WO2017121352A1 - 天然乳胶的保存方法以及制得的乳胶制品 - Google Patents

天然乳胶的保存方法以及制得的乳胶制品 Download PDF

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WO2017121352A1
WO2017121352A1 PCT/CN2017/070958 CN2017070958W WO2017121352A1 WO 2017121352 A1 WO2017121352 A1 WO 2017121352A1 CN 2017070958 W CN2017070958 W CN 2017070958W WO 2017121352 A1 WO2017121352 A1 WO 2017121352A1
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latex
natural latex
bamboo charcoal
natural
added
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PCT/CN2017/070958
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English (en)
French (fr)
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张金柱
刘顶
张小鸽
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济南圣泉集团股份有限公司
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Publication of WO2017121352A1 publication Critical patent/WO2017121352A1/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J2307/00—Characterised by the use of natural rubber
    • C08J2307/02—Latex
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the invention relates to the field of natural latex technology, in particular to a method for preserving natural latex and a prepared latex product.
  • Natural latex is a fresh latex that flows from the gum tree. It 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 is compressed, 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 primary 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.
  • the first object of the present invention is to provide a method for preserving natural latex, which uses bamboo charcoal to preserve natural latex, so that natural latex can be added without or with less ammonia stabilizer, and has less irritating odor or even irritating odor. And the shelf life of the deposit is not affected.
  • a second object of the present invention is to provide a latex mixture obtained by the above method for preserving natural latex.
  • a third object of the present invention is to provide a latex product made from the above latex mixture.
  • a method for preserving natural latex wherein bamboo charcoal is added to the natural latex for preservation.
  • the method for preserving the natural latex uses the bamboo charcoal to preserve the natural latex, so that the natural latex can be added without ammonia stabilizer or less ammonia stabilizer, and the ammonia-free or low-ammonia storage is carried out, so that the preserved natural latex has a smaller The irritating odor does not even irritate the odor and the shelf life of the deposit is not affected.
  • bamboo charcoal as a preservative, also provides antibacterial and antibacterial functions and far-infrared functions for natural latex tape, which is beneficial to the wide application of natural latex.
  • the natural latex of the present invention is a latex which flows out from the gum tree and is in the form of an emulsion.
  • the natural latex of the present invention comprises fresh latex oozing out of the gum tree, the fresh latex being preserved by the addition of bamboo charcoal.
  • the natural latex may be a fresh latex directly removed from the rubber tree; the present invention preferably preserves the fresh latex flowing out of the gum tree to prevent spoilage of the fresh latex.
  • bamboo charcoal in the present invention is commercially available bamboo charcoal or bamboo charcoal prepared by a prior art method.
  • bamboo charcoal is a kind of charcoal which is made from high-altitude bamboo of three years or more and is fired at a temperature of nearly one thousand degrees.
  • the bamboo charcoal is added in an amount of more than 0 or less than 10% by mass of the natural latex.
  • the invention adopts bamboo charcoal to carry out the ammonia-free or low-ammonia preservation of the natural latex, and the bamboo charcoal has an excellent antibacterial effect on the bacteria contained in the natural latex due to external pollution, and can preserve the natural latex well.
  • the percentage of bamboo charcoal in the mass of natural latex is greater than 0 and less than or equal to 10%.
  • the percentage of bamboo charcoal to the natural latex mass may be 0.1%, 0.3%, 0.5%, 0.7%, 1%, 3%, 5%, 6%, 7.8%, 8.9%, 10%, etc. .
  • the bamboo charcoal is added in an amount of from 0.3% to 7% by mass of the natural latex.
  • the bamboo charcoal is added in an amount of 0.5% to 5% by mass of the natural latex.
  • the natural latex may be an untreated natural latex or a natural latex which has been treated with a preservative.
  • the natural latex is a natural latex material treated with a preservative and then preserved by bamboo charcoal to enhance its preservation.
  • 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.
  • Natural latex is a special oil-in-water colloidal system that is a complex rubber-water based dispersion.
  • rubber particles and non-rubber particles constitute a dispersed phase;
  • whey constitutes a dispersion medium,
  • the whey is composed of a substance soluble in water such as protein, phospholipid, inorganic salt and saccharide; the source of the natural latex of the present invention is not particularly limited.
  • the bamboo charcoal is powdered bamboo charcoal or slurry bamboo charcoal.
  • powder bamboo charcoal or slurry bamboo charcoal to facilitate the uniform distribution of natural latex and bamboo charcoal, to achieve better preservation.
  • the powdered bamboo charcoal has a particle size of less than 100 nm.
  • the invention adds bamboo charcoal to preserve the natural latex, and the bamboo charcoal is uniformly mixed in the natural latex by means of dispersion, which is beneficial to the stable preservation of the natural latex.
