WO2011108660A1 - Procédé de production d'un caoutchouc naturel modifié - Google Patents

Procédé de production d'un caoutchouc naturel modifié Download PDF

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WO2011108660A1
WO2011108660A1 PCT/JP2011/054944 JP2011054944W WO2011108660A1 WO 2011108660 A1 WO2011108660 A1 WO 2011108660A1 JP 2011054944 W JP2011054944 W JP 2011054944W WO 2011108660 A1 WO2011108660 A1 WO 2011108660A1
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Prior art keywords
latex
polymer
rubber
natural rubber
modified natural
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PCT/JP2011/054944
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English (en)
Japanese (ja)
Inventor
直生 岩瀬
今井　英幸
明繁 瀬尾
河原　成元
祥正 山本
圭一郎 塩原
Original Assignee
豊田合成 株式会社
国立大学法人 長岡技術科学大学
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Priority to CN2011800120188A priority Critical patent/CN102858805A/zh
Priority to JP2012503259A priority patent/JP5739867B2/ja
Publication of WO2011108660A1 publication Critical patent/WO2011108660A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/04—Oxidation
    • C08C19/06—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/04—Purifying; Deproteinising
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C2/00—Treatment of rubber solutions
    • C08C2/02—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention relates to a method for producing a modified natural rubber, and more particularly, to a method for producing a modified natural rubber capable of simplifying the production process after the epoxidation process.
  • Plant-derived materials are expected to suppress the consumption of limited petroleum resources and to suppress global warming because carbon dioxide is absorbed during the plant growth process.
  • Plant-derived natural rubber (rubber-like polymer) is collected from rubber trees as a polymer. Natural rubber is excellent in processability and strength. On the other hand, natural rubber is inferior in weather resistance and ozone resistance. For this reason, various modifications of natural rubber have been attempted for the purpose of improving rubber properties and imparting new rubber properties. Various modified natural rubbers have been developed for the purpose of improving the application range and convenience.
  • Patent Document 1 describes a modified nature in which unsaturated double bonds in the main chain are reduced to reduce unsaturated double bonds, and a part of the unsaturated double bonds are epoxidized and opened to give a hydroxyl group.
  • a rubber is disclosed.
  • the modified natural rubber disclosed in this document has excellent weather resistance and ozone resistance because unsaturated double bonds are reduced.
  • the modified natural rubber disclosed in this document is excellent in cross-linking ability because it has a hydroxyl group.
  • Such modified natural rubber is applied, for example, to automotive window frame parts such as weather strips and parts used around water such as water hoses.
  • a modified natural rubber in which the unsaturated double bond in the main chain is reduced to reduce the unsaturated double bond, and a part of the unsaturated double bond is epoxidized and opened to give a hydroxyl group to the above rubber The following method is used as a method for producing from a polymer. First, in the epoxidation process, an organic peracid is added to a latex in which a rubber-like polymer is dispersed in water, and a part of the unsaturated double bond in the main chain of the rubber-like polymer is epoxidized to epoxidize it. A rubbery polymer is produced.
  • the organic acid and the organic acid salt derived from the organic peracid added in the epoxidation step may be present in the reaction system.
  • undesired side reactions such as cyclization and formation of crosslinks may be caused in the epoxidized rubber-like polymer, and rubber properties may be lost. Therefore, conventionally, after the epoxidation step, the epoxidized rubber-like polymer in the latex is solidified and isolated from the dispersion medium, whereby the epoxidized rubber-like polymer and the organic peracid-derived substance are combined. It was separated.
  • a latex in which a plant-derived rubbery polymer having a plurality of unsaturated double bonds in the main chain is dispersed in water as a dispersion medium.
  • the organic peracid-derived substance generated from the organic peracid in the polymerization step is removed from the latex, and the content of the organic peracid-derived substance in the latex is 35 masses per 100 parts by mass of the epoxidized rubber-like polymer.
  • the removing step it is preferable to replace a part of the dispersion medium in which the substance derived from the organic peracid in the latex is dissolved with a new dispersion medium.
  • the latex after the epoxidation step is subjected to a centrifugal separation treatment, whereby the latex is mainly composed of an upper layer in which the epoxidized rubber-like polymer is dispersed, and is mainly organic. It is preferable to separate into a lower layer in which the peracid-derived substance is dissolved, and to remove the lower layer and add a new dispersion medium to the upper layer.
