CN107325466B - Thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material and preparation method and application thereof - Google Patents
Thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polyvinyl alcohol/graphene hydrophobic composite material capable of being thermoplastically processed, a preparation method and application thereof, belonging to the field of high polymer materials. The weight ratio of the graphene to the polyvinyl alcohol is 0.1: 100-20: 100; the alcoholysis degree of the polyvinyl alcohol is 68-80%. The preparation method can mix the polyvinyl alcohol solution and the graphene or graphene solution, spray-dry and process the mixture into the hydrophobic material through thermoplasticity. The method has the advantages of simple preparation process, easy operation, good applicability and lower equipment cost.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material and a preparation method and application thereof.
Background
The polyvinyl alcohol has excellent biocompatibility, oil resistance, solvent resistance, gas barrier property and other properties, and is widely applied to the industries of textile, food, medicine, construction, printing, steel, polymer chemical industry and the like. Because a large number of hydroxyl groups are arranged on a polyvinyl alcohol polymer chain, a large number of intra-molecular and intermolecular hydrogen bonds can be formed, so that the melting temperature and the decomposition temperature of the polyvinyl alcohol with high alcoholysis degree are close, the thermoplastic processing is difficult to realize, and the application of the polyvinyl alcohol is limited to a great extent.
At present, for the melt processing modification technology of polyvinyl alcohol, patent CN102234405B discloses a water-resistant polyvinyl alcohol film composition and a melt preparation method thereof, wherein the method mainly uses small molecules and high molecules as a compound plasticizer, and although the compound plasticizer can be extruded and granulated by a screw, certain damage can be generated to screw processing equipment due to the presence of water in the plasticizer. Patent CN101845185A discloses a thermoplastically processable polyvinyl alcohol alloy and a manufacturing process thereof, which utilizes the blending of polyvinyl alcohol and polyamide to effectively realize the characteristic of thermoplastically processable, but the addition of polyamide can reduce the compactness of polyvinyl alcohol, thereby reducing the barrier property.
Because the polyvinyl alcohol is prepared by hydrolyzing polyvinyl acetate, when the alcoholysis degree of the polyvinyl alcohol is lower, the hydrogen bond interaction between adjacent molecules and between molecules is weakened, and further, the melting point of the polyvinyl alcohol can be reduced, and the possibility of thermoplastic processing is realized. However, as the alcoholysis degree decreases, the barrier property and water resistance of polyvinyl alcohol deteriorate, and therefore, it is a key to research to improve the barrier property and water repellency of polyvinyl alcohol. Lai C L et al (Lai C L, Chen J T, Fu Y J, et al. Bio-insulated cross-linking with borate for enhancing gas-barrier properties of poly (vinyl alcohol)/graphene oxide composite films [ J ]. Carbon,2015,82:513-522.) polyvinyl alcohol/graphene oxide was crosslinked with borate, coated and dried by a solution coating method to prepare an elastic transparent high-barrier composite film. The hydroxyl content of the material can be reduced from 40.8% to 27.0% by adding 0.25 wt% of borax for crosslinking for 1 hour, but the oxygen content of the material is not obviously changed, that is, the borax only plays a crosslinking role and does not have an obvious reduction effect on the graphene oxide.
Patent CN102807682A mentions that a modified polyvinyl alcohol film with a hydrophobic single surface can be prepared by spraying a silane coupling agent, isocyanate and a fatty alcohol solution on the surface of a polyvinyl alcohol film in sequence and then air-drying, and because the modifier in each step needs to be dissolved by an organic solvent, a certain time is needed for air-drying after spraying, the operation period is long, and the consumption of the organic solvent is large. Patent CN104311856A mentions that a hydrophobic plant leaf is used as a template, and polyvinyl alcohol is made into a hydrophobic polyvinyl alcohol film under the action of the template, which makes it difficult to prepare a large area due to the need of a mold release treatment at the later stage of the template method, and the used polyvinyl alcohol cannot be processed by thermoplasticity.
