide, and the reaction temperature was controlled to about 35 ℃ for 5 hours. After completion of the reaction, melanin was precipitated by adjusting the pH of the reaction solution to 2 with hydrochloric acid, filtered, washed with 50g/L aqueous solution containing sodium sulfate until the pH of the solid reached 6, and vacuum-dried. (see, Chinese patent publication No. CN101233196A entitled: method for producing melanin, melanin produced by the method, functional film containing the melanin, and method for producing the same, and published: 7/30/2008 of Heiranliangsu et al).
4.2 preparation of composite Material composed of Melanin and graphene
0.5g of dispersant polyvinylpyrrolidone is dispersed into 1kg of deionized water, then about 1L of graphene oxide is added to prepare 2mg/ml graphene oxide aqueous suspension, wherein the carbon/oxygen ratio of the graphene oxide is 6, the sheet diameter is 600nm, and then silane coupling agent KH550 is added for sanding treatment; weighing 1g of melanin with the thickness of 80nm obtained by oxidative polymerization of leucine, dispersing the melanin into graphene oxide aqueous suspension, stirring and dispersing the melanin uniformly, adding ammonia water, adjusting the pH to 9.5, and then carrying out microjet homogeneous reflux treatment for 6 times to form physical surface modification, intercalation or chemical bonds between the melanin and graphene. And heating the mixed solution to 60 ℃, stirring, reducing graphene oxide under the action of melanin to obtain a melanin-modified graphene composite material, washing with water, spray-drying to obtain powder, and finally dispersing the powder for use.
4.3 preparation of composite modified latex Material consisting of Melanin and graphene
Adding a stabilizer KOH and a surfactant oleic acid into the latex solution, and continuously stirring for 1h at 40 ℃; then dispersing the composite material consisting of melanin and graphene in water to prepare a suspension with the mass concentration of 1%, slowly adding the suspension into the latex solution, and continuously stirring for 2 hours; then adding accelerating agent zinc diethyldithiocarbamate, anti-aging agent 2, 6-di-tert-butyl-4-methylphenol, vulcanizing agent sulfur and vulcanizing activator zinc oxide to obtain composite material modified latex mixed solution consisting of melanin and graphene, and finally processing to obtain composite material modified latex material consisting of melanin and graphene.
The modified latex materials prepared in the examples 1-4 and the comparative examples 1-1 and 1-2 are subjected to an ultraviolet resistance test (test standard GB/T1883022), an antioxidant performance test (DPPH test method), an antibacterial performance test (test standard GB/T20944.3-2008), a far infrared test (test standard GB/T30127-2013), a tensile strength performance test (test standard GB/T14344-. See tables 1 and 2 for specific results.
TABLE 1 Performance parameters of modified latex materials prepared in examples 1-4 and comparative examples 1-1, 1-2
TABLE 2 Performance parameters of the modified latex materials prepared in example 1 and comparative examples 1-1, 1-2, and example 2 and comparative examples 2-1, 2-2
As can be seen from table 1, the latex material modified by the composite composed of melanin and graphene has good ultraviolet resistance, oxidation resistance, antibacterial property, far infrared ray, tensile strength, tear strength, hardness and resilience. And as can be seen from the comparison between example 1 and comparative example 1-1, the ultraviolet resistance and oxidation resistance of the latex material modified by the composite composed of melanin and graphene are better than those of the latex material modified by graphene alone, the hardness and resilience of the latex material are improved, and the tensile strength and tear strength of the modified latex material are obviously improved; compared with the latex material modified by singly utilizing the melanin, the latex material modified by the compound formed by the melanin and the graphene has the advantages of good ultraviolet resistance, oxidation resistance and antibacterial property, the resilience of the latex material is improved, and the tensile strength and the tearing strength of the modified latex material are obviously improved.
By comparing the two examples in table 2 with pure natural latex, the latex material modified by the compound composed of melanin and graphene according to the invention is found to be improved by 260-270% and 300-322% in tensile strength and tear strength compared with pure latex; the tensile strength and the tearing strength of the simple graphene modified latex material are only improved by 76-81% and 60-70%; the tensile strength and the tearing strength of the pure melanin-modified latex material are only improved by 66-81 percent and 60-66 percent; compared with the overall strength, the composite modified latex material composed of the melanin and the graphene is almost the sum of the simple graphene and the simple melanin modified latex material in terms of tensile strength and tearing strength. Therefore, it can be seen that the graphene and the melanin are compounded together to modify the latex to have a synergistic effect.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it will be appreciated that those skilled in the art, on reading the above teachings of the present invention, may make modifications or adaptations to the present invention which are equally within the scope of the present invention as defined by the appended claims.
