WO2022205791A1 - 一种石墨烯改性pet薄膜材料以及制备方法 - Google Patents

一种石墨烯改性pet薄膜材料以及制备方法 Download PDF

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WO2022205791A1
WO2022205791A1 PCT/CN2021/118379 CN2021118379W WO2022205791A1 WO 2022205791 A1 WO2022205791 A1 WO 2022205791A1 CN 2021118379 W CN2021118379 W CN 2021118379W WO 2022205791 A1 WO2022205791 A1 WO 2022205791A1
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graphene
modified
modified pet
ethylene glycol
film material
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French (fr)
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吴丹丹
陈登龙
吴婷婷
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福建师范大学泉港石化研究院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention belongs to the technical field of PET materials, in particular to a graphene-modified PET film material and a preparation method.
  • PET Polyethylene terephthalate
  • graphene As a popular emerging material in recent years, graphene has broad application prospects in electronics, optics, magnetism, biomedicine, catalysis, energy storage and sensors. The dense internal structure determines that graphene has excellent barrier properties. How to Better use of graphene in different materials to improve the overall barrier performance of the material and meet the barrier requirements in different fields has also become a research direction in recent years.
  • the invention patent with the publication number CN106349462A discloses the preparation of a high-barrier nano-modified PET composite material for packaging products. First, graphene or white graphene is treated with a surfactant to obtain a modified nano-material powder. Nano-modified PET composites were prepared by in-situ polymerization or melt blending.
  • the PET composite material prepared by the above method has a lack of bonding between graphene and the PET matrix, is not stable enough, and has insufficient compatibility, so that the PET composite material cannot achieve the ideal barrier effect in some fields.
  • the purpose of the present invention is to provide a graphene-modified PET film material, in which the graphene can be more stably combined with the PET matrix, thereby improving the overall barrier effect of the material.
  • a graphene-modified PET film material with graphite and ethylene glycol as raw materials, under the atmosphere of supercritical carbon dioxide, modified graphene is prepared by ball milling, Then the modified graphene is synthesized with another terephthalic acid and ethylene glycol by in-situ polymerization to obtain graphene-modified PET composite material pellets, and then the graphite is obtained through a multi-layer stretching extrusion system.
  • Alkene modified PET film material Alkene modified PET film material.
  • edge carboxylated graphene can be obtained under the atmosphere of carbon dioxide, and in this solution, when modified graphene is produced by ball milling, the raw material not only adds graphite.
  • ethylene glycol also exists at the same time, and supercritical carbon dioxide is used, so that the fluid state of supercritical carbon dioxide can be used to bring the ethylene glycol in the same fluid state into the graphene sheet and disperse evenly, so that supercritical carbon dioxide
  • the carboxyl groups on the edge carboxylated graphene immediately undergo esterification reaction with ethylene glycol to obtain modified graphene, which effectively overcomes the problem of graphene re-agglomeration after exfoliation.
  • the modified graphene has alcoholic hydroxyl groups and can participate in the polycondensation reaction with terephthalic acid and ethylene glycol taken separately to form graphene-modified PET composite material pellets.
  • the graphene-modified PET composite material pellets The graphene and the PET matrix are combined in the form of chemical bonds, and the graphene sheet is extremely thin and well dispersed, so the combination of graphene and the PET matrix is more stable, so that the final graphene modified PET film is obtained.
  • the overall barrier properties of the material are good.
  • the graphite is one or more of flake graphite, expanded graphite, bulk graphite, and amorphous graphite.
  • the graphite is flake graphite.
  • the barrier property of the graphene-modified PET film material finally obtained is better.
  • the mass fraction of modified graphene in the graphene-modified PET composite pellets is 0.1wt%-1.0wt%.
  • the mass fraction of modified graphene in the graphene-modified PET composite pellets is 0.3wt%-0.5wt%.
  • Another object of the present invention is to provide a method for preparing a graphene-modified PET film material, which has the advantages of simple process and easy operation.
  • the above-mentioned object of the present invention is prepared by the following method:
  • modified graphene add 1 weight part of graphite, more than 10 weight parts of ethylene glycol and an appropriate amount of catalyst in the ball mill tank, then the tank body is sealed with flange screws, and the tank is charged into the tank through an inflation device for Expel carbon dioxide gas from the air in the tank; then pour carbon dioxide gas into the tank until the pressure reaches 7.3-15MPa, close the valve, and the carbon dioxide injected into the tank is in a supercritical state; Under -600r/min, ball mill for 24-72 hours to obtain the modified graphene;
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • the initial materials such as graphite, ethylene glycol and catalyst are added into the ball mill tank at the same time, and then the air is removed by flushing carbon dioxide gas to avoid excessive impurities in the later reaction, and then carbon dioxide is flushed again.