  • the organic peracid-derived substance is removed from the latex to separate the epoxidized rubber-like polymer and the organic peracid-derived substance.
  • the epoxidation step and the reduction / ring-opening step can be continuously performed in the latex state without isolating and purifying the epoxidized rubber-like polymer from the latex. For this reason, the work efficiency at the time of manufacture improves.
  • Natural rubber latex collected from plants contains various proteins in addition to rubbery polymers.
  • a modified natural rubber is produced using a natural rubber latex mixed with such a protein as a raw material, the physical properties of the resulting modified natural rubber may become unstable or the quality may be lowered. Therefore, when producing a modified natural rubber using a natural rubber latex mixed with protein as a raw material, it is desirable to perform a deproteinization treatment to remove the protein.
  • the production process of the modified natural rubber can be simplified.
  • a plant-derived rubber-like polymer having a plurality of unsaturated double bonds in the main chain is used as a raw material. Then, the unsaturated double bond in the main chain is reduced to reduce the unsaturated double bond, and a part of the unsaturated double bond is epoxidized and opened to provide a modified natural rubber having a hydroxyl group. To manufacture.
  • the method for producing a modified natural rubber in the present embodiment includes an epoxidation step, a removal step, and a reduction / ring-opening step.
  • epoxidation step a part of unsaturated double bonds of a plant-derived rubber-like polymer having a plurality of unsaturated double bonds in the main chain is epoxidized to obtain an epoxidized rubber-like polymer.
  • the organic peracid-derived substance generated in the epoxidation step is removed.
  • part or all of the unsaturated double bond remaining in the epoxidized rubber-like polymer is reduced, and part or all of the epoxy group of the epoxidized rubber-like polymer is opened.
  • ⁇ Raw material> As a raw material, natural rubber latex containing a plant-derived rubber-like polymer having a plurality of (two or more) unsaturated double bonds in the main chain can be used. Specifically, a field latex obtained from a natural rubber tree and a processed product obtained by treating the field latex can be used. Examples of the treated product include latex in which field latex is concentrated to increase the rubbery polymer concentration, latex in which field latex is treated with ammonia, latex in which field latex is deproteinized, and a mixture thereof. Further, a solid rubber obtained by isolating and purifying a rubber-like polymer from natural rubber latex can also be used as a raw material.
  • the deproteinization treatment method examples include known methods described in JP-A Nos. 6-56902 and 2004-99696.
  • the nitrogen content in the natural rubber latex is preferably set to 0.1 parts by mass or less with respect to 100 parts by mass of the rubbery polymer, and more preferably set to 0.05 parts by mass or less. preferable.
  • ⁇ Epoxidation process> In the epoxidation step, an organic peracid is reacted with the rubber-like polymer, and a part of the unsaturated double bond of the main chain of the rubber-like polymer is substituted with an epoxy group to obtain an epoxidized rubber-like polymer.
  • a natural rubber latex or a solid rubber as a raw material is dispersed in water as a dispersion medium to prepare a reaction system latex.
  • reaction latex used in the production process is described as reaction latex.
  • organic peracid is reacted with the rubber-like polymer in the prepared reaction latex to perform epoxidation.
  • organic peracids include perbenzoic acid, peracetic acid, performic acid, perphthalic acid, perpropionic acid, trifluoroperacetic acid, and perbutyric acid. These organic peracids may be added directly to the reaction system latex.
  • a component capable of generating an organic peracid may be added to generate the organic peracid in the reaction system latex.
  • formic acid can be produced by sequentially adding formic acid and hydrogen peroxide.
  • acetic anhydride and hydrogen peroxide may be added sequentially.
  • the reaction system latex is neutralized with a base such as an aqueous ammonia solution.
  • a base such as an aqueous ammonia solution.
  • the organic peracid and the organic acid present in the reaction system latex are neutralized to produce an organic peracid and a salt of the organic acid.
  • the organic peracid is peracetic acid and neutralization is performed using an aqueous ammonia solution, acetic acid is generated from the peracetic acid, and the reaction system latex containing acetic acid is neutralized. Is generated.