The graphene is exfoliated from the graphite material by sp carbon atoms2The hybrid rail is composed of a two-dimensional material with only one atomic thickness, has excellent electric and heat conducting properties, mechanical properties, gas barrier property and the like, and is widely concerned by the fields of physics, chemistry, materials, electronics, energy and the like. Taherian F et al (Taherian F, Marcon V, van der Vegt N F A, et al]Langmuir,2013,29(5): 1457-.
The graphene with a complete structure is a two-dimensional crystal formed by combining carbon six-membered rings without any unstable bonds, has high chemical stability, is in an inert state on the surface, has weak interaction with other media (such as solvents and the like), has strong van der waals force between graphene sheets, is easy to generate aggregation, and needs to be effectively functionalized in order to improve the molding processability of the graphene. Patent CN101602504A discloses a method for preparing graphene based on ascorbic acid, wherein ascorbic acid is used to replace highly toxic hydrazine hydrate to reduce graphene oxide, but when the reduction time is too long, the reduced graphene converges into an integrated block, and a graphene solution which exists stably and is dispersed uniformly cannot be prepared.
Disclosure of Invention
The invention is proposed to solve the above-mentioned problems of the prior art and to prepare a thermoplastically processable hydrophobic polyvinyl alcohol material in order to improve the hydrophobicity and barrier properties of polyvinyl alcohols with a low degree of alcoholysis.
The invention provides a polyvinyl alcohol/graphene hydrophobic composite material capable of being thermoplastically processed. In particular to a polyvinyl alcohol/graphene hydrophobic composite material which can be thermoplastically processed and a preparation method and application thereof.
One of the objects of the present invention is to provide a thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material.
The invention relates to a polyvinyl alcohol/graphene hydrophobic composite material capable of being thermoplastically processed, which comprises polyvinyl alcohol and graphene; the weight ratio of the graphene to the polyvinyl alcohol is 0.1: 100-20: 100, preferably 0.3: 100-15: 100, and more preferably 0.3: 100-10: 100;
the contact angle of the composite material and water is greater than or equal to 90 degrees, preferably greater than or equal to 95 degrees, and more preferably greater than or equal to 100 degrees.
The degree of alcoholysis of the polyvinyl alcohol can be 68-80%.
The graphene is preferably partially oxidized graphene. The molar ratio of carbon to oxygen in the partially oxidized graphene can be 3-18, preferably 5-15, and more preferably 5-10.
Graphene is hydrophobic without oxygen-containing functional groups, and graphene oxide is hydrophilic with oxygen-containing functional groups. In the invention, in order to prepare the composite material with good hydrophobicity and barrier property, the graphene modified polyvinyl alcohol is used, and the partially oxidized graphene is preferably used for modifying the polyvinyl alcohol.
The composite material may be free of plasticizers.
The invention also aims to provide a preparation method of the thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material. According to the method, a polyvinyl alcohol/graphene composite particle with hydrophobic property is prepared from a polyvinyl alcohol and graphene mixed solution through spray drying, and then various thermoplastic processing is carried out.
The preparation method comprises the following steps: uniformly mixing the graphene solution and the polyvinyl alcohol solution, standing for a period of time, preparing polyvinyl alcohol/graphene hydrophobic composite particles by using spray drying equipment, and then preparing the polyvinyl alcohol/graphene hydrophobic composite material capable of being processed in a thermoplastic manner by using thermoplastic processing equipment.
Specifically, the preparation method of the composite material comprises the following steps:
step 1), uniformly mixing graphene or a graphene solution with a polyvinyl alcohol solution, and standing for a period of time;
step 2), carrying out spray drying on the mixture obtained in the step 1) to prepare polyvinyl alcohol/graphene hydrophobic composite material particles;
and 3) performing thermoplastic processing on the polyvinyl alcohol/graphene hydrophobic composite particles prepared in the step 2) to obtain the polyvinyl alcohol/graphene hydrophobic composite material capable of being processed in a thermoplastic manner.