  • the pressure is adjusted so that the injected carbon dioxide is converted into supercritical carbon dioxide, and the modified graphene is finally obtained by ball milling in the atmosphere of the supercritical carbon dioxide.
  • the exfoliated graphene is immediately surrounded by a large amount of ethylene glycol, and the carboxyl groups on the surface edge of the modified graphene react with ethylene glycol to avoid the agglomeration of the exfoliated graphene; at the same time, on the modified graphene
  • the multi-layer stretch extrusion system obtains graphene modified PET film material.
  • the mass ratio of ethylene glycol/graphene in S1 is greater than 10.
  • the monomer molar ratio of the ethylene glycol used in the S1 step and the S2 step to the terephthalic acid used in the S2 step is between 1.05-1.3.
  • the catalyst is one or both of Sb(OAc) 3 , Co(OAc) 2 , Sb 2 O 3 , and H 3 PO 4 .
  • the present invention links the graphene and the PET matrix together through chemical bonds, enhances the interaction between the graphene and the PET matrix, and effectively binds the motion range of the polymer molecular chain, thereby effectively improving the barrier performance of the PET material;
  • the method of grouping and reacting the required raw material ethylene glycol, by adding ethylene glycol and supercritical carbon dioxide while using graphite ball milling to obtain graphene makes graphene more and more stable with PET.
  • the matrix is combined to improve the barrier properties of the PET material;
  • the present invention can improve the overall reaction speed by reacting the required raw material ethylene glycol in groups.
  • a graphene-modified PET film material is prepared according to the following method:
  • step S2 take the modified graphene obtained in step S1 in a four-necked flask, be warming up to 260 DEG C under nitrogen protection to react and reflux for 2 hours to obtain the first solution; then take 166.13g of terephthalic acid and 44.48g of ethylene glycol In the three-necked flask, the temperature was raised to 200°C under the protection of nitrogen, so that all terephthalic acid was dissolved to obtain the second solution; the second solution was added to the first solution, the reaction was continued for 3 hours, and then the temperature was raised to 270-290°C. °C, carry out polycondensation reaction under vacuum condition, finish the polymerization reaction after 4 hours of reaction, discharge material under nitrogen protection, solidify and cut into pellets to obtain graphene-modified PET composite material pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • any values are not limited to the precise ranges or values, which are to be understood to include values near those ranges.
  • the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.
  • Embodiment 1 a kind of graphene-modified PET film material, prepared according to the following method:
  • step S2 prepare graphene-modified PET composite material pellets by in-situ polymerization: take the modified graphene obtained in step S1 in a four-necked bottle, heat up to 260° C. under nitrogen protection, and react and reflux for 2 hours to obtain a first solution Then get 166.13g terephthalic acid and 41.38g ethylene glycol in the there-necked flask, be warming up to 200 °C under the protection of nitrogen, make terephthalic acid all dissolve, obtain the second solution; Finally, the second solution is added to In the first solution, the reaction was continued for 3 hours, then the temperature was raised to 270-290° C., a polycondensation reaction was carried out under vacuum conditions, the reaction was terminated after 4 hours, the material was discharged under the protection of nitrogen, and cured and pelletized to obtain graphene-modified PET. Composite pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • Embodiment 2 a kind of graphene-modified PET film material, prepared according to the following method:
  • step S2 take the modified graphene obtained in step S1 in a four-necked flask, be warming up to 260 DEG C under nitrogen protection to react and reflux for 2 hours to obtain the first solution; then take 166.13g of terephthalic acid and 44.48g of ethylene glycol In the three-necked flask, the temperature was raised to 200°C under the protection of nitrogen, so that all terephthalic acid was dissolved to obtain the second solution; the second solution was added to the first solution, the reaction was continued for 3 hours, and then the temperature was raised to 270-290°C. °C, carry out polycondensation reaction under vacuum condition, finish the polymerization reaction after 4 hours of reaction, discharge material under nitrogen protection, solidify and cut into pellets to obtain graphene-modified PET composite material pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • Embodiment three a kind of graphene-modified PET film material, prepared according to the following method:
  • step S2 prepare graphene-modified PET composite material pellets by in-situ polymerization: take the modified graphene obtained in step S1 in a four-necked bottle, heat up to 260° C. under nitrogen protection, and react and reflux for 2 hours to obtain a first solution Then get 166.13g terephthalic acid and 41.38g ethylene glycol in the there-necked flask, be warming up to 200 °C under the protection of nitrogen, make terephthalic acid all dissolve, obtain the second solution; Finally, the second solution is added to In the first solution, the reaction was continued for 3 hours, then the temperature was raised to 270-290° C., a polycondensation reaction was carried out under vacuum conditions, the reaction was terminated after 4 hours, the material was discharged under the protection of nitrogen, and cured and pelletized to obtain graphene-modified PET. Composite pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • step S2 preparing graphene-modified PET composite pellets by in-situ polymerization: take the modified graphene obtained in step S1 in a four-necked bottle, heat up to 260° C. under nitrogen protection for reaction and reflux for 2 hours to obtain the first solution; then take 166.13g of terephthalic acid and 50.69g of ethylene glycol in a three-necked flask, heat up to 200°C under the protection of nitrogen, so that all terephthalic acid is dissolved to obtain a second solution; In the first solution, continue to react for 3 hours, then be heated to 270-290 ° C, carry out polycondensation reaction under vacuum conditions, finish the polymerization reaction after 4 hours of reaction, discharge material under nitrogen protection, and solidify and pelletize to obtain graphene modification PET composite pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • Embodiment 5 a kind of graphene-modified PET film material, prepared according to the following method:
  • step S2 prepare graphene-modified PET composite material pellets by in-situ polymerization: take the modified graphene obtained in step S1 in a four-necked bottle, heat up to 260° C. under nitrogen protection, and react and reflux for 2 hours to obtain a first solution Then get 166.13g terephthalic acid and 47.59g ethylene glycol in the there-necked flask, be warming up to 200 °C under the protection of nitrogen, make terephthalic acid all dissolve, obtain the second solution; The second solution is added to at last In the first solution, the reaction was continued for 3 hours, then the temperature was raised to 270-290° C., a polycondensation reaction was carried out under vacuum conditions, the reaction was terminated after 4 hours, the material was discharged under the protection of nitrogen, and cured and pelletized to obtain graphene-modified PET. Composite pellets.
  • the graphene-modified PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain a graphene-modified PET film material.
  • Comparative Example 1 First, add ball mill beads and graphite powder in proportion to the ball mill tank, seal the tank body with flange screws, pour carbon dioxide gas into the tank body, slowly open the air valve at the other end of the tank body, and ventilate for 15 minutes to empty. To remove the air in the tank, close the air outlet valve tightly, and recharge the carbon dioxide gas in the tank to 15MPa, so that the re-injected carbon dioxide is in a supercritical state, and the valve is closed tightly. Turn on the planetary ball mill, grind continuously at 500 rpm for 48 hours, then remove the ball mill tank, take a section of the plastic gas pipeline and connect it to the gas valve, and the other end into the water tank, slowly open the gas valve, and drain the tank.
  • the modified graphene is prepared; then 0.722g of this modified graphene and the PET master batch are placed in dry mixing Mix evenly in the machine, add the mixed materials into the kneader, melt and knead and extrude to prepare the graphene PET composite material, and the graphene PET composite material pellets are passed through a multi-layer stretching extrusion system to obtain graphene Modified PET film material.
  • Comparative Example 2 The difference from Example 5 is that in the process of preparing modified graphene by ball milling under the atmosphere of supercritical carbon dioxide, ethylene glycol was not added; Graphite is used as a raw material, and modified graphene is obtained by ball milling, and then the modified graphene is used for in-situ polymerization with terephthalic acid and ethylene glycol, and finally a graphene-modified PET film material is obtained.
  • Comparative Example 3 The difference from Example 5 is that when the modified graphene is prepared by ball milling, it is not supercritical carbon dioxide, but ordinary carbon dioxide gas.
  • Comparative example four in the four-necked flask, add the catalyst (Sb(OAc) 3 ) of 74.48g ethylene glycol, 166.13g terephthalic acid and 0.4 g, then feed nitrogen and fully stir for 30 minutes, then under nitrogen protection The temperature was raised to 200°C, and the temperature was raised to 260°C after the phthalic acid was completely dissolved, and the reaction was carried out for 3 hours, and then the temperature was raised to 270-290°C, and the polycondensation reaction was carried out under vacuum conditions.