Claims (13)
1. The composite material modified latex material composed of melanin and graphene is characterized by comprising the following components in parts by weight:
the mass ratio of the melanin to the graphene in the composite material composed of the melanin and the graphene is 1: 1-10.
2. The latex material modified by the composite material composed of melanin and graphene according to claim 1, wherein the composite material composed of melanin and graphene is formed by chemical bonding of the melanin and the graphene through a reduction reaction of the graphene on the surface of the melanin.
3. The latex material modified by the composite material composed of melanin and graphene according to claim 2, wherein the preparation method of the composite material composed of melanin and graphene comprises the following steps:
(1) dispersing graphene and a coupling agent into deionized water containing a dispersing agent, and performing one or more of shearing stirring, physical grinding, ultrasonic treatment, colloid mill treatment, sand mill treatment and high-pressure homogenization treatment to obtain a uniform graphene aqueous suspension; and
(2) adding melanin into the graphene water suspension, uniformly stirring, controlling the pH value of the system to be 6.5-12.5, heating to 50-80 ℃, continuously reacting for 1-8 hours, completing the grafting reaction of the melanin and graphene to obtain a dispersion liquid of a composite material consisting of the stably dispersed melanin and graphene, and performing spray drying to obtain the composite material consisting of the melanin and the graphene.
4. The composite material modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the modified latex material further comprises the following components by weight:
5. the composite material modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the graphene is selected from one or more of graphene derivatives, graphene oxide and derivatives thereof, or biomass graphene and derivatives thereof.
6. The composite modified latex material composed of melanin and graphene according to claim 5, wherein the graphene is selected from graphene oxide.
7. The composite material modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the melanin is selected from plants, animals, microbial cultures or artificially synthesized melanin, and the surface of the melanin contains one or more of hydroxyl, amino and sulfhydryl groups.
8. The latex material modified by a composite material composed of melanin and graphene according to claim 7, wherein the artificially synthesized melanin is synthesized by using one or more of cysteine, catechol, tyrosine, dopamine, 1, 8-dihydroxynaphthalene, 5, 6-dihydroxyindole, tryptophan, phenylalanine, serotonin and the like as raw materials.
9. The composite material modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the coupling agent is one or more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
10. The composite modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the dispersant is selected from one or more of polyvinylpyrrolidone, casein, sodium carboxymethylcellulose, casein, triethanolamine, sodium hexametaphosphate, dispersant NF, hexadecyl benzene sulfonic acid sodium, dodecyl benzene sulfonic acid sodium, stabilizer LW, peregal 0, isopropyl naphthalene sulfonic acid sodium and isobutyl naphthalene sulfonic acid sodium.
11. The composite material modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the stabilizer is selected from one or more of KOH, ammonia water, stabilizer LW and casein.
12. The composite modified latex material composed of melanin and graphene according to claim 1 or 2, wherein the surfactant is selected from one or more of oleic acid, peregal O, sodium hexametaphosphate, a dispersant NF, hexadecylbenzene sulfonic acid, sodium hexadecylbenzene sulfonate, sodium isopropyl naphthalene sulfonate and sodium isobutyl naphthalene sulfonate.
13. A method for preparing a composite material modified latex material composed of melanin and graphene according to any one of claims 1 to 12, which comprises the following steps:
(1) dispersing graphene and a coupling agent into deionized water containing a dispersing agent, and performing one or more of shearing stirring, physical grinding, ultrasonic treatment, colloid mill treatment, sand mill treatment and high-pressure homogenization treatment to obtain a uniform graphene aqueous suspension;
(2) adding melanin into the graphene water suspension, uniformly stirring, controlling the pH value of the system to be 6.5-12.5, heating to 50-80 ℃, continuously reacting for 1-8 hours, completing the grafting reaction of the melanin and graphene to obtain a composite material dispersion liquid consisting of stably dispersed melanin and graphene, and performing spray drying to obtain a composite material consisting of the melanin and the graphene;
(3) dissolving a composite material consisting of melanin and graphene in water to prepare a suspension liquid with the mass concentration of 0.1-3% so as to obtain a uniform and stable composite material dispersion liquid consisting of the melanin and the graphene;
(4) adding a stabilizer and a surfactant into the latex solution, and continuously stirring for 0.5-6 hours; slowly adding the composite material dispersion liquid composed of the melanin and the graphene, continuously stirring and grinding for 0.5-8 h, and adding an accelerator, an anti-aging agent, a vulcanizing agent and a vulcanization activator to obtain a latex mixed liquid;
(5) and vulcanizing the latex mixed solution, dipping and molding by using a mold, and heating and drying to obtain the melanin and graphene composite modified latex material.
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