CN117881735A - Peroxide crosslinkable rubber composition containing organic filler - Google Patents
Peroxide crosslinkable rubber composition containing organic filler Download PDFInfo
- Publication number
- CN117881735A CN117881735A CN202280057111.9A CN202280057111A CN117881735A CN 117881735 A CN117881735 A CN 117881735A CN 202280057111 A CN202280057111 A CN 202280057111A CN 117881735 A CN117881735 A CN 117881735A
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- CN
- China
- Prior art keywords
- rubber composition
- rubber
- peroxide
- particularly preferably
- filler
- 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.)
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- 239000005060 rubber Substances 0.000 title claims abstract description 288
- 239000000203 mixture Substances 0.000 title claims abstract description 242
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 89
- 239000012766 organic filler Substances 0.000 title claims abstract description 87
- 238000004073 vulcanization Methods 0.000 claims abstract description 78
- 239000000945 filler Substances 0.000 claims abstract description 73
- 238000007906 compression Methods 0.000 claims abstract description 38
- 230000006835 compression Effects 0.000 claims abstract description 38
- 239000004636 vulcanized rubber Substances 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 238000010335 hydrothermal treatment Methods 0.000 claims description 25
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- -1 alkylaryl peroxides Chemical class 0.000 claims description 10
- 239000000806 elastomer Substances 0.000 claims description 10
- 150000001451 organic peroxides Chemical class 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 4
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
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- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 claims description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
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- 239000008117 stearic acid Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
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- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Abstract
The present invention relates to a vulcanizable rubber composition comprising a vulcanization system VS comprising at least one peroxide, a rubber component K comprising at least one rubber capable of being crosslinked by at least one peroxide of VS, and a composition comprising at least one rubber component 14 C content in the range of 0.20 to 0.45Bq/g carbon and d99 value<Filler component F of the organic filler of 25.0 μm. The invention also relates to a kit of parts comprising as part (A) a rubber composition comprising the above-mentioned components K and F, and as part (B) a vulcanization system VS comprising at least one peroxide; to sulfur obtainable therefrom, respectivelyA rubber composition; to the use of one of the above-mentioned products for the production of industrial rubber articles, preferably those having a sealing function; to the corresponding technical rubber articles themselves, preferably those having a sealing function; and to the use of an organic filler for increasing the elongation at break of a vulcanized rubber composition while reducing the compression set.
Description
The present invention relates to a vulcanizable rubber composition comprising a vulcanization system VS comprising at least one peroxide, a rubber component K comprising at least one rubber capable of being crosslinked by at least one peroxide of VS, and a composition comprising at least one rubber component 14 C content in the range of 0.20 to 0.45Bq/g carbon and d99 value<A filler component F of an organic filler of 25.0 μm; to a kit of parts comprising as part (A) a rubber composition comprising the above-mentioned components K and F, and as part (B) a vulcanization system VS comprising at least one peroxide; to vulcanized rubber compositions obtainable therefrom, respectively; to the use of one of the above-mentioned products for the production of industrial rubber articles, preferably those having a sealing function; to the corresponding technical rubber articles themselves, preferably those having a sealing function; and to the use of an organic filler for increasing the elongation at break of a vulcanized rubber composition while reducing the compression set.
Background
The use of reinforcing fillers in rubber compositions is known in the art. In particular, mention should be made here of industrial carbon blacks, such as furnace blacks, for this purpose. Industrial carbon black remainsMaximum amount of reinforcing filler. Industrial carbon blacks are produced on the basis of highly aromatic petrochemical oils by incomplete combustion or pyrolysis of hydrocarbons. However, from an environmental point of view, it is desirable to avoid or minimize the use of fossil energy sources to produce the filler. It is particularly important to note here that one ton of industrial carbon black is produced, about 1 ton of CO being released during the production process 2 Depending on the specific surface area of the carbon black. Furthermore, industrial carbon blacks may not generally be useful for certain applications due to color reasons.
There are a number of different fields of application for rubber compositions containing reinforcing fillers. They can be used, for example, in the tire industry, but also in the field of industrial rubber articles, here for example, for providing corresponding articles, such as elastomeric seals, with good sealing functions. Elastomeric seals generally must ensure their sealing function over a long period of time under different and even varying operating conditions (e.g., at elevated temperatures and/or pressures).
The most important crosslinking method in the rubber industry is sulfur vulcanization. However, elastomers crosslinked by sulfur generally do not have sufficient heat resistance and too high permanent set, which is why such crosslinking methods are generally disadvantageous in the vulcanization field of rubber compositions for producing the above-mentioned industrial rubber articles having good sealing functions (e.g., for producing elastomer seals), and are therefore not preferred crosslinking methods. Peroxide crosslinking is the second most important method of crosslinking rubber following sulfur vulcanization. Crosslinking by peroxides is of great technical importance, in particular for rubbers without double bonds in the main chain, such as EPDM. Elastomers crosslinked by peroxide generally have better heat resistance (stable c—c bonds) and low permanent set than elastomers crosslinked by sulfur.
For example, in order to obtain predictions about the load-bearing capacity of the rubber composition used to make the seal, so-called compression set (DVR, german to druckverformulation) is typically measured under conditions of use or more stringent conditions (e.g., higher temperatures). Compression set refers to the amount of deformation remaining in the sample body after removal of the load. Compression set testing is used to evaluate the viscoelastic behavior of an elastomer under compression-induced long-term static deformation. As a comparative test method, it can be used for evaluating an elastomer used as a sealing element, a damping element, or the like for mechanical engineering. Thus, by compressing the set, the percentage of deformation remaining in the elastomer relative to the initial deformation after a long period of time, constant pressure loading and subsequent relaxation can be determined. Which is an important factor describing the mechanical curing of an elastomer in relation to its recovery after deformation (e.g. pressure and/or stress). This curing also affects chemical curing processes, such as thermal oxidative curing. For example, in order to obtain predictions concerning the load-bearing capacity of the rubber compositions used to make seals, tensile-elongation behaviour, for example at room temperature and after hot air curing, is tested in addition to compression set. In general, both high elongation at break and low compression set at room temperature are targets. In the case of the above-mentioned peroxide crosslinking, both properties generally depend on the crosslinking density of the peroxide crosslinking and are generally controlled by the amount of peroxide and possibly also of certain auxiliaries. However, the higher the crosslink density, the lower the elongation at break and compression set generally, while as noted above, low elongation at break is disadvantageous, particularly as noted above, in terms of curing, but also in relation to the cracking performance. When using conventional reinforcing fillers (e.g., carbon black) and inorganic fillers (e.g., silicic acid), these two properties (elongation at break and crosslink density) are generally not optimized independently of each other.
Thus, there is a need for new rubber compositions which are capable of crosslinking by peroxides and which do not exhibit the above-mentioned disadvantages.
Object of the Invention
It is therefore an object of the present invention to provide peroxide-curable rubber compositions which are suitable for providing industrial rubber articles and/or components of these articles, in particular those having an excellent sealing function, wherein the peroxide-curable rubber compositions obtainable therefrom must not only exhibit high heat resistance, but also should have the feature of high elongation at break and at the same time low compression set. In particular, the novel rubber compositions which can be vulcanized by means of peroxides should allow an optimal adjustment and balancing of these two parameters, with the advantage of in particular curing and cracking properties.
Solution scheme
This object is achieved by the subject matter claimed in the patent claims and by preferred embodiments of these subject matter as described in the following description.
The first subject of the present invention is a vulcanizable rubber composition comprising a rubber component K, a filler component F and a vulcanization system VS, wherein,
the vulcanization system VS comprises at least one peroxide,
The rubber component K comprises at least one rubber which can be crosslinked by at least one peroxide of the vulcanization system VS, and
the filler component F comprises at least one organic filler, which 14 C content is in the range of 0.20 to 0.45Bq/g carbon, and d99 value<25.0μm。
Another subject of the invention is a kit of parts comprising in spatially separated form:
a rubber composition as part (a) comprising at least the above-mentioned rubber component K used according to the invention and at least the filler component F used according to the invention, wherein, however, part (a) of the kit of parts does not comprise at least one peroxide of the vulcanization system VS used according to the invention; and
the vulcanization system VS used according to the invention as component (B) comprises at least one peroxide.
Another subject of the invention is a vulcanizable rubber composition obtainable by vulcanizing the vulcanizable rubber composition according to the invention or obtainable by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (a) and (B) of the kit of parts according to the invention.
A further subject of the invention is the use of the vulcanizable rubber composition according to the invention, the kit of parts according to the invention or the vulcanized rubber composition according to the invention for the production of industrial rubber articles, preferably for the production of industrial rubber articles with sealing function, in particular seals, profiles, dampers, rings and hoses.
Another subject of the invention is an industrial rubber article produced by using the vulcanizable rubber composition according to the invention, the kit of parts according to the invention or the vulcanized rubber composition according to the invention, preferably those having a sealing function, in particular seals, profiles, dampers, rings or hoses.
The invention also relates to the use of the organic filler used according to the invention for increasing the elongation at break and at the same time reducing the compression set of a vulcanized rubber composition which can be obtained by vulcanization with at least one peroxide, wherein the vulcanizable rubber composition used for this purpose comprises, in addition to at least one peroxide and the organic filler, at least one rubber which can be crosslinked with at least one peroxide.
It has been found that the organic fillers used according to the invention are environmentally friendly alternatives to known fillers, in particular inorganic fillers, and carbon black for rubber applications crosslinked by peroxides. Furthermore, it has been found that the organic fillers used according to the invention are suitable per se for incorporation directly into rubber compositions, in particular for the production of industrial rubber articles, preferably those having a sealing function, such as profiles, seals, dampers, rings and/or hoses.
