WO2017101739A1 - 石墨烯在保存天然乳胶中的应用和乳胶制品 - Google Patents

石墨烯在保存天然乳胶中的应用和乳胶制品 Download PDF

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WO2017101739A1
WO2017101739A1 PCT/CN2016/109240 CN2016109240W WO2017101739A1 WO 2017101739 A1 WO2017101739 A1 WO 2017101739A1 CN 2016109240 W CN2016109240 W CN 2016109240W WO 2017101739 A1 WO2017101739 A1 WO 2017101739A1
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graphene
latex
natural latex
preserving
natural
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PCT/CN2016/109240
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English (en)
French (fr)
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唐一林
张金柱
许日鹏
刘顶
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济南圣泉集团股份有限公司
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Publication of WO2017101739A1 publication Critical patent/WO2017101739A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex

Definitions

  • the invention relates to the technical field of natural latex, in particular to an application of graphene in preserving natural latex and a latex product.
  • Natural latex generally refers to natural latex, which belongs to rubber-based thermoplastic synthetic resin. It has high elasticity, good film forming performance when bonding, and rubber film is flexible and flexible. In order to improve the heat resistance, durability and aging resistance of natural latex, the natural latex is often vulcanized and used as a base. The fresh latex flowing from the gum tree has good fluidity and a special sweet smell. Natural latex generally contains ingredients such as proteins and sugars, which solidify natural latex under the action of microorganisms or enzymes. Fresh latex can be obviously spoiled or deteriorated after 6 to 12 hours without any treatment. Corrosion is faster when the temperature is high, which adversely affects the rubber making process and product quality, thus affecting rubber production and farmers. Economic income.
  • the spoiled latex has a high viscosity, it is difficult to filter and settle, and the condensate will block the sieve hole of the filter screen. It is very difficult to clean; the spoiled latex has low stability, and local solidification is likely to occur when the acid is solidified, so that the clot is hard and soft. First, it affects the tableting operation and the drying of the film; after the spoiled latex enters the high-speed rotating centrifuge, under the strong mechanical force, it is easy to solidify and block the centrifuge, so it is necessary to frequently stop the washing and dismounting, shortening the normal operation of the centrifuge.
  • the impurities in the spoiled metamorphic latex are not easy to remove, so the harmful impurities remaining in the primary product are more, the product quality is poor; the spoiled metamorphic latex produces more CO 2 If these gases do not come out when the latex solidifies and compresses, bubbles form in the film. At the same time, due to the spoilage effect of bacteria, the film is often discolored, watermarks are generated, and the appearance quality of the film is lowered.
  • the spoiled metamorphic latex has the highest volatile fatty acid content, and the obtained concentrated natural latex has high volatile fatty acid value and low mechanical stability. It is difficult to achieve the required quality indicators. If the latex has naturally solidified, the resulting rubber is damaged or removed by the protein and its decomposition products, and the aging resistance is also poor. After the latex is spoiled, the grade rate of the obtained preliminary product is inevitably lowered.
  • the latex In order to prevent the latex from being spoiled or deteriorated before initial processing or preparation, the latex must be preserved.
  • natural latex is added with ammonia and other stabilizers to achieve antibacterial effects, thereby preserving the latex.
  • ammonia the major problem in the product after adding ammonia: one is the odor problem, the human body is unacceptable to the smell of ammonia volatilized in the product or may cause skin allergies, which may cause irritation or injury to human health, and may also affect the export of the product;
  • the other is the chemical problem.
  • the vulcanization process of natural latex is a chemical cross-linking process. The presence of ammonia can cause harmful side reactions in this process, causing difficulty in vulcanization. It has certain application to the application of natural latex and the development of modification technology. limits.
  • a low ammonia preservative is used to preserve the natural latex.
  • Calvert et al. Calvert et al., 1984
  • TMTD/zinc oxide plus ammonia and other reagents as a preservation system to control the lower ammonia content.
  • the prior art uses technical means to remove ammonia from the natural latex after ammonia storage. However, it is still difficult to ensure that the shelf life of natural latex storage is not affected by the prior art.
  • the present application provides a use of graphene in preserving natural latex and a latex product.
  • the present invention preserves natural latex with graphene, and the shelf life of the storage is not affected, and the irritating odor is small, which is advantageous for the application of the latex product.
  • the invention provides a use of graphene in preserving natural latex.
  • the natural latex is a fresh latex from which the gum tree flows.
  • graphene is introduced into the fresh latex flowing out of the gum tree, and the amount of graphene introduced is less than 10% of the mass of the fresh latex.
  • the graphene for preserving natural latex according to the present invention can be obtained by various preparation methods, such as mechanical stripping method, epitaxial growth method, chemical vapor deposition method, graphite redox method, and
  • the graphene is prepared by hydrothermal carbonization of biomass resources, as well as other methods in the prior art.
  • some impurity elements, other allotropes or layers of carbon elements may be present.
  • Non-monolayer or even multi-layer graphene structures for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.
  • the graphene utilized in the present invention also includes the above-mentioned non-strict theoretical graphene.
  • the graphene is a powder graphene or graphene slurry.
  • the graphene is biomass graphene.
  • a sheet structure prepared using biomass as a carbon source is called biomass graphene.
  • the biomass carbon source is selected from any one or a combination of at least two of plant and/or agricultural and forestry waste; preferably any one or at least two of softwood, hardwood, forestwood, and agricultural and forestry waste. combination.
  • the agricultural and forestry waste is selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalk, husk and reed, or at least 2 species.
  • a combination of corn cobs is preferred.
  • the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose.
  • the biomass graphene contains a sheet structure of graphene of 10 or less layers, an sp 3 hybrid structure of carbon, and a mineral element.
  • the sheet structure of the graphene is a six-membered ring-shaped honeycomb sheet structure of carbon having a thickness of 100 nm or less.
  • the mineral elements in the graphene include Fe, Si, and Al elements, and any one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co.
  • the content of mineral elements in the graphene is from 0.5% by weight to 6% by weight of the graphene.
  • the graphene has a carbon element content of greater than or equal to 80% by weight of the graphene.
  • an ammonia preservative and/or other natural latex preservative is also added to the natural latex.
  • the other natural latex preservative may be a natural latex preservative of the prior art such as chitosan, sodium pentachlorophenol, thiol benzothiazole, dihydroxypropyl salt of dodecanoic acid, and the like.