  • a removal process is a process of removing the organic acid and organic acid salt which are the substances derived from an organic peracid from the reaction system latex after an epoxidation process, and reducing those density
  • the total content of the organic acid derived from the organic peracid and the salt thereof in the reaction system latex is 35 parts by mass or less, preferably 30 parts by mass or less, more preferably 100 parts by mass of the epoxidized rubber polymer. Is reduced to 25 parts by mass or less.
  • the reaction system latex can be separated into an upper layer and a lower layer (separation operation) by centrifuging the reaction system latex after the epoxidation step.
  • the upper layer is a latex (cream) layer in which mainly an epoxidized rubber-like polymer is dispersed at a high concentration.
  • the lower layer is a liquid layer in which a substance derived from an organic peracid is dissolved. For example, if the centrifugation treatment is performed for several tens of minutes at 5000 to 15000 G, the reaction system latex can be separated as described above.
  • the dispersion medium added in the redispersion operation may be the same as or different from the composition during the epoxidation step.
  • the separation operation and the redispersion operation the dispersion medium in which the substance derived from the organic peracid in the reaction system latex is dissolved is replaced with a new dispersion medium.
  • the concentration of the organic peracid-derived substance is reduced.
  • the deproteinization treatment can be performed simultaneously in the removal step. Specifically, a protein denaturant is added to the reaction system latex before the centrifugation treatment to denature the protein in the reaction system latex.
  • a protein denaturant is added to the reaction system latex before the centrifugation treatment to denature the protein in the reaction system latex.
  • the protein in the reaction system latex moves to a liquid lower layer in which a substance derived from organic peracid exists. For this reason, the protein which modified
  • Examples of protein denaturants include urea compounds (urea derivatives, urea double salts) represented by the following general formula (1), and sodium hypochlorite.
  • Examples of urea compounds represented by the following general formula (1) include urea, methyl urea, ethyl urea, n-propyl urea, i-propyl urea, n-butyl urea, i-butyl urea, and n-pentyl urea.
  • urea, methylurea, and ethylurea are particularly preferable.
  • the nitrogen content in the reaction system latex is preferably set to 0.1 parts by mass or less with respect to 100 parts by mass of the epoxidized rubber-like polymer, and 0.05 parts by mass or less. It is more preferable to set.
  • the reduction / ring-opening step reduces part or all of the unsaturated double bonds remaining in the epoxidized rubber-like polymer in the reaction system latex, and part or all of the epoxy groups of the epoxidized rubber-like polymer. Is a step of opening the ring.
  • Known reduction methods and ring-opening methods carried out in the state of latex as reduction of unsaturated double bonds of epoxidized rubber-like polymer and ring-opening reaction of epoxy groups (hereinafter referred to as reduction / ring-opening reaction) Can be used.
  • organic acid salts include sodium salts, potassium salts, calcium salts, amine salts (primary to tertiary) of carboxylic acids such as benzoic acid, acetic acid, formic acid, phthalic acid, propionic acid, trifluoroacetic acid, and butyric acid, And ammonia salts.
  • the organic acid salt may be an organic acid salt derived from an organic peracid that remains in the reaction latex without being removed during the removal step, or may be a newly added organic acid salt during the reduction / ring-opening reaction. There may be.
  • the content of the organic acid salt during the reduction / ring-opening reaction is preferably 0.1 to 35 parts by mass and preferably 1.7 to 25 parts by mass with respect to 100 parts by mass of the epoxidized rubber polymer. More preferred.
  • Examples of the known reduction method and ring-opening method performed in the latex state described above include, for example, a method in which hydrogen is brought into contact with the epoxidized rubber-like polymer in the presence of a hydrogenation catalyst.
  • a method of bringing hydrogen gas into contact with the epoxidized rubber-like polymer in the presence of a hydrogenation catalyst will be described as a reduction / ring-opening reaction.
  • a hydrogenation catalyst is added to the reaction system latex after the removal step, and the pH of the reaction system latex is adjusted to a range of 7-8.
  • the organic peracid-derived organic acid salt is not contained in the reaction latex after the removing step, a predetermined amount of the organic acid salt is added to the reaction latex before adjusting the pH.
  • an organic acid salt may be added to the reaction system latex. In this case, the condition is that the pH of the reaction latex after the addition of the organic acid salt is maintained in the range of 7-8.