Wherein, the weight concentration of the polyvinyl alcohol solution in the step 1) is 0.1-20%, preferably 0.1-15%, and more preferably 0.1-10%;
the graphene or the graphene in the graphene solution is preferably partially oxidized graphene. The preparation of the graphene and the partial graphene oxide comprises the steps of reducing the graphene oxide by at least one of a chemical reduction method and a radiation reduction method; the solvent used in the graphene solution and the polyvinyl alcohol solution is not particularly limited, and may include, for example, one of the following: alcohol, acid, ester, water. Among them, water is preferred. These solvents may be used alone or in any combination of two or more thereof. The standing for a period of time is to further improve the reduction degree of the graphene oxide, so that the residual hydroxyl, carboxylic acid group, epoxy group and other groups on the graphene and the hydroxyl, ester group and other groups carried on the polyvinyl alcohol generate hydrogen bond interaction. The standing time can be 0-10 days.
The graphene and the partially oxidized graphene in the present invention are also commercially available, and can be self-made. If the graphene or the partially oxidized graphene is obtained from the market, the graphene or the partially oxidized graphene is directly mixed with the polyvinyl alcohol solution in the step 1) of the preparation method. If the method is self-made, the graphene oxide or partial graphene oxide is obtained by reducing the graphene oxide, the solution containing the graphene or partial graphene oxide after the reduction of the graphene oxide can be directly mixed with the polyvinyl alcohol solution, or the graphene oxide suspension can be uniformly mixed with the reducing agent and the polyvinyl alcohol solution, and then the mixture is stood, and after the reduction reaction is finished, the subsequent steps of spray drying and the like are carried out. The graphene solution generally refers to a graphene suspension or a graphene emulsion.
The reduction method for preparing graphene and partial graphene oxide by reducing graphene oxide according to the present invention may be any one of the methods disclosed in the prior art, and is not particularly limited, and may include, for example, any one of the following: chemical reduction method, radiation reduction method, etc. These methods may be used alone or in combination of both methods.
The reducing agent used in the chemical reduction method is not particularly limited, and for example, at least one of the following substances may be added to the graphene oxide suspension: borohydride, hydrogen halide, sulfur-containing reducing agents, nitrogen-containing reducing agents, oxygen-containing reducing agents, mixtures of metals and acids, and the like. Among them, nitrogen-containing reducing agents and/or oxygen-containing reducing agents are preferable. These reducing agents may be used alone or in any combination of two or more thereof; the nitrogen-containing reducing agent and the oxygen-containing reducing agent are not particularly limited, and may include at least one of the following substances: hydrazine hydrate, pyrrole, ethylenediamine, methanol, ethanol, benzyl alcohol, ascorbic acid, a mixture of ascorbic acid and ammonia (wherein ascorbic acid and ammonia may be mixed in any ratio), and the like. Among them, ascorbic acid is preferable. These reducing agents may be used alone or in any combination of two or more thereof. The dosage of the reducing agent is the dosage commonly used in the prior art, and generally, the weight ratio of the nitrogenous reducing agent to the graphene oxide to the oxygenated reducing agent to the graphene oxide can be selected to be 0.1: 1-10: 1, and preferably 0.5: 1-5: 1. The mixture of metal and acid may be selected from at least one of a mixture of aluminum and hydrochloric acid, a mixture of iron and hydrochloric acid, and a mixture of zinc and sulfuric acid.
The radiation reduction method includes irradiating graphene oxide, and the irradiation source used in the radiation reduction method is not particularly limited, and may include, for example, irradiating a graphene oxide suspension with at least one of: alpha rays, beta rays, gamma rays, X rays, etc. Among them, gamma rays are preferable. These irradiation sources may be used alone or in any combination of two or more thereof. The radiation dose used by the radiation reduction method can be the common dose in the prior art, and generally 30-80 KGy is adopted. Specifically, the radiation dose can be selected to be 10 KGy/day, and the irradiation time is 3-8 days.
The spray drying equipment used in the step 2) has the air inlet temperature of 100-250 ℃, preferably 150-250 ℃, the air outlet temperature of 70-150 ℃, preferably 70-110 ℃; the particle diameter of the polyvinyl alcohol/graphene hydrophobic composite material obtained by spray drying is 5-100 mu m.
