Vulcanization-activated composition, method for preparing same, and use thereof

Abstract

The present invention relates to a process for preparing a vulcanization-activated composition comprising at least one of the following steps: mixing at least 5 wt% and at most 75 wt% of particles of an oxygen-containing zinc compound with at least 1 wt% and at most 75 wt% of at least one vegetable oil or at least one vegetable oil derivative, thereby forming a composition (A); wherein the vegetable oil or vegetable oil derivative comprises, based on the total weight of the vegetable oil or vegetable oil derivative: at least 8% by weight of at least one fatty acid residue; the fatty acid residues comprise at least two unsaturations.

Description

Technical Field

[0001] The present invention relates to the field of processes for preparing sulfur-activating compositions based on vegetable oils or vegetable oil derivatives. Background Art

[0002] Vulcanization is a cross-linking reaction that occurs when a vulcanizable polymer is exposed to a vulcanizing agent (usually sulfur) and heat, which is necessary to establish chemical bonds between the vulcanizing agent and the reactive sites of the polymer chains, thereby forming a three-dimensional network.

[0003] Once a polymer has been vulcanized, it possesses specific mechanical and elastic properties that make it suitable for a variety of applications, such as tires and the like.

[0004] In order to activate the vulcanization reaction between the polymer and the vulcanizing agent, it is known to use a vulcanization activator (such as a divalent metal oxide compound, etc.), and the most commonly used of these vulcanization activators is zinc oxide ZnO.

[0005] Vulcanization activation compositions are known to those skilled in the art. Mention may be made of EP 3896129 A1, which discloses a composition comprising 20 to 80% by weight of at least one vulcanization activator; 10 to 40% by weight of at least one wax selected from the group consisting of paraffin waxes, microcrystalline waxes, polyolefin waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, their derivatives and mixtures thereof; and 10 to 40% by weight of at least one inorganic filler or carbon black.

[0006] When these compositions are used in a vulcanization process, for example, in the vulcanization of rubber, it will be found that the ZnO and other compounds in the activation composition are at least partially (or entirely) present in the vulcanized rubber inside. Unfortunately, known ZnO migrates out from rubber and pollutes the environment. For example, if the vulcanized rubber is in contact with water for a long time, this situation will occur. It has been observed that at least a portion of ZnO can migrate out from rubber and pollute the water in direct contact with it. Known ZnO is ecotoxic. Therefore, it is necessary to develop a vulcanization activation composition that reduces the ZnO amount released into the environment by the vulcanized rubber or at least only releases a spot of ZnO.

[0007] In addition, commonly used waxes (such as paraffin wax, microcrystalline wax, polyolefin wax and Fischer-Tropsch wax etc.) are synthetic waxes. Generally speaking, the industry is seeking to reduce the ecological footprint of its production method. Therefore, it is necessary to reduce the use of synthetic materials in the vulcanization activation composition. Summary of the Invention

[0008] Surprisingly, the inventors have found that it is possible with the composition according to the invention to solve, among other things, the problems identified above.

[0009] The present invention relates to a method for preparing a vulcanization activation composition [hereinafter referred to as composition (A)], comprising at least one mixing step of:

[0010] at least 5% and at most 95% by weight, preferably at least 5% and at most 75% by weight, of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and

[0011] at least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative, thereby forming composition (A), said % by weight being based on the total weight of said composition (A);

[0012] Wherein, the vegetable oil or vegetable oil derivative contains at least 8 weight % of at least one fatty acid residue based on the total weight of the vegetable oil or vegetable oil derivative; and the fatty acid residue contains at least two unsaturations.

[0013] The present invention also relates to a vulcanization activation composition obtained by the above method.

[0014] The present invention also relates to the use of the vulcanization activation composition obtained by the above method in a vulcanization method. DETAILED DESCRIPTION

[0015] According to the present invention, the term "comprising" is inclusive and open-ended and does not exclude the addition of unlisted elements, compositions or method steps.

[0016] In the context of the present invention, if it is stated that an element or component is selected from a list of named elements or components, it should be understood that the element or component can also be any of the elements or components named in the list, or can also be selected from a group consisting of two or more explicitly listed elements or components.

[0017] Composition (A)

[0018] As described above, the present invention relates to an activating composition [composition (A)] for use in a vulcanization process.

[0019] Vulcanization methods are known to those skilled in the art. Generally speaking, vulcanization is a chemical crosslinking reaction that occurs when a vulcanizable polymer (such as natural rubber) is exposed to a vulcanizing agent (usually sulfur) and heat.

