EP3898821A1 - Elastomer mixture and method of its preparation - Google Patents
Elastomer mixture and method of its preparationInfo
- Publication number
- EP3898821A1 EP3898821A1 EP19845786.3A EP19845786A EP3898821A1 EP 3898821 A1 EP3898821 A1 EP 3898821A1 EP 19845786 A EP19845786 A EP 19845786A EP 3898821 A1 EP3898821 A1 EP 3898821A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rubber
- gypsum
- mixing
- weigh
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Definitions
- This invention relates to an elastomer mixture for production of rubber and rubber-metallic products, mainly for various types and sizes of solid wheels for transportation equipment, and belongs to the field of material engineering. It relates to polymers and composites, more specifically production of rubber and rubber-metallic products.
- the elastomer mixture according to this invention is primarily intended for products produced by rubber industry that has recently used, almost exclusively, rubber mixtures with carbon black-based fillers, wherein parameters of the final product should meet criteria such as low rolling resistance, high rebound elasticity, required hardness, etc.
- Patent document CN104629107 discloses an elastomer mixture for production of antiskid tires, which contains rubber, butyl rubber, epoxy resin, carbon black, methacrylate, paraffin wax, polyethylene glycol and additives and agents.
- Patent document CN104327431 discloses an elastomer mixture containing polymeric compounds, protein mixture, cellulose compounds, phosphate, tartaric acid as a cellulose compound filler, polymers, sulfonate, carbon black, magnesium oxide, vulcanizing agent and propenyl ether.
- Document CN104327431 discloses an elastomer material in which a matrix is a synthetic mixed elastomer based on fluorocarbons (fluorobutadiene rubber) to which is added lots of additives.
- a matrix is a synthetic mixed elastomer based on fluorocarbons (fluorobutadiene rubber) to which is added lots of additives.
- fluorocarbons fluorobutadiene rubber
- One of them is calcium sulfate dihydrate, but clearly as a pure substance.
- the material is characterized by high resistance to aging, radiation and it has high purity.
- the main disadvantage is a complicated recipe with a combination of many different types of fillers (cellulose compounds, carbon black, magnesium oxide, calcium sulfate dihydrate). Quantity of used fillers increases the difficulty of preparation of the mixture and the fact that they are pure substances increases a price of the final product.
- Patent document CN104031298 discloses an elastomer mixture for production of a flame- retardant rubber containing several rubber types, fatty acids, zinc oxide, aromatic oil, carbon black, white carbon black, PEG, agents, antioxidants, sulfate, sulfur and microcrystalline wax.
- Gypsum (calcium sulfate dihydrate CaSCE ⁇ EhO) or silica has proven to be a suitable substitute or partial substitute of the filler.
- Silica is an industrially used light active filler, which is manufactured and has a high price.
- Patent document CN102234387 discloses an elastomer mixture containing several types of rubber, zinc oxide, stearic acid, paraffin as a softener, sulfur, vulcanization accelerator, carbon black and calcium sulfate as a filler.
- the disadvantage of the present invention is the quite complicated recipe, as it contains three types of rubber and two types of carbon black.
- the calcium sulphate filler is used as a partial substitute for carbon black, however, the elastomer mixture according to the present invention contains a relatively high content of ecologically harmful carbon black and also the total fillers content is relatively high.
- the use of environmentally harmful softener is also a disadvantage.
- the required qualitative parameters of these products mainly include low values of rolling resistance combined with high rebound elasticity while maintaining the required hardness of the vulcanizates.
- the role of this invention is to design elastomer mixture for production of rubber and rubber- metallic products, mainly for solid wheels of different types and sizes for transportation equipment, and method of its preparation that would be environmentally and economically beneficial, while retaining or improving required parameters of the final products.
- Main required qualitative parameters of these products include low values of rolling resistance combined with high rebound elasticity, while retaining the required vulcanizate hardness.
- the solution of the elastomer mixture design according to this invention includes a proposal of production conditions that vary, due to the required properties of vulcanizates, depending on composition of each mixture.
- the nature of this invention is elastomer mixture recipe that includes partial substitution of nonecological carbon black with gypsum obtained as byproduct from power engineering. At the same time, substitution of carbon black with the alternative filler - energo-gypsum facilitates simplification of elastomer mixture composition, which therefore does not require use of softeners, thereby reducing the negative impact of aromatic oils on environment.
- the elastomer mixture according to this invention contains rubber, carbon black and gypsum as fillers, zinc oxide, stearic acid, sulfur, vulcanization accelerator and the nature composition of the elastomer mixture contains 100 parts by weight of natural rubber per 20 to 40 parts by weight of carbon black, 40 to 60 parts by weight of gypsum (calcium sulfate dihydrate CaSCri 2H2O), 3 to 6 parts by weight of zinc oxide, 1 to 4 parts by weight of stearic acid, 1 to 5 parts by weight of sulfur and 1 to 4 parts by weight of vulcanization accelerator.