  • the manner of dispersion may be physical dispersion, chemical dispersion (addition of a dispersant), or a combination of the two.
  • the natural latex and the bamboo charcoal are uniformly dispersed and then stored;
  • the method of dispersing adopts either or both of physical dispersion and chemical dispersion
  • the physical dispersion includes ultrasonic dispersion and high shear agitation dispersion
  • the chemical dispersion is carried out by adding a dispersing agent.
  • Dispersing agent dispersing is a chemical dispersing method, and the dispersing agent of the present invention mixes bamboo charcoal and natural latex evenly, and further preserves.
  • the dispersing agent comprises any one or more of sodium carboxymethylcellulose, polyvinyl alcohol, Tween 80, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, preferably ten Sodium dialkylbenzene sulfonate;
  • the mass ratio of the dispersing agent to the bamboo charcoal is preferably from 0.08 to 1:1, more preferably from 0.1 to 0.5:1.
  • the natural latex is further added with graphene, and the amount of the graphene added is preferably 0.05% to 0.2% by mass of the natural latex.
  • the graphene in 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, or hydrothermal carbonization of biomass resources.
  • Method, and graphene prepared by other methods in the prior art are difficult to achieve large-scale preparation of graphene in a strictly theoretical manner by any method.
  • other allotropes in which graphene is prepared in the prior art, and the number of layers is not a single layer or even more
  • the graphene structure of the layer for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.
  • the graphene utilized in the present invention also includes the above-described non-strict theoretical graphene.
  • the graphene prepared by using graphite ore as a raw material may contain certain mineral elements existing in the graphite ore, such as Si, Al, and the like.
  • At least Fe, Si, and Al may further contain one or more of K, Na, Ca, Mg, P, Mn, and Co.
  • the graphene referred to in the present invention is specifically a mixture containing graphene.
  • the graphene is prepared by using biomass as a raw material, that is, biomass graphene.
  • biomass graphene to preserve natural latex is slightly better than other graphenes.
  • Existing methods for preparing biomass graphene include, for example, the method disclosed in CN104118873A; the method disclosed in CN104016341A; the method disclosed in CN104724696A; the method disclosed in CN104724699A; and the method disclosed in CN105060289A.
  • the graphene is prepared by the following method:
  • the temperature increase rate in the steps (3) and (4) is 14 ° C / min to 18 ° C / min.
  • a natural latex preservative is further added to the natural latex, and the natural latex preservative is added in an amount of more than 0 and less than 0.35% by mass of the natural latex.
  • the natural latex preservative is added in an amount of 0.1% by mass or less based on the mass of the natural latex.
  • the natural latex preservative is added in an amount of 0.05% by mass or less based on the mass of the natural latex.
  • the natural latex preservative comprises any one or more of an ammonia preservative, chitosan, sodium pentachlorophenol, thiol benzothiazole, and dihydroxypropyl dodecanoate.
  • the ammonia preservative of the present invention includes ammonia water and/or liquid ammonia.
  • the natural latex preservative is an ammonia preservative.
  • the invention adopts bamboo charcoal 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 shelf life of the storage is long, the irritating odor is small, and the latex is favorable.
  • the application of the product; in addition, the natural latex preserved by the bamboo charcoal of the present invention also exerts an unexpected far infrared function.
  • the present invention also provides a latex mixture obtained by the above method for preserving latex.
  • the latex mixture provided by the invention has less irritating odor and even no irritating odor, has antibacterial and antibacterial function, has a long shelf life of storage, and is safer.
  • the natural milk preserved by bamboo charcoal of the present invention is used.
  • the glue also has a far-infrared function, which can promote the microcirculation of the human body and is beneficial to human health.
  • the invention also provides a latex article made from the latex mixture.
  • the invention adopts the above-mentioned natural latex preserved by bamboo charcoal as a raw material, and can 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, a woven article.
  • Latex products include adhesives, carpet backings, latex papers, non-woven fabrics, artificial leathers, latex cements, latex asphalts, latex tapes, latex coatings or matte mats, as well as other prior art latex articles.
  • 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 natural latex mixture obtained by the bamboo charcoal preservation method can be 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 the far infrared function and the 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, thereby promoting the microcirculation of the human body and benefiting human health.
  • the latex product provided by the present invention has excellent mechanical properties, adsorption function, moisture wicking function, and the like, and has excellent application properties.
  • the latex article provided by the present invention is preferably produced by the following method:
  • 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 bamboo charcoal are uniformly mixed to obtain a latex mixture.
  • the solid bamboo charcoal or the bamboo charcoal-containing solution may be mixed with the natural latex, and the natural latex may be preserved by dispersion.
