• 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:
    Chemical direct reclaiming of rubber by mixing pui- verulent scrap rubber having a particle size of at most 1 mm. preferably at most 0.4 mm. with a reducing agent, an oxidizable iron metal chloride and at least one plasticizer. The mixture is agitated for a short time, at most.30 min. and normally at most 15 min., in the solid phase in air at a temperature of not more than 100°C, usually approximately room temperature, in a powder mixer for direct degradation of double bonds in the rubber. The reducing agent is from 0.2 to 1 weight %, preferably from 0.2 to 0.8 weight % of phenyl hydrazine or from 0.2 to 0.8 weight % of diphenyl guanidine. The iron metal chloride is admixed in an amount of from 0.1 to 0.4 weight % and is preferably ferrous chloride. The plasticizer shall comprise at least one member from the group tall oil pitch and dipentene, and this plasticizer may optionally be used in mixture with some other plasticizer, such as mineral process oil. The total amount of plasticizer is at most 17.5 weight %. The amount of a plasticizer other than tall oil pitch and dipentene is at most 10 weight %. The amount of dipentene is at most 5 weight % and is from 0.5 to 5 weight % if the dipentene is used as the only plasticizer or is used in mixture with another plasticizer. The amount of tall oil pitch is at most 17.5 weight % and is from 7 to 17.5 weight % if the tall oil pitch is used as the only plasticizer or is used in mixture with a plasticizer other than dipentene. If tall oil pitch is used in mixture with dipentene. the amount of tall oil pitch varies in inverse proportion to the amount of dipentene and is from 8 to 16 weight % with dipentene amounts of from 5 to 0,5 weight %. All of the percentages are calculated on the mixture of pulverulent rubber scrap, reducing agent, iron metal chloride and plasticizer. Without preceding refining, the reclaimed pulverulent rubber with a low admixture percentage (for example about 6%) of raw rubber (natural rubber or styrene butadiene rubber) can be used directly for the manufacture of vulcanized rubber products.
    公开号:SU936799A3
    申请号:SU792783400
    申请日:1979-07-02
    公开日:1982-06-15
    发明作者:Эдвард Марквик Нильс
    申请人:Треллеборг Аб (Фирма)；
    IPC主号:
    专利说明:

    3 more than 0.8 mm. The mixing is carried out in a mixer, which is equipped with a mixing impeller in the lower part of the cylindrical tank. The impeller is set in motion with a peripheral speed of 2000 m / min. First, the old rubber powder is loaded into the mixer with the impeller, then dipentene and tal oil resin are added and, after stirring, Lt phenylhydraZIN is added for some time. Ferric chloride is added in a mixture with methyl alcohol. After the addition of chloride jelly La, stirring is continued for 7 minutes. The composition of the regenerator mixture is presented / 1en in table. 1. J Mixing is carried out in the solid phase with vigorous stirring of the material In air, which is in the mixing tank. In the process of mixing, phenylhydraine together with the oxygen of the air provides splitting of the rubber particles to such a size that the rubber powder can be used to make vulcanizable products. The initial temperature of the mixing process is at room temperature, although temperatures up to can be applied. The added phenylhydrazine reacts completely with the rubber powder, but several decades of benzene and nitrogen-containing gas are produced, which are found in the atmosphere of a powder mixer. After 1 day, the thus obtained powdery reconstituted rubber material is examined and compared with known industrial reconstituted rubber materials. For the purpose of this study, rubbers are used that contain: Powdered reduced materials, parts by weight; 100 Zinc oxide, parts by weight. 2 Stearic acid, parts by weight 0.80 Sulfur, part 1 SANTOCOR G (accelerator) (cyclohexylbenzothiazylsulfandiamide), part 0, BО 9 Industrial reduced rubber material is used as a material for comparison. After processing the three rubber mixtures, they are collandated to sheets with a thickness of 2 mm, which are vulcanized for 10 minutes at. After that, the hardness, tensile strength, elongation at break, tear resistance and density of the three materials are studied. The properties of the mixture are presented in table. 