  • PET pellets are obtained by solidifying and dicing.
  • the PET film material is obtained by passing the PET pellets through a multi-layer stretch extrusion system.
  • Comparing Examples 1 to 5 with Comparative Example 1 it can be found that the gas barrier properties of Examples 1 to 5 are better than those of Comparative Example 1, because the graphene in Examples 1 to 5 is a chemical bond with The combination of the PET matrix enhances the interaction between graphene and the polymer matrix, effectively constrains the motion range of the polymer molecular chain, thereby improving the barrier properties of the PET material.
  • Examples 1 to 5 show that the gas barrier properties of Examples 1 to 5 are better than those of Comparative Example 3.
  • the modified graphene is produced by ball milling in Examples 1 to 5, the The atmosphere at the place is supercritical carbon dioxide atmosphere, and the fluid state of supercritical carbon dioxide is used to bring the ethylene glycol in the same fluid state into the graphene sheet and disperse evenly, so that after supercritical carbon dioxide carboxylates the edge of graphene, the edge Carboxylated graphene can use its carboxyl groups to more easily undergo esterification with ethylene glycol to obtain modified graphene, so that the graphene in this modified graphene is more and more stable with carboxyl groups and ethylene glycol.
  • the graphene modified PET film material formed by polycondensation reaction with another terephthalic acid and ethylene glycol has better barrier properties.
  • Example 1 Comparing Example 1 to Example 5, it can be found that with the increase of the addition amount of graphene, the barrier properties of the graphene-modified PET film material to water vapor and oxygen show a trend of first increasing and then decreasing, because the addition amount is too high. Most of them lead to particle aggregation, which reduces the homogeneity of graphene particles in the polymer, cannot effectively prolong the gas diffusion path, and eventually leads to a decrease in gas barrier properties.

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Abstract

本发明涉及PET材料技术领域，具体公开了一种石墨烯改性PET薄膜材料及其制备方法，本发明在利用球磨法将石墨制作成石墨烯的时候，加入超临界二氧化碳和乙二醇，利用超临界二氧化碳的流体状态把乙二醇带入石墨烯片层中并分散均匀，使得超临界二氧化碳将石墨烯的边缘羧基化后，该边缘羧基化的石墨烯上的羧基立即与乙二醇发生酯化反应得到改性石墨烯，再利用该改性石墨烯与对苯二甲酸、乙二醇进行缩聚反应等形成石墨烯改性PET复合材料粒料，再经过拉伸挤出得到石墨烯改性PET薄膜材料。本发明的石墨烯与PET基体能够更加稳定地进行结合，从而大幅度地提升了石墨烯在PET基体中的阻隔效应，提升了石墨烯改性PET薄膜材料的整体阻隔性能。