  • the rubber auxiliaries are raw materials of latex products well known to those skilled in the art, such as vulcanizing agents, antioxidants, antioxidants, plasticizers and the like.
  • the rubber adjuvant includes a vulcanizing agent and an antioxidant; in another embodiment of the present invention, the rubber auxiliary comprises 3 to 5 parts by mass of a vulcanizing agent, 5 to 8 a mass part of the gelling agent, 2 to 3 parts by mass of the antioxidant, and 1 to 2 parts by mass of the sodium stearate; the mass fraction of the natural latex treated with the bamboo charcoal is 85 to 100 parts; in addition, the embodiment of the present invention may also 0.1 to 0.2 parts by mass of a functional ingredient such as natural essential oil is added.
  • the pillow mold After foaming to obtain a foamed material, it is introduced 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. After the curing is completed, 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.
  • a latex mixture obtained by mixing a natural latex and a rubber auxiliary agent after the bamboo charcoal preservation treatment may also be used to prepare a latex product such as a latex mattress or a latex glove.
  • 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 result shows that this The latex product provided by the 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 provided by the invention has less ammonia stabilizer, less irritating odor, and has excellent mechanical properties, adsorption function and moisture wicking function, and is advantageous for application.
  • the method for preserving natural latex uses bamboo charcoal to preserve the natural latex, so that the natural latex can be preserved without ammonia or with less ammonia stabilizer, and the natural latex can be preserved without ammonia or low ammonia. It has less irritating odor and even no irritating odor, and the shelf life of storage is not affected.
  • bamboo charcoal acts as a preservative, and also has antibacterial and antibacterial functions and far-infrared function for natural latex tape, which is beneficial to the wide application of natural latex. .
  • the present invention further disperses the bamboo charcoal and the natural latex by additionally adding a dispersing agent or physically, so that the two are uniformly mixed to improve the preservation effect.
  • any one or two of natural latex preservative and graphene are added to the natural latex to further enhance the preservation time and the performance of preserving the natural latex.
  • the present invention also provides a latex mixture obtained by a method for preserving natural latex and a latex product prepared by the latex mixture, and the prepared latex product has an antibacterial and antibacterial function, has a small irritating odor, and has a long shelf life of storage; Infrared function and excellent mechanical properties, adsorption function and moisture wicking function.
  • Example 1 In the fresh latex, different amounts of bamboo charcoal were separately added for storage, which are Examples 1-10.
  • Example 1 the amount of bamboo charcoal added is 0.1% of the mass of the fresh latex; in Example 2, the amount of bamboo charcoal added is 0.3% of the mass of the fresh latex; in Example 3, the added amount of bamboo charcoal accounts for the fresh latex.
  • the percentage of the mass is 0.5%; in Example 4, the amount of bamboo charcoal added is 0.7% of the mass of the fresh latex; in Example 5, the amount of bamboo charcoal added is 1% of the mass of the fresh latex; in Example 6, The amount of bamboo charcoal added is 3% of the mass of fresh latex; in Example 7, the amount of bamboo charcoal added is 5% of the mass of fresh latex; in Example 8, the percentage of bamboo charcoal added to the mass of fresh latex is 7 %; In Example 9, the amount of bamboo charcoal added was 9% of the mass of the fresh latex; in Example 10, the amount of bamboo charcoal added was 10% of the mass of the fresh latex.
  • the added dispersant was sodium carboxymethylcellulose in an amount of 0.02% by weight of the fresh latex; in Example 12, the added dispersant was polyvinyl alcohol in an amount of 0.02% by weight of the fresh latex.
  • the added dispersant was sodium dodecylbenzenesulfonate in an amount of 0.04% by weight of the fresh latex; in Example 14, the added dispersant was sodium dodecylbenzenesulfonate and spit.
  • Example 15 a mixture of Wen 80 in an amount of 0.05% by weight of fresh latex; in Example 15, the added dispersant is a mixture of sodium carboxymethylcellulose, polyvinyl alcohol, Tween 80 and sodium lauryl sulfate, added The amount is 0.25% by weight of the fresh latex; in Example 16, the added dispersing agent is sodium carboxymethylcellulose, polyvinyl alcohol, Tween 80, sodium lauryl sulfate and sodium dodecylbenzenesulfonate. The mixture was added in an amount of 0.5% by weight of the fresh latex.
  • Example 17 added chitosan in an amount of 0.1% by weight of fresh latex;
  • Example 18 added liquid ammonia in an amount of 0.1% by weight of fresh latex;
  • Example 19 added liquid ammonia in an amount of 0.05 based on the weight of fresh latex %;
  • Example 20 was added liquid ammonia in an amount of 0.3% by weight of fresh latex;
  • Example 21 was added a mixture of sodium pentachlorophenol and thiol benzothiazole in an amount of 0.1% by weight of fresh latex;
  • Example 22 A mixture of liquid ammonia, chitosan, sodium pentachlorophenol, thiol benzothiazole and dihydroxypropyl dodecanoate was added in an amount of 0.1% by weight of the fresh latex.