The thermoplastic processing temperature in the step 3) is 150-250 ℃, preferably 175-250 ℃, and more preferably 175-220 ℃;
the thermoplastic processing equipment is not particularly limited and may be thermoplastic processing equipment known in the industry, for example, including one of the following: single screw extruder, twin screw extruder, internal mixer, casting machine, injection molding machine, plate vulcanizing machine, etc. These processing apparatuses may be used alone or in any combination of two or more thereof; the hot working temperature used is from 150 ℃ to 250 ℃, preferably from 175 ℃ to 250 ℃, more preferably from 175 ℃ to 220 ℃.
The invention also aims to provide application of the thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material. The thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material can be used as various waterproof barrier products independently or in combination with other materials, and comprises film products, pipes, hollow containers and the like.
The thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material and the preparation method thereof can be used for mixing aqueous solutions and suspensions of two hydrophilic materials, spray drying and thermoplastically processing the mixture into a hydrophobic material. Compared with the traditional hydrophobic material preparation method, the preparation method disclosed by the invention is simple in preparation process, easy to operate, good in applicability and low in equipment cost, and not only is the production efficiency and the operation safety improved, but also the energy consumption and the production cost are reduced. The composite material can be used as various waterproof barrier products independently or in combination with other materials, and has wide application prospect.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples. Example 1
Ultrasonically mixing a graphene oxide suspension (9 mg/ml, carbon-oxygen ratio of 2.03 and deionized water as a solvent) and ascorbic acid (national drug group chemical reagent limited, analytical purity) in deionized water according to a weight ratio of 1:2, then adding a prepared polyvinyl alcohol solution (Nippon Coli, CP-1000 and alcoholysis degree of 78%) with a weight concentration of 20% for ultrasonic mixing, standing at room temperature for one day, and performing spray drying (Shanghai Dachuan original drying equipment limited); wherein the carbon-oxygen ratio of the obtained partial graphene oxide after the graphene oxide and the ascorbic acid are mixed for one day is 7.81, the weight ratio of the partial graphene oxide and the polyvinyl alcohol is 2:100, the weight percentage concentration of the polyvinyl alcohol in the mixed solution is 10%, the air inlet temperature of the spray dryer is 175 ℃, and the air outlet temperature is 70 ℃, wherein the carbon-oxygen ratio is obtained by testing the respective mole fractions of carbon and oxygen through X-ray photoelectron spectroscopy (XPS) and then comparing the two.
And (3) tabletting by using a flat vulcanizing machine after spray drying, wherein the temperature of an upper pressing plate is 200 ℃, the temperature of a lower pressing plate is 200 ℃, the preheating time is 5 minutes, the pressing time is 5 minutes, the pressure is 5MPa, and the cooling time is 5 minutes. The contact angle test is carried out according to a newly modified 'nano thin film contact angle measurement method' (standard number: GB/T30447-2013). The contact angle tester (EASYDROP, germany) performed tests showed a contact angle of 99.4 °. Example 2
The same as example 1 except that the weight ratio of graphene oxide to ascorbic acid was 1:3, the carbon-oxygen ratio of partially oxidized graphene obtained after mixing graphene oxide and ascorbic acid for one day was 8.76, and the contact angle was 105.9 ° as measured by a contact angle tester.
Example 3
The contact angle tester showed a contact angle of 101.8 ° as measured with the same contact angle tester as example 1 except that the weight ratio of graphene oxide to polyvinyl alcohol was 5: 100.
Example 4
The carbon-oxygen ratio of partially oxidized graphene obtained after mixing of graphene oxide and ascorbic acid for six days was 11.43 except that the mixture was left at room temperature for six days after mixing of graphene oxide and polyvinyl alcohol, and the rest was the same as in example 1, and the contact angle was 103.3 ° as a result of the test performed by the contact angle tester.
Example 5
The contact angle tester showed a contact angle of 93.2 ° as measured with the same contact angle tester as example 1 except that the weight ratio of graphene oxide to polyvinyl alcohol was 0.5: 100.