Description

一种石墨烯改性PET薄膜材料以及制备方法 技术领域
本发明属于PET材料技术领域，具体涉及一种石墨烯改性PET薄膜材料以及制备方法。
 背景技术
聚对苯二甲酸乙二醇酯(PET)是由对苯二甲酸与乙二醇缩聚而成，由于其具有良好的透明性、化学稳定性、力学强度高、可回收利用等优点，已逐渐成为食品、饮料、药品包装等领域的首选材料。然而在这些应用中存在的共性问题是PET的阻隔性能不足，影响最终制品的性能。
石墨烯作为近年热门的新兴材料，在电子学、光学、磁学、生物医学、催化、储能和传感器等方面具有广阔的应用前景，致密的内部结构决定了石墨烯具有优异的阻隔性能，如何将石墨烯更好地运用在不同材料中，以提升材料整体的阻隔性能，达到不同领域的阻隔要求，也成为了人们近几年的研究方向。
公布号为CN106349462A的发明专利公布了一种包装制品用高阻隔纳米改性PET复合材料的制备，先将石墨烯或白石墨烯用表面活性剂处理，得到改性纳米材料粉体，然后通过原位聚合法或熔融共混法制备纳米改性PET复合材料。
但是上述这种方法制备得到的PET复合材料，其石墨烯与PET基体的结合度有所欠缺，不够稳定，相容性不够好，从而导致PET复合材料并不能达到某些领域理想的阻隔效果。
如何改进石墨烯与PET的复合方法，提高石墨烯在PET基体中的稳定性，提升PET复合材料的整体阻隔性能，以适用具有更高阻隔要求的环境，成为了人们亟待解决的问题。
 技术问题
如何解决石墨烯在PET中的高度分散问题，从而进一步提高石墨烯基PET阻隔材料的阻隔性能。
 技术解决方案
本发明的目的在于提供一种石墨烯改性PET薄膜材料，该材料中的石墨烯能够与PET基体更加稳定得结合在一起，从而提升了该材料整体的阻隔效果。
本发明的上述目的是通过以下技术方案得以实现的：一种石墨烯改性PET薄膜材料，以石墨和乙二醇为原料，在超临界二氧化碳的氛围下，通过球磨制备得到改性石墨烯，然后将所述改性石墨烯与另取的对苯二甲酸、乙二醇采用原位聚合法合成得到石墨烯改性PET复合材料粒料，然后通过多层拉伸挤出系统获得所述石墨烯改性PET薄膜材料。
现有技术中在利用球磨法将石墨制作成石墨烯的时候，处于二氧化碳氛围下可以得到边缘羧基化的石墨烯，而本方案在通过球磨法制作改性石墨烯时，原料不仅仅加入了石墨，乙二醇也是同时存在的，并且使用的是超临界二氧化碳，这样可以利用超临界二氧化碳的流体状态把同为流体状态的乙二醇带入石墨烯片层中并分散均匀，使得超临界二氧化碳将石墨烯的边缘羧基化后，该边缘羧基化的石墨烯上的羧基立即与乙二醇发生酯化反应得到改性石墨烯，有效的克服了剥离后石墨烯再团聚的问题。同时该改性石墨烯上具有醇羟基能够参与与另取的对苯二甲酸、乙二醇进行的缩聚反应从而形成石墨烯改性PET复合材料粒料，该石墨烯改性PET复合材料粒料中的石墨烯与PET基体以化学键键合的形式结合在一起，并且石墨烯片层极薄、分散良好，故石墨烯与PET基体的结合更加稳定，从而使最后得到的石墨烯改性PET薄膜材料的整体阻隔性能较好。
进一步地，所述石墨为鳞片石墨、膨胀石墨、块状石墨、无定形石墨中的一种或多种。
进一步地，所述石墨为鳞片石墨。
采用上述技术方案，当选用的石墨原料为鳞片石墨时，其最后得到的石墨烯改性PET薄膜材料的阻隔性能更好。
进一步地，所述石墨烯改性PET复合材料粒料中的改性石墨烯的质量分数为0.1wt%-1.0wt%。
进一步地，所述石墨烯改性PET复合材料粒料中的改性石墨烯的质量分数为0.3wt%-0.5wt%。
采用上述技术方案，当制备得到的石墨烯改性PET复合材料粒料中的改性石墨烯的质量分数为0.3wt%-0.5wt%时，其最后得到的石墨烯改性PET薄膜材料的阻隔性能最佳。
本发明的另一目的在于提供一种石墨烯改性PET薄膜材料的制备方法，具有工艺简单、易于操作的优点。
本发明的上述目的，通过以下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中加入1重量份的石墨、10重量份以上的乙二醇和适量催化剂，然后将罐体用法兰螺丝密封，通过充气装置向罐体内冲入用于排除罐体内空气的二氧化碳气体；然后向罐体内另冲入二氧化碳气体，直到压力达到7.3-15MPa，关紧阀门，此时另冲入的二氧化碳处于超临界状态；然后在32℃-100℃、转速300-600r/min下，球磨24-72小时，即得到所述改性石墨烯；
S2、原位聚合法制备石墨烯改性PET复合材料粒料：首先在四口瓶中加入S1制备的改性石墨烯的溶液，在氮气保护下升温至200-265℃反应回流1-2小时，得到第一溶液；然后另取适量的对苯二甲酸和乙二醇，并在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将所述第二溶液加到所述第一溶液中，继续反应2-4小时，升温至270-290℃，于真空条件下进行缩聚反应，反应2-4小时后结束，在氮气保护下出料，固化切粒即得到所述石墨烯改性PET复合材料粒料；
S3、将所述石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