2. Example 2. Regeneration is performed on a laboratory scale. As a mixer, a conventional mixing device for domestic use with two rotating in opposite directions mixing wings and a rotating tank is used. The mixing | / device is driven at maximum speed. In this case, the particle size of the rubber powder is not more than 0 mm. The sequence of addition of the various components is as follows: rubber powder, dipentene, phenylhydrazine, iron chloride, and an antiblock agent. The latter is added 12 minutes after the iron chloride has been added. The total mixing time, calculated from the time of adding ferric chloride, is 15 minutes. The stirring process is carried out at room temperature, and during the reaction the temperature rises. The temperature continues to rise slightly for about 1 hour after the end of the stirring period. After one-day storage, the recovered material is mixed with a curative and vulcanized in the form of sheets with a thickness of 2 mm for 10 minutes. Vulcanized sheets have a Shore hardness of 62, a tensile strength of 6.8 MPa and an elongation at break of 230%. This example shows that dipenten can only be used as a plasticizer. Example 3. Rubber regeneration is carried out on a laboratory scale in the same manner as in Example 2. In this case, two plasticizers are used, namely dipentene and process oil, i.e. aromatic mineral oil such as spun oil (ESL 305). The final recovered material is volcanic and is investigated in the same way as the recovered material in Example 2. The vulcanized sheets were found to have a Shore hardness of 65, a tensile strength of 6.3 MPa and an elongation at break of 190 Example t. The regeneration is carried out on a large scale using a belt type mixer. Stirring time 15 WIH. Rubber powder has a particle size of not more than 0.6 mm. The sequence of addition of the various components is the same as in Example 1. The material obtained in this manner was investigated using the following composition, weight. h .:. Powdered reduced material100 ZnO2 Stearic acid 0.80 Sulfur1 Accelerator 0.60 Process oil2 In this case, SULFENAX CD (cyclohexylbenzothiazylsulfonamide) is used as an accelerator, and the above-mentioned aromatic mineral oil ESL 385 is used as a process oil. for 10 min, the following properties were established: Bo shore hardness, tensile strength of 7.0 MP, elongation at break of 2 W and density of 1.18 g / cm. Examples 5-7. These npimers use laboratory equipment, the same as in the example and the examples are carried out to illustrate the effect of dipentene compared to mineral oil (technological oil as a plasticizer. In this case, the rubber used is obtained from only auto mobile tires that contain 50% carbon black and ground to a particle size less than 0.59 mm (30 IU of the SDS sieve system). The composition of the regenerative mixture according to examples 5-7 is given in Table 3B Table 4 shows the properties of the mixture si in examples 5-7. Compo The composition of the composition is added to the mixer in the sequence shown in Table 3. The iron chloride is added as a solution in methanol. The addition time is 5 minutes, after which the mixer is operated for another 30 minutes. At the end of the mixing process, each powdered reduced material leaves overnight, after which the powder is used in the test composition, containing, by weight.h .: Powdered reduced material100 Zinc oxide .2.0 Stearic acid 0.9 Sulfur1.1 SANtOCVRE0.8 Mixing is performed in a mixing mill in for 20 minutes The test sheet is vulcanized for 10 minutes at. From the results table. 3 it can be seen that only mineral oil in an amount of approximately 4.7 wt.