  • chitosan sodium pentachlorophenol
  • thiol benzothiazole dihydroxypropyl salt of dodecanoic acid, and the like.
  • One or more additions may be a natural latex preservative of the prior art such as chitosan, sodium pentachlorophenol, thiol benzothiazole, dihydroxypropyl salt of dodecanoic acid, and the like.
  • the ammonia preservative is added in an amount of less than 0.35% by weight based on the mass of the natural latex.
  • a dispersing agent is further added to the natural latex.
  • the dispersing agent is selected from one or more of sodium carboxymethylcellulose, polyvinyl alcohol, Tween 80, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate.
  • the mass ratio of the dispersant to graphene is from 0.04:1 to 1:1.
  • the natural latex is a natural latex material treated with a preservative.
  • the present invention uses graphene to preserve natural latex, so that no additional ammonia stabilizer or less ammonia stabilizer can be used in the natural latex.
  • the natural latex preserved by the graphene of the invention has less irritating odor and even no irritating odor, and the shelf life of the storage is not affected, which is beneficial to the application of the latex product.
  • the natural latex preserved with graphene of the present invention also has a far infrared function.
  • the present invention also provides a latex product made from the natural latex obtained by the application of graphene described above in the preservation of natural latex.
  • the natural latex described herein refers to a natural latex obtained by preserving the fresh latex of the gum tree with graphene preservation and/or other preservative treatment.
  • the latex article comprises an impregnated article, a sponge article, an extruded article, a cast film article or a woven article.
  • the latex product includes an adhesive, a carpet backing, a latex paper, a non-woven fabric, an artificial leather, a latex cement, a latex asphalt, a latex tape, a latex paint or a matte, and the like, and other latex products of the prior art.
  • the sponge product includes a pillow, a mattress, a cushion, a cushion, a sofa, a waist protector, an insole, a brassiere, a car seat, a toilet seat or a hand warmer.
  • the present invention can be added to the natural latex without adding or adding a small amount of ammonia or other preservative.
  • graphene is used as a preservative, and also has an antibacterial and antibacterial function and a far infrared function for a natural latex tape.
  • the latex product provided by the invention is made of the natural latex preserved above, and the latex product has the functions of antibacterial and antibacterial, small irritating smell and long shelf life of storage.
  • the latex product provided by the invention also has the function of far infrared, can promote the microcirculation of the human body and is beneficial to human health.
  • the natural latex preserved by the graphene of the invention is used for preparing the corresponding latex product, and the antibacterial and antibacterial function and the far infrared function can be achieved without adding other substances having far infrared function and antibacterial antibacterial function, and the irritating odor is small. , the effect of long shelf life of storage.
  • the invention can reduce the production steps and the process is simple.
  • the latex product provided by the invention does not need to be treated with antibacterial and antibacterial and far infrared in the preparation process, and can directly have a far infrared function to promote microcirculation of the human body.
  • the latex product has excellent mechanical properties, adsorption function, moisture wicking function, etc., and has good application performance.
  • the invention provides an application of graphene in preserving natural latex.
  • the natural latex preserved by the graphene of the invention has less irritating odor, even no irritating odor, and the shelf life of the storage is not affected.
  • the natural latex may be a fresh latex that is directly removed from the rubber tree; the present invention preferably preserves the fresh latex that flows out of the gum tree.
  • the natural latex is a special oil-in-water colloidal system and is a complex rubber-water based dispersion system.
  • rubber particles and non-rubber particles constitute a dispersed phase;
  • whey constitutes a dispersion medium, and whey is composed of a substance soluble in water such as proteins, phospholipids, inorganic salts and sugars;
  • the source of the natural latex is not particularly limited.
  • the natural latex may also be a natural latex material treated with a preservative, and then preserved by graphene to enhance its preservation effect.
  • the present invention is not particularly limited to the preservative and the treatment method, and a preservative and a treatment method which are commonly used in the art may be employed.
  • the invention adopts graphene to carry out ammonia-free/low-ammonia preservation of natural latex, and graphene has excellent antibacterial effect on bacteria contained in natural latex due to external pollution, and can preserve natural latex well.
  • the graphene when the low-ammonia preservation natural latex, especially the fresh latex, the graphene accounts for more than 0% and less than 10% of the mass of the natural latex, for example, 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, 5%, 6%, 7.8%, 8.9%, 10%, etc.
  • the present invention may employ powdered graphene or a graphene slurry.
  • the source of the graphene of the present invention is not particularly limited, and may be a commercially available product or may be prepared.
  • the graphene is preferably biomass graphene.
  • the biomass graphene contains a sheet structure of graphene of 10 or less layers, a sp 3 hybrid structure of carbon, and a mineral element; the mineral elements include Fe, Si, and Al elements.
  • the mineral element element content is from 0.5% by weight to 6% by weight of the biomass graphene, preferably from 1.5% by weight to 5% by weight.
  • the mineral element preferably further includes any one or more of P, Ca, Na, Ni, Mn, K, Mg, Cr, S, and Co; the mineral element exists as a simple substance and/or a compound, and the compound These include oxides and carbides that are adsorbed on the surface or inside of the biomass graphene.
  • the biomass graphene has a carbon content of ⁇ 80 wt%, preferably greater than 85 wt%, still more preferably greater than 90 wt%, and most preferably greater than 95 wt%.
  • the graphene is a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 100 nm or less.
  • the biomass graphene can be produced by a biomass resource hydrothermal carbonization process.
  • a biomass resource hydrothermal carbonization process Specifically, the following are only examples:
  • the heating rate in the steps (3), (4) is 14 ° C / min - 18 ° C / min.
  • the biomass graphene prepared in the above method 1 (the graphene prepared in the prior art may have some impurity elements, other allotropes of carbon elements or graphene structures having a non-monolayer or even a plurality of layers,
  • the graphene prepared by the biomass method is also a mixture containing graphene, amorphous carbon and non-carbon non-oxygen elements.
  • Method 2 The method disclosed in CN104118873A.
  • Method 3 The method disclosed in CN104016341A.
  • Method 4 The method disclosed in CN104724696A.
  • Method 5 Method disclosed in CN104724699A.
  • Method 6 The method disclosed in CN105060289A.
  • the natural latex when the ammonia-free/low-ammonia storage is preserved, the natural latex is not required to be added with an ammonia stabilizer or an ammonia stabilizer (also referred to as an ammonia preservative).
  • an ammonia stabilizer or an ammonia stabilizer also referred to as an ammonia preservative
  • a certain amount of ammonia stabilizer and/or other natural latex preservative may be added to the natural latex, especially the fresh latex.