Example 6
The contact angle tester showed a contact angle of 100.7 ° as in example 1, except that the weight ratio of graphene oxide to polyvinyl alcohol was 10: 100.
Comparative example 1
A10% polyvinyl alcohol aqueous solution was prepared, spray-dried, and then tabletted using a flat vulcanizer under the same processing conditions as in example 1. The contact angle tester performed a test indicating that the contact angle was 38.7 °.
Comparative example 2
Polyvinyl alcohol and ascorbic acid are mixed evenly in deionized water by ultrasonic in a weight ratio of 100:4, spray-dried after being placed for one day at room temperature, and then tabletted by a flat-plate vulcanizing machine under the same processing conditions as in example 1. The contact angle tester performed a test indicating that the contact angle was 62.2 °.
Comparative example 3
The graphene oxide suspension (NanoTech technologies, Inc., 9mg/ml, 2.03 carbon to oxygen ratio, deionized water as solvent) was coated and then dried at 200 ℃ for 10 minutes. The contact angle tester performed a test indicating that the contact angle was 54 °.
Comparative example 4
The graphene oxide suspension (Nanjing Ginko nanotechnology Co., Ltd., 9mg/ml, carbon-oxygen ratio of 2.03 and deionized water as solvent) and ascorbic acid were ultrasonically mixed uniformly in deionized water in a weight ratio of 1:2, placed at room temperature for one day, and then coated and dried at 200 ℃ for 10 minutes. The contact angle tester performed a test indicating that the contact angle was 68.9 °.
Comparative example 5
The graphene oxide suspension (9 mg/ml, carbon-oxygen ratio of 2.03, deionized water as solvent) and the polyvinyl alcohol solution were mixed by ultrasound, and spray-dried after being left at room temperature for one day, wherein the weight ratio of the graphene oxide to the polyvinyl alcohol was 2:100, the weight fraction of the polyvinyl alcohol in the mixed solution was 10%, and the processing conditions were the same as those in example 1. The contact angle tester performed a test indicating that the contact angle was 56.4 °.
Claims (26)
1. A thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material, characterized in that:
the composite material comprises graphene and polyvinyl alcohol, wherein the weight ratio of the graphene to the polyvinyl alcohol is 0.5: 100-10: 100; the alcoholysis degree of the polyvinyl alcohol is 68-80%; the graphene is partially oxidized graphene; the molar ratio of carbon to oxygen in the partially oxidized graphene is 7.81-11.43;
the contact angle between the composite material and water is more than or equal to 90 degrees;
the composite material is prepared by a method comprising the following steps:
and (3) uniformly mixing the mixed solution of the polyvinyl alcohol and the graphene by ultrasonic, and then carrying out spray drying.
2. The composite material of claim 1, wherein:
the contact angle between the composite material and water is greater than or equal to 95 degrees.
3. The composite material of claim 2, wherein:
the contact angle between the composite material and water is more than or equal to 100 degrees.
4. The process for the preparation of the thermoplastically processable polyvinyl alcohol/graphene hydrophobic composite material according to any of claims 1 to 3, characterized in that it comprises the following steps:
step 1), uniformly mixing graphene or a graphene solution with a polyvinyl alcohol solution, and standing;
step 2), carrying out spray drying on the mixture obtained in the step 1) to prepare polyvinyl alcohol/graphene hydrophobic composite material particles;
and 3) performing thermoplastic processing on the polyvinyl alcohol/graphene hydrophobic composite particles prepared in the step 2) to obtain the polyvinyl alcohol/graphene hydrophobic composite material capable of being processed in a thermoplastic manner.
5. The production method according to claim 4, characterized in that:
the weight concentration of the polyvinyl alcohol solution in the step 1) is 0.1-20%.
6. The production method according to claim 5, characterized in that:
the weight concentration of the polyvinyl alcohol solution in the step 1) is 0.1-15%.
7. The production method according to claim 6, characterized in that:
the weight concentration of the polyvinyl alcohol solution in the step 1) is 0.1-10%.