% (Calculated on the total amount of material introduced into the mixer) or 5 parts per 100 parts of rubber by weight gives a powdered recovered material with a very poor process in the mixing the mill. Such powdered recovered material cannot be used for industrial production, since the process proceeds in a mixing process 11 (it is very important for the mill to make rational and high-quality rubber compounding. The Mooney viscosity is over 200. When the mineral oil content is significantly increased (to 12.1% 1 h per 100 gels of rubber. The process in the mixing mill is still very poor, and a brittle uncured sheet is obtained, which is very difficult to handle without However, an increased amount of plasticizer reduces the Mooney viscosity, but, in general, such a powdered recovered material also cannot be considered suitable from an industrial point of view. When adding a small amount of dipentene as a plasticizer (approximately 2.75 wt.% or 3 hours per 100 hours of rubber separately from the mineral process oil 79 in Example 5 was obtained; a noticeable improvement of the process in the mixing mill. This is evident from the example, which testifies to the clear effect of dipentene as a plasticizer in the direct reduction of old rubber in the solid phase. Examples 8-10. In these examples, the same equipment is used — laboratory equipment, old rubber, blend composition, addition time, operating time, mixer, and holding time of the recovered material as in Examples 5–7. The composition of the regenerative mixture according to examples is given in table. 5. In. 6 shows the properties of the mixture in examples 8-10. Examples 8-10 show the effect of a tar oil resin as a plasticizer and the possibility of using diphenylguanidine instead of phenyl hydrazine as a peptizing agent. In Examples 8 and 9, phenylhydrazine is dissolved in methanol, and iron chloride is dispersed in tall oil resin and the components added to the mixer in the following sequence: old rubber, phenylhydrazine (dissolved in methanol, iron chloride (dispersed in tall oil resin and (in example 8 process oil. In example 10, iron chloride is dissolved in methanol and then mixed with tall oil resin. The components are then added to the mixer in the following sequence; old cuts, otherwise, diphenylbuanidine (powder and a mixture of iron chloride and tall oil resin. In all cases, the tall oil resin is preheated to make it easier to handle. By comparing the results presented in Tables t and 5, it can be established that the resin tall oil, either alone or mixed with process oil, provides suitable reconstituted materials, and dipentene can be dispensed with.Phenylhydrazine can also be replaced by diphenylguanidine. This is advantageous from different points of view, since phenylhydrazine is expensive, unresponsive in circulation and affects the skin. Powdered diphenylguanidine is much cheaper and easier to handle. Examples 11-16. In these experiments, use the same laboratory equipment, old rubber and the dwell time of the recovered material, as in Examples 5-7. The reduction is carried out at room temperature. The amount of loaded old rubber was 300 g. The addition was carried out for 3 minutes, and the mixer then operated for 12 minutes, so that the total time in the mixer was 15 minutes. After exposure overnight, the powdered recovered material is used in the test composition containing, by weight.h .: Powdered reduced material .9.7,7 Natural rubber 6.0 Zinc oxide 1.9 Stearic acid 0.8 Sulfur ".1.0 SANTOCVRpJy0.6 Composition contains natural rubber to reduce Mooney viscosity and improve utilization of reconstituted rubber material under normal conditions. Stirring is performed in a laboratory stirring mill and the resulting unvulcanized mixture is used to prepare the test sheets. Which vulcanize for 10 minutes at. The composition of the regenerative mixture in examples 11-16 are presented in table. 7. In table. 8 shows the properties of the mixture in examples 11-16. Examples 11-16 show the effect of the plasticizer. Resin tall oil leads to good recovery of old rubber. From the data table. 