  • other natural latex preservatives may be natural latex preservatives of the prior art such as chitosan, sodium pentachlorophenol, thiol benzothiazole, and dihydroxypropyl dodecanoate.
  • the ammonia preservative is added in an amount of less than 0.35 wt%, preferably less than or equal to 0.1 wt%, more preferably less than or equal to 0.05 wt%, based on the mass of the natural latex.
  • an ammonia stabilizer may be added to the natural latex to render the natural latex free of ammonia. Therefore, the natural latex preserved in the graphene-free ammonia/low ammonia of the present invention has a small irritating odor, even no irritating odor, and the shelf life of the storage is not affected.
  • the graphene is added to preserve the natural latex, and the graphene is preferably uniformly mixed in the natural latex by means of dispersion, which is favorable for stable storage of the natural latex.
  • the dispersion is in the form of physical dispersion, dispersant dispersion or physical dispersion, and dispersant dispersion.
  • the physical dispersion includes ultrasonic dispersion or agitation of strong shear force, and the like.
  • the dispersant dispersion is a chemical dispersion method, and the present invention may add a dispersant to uniformly mix the graphene and the natural latex;
  • the dispersant is preferably selected from sodium carboxymethyl cellulose, polyvinyl alcohol, Tween 80, One or more of sodium lauryl sulfate and sodium dodecylbenzenesulfonate are more preferably sodium dodecylbenzenesulfonate.
  • the mass ratio of the dispersant to graphene is (0.04-1):1, preferably (0.08-1):1, more preferably (0.1-0.5):1.
  • the invention adopts graphene to preserve the natural latex, and exerts an unexpected antibacterial and antibacterial effect, so that the natural latex does not need to add an ammonia stabilizer or a little ammonia stabilizer, and the storage has a long shelf life and a small irritating smell, which is favorable for the odor.
  • the natural latex preserved with graphene of the present invention also exerts an unexpected far infrared function.
  • the present invention also provides a latex article made from the natural latex obtained by the application of graphene described above in the preservation of natural latex.
  • the natural latex described herein refers to a natural latex obtained by preserving the fresh latex of the gum tree with graphene preservation and/or other preservative treatment.
  • the invention uses the above natural latex preserved by graphene as a raw material to produce various types of latex products, such as latex pillows, latex mattresses, latex gloves and the like.
  • the latex product provided by the invention has the functions of antibacterial and antibacterial, has small irritating odor and long shelf life of storage.
  • the latex article comprises an impregnated article, a sponge article, an extruded article, a cast film article or a woven article.
  • the latex product includes an adhesive, a carpet backing, a latex paper, a non-woven fabric, an artificial leather, a latex cement, a latex asphalt, a latex tape, a latex paint or a matte, and the like, and other latex products of the prior art.
  • the sponge product comprises a pillow, a mattress, a cushion, a cushion, a sofa, a waist protector, an insole, a bra, a car seat, a toilet seat or a hand warmer.
  • the latex article is preferably prepared as follows:
  • the natural latex and the rubber auxiliaries preserved by the graphene are mixed and foamed to obtain a foamed material; the foamed material is vulcanized in a pillow mold, and dried to obtain a latex pillow.
  • the natural latex and the rubber auxiliary agent preserved by graphene are uniformly mixed to obtain a latex mixture.
  • the content of the natural latex treated with graphene preservation is as described above.
  • the solid graphene or the graphene-containing solution may be mixed with the natural latex, and the natural latex may be preserved by dispersion.
  • the rubber adjuvant is a raw material of a latex product well known to those skilled in the art, and includes, for example, a vulcanizing agent, an antioxidant, an antioxidant, a plasticizer, and the like.
  • the rubber adjuvant comprises a vulcanizing agent and an antioxidant.
  • the rubber adjuvant includes 3-5 parts by mass of a vulcanizing agent, 5-8 parts by mass of a gelling agent, 2-3 parts by mass of an antioxidant, and 1-2 parts by mass of a hardener.
  • Sodium oleate; the mass fraction of the graphene-treated natural latex is 85-100 parts.
  • 0.1 to 0.2 parts by mass of a functional ingredient such as natural essential oil may be added.
  • the embodiment of the present invention introduces the foam mold into the inner cavity of the pillow mold through a catheter, and the cavity of the pillow mold is filled with foam when the cavity is sealed; the pillow mold is moved into the heating chamber, and the high temperature steam is filled in the heating chamber.
  • the foam in the pillow mold is vulcanized and solidified.
  • the heating chamber is removed, cooled, and the mold is opened to obtain a formed latex pillow.
  • the invention has no special limitation on the curing process conditions, the pillow mold and the like, and is generally used in the art.
  • the latex mixture obtained by mixing the natural latex and the rubber auxiliary after the graphene preservation treatment can also prepare a latex such as a latex mattress or a latex glove. Rubber products.
  • the latex mixture may include conventional rubber auxiliaries such as lubricants, flame retardants, and fillers.
  • the latex mixture can be directly vulcanized and formed directly in a corresponding mold or the like without performing a process such as foaming; that is, various types of latex products are prepared by a conventional processing method.
  • the present invention After obtaining a latex article such as a latex pillow, the present invention performs its performance test. The results show that the latex product provided by the present invention has an antibacterial and antibacterial function.
  • the latex product provided by the invention has excellent far-infrared function and can promote microcirculation of the human body.
  • the latex product contains less ammonia stabilizer, has less irritating odor, and has excellent mechanical properties, adsorption function and moisture wicking function, and is advantageous for application.
  • the third intermediate is sequentially washed with a 5% by weight NaOH solution, a 10% by weight HCl solution, and washed with water to obtain graphene;
  • the heating rate in the steps (3), (4) is 15 ° C / min - 16 ° C / min.
  • the biomass graphene contains a sheet structure of graphene of 10 or less layers, a sp 3 hybrid structure of carbon, and a mineral element; the mineral elements include Fe, Si, and Al elements.
  • biomass graphene A (mineral element content 4wt%), biomass graphene B (mineral element content 1wt%) and biomass graphene C (mineral element content 2.5wt%) were prepared separately;
  • the mineral elements mainly include P, Si, Ca, Al, Fe, and Mg elements.
  • Graphene oxide G "Model: SE2430W” produced by Changzhou Sixth Element Materials Technology Co., Ltd.