  • Example 23 sodium carboxymethylcellulose and liquid ammonia were separately added, and the amount of sodium carboxymethylcellulose added was 0.02%, and the amount of liquid ammonia added was 0.1% by weight of fresh latex;
  • Example 24 was further added with polyethylene. Alcohol and liquid ammonia, the amount of polyvinyl alcohol added was 0.04% by weight of fresh latex, and the amount of liquid ammonia added was 0.1%.
  • Example 25 Adding biomass graphene, the mass of the biomass graphene is 0.05% by weight of the fresh latex;
  • Example 26 adding biomass graphene, the mass of the biomass graphene is 0.1% by weight of the fresh latex;
  • Example 27 is added Commercially available graphene, commercially available graphene has a mass of 0.1% by weight of fresh latex;
  • Example 28 adds biomass graphene, biomass graphene has a mass of 0.2% by weight of fresh latex;
  • Example 29 adds biomass graphene And the quality of sodium carboxymethylcellulose, biomass graphene and sodium carboxymethylcellulose are 0.1% and 0.1%, respectively, of the weight of fresh latex;
  • Example 30 adds biomass graphene and liquid ammonia, biomass graphene and The mass of liquid ammonia is 0.1% and 0.1% of the weight of fresh latex, respectively;
  • Example 31 adds biomass graphene, sodium carboxymethyl cellulose and liquid ammonia, biomass graphite The mass of the mass of the biomass graphite
  • biomass graphene is prepared by the following method:
  • the third intermediate is sequentially subjected to sodium hydroxide alkali washing, hydrochloric acid pickling, and water washing to obtain graphene;
  • the heating rate in the steps (3) and (4) was 16 ° C / min.
  • biomass graphene has a slightly better preservation effect.
  • liquid ammonia having a mass percentage of 0.35% was added and stored under the above storage conditions.
  • liquid ammonia having a mass percentage of 1% was added and stored under the above storage conditions.
  • liquid ammonia having a mass percentage of 2% was added and stored under the above storage conditions.
  • activated carbon having a mass percentage of 7% was added and stored under the above storage conditions.
  • the activated carbon is JL-202 commercially available from Nanjing Jiali Carbon Co., Ltd., and the raw material for preparation is a shell.
  • the storage time is sealed and stored at a temperature below 25 °C.
  • the bamboo charcoal used therein is commercially available bamboo charcoal.
  • Examples 1-10 of Table 1 As the amount of bamboo charcoal added increases, the preservation time of the natural latex gradually increases, and the plastic initial value and plastic retention rate of the natural raw rubber made of the preserved natural latex are also continuously increased. Enhancement, indicating that the performance of natural rubber is continuously optimized; compared with Example 3, Examples 11-16 additionally add a dispersing agent, which makes the bamboo charcoal achieve better dispersion effect, and further preserves the preservation time of the natural latex.
  • Example 17-22 additionally add a natural latex preservative, which further increases the preservation time of the natural latex;
  • Examples 23-24 additionally added a dispersant and a preservative, which further increased the preservation time of the natural latex; compared with Example 3, Examples 25-28 additionally added graphene, and the preservation time of the natural latex was remarkable.
  • Increased, the plastic initial value and plastic retention rate of the natural raw rubber made from the preserved natural latex also significantly increased, indicating that graphene can significantly improve the preservation effect;
  • Outer graphene Example 29-31 adds additional embodiment dispersants, preservatives, etc., to further increase the preservative effect.
  • Latex pillows were prepared using the natural latex mixture treated with bamboo charcoal in the above Examples 1 to 31 and the natural latex mixture of Comparative Examples 1 to 4.
  • Latex pillows are prepared in the following manner:
  • a vulcanizing agent insoluble sulfur
  • a vulcanization accelerator diphenyl hydrazine
  • a dispersing agent sodium stearate
  • the obtained latex mixture, 5 parts of gelling agent (sodium fluorosilicate), and 5 parts of zinc oxide were respectively introduced into a latex foaming machine, and the expansion ratio was adjusted to form a foam density of 40, and then the foam was introduced into the pillow mold through a pipe.
  • 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 preservatives; while the bamboo charcoal is used as a preservative, it also has an antibacterial and antibacterial function and a far infrared function for the natural latex tape.
  • the latex product provided by the invention has the functions of antibacterial and antibacterial, has the characteristics of small irritating smell and long shelf life of storage.
  • the latex product provided by the invention also has a far infrared function and can promote microcirculation of the human body. Conducive to human health.