Furthermore, it has been found that the rubber composition according to the invention is characterized by a high elongation at break and only a low compression set after vulcanization by means of peroxides. Furthermore, it has been shown that an optimal balance of these two parameters to be adjusted can be achieved by the vulcanizable rubber composition according to the invention. It has been found herein that these advantageous effects are due to the use of the organic filler used according to the invention in the rubber composition. In particular, it has surprisingly been found that the organic filler used according to the invention is chemically incorporated into the polymer cross-links within the temperature and time window given for the vulcanization by the peroxide. By this combination of reinforcing fillers, in particular by the specific surface chemistry with the organic fillers used according to the invention, the mobility of the polymer chains of the partial rubber is limited, which leads to an increase in the storage modulus and a decrease in the loss modulus during dynamic deformation. Thus, this advantageous special feature of the organic filler used according to the invention makes it possible to reduce polymer-polymer crosslinking and still achieve low compression set and high elongation at break.
It has been found that the rubber compositions according to the invention not only exhibit high heat resistance after vulcanization, but also have improved, i.e. reduced, compression set, which is particularly important when the resulting products are used in the technical rubber article field, such as seals, dampers, hoses and rings (e.g. O-rings). In particular, it has surprisingly been found that at least partial replacement of technical carbon black with the organic filler used according to the invention in rubber compounds crosslinked by peroxide results in an improvement, that is to say a reduction in compression set, and in particular in a significant reduction in the crosslinking density compared with rubber compounds containing technical carbon black and crosslinked by peroxide. In particular, this makes it possible to set a high elongation at break, so that the operating field of targeted regulation of rubber properties can be widened.
Furthermore, it has surprisingly been found that the rubber composition according to the invention can be used, in particular after vulcanization, for elastomeric components having a sealing function and elastomeric components having dynamic properties or low deformation behaviour.
Detailed Description
The term "comprising" as used in the present invention, for example in connection with the process steps or stages in the context of the vulcanizable rubber composition according to the invention and the process described herein, preferably has the meaning of "consisting of … …". In this context, for example, for the vulcanizable rubber composition according to the invention, one or more other ingredients optionally contained as described below may be contained therein in addition to the ingredients that must be present therein. All ingredients may be present in each of the alternative embodiments of them mentioned below. With respect to the methods according to the present invention and described herein, these methods may have additional optional method steps and stages in addition to the mandatory steps and/or stages.
The compositions described herein, such as vulcanizable rubber compositions according to the invention, comprise all the ingredients (in each case all the mandatory ingredients, and also all the optional ingredients) in amounts of up to 100% by weight, respectively.
Vulcanizable rubber composition
The vulcanizable rubber composition according to the invention comprises a rubber component K, a filler component F and a vulcanization system VS.
Preferably, the vulcanization system VS does not comprise any free sulfur, and in particular, the vulcanizable rubber composition according to the invention does not itself comprise any free sulfur. In other words, the vulcanizable rubber composition according to the invention is preferably not capable of being vulcanized by sulfur vulcanization, which may be performed before, after or simultaneously with peroxide crosslinking. Preferably, the vulcanizable rubber composition according to the invention is therefore crosslinked only by peroxides.
Filler component F
The filler component F of the vulcanizable rubber composition according to the invention comprises at least one organic filler.
Since the fillers used according to the invention have organic properties, inorganic fillers such as precipitated silicic acid do not belong to this category.
The term filler, in particular organic fillers, is known to the person skilled in the art. Preferably, the organic filler used according to the invention is a reinforcing filler, i.e. an active filler. The reinforcing or reactive filler may alter the viscoelastic properties of the rubber by interacting with the rubber within the rubber composition as compared to the non-reactive (non-reinforcing) filler. For example, they can affect the viscosity of the rubber and can improve the breaking behaviour of the vulcanizate, for example with respect to tear strength, tear propagation resistance and wear. On the other hand, the non-reactive filler dilutes the rubber matrix.
The organic filler used according to the invention 14 The C content is from 0.20 to 0.45Bq/g carbon, preferably from 0.23 to 0.42Bq/g carbon. The above-mentioned needs 14 The C content is determined by the organic filler obtained from the biomass being further treated or reacted, preferably by fractional distillationThis is achieved in that the fractionation can be carried out thermally, chemically and/or biologically, and preferably thermally and/or chemically. The fillers obtained from fossil materials, in particular fossil fuels, therefore do not fall into the definition of the fillers according to the invention used according to the invention, since they do not have corresponding fillers 14 C content.
Herein, biomass is defined as in principle any biomass, wherein the term "biomass" herein includes so-called plant biomass, i.e. biomass derived from plants, animal biomass, i.e. biomass derived from animals, as well as microbial biomass, i.e. biomass derived from microorganisms including fungi, whether biomass is dry biomass or fresh biomass, which is derived from dead or living organisms. Particularly preferred biomass for use herein in the production of the filler is plant biomass, preferably dead plant biomass. Dead plant biomass includes dead, waste or shed plants and parts thereof, and the like. These include, for example, broken and torn leaves, cereal straw, side branches, branches and branches, fallen leaves, cut or pruned trees, as well as seeds and fruits and parts derived therefrom, as well as sawdust, shavings/chips and other products from wood processing.
Preferably, the carbon content of the organic filler is in the range of >60 to <90 wt%, particularly preferably >60 to <85 wt%, more particularly preferably >60 to <82 wt%, more preferably >60 to <80 wt%, respectively, relative to the ashless and anhydrous filler. The following method section refers to a method for determining carbon content. In this regard, organic fillers differ from carbon blacks, such as industrial carbon blacks, carbon blacks made from fossil feedstocks, and carbon blacks made from renewable feedstocks, in that the carbon blacks have a corresponding carbon content of at least 95% by weight.
Preferably, the oxygen content of the organic filler is in the range of >8 to <30 wt.%, particularly preferably >10 to <30 wt.%, more particularly preferably >15 to <30 wt.%, still more particularly preferably >20 to <30 wt.%, relative to the ashless and anhydrous filler, respectively. The oxygen content can be determined by pyrolysis, for example using a EuroEA3000 CHNS-O analyzer from Eurovector S.p.A.
Preferably, the BET surface area (according to the specific total surface area of Brunauer, emmett and Teller) of the organic filler is>10m 2 /g to<150m 2 In the range from 20 to 120m, particularly preferably in the range from/g 2 In the range of/g, more preferably from 30 to 110m 2 In the range of from 40 to 100m 2 In the range of from 40 to < 100m, most preferably 2 In the range of/g.
Preferably, the organic filler has an STSA surface area of 10m 2 /g to<200m 2 And/g. The following method section refers to a method for determining STSA surface area (statistical thickness surface area). Preferably, the organic filler has an STSA surface area of 10 to 150m 2 In the range of from 20 to 120m 2 In the range of from 30 to 110m, more particularly preferably 2 In the range of from 40 to 100m 2 In the range of from 40 to < 100m, most preferably 2 In the range of/g.
Preferably, the organic filler has at least one functional group selected from the group consisting of phenolic OH groups, phenoxide groups, aliphatic OH groups, carboxylic acid groups, carboxylate groups, and mixtures thereof.
Preferably, the organic filler used according to the invention is a lignin-based organic filler produced from biomass and/or biomass components. For example, lignin used to produce lignin-based organic fillers may be separated and extracted and/or dissolved from biomass. Suitable methods for obtaining lignin from biomass to produce lignin-based organic fillers are, for example, hydrolysis methods or pulping methods, such as kraft pulping. The term "lignin-based" as used in the present invention preferably means that one or more lignin units and/or one or more lignin scaffolds are present in the organic filler used according to the present invention. Lignin is a solid biopolymer that is incorporated into the plant cell wall, thereby affecting the lignification of plant cells. They are therefore present in biomass, in particular in biorenewable raw materials, and therefore represent (in particular in the form of hydrothermal treatment) an environmentally friendly filler substitute.
Preferably, the lignin, and preferably the organic filler used according to the invention itself (if it is a lignin-based filler) is present at least partly in the form of a hydrothermal treatment, and particularly preferably in each case can be obtained by means of a hydrothermal treatment. Particularly preferably, the organic filler used according to the invention is based on lignin obtainable by hydrothermal treatment. Suitable hydrothermal treatment methods, in particular of lignin and lignin-containing organic fillers, are described for example in WO 2017/085278 A1 and WO 2017/194346 A1 and EP 3 470 457 A1. Preferably, the hydrothermal treatment is carried out in the presence of liquid water at a temperature of >100 ℃ to <300 ℃, particularly preferably >150 ℃ to <250 ℃. Preferably, the organic filler is a lignin-based filler, wherein preferably at least lignin and even more preferably the organic filler itself is at least partially present in a form obtainable (and particularly preferably obtainable) by a hydrothermal treatment, wherein the hydrothermal treatment is preferably carried out at a temperature of >100 ℃ to <300 ℃, particularly preferably >150 ℃ to <250 ℃. Alternatively, the starting material used for this purpose, such as lignin-containing raw materials, in particular lignin, may have been reacted with at least one crosslinking agent before being subjected to the hydrothermal treatment. The crosslinking agent preferably has at least one functional group capable of reacting with the crosslinkable group of lignin. The crosslinking agent preferably has at least one functional group selected from the group consisting of: aldehyde groups, carboxylic acid anhydrides, epoxy groups, hydroxyl groups, and isocyanate groups, or combinations thereof. Preferably, the cross-linking agent is selected from aldehydes, epoxides, anhydrides, polyisocyanates and/or polyols, in particular from aldehydes, such as formaldehyde, furfural and/or furfural. In this method, the crosslinking agent may react with free ortho and para positions of the phenolic ring, with aromatic and aliphatic OH groups, and/or with the carboxyl groups of lignin.