  • the biomass graphene A prepared by the preparation example 0.5% of the biomass graphene A prepared by the preparation example is added, and different kinds and amounts of dispersing agents are added at the same time, so that the graphene can achieve a better dispersing effect, which is favorable for the preservation of the natural latex.
  • biomass graphene B 0.5% of biomass graphene B, biomass graphene C, graphene D, graphene E, graphene F, and graphene oxide G were respectively added.
  • the storage time in Table 1 below is the storage time under the following conditions: storage temperature below 25 ° C, sealed and stored.
  • the natural rubber was prepared by using the natural latex in the above Examples 1-25 and Comparative Examples 1-4, and the preparation method was as follows: coagulation of fresh natural latex stored for 20 days with glacial acetic acid, followed by bucking, granulation and drying. The natural raw rubber sample is obtained; the initial plastic value and the plastic retention rate are detected (the detection method is tested by the SN/T 0541.2-1996 import and export standard rubber inspection method). The specific values are shown in Table 1 below.
  • the latex latex treated with the graphene-treated natural latex and the natural latex of the above Comparative Examples 1-4 was prepared by the above Examples 1-25, and the following examples are illustrated:
  • the inner cavity, the cavity of the pillow mold is filled with foam when the mold is sealed; the pillow mold is moved to the vulcanization chamber for vulcanization (temperature is 20-30 ° C, time is 30 min), after the vulcanization is completed, the mold is moved to the heating chamber, The latex in the pillow mold is matured at 90 ° C; finally, the heating chamber is removed, cooled, and the mold is opened to obtain a formed latex pillow, and then the latex pillow is washed and dried to obtain a finished latex pillow.
  • the far infrared performance and antibacterial performance of the latex pillow are tested.
  • the test standards are as follows:
  • Antibacterial test data according to: GB/T 31402-2015 "plastic and plastic surface antibacterial performance test method", taking Staphylococcus aureus as an example.
  • Latex pillow odor detection Oeko-Tex Standard 200 for odour detection. Specific method: The test object was placed in a closed system, and the time, temperature and humidity were recorded, which were judged by 6 individuals, and 6 testers were independently performed.
  • the present invention can be added to the natural latex without adding or adding a small amount of ammonia or other preservative.
  • graphene is used as a preservative, and in particular, biomass graphene is also an excellent antibacterial and far-infrared function of natural latex tape.
  • the latex product provided by the invention is made of the natural latex preserved above, and the latex product has the functions of antibacterial and antibacterial, small irritating smell and long shelf life of storage.