  • the latex product has excellent mechanical properties, adsorption function and moisture wicking function, which is beneficial to the application.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

天然乳胶的保存方法以及制得的乳胶制品，在天然乳胶中添加竹炭进行保存。该天然乳胶中可不加氨稳定剂或少加氨稳定剂，实行无氨或低氨保存，使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。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。此外，该乳胶制品还具有远红外功能，能够促进人体的微循环，并且具有优异的力学性能、吸附功能和吸湿排汗功能等。其应用性能优异，利于天然乳胶的广泛应用。

Description

[根据细则37.2由ISA制定的发明名称]　天然乳胶的保存方法以及制得的乳胶制品 技术领域
本发明涉及天然乳胶技术领域，具体而言，涉及一种天然乳胶的保存方法以及制得的乳胶制品。
背景技术
天然乳胶为从胶树流出的鲜胶乳，其流动性好，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；腐败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。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种天然乳胶的保存方法，采用竹炭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。
本发明的第二目的在于提供一种上述的天然乳胶的保存方法得到的乳胶混合物。
本发明的第三目的在于提供由上述的乳胶混合物制成的乳胶制品。
为了实现本发明的上述目的，特采用以下技术方案：
一种天然乳胶的保存方法，在所述天然乳胶中添加竹炭进行保存。
本发明提供的天然乳胶的保存方法，采用竹炭对天然乳胶进行保存，这样天然乳胶中可不加氨稳定剂或少加氨稳定剂，实行无氨或低氨保存，使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。另外，竹炭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，利于天然乳胶的广泛应用。
本发明所述天然乳胶为从胶树流出的乳胶，成乳液状。
优选地，本发明所述天然乳胶包括胶树流出的新鲜胶乳，所述新鲜胶乳通过加入竹炭进行保存。
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，以防止新鲜胶乳发生腐败。
本发明中的竹炭为市售竹炭或以现有技术方法制备的竹炭。一般地，竹炭是以三年生以上高山毛竹为原料，经近千度高温烧制而成的一种炭。
优选地，所述竹炭的添加量占所述天然乳胶质量的百分比大于0小于等于10％。
本发明采用竹炭对天然乳胶进行无氨或低氨保存，竹炭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。本发明保存天然乳胶尤其是保存新鲜胶乳时，竹炭占天然乳胶质量的百分比大于0且小于等于10％。如在一些实施例中，竹炭占天然乳胶质量的百分比可以为0.1％、0.3％、0.5％、0.7％、1％、3％、5％、6％、7.8％、8.9％、10％等等。
更优选地，所述竹炭的添加量占所述天然乳胶质量的百分比为0.3％-7％。
更优选地，所述竹炭的添加量占所述天然乳胶质量的百分比为0.5％-5％。
本发明中，天然乳胶可以为未经处置的天然乳胶，也可以为已经采用保存剂处理后的天然乳胶。
如在本发明的一些实施例中，天然乳胶是用保存剂处理过的天然乳胶材料，然后再经竹炭保存，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。
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；本发明对天然乳胶的来源没有特殊限制。
优选地，所述竹炭为粉体竹炭或浆料竹炭。采用粉体竹炭或浆料竹炭以利于天然乳胶与竹炭分布均匀，达到更好的保存效果。
优选地，所述粉体竹炭的粒径小于100nm。
本发明加入竹炭保存天然乳胶，通过分散的方式使竹炭在天然乳胶中混合均匀，利于天然乳胶的稳定保存。分散的方式可以为物理分散、化学分散(添加分散剂)、或者两者结合进行分散。
优选地，所述天然乳胶与竹炭分散均匀后进行保存；
所述分散的方式采用物理分散、化学分散中的任一种或两种；
所述物理分散包括超声波分散和高剪切力的搅拌分散；
所述化学分散为添加分散剂进行分散。
采用分散剂分散属于化学分散方法，本发明添加分散剂使竹炭和天然乳胶混合均匀，进而进行保存。
优选地，所述分散剂包括羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠、十二烷基苯磺酸钠中的任一种或多种，优选为十二烷基苯磺酸钠；
所述分散剂与所述竹炭的质量比优选为0.08～1∶1，更优选为0.1～0.5∶1。
优选地，所述天然乳胶中还添加石墨烯，所述石墨烯的添加量占所述天然乳胶的质量百分数优选为0.05％-0.2％。
经试验验证，石墨烯能显著提高天然乳胶的保存效果，保存效果包括：延长保存时间、保存得到的天然乳胶加工制成的产品的性能更为优良。