Preferably, the pH of the organic filler is in the range of 7 to 9, particularly preferably in the range of >7 to <9, more particularly preferably in the range of >7.5 to < 8.5.
The organic filler used according to the invention has a d99 value <25.0 μm. The method for determining the d99 value is described in the method section below and is carried out by laser diffraction according to ISO 13320:2009. The d90 and d25 values mentioned below are determined in the same manner. Those skilled in the art will appreciate that the organic fillers used according to the present invention are present in the form of particles, and that the average particle size (average grain size) of these particles is described by the d99 values mentioned above, and also by the d90 and d25 values mentioned above.
Preferably, the organic filler has a d99 value of <20.0 μm, more preferably <15.0 μm, particularly preferably <10 μm, more particularly preferably <9.0 μm, more preferably <8.0 μm, more preferably <7.0 μm, most preferably <6.0 μm, which is preferably determined by laser diffraction according to ISO 13320:2009, respectively.
Preferably, the d90 value of the organic filler is <7.0 μm, particularly preferably <6.0 μm, more particularly preferably <5.0 μm, and/or the d25 value is preferably <3.0 μm, particularly preferably <2.0 μm, more particularly preferably <1.0 μm, which are preferably determined by laser diffraction according to ISO 13320:2009, respectively.
Preferably, the rubber composition comprises at least one organic filler in an amount ranging from 10 to 150phr, particularly preferably from 15 to 130phr, more particularly preferably from 20 to 120phr, even more preferably from 30 to 100phr, most preferably from 40 to 80 phr.
Phr (parts per hundred parts by weight of rubber) specifications used herein are the number specifications commonly used in compounding formulations in the rubber industry. The amounts in parts by weight of the individual components are always relative to the total mass of 100 parts by weight of all rubber present in the compound.
In addition to the at least one organic filler used according to the invention, the filler component F may also comprise one or more other fillers different from the organic filler used according to the invention. Preferably, the proportion (in phr) of at least one organic filler used according to the invention in the rubber composition is higher than the corresponding proportion of one or more other fillers.
In the case where the organic filler according to the invention is used only as a partial replacement for ordinary technical carbon black, the rubber composition according to the invention may also comprise technical carbon black, in particular furnace carbon black, for example classified as universal carbon black according to ASTM code N550. For a surface area of STSA that can fall under ASTM code N550 of 8 to 150m 2 This is especially true for industrial carbon blacks in the range of/g. Alternatively or additionally, the rubber compositions of the present invention may also contain carbon blacks other than those described above, in particular those having STSA surface areas of from 20 to 60m 2 Carbon black/g.
Additionally or alternatively, the rubber compositions according to the invention may contain inorganic fillers, in particular for example those having different particle sizes, particle surfaces and chemical properties having different potential to influence the vulcanization behaviour. In the case of other fillers, these fillers should preferably have properties as similar as possible to those of the organic fillers according to the invention used in the rubber compositions according to the invention, in particular in terms of their pH value.
If other fillers are used, they are preferably phyllosilicates, such as clay minerals, for example talc; carbonates, such as calcium carbonate; silicates, such as calcium silicate, magnesium silicate, and aluminum silicate; and oxides such as magnesium oxide and silica or silicic acid.
The rubber composition according to the invention may also comprise such inorganic fillers, such as silica or silicic acid, in particular in the case that the organic fillers used according to the invention are used only as partial substitutes for ordinary silicic acid or silica.
However, in the context of the present invention, zinc oxide does not belong to the inorganic filler, since zinc oxide assumes the role of an additive that promotes vulcanization. However, additional fillers must be carefully selected because silica tends to bind organic molecules to its surface, thereby inhibiting its action.
Inorganic fillers, of which silica and other fillers having Si-OH groups on their surface are preferred, may be surface treated (surface modified). In particular, it may be advantageous to carry out the silylation with organosilanes, for example alkylalkoxysilanes or aminoalkylalkoxysilane or mercaptoalkylalkoxysilane. The alkoxysilane groups may be bonded to the surface of the silicate or silica, for example by hydrolytic condensation, or to other suitable groups.
Fillers other than the organic fillers according to the invention may be used alone or in combination with each other. In the case of the use of other fillers, their proportion is preferably less than 40phr, particularly preferably from 20 to 40phr, particularly preferably from 25 to 35phr.
Rubber component K
The rubber component K of the vulcanizable rubber composition according to the invention comprises at least one rubber which can be crosslinked by at least one peroxide of the vulcanization system VS.
Any kind of rubber is suitable for producing the rubber composition according to the invention, as long as it is capable of being crosslinked by at least one peroxide. Suitable rubbers, including Natural Rubber (NR) and synthetic rubbers, are known to those skilled in the art. Examples of the rubber which cannot be crosslinked by peroxide are chlorinated isobutylene-isoprene rubber (CIIR; chloro-isobutylene-isoprene rubber), isobutylene-isoprene rubber (IIR), epichlorohydrin rubber (ECO/CO/ETER) and propylene oxide rubber (GPO).
Preferably, the at least one rubber of rubber component K is selected from the group consisting of rubbers which do not have carbon-carbon double bonds in their main chain, preferably do not have any carbon-carbon double bonds throughout their structure, particularly preferably from the group consisting of: HNBR (hydrated acrylonitrile-butadiene rubber), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), acrylate-ethylene rubber (AEM), ethylene-vinyl acetate rubber (EVM), chlorinated rubber, in particular chlorinated polyethylene (CM), silicone rubber (Q), chlorosulfonated polyethylene (CSM), fluororubber elastomer (FPM), and mixtures thereof.
Vulcanization system VS
The vulcanization system VS of the vulcanizable rubber composition according to the invention comprises at least one peroxide. The peroxide acts as a vulcanizing agent.
The vulcanizable rubber composition according to the invention may be vulcanized due to the presence of the vulcanization system VS and the peroxides contained therein.
The vulcanization reaction is initiated by thermal decomposition of the peroxide, which results in the formation of two free radicals. The radical transfer to the rubber is effected by substitution of hydrogen atoms or by double bonds (if present) added to the polymer. The crosslinking efficiency can be significantly improved by using free radical transfer substances, so-called auxiliaries. The rubber polymer radicals can react in different ways, depending on their structure and the auxiliaries present.
The at least one peroxide of the vulcanization system VS preferably comprises, in particular represents, at least one organic peroxide, particularly preferably an organic peroxide selected from the group consisting of dialkyl peroxides, alkylaryl peroxides, diaryl peroxides, alkyl peresters, aryl peresters, diacyl peroxides, polyvalent peroxides and mixtures thereof, more particularly preferably an organic peroxide selected from the group consisting of di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, dicumyl peroxide, tert-butylcumene peroxide, tert-butyl perbenzoate, dibenzoyl peroxide, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane and bis- (tert-butylperoxy) -diisopropylbenzene and mixtures thereof.
The proportion of peroxide in the rubber composition according to the invention is preferably from 0.5 to 10phr, particularly preferably from 1.0 to 8phr, and particularly preferably from 1.5 to 6phr.
Preferably, the vulcanization system VS of the rubber composition, particularly preferably of the rubber composition, comprises at least one at least monounsaturated and preferably polyunsaturated organic compound, preferably selected from the group consisting of: di (meth) acrylates, bismaleimides, triallyl compounds and unsaturated polymers such as 1, 2-polybutadiene and trans-polyoctene rubbers, preferably having a number average molecular weight (Mn) of <10,000g/mol, particularly preferably <5,000g/mol, more particularly preferably <2,500g/mol, more preferably <1,500g/mol, especially <1,000g/mol, most preferably <500g/mol, respectively, and mixtures thereof; and is particularly preferably selected from the group consisting of: ethylene glycol di (meth) acrylate (EDMA), trimethylolpropane tri (meth) acrylate (TRIM), N, N' -m-phenylene bismaleimide (MPBM), diallyl terephthalate (DATP), triallyl cyanurate (TAC), 1, 4-butanediol di (meth) acrylate, and mixtures thereof. At least one organic compound which is at least monounsaturated and preferably polyunsaturated is preferably used as an aid as described above in order to increase the crosslinking yield and thereby achieve better compression set results. The adjuvants bridge the steric effect and inhibit the reaction to crosslinking inactivity.
The proportion of auxiliaries in the rubber compositions according to the invention is preferably from 0.5 to 10phr, particularly preferably from 1.0 to 8phr, and particularly preferably from 1.5 to 6phr.
The vulcanization system VS of the vulcanizable rubber composition according to the invention may comprise one or more other vulcanizing agents besides peroxides, and/or vulcanization-promoting additives, such as zinc oxide and/or fatty acids, such as stearic acid.
The vulcanization system VS of the vulcanizable rubber composition according to the invention may comprise one or more vulcanization-promoting additives, but is not itself capable of initiating vulcanization. Such additives include, for example, vulcanization accelerators, such as saturated fatty acids having from 12 to 24, preferably from 14 to 20, particularly preferably from 16 to 18, carbon atoms, such as stearic acid, and zinc salts of, for example, the abovementioned fatty acids. Thiazoles may also belong to these additives.
If vulcanization-promoting additives and in particular the abovementioned fatty acids and/or zinc salts thereof, preferably stearic acid and/or zinc stearate, are used in the rubber composition according to the invention, their proportion is from 0 to 10phr, particularly preferably from 1 to 8phr and particularly preferably from 2 to 6phr.
The vulcanization system VS of the vulcanizable rubber composition according to the invention may also comprise one or more other vulcanizing agents other than peroxides, for example preferably zinc oxide. In addition to peroxides, particular preference is given to using such vulcanizing agents of the vulcanization system VS.