  • the latex product provided by the invention also has the function of far infrared, can promote the microcirculation of the human body and is beneficial to human health.
  • the latex product has excellent mechanical properties, adsorption function and moisture wicking function, which is beneficial to the application.
  • the present invention illustrates the process of the present invention by the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps. Can be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

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Abstract

本发明涉及天然乳胶技术领域，本发明提供了一种石墨烯在保存天然乳胶中的应用和乳胶制品。本发明采用石墨烯对天然乳胶进行保存，这样天然乳胶中可不需另加或少加氨稳定剂，具有较小的刺激气味甚至没有刺激气味，并且存放的保质期不受影响。本发明提供的乳胶制品由上文保存得到的天然乳胶制成；本发明提供的乳胶制品具有抗菌抑菌的功能，刺激气味小，存放的保质期长。此外，本发明提供的乳胶制品还具有远红外功能，能够促进人体的微循环。所述乳胶制品具有优异的力学性能、吸附功能和吸湿排汗功能等，应用性能好。

Description

石墨烯在保存天然乳胶中的应用和乳胶制品
本申请要求于2015年12月16日提交中国专利局、申请号为CN201510943516.4、名称为“石墨烯在保存天然乳胶中的应用和乳胶制品”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及天然乳胶技术领域，尤其涉及一种石墨烯在保存天然乳胶中的应用和乳胶制品。
背景技术
天然乳胶一般指天然胶乳，属于橡胶类的热塑性合成树脂，具有高弹性、粘接时成膜性能良好、胶膜富于柔韧性等特点。为了提高天然胶乳的耐热性、耐久性和耐老化性能，常对天然胶乳进行硫化后再作为基料使用。从胶树流出的鲜胶乳流动性好，带有特殊的甜香气味。天然乳胶中一般含有蛋白质和糖类等成分，会在微生物或酶的作用下使天然乳胶凝固。新鲜的胶乳如不经任何处理，一般经过6至12个小时就会发生明显的腐败或变质，温度高时腐败更快，从而对制胶工艺和产品质量产生不利影响，进而影响橡胶产量和农民的经济收入。
例如，腐败的胶乳粘度大，过滤和沉降困难，而且凝粒会堵塞过滤筛的筛孔，清洗非常困难；腐败的胶乳稳定性低，加酸凝固时易产生局部凝固，致使凝块软硬不一，从而影响压片操作和胶片的干燥；腐败的胶乳进入高速旋转的离心机以后，在强烈的机械力作用下，容易凝固而堵塞离心机，因而要经常停机拆洗，缩短了离心机正常运转时间，降低了生产效率和干胶制成率；腐致变质胶乳中的杂质不易除去，因而残留在初制品中的有害杂质较多，产品质量较差；腐败变质胶乳所产生的CO2较多，如果这 些气体在胶乳凝固和压片时来不及逸出，则会在胶片中形成气泡。同时，由于细菌的腐败作用，往往会使胶片变色，产生水印等，降低胶片的外观质量；腐败变质胶乳的挥发脂肪酸含最高，制得的浓缩天然胶乳的挥发脂肪酸值也高，机械稳定度低，很难达到规定的质量指标。如果胶乳已经自然凝固，则所得橡胶因蛋白质及其分解产物受到破坏或被除去，耐老化性能也较差。胶乳发生腐败之后，所得初制品的等级率必然降低。
为了防止胶乳在初加工或制成制品前不发生腐败或变质，就必须做好胶乳的保存工作。通常天然乳胶中都要加入氨和其他稳定剂来达到抑菌等效果，从而保存胶乳。但是加入氨后的产品存在两大问题：一个是气味问题，人体对于产品中挥发出的氨的气味难以接受或者会引起皮肤过敏，对人体健康有刺激、伤害，也可能会影响产品的出口；另一个是化学问题，天然乳胶的硫化过程是一个化学交联的过程，氨的存在会使这一过程发生有害的副反应，造成硫化困难，对天然乳胶的应用及改性技术的发展有着一定的限制。
现有技术中有用低氨保存剂保存天然乳胶，如Calvert等(Calvert et al.，1984)用TMTD/氧化锌加上氨及其它试剂作为保存体系，控制氨含量更低。或者，现有技术用技术手段去除氨保存后天然乳胶中的氨。但是，现有技术仍难以保证天然乳胶存放的保质期不受影响。
发明内容
有鉴于此，本申请提供一种石墨烯在保存天然乳胶中的应用和乳胶制品，本发明用石墨烯保存天然乳胶，其存放的保质期不受影响，且刺激气味小，利于乳胶产品的应用。
本发明提供一种石墨烯在保存天然乳胶中的应用。
优选地，所述天然乳胶为胶树流出的新鲜胶乳。
优选地，在胶树流出的新鲜胶乳中引入石墨烯，石墨烯的引入量在新鲜胶乳质量的10％以下。
本发明所述的用于保存天然乳胶的石墨烯可通过不同制备方法得到，例如机械剥离法、外延生长法、化学气相沉淀法，石墨氧化还原法，还可 以是通过对生物质资源水热碳化法，以及现有技术中其他方法制备的石墨烯。但是，无论哪种方法都很难实现大规模制备得到严格意义理论上的石墨烯，例如现有技术制备得到的石墨烯中会存在某些杂质元素、碳元素的其他同素异形体或层数非单层甚至多层的石墨烯结构(例如3层、5层、10层、20层等)，本发明所利用的石墨烯也包括上述非严格意义理论上的石墨烯。
优选地，所述石墨烯是为粉体石墨烯或石墨烯浆料。
优选地，所述石墨烯为生物质石墨烯。以生物质为碳源制备的片层结构，称为生物质石墨烯。所述生物质碳源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选针叶木、阔叶木、林叶木、农林废弃物中的任意1种或至少2种的组合。优选地，所述农林废弃物选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆、果壳和芦苇中的任意1种或至少2种的组合，优选玉米芯。所述生物质碳源为纤维素和/或木质素，优选纤维素，进一步优选多孔纤维素。
优选地，所述生物质石墨烯含有10层以下石墨烯的片层结构、碳的sp3杂化结构和矿质元素。
优选地，所述石墨烯的片层结构为厚度在100nm以下的碳的六元环蜂窝状片层结构。
优选地，所述石墨烯中的矿质元素包括Fe、Si和Al元素，以及P、Ca、Na、Ni、Mn、K、Mg、Cr、S和Co中的任意一种或多种。
优选地，所述石墨烯中的矿质元素含量为石墨烯的0.5wt％-6wt％。
优选地，所述石墨烯中的碳元素含量大于等于石墨烯的80wt％。
优选地，所述天然乳胶中还加入氨保存剂和/或其他天然乳胶保存剂。