本发明中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碳元素的其他同素异形体、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)或其它元素，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。
对于上述的“其它元素”：
利用石墨矿为原料制备得到的石墨烯中，可能含有石墨矿中自身存在的某些矿质元素，例如Si、Al等。
利用生物质作为原料制备得到的生物质石墨烯中，由于原料来自于植物，植物自身需要从土壤中吸收矿质元素，这些矿质元素在制备生物质石墨烯过程中得到了选择性的保留，矿质元素至少为Fe、Si、Al，还可含有K、Na、Ca、Mg、P、Mn和Co中的一种或几种。
因此，本发明中所指的石墨烯具体为一种含有石墨烯的混合体。
优选地，所述石墨烯是以生物质为原料制备得到，也即生物质石墨烯。采用生物质石墨烯保存天然乳胶，比其他石墨烯的保存效果略优。
现有的生物质石墨烯的制备方法举例如：CN104118873A公开的方法；CN104016341A公开的方法；CN104724696A公开的方法；CN104724699A公开的方法；CN105060289A公开的方法。
优选地，所述石墨烯采用以下方法制备：
(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进行碱洗、酸洗、水洗，得到石墨烯；
其中，所述步骤(3)、(4)中的升温速率为14℃/min～18℃/min。
优选地，所述天然乳胶中还添加天然乳胶保存剂，所述天然乳胶保存剂的添加量占所述天然乳胶的质量百分数大于0小于0.35％。
更优选地，所述天然乳胶保存剂的添加量占所述天然乳胶的质量百分数小于等于0.1％。
更优选地，所述天然乳胶保存剂的添加量占所述天然乳胶的质量百分数小于等于0.05％。
优选地，所述天然乳胶保存剂包括氨保存剂、壳聚糖、五氯酚钠、硫醇基苯并噻唑、十二烷酸二羟丙基盐中的任一种或多种。
本发明所述氨保存剂包括氨水和/或液氨。
为了达到更好的杀菌效果，以延长天然乳胶的保存期，优选地，所述天然乳胶保存剂为氨保存剂。
本发明采用竹炭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，本发明用竹炭保存的天然乳胶还起到了意想不到的远红外功能。
本发明还提供了上述的乳胶的保存方法得到的乳胶混合物。
本发明提供的乳胶混合物有较小的刺激气味甚至没有刺激气味，具有抗菌抑菌功能，存放的保质期长，更为安全，另外，本发明采用竹炭保存的天然乳 胶还具有远红外功能，能够促进人体的微循环，利于人体健康。
本发明还提供了由所述的乳胶混合物制成的乳胶制品。
本发明以上述用竹炭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。
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、织造制品。
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。
本发明采用竹炭保存得到的天然乳胶混合物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，利于人体健康。
此外，本发明提供的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，应用性能优异。
本发明提供的乳胶制品优选按照以下方法制得：
将用竹炭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。
本发明将用竹炭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。该制备方法中，可将固体竹炭或者含竹炭的溶液与天然乳胶混合，经分散，对天然乳胶进行保存。
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。如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；在本发明的另一个实施例中，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；经过竹炭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。
本发明中，发泡得到发泡材料后，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，采用竹炭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，本发明提供的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。
与现有技术相比，本发明的有益效果为：
(1)本发明提供的天然乳胶的保存方法，采用竹炭对天然乳胶进行保存，这样天然乳胶中可不加氨稳定剂或少加氨稳定剂，实行无氨或低氨保存，使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；竹炭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，利于天然乳胶的广泛应用。
(2)本发明还通过额外增加分散剂或采用物理方法将竹炭与天然乳胶分散，以使两者混合均一，提高保存效果。
(3)本发明提供的天然乳胶的保存方法，天然乳胶中还添加天然乳胶保存剂、石墨烯中的任一种或两种，以进一步提升保存时间以及保存天然乳胶的性能。