7, it can be seen that such high contents as 20 parts of tall oil pitch on a limited liability company including powdered old rubber give good results. At low contents of tall oil resin, namely, tall oil resin contents below 8 hours per 100 parts of powdered old rubber, it is necessary to increase the effect of tall oil resin by adding dipentene (Example 1. Diphentene can be completely dispensed with oils about 10 hours for 100 hours of powdered old rubber. As can be seen from approximately 15, 16, as well as 3 and 7, dipentene results in a good recovered material even in cases where it is used with other plasticizers in e mineral oil. However, one of the deficiencies of dipentene is its unpleasant odor. The use of a plasticizer in the form of mineral oil alone does not give a satisfactory result, as can be seen from examples 5, 6 and 16. The properties related to the process occurrence the mill is bad in this case, and Mooney viscosity may be too high if unvulcanized natural rubber is added to the rubber compound. When the content of mineral oil 8h. per 100 parts of rubber add 1 part of dipentene to 100 parts of rubber (example 15 leads to an improvement in the process in the mixing mill. Good results were obtained when adding 3 hours, dipentene to 100 parts of rubber, as follows from example 16 Examples 17 and 18. In these examples, phenylhydrazine and diphenylguanidine were compared as components of the rare-system.These examples use the same laboratory equipment, old rubber, the retention time of the recovered material, the load amount, the addition time, and the total time in the mixture Barely, as in examples 11-16. Reduction is carried out at room temperature. A mixture containing,%; Powdered reduced substance 95.2 Zinc oxide2.0 Stearic acid 0.8 Sulfur, 0 SANTOCVRE Hohr 1.0 Stirring is used for the study. The test sheet is vulcanized for 15 minutes with the composition of the regeneration mixture according to examples 17-18 given in Table 9. In this case, the content of diphenylguanidine is less than phenylhydrazine, as it acts as a vulcanization accelerator, and this action may occur during the vulcanization process of the final product. Example 19. This example represents the recovery of powdered old rubber on a factory scale. For this purpose, a belt type mixer with a capacity of 1 m is used. The loading amount is 350 kg of powdered old rubber, which is ground to a particle size less than 0.59 mm (- 80 mesh US sieve system). When powdered rubber is loaded into the mixer, it has 10 ° C. After diphenylguanidine powder is added, the mixer works for 2 minutes. After that, tall oil resin is added, which is preheated to, which leads to an increase in the temperature of the loaded material by 6 ° C. Finally, ferric chloride dissolved in methanol is added. The addition of tall oil resin and iron chloride was carried out for 5 minutes. After all the ferric chloride is added, the mixer works for another 15 minutes. Before the study, the recovered material is left overnight. For the study of the recovered material, the composition under investigation was used, containing, by weight: Powdered, reconstituted material Natural rubber Zinc oxide Stearic acid Sulfur SANTOCVRE Stirring is carried out in a Banbury smoglet. The resulting rubber mixture is used to prepare the test sheets, which are vulcanized for 10 minutes at 1 dO C. The composition of the regenerative composition of example 19 is given in table. 11. The properties of the mixture according to example 19 are given in table. 12. A good recovered material is obtained when it is produced at the factory. So, from the presented tabl persons (1-12), it follows that in all properties, the regenerate obtained by the proposed method significantly exceeds the known regenerate.
    eleven
    12
    936799 Table
    Remiomy powder
    Dipenten
    Resin thalomgoil
    Technological oil
    :: Ar01 $ atopic or mineral oil E 5J "385 Yuaed kaolin
    9 ".b52609"
    190
    2, g | 3.01,05 «1,5
    -19,56.83
    1.99Table 2 Old tires 300.093.90300.0 Process oil 15.0,, 0 Dipentene - Phenylhydrazine 3.0.0,, 0 1.50,, 5 15.0 15.0 15.0 Methanol
    Initially, Perratura, With mix
    25.5. 26.0
    The process in the mixing mill is very bad. A brittle, difficult-to-process unvulcanized sheet was obtained. The process in the mixing mill is satisfactory.
    25.5 26.0
    25.5
    28 86,38300,091,32 12,1215,0,57. , 7 0,873.0 0.91 0.1 "31.50,
    15 Powdered old rubber 300, 0 87.3 300.0
    Technological 15, 4 if, 37 something oil
    Resin tall oil 2k, 0 6.99 2i, 0 7.33 24.0 7.34
    3.0 1.5
    15.0
    25.5
    32
    The process in the mixing mill is satisfactory. The process in the mixing mill is better.
