• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PROCESS FOR PRODUCING SURFACE MODIFIED CARBON BLACK A process for producing surface modified carbon black is described. The process comprises the step of treating carbon black with a sulfur compound in an amount ranging from 0.005% to 1% of the carbon black to carry out in situ formation of surface groups to produce the surface-modified carbon black that when combined with a polymeric composition it alters the carbon black polymer interaction to decrease the hysteresis of the polymeric composition. Furthermore, the cure time required for polymeric composition comprising surface-modified carbon black is less compared to the cure time required for polymeric composition comprising unmodified carbon black. Figure 1 shows the cure curve A for the polymer composition comprising the unmodified carbon black and the cure curve B for the polymer composition comprising the surface-modified carbon black.
    公开号:BR112014009803B1
    申请号:R112014009803-4
    申请日:2012-10-23
    公开日:2021-07-06
    发明作者:Juan Rodriguez；Ranjan Ghosal
    申请人:Aditya Birla Nuvo Limited；
    IPC主号:
    专利说明:

    DESCRIPTION FIELD
    The present description relates to a low hysteresis carbon black and an improved process for obtaining the low hysteresis carbon black. FUNDAMENTALS
    [0002] A variety of carbon blacks are known in the art. These carbon blacks mainly differ in properties from each other and are made through different processes. The use of carbon black depends on its properties. Since carbon black as such cannot be sufficiently characterized by its chemical composition or by its ingredients, it has become widely accepted to characterize carbon black by the properties it exhibits. In this way, carbon black can, for example, be characterized by its surface area, which is generally an inverse measure of the primary particle size. Another important feature of carbon black is its structure, which is a measure of the complexity of individual carbon black aggregates or the number of primary particles "fused" together in a carbon black aggregate.
    [0003] A common application of Carbon Black is as a performance enhancing filler in rubber and other polymers. The reinforcing action of carbon black depends on the interaction, both chemical and physical, between carbon black and the polymer matrix. This interaction also controls the performance of the filled rubber/polymer and its applications in various aspects. Efforts have been made to correlate the properties of rubber incorporating carbon black and the properties of carbon black. No unique property of carbon black is found which, if made high or low enough, results in an ideal rubber composition. When certain properties of carbon black are related to the abrasion resistance of rubber, others are related to tensile strength or heat formation.
    [0004] It is observed that the high abrasion resistance of a carbon black/rubber composition is a desirable property of such a composition. Another desirable property is low heat buildup or low hysteresis. Heat build-up is a measure of how much of the elastic deformation energy put into a product made of a carbon black/rubber compound remains in the compound as heat after the deformation forces are released. Hysteresis or heat build-up is measured by measuring the temperature of a deformed sample. This property is extremely crucial when manufacturing tires with such carbon black/rubber composition. The greater the heat build-up, the greater the energy loss of the vehicle using the tires (in consequence, the lower fuel consumption); also, chances are that tires made from such rubbers will be destroyed sooner. It is, therefore, very desirable to reduce the heat build-up of rubber compositions by providing carbon black with low hysteresis. Several attempts have been made in the past to provide processes for the production of carbon black with low hysteresis. Some of these processes are listed below.
    [0005] US Patent No. 4988493 describes a process and a mechanism for the production of carbon blacks that give low hysteresis and good wear when used in rubber compounds for reinforcement, in particular, in rubber tires. provision of a linear, substantially non-turbulent flow of flue gas in a feedstock oil injection zone, in a reporter, the provision of at least two independently controlled streams of carbon black feedstock oil in separate segments of the flue gas flow in the feedstock oil injection zone, in which the separated carbon black forms reactions are respectively carried out in separate segments of the flue gas flow, and immediately thereafter, the supply of the flue gas segments results in said reactions that form separate carbon black were carried out in an aggregate forming zone by which a A carbon black product is produced which, when compounded into rubber compositions, provides said rubber compositions with low hysteresis and improved wear resistance properties.
    [0006] US Patent No. 4327069 describes a process for producing negative tint residual carbon black by the pyrolytic decomposition of hydrocarbons in a carbon black furnace. The process comprises producing a first carbon black forming mixture, in a first carbon black forming zone which is a high structure zone, which passes from the first carbon black forming mixture from the first carbon black forming zone. forming carbon black to a second carbon black forming zone that is a zone of low structure to produce a second carbon black forming mixture that passes to the second carbon black forming mixture in an extinction zone where the second carbon black forming mixture is contacted with an extinguishing fluid to produce a smoke containing carbon black at a temperature below the carbon black forming temperature and separating carbon black from the residual negative hue of the smoke.