(4)本发明还提供了天然乳胶的保存方法得到的乳胶混合物以及该乳胶混合物制成的乳胶制品，制成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；具备远红外功能以及优异的力学性能、吸附功能和吸湿排汗功能等。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试 剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
实施例1～10
在新鲜胶乳中，分别添加不同质量的竹炭进行保存，分别为实施例1-10。实施例1中，竹炭的添加量占新鲜胶乳质量的百分比为0.1％；实施例2中，竹炭的添加量占新鲜胶乳质量的百分比为0.3％；实施例3中，竹炭的添加量占新鲜胶乳质量的百分比为0.5％；实施例4中，竹炭的添加量占新鲜胶乳质量的百分比为0.7％；实施例5中，竹炭的添加量占新鲜胶乳质量的百分比为1％；实施例6中，竹炭的添加量占新鲜胶乳质量的百分比为3％；实施例7中，竹炭的添加量占新鲜胶乳质量的百分比为5％；实施例8中，竹炭的添加量占新鲜胶乳质量的百分比为7％；实施例9中，竹炭的添加量占新鲜胶乳质量的百分比为9％；实施例10中，竹炭的添加量占新鲜胶乳质量的百分比为10％。
实施例11～16
在新鲜胶乳中，添加其质量百分比为0.5％的竹炭，同时加入分散剂，以使竹炭达到更好的分散效果，利于对天然乳胶保存。实施例11中，添加的分散剂为羧甲基纤维素钠，添加量为新鲜胶乳重量的0.02％；实施例12中，添加的分散剂为聚乙烯醇，添加量为新鲜胶乳重量的0.02％；实施例13中，添加的分散剂为十二烷基苯磺酸钠，添加量为新鲜胶乳重量的0.04％；实施例14中，添加的分散剂为十二烷基苯磺酸钠和吐温80的混合物，添加量为新鲜胶乳重量的0.05％；实施例15中，添加的分散剂为羧甲基纤维素钠、聚乙烯醇、吐温80和十二烷基硫酸钠的混合物，添加量为新鲜胶乳重量的0.25％；实施例16中，添加的分散剂为羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠的混合物，添加量为新鲜胶乳重量的0.5％。
实施例17～22
在新鲜胶乳中，添加其质量百分比为0.5％的竹炭，同时加入其他天然乳胶保存剂，以达到更好的保存效果。实施例17添加壳聚糖，添加量为新鲜胶乳重量的0.1％；实施例18添加液氨，添加量为新鲜胶乳重量的0.1％；实施例19添加液氨，添加量为新鲜胶乳重量的0.05％；实施例20添加液氨，添加量为新鲜胶乳重量的0.3％；实施例21添加五氯酚钠和硫醇基苯并噻唑的混合物，添加量为新鲜胶乳重量的0.1％；实施例22添加液氨、壳聚糖、五氯酚钠、硫醇基苯并噻唑和十二烷酸二羟丙基盐的混合物，添加量为新鲜胶乳重量的0.1％。
实施例23～24
在新鲜胶乳中，添加其质量百分比为0.5％的竹炭，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。实施例23还分别加入羧甲基纤维素钠和液氨，以新鲜胶乳重量计，羧甲基纤维素钠添加量为0.02％，液氨添加量为0.1％；实施例24还分别加入聚乙烯醇和液氨，以新鲜胶乳重量计，聚乙烯醇添加量为0.04％，液氨添加量为0.1％。
实施例25～28
在新鲜胶乳中，添加其质量百分比为0.5％的竹炭，同时加入石墨烯，以达到更好的保存效果。实施例25添加生物质石墨烯，生物质石墨烯的质量为新鲜胶乳重量的0.05％；实施例26添加生物质石墨烯，生物质石墨烯的质量为新鲜胶乳重量的0.1％；实施例27添加市售石墨烯，市售石墨烯的质量为新鲜胶乳重量的0.1％；实施例28添加生物质石墨烯，生物质石墨烯的质量为新鲜胶乳重量的0.2％；实施例29添加生物质石墨烯和羧甲基纤维素钠，生物质石墨烯和羧甲基纤维素钠的质量分别为新鲜胶乳重量的0.1％和0.1％；实施例30添加生物质石墨烯和液氨，生物质石墨烯和液氨的质量分别为新鲜胶乳重量的0.1％和0.1％；实施例31添加生物质石墨烯、羧甲基纤维素钠和液氨，生物质石墨 烯、羧甲基纤维素钠和液氨的质量分别为新鲜胶乳重量的0.1％、0.02％和0.1％。
其中，生物质石墨烯采用以下方法制备：
(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)在氮气的条件下，将前驱体在160℃保温2h，得到第一中间体；
(3)在氮气的条件下，将第一中间体升温至400℃保温3.5h，得到第二中间体；
(4)在氮气的条件下，将第二中间体升温至1200℃保温3h，得到第三中间体；
(5)将第三中间体依次进行氢氧化钠碱洗、盐酸酸洗、水洗，得到石墨烯；
其中，步骤(3)、(4)中的升温速率为16℃/min。
另外，还采用采用生物质石墨烯的保存效果稍优。
比较例1
在新鲜胶乳中，不添加任何保存剂，在上述保存条件下进行保存。
比较例2
在新鲜胶乳中，添加其质量百分比为0.35％的液氨，在上述保存条件下进行保存。
比较例3
在新鲜胶乳中，添加其质量百分比为1％的液氨，在上述保存条件下进行保存。
比较例4
在新鲜胶乳中，添加其质量百分比为2％的液氨，在上述保存条件下进行保存。
比较例5
在新鲜胶乳中，添加其质量百分比为7％的活性炭，在上述保存条件下进行保存。所述活性炭为商购于南京佳力炭业有限公司的JL-202，其制备原料为果壳。
其中的保存时间均为在温度25℃以下密封保存。其中所用竹炭均为市售竹炭。
不同组别经过竹炭处理的天然乳胶、比较例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)。相关数据和结果参见表1。