If other vulcanizing agents such as zinc oxide are used in the rubber composition according to the invention, their proportion is preferably from 0 to 10phr, more preferably from 1 to 8phr, and particularly preferably from 2 to 6phr.
In addition to the at least one peroxide, free sulfur may also be added to the VS cure system as another curative. However, as already mentioned above, this is not preferred.
The vulcanization of the rubber composition of the present invention is preferably carried out using at least one peroxide, such as in particular at least one organic peroxide in combination with zinc oxide and/or preferably with at least one fatty acid.
Other Components of vulcanizable rubber composition
The rubber composition according to the invention may contain other optional ingredients such as plasticizers/softeners and/or antidegradants and/or resins, in particular resins which increase adhesion.
By using the softener, it is possible to influence the properties of the unvulcanized rubber composition, such as in particular the processability, but also the properties of the vulcanized rubber composition, such as its flexibility, in particular at low temperatures. Particularly suitable softeners in the context of the present invention are mineral oils selected from paraffinic oils (substantially saturated chain hydrocarbons) and naphthenic oils (substantially saturated cyclic hydrocarbons). Aromatic hydrocarbon oils may also and even are preferred. However, mixtures of paraffinic and/or naphthenic oils may also be advantageous as softeners in terms of adhesion of the rubber composition to other rubber-containing components in the tire (e.g., carcass). Other possible softeners are, for example, esters of aliphatic dicarboxylic acids, such as adipic acid or sebacic acid, paraffin waxes and polyethylene waxes. Among softeners, paraffinic and naphthenic oils are particularly suitable for the context of the present invention; however, most preferred are aromatic oils, especially aromatic mineral oils.
Preferably, the softener, of which paraffinic and/or naphthenic, in particular aromatic processing oils, are particularly preferred, is used in an amount of from 0 to 100phr, preferably from 10 to 70phr, particularly preferably from 20 to 60phr, in particular from 20 to 50 phr.
Examples of antidegradants are quinolines such as TMQ (2, 4-trimethyl-1, 2-dihydroquinoline), and diamines such as 6-PPD (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine).
So-called adhesion-enhancing resins can be used to improve the adhesion of the vulcanized rubber mixtures of the present invention to other adjacent rubber components. Particularly suitable resins are those based on phenols, preferably selected from the group consisting of phenolic resins, phenol-formaldehyde resins and phenol-acetylene resins. In addition to phenol-based resins, it is also possible toTo use aliphatic hydrocarbon resins, e.g. Escorez from ExxonMobil TM 1102RM, and aromatic hydrocarbon resins. Aliphatic hydrocarbon resins are particularly capable of improving adhesion to other rubber components of the tire. They generally have lower adhesion than phenol-based resins and can be used alone or as a mixture with phenol-based resins.
If an adhesion enhancing resin is indeed used, it is preferably selected from the group consisting of phenol-based resins, aromatic hydrocarbon resins and aliphatic hydrocarbon resins. Preferably, their proportion is from 0 to 15phr or from 1 to 15phr, particularly preferably from 2 to 10phr, and very particularly preferably from 3 to 8phr.
Kit of parts
Another subject of the invention is a kit of parts comprising or consisting of the following in spatially separated form:
a rubber composition as part (a) comprising at least the above-mentioned rubber component K used according to the invention and at least the filler component F used according to the invention, wherein, however, part (a) of the kit of parts does not comprise at least one peroxide of the vulcanization system VS used according to the invention; and
the vulcanization system VS used according to the invention as component (B) comprises at least one peroxide.
Therefore, the part (a) itself cannot be vulcanized by a peroxide, and thus represents a rubber composition which cannot be vulcanized by a peroxide at this time. The vulcanization can be carried out by means of peroxides only after mixing of the components (A) and (B).
Preferably, components K and F of the rubber composition according to the invention on the one hand and the vulcanization system VS on the other hand are spatially separated from one another in the kit of parts and can therefore be stored. The kit of parts is used to prepare a vulcanizable rubber composition. For example, a rubber composition according to the invention comprising components K and F and possibly other ingredients (including vulcanizing agents other than peroxides, such as zinc oxide and/or at least one fatty acid) may be used as component (a) in stage 1 of the process for preparing a vulcanizable rubber composition described below, and a second component of the component kit (i.e. sulfur system VS) may be used as component (B) comprising at least peroxide in stage 2 of the process.
The vulcanizable composition preferably comprises components K and F of the rubber composition according to the invention and the associated vulcanization system VS comprising at least one peroxide in the form of a homogeneous mixture, so that the vulcanizable rubber composition can be vulcanized directly, in contrast to the rubber composition comprising components K and F and the vulcanization system VS comprising at least one peroxide which are thus spatially separated from each other in the kit of parts.
All the preferred embodiments described above in relation to the vulcanizable rubber composition according to the invention are also preferred embodiments of the kit of parts according to the invention.
Preferably, the kit of parts according to the invention comprises:
a rubber composition comprising at least components K and F as part (A); and
as part (B) a vulcanization system VS comprising at least one peroxide and zinc oxide, wherein zinc oxide may alternatively be present in part (a).
Particularly preferably, the kit of parts according to the invention comprises:
a rubber composition comprising at least components K and F as part (A); and
as part (B) a vulcanization system comprising at least one peroxide, zinc oxide and at least one saturated fatty acid, such as stearic acid and/or optionally zinc stearate, wherein at least zinc oxide and/or fatty acid may alternatively be present within part (a).
Process for preparing vulcanizable rubber composition
Another subject of the invention is a process for preparing the vulcanizable rubber composition according to the invention.
All the preferred embodiments described hereinabove in relation to the vulcanizable rubber composition according to the invention and the kit of parts according to the invention are also preferred embodiments of the method according to the invention.
The production of the vulcanizable rubber composition according to the invention is preferably carried out in two stages, namely stages 1 and 2, described in more detail below. However, as explained further below, single-stage process controls are also possible as alternatives.
Two-stage process
In the first stage (stage 1), the rubber composition as a base mixture (masterbatch) is first prepared by mixing all the ingredients (but without at least one peroxide) used to prepare the vulcanizable rubber composition according to the invention with one another. In the second stage (stage 2), at least the peroxide and optional additional components of the vulcanization system VS are mixed into the rubber composition obtained after stage 1.
Stage 1
Preferably, at least one rubber contained in the rubber component K of the rubber composition according to the present invention is provided, and a resin different therefrom, preferably those improving adhesion, may be optionally used. However, the latter may also be added later together with other additives. Preferably, the rubber has a temperature of at least room temperature (23 ℃) or is preferably used after preheating to a temperature of at most 50 ℃, preferably at most 45 ℃ and particularly preferably at most 40 ℃. It is particularly preferred that the rubber is pre-plasticated (pre-plasticated) for a short period of time before the other ingredients are added. If inhibitors such as magnesium oxide are used for subsequent vulcanization control, they are preferably added at this time as well.
At least one organic filler and optionally further fillers, preferably in addition to zinc oxide, are then added, as are used as components of the vulcanization system in the rubber composition according to the invention as described above, and are therefore not regarded herein as fillers. Preferably, the at least one organic filler and optionally the other filler are added in an incremental manner.
Advantageously, but not necessarily, the softener and other ingredients, such as vulcanizing agents (rather than peroxides), for example stearic acid and/or zinc stearate and/or zinc oxide, are added only after the addition of the at least one organic filler or other filler (if used). This facilitates the incorporation of at least one organic filler and other fillers, if present. However, it may be advantageous to incorporate a portion of the organic filler, or if present, other fillers as well as softeners and any other ingredients optionally used.
The maximum temperature obtained during the preparation of the rubber composition in the first stage (dump temperature) should not exceed 170 ℃, since above these temperatures the reactive rubber and/or the organic filler may be partially decomposed. Temperatures of >170 ℃, e.g. up to <200 ℃, are also possible, depending in particular on the rubber used. Preferably, the maximum temperature in the preparation of the rubber composition of the first stage is from 80 ℃ to <200 ℃, particularly preferably from 90 ℃ to 190 ℃, most preferably from 95 ℃ to 170 ℃.
The mixing of the components of the rubber composition is generally carried out by means of an internal mixer equipped with tangential or intermeshing (i.e. intermeshing) rotors. The latter generally allows better control of temperature. Mixers with tangential rotors are also known as tangential mixers. However, mixing can also be carried out using, for example, a twin-roll mixer. Depending on the rubber used, the mixing process can be carried out conventionally, starting from the addition of the polymer; or upside down, i.e. finally after addition of all other components of the mixture. The reverse method is mainly used for rubber EPM and EPDM.
After the rubber composition is prepared, it is preferably cooled before the second stage is carried out. This type of process is also known as curing. Typical maturation times are from 6 to 24 hours, preferably from 12 to 24 hours.
Stage 2
In the second stage, at least the peroxide, but preferably the additional components of the vulcanization system VS, are incorporated into the rubber composition of the first stage, so as to obtain the vulcanizable rubber composition according to the invention. Preferably, if adjuvants are present/used, they are also incorporated in stage 2.
If zinc oxide and optionally at least one saturated fatty acid such as stearic acid are used as the vulcanization system in addition to peroxide, the addition of all these components can be carried out in stage 2. However, it is also possible to integrate these components in addition to the peroxide into the rubber composition already in stage 1.
The maximum temperature ("let-down temperature") obtained during the preparation of the mixture of the vulcanization system and the rubber composition in the second stage must be kept below the temperature at which the peroxide starts to crack, and should preferably not exceed 130 ℃, particularly preferably 125 ℃. The preferred temperature range is from 70℃to 125℃and particularly preferably from 80℃to 120 ℃. When the temperature is higher than the highest temperature of 105 ℃ to 120 ℃ of the crosslinking system, scorch may occur.
After mixing the vulcanization system in stage 2, the composition is preferably cooled.