    [0007] The process known from the prior art requires complex process control to obtain carbon black with low hysteresis. Therefore, a need is felt for a simple process for the production of carbon black in which the surface chemistry of the carbon black is conveniently changed during the manufacturing process for the production of carbon black, which, when combined with the Rubber compositions decrease hysteresis and thereby decrease heat build-up in the rubber composition to thereby provide high performance tyres. GOALS
    [0008] Therefore, it is an objective of the present description to provide a simple and economical process for the preparation of surface-modified carbon black which, when combined with rubber/polymer composition as reinforcement helps to reduce hysteresis; surface-modified carbon black is particularly suitable for manufacturing high-performance rubber tyres.
    [0009] These objectives and other advantages of the present description will become more evident from the following description. SUMMARY
    [00010] In accordance with the present description, there is provided a process for producing a surface-modified carbon black comprising the step of treating common carbon black sulfur-containing compound to obtain the surface-modified carbon black which when combined with the polymer composition alters the carbon black-polymer interaction to decrease the hysteresis of the polymer composition by at least 1%, preferably by about 1% to 20%.
    [00011] Typically, the sulfur-containing compound is selected from the group consisting of sodium, sulfate, sodium sulfide, sodium sulfite, sodium polysulfide, sodium thiosulfate, phenylene disulfide, alkali metal sulfate, alkali metal sulfite, alkali metal sulfide, alkaline earth metal sulfate, alkaline earth metal sulfite, alkaline earth metal sulfide and mixtures thereof.
    [00012] Typically, the sulfur containing compound is used in an amount in the range of 0.005 to 1% of the carbon black.
    [00013] According to the present description, the sulfur-containing compound is added during the manufacture of carbon black or after the manufacture of carbon black.
    [00014] Typically, the method step of treating carbon black with a sulfur-containing compound is performed by a technique selected from the group consisting of pouring, spraying, injecting, dispersing and diffusing.
    [00015] According to one of the embodiments of the present description the sulfur-containing compound is in dispersion form.
    [00016] According to another embodiment of the present description, the process further comprises a step of mixing the sulfur-containing compound with the process water to form carbon black globules. BRIEF DESCRIPTION OF THE ATTACHED DRAWINGS
    [00017] The invention will now be described with the help of the accompanying drawings, in which: FIGURE 1 illustrates a comparison of cure curves of rubber compounds prepared with N234 (A) unmodified carbon black and treated modified carbon black N234 sodium sulfide (B), in accordance with the present description and FIGURE 2 illustrates a comparison of Tan Delta (δ) curves of rubber compounds prepared with N234 (A) unmodified carbon black and treated with modified carbon black N234 sodium sulfide (B), according to the present description. DETAILED DESCRIPTION
    [00018] The present description considers a surface-modified carbon black, which when combined with the polymeric composition, alters the carbon black-polymer interaction to decrease the hysteresis of the polymeric composition by at least 1%. The properties of carbon black that form a useful additive/reinforcement in the polymer are established in carbon black during its manufacture. Properties such as particle size, shape and degree of aggregation are controlled by regulating operating parameters during the manufacturing process. It is observed that the carbon black surface chemistry formed in the manufacturing process impacts the performance of carbon black as a polymer composition reinforcement. The surface chemistry of carbon black can be changed by introducing surface modifying compounds into the carbon black surface, preferably during carbon black manufacture. One benefit of changing carbon black surface chemistry is to modify the polymer-carbon black interactions when carbon black is added to the polymer composition, in order to reduce the hysteresis of the carbon black-polymer compound. The carbon black obtained according to the process of the present description is particularly suitable for the manufacture of rubber compositions with low hysteresis for use in the manufacture of tires with low heat build-up.
    [00019] The process to produce surface-modified carbon black comprises the step of treating sulfur-containing common carbon black compound in an amount in the range of 0.005% to 1% of the carbon black to carry out the formation of surface groups. The surface-modified carbon black thus obtained when combined with the polymer composition alters the carbon black-polymer interaction to decrease the polymer composition hysteresis by at least 1%, preferably by about 1% to 20%. The sulfur-containing compound is selected from the group consisting of sodium sulfate, sodium sulfide, sodium sulfite, sodium polysulfide, sodium thiosulfate, phenylene disulfide, alkali metal sulfate, alkali metal sulfite, alkali metal sulfide, alkaline earth metal sulphate, alkaline earth metal sulphite, alkaline earth metal sulphide and mixtures thereof.