表1不同组别保存得到的天然乳胶的性能
Figure PCTCN2017070958-appb-000001
Figure PCTCN2017070958-appb-000002
Figure PCTCN2017070958-appb-000003
从表1的实施例1-10可以看出，随着竹炭的添加量增多，天然乳胶的保存时间逐渐延长，由保存的天然乳胶制成的天然生胶的塑性初值和塑性保持率也不断增强，说明天生生胶的性能不断优化；相对于实施例3，实施例11-16额外添加了分散剂，分散剂使竹炭达到更好的分散效果，使天然乳胶的保存时间进一步延长，由保存的天然乳胶制成的天然生胶的塑性初值和塑性保持率也进一步增强；相对于实施例3，实施例17-22额外添加了天然乳胶保存剂，进一步增加了天然乳胶的保存时间；相对于实施例3，实施例23-24额外添加分散剂和保存剂，进一步增加了天然乳胶的保存时间；相对于实施例3，实施例25-28额外添加了石墨烯，天然乳胶的保存时间显著增加，由保存的天然乳胶制成的天然生胶的塑性初值和塑性保持率也显著增强，说明石墨烯能显著提高保存效果；除石墨烯外，实施例29-31额外增加了分散剂、保存剂等，进一步增加保存效果。
采用上述实施例1～31经过竹炭处理的天然乳胶混合物、比较例1～4中的天然乳胶混合物制备乳胶枕头。
乳胶枕头采用以下方式制备：
以质量份数计，将85～100份天然乳胶混合物(实施例1～28、比较例1～4)、 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。
将得到的乳胶混合物料、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。
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不同组别制得的乳胶枕头的检测结果
Figure PCTCN2017070958-appb-000004
Figure PCTCN2017070958-appb-000005
由以上实施例可知，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；竹炭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。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (13)

  1. 一种天然乳胶的保存方法，其特征在于，在所述天然乳胶中添加竹炭进行保存。
  2. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述天然乳胶包括胶树流出的新鲜胶乳，所述新鲜胶乳通过加入竹炭进行保存。
  3. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述天然乳胶中，所述竹炭的添加量占所述天然乳胶质量的百分比大于0小于等于10％。
  4. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述保存方法还包括向所述天然乳胶中添加石墨烯。
  5. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述天然乳胶中，所述竹炭的添加量占所述天然乳胶质量的百分比0.3％-7％，更优选为0.5％-5％。
  6. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述竹炭为粉体竹炭或浆料竹炭；
    所述粉体竹炭的粒径优选小于100nm。
  7. 根据权利要求1所述的天然乳胶的保存方法，其特征在于，所述天然乳胶与竹炭分散均匀后进行保存；
    所述分散的方式采用物理分散、化学分散中的任一种或两种；
    所述物理分散包括超声波分散和高剪切力的搅拌分散；
    所述化学分散为添加分散剂进行分散。
  8. 根据权利要求7所述的天然乳胶的保存方法，其特征在于，所述分散剂包括羧甲基纤维素钠、聚乙烯醇、吐温80、十二烷基硫酸钠、十二烷基苯磺酸钠中的任一种或多种，优选为十二烷基苯磺酸钠；
    所述分散剂与所述竹炭的质量比优选为0.08～1∶1，更优选为0.1～0.5∶1。
  9. 根据权利要求4所述的天然乳胶的保存方法，其特征在于，所述石墨烯的添加量占所述天然乳胶的质量百分数为0.05％-0.2％；
    优选地，所述石墨烯是以生物质为原料制备得到；
    更优选地，所述石墨烯采用以下方法制备：
    (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进行碱洗、酸洗、水洗，得到石墨烯；
    其中，所述步骤(3)、(4)中的升温速率为14℃/min～18℃/min。
  10. 根据权利要求1-9任一项所述的天然乳胶的保存方法，其特征在于，所述天然乳胶中还添加天然乳胶保存剂，所述天然乳胶保存剂的添加量占所述天然乳胶的质量百分数大于0小于0.35％；优选小于等于0.1％，更优选小于等于0.05％；
    优选地，所述天然乳胶保存剂包括氨保存剂、壳聚糖、五氯酚钠、硫醇基苯并噻唑、十二烷酸二羟丙基盐中的任一种或多种。
  11. 权利要求1-10任一项所述的天然乳胶的保存方法得到的乳胶混合物。
  12. 由权利要求11所述的乳胶混合物制成的乳胶制品。
  13. 根据权利要求12所述的乳胶制品，其特征在于，所述乳胶制品包括浸渍制品、海绵制品、压出制品、铸膜制品、织造制品。
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