  • the pH of the reaction system latex is adjusted to the range of 7 to 8 after adding the hydrogenation catalyst.
  • the hydrogenation catalyst a homogeneous catalyst and a heterogeneous catalyst can be used.
  • the hydrogenation catalyst include metal catalysts such as nickel, ruthenium, platinum, palladium, and rhodium.
  • hydrogen is supplied into the reaction system latex in an air atmosphere, an inert gas atmosphere such as argon or nitrogen, or a hydrogen atmosphere.
  • hydrogen gas such as high-pressure hydrogen gas may be directly supplied, or hydrogen generated in the reaction system may be supplied by adding a component capable of generating hydrogen (hydrogen donor).
  • hydrogen is brought into contact with the epoxidized rubber-like polymer in the reaction system latex at a predetermined temperature for a predetermined time.
  • the hydrogenation rate of the modified natural rubber as a product is preferably 80% or more.
  • the hydrogenation rate of the modified natural rubber can be adjusted by changing the treatment temperature and treatment time in the reduction / ring-opening reaction.
  • the treatment temperature in the reduction / ring-opening reaction is preferably set in the range of 0 to 100 ° C, more preferably in the range of 40 to 80 ° C. When the treatment temperature is less than 0 ° C., it becomes difficult to sufficiently advance the reaction. If the treatment temperature exceeds 100 ° C., the molecular chain of the epoxidized rubber-like polymer may be broken, leading to a reduction in molecular weight.
  • the hydrogenation rate of the modified natural rubber can be calculated by the following formula.
  • the “number of double bonds of rubber polymer” in the formula (number before epoxidation) and “remaining number of double bonds of modified natural rubber” can be obtained from, for example, the measurement result of 1H-NMR. it can.
  • the recovery step is a step of recovering the modified natural rubber in the reaction system latex.
  • the modified natural rubber is recovered using a known method for recovering the rubber component from the latex in which the rubber component is dispersed. For example, by adding methanol to the reaction system latex, the modified natural rubber in the reaction system latex is condensed and precipitated. The modified natural rubber can be isolated by collecting the precipitate. At that time, it is preferable to remove the hydrogenation catalyst in the reaction system latex before adding methanol.
  • a method for removing the hydrogenation catalyst for example, a method of adding a complexing agent such as dimethylglyoxime to the reaction system latex to precipitate and remove the hydrogenation catalyst can be mentioned.
  • the organic peracid-derived substance is removed from the reaction system latex in the state of the latex in which the epoxidized rubber-like polymer is dispersed. Then, the reaction latex from which the organic peracid-derived substance has been removed is treated in a subsequent reduction / ring-opening step. Therefore, as in the past, it is necessary to solidify the epoxidized rubber-like polymer from the reaction system latex, isolate and purify, and re-disperse the solidified epoxidized rubber-like polymer to form a latex. And not.
  • the isolation process and redispersion process of the epoxidized rubber-like polymer which were performed between the epoxidation process and the reduction / ring-opening process are omitted. Therefore, the manufacturing process after the epoxidation process can be simplified. Also, without isolating and purifying the rubber component (rubber-like polymer or epoxidized rubber-like polymer) from the reaction system latex, the epoxidation step and the reduction / ring-opening step are continuously performed in the latex state. It can be carried out. For this reason, the working efficiency at the time of manufacture and the yield of the natural modified rubber which is the final product are improved.
  • the protein present in the reaction latex is removed together with the organic peracid-derived substance. Therefore, it is not necessary to newly add a separation operation for separating the rubber component and the protein. Therefore, the increase in the work amount accompanying the addition of the deproteinization step can be minimized.
  • the reduction / ring-opening reaction is performed under conditions of pH 7 to 8 and in the presence of an organic acid salt. Thereby, the cyclization of the epoxidized rubber-like polymer during the reduction / ring-opening reaction can be suppressed.
  • the present embodiment may be modified as follows. -You may abbreviate
  • reaction system latex adjustment As a natural rubber latex of raw material, singleHA latex (rubber component concentration (rubber-like polymer concentration) 60.2% by mass, ammonia content 0.7% by mass, average particle size of rubber particles about 1 ⁇ m) manufactured by GOLDEN HOPE PLATATION used. And while diluting the said raw material latex using distilled water, sodium dodecyl sulfate (henceforth SDS) which is an anionic surfactant was added. Thus, a reaction latex having a rubber component concentration (rubber polymer concentration) of 10% by mass and an SDS concentration of 1% by mass was prepared.