In the two-stage process described above, therefore, the rubber composition is first obtained in a first stage, which is supplemented in a second stage to form a vulcanizable rubber composition.
Single stage process
In the case of the single-stage process, all the ingredients used to produce the vulcanizable rubber composition according to the invention are mixed together in one step, including the vulcanization system. Preferably, the peroxide of the vulcanization system, preferably together with the coagent, is added to the rubber compound only after the total amount of rubber used and the total amount of filler used and any additional components have been added. Preferably, the addition of the filler used is carried out in such a way that it is added in at least two portions at different times, wherein preferably the total amount of rubber used has been provided at the first addition. Particularly in the case of the single-stage process, there is no cooling/no relaxation before adding the components of the vulcanization system.
Method for further processing of vulcanizable rubber composition according to the invention
The vulcanizable rubber composition thus prepared is subjected to a deformation process preferably tailored or customized for the final article prior to vulcanization. The rubber composition is formed into a suitable shape as required by the vulcanization process, preferably by extrusion or calendering. In this process, the curing can be carried out in a curing mold using pressure and temperature, or in a pressureless controlled temperature tunnel, where air or liquid material provides heat transfer.
Vulcanizable rubber composition
Another subject of the invention is a vulcanizable rubber composition obtainable by vulcanizing the vulcanizable rubber composition according to the invention or obtainable by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (a) and (B) of the kit of parts according to the invention.
All the preferred embodiments described hereinabove in relation to the vulcanizable rubber composition according to the invention and the kit of parts according to the invention, as well as the method according to the invention, are also preferred embodiments of the vulcanizable rubber composition according to the invention.
Typically, vulcanization is carried out under pressure and/or heat. Suitable vulcanization temperatures are preferably from 140℃to 200℃and particularly preferably from 150℃to 180 ℃. Alternatively, the vulcanization is carried out at a pressure in the range 50 to 175 bar. However, it is also possible to carry out the vulcanization in a pressure range of 0.1 to 1 bar, for example in the case of profiles.
The shore a hardness of the vulcanized rubber composition obtained from the vulcanizable rubber composition according to the present invention is preferably greater than 40 to less than 80, particularly preferably 45 to 75, most preferably 50 to 70; and/or a tensile strength of greater than 8MPa, particularly preferably greater than 8.5MPa, and more particularly preferably greater than 9MPa; and/or an elongation at break of >300%, preferably >350%, particularly preferably >400%; and/or compression set (70 ℃ after 22 hours) of at most 13.0%, preferably <13.0%; and/or compression set (100 ℃ after 22 hours) of at most 20.0%, preferably <20.0%, particularly preferably <19.5%. Methods for determining shore a hardness, tensile strength, elongation at break and compression set are given in the method description below.
Use of the same
A further subject of the invention is the use of the vulcanizable rubber composition according to the invention, the kit of parts according to the invention or the vulcanized rubber composition according to the invention for the production of industrial rubber articles, preferably for the production of industrial rubber articles with sealing function.
All the preferred embodiments described hereinabove in relation to the vulcanizable rubber composition according to the invention, the kit of parts according to the invention, the method according to the invention and the vulcanized rubber composition according to the invention are also preferred embodiments in relation to the above-described use according to the invention.
The term "technical rubber article" (also referred to as mechanical rubber article, MRG) is known to the person skilled in the art. Examples of industrial rubber articles are profiles, seals, dampers and/or hoses.
Industrial rubber product
Another subject of the invention is an industrial rubber article produced by using the vulcanizable rubber composition according to the invention, the kit of parts according to the invention or the vulcanized rubber composition according to the invention, preferably those having a sealing function.
All the preferred embodiments described hereinabove in connection with the vulcanizable rubber composition according to the invention, the kit of parts according to the invention, the method according to the invention, the vulcanized rubber composition according to the invention and the use according to the invention are also preferred embodiments in connection with the above-described industrial rubber articles according to the invention.
Use of the organic filler used according to the invention
The invention also relates to the use of the organic filler used according to the invention for increasing the elongation at break and at the same time reducing the compression set of a vulcanized rubber composition which can be obtained by vulcanization with at least one peroxide, wherein the vulcanizable rubber composition used for this purpose comprises, in addition to at least one peroxide and the organic filler, at least one rubber which can be crosslinked with at least one peroxide.
All the preferred embodiments described hereinabove in connection with the vulcanizable rubber composition according to the invention, the kit of parts according to the invention, the method according to the invention, the vulcanized rubber composition according to the invention, the above-mentioned industrial rubber article according to the invention and the use according to the invention are also preferred embodiments in connection with the use according to the invention of the organic filler used according to the invention. Elongation at break and compression set are determined as described in the "methods" section below.
Measurement method
14 Determination of C content
14 The determination of the C content (biobased carbon content) is carried out by the radiocarbon method in accordance with DIN EN 16640:2017-08.
2. Determination of particle size distribution
Particle size distribution can be determined by laser diffraction of a material dispersed in water (1 wt% in water) according to ISO 13320:2009 and subjected to an ultrasonic treatment of 12,000ws before measurement. The volume fraction is for example designated d99 in μm (particle diameter below which 99% of the sample volume is below).
3. Determination of carbon content
The carbon content is determined by elemental analysis in accordance with DIN 51732:2014-7.
4. Determination of oxygen content
Oxygen content was determined by pyrolysis using a EuroEA3000 CHNS-O analyzer from EuroVector S.p.A.company. Here, the CHNS content was determined by the above-mentioned analysis apparatus, and then the oxygen content was calculated as a difference (100-CHNS).
5. Determination of the dry matter content of the organic filler used
The dry matter content of the samples is determined as follows in accordance with DIN 51718:2002-06. For this purpose, the MA100 moisture balance from Sartorius company was heated to a drying temperature of 105 ℃. If the dried sample is not already in powder form, it is ground or milled into a powder using a mortar. About 2g of the sample to be measured is weighed on a suitable aluminum pan in a moisture balance and the measurement is started. Once the sample weight does not change by more than 1mg within 30 seconds, the weight is considered constant and the measurement is terminated. The dry matter content corresponds to the sample content (in wt.%) shown. The assay was repeated at least once for each sample. The weighted average is reported.
6. Determination of the pH value of the organic filler used
The pH was determined according to ASTM D1512 as follows. If the dried sample is not already in powder form, it is ground or milled into a powder using a mortar. In each case, 5g of the sample and 50g of completely deionized water were weighed into a glass beaker. The suspension was heated to 60 ℃ using a magnetic stirrer and stirring plate with heating function and stirred continuously and maintained at 60 ℃ for 30 minutes. Subsequently, the heating function of the stirrer is deactivated, so that the mixture cools while stirring. After cooling, the evaporated water was again supplemented with fully deionized water and stirred again for 5 minutes. The pH of the suspension was measured with a calibrated measuring instrument. The temperature of the suspension should be 23 ℃ (±0.5 ℃). Two determinations were made for each sample and the average value was reported.
7. Determination of ash content of organic filler
The anhydrous ash content of the samples was determined by thermogravimetric analysis according to DIN 51719 standard as follows: prior to weighing, the samples were ground or crushed with a mortar. The dry matter content of the weighing material is determined before the ash is determined. Sample material was weighed in a crucible to the nearest 0.1mg. The furnace including the sample was heated to a target temperature of 815 deg.c at a heating rate of 9 deg.k/min and then held at this temperature for 2 hours. The furnace was then cooled to 300 ℃ and the sample was then removed. The sample was cooled to ambient temperature in a desiccator and weighed again. The remaining ash is correlated to the initial weight to determine the weight percent of ash. Three determinations were made for each sample and the average value was reported.
8. Determination of BET and STSA surface areas of organic fillers
The specific surface area of the filler to be investigated is determined by nitrogen adsorption according to the ASTM D6556 (2019-01-01) standard provided for industrial carbon black. According to this standard, BET surface area (according to the specific total surface area of Brunauer, emmett and Teller) and outer surface area (STSA surface area; statistical thickness surface area) were determined as follows.
The sample to be analyzed is dried at 105 ℃ until the dry matter content is more than or equal to 97.5 weight percent before measurement. In addition, the cell was dried in a drying oven at 105 ℃ for several hours before weighing the sample. The sample was then filled into the measuring cell using a funnel. If the upper measuring cell shaft is contaminated during filling, it is cleaned using a suitable brush or pipe cleaner. In the case of a strongly flying (electrostatic) material, glass wool is additionally weighed into the sample. Glass wool is used to retain any material that may fly and contaminate the equipment during baking.
The sample to be analyzed is baked at 150 ℃ for 2 hours, al 2 O 3 The standard was baked at 350℃for 1 hour. According to the pressure range, the following N is used 2 The dosage is measured:
p/p0＝0-0.01:N 2 the dosage is as follows: 5ml/g
p/p0＝0.01-0.5:N 2 The dosage is as follows: 4ml/g.
To determine BET, extrapolation is performed using at least 6 measurement points in the range of p/p0=0.05-0.3. For the determination of STSA, adsorption N at t=0.4-0.63 nm (corresponding to p/p0=0.2-0.5) 2 Extrapolation is performed using at least 7 measurement points over the layer thickness range of (2).
9. Measurement of hardness
The Shore A hardness of the vulcanized rubber compositions was determined according to ISO 48-4:2021-02 using a digital Shore hardness tester from Sauter GmbH at 23 ℃. In order to achieve the standard required sample thickness of at least 6mm, the sample consists of no more than three layers. For this purpose, 3S 2 bars, which are punched for tensile testing according to ISO 37:2011, are stacked on top of each other. Five measurements were made at different points in each sample stack. The results obtained represent the average of these five measurements. Between vulcanization and testing, the samples were stored at laboratory room temperature for at least 16 hours.