优选地，所述其他天然乳胶保存剂可以是壳聚糖、五氯酚钠、硫醇基苯并噻唑、十二烷酸二羟丙基盐等现有技术中的天然乳胶保存剂，可以选择一种或多种加入。
优选地，所述氨保存剂的加入量占天然乳胶质量的百分比小于0.35wt％。
优选地，所述天然乳胶中还加入分散剂。
优选地，所述分散剂选自羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠中的一种或多种。
优选地，所述分散剂与石墨烯的质量比为0.04:1-1:1。
优选地，所述天然乳胶为用保存剂处理过的天然乳胶材料。
与现有技术相比，本发明采用石墨烯对天然乳胶进行保存，这样天然乳胶中可不需要另加氨稳定剂或少加氨稳定剂。本发明以石墨烯保存的天然乳胶具有较小的刺激气味甚至没有刺激气味，并且存放的保质期不受影响，利于乳胶产品的应用。
此外，本发明用石墨烯保存的天然乳胶还具有远红外功能。
本发明还提供一种乳胶制品，由上文所述的石墨烯在保存天然乳胶中的应用过程得到的天然乳胶制成。此处所述的天然乳胶是指胶树流出的新鲜胶乳用石墨烯保存和/或其他保存剂处理后得到的天然乳胶。
优选地，所述乳胶制品包括浸渍制品、海绵制品、压出制品、铸膜制品或织造制品。所述乳胶制品包括胶粘剂、地毯背衬、胶乳纸张、不织布、人造革、乳胶水泥、乳胶沥青、乳胶胶布、乳胶涂料或毛棕垫等，还包括其他现有技术中的乳胶制品。
更进一步地，所述海绵制品包括枕头、床垫、坐垫、靠垫、沙发、护腰、鞋垫、乳罩、汽车座椅、马桶坐垫或暖手宝。
与现有技术相比，本发明在天然乳胶保存时可不需加入或少量加入氨或其他保存剂。在本发明中，石墨烯在作为保存剂的同时，还为天然乳胶带来了抗菌抑菌功能和远红外功能等。本发明提供的乳胶制品由上文保存得到的天然乳胶制成，该乳胶制品具有抗菌抑菌的功能，刺激气味小，存放的保质期长的特点。本发明提供的乳胶制品还具有远红外功能，能够促进人体的微循环，利于人体健康。
本发明用石墨烯保存得到的天然乳胶用于制备相应乳胶制品时，无需再加入其它具备远红外功能和抗菌抑菌功能的物质，即可达到抗菌抑菌的功能和远红外功能，刺激气味小，存放的保质期长的效果。同时，在天然乳胶采集后保存到制备乳胶制品的过程中，若要达到抗菌抑菌功能，本发明则可减少生产步骤，工艺简便。或者说本发明提供的乳胶制品在制备过程中，无需进行抗菌抑菌和远红外方面的处理，直接生产即可具备远红外功能，从而促进人体的微循环。
此外，所述乳胶制品具有优异的力学性能、吸附功能和吸湿排汗功能等，应用性能好。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种石墨烯在保存天然乳胶中的应用。
本发明以石墨烯保存的天然乳胶具有较小的刺激气味，甚至没有刺激气味，并且存放的保质期不受影响。
本发明实施例可在天然乳胶中加入石墨烯，进行无氨/低氨保存。所述天然乳胶可以是从橡胶树上直接取下的新鲜胶乳；本发明优选对胶树流出的新鲜胶乳进行保存。所述天然乳胶是一种特殊的水包油型胶体体系，是复杂的橡胶-水基型分散体系。在天然乳胶中，橡胶粒子、非橡胶粒子组成分散相；乳清组成分散介质，而乳清是由蛋白质、磷脂、无机盐和糖类等能溶于水的物质所构成的；本发明对所述天然乳胶的来源没有特殊限制。
在本发明的一些实施例中，所述天然乳胶也可以是用保存剂处理过的天然乳胶材料，再经石墨烯保存，增强其保存效果。此处，本发明对保存剂以及处理方法没有特殊限制，采用本领域常用的保存剂和处理方法即可。
本发明采用石墨烯可对天然乳胶进行无氨/低氨保存，石墨烯对天然乳胶因外界污染而含有的细菌有优异的抗菌作用，可以很好地保存天然乳胶。在本发明实施例低氨保存天然乳胶尤其是保存新鲜胶乳时，所述石墨烯占天然乳胶质量的百分比大于0且小于10％，例如0.1％、0.3％、0.5％、0.7％、1％、3％、5％、6％、7.8％、8.9％、10％等。本发明可以采用粉体石墨烯，也可以采用石墨烯浆料。本发明对所述石墨烯的来源没有特殊限制，可以采用市售产品，也可以制备获得。
在本发明的一个实施例中，所述石墨烯优选为生物质石墨烯。所述生物质石墨烯含有10层以下石墨烯的片层结构、碳的sp3杂化结构和矿质元 素；所述矿质元素包括Fe、Si和Al元素。在本发明的实施例中，所述矿质元素元素含量为生物质石墨烯的0.5wt％-6wt％，优选为1.5wt％-5wt％。所述矿质元素优选还包括P、Ca、Na、Ni、Mn、K、Mg、Cr、S和Co中的任意一种或多种；所述矿质元素以单质和/或化合物的形式存在，化合物包括氧化物、碳化物，它们吸附在生物质石墨烯的表面或内部。在本发明的实施例中，所述生物质石墨烯中碳元素含量≥80wt％，优选大于85wt％，再优选大于90wt％，最优选大于95wt％。在本发明的实施例中，所述石墨烯为具有厚度在100nm以下的碳的六元环蜂窝状片层结构。
在本发明的实施例中，所述生物质石墨烯可利用生物质资源水热碳化法制得。具体地，以下仅举例说明：
方法1：
(1)在催化剂的作用下，将生物质碳源进行催化处理，得到前驱体；
(2)在保护性气体的条件下，将所述前驱体在140℃-180℃保温1.5h-2.5h，得到第一中间体；
(3)在保护性气体的条件下，将所述第一中间体升温至350℃-450℃保温3h-4h，得到第二中间体；
(4)在保护性气体的条件下，将所述第二中间体升温至1100℃-1300℃保温2h-4h，得到第三中间体；
(5)将所述第三中间体依次碱洗、酸洗、水洗，得到石墨烯；
所述步骤(3)、(4)中的升温速率为14℃/min-18℃/min。
上述方法1中制备得到的生物质石墨烯(现有技术制备得到的石墨烯中会存在某些杂质元素、碳元素的其他同素异形体或层数非单层甚至多层的石墨烯结构，而此生物质方法制备出的石墨烯也为混合物)中，含有石墨烯、无定形碳和非碳非氧元素。
方法2：CN104118873A公开的方法。
方法3：CN104016341A公开的方法。
方法4：CN104724696A公开的方法。
方法5：CN104724699A公开的方法。
方法6：CN105060289A公开的方法。
在本发明实施例中，所述无氨/低氨保存即保存天然乳胶时，可不需要另加氨稳定剂或少加氨稳定剂(也称氨保存剂)。在本发明的一个实施例中，可以在天然乳胶尤其是新鲜胶乳中，少加一定量的氨稳定剂和/或其他天然乳胶保存剂。在本发明中，其他天然乳胶保存剂可以是壳聚糖、五氯酚钠、硫醇基苯并噻唑、十二烷酸二羟丙基盐等现有技术中的天然乳胶保存剂。
在本发明的一个实施例中，所述氨保存剂的加入量占天然乳胶质量的百分比小于0.35wt％，优选小于等于0.1wt％，更优选小于等于0.05wt％。在本发明的另一个实施例中，可以在天然乳胶中不加入氨稳定剂，使天然乳胶中不含氨。因此，本发明以石墨烯无氨/低氨保存的天然乳胶具有较小的刺激气味，甚至没有刺激气味，并且存放的保质期不受影响。
本发明实施例加入石墨烯保存天然乳胶，优选通过分散的方式使石墨烯在天然乳胶中混合均匀，利于天然乳胶的稳定保存。在本发明实施例中，所述分散的方式为物理分散、采用分散剂分散或物理分散结合采用分散剂分散的方式。其中，所述物理分散包括超声波分散或强剪切力的搅拌等。