  • rubber component concentration rubber-like polymer concentration
  • reaction system latex To 100 g of the reaction system latex, 10 ml of peracetic acid was added dropwise at a rate of 1 ml / second. And reaction system latex and peracetic acid were made to react, shaking for 3 hours on 6 degreeC conditions. Thereafter, the reaction system latex was centrifuged (15 ° C., 10000 G, 30 minutes). Thereby, the reaction system latex was separated into a creamy upper layer and a liquid lower layer (separation operation). The upper creamy latex was recovered and a 1% by mass SDS aqueous solution was added to the upper layer. Thus, a reaction system latex having a rubber component concentration (epoxidized rubber-like polymer concentration) of 10% by mass was prepared again (redispersion operation).
  • rubber component concentration epoxidized rubber-like polymer concentration
  • the reconstituted reaction system latex was neutralized using 28% aqueous ammonia. After neutralization, 0.1 part by mass of urea was added to 100 parts by mass of the rubber component in the reaction system latex. And it stirred at 25 degreeC for 2 hours, and modified
  • the rubber component concentration epoxidized rubber-like polymer concentration
  • the concentration of acetic acid and ammonium acetate present in the reaction system latex was quantified using 1H-NMR. Specifically, a known amount of an internal standard (standard substance) is added to the reaction system latex to be subjected to 1H-NMR, 1H-NMR measurement is performed, and a peak based on the internal standard in the obtained NMR spectrum; The peaks based on acetic acid and ammonium acetate were compared. And it confirmed that the total content of the acetic acid derived from peracetic acid and ammonium acetate in reaction system latex was 35 mass parts or less with respect to 100 mass parts of epoxidized rubber-like polymers.
  • Tables 1 and 2 show the production methods of Examples and Comparative Examples, and modified natural rubbers obtained by the production methods, respectively.
  • “the number of repetitions of separation operation and redispersion operation”, “concentration of rubber component in reaction system latex (epoxidized rubber-like polymer concentration) in reduction / ring-opening step”, and “reduction / ring-opening step” “Catalyst amount” and "pH during reduction / ring-opening process” are changed.
  • a separation latex and a redispersion operation were performed without performing a neutralization treatment, and a reaction system latex to be treated in the reduction / ring opening step was prepared.
  • the pH of the reaction system latex was adjusted to 7 by repeating the separation operation and the redispersion operation and performing dilution treatment.
  • the reaction system latex of pH 7 is simply heated at 70 ° C. for 9 hours, and the addition of a hydrogenation catalyst, pH adjustment with an aqueous sodium hydroxide solution, and bubbling of hydrogen gas are not performed. It was.
  • Comparative Examples 2 and 3 are examples in which the pH during the reduction / ring-opening reaction was 9 and 6, respectively.
  • Comparative Example 4 is an example in which a reduction / ring-opening reaction was performed in the absence of an organic acid salt. In these cases as well, as in Comparative Example 1, the epoxidized rubber-like polymer in the reaction system latex was cyclized, and the desired modified natural rubber could not be obtained.
  • the results of Comparative Examples 1 to 3 show that, in order to suppress cyclization of the epoxidized rubber-like polymer during the reduction / ring-opening reaction, the pH is in the range of 7 to 8 and in the presence of the organic acid salt. This suggests that a reduction / ring-opening reaction is necessary.
  • ⁇ Analysis of modified natural rubber> The hydrogenation rate of the modified natural rubber obtained by the production method of each example was calculated based on the measurement result using 1H-NMR. Further, a component having a particularly high molecular weight (hereinafter referred to as a high molecular weight component) contained in the resulting modified natural rubber was measured by the following method. Modified natural rubber finely chopped in toluene was added to a concentration of 0.1% by mass and immersed for one week. Then, the toluene solution was separated into a sol component soluble in toluene and a gel component unnecessary for toluene by centrifuging (15 ° C., 10,000 G, 30 minutes).