    [00020] According to the present description, carbon black is treated with a sulfur-containing compound by a technique selected from the group consisting of pouring, spraying, injecting, dispersing and diffusing. The sulfur-containing compound is preferably introduced into the carbon black during the manufacture of carbon black in the furnace reactor by a selected method of pouring, spraying, injecting, dispersing and diffusing, resulting in the surface-modified carbon black whose surface is treated, such as to provide beneficial properties of reduced hysteresis in the polymer composition where the modified carbon black is used as a reinforcement. The sulfur-containing compound may alternatively be modified by a technique such as post-manufacturing carbon black surface spraying. According to one of the embodiments of the present description the sulfur-containing compound is in dispersion form. Typically, the dispersion is prepared by mixing the sulfur-containing compound with a solvent, preferably water, for convenient surface introduction of carbon black. The sulfur-containing compound can be mixed with the supplied process water to form carbon black globules during the manufacturing process.
    [00021] The sulfur-containing compound when added in an amount in the range of 0.005% to 1% of the carbon black, results in the formation of surface groups in the carbon black, which alters the polymer-carbon black interactions due to the formation between carbon black particles and polymer molecules when added to the polymer composition to reduce composition hysteresis. The lower hysteresis manifests itself in the lower Tan Delta (δ) form of the composition. Tan Delta (δ), the ratio of the viscous component to the elastic component of the strain response, is a measure of the hysteresis of the composition. A lower Tan Delta (δ) a composition with lower hysteresis. The results indicating Tan Delta (δ) reduced in surface-modified carbon black are illustrated in Figure 2.
    [00022] The description will now be described with reference to the following non-limiting examples which do not limit the scope and scope of the description. EXAMPLES Example 1:
    [00023] 500 g of non-globule-formed carbon black (N234 grade) were placed on a tray and sprayed evenly with a solution of 2.5 g of Na2S in water (500mL), with slow exposure of all black surfaces of tobacco to the solution. Carbon black was turned over several times within a 2 hour period to provide good coverage. The resulting modified carbon black was heated in an oven under a reducing atmosphere at 800°C for 8 hours, rotating 4 to 5 times every 2 hours. Dry modified carbon black was used to prepare a rubber compound and tested (Labeled: N234-1-LAB). The properties of this compound were compared to those of a rubber compound prepared using N234 unmodified carbon black (Labeled: N234-UNMOD). Preparation of rubber compound
    [00024] The composition of the rubber compounds tested is given below.

    [00025] The ingredients were mixed in a 2-roll mill at a friction ratio of 1:1.4 for a duration of about 24 minutes. The rollers were kept at a temperature of 70°C. Testing the properties of rubber:
    [00026] The properties of the prepared rubber compounds were tested. A summary of the test results is given in Table 1. Table 1: Comparison of properties of rubber compounds using unmodified carbon black N234 and modified carbon black treated with sodium sulfide N234 in laboratory scale production
    Example 2:
    [00027] 100 ppm of sodium sulfide (Na2S) per unit of carbon black mass, were added to the manufacturing process in the globule formation step, by adding a 2% solution of Na2S in water (previously prepared) at an appropriate flow rate in the globule former. The treated carbon black was then dried as per the usual industrial process in a rotary dryer. The treated carbon black samples, formed into globules, were collected and compounded with test rubber (Labeled: N234-2-IND). Preparation of rubber compound
    [00028] The composition of the rubber compounds tested is given below.

    [00029] The ingredients were mixed in a 2-roll mill at a friction ratio of 1:1.4 for a duration of about 24 minutes. The rollers were kept at a temperature of 70°C. Rubber properties test
    [00030] The properties of the prepared rubber compounds were tested. A summary of the test result is given in Table 2. Table 2: Comparison of properties of rubber compounds using unmodified N234 and N234 sodium sulphide treated modified carbon black in industrial process

    [00031] From examples 1 and 2 it is clearly demonstrated that a significant reduction in Tan Delta (δ) is achieved by both laboratory and industrial treatment. However, industrial treatment of carbon black during its manufacture with very small amounts of sodium sulfide is more effective in reducing the Tan Delta (δ) of the rubber compound.
    [00032] The curing curves of rubber, composited with unmodified carbon black N234 and modified carbon black treated with sodium sulfide N234 are shown in Figure 1 of the accompanying drawings. Hysteresis in rubber compounds prepared using carbon black is estimated by measuring the Tan Delta (δ) cure of the compound and is shown in Figure 2 of the accompanying drawings.