10. Determination of crosslink Density/reaction kinetics
The crosslink density and the reaction kinetics of the rubber compositions were determined in accordance with DIN 53529-3:1983-06 at 175℃but 3℃deviation. The measurement time was 15 minutes. In the process, the minimum and maximum torque (M L 、M H ). Thereby calculating the difference delta (M H -M L ) (maximum Torque reduction)To minimize torque). Further, the slave minimum torque M is determined L The time starting torque of (a) respectively reaches the maximum torque M H 10%, 50% and 90% of the time period. The time period is designated as T 10 、T 50 And T 90 。
11. Determination of elongation under tension
The elongation under tension, including tensile strength and elongation at break, was determined for the vulcanized rubber composition according to ISO 37:2011.
12. Determination of compression set
The compression set of the vulcanized rubber composition was determined in accordance with DIN ISO 815-1:2016-09. Three specimens were tested for each sample. Immediately prior to vulcanization, the mixture is plasticized on a roll to improve flow properties. Care was taken to ensure that the mixture was warm to the touch with the hand. Strips corresponding to the cavity width in the die were cut from a web of approximately 7mm thickness to prevent the flow path from becoming too long (which has an effect on strength). The pressure of the vulcanizer was 200 bar. The test specimens were vulcanized using a preprogrammed press cycle according to the following table:
| circulation step | Value of | Heating rate [ DEGC/min] |
| Heating (. Degree. C.) | 175.0 | 50 |
| Closing(s) | 5 | |
| Hold(s) | 1 | |
| Opening(s) | 0.3 | |
| Hold(s) | 1 | |
| Closing(s) | 2 | |
| Hold(s) | 1 | |
| Opening(s) | 0.3 | |
| Closing(s) | 2 | |
| Hold (min) | T 90 +6 | |
| Opening(s) | 4 |
The vulcanization time corresponds to T 90 The value, which is determined as part of the determination of the crosslink density/reaction kinetics, is increased by one minute per millimeter of sample thickness (i.e., by six when using a vulcanization mold conforming to DIN ISO 815-1B). The cured sample was immediately removed from the curing mold to avoid uncontrolled further crosslinking. Care was taken to ensure that the sample was not damaged during removal. The use of tools to pry out the sample is only allowed if damage to the sample can be absolutely excluded. The sample was placed on a cooling table for cooling. After cooling, the protruding edges are removed. Between vulcanization and testing, the samples were stored at room temperature for at least 16 hours. The heating cabinet is preheated to the test temperature. The load exposure time was 22 hours, measured from the moment the compression set unit was put into the heating box. The test temperature was 70℃or 100 ℃. The compressive stress applied was 25% of the original thickness of the test specimen. Once the test temperature is reached inside the heating box, the central area of the heating box is immediately loaded with a compression deformation unit containing the test specimen after the application of compressive stress. After the desired test duration has ended, the compression set unit is removed from the heating box along the path of procedure a, immediately releasing the sample from any load and rapidly placing it on the cooling station. They were left to stand there for 30 minutes for recovery, and then their thickness was measured.
13. Determination of the Density of vulcanizable rubber compositions
The density of the vulcanizate was determined according to ISO 2781:2018 method A. Ethanol (96%) was used as immersion medium. The results obtained represent the average of three measurements. Between vulcanization and testing, the samples were stored at room temperature for at least 16 hours.
14. Material density of filler used
The material density of the filler was determined by helium pycnometer according to ISO 21687.
15. Determination of the OH groups available on the surface (OH group Density)
The available acidic hydroxyl groups on the surface, including phenolic OH groups and phenolic acid ester/salt groups, are determined qualitatively and quantitatively by colorimetry according to the Sipponen method. The method of Sipponen is based on the adsorption of the basic dye Azure B onto the accessible acidic hydroxyl groups of the filler surface and is described in detail in paper "Determination of surface-accessible acidic hydroxyls and surface area of lignin by cation dye adsorption" (Bioresource Technology 169 (2014) 80-87). The amount of available acidic hydroxyl groups on the surface is given in mmol/g filler.
Examples and comparative examples
The following examples and comparative examples serve to illustrate the invention but should not be construed as limiting in any way.
1. Preparation of the organic filler used according to the invention
1.1 as the organic filler of the present invention, lignin L1 obtainable by hydrothermal treatment is used.
Lignin L1 obtainable by hydrothermal treatment is prepared according to the method described in WO 2017/085278 A1 for producing lignin obtainable by hydrothermal treatment.
For this purpose, a lignin-containing liquid is provided. First, water and lignin were mixed to prepare a lignin-containing liquid having an organic dry mass content of 15%. Subsequently, lignin is mostly dissolved in lignin-containing liquids. For this purpose, the pH is adjusted by adding NaOH. The preparation of the solution was facilitated by vigorous mixing at 80℃for 3 hours. The lignin-containing liquid is subjected to a hydrothermal treatment, whereby a solid matter is obtained. In this process, the prepared solution was heated to a reaction temperature of 220℃at 2K/min and then maintained for a reaction time of 8 hours. Subsequently, cooling is performed. As a result, an aqueous suspension of the solid matter is obtained. By filtration and washing, the solid material is largely dehydrated and washed. The subsequent drying and heat treatment were carried out in a fluidized bed under nitrogen, wherein the temperature was raised to 50℃for 2.5 hours at 1.5K/min for drying, then to 190℃for 15 minutes at a rate of 1.5K/min for heat treatment, and then cooled again. The dried solid material was deagglomerated with nitrogen on a reverse jet mill to a d99 value < 10 μm (determined according to the assay method described above).
Lignin L1 obtainable by hydrothermal treatment was characterized by the method cited above as shown in table 1.1 below.
TABLE 1.1 Properties of lignin L1 obtainable by hydrothermal treatment
| Testing | Unit (B) | Lignin L1 |
| STSA | m 2 /g | 51.6 |
| BET | m 2 /g | 55.5 |
| 14 C content | Bq/g C | 0.23 |
| Oxygen content | Weight percent | 20.7 |
| Carbon content | Weight percent | 72.7 |
| Ash content | Weight percent | 3.4 |
| pH value of | ./. | 9.0 |
| Dry matter content | Weight percent | 97.9 |
| Density of material | g/cm 3 | 1.32 |
| d99 | μm | 5.51 |
| d90 | μm | 3.51 |
| d25 | μm | 0.80 |
1.2 in a similar way to the method described in 1.1, a second lignin L2 obtainable by hydrothermal treatment was prepared, which was characterized by the method cited above as shown in table 1.2 below.
TABLE 1.2 Properties of lignin L2 obtainable by hydrothermal treatment
| Testing | Unit (B) | Lignin L2 |
| STSA | m 2 /g | 44.7 |
| BET | m 2 /g | 49.1 |
| 14 C content | Bq/gC | 0.23 |
| Oxygen content | Weight percent | 22.2 |
| Carbon content | Weight percent | 71.2 |
| pH value of | ./. | 8.7 |
| Density of OH groups | [mmol/g] | 0.32 |
| Density of material | g/cm 3 | 1.33 |
| d97 | μm | 4.0 |
| d50 | μm | 1.1 |
1.3 in a similar way to the method described in 1.1, a third lignin L3 obtainable by hydrothermal treatment was prepared, which was characterized by the method cited above as shown in table 1.3 below. However, unlike the method described in 1.1, the hydrothermal treatment is performed in such a manner that the prepared lignin-containing solution is heated to a reaction temperature of 230 ℃ at 1.5K/min and then is maintained for a reaction time of 1 hour. In addition, lignin-containing liquids are modified with formaldehyde prior to hydrothermal treatment. Finally, final grinding was performed on a steam jet mill.
TABLE 1.3 Properties of lignin L3 obtainable by hydrothermal treatment
| Testing | Unit (B) | Lignin L3 |
| STSA | m 2 /g | 43.3 |
| BET | m 2 /g | 48.3 |
| pH value of | ./. | 8.8 |
| Density of OH groups | [mmol/g] | 0.14 |
| Density of material | g/cm 3 | 1.33 |
| d97 | μm | 5.6 |
| d50 | μm | 1.1 |
2. Preparation of vulcanizable rubber composition
2.1 vulcanizable rubber composition was prepared by a two stage process.
In the first stage, a rubber composition as a base mixture (masterbatch) is prepared by compounding the ingredients of the rubber composition according to the invention comprising rubber composition K and filler component F. In the second stage, the components of the crosslinking system (vulcanization system VS) are mixed.
Stage 1
EPDM was used as rubber. The preparation of the EPDM-based rubber composition was carried out in a laboratory mixer from Haake company, which has a chamber volume of 350ml. Rubber was first added and mixed at 50rpm for 1 minute. When carbon black is used as the sole filler (comparative example KV 1), 50% of the carbon black (together with 50% of the processing oil used) is added after 1 minute, and 50% of the carbon black (together with the other 50% of the processing oil used) is added after 3 minutes. In the case of partial replacement of the technical carbon black with the filler used according to the invention (according to examples KL1 and KL2 of the invention), 100% of the organic filler used according to the invention (together with 50% of the processing oil used) is added after 1 minute, and 100% of the technical carbon black (together with the other 50% of the processing oil used) is added after 3 minutes. In both cases, the remaining ingredients of the base mixture (zinc oxide and stearic acid, see table 2.1 below) were added after 3 minutes. Thereafter, the ingredients of the mixture were mixed dispersedly and distributively until the mixing process was stopped after 10 minutes, and the rubber composition was taken out of the laboratory mixer. Under these mixing conditions, the final temperature of the rubber composition reaches 125℃to 135 ℃. After the rubber composition is prepared, it is cooled (cured/stored) before proceeding to the second stage.