- the gypsum is energo-gypsum, a byproduct of flue gas desulfurization process in thermal power stations.
- the recipe is simple and the simple nature of the elastomer mixture recipe according to this invention is based on use of single type of rubber and single type of carbon black.
- the carbon black and the energo-gypsum are used as fillers.
- the overall content of fillers in the elastomer mixture according to this invention is lower than that of the currently known elastomer mixtures intended for use in similar products whereas the content of the alternative filler - energo-gypsum prevails over the content of the standard filler - carbon black, unlike the currently known solutions, where carbon black is prevalent.
- Environmental benefits of the elastomer mixture according to this invention include mainly:
- Elastomer mixture according to this invention is more economical as previously known elastomer mixtures, which also reduces the price of final products made of the elastomer mixture according to this invention.
- the elastomer mixture according to this invention also shows improvement of important properties, such as low rolling resistance, high rebound elasticity, while maintaining the optimum hardness.
- the elastomer mixture can be prepared from any natural rubber classified as TSR (technically specified rubber), such as SMR-10, SIR-20 and SVR-CV60.
- the following carbon black types can be used: N339, N330, N326, N351.
- Any accelerator from the following group can be used to accelerate the vulcanization: N-tert-butyl-2-benzothiazolesulfenamide (TBBS), N-cyclohexyl-2- benzothiazolesulfenamide (CBS), 2-(4-morpholinothio)benzothiazole (MBS), mercaptobenzothiazole disulfide (MBTS).
- Preparation of the elastomer mixture according to this invention is carried out as two-stage mixing, i.e. it is performed in two stages. Individual ingredients of the elastomer mixture are added to the rubber in stepwise manner, while mixing at 90 to 120 °C and 50 to 80 revolutions per min, as follows:
- Stage I of mixing includes the following steps:
- stage II of mixing After the stage I of mixing, additional homogenization is performed on twin cylinder, then the mixture is let stand for 24 to 48 hours. After standing, the mixture is mixed for 180 to 300 seconds for additional blending (plastification), followed by the stage II of mixing.
- Stage of mixing includes the following step:
- Fig. 1 Vulcanization curve of the prepared elastomer mixture with alternative energo-gypsum filler
- Elastomer mixture with alternative energo-gypsum filler which is a power generation byproduct (PGBP) is prepared according to the recipe shown in Table 1 using the laboratory blender Plastograf Bradender with chamber volume 80 cm 3 .
- the elastomer mixture is prepared by two-stage mixing. Mixing is performed at 90 °C and 50 rpm. Mixing times of respective ingredients and sequence of their addition are specified in Table 2. Individual ingredients are added in the sequence shown and each ingredient is only added after mixing of the previous one (column 3). For the fillers energo-gypsum + carbon black N339, the time is measured only after mixing in the whole filler volume from the loading funnel of the blender.
- dsk number of parts of additive per 100 parts of rubber Table 2. Feeding sequence of the additives into the mixture and the respective mixing time
- Safety value of the mixture expresses time, during which mixture warmed up to the vulcanization temperature does not vulcanize and is plastic - i.e. it retains fluid properties so it can fill even forms of complex shapes.
- Safety value of the mixture is also important in molding of products using an injection molding machine, which aspirates mixture into the reservoir of the injection molding machine and then warms it up. For mixture with low value of processing safety, undesirable premature vulcanization may occur during its storage in the injection molding machine’s reservoir.
- Vulcanization of the mixture is mainly observed inside injection nozzles and as impaired product quality. Particles (aggregates) of vulcanized mixture appear that are carried out of the injection nozzles by mixture during injection. On the other hand, too high safety value of the mixture causes elongation of the vulcanization process and increased costs of the process.
- Table 3 shows the measured vulcanization characteristics of the prepared elastomer mixture with alternative energo-gypsum filler (PGBP) compared to the vulcanization characteristics of the other two industrially used rubber mixtures (designated X, Y). Table 3. Vulcanization characteristics of the prepared elastomer mixture with alternative energo-gypsum filler (PGBP) and two industrially used rubber mixtures
- the processing safety value of the elastomer mixture prepared according to this embodiment with the alternative energo-gypsum filler is in the range between the values shown by the industrially used mixtures X and Y. From the comparison, it can be concluded that the elastomer mixture prepared according to this embodiment achieved a slight increase in time of the processing safety of the mixture compared to the X mixture. It can be stated that the elastomer mixture containing energo-gypsum is also more suitable for molding of products of complex shapes. At the same time, it has lower safety value compared to the Y mixture, which eliminates the risk of prolonging the vulcanization process and the associated cost increase.
- the elastomer energo-gypsum mixture prepared according to this embodiment achieved the lowest value compared to the industrially used X and Y mixtures. Again, it can be pointed out that costs associated with the vulcanization process will be lower in the case of the elastomer energo-gypsum mixture compared to the X and Y mixtures.