进一步地，所述采用分散剂分散属于化学分散方法，本发明可添加分散剂使石墨烯和天然乳胶均匀混合；所述分散剂优选自羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠中的一种或多种，更优选为十二烷基苯磺酸钠。在本发明的实施例中，所述分散剂与石墨烯的质量比为(0.04-1)：1，优选(0.08-1)：1，更优选为(0.1-0.5)：1。
本发明采用石墨烯对天然乳胶进行保存，起到了意想不到的抑菌抗菌功效，这样天然乳胶中可不需要另加氨稳定剂或少加氨稳定剂，其存放的保质期长，刺激气味小，利于乳胶产品的应用。
此外，本发明用石墨烯保存的天然乳胶还起到了意想不到的远红外功能。
本发明还提供了一种乳胶制品，由上文所述的石墨烯在保存天然乳胶中的应用过程得到的天然乳胶制成。此处所述的天然乳胶是指胶树流出的新鲜胶乳用石墨烯保存和/或其他保存剂处理后得到的天然乳胶。
本发明以上述用石墨烯保存的天然乳胶作为原料，可生产各类乳胶制品，例如乳胶枕头、乳胶床垫、乳胶手套等。本发明提供的乳胶制品具有抗菌抑菌的功能，刺激气味小，存放的保质期长。
在本发明的实施例中，所述乳胶制品包括浸渍制品、海绵制品、压出制品、铸膜制品或织造制品。所述乳胶制品包括胶粘剂、地毯背衬、胶乳纸张、不织布、人造革、乳胶水泥、乳胶沥青、乳胶胶布、乳胶涂料或毛棕垫等，还包括其他现有技术中的乳胶制品。其中，所述海绵制品包括枕头、床垫、坐垫、靠垫、沙发、护腰、鞋垫、乳罩、汽车座椅、马桶坐垫或暖手宝等。
在本发明的一个实施例中，所述乳胶制品优选按照以下方法制得：
将用石墨烯保存处理的天然乳胶和橡胶助剂混合，进行发泡，得到发泡材料；将所述发泡材料在枕头模具中进行硫化，经干燥得到乳胶枕头。
本发明实施例将用石墨烯保存处理的天然乳胶和橡胶助剂混合均匀，得到乳胶混合物料。其中，所述用石墨烯保存处理的天然乳胶的内容如前文所述。在本发明实施例中，可将固体石墨烯或者含石墨烯的溶液与天然乳胶混合，经分散，对天然乳胶进行保存。
在本发明中，所述橡胶助剂为本领域技术人员熟知的乳胶制品原料，如包括硫化剂、防老剂、抗氧化剂、增塑剂等。在本发明的一个实施例中，所述橡胶助剂包括硫化剂和抗氧化剂。在本发明的一个实施例中，所述橡胶助剂包括3-5质量份的硫化剂、5-8质量份的胶凝剂、2-3质量份的抗氧化剂、1-2质量份的硬脂酸钠；经过石墨烯处理的天然乳胶的质量份为85-100份。此外，本发明实施例还可以添加0.1-0.2质量份的天然香精油等功能成分。
发泡得到发泡材料后，本发明实施例通过导管将其导入枕头模具的内腔，枕头模具内腔注满泡沫时合模密封；将枕头模具移至加热室内，在加热室内充入高温蒸汽，使得枕头模具内的泡沫硫化固化，固化完成后移出加热室，冷却，打开模具得到成形的乳胶枕头。本发明对固化的工艺条件、枕头模具等设备没有特殊限制，采用本领域常用的即可。
在本发明另外的实施例中，采用石墨烯保存处理后的天然乳胶和橡胶助剂混合得到的乳胶混合物料，也可以制备得到乳胶床垫或乳胶手套等乳 胶制品。在本发明这些实施例中，乳胶混合物料可以包括润滑剂、阻燃剂和填料等常规的橡胶助剂。在本发明这些实施例中，乳胶混合物料可以直接在相应的模具等设备中直接硫化、成型，而无需进行发泡等工艺；即采用传统的加工方法，制备得到各类乳胶制品。
得到如乳胶枕头的乳胶制品后，本发明对其进行性能测试。结果显示，本发明提供的乳胶制品具有抗菌抑菌的功能。
并且，本发明提供的乳胶制品具有优良的远红外功能，能够促进人体的微循环。此外，所述乳胶制品含氨稳定剂少，刺激气味小，同时具有优异的力学性能、吸附功能和吸湿排汗功能等性能，利于应用。
为了进一步理解本申请，下面结合实施例对本申请提供的石墨烯在保存天然乳胶中的应用和乳胶制品进行具体地描述。
石墨烯种类：
制备例：生物质石墨烯的具体制备工艺
(1)在氯化亚铁的作用下，将玉米芯纤维素进行催化处理，得到前驱体；
(2)在氮气的条件下，将所述前驱体在150℃保温2h，得到第一中间体；
(3)在氮气的条件下，将所述第一中间体升温至400℃保温3.5h，得到第二中间体；
(4)在氮气的条件下，将所述第二中间体升温至1200℃保温3h，得到第三中间体；
(5)将所述第三中间体依次用浓度为5wt％的NaOH溶液碱洗、浓度为10wt％的HCl溶液酸洗、水洗，得到石墨烯；
所述步骤(3)、(4)中的升温速率为15℃/min-16℃/min。
所述生物质石墨烯含有10层以下石墨烯的片层结构、碳的sp3杂化结构和矿质元素；所述矿质元素包括Fe、Si和Al元素。
根据催化剂用量不同分别制备得到：生物质石墨烯的A(矿质元素含量4wt％)、生物质石墨烯B(矿质元素含量1wt％)和生物质石墨烯C(矿质元素含量2.5wt％)；其中所述矿质元素主要包括P、Si、Ca、Al、Fe、Mg元素。
石墨烯D：常州第六元素材料科技股份有限公司生产的“型号：SE1231”。
石墨烯E：常州第六元素材料科技股份有限公司生产的“型号：SE1132”。
石墨烯F：常州第六元素材料科技股份有限公司生产的“型号：SE1430”。
氧化石墨烯G：常州第六元素材料科技股份有限公司生产的“型号：SE2430W”。
实施例1-10
在新鲜胶乳中，添加不同质量的由制备例制得的生物质石墨烯A进行保存。
相关数据和结果参见表1。
实施例11-14
在新鲜乳胶中，添加0.5％的由制备例制得的生物质石墨烯A，同时加入不同种类和含量的分散剂，以使石墨烯达到更好的分散效果，利于对天然乳胶保存。
相关数据和结果参见表1。
实施例15-17
在新鲜乳胶中，添加0.5％的由制备例制得的生物质石墨烯A，同时加入其他天然乳胶保存剂，以达到更好的保存效果。
相关数据和结果参见表1。
实施例18-19
在新鲜乳胶中，添加0.5％的由制备例制得的生物质石墨烯A，同时加入分散剂和其他天然乳胶保存剂，进而提高保存效果。
相关数据和结果参见表1。
实施例20-25
在新鲜乳胶中，分别添加0.5％的生物质石墨烯B、生物质石墨烯C、石墨烯D、石墨烯E、石墨烯F和氧化石墨烯G。
相关数据和结果参见表1。
对比例1
在新鲜乳胶中，不添加任何保存剂，在上述保存条件下进行保存。
对比例2
在新鲜乳胶中，添加0.35％的NH3，在上述保存条件下进行保存。
对比例3
在新鲜乳胶中，添加1％的NH3，在上述保存条件下进行保存。
对比例4在新鲜乳胶中，添加2％的NH3，在上述保存条件下进行保存。
下表1中保存时间为以下条件下的保存时间：保存温度25℃以下，密封保存。
另外，采用上述实施例1-25以及对比例1-4中的天然乳胶制备天然生胶，制备方法为用冰醋酸将保存20天的新鲜天然乳胶凝固，然后进行绉片、造粒、干燥操作，得到天然生胶样品；检测其塑性初值和塑性保持率(检测方法采用SN/T 0541.2-1996进出口标准橡胶检验方法检测)。具体数值见下表1所示。
表1实施例1-25保存天然乳胶和天然乳胶制品(天然生胶)以及对比例1-4的相关数据和结果
Figure PCTCN2016109240-appb-000001
Figure PCTCN2016109240-appb-000002