  • a gel component unnecessary for toluene was recovered as a high molecular weight component, and this was dried at 50 ° C. for one week.
  • the weight of the high molecular weight component after drying was measured, and the ratio of the high molecular weight component contained in the modified natural rubber was calculated from the ratio to the charged amount.
  • Table 3 shows the hydrogenation rate of the modified natural rubber obtained by the production method of each example and the ratio of the high molecular weight component.
  • Reference Example 1 shown in Table 3 is an example in which modified natural rubber was produced using a conventional method.
  • the removal step and the reduction / ring-opening step are different from those in each Example.
  • the epoxidized rubber-like polymer in the latex was coagulated and isolated from the dispersion medium. Then, the isolated epoxidized rubber-like polymer was dried and allowed to stand for another month to remove acetic acid and acetate.
  • the dried epoxidized rubber-like polymer was dissolved in p-xylene, and paratoluenesulfonyl hydrazide was added to the p-xylene solution.
  • restoration and ring-opening reaction were performed by recirculating
  • the modified natural rubber obtained by the production method of each example was hydrogenated in the range of 30 to 90% hydrogenation rate. That is, the desired modified natural rubber was obtained.
  • the proportion of epoxy groups in the modified natural rubber was measured using 1H-NMR. As a result, the number of epoxy groups was reduced to a level where measurement was impossible. From this, it can be inferred that almost all of the epoxy groups introduced in the epoxidation step were opened in the reduction / ring-opening step to form hydroxyl groups.
  • the modified natural rubber obtained by the production method of each example contained a high molecular weight component in a proportion of 35% or more.
  • the modified natural rubber obtained by the production method of Reference Example 1 did not contain the high molecular weight component as described above.
  • the difference in the content of the high molecular weight component between each example and the reference example is considered to result from the difference in the treatment temperature during the reduction / ring-opening reaction.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé de production d'un caoutchouc naturel modifié, comprenant une étape d'époxydation, une étape d'élimination, et une étape de réduction et d'ouverture de cycle. Lors de l'étape d'époxydation, dans un latex dans lequel un polymère caoutchouteux dérivé de plantes ayant une pluralité de double-liaisons insaturées dans la chaîne principale est dispersé dans l'eau servant de milieu de dispersion, un peracide organique est mis en réaction avec le polymère caoutchouteux. De cette manière, par le biais de l'époxydation d'une partie des double-liaisons insaturées dans le polymère caoutchouteux, un polymère caoutchouteux époxydé est obtenu. Lors de l'étape d'élimination, les substances dérivées du peracide organique générées à partir du peracide organique lors de l'étape d'époxydation sont éliminées du latex, la teneur des substances dérivées du peracide organique dans le latex étant de ce fait abaissée à une teneur inférieure ou égale à 35 parties en poids en se basant sur les 100 parties en poids du polymère caoutchouteux époxydé. Lors de l'étape de réduction et d'ouverture de cycle, dans des conditions de pH de 7 à 8 et en présence d'un sel d'acide organique, une partie ou la totalité des double-liaisons insaturées restantes dans le polymère caoutchouteux époxydé dans le latex sont réduites, et une partie ou la totalité des groupes époxy dans le polymère caoutchouteux époxydé subissent une ouverture de cycle.
PCT/JP2011/054944 2010-03-05 2011-03-03 Procédé de production d'un caoutchouc naturel modifié WO2011108660A1 (fr)

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JPH06329702A (ja) * 1993-05-24 1994-11-29 Kao Corp 改質天然ゴムおよびその製造方法
JP2004176013A (ja) * 2002-11-29 2004-06-24 Nagaoka University Of Technology 液状エポキシ化天然ゴム及びその製造方法
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JP2010084077A (ja) * 2008-10-01 2010-04-15 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及びタイヤ
JP2010248388A (ja) * 2009-04-16 2010-11-04 Toyoda Gosei Co Ltd 改質天然ゴム及びその製造方法

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JPWO2021261489A1 (fr) * 2020-06-24 2021-12-30
WO2021261489A1 (fr) * 2020-06-24 2021-12-30 根上工業株式会社 Particules de caoutchouc et procédé pour la production de celles-ci
JP7153412B2 (ja) 2020-06-24 2022-10-14 根上工業株式会社 ゴム粒子及びその製造方法

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