[0020] Preferably, when less than 10 parts by weight, more preferably less than 8 parts by weight, still more preferably less than 6 parts by weight of the composition (A) relative to 100 parts by weight of the polymer (V) is contained in the composition (C), the composition (A) is suitable for use in a vulcanization method of a vulcanizable composition comprising a polymer (V) [composition (C)].

[0021] The mixing

[0022] The method according to the invention comprises at least one mixing step of:

[0023] Based on the total weight of the composition (A)

[0024] at least 5% to a maximum of 95% by weight, preferably at least 5% to a maximum of 75% by weight, of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and

[0025] • At least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative, thereby forming composition (A).

[0026] Described mixing can be carried out by any equipment (mean) known to those skilled in the art for producing vulcanization activation composition.Specifically, described mixing can be for example carried out in mixer, stirrer or any other machine for mixing described compound (OZ) and vegetable oil or vegetable oil derivative.

[0027] Preferably, the mixing is carried out at a temperature and for a period of time that prevents a substantial portion of the compound (OZ) and the vegetable oil or vegetable oil derivative from reacting or degrading, while making it possible to obtain a homogeneous mixture of the compound (OZ) and the vegetable oil or the vegetable oil derivative. The temperature and the mixing period prevent, for example, a substantial portion of the unsaturations in the vegetable oil or vegetable oil derivative from reacting or degrading.

[0028] Preferably, mixing occurs at a temperature of at most 100° C., more preferably at most 80° C., even more preferably at most 70° C., even more preferably at most 60° C., even more preferably at most 50° C., even more preferably at most 40° C. This has the effect of reducing or avoiding reactions between the natural oil and the compound (OZ), such as the formation of a complex between zinc and fatty acids, or avoiding degradation reactions of the vegetable oil or the vegetable oil derivative.

[0029] The mixing may be performed at a temperature of preferably at least 10°C, more preferably at least 15°C, more preferably at least 17°C, more preferably at least 20°C.

[0030] In a preferred embodiment, the mixing is carried out at a temperature of at least 10°C and at most 40°C, more preferably at least 15°C and at most 40°C, more preferably at least 17°C and at most 40°C, more preferably at least 20°C and at most 40°C.

[0031] Preferably, the mixing is performed for no more than 30 minutes, or no more than 20 minutes, or no more than 10 minutes, or no more than 5 minutes, or no more than 1 minute, or no more than 30 seconds.

[0032] Preferably, during said mixing process, the temperature is controlled by at least one thermocouple.

[0033] Depending on the amount of the compound (OZ) and the vegetable oil or vegetable oil derivative, the compound (A) may be a pulverulent composition of particles of the compound (OZ) at least partially coated with the vegetable oil or vegetable oil derivative, or the composition (A) may be a pasty or liquid composition.

[0034] In a preferred embodiment, the composition (A) is a powder composition of at least partially coated OZ compound particles, and the method comprises at least one mixing step of:

[0035] Based on the total weight of the composition (A)

[0036] 20% and up to 60% by weight of particles of compound (OZ), and

[0037] • At least 1% and at most 35% by weight of at least one vegetable oil or at least one vegetable oil derivative, forming the composition (A).

[0038] In this embodiment, the D50 of the composition (A) is at least 1 μm, preferably at least 2 μm, more preferably at least 3 μm. Preferably, the D50 of the composition (A) is at most 20 μm, more preferably at most 15 μm.

[0039] In this embodiment, the D50 of the composition (A) is preferably at least 1 μm and at most 20 μm, more preferably at least 2 μm and at most 15 μm.

[0040] In a preferred embodiment, up to 70% by weight, preferably up to 68% by weight, of particles of the compound (OZ), based on the total weight of the composition (A), are admixed in the mixing step.

[0041] Preferably, at least 25 wt.-%, more preferably at least 30 wt.-%, based on the total weight of said composition (A) are mixed in the mixing step.

[0042] In another preferred embodiment, the composition (A) is a pasty or liquid composition, and the method comprises at least one mixing step of:

[0043] Based on the total weight of the composition (A)

[0044] at least 20% and at most 60% by weight of particles of compound (OZ), and

[0045] • At least 15% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative, forming the composition (A).

[0046] In this embodiment, up to 50% by weight, preferably up to 40% by weight, of particles of compound (OZ), based on the total weight of the composition (A), are admixed in the mixing step.

[0047] In this same embodiment, preferably at most 65 wt.-%, more preferably at most 55 wt.-%, even more preferably at most 45 wt.-%, even more preferably at most 40 wt.-%, based on the total weight of said composition (A) are mixed in the mixing step.

[0048] In this same embodiment, at least 20% by weight, more preferably at least 25% by weight, based on the total weight of said composition (A), of said at least one vegetable oil or said at least one vegetable oil derivative are mixed in the mixing step.

[0049] Compound (OZ)

[0050] In the context of the present invention, an "oxygen-containing zinc compound" can be defined as a compound containing zinc and oxygen atoms. Specifically, the compound (OZ) is a vulcanization activator. Specifically, the oxygen-containing zinc compound can be selected from the group consisting of zinc oxide, zinc hydroxide, zinc carbonate, zinc hydroxycarbonate, and mixtures or derivatives thereof. Preferably, the oxygen-containing zinc compound is zinc oxide (ZnO).

[0051] Preferably, the method comprises mixing at least 10 wt.-% of the compound (OZ), more preferably at least 12 wt.-%, more preferably at least 15 wt.-%, more preferably at least 20 wt.-%, more preferably at least 25 wt.-%, more preferably at least 30 wt.-%, more preferably at least 40 wt.-%, more preferably at least 50 wt.-%, more preferably at least 60 wt.-% of the compound (OZ), based on the total weight of the composition (A).

[0052] Preferably, the process comprises mixing at most 70 wt.-% of said compound (OZ), more preferably at most 65 wt.-%, more preferably at most 55 wt.-%, more preferably at most 50 wt.-%, more preferably at most 45 wt.-%, more preferably at most 40 wt.-%, more preferably at most 35 wt.-% of said compound (OZ), based on the total weight of said composition (A).

[0053] In a preferred embodiment, the mixture comprises at least 10% by weight and at most 70% by weight, preferably at least 12% by weight and at most 65% by weight, more preferably at least 15% by weight and at most 60% by weight, more preferably at least 15% by weight and at most 55% by weight, more preferably at least 15% by weight and at most 50% by weight of compound (OZ), based on the total weight of the composition (A).

[0054] Preferably, the D50 of compound (OZ) is at least 100 nm, more preferably at least 200 nm, even more preferably at least 300 nm, even more preferably at least 400 nm, even more preferably at least 500 nm, even more preferably at least 600 nm, even more preferably at least 700 nm, even more preferably at least 800 nm, even more preferably at least 1 μm, even more preferably at least 2 μm.

[0055] If desired, the D50 of the compound (OZ) may be at most 500 μm, or at most 100 μm, or at most 20 μm, or at most 15 μm.

[0056] In a preferred embodiment, the D50 of the compound (OZ) is at least 100 nm and at most 500 μm, preferably at least 300 nm and at most 100 μm, more preferably at least 500 nm and at most 20 μm, even more preferably at least 1 μm and at most 20 μm.

[0057] In the context of the present invention, the symbol D x Denotes the diameter in μm relative to which X volume % of the total volume of particles measured consists of smaller particles. Within the framework of the present invention, all D50 particle size measurements are laser particle size measurements performed in water.

[0058] Within the framework of the present invention, all BET specific surface area values ​​for any product (such as coated particles or any given compound) are measured by adsorption manometry of a nitrogen and helium mixture after degassing under vacuum conditions at 50° C. for at least 1 hour and calculated according to the BET method.

[0059] If desired, the OZ compound may have at least 1 m 2 / g, preferably at least 2m 2 / g of BET surface area.

[0060] If desired, the OZ compound may have a maximum of 100 m 2 / g, preferably up to 60m 2 / g of BET surface area.

[0061] In a preferred embodiment, the OZ compound has at least 1 m 2 / g and up to 100m 2 / g, preferably at least 2m 2 / g and up to 60m 2 / g of BET surface area.

[0062] If desired, the OZ compound has a D50 of at least 0.25 μm, preferably at least 3 μm, more preferably at least 5 μm, as measured by a laser particle size analyzer in methanol after ultrasonic treatment for 3 minutes.

[0063] If necessary, the OZ compound has a D50 of at most 5000 μm, preferably at most 4000 μm, more preferably at most 3000 μm, at most 100 μm, at most 50 μm, at most 10 μm, at most 7 μm, as measured by a laser particle size analyzer in water after ultrasonic treatment for 3 minutes.

[0064] In one embodiment, the OZ compound has a D50 of at least 0.25 μm and at most 4000 μm, at least 3 μm and at most 3000 μm, more preferably at least 5 μm and at most 100 μm, even more preferably at least 5 μm and at most 50 μm, even more preferably at least 5 μm and at most 10 μm, even more preferably at least 5 μm and at most 7 μm, as measured by a laser particle size analyzer in methanol after ultrasonic treatment for 3 minutes.

[0065] The natural oil

[0066] In the context of the present invention, the term "vegetable oil" has the ordinary meaning known to those skilled in the art. Generally speaking, a vegetable oil is an oil obtained from a plant or a part of a plant, such as a seed. Vegetable oils that can be used within the framework of