By the above stage 1, two rubber compositions (KL 1 and KL 1) used according to the invention were obtained, which simultaneously contained EPDM of rubber as rubber component K, and lignin L1 obtained by hydrothermal treatment of an organic filler as filler component. In addition, a comparative rubber composition (KV 1) containing EPDM of the rubber as the rubber component K and containing only the commercially available carbon black of the organic filler as the filler component (and containing no lignin L1) was obtained in this way. The specific composition of the rubber composition can be found in table 2.1 below.
Stage 2
In the second stage, the components of the crosslinking system are incorporated into the rubber composition of the first stage, thereby obtaining a vulcanizable rubber composition. Here, first, the mixtures KL1, KL2 and KV1 from the first stage were respectively dispersed again and mixed for 0 to 2 minutes. The addition of the Vulcanization System (VS) is then carried out over a period of 2 to 2.5 minutes. For this purpose, organic peroxides and polyunsaturated organic compounds as coagents are used as VS. After addition, the mixture was mixed for an additional 2.5 to 5 minutes. The final temperature is here between 90 ℃ and 100 ℃.
By the above stage 2, two vulcanizable rubber compositions (VKL 1 and VKL 1) according to the invention are obtained after the addition of the vulcanization system VS, which can then be vulcanized after the completion of stage 2. In addition, a vulcanizable comparative rubber composition (VKV 1) is obtained in this way, which can also be vulcanized after stage 2 is complete. The specific composition of the vulcanizable rubber composition can be found in table 2.1 below.
TABLE 2.1-vulcanizable rubber compositions VKL1, VKL2 (according to the invention) and VKV (comparative example)
Using a commercially available product from Arlanxeo Deutschland GmbH company4465 as EPDM (rubber of rubber component K). As zinc oxide, a commercial product ZINKOXID Weisssiegel from the company bruggemann was used. Use from->The commercial product Palmera B1805 from GmbH company acts as stearic acid. Using a catalyst from Lehmann&Voss&Commercial product LUVOMAXX BC N-550 from Co company as technical carbon black (filler of filler component F). The organic filler L1 has been described hereinabove. Using a commercially available product from Hansen und Rosenthal KG company1927 as processing oil. Commercial product Di-/from Ashland company was used>40 as peroxide. Trimethylolpropane tri (meth) acrylate (TRIM) is used as an auxiliary agent。
2.2 other vulcanizable rubber compositions VKL3, VKL4 and VKL5 (all according to the invention) and VKV2 (comparative) were prepared in a single stage process similar to the process described in 2.1.
EPDM was used as rubber. The preparation of the EPDM-based rubber composition was carried out in a laboratory mixer from Haake company, which has a chamber volume of 350ml. The rubber was first provided and compounded at 50rpm for 1 minute. When carbon black is used as sole filler or when the filler used according to the invention is used as sole filler, 50% of the filler (together with 50% of the processing oil used, 100% of the calcium oxide used, 100% of the chalk used, 100% of the PEG used and 100% of the stearic acid used) is added after 1 minute and 50% of the filler (together with the other 50% of the processing oil used) is added after 4 minutes, respectively. In the case of partial replacement of technical carbon black with filler used according to the invention, 100% of filler used according to the invention (together with 50% of the processing oil used, 100% of the calcium oxide used, 100% of the chalk used, 100% of the PEG used and 100% of the stearic acid used) is added after 1 minute, and 100% of technical carbon black (together with a further 50% of the processing oil used) is added after 4 minutes. After 6 minutes, the Vulcanization System (VS) was added. For this purpose, organic peroxides and polyunsaturated organic compounds as coagents are used as VS. Thereafter, the ingredients of the mixture were mixed dispersedly and distributively until the mixing process was stopped after 10 minutes, and the rubber composition was taken out of the laboratory mixer. Under these mixing conditions, the final temperature of the rubber composition reaches 110℃to 115 ℃.
The specific composition of these vulcanizable rubber compositions can be found in table 2.2 below.
TABLE 2 vulcanizable rubber compositions VKL3, VKL4 and VKL5 (all according to the invention) VKV (comparative example)
Using a commercially available product from Arlanxeo Deutschland GmbH company5470C as EPDM (rubber of rubber component K). The commercial product calcium carbonate from company Heinrich Heller GmbH was used +.>LB10T as chalk. Use from->The commercial product Palmera B1805 from GmbH company acts as stearic acid. Using a catalyst from Lehmann&Voss&Commercial product LUVOMAXX BC N-55 from Co company as technical carbon black (filler of filler component F). The organic filler L2 has been described hereinabove. Using a commercially available product from Hansen und Rosenthal KG company1927 as processing oil. Commercial product Di-/from Ashland company was used>40 as peroxide. Trimethylolpropane tri (meth) acrylate (TRIM) is used as an auxiliary agent. Polyethylene glycol 4000 was used as PEG. A commercially available product from Kettliz GmbH was used +.>GR 80 acts as calcium oxide.
2.3 other vulcanizable rubber compositions VKL6 and VKL7 (all according to the invention) and VKV (comparative) were prepared in a single stage mixing process similar to the process described in 2.1. However, in the case of VKV, a different Vulcanization System (VS) is used instead of peroxide (and coagent), i.e. sulfur (and three different accelerators B1, B2 and B3).
EPDM was used as rubber. The preparation of the EPDM-based rubber composition was carried out in a laboratory mixer from Haake company, which has a chamber volume of 350ml. The rubber was first provided and compounded at 50rpm for 1 minute. When peroxide was used as VS (VKL 6 and VKL 7), 50% of the filler used according to the invention (together with 50% of the process oil used, 100% of the zinc oxide used and 100% of the stearic acid used) was added thereto after 1 minute, and then the remaining 50% of the filler was added to the resulting mixture after 4 minutes (together with the other 50% of the process oil used; see table 2.3). After 6 minutes, the Vulcanization System (VS) was added. For this purpose, organic peroxides and polyunsaturated organic compounds as coagents are used as VS. Thereafter, the ingredients of the mixture were mixed dispersedly and distributively until the mixing process was stopped after 10 minutes, and the rubber composition was taken out of the laboratory mixer. Under these mixing conditions, the final temperature of the rubber composition reaches 110℃to 115 ℃. VKV3 (comparative) was produced in a similar manner. In this case, sulfur and three different accelerators B1, B2 and B3 were added in amounts after 6 minutes, instead of peroxide (and coagent). Thereafter, the ingredients of the mixture were mixed dispersedly and distributively until the mixing process was stopped after 10 minutes, and the rubber composition was taken out of the laboratory mixer. Under these mixing conditions, the final temperature of the rubber composition reached 108 ℃.
The specific composition of these vulcanizable rubber compositions can be found in table 2.3 below.
TABLE 2 3 vulcanizable rubber compositions VKL6 and VKL7 (all according to the invention) and VKV (comparative)
Using a commercially available product from Arlanxeo Deutschland GmbH company5470C as EPDM (rubber of rubber component K). Use from->The commercial product Palmera B1805 from GmbH company acts as stearic acid. The organic filler L3 has been described hereinabove. Using a commercially available product from Hansen und Rosenthal KG companyProduct(s)1927 as processing oil. Commercial product Di-/from Ashland company was used>40 as peroxide. Trimethylolpropane tri (meth) acrylate (TRIM) is used as an auxiliary agent. As zinc oxide, a commercial product ZINKOXID Weisssiegel from the company bruggemann was used. Use of +.about.Schill+Seilbacher company>SU95 acts as sulfur (cross-linker). Using product MBTS 80GE F GREEN (B1) from Vibiplast S.r.l., inc., +.f. from RheinChemie Additive, inc.>ZBEC-70 (B2) and +.sup.48 from RheinChemie Additive company>TP-50 (B3) as an accelerator.
3. Inspection and testing of vulcanizable rubber compositions and vulcanizable rubber compositions obtainable therefrom
3.1 crosslink Density and reaction kinetics
The properties of the original mixture of rubber compositions obtained after the second stage were examined. Here, the reaction kinetics and the crosslink density were measured according to the methods described above.
Tables 3.1 and 3.2 summarize the torque values for minimum and maximum (M L 、M H ) Difference delta (M) H -M L ) Time period T 10 、T 50 And T 90 The results obtained.
TABLE 3.1
The rubber compositions VKL1 and VKL2 according to the invention show comparable reaction kinetics compared to VKV1 (T 10 、T 50 、T 90 ). There is a slight deviation in the crosslink density, which represents the difference between the maximum and minimum torques, delta (M H -M L ) The unit is dNm.
TABLE 3.2
In contrast to VKV, the rubber compositions VKL3, VKL4 and VKL5 according to the invention are directed to T 10 And T 50 Shows comparable reaction kinetics and comparable crosslink density, which represents the difference between maximum and minimum torque, delta (M H -M L ) The unit is dNm. For T 90 Deviations occur.
3.2 tensile Strength, elongation at Break and Shore A hardness and compression set
The rubber composition obtained after the second stage was isothermally vulcanized at 175℃for 6 minutes (VKV, VKL1 and VKL 2). The rubber composition obtained after the single stage was vulcanized at 170℃for 11 (VKV), 14 (VKL 3 and VKL 4) or 15 (VKL 5) minutes, respectively. Tensile strength, elongation at break, modulus 100 to 300, shore A hardness and compression set were then determined according to the methods described above.
Tables 3.3 and 3.4 summarize the results obtained.