    [00033] The cure curves A and B illustrated in Figure 1 clearly show that the rubber compound containing the modified carbon black treated with N234 sodium sulfide of the present description cures more easily, probably because of the higher interactions between the carbon black polymer. rubber and the surface groups in the treated carbon black compared to the rubber compound with unmodified carbon black. Also, the Tan Delta (δ) A and B curves illustrated in Figure 2 show that the rubber compound prepared with the modified carbon black treated with N234 sodium sulfide of the present description has a smaller Tan Delta (δ) and, therefore, less hysteresis than the rubber compound made with unmodified carbon black. TECHNICAL ADVANTAGES
    [00034] The process as described in the present description has several technical advantages, including but not limited to carrying out the description, provides a simple and economical process for producing surface-modified carbon black where the carbon black is treated with a compound of sulfur in an amount in the range of 0.005% to 1% of the carbon black in an amount in the range of 0.005% to 1% of the carbon black to carry out IN SITU formation of surface groups to produce the surface modified carbon black whereas when combined with a polymeric composition alters the Polymer-Carbon Black Interaction to decrease the hysteresis of the polymeric composition by at least 1%, preferably by about 1% to 20%, surface-modified carbon black is particularly suitable for the manufacture of high-performance tires with reduced hysteresis and low heat build-up.
    [00035] Throughout this descriptive report, the word "comprises" or variations, such as "comprises" or "comprises", will be understood to imply the inclusion of an established element, integer or step or group of elements, integers or steps, but not the inclusion of any other element, integer or step or group of elements, integers or steps.
    [00036] The use of the expression "at least" or "at least one" suggests the use of one or more elements or ingredients or quantities, as I dare to occur in the embodiment of the invention to achieve one or more of the objectives or desired results .
    [00037] Any discussion of documents, actions, materials, devices, articles or the like that have been included in this descriptive report is solely for the purpose of providing a context for the invention. This is not to be taken as an admission that any or all of these matters form part of the background of the prior art or were common general knowledge in the field relevant to the invention as existed anywhere prior to the priority date of this application.
    [00038] The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is considered that values higher/lower than the numerical values assigned to the parameters, dimensions or quantities are within the scope of the invention, unless there is a statement in the descriptive report that specifies otherwise. In view of the wide variety of embodiments to which the principle of the present invention can be applied, it is to be understood that the illustrated embodiments are exemplary only. While considerable emphasis has been placed here on the particular features of this invention, it will be appreciated that various modifications can be made and that many changes can be made to the preferred embodiments without departing from the principle of the invention. These and other modifications in the nature of the invention or in the preferred embodiments will be apparent to those skilled in the art from the description herein, whereby it is to be distinctly understood that the foregoing descriptive material is to be construed merely as illustrative of the invention and not as a limitation.
    权利要求:
    Claims (9)
    [0001]
    1. Process for producing a surface-modified carbon black, characterized in that it comprises the step of treating common carbon black sulfur-containing compound to obtain surface-modified carbon black which when combined with the polymer composition alters the polymer interaction - carbon black to decrease the hysteresis of the polymeric composition, measured in % reduction in Tan Delta (δ) of the composition by at least 1% compared to the corresponding polymeric composition combined with an unmodified carbon black, wherein the compound sulfur containing is selected from the group consisting of alkali metal sulfate, alkali metal sulfite, alkali metal sulfide, alkaline earth metal sulfate, alkaline earth metal sulfite, alkaline earth metal sulfide and mixtures thereof.
    [0002]
    2. Process according to claim 1, characterized in that the sulfur-containing compound is selected from the group consisting of sodium sulfate, sodium sulfide, sodium sulfite, sodium polysulfide, sodium thiosulfate, and mixtures thereof .
    [0003]
    3. Process according to claim 1, characterized in that the sulfur-containing compound is used in an amount ranging from 0.005 to 1% of the carbon black.
    [0004]
    4. Process according to claim 1, characterized in that the decrease in hysteresis of the polymeric composition is in the range of 1% to 20%.
    [0005]
    5. Process according to claim 1, characterized in that the sulfur-containing compound is added during the manufacture of carbon black.
    [0006]
    6. Process according to claim 1, characterized in that the sulfur-containing compound is added after the manufacture of carbon black.
    [0007]
    7. Process according to claim 1, characterized in that the step of the method of treating carbon black with a sulfur-containing compound is performed by a technique selected from the group consisting of pouring, spraying, injecting, dispersing and diffusing .
    [0008]
    8. Process according to claim 1, characterized in that the sulfur-containing compound is in the form of dispersion.
    [0009]
    9. Process according to claim 1, characterized in that it further comprises a step of mixing the sulfur-containing compound with the process water to form carbon black globules.
    类似技术:
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    KR101917589B1|2018-11-13|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09C 1/56 (2006.01), C08K 9/02 (2006.01), C09C 1/4 |
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    IN2992/MUM/2011|2011-10-24|
    IN2992MU2011|2011-10-24|
    PCT/IN2012/000698|WO2013098838A2|2011-10-24|2012-10-23|An improved process for the production of carbon black|
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