采用上述技术方案，在球磨罐中同时加入石墨、乙二醇、催化剂这些初始料，然后通过冲入二氧化碳气体排除空气，避免在后期反应中产生过多的杂质，然后再另冲入二氧化碳，通过调整压力，使得另冲入的二氧化碳转变成超临界二氧化碳，在该超临界二氧花碳的氛围下，通过球磨最后得到的改性石墨烯。该改性石墨烯在制备过程中，剥离的石墨烯立即被大量的乙二醇包围且其表面边缘的羧基与乙二醇反应可避免已剥离石墨烯的团聚；同时，该改性石墨烯上具有的醇羟基可参与与之后另取的对苯二甲酸、乙二醇进行的缩聚反应并切粒得到石墨烯改性PET复合材料粒料，最后将该石墨烯改性PET复合材料粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
现有技术中在利用带活性基团的石墨烯与乙二醇、苯二甲酸等发生原位聚合时是直接将其混合反应的。经过我们研究发现现有技术的这种方式整体反应速度较慢，且石墨烯与PET基体的化学结合量较少且不够稳定。而本方案在石墨烯羧基化的同时，将其与乙二醇进行化学键键合，之后再与另取的乙二醇、苯二甲酸进行原位聚合，这样一来能够提高整体的反应速度，同时也使得PET基体上能够结合更多的石墨烯，使得结合的稳定性更好；另外，由于在石墨烯进行边缘羧基化时，采用的是超临界二氧化碳，该超临界二氧化碳会将乙二醇带入石墨烯片层并分散均匀，使得边缘羧基化的石墨烯能够更容易与乙二醇发生酯化反应得到改性石墨烯。
进一步地，S1中的乙二醇/石墨烯的质量比大于10。
进一步地，S1步骤、S2步骤中所用到的乙二醇加起来与S2步骤中所用到的对苯二甲酸的单体摩尔比为1.05-1.3之间。
进一步地，所述的催化剂为Sb(OAc) 3、Co(OAc) 2、Sb 2O 3、H 3PO 4中的一种或两种。
有益效果
本发明具有以下有益效果：
1、本发明将石墨烯与PET基体通过化学键连在一起，增强石墨烯与PET基体的相互作用，有效地束缚了聚合物分子链的运动范围，从而有效提升了PET材料的阻隔性能；
2、本发明通过将所需原料乙二醇分组反应的方法，通过在利用石墨球磨得到石墨烯的同时，加入乙二醇和超临界二氧化碳的方法，使得石墨烯能够更多且更加稳定地与PET基体结合在一起，从而提升PET材料的阻隔性能；
3、本发明通过将所需原料乙二醇分组反应的方法，能够提高整体的反应速度。
 本发明的最佳实施方式
一种石墨烯改性PET薄膜材料，按照如下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、0.722g石墨鳞片、30g乙二醇和0.003g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内二氧化碳气体至15MPa，关紧出气阀门，再次冲入的二氧化碳气体在此压力下为超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在50℃、500转/min的转速下连续研磨48小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得到改性石墨烯。
S2、取S1步骤中得到的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和44.48g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，于真空条件下进行缩聚反应，反应4小时后结束聚合反应，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
 本发明的实施方式
以下结合实施例对本发明作进一步详细说明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
实施例一：一种石墨烯改性PET薄膜材料，按照如下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、0.238g石墨鳞片、30g乙二醇和0.002g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内冲入二氧化碳气体，直到压力达到15MPa，关紧阀门，这里，再次冲入的二氧化碳气体在此压力下为超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在35℃、500转/min的转速下连续研磨24小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得到改性石墨烯。
S2、原位聚合法制备石墨烯改性PET复合材料粒料：取S1步骤中得到的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和41.38g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，于真空条件下进行缩聚反应，反应4小时后结束，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
实施例二：一种石墨烯改性PET薄膜材料，按照如下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、0.722g石墨鳞片、30g乙二醇和0.003g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内二氧化碳气体至15MPa，关紧出气阀门，再次冲入的二氧化碳气体在此压力下为超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在50℃、500转/min的转速下连续研磨48小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得到改性石墨烯。