TABLE 3.3
The tensile-elongation behavior shows that the rubber compositions VKL1 and VKL2 according to the invention have a low tensile strength but a significantly increased elongation at break compared to VKV1. In the case of peroxide crosslinking, the elongation at break depends on the crosslinking density and therefore on the amount of crosslinking component used. It can be seen from table 3.1 that the crosslink density was relatively low. It is noted that if the crosslink density is adjusted, then VKL2 may achieve higher modulus values at low elongation than VKV1. The low elongation range is particularly important for rubber articles, as these elongations occur during use. However, the industrial rubber data is characterized in that, although the crosslink density of the rubber compounds VKL1 and VKL2 containing the organic filler L1 is relatively low, the compression set values at 70 ℃ and 100 ℃ are low as compared with the composition VKV1 having a higher crosslink density.
The use of L1 achieves improved compression set (lower) with the same amounts of peroxide and coagent (VKV and VKL 1) while a significantly higher elongation at break at the same hardness (shore a). Even with a slight increase in peroxide level (VKL 2), a further improvement in compression set was shown, but the elongation at break was still significantly higher than VKV1. The tensile elongation and compression set can be flexibly adjusted by using the rubber composition containing L1. Another advantage of the rubber compositions VKL1 and VKL2 is that the stress value can be set up to about 200% (see modulus 100 of VKL 2) at low elongation and at higher elongation at break than in the case of VKV. This improves the sealing function.
The results shown in table 3.3 are graphically presented in fig. 1, 2, 3 and 4. The measured stretch-elongation behavior is summarized in fig. 1. Fig. 2 summarizes the stress values measured at 100%, 200% and 300% elongation. Fig. 3 summarizes the measured values of tensile strength, elongation at break and shore a hardness. FIG. 4 outlines the measured compression set at various temperatures.
TABLE 3.4
The tensile elongation behavior here also shows that the rubber compositions VKL3, VKL4 and VKL5 according to the invention have a slightly lower tensile strength than VKV, but advantageously have a significantly increased elongation at break. The data also show in particular that the compression set values at 70℃are advantageously lower for the rubber mixtures VKL4 and VKL5 comprising the organic filler L2 compared with the composition VKV.
3.3 comparing compression set at peroxide crosslinking with Sulfur crosslinking (VKL 6 and VKL7 and VKV 3)
The rubber compositions VKL6 and VKL7 and VKV obtained after the single stage were isothermally vulcanized at 170 ℃ for 8.5 minutes (VKL 6 and VKL 7) and 13 minutes (VKV 3), respectively. Compression set was then measured according to the method described above for 22 hours at 70 ℃ and 22 hours at 100 ℃. The results are shown in Table 3.5.
TABLE 3.5
The data comparison shows in particular that the compression set values at 70℃and 100℃of the rubber mixtures VKL6 and VKL7 crosslinked by peroxide and containing the organic filler L3 are advantageously lower than in the case of the comparative compound VKV crosslinked by sulfur.
Claims (16)
1. A vulcanizable rubber composition comprising a rubber component K, a filler component F and a vulcanization system VS, wherein,
the vulcanization system VS comprises at least one peroxide,
the rubber component K comprises at least one rubber which can be crosslinked by at least one peroxide of the vulcanization system VS, and
the filler component F comprises at least one organic filler, which 14 C content is in the range of 0.20 to 0.45Bq/g carbon, and d99 value<25.0μm。
2. Rubber composition according to claim 1, wherein the organic filler has a d99 value of <20.0 μm, preferably <15.0 μm, particularly preferably <10 μm, more particularly preferably <9.0 μm, more preferably <8.0 μm, more preferably <7.0 μm, most preferably <6.0 μm, preferably determined by laser diffraction according to ISO 13320:2009, respectively.
3. Rubber composition according to claim 1 or 2, characterized in that the organic filler has a d90 value <7.0 μm, preferably <6.0 μm, particularly preferably <5.0 μm, and/or a d25 value <3.0 μm, preferably <2.0 μm, particularly preferably <1.0 μm, preferably determined by laser diffraction according to ISO 13320:2009, respectively.
4. The rubber composition as claimed in any one or more of the preceding claims, wherein the BET surface area of the organic filler is in the range of from 10 to 150m 2 In the range from 20 to 120m, particularly preferably in the range from/g 2 In the range of from 30 to 110m, even more preferably 2 In the range of from 40 to 100m 2 In the range of/g, most preferably 40m 2 /g to < 100m 2 In the range of/g.
5. Rubber composition according to any one or more of the preceding claims, characterized in that the oxygen content of the organic filler ranges from >8 to <30 wt%, preferably >10 to <30 wt%, particularly preferably >15 to <30 wt%, very particularly preferably >20 to <30 wt%, respectively, with respect to the ashless and anhydrous filler.
6. Rubber composition according to any one or more of the preceding claims, characterized in that the carbon content of the organic filler ranges from >60 to <90 wt%, preferably >60 to <85 wt%, particularly preferably >60 to <82 wt%, very particularly preferably >60 to <80 wt%, respectively, with respect to the ashless and anhydrous filler.
7. Rubber composition according to any one or more of the preceding claims, characterized in that it comprises at least one organic filler in an amount of 10 to 150phr, particularly preferably 15 to 130phr, more particularly preferably 20 to 120phr, even more preferably 30 to 100phr, most preferably 40 to 80 phr.
8. Rubber composition according to any one or more of the preceding claims, wherein the organic filler is a lignin-based filler, wherein preferably at least the lignin and even more preferably the organic filler itself is at least partly present in a form obtainable by a hydrothermal treatment, and particularly preferably obtainable by a hydrothermal treatment, wherein the hydrothermal treatment is preferably carried out at a temperature of >100 ℃ to <300 ℃, particularly preferably >150 ℃ to <250 ℃.
9. Rubber composition according to any one or more of the preceding claims, characterized in that the at least one peroxide of the vulcanization system VS comprises, in particular represents, at least one organic peroxide, preferably an organic peroxide selected from the group consisting of dialkyl peroxides, alkylaryl peroxides, diaryl peroxides, alkyl peresters, aryl peresters, diacyl peroxides, polyvalent peroxides and mixtures thereof, particularly preferably an organic peroxide selected from the group consisting of di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, dicumyl peroxide, tert-butylcumene peroxide, tert-butyl perbenzoate, dibenzoyl peroxide, 1-di (tert-butylperoxy) -3, 5-trimethylcyclohexane and bis- (tert-butylperoxy) -diisopropylbenzene and mixtures thereof.
10. The rubber composition as claimed in one or more of the preceding claims, characterized in that at least one rubber of the rubber component K is selected from the group consisting of rubbers which do not have carbon-carbon double bonds in their main chain, preferably do not have any carbon-carbon double bonds in their entire structure, particularly preferably from the group consisting of: HNBR (hydrated acrylonitrile-butadiene rubber), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), acrylate-ethylene rubber (AEM), ethylene-vinyl acetate rubber (EVM), chlorinated rubber, in particular chlorinated polyethylene (CM), silicone rubber (Q), chlorosulfonated polyethylene (CSM), fluororubber elastomer (FPM), and mixtures thereof.
11. Rubber composition according to any one or more of the preceding claims, characterized in that it comprises at least one at least monounsaturated and preferably polyunsaturated organic compound, which is preferably part of the vulcanization system VS of the rubber composition and which is preferably selected from the group consisting of: di (meth) acrylates, bismaleimides, triallyl compounds and unsaturated polymers such as 1, 2-polybutadiene and trans-polyoctene rubbers, preferably having a number average molecular weight (Mn) of <10,000g/mol, particularly preferably <5,000g/mol, more particularly preferably <2,500g/mol, still more preferably <1,500g/mol, in particular <1,000g/mol, most preferably <500g/mol, respectively, and mixtures thereof; and is particularly preferably selected from the group consisting of: ethylene glycol di (meth) acrylate (EDMA), trimethylolpropane tri (meth) acrylate (TRIM), N, N' -m-phenylene bismaleimide (MPBM), diallyl terephthalate (DATP), triallyl cyanurate (TAC), 1, 4-butanediol di (meth) acrylate, and mixtures thereof.
12. A kit of parts comprising in spatially separated form:
rubber composition as defined in any one or more of claims 1 to 11 as part (a) comprising at least the above-mentioned rubber component K and at least the filler component F, respectively, however, wherein part (a) does not comprise at least one peroxide of the vulcanization system VS as defined in any one or more of claims 1 to 11; and
vulcanization system VS as defined in any one or more of claims 1 to 11 as part (B) comprising at least one peroxide.
13. Vulcanized rubber composition obtainable by vulcanizing the vulcanizable rubber composition as defined in any one or more of claims 1 to 11 or by vulcanizing a vulcanizable rubber composition obtainable by combining and mixing the two parts (a) and (B) of the kit of parts as defined in claim 12.
14. Use of the vulcanizable rubber composition according to any one or more of claims 1 to 11, the kit of parts according to claim 12 or the vulcanized rubber composition according to claim 13 for the production of industrial rubber articles, preferably for the production of industrial rubber articles with sealing function, in particular seals, profiles, dampers, rings and hoses.
15. Industrial rubber article produced by using the vulcanizable rubber composition of any one or more of claims 1 to 11, the kit of parts of claim 12 or the vulcanized rubber composition of claim 13, preferably having a sealing function, in particular a seal, profile, damper, ring or hose.
16. Use of an organic filler according to any one or more of claims 1 to 6 and 8 for increasing the elongation at break and at the same time reducing the compression set of a vulcanized rubber composition obtainable by vulcanization of at least one peroxide, wherein the vulcanizable rubber composition for said purpose comprises, in addition to said at least one peroxide and said organic filler, at least one rubber capable of being crosslinked by at least one peroxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| EP21192648.0 | 2021-08-23 | ||
| EP21199589 | 2021-09-28 | ||
| EP21199589.9 | 2021-09-28 | ||
| PCT/EP2022/073490 WO2023025808A1 (en) | 2021-08-23 | 2022-08-23 | Peroxide-crosslinkable rubber compositions containing organic fillers |
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