    sixteen
    936799 Table S
    0.64 0, 87 2.1
    0.46 0.46 1.5 0.43 1.5 15.0 15.0
    25.5
    25.5
    28.5
    30 91.57 300.0 91.7
    19,100 10
    0.25 0.23 0.25 0.22 0.50 0.45
    100
    20
    936799 Table 8
    90.6
    90.29 100
    9.05 9.03 10
    0.30 0.27 1.00
    ,five
    +2.9 The process in the mixing mill is very bad; brittle, difficult to process unvulcanized sheet, obtained despite the addition of unvulcanized natural rubber to the composition of the study. The process in the mixing mill is satisfactory. The process in the mixing mill is good. The process in the mixing mill is excellent. Table 9
    21
    ,Indicators
    Mooney Viscosity
    M 1 h - 1 72
    Hardness
    on Shore 70
    Strength on
    gap, IPa 8,
    Elongation at
    gap,% 230
    Specific gravity,
    g / cm 1.20
    Content Components
    T1ori1koo6razna
    old rubber 100
    Tar resin
    oils13,9
     ,five
    Diphenylguanidine 0.3
    Methanol1 0
    Indicators I Mixes Mooney Viscosity
    Hardness
    Shora
    Strength on
    gap, npa
    Elongation.
    at break,%
    Specific gravity,
    22
    936799
    Table 10
    Mix by example
    L
    T a
    ... by example
    weight.h.
    权利要求:
    Claims (1)
    [1]
    t alley | Mepj f 23 Formula of the Invention A method of rubber regeneration by mixing rubber in a dispersed form with a regeneration activator, ferric chloride and a softener, characterized in that, in order to accelerate the method and improve the quality of the regenerate, phenylhydrazine or diphenylguanidine, and as a miller, 8 is dipentene or tall oil, or a mixture of one of them with an aromatic oil at a ratio of components, weight: 1.05-2.7 Dipentene 6.76-16.56 Tall oil Aromatic 7.16-7.35 Butter jelly 0, 22-0,75 zo 92i Phenylhydrazine 0.21-0.9 Diphenylguanidine 0,2b-0, Rubber in a dispersed formUntil 100 The content of the mixture of dipentene and aromatic oil is 8.21-10.09 weight, the content of Zchipyonten and tall oil is 7.81-7.88 weight ,% and the content of a mixture of tall and aromatic oils is 11.36% by weight, and the mixture is carried out at 20-100 ° C for 3-30 minutes, followed by the introduction of kaolin in an amount of 6% L. Sources of information taken into account during examination 1. Chemical Abst. 8, 1976, ref. "5783 (prototype).
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    同族专利:
    公开号 | 公开日
    NO792199L|1980-01-04|
    AU5414579A|1981-06-25|
    TR21093A|1983-07-01|
    EP0006834A2|1980-01-09|
    DE2962132D1|1982-03-25|
    SE7807479L|1980-01-04|
    EP0006834A3|1980-01-23|
    JPS5699243A|1981-08-10|
    DD148500A5|1981-05-27|
    FI792089A|1980-01-04|
    EP0006834B1|1982-02-17|
    BR8000004A|1981-07-07|
    CA1115448A|1981-12-29|
    SE7905528L|1980-01-04|
    US4264481A|1981-04-28|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE7807479A|SE7807479L|1978-07-03|1978-07-03|WAY TO REGENERATE GUM AND THE USE OF ITS ONLY SET OF REGENERATED GUMMIT FOR MANUFACTURE OF VULGED GUM PRODUCTS|
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    AU54145/79A|AU5414579A|1978-07-03|1979-12-21|Process of reclaiming rubber|
    JP17392379A|JPS5699243A|1978-07-03|1979-12-29|Reclaiming of rubber|
    BR8000004A|BR8000004A|1978-07-03|1980-01-02|RUBBER RECOVERY PROCESS|
    DD80218297A|DD148500A5|1978-07-03|1980-01-03|METHOD FOR REGENERATING RUBBER|
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