S2、取S1步骤中得到的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和44.48g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，于真空条件下进行缩聚反应，反应4小时后结束聚合反应，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
实施例三：一种石墨烯改性PET薄膜材料，按照如下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、1.219g石墨鳞片、30g乙二醇和0.007g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内二氧化碳气体，直到压力达到15MPa，关紧阀门，此时，这种再次冲入的二氧化碳气体在此压力下超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在90℃、500转/min的转速下连续研磨48小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得改性石墨烯。
S2、原位聚合法制备石墨烯改性PET复合材料粒料：取S1步骤中得到的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和41.38g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，于真空条件下进行缩聚反应，反应4小时后结束，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
实施例四：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、1.728g石墨鳞片、30g乙二醇和0.009g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内二氧化碳气体，直到压力达到15Mpa，关紧阀门，此时，再次冲入的二氧化碳气体在此压力下为超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在100℃、500转/min的转速下连续研磨60小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得改性石墨烯。
S2、原位聚合法制备石墨烯改性PET复合材料粒料：取S1步骤中得到的的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和50.69g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，真空条件下进行缩聚反应，反应4小时后结束聚合反应，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
实施例五：一种石墨烯改性PET薄膜材料，按照如下方法制备得到：
S1、改性石墨烯的制备：在球磨罐中按比例加入球磨珠、2.437g石墨鳞片、30g乙二醇和0.012g催化剂(H 3PO 4)，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气。关紧出气阀门，再次向罐体内二氧化碳气体，直到压力达到15MPa，关紧阀门，此时，再次冲入的二氧化碳气体在此压力下为超临界状态，即成为了超临界二氧化碳。打开行星式球磨机，在100℃、500转/min的转速下连续研磨60小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得改性石墨烯。
S2、原位聚合法制备石墨烯改性PET复合材料粒料：取S1步骤中得到的改性石墨烯于四口瓶中，在氮气保护下升温至260℃反应回流2小时，得到第一溶液；然后取166.13g对苯二甲酸和47.59g乙二醇于三口烧瓶中，在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将第二溶液加到第一溶液中，继续反应3小时，随后升温至270-290℃，于真空条件下进行缩聚反应，反应4小时后结束，在氮气保护下出料，固化切粒即得到石墨烯改性的PET复合材料粒料。
S3、将石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
对比例一：首先，在球磨罐中按比例加入球磨珠和石墨粉，将罐体用法兰螺丝密封，向罐体内冲入二氧化碳气体，缓慢打开罐体另一端气阀，通气15分钟以便排空罐体内的空气，关紧出气阀门，再次向罐体内二氧化碳气体至15MPa，使得该再次冲入的二氧化碳处于超临界状态，关紧阀门。打开行星式球磨机，在500转/min的转速下连续研磨48小时后取下球磨罐，取塑料气体管路一段连接于气体阀门，另一端通入水槽中，缓慢打开气体阀门，排尽罐体内气体，保持气阀打开状态，取下紧固螺丝，打开球磨罐，经分样筛选，即制备得改性石墨烯；然后将这种改性石墨烯0.722g与PET母粒体放在干混机中混合均匀，将混合好的物料加入到混炼机中熔融混炼后挤出，制备得到石墨烯PET复合材料，将石墨烯PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