- Alternative filler energo-gypsum likely affects and accelerates the vulcanization process by its ions content (S04 2 ).
- Vulcanization curve of the prepared elastomer mixture with alternative energo-gypsum filler is shown in Fig. 1.
- Table 4 shows the measured tensile strength and elongation values of the prepared mixture with alternative energo-gypsum filler, as well as the mixture commonly used to produce solid wheels in industry. Comparison of the data in Table 4 shows that the mixture with the alternative energo-gypsum filler achieves higher tensile strength values than the traditionally used mixture. The higher tensile strength with the alternative filler allows its application in the production of tensile products.
- Carbon black belongs to active, toughening fillers and their increasing content also increases hardness value of the vulcanizate.
- alternative energo-gypsum filler is a semi-toughening filler (hardness only increases up to certain limit of filler content within the mixture).
- Rebound elasticity can be defined as the ratio of returned energy to energy spent for deformation of testing body during impact of pendulum ply.
- rolling resistance can be described as decrease of rolling resistance value with increasing rebound elasticity value - less energy is spent for movement. Operation of solid wheel-like product type requires less energy for movement of the transportation equipment, even with higher loads.
- the values of hardness and rebound elasticity are closely interrelated and with use of common fillers such as carbon black, the rebound elasticity drops with increasing hardness values. Therefore, when using of carbon black, the rebound elasticity values must be increased by softening the mixture by addition of softener or by reducing the carbon black content. This brings about increased rubber content in the mixture, leading to increased prices of both the mixture and the final product.
- the higher price of the mixture currently used in the industry is also related, besides the price of the softener, to its incorporation during mixing as well as ensuring good manipulation (most softeners require warming to required temperatures in order to achieve lower viscosity and, thereby, improved manipulation in the weighing process).
- Elastomer mixture with alternative energo-gypsum filler according to this invention does not require addition of softeners, which eliminates all the negative effects mentioned above.
- Elastomer mixture with alternative energo-gypsum filler as the power generation byproduct (PGBP) is prepared as in Example 1 except that are used: natural rubber SIR-20, carbon black type N330 and vulcanization accelerator CBS and composition of the mixture is following:
- the preparation method is identical to the preparation method as in Example 1 except that the mixing is performed at 100 °C and 70 rpm. and mixing time is shown in the following table:
- Elastomer mixture with alternative energo-gypsum filler as the power generation byproduct (PGBP) is prepared as in Example 1 except that are used: natural rubber SVR-CV60, carbon black type N326 and vulcanization accelerator MBS and composition of the mixture is following:
- the preparation method is identical to the preparation method as in Example 1 except that mixing is performed at 105 °C and 60 rpm. and mixing time is shown in the following table:
- Elastomer mixture with alternative energo-gypsum filler as the power generation byproduct (PGBP) is prepared as in Example 1 except that are used: carbon black type N351 and vulcanization accelerator MBTS and composition of the mixture is following:
- the preparation method is identical to the preparation method as in Example 1 except that mixing is performed at 115 °C and 75 rpm. and mixing time is shown in the following table:
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SK50073-2018A SK289160B6 (en) | 2018-12-19 | 2018-12-19 | Elastomeric mixture and method of its preparation |
PCT/SK2019/050015 WO2020130952A1 (en) | 2018-12-19 | 2019-12-11 | Elastomer mixture and method of its preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3898821A1 true EP3898821A1 (en) | 2021-10-27 |
Family
ID=69400615
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19845786.3A Pending EP3898821A1 (en) | 2018-12-19 | 2019-12-11 | Elastomer mixture and method of its preparation |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3898821A1 (en) |
SK (1) | SK289160B6 (en) |
WO (1) | WO2020130952A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102234387B (en) * | 2011-04-19 | 2012-07-25 | 刘立文 | Calcium sulfate whisker modified rubber and preparation process thereof |
CN103497377A (en) * | 2013-10-11 | 2014-01-08 | 昆山纯柏精密五金有限公司 | Shoe sole rubber composition |
CN105419019A (en) * | 2015-12-15 | 2016-03-23 | 宁国天运橡塑制品有限公司 | Rubber damper for automobiles |
CN106349523A (en) * | 2016-08-25 | 2017-01-25 | 仇颖超 | Preparation method of antiskid abrasion-resistant rubber sole material |
CN108559138A (en) * | 2018-04-10 | 2018-09-21 | 贵州师范大学 | The antistatic rubber made of ester exchange at phosphorus fills out core rubber shoes sizing material and preparation method |
-
2018
- 2018-12-19 SK SK50073-2018A patent/SK289160B6/en unknown
-
2019
- 2019-12-11 WO PCT/SK2019/050015 patent/WO2020130952A1/en unknown
- 2019-12-11 EP EP19845786.3A patent/EP3898821A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2020130952A1 (en) | 2020-06-25 |
SK289160B6 (en) | 2024-02-14 |
SK500732018A3 (en) | 2020-07-01 |
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