实施例26
采用上述实施例1-25经过所述石墨烯处理的天然乳胶、上述对比例1-4中的天然乳胶制备乳胶枕头，以下举例说明：
以质量份数计，将85-100份经过所述石墨烯处理的天然乳胶(实施例1-25经过所述石墨烯处理的天然乳胶、上述对比例1-4中的天然乳胶)、1-5份硫化剂(不溶性硫磺)、0.1-1份硫化促进剂(二苯胍)、0.1-1份分散剂(硬脂酸钠)混合均匀，得到乳胶混合物料。
将上述的乳胶混合物料、5份胶凝剂(氟硅酸钠)、5份氧化锌分别导入乳胶发泡机中，调节发泡倍率至形成泡沫密度为40，然后通过管道把泡沫导入枕头模具的内腔，枕头模具内腔注满泡沫时进行合模密封；将枕头模具移至硫化室进行硫化(温度为20-30℃，时间为30min)，硫化完成后将模具移至加热室内，在90℃条件下使得枕头模具内的乳胶熟化；最后移出加热室，冷却，打开模具，得到成形的乳胶枕头，然后将乳胶枕头水洗，烘干得到成品乳胶枕头。
按照上文所述的方法，测试所得乳胶枕头的性能，结果参见表2。
对乳胶枕头的远红外性能和抗菌性能等进行检测，检测标准如下：
红外检测数据依据：GBT 7286.1-1987《金属与非金属材料全法向发射率试验方法》；
抑菌检测数据依据：GB/T 31402-2015《塑料、塑料表面抗菌性能试验方法》中，以金黄色葡萄球菌为例。
乳胶枕头气味检测，采用Oeko-Tex Standard 200进行气味检测。具体方法：将测试物置于以密闭系统中，记录下时间、温度、湿度，由6个人评判，6名检测人员独立进行。
气味测试标准(此测试中，排除乳胶本身的气味)：
1级：无气味；
2级：轻微气味；
3级：可容忍的气味；
4级：讨厌的气味；
5级：不可容忍的气味。
表2实施例1-26保存天然乳胶制品(以乳胶枕头为例)以及对比例的相关数据和结果
Figure PCTCN2016109240-appb-000003
Figure PCTCN2016109240-appb-000004
Figure PCTCN2016109240-appb-000005
由对比例1的测试结果可知，在不添加任何保存剂的条件下，无法形成制品。
由对比例2-4的测试结果可知，添加氨保护剂时天然乳胶保存时间、天然生胶的塑性初值、天然生胶的塑性保持率、乳胶制品的远红外法向发射率以及抑菌率均显著低于添加相同量的本发明石墨烯保护剂时的效果，虽然随着氨保护剂添加量的增加，上述测试参数结果有所提高，但其制品刺激气味的级别也从2级上升到“令人讨厌的”4级，其整体效果显著劣于添加本发明石墨烯保护剂时的效果。
由以上实施例和对比例可知，本发明在天然乳胶保存时可不需加入或少量加入氨或其他保存剂。在本发明中，石墨烯在作为保存剂的同时，尤其是生物质石墨烯还为天然乳胶带来了优异的抗菌抑菌功能和远红外功能等。本发明提供的乳胶制品由上文保存得到的天然乳胶制成，该乳胶制品具有抗菌抑菌的功能，刺激气味小，存放的保质期长的特点。本发明提供的乳胶制品还具有远红外功能，能够促进人体的微循环，利于人体健康。同时，该乳胶制品具有优异的力学性能、吸附功能和吸湿排汗功能等性能，利于应用。
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意味着本发明必须依赖上述工艺步骤 才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (20)

  1. 一种石墨烯在保存天然乳胶中的应用。
  2. 根据权利要求1所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶为胶树流出的新鲜胶乳。
  3. 根据权利要求2所述的石墨烯在保存天然乳胶中的应用，其特征是，在胶树流出的新鲜胶乳中引入石墨烯，石墨烯的引入量在新鲜胶乳质量的10％以下。
  4. 根据权利要求1-3中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述石墨烯为粉体石墨烯或石墨烯浆料。
  5. 根据权利要求1-4中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述石墨烯为生物质石墨烯。
  6. 根据权利要求5所述的石墨烯在保存天然乳胶中的应用，其特征是，所述生物质石墨烯含有10层以下石墨烯的片层结构、碳的sp3杂化结构和矿质元素。
  7. 根据权利要求6所述的石墨烯在保存天然乳胶中的应用，其特征是，所述石墨烯的片层结构为厚度在100nm以下的碳的六元环蜂窝状片层结构。
  8. 根据权利要求6所述的石墨烯在保存天然乳胶中的应用，其特征是，所述矿质元素包括Fe、Si和Al元素，以及P、Ca、Na、Ni、Mn、K、Mg、Cr、S和Co中的任意一种或多种。
  9. 根据权利要求6或8所述的石墨烯在保存天然乳胶中的应用，其特征是，所述矿质元素含量为石墨烯的0.5wt％-6wt％。
  10. 根据权利要求5-9中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述生物质石墨烯的碳元素含量大于等于石墨烯的80wt％。
  11. 根据权利要求1-10中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶中还加入天然乳胶保存剂。
  12. 根据权利要求11所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶保存剂为氨保存剂。
  13. 根据权利要求12所述的石墨烯在保存天然乳胶中的应用，其特征是，所述氨保存剂的加入量占天然乳胶质量的百分比小于0.35wt％。
  14. 根据权利要求11所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶保存剂为壳聚糖、五氯酚钠、硫醇基苯并噻唑、十二烷酸二羟丙基盐。
  15. 根据权利要求1-14中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶中还加入分散剂。
  16. 根据权利要求15所述的石墨烯在保存天然乳胶中的应用，其特征是，所述分散剂选自羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠中的一种或多种。
  17. 根据权利要求15或16所述的石墨烯在保存天然乳胶中的应用，其特征是，所述分散剂与石墨烯的质量比为0.04:1-1:1。
  18. 根据权利要求1-17中任一项所述的石墨烯在保存天然乳胶中的应用，其特征是，所述天然乳胶为用保存剂处理过的天然乳胶材料。
  19. 一种乳胶制品，由权利要求1-18中任一项所述的石墨烯在保存天然乳胶中的应用过程得到的天然乳胶制成。
  20. 根据权利要求19所述的乳胶制品，其特征是，所述乳胶制品包括浸渍制品、海绵制品、压出制品、铸膜制品或织造制品。
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