对比例二：与实施例五的区别在于，在超临界二氧化碳的氛围下，通过球磨制备得到改性石墨烯的过程中，不加入乙二醇；而是在利用超临界二氧化碳的氛围下，以石墨为原料，通过球磨得到改性石墨烯后，再利用这种改性石墨烯与对苯二甲酸和乙二醇进行原位聚合，最后得到石墨烯改性PET薄膜材料。
对比例三：与实施例五得区别在于，在用球磨法制备改性石墨烯时，其用到的并不是超临界二氧化碳，而是普通的二氧化碳气体。
对比例四：在四口瓶中，加入74.48g乙二醇、166.13g对苯二甲酸和0.4 g的催化剂(Sb(OAc) 3)，随后通入氮气并充分搅拌30分钟，之后在氮气保护下升温至200℃，待苯二甲酸全部溶解后升温至260℃，反应3小时，随后升温至270-290℃，真空条件下进行缩聚反应，反应4小时后结束聚合反应，在氮气保护下出料，固化切粒即得到PET粒料。将PET粒料通过多层拉伸挤出系统获得PET薄膜材料。
对实施例一至实施例五，对比例一至对比例四所得的样品进行阻隔性能的相关测试，得到表1。
表1  性能测试结果
Figure dest_path_image001
经检测，由表1数据可知：
实施例一至实施例五与对比例一相比，可以发现，实施例一至实施例五的气体阻隔性能均优于对比例一，这是因为实施例一至实施例五中的石墨烯是以化学键与PET基体结合的，增强了石墨烯与聚合物基体的相互作用，有效地束缚了聚合物分子链的运动范围，从而提升了PET材料的阻隔性能。
实施例一至实施例五与对比例二相比，可以发现实施例一至实施例五的气体阻隔性能优于对比例二，这是因为实施例一至实施例五是将原料分为了两组，在石墨烯羧基化的同时，将其与乙二醇进行化学键键合，之后再与另取的乙二醇、苯二甲酸进行原位聚合，这样一来能够提高整体的反应速度，同时也使得PET基体上能够结合更多的石墨烯，使得结合的稳定性更好，从而提升了PET材料的阻隔性能。
实施例一至实施例五与对比例三相比，可以发现实施例一至实施例五的气体阻隔性能优于对比例三，实施例一至实施例五在通过球磨法制作改性石墨烯时，其所处的氛围是超临界二氧化碳氛围，利用超临界二氧化碳的流体状态把同为流体状态的乙二醇带入石墨烯片层且分散均匀，使得超临界二氧化碳将石墨烯的边缘羧基化后，该边缘羧基化石墨烯能够利用其羧基更容易与乙二醇发生酯化反应得到改性石墨烯，使得这种改性石墨烯中的石墨烯更够更多且更加稳定地与羧基和乙二醇结合，之后再与另取的对苯二甲酸、乙二醇进行缩聚反应等形成的石墨烯改性PET薄膜材料，其阻隔性能更好。
比较实施例一至实施例五，可以发现随着石墨烯的加入量增加，石墨烯改性PET薄膜材料对水蒸气和氧气的阻隔性呈先增大后减小的趋势，这是因为添加量过多导致导致粒子聚集使得石墨烯粒子在聚合物中的均一性下降，不能有效地延长气体的扩散路径，最终导致气体阻隔性下降。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (7)

  1. 一种石墨烯改性PET薄膜材料，其特征在于，以石墨和乙二醇为原料，在超临界二氧化碳的氛围下，通过球磨制备得到改性石墨烯，然后将所述改性石墨烯与另取的对苯二甲酸、乙二醇采用原位聚合法合成得到石墨烯改性PET复合材料粒料，然后通过多层拉伸挤出系统获得所述石墨烯改性PET薄膜材料。
  2. 根据权利要求1所述的一种石墨烯改性PET薄膜材料，其特征在于，所述石墨为鳞片石墨、膨胀石墨、块状石墨、无定形石墨中的一种或多种。
  3. 根据权利要求1所述的一种石墨烯改性PET薄膜材料，其特征在于，所述石墨烯改性PET复合材料粒料中的改性石墨烯的质量分数为0.1wt%-1.0wt%。
  4. 一种根据权利要求1所述的石墨烯改性PET薄膜材料的制备方法，其特征在于，按照如下方法制备得到：
    S1、改性石墨烯的制备：在球磨罐中加入1重量份的石墨、10重量份以上的乙二醇和适量催化剂，然后将罐体用法兰螺丝密封，通过充气装置向罐体内冲入用于排除罐体内空气的二氧化碳气体；然后向罐体内另冲入二氧化碳气体，直到压力达到7.3-15MPa，关紧阀门，此时另冲入的二氧化碳处于超临界状态；然后在32℃-100℃、转速300-600r/min下，球磨24-72小时，即得到所述改性石墨烯；
    S2、原位聚合法制备石墨烯改性PET复合材料粒料：首先在四口瓶中加入S1制备的改性石墨烯的溶液，在氮气保护下升温至200-265℃反应回流1-2小时，得到第一溶液；然后另取适量的对苯二甲酸和乙二醇，并在氮气的保护下升温至200℃，使对苯二甲酸全部溶解，得到第二溶液；最后将所述第二溶液加到所述第一溶液中，继续反应2-4小时，升温至270-290℃，于真空条件下进行缩聚反应，反应2-4小时后结束，在氮气保护下出料，固化切粒即得到所述石墨烯改性PET复合材料粒料；
    S3、将所述石墨烯改性PET复合材粒料通过多层拉伸挤出系统获得石墨烯改性PET薄膜材料。
  5. 根据权利要求4所述的一种石墨烯改性PET薄膜材料的制备方法，其特征在于，S1中的乙二醇/石墨烯的质量比大于10。
  6. 根据权利要求4所述的一种石墨烯改性PET薄膜材料的制备方法，其特征在于，S1中的乙二醇/石墨烯的质量比大于10。
  7. 根据权利要求4所述的一种石墨烯改性PET薄膜材料的制备方法，其特征在于，所述催化剂为Sb(OAc) 3、Co(OAc) 2、Sb 2O 3、H 3PO 4中的一种或两种。
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