8. The method of claim 4, wherein:
the solvent of the graphene solution and the polyvinyl alcohol solution is at least one selected from alcohol, acid, ester and water.
9. The method of claim 8, wherein:
the solvent of the graphene solution and the polyvinyl alcohol solution is selected from water.
10. The method of claim 4, wherein:
the preparation of the graphene comprises at least one of a chemical reduction method and a radiation reduction method.
11. The method of manufacturing according to claim 10, wherein:
the chemical reduction method comprises the steps of adding at least one of borohydride, hydrogen halide, sulfur-containing reducing agent, nitrogen-containing reducing agent, oxygen-containing reducing agent, metal and acid mixture into graphene oxide solution;
the irradiation reduction method comprises the step of irradiating the graphene oxide, wherein an irradiation source comprises at least one of alpha rays, beta rays, gamma rays and X rays.
12. The method of claim 11, wherein:
the chemical reduction method comprises the step of adding at least one of a nitrogenous reducing agent and an oxygen-containing reducing agent into the graphene oxide solution.
13. The method of claim 11, wherein:
the irradiation source is gamma rays.
14. The method of claim 11, wherein:
the weight ratio of the nitrogenous reducing agent to the graphene oxide and the weight ratio of the oxygenated reducing agent to the graphene oxide are both 0.1: 1-10: 1.
15. The method of claim 14, wherein:
the weight ratio of the nitrogenous reducing agent to the graphene oxide and the weight ratio of the oxygen-containing reducing agent to the graphene oxide are both 0.5: 1-5: 1.
16. The method of claim 14, wherein:
the nitrogenous reducing agent and the oxygen-containing reducing agent comprise at least one of hydrazine hydrate, pyrrole, ethylenediamine, methanol, ethanol, benzyl alcohol, ascorbic acid and ammonia.
17. The method of manufacturing according to claim 16, wherein:
the nitrogenous reducing agent and the oxygen-containing reducing agent are both selected from ascorbic acid.
18. The method of claim 11, wherein:
the radiation dose used by the radiation reduction method is 30-80 KGy.
19. The method of claim 4, wherein:
in the spray drying technology in the step 2), the air inlet temperature is 100-250 ℃, and the air outlet temperature is 70-150 ℃.
20. The method of claim 19, wherein:
the air inlet temperature is 150-250 ℃, and the air outlet temperature is 70-110 ℃.
21. The method of claim 19, wherein:
the particle diameter of the polyvinyl alcohol/graphene hydrophobic composite material is 5-100 mu m.
22. The method of claim 4, wherein:
the thermoplastic processing temperature in the step 3) is 150-250 ℃.
23. The method of claim 22, wherein:
the thermoplastic processing temperature in the step 3) is 175-250 ℃.
24. The method of claim 23, wherein:
the thermoplastic processing temperature in the step 3) is 175-220 ℃.
25. Use of a thermoplastically processible polyvinyl alcohol/graphene hydrophobic composite material according to any of claims 1 to 3, characterized in that:
the composite material is used for waterproof barrier materials.
26. Use of a thermoplastically processible polyvinyl alcohol/graphene hydrophobic composite material according to claim 25, characterized in that:
the composite material is used for waterproof and barrier film products, pipes and hollow containers.
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| US6410637B1 (en) * | 2000-11-28 | 2002-06-25 | Xerox Corporation | Water-based composition for coating a donor member |
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| CN105111722A (en) * | 2015-08-21 | 2015-12-02 | 安徽天堂唯高塑业科技有限公司 | Safety steering wheel protection layer sheath material and preparation method thereof |
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| US6410637B1 (en) * | 2000-11-28 | 2002-06-25 | Xerox Corporation | Water-based composition for coating a donor member |
| KR20060108066A (en) * | 2005-04-12 | 2006-10-17 | 양경준 | Conductivity hydrogel type heating phase change material |
| CN103205075A (en) * | 2012-01-17 | 2013-07-17 | 帛宏兴业股份有限公司 | Heat radiation material, heat radiation structure, and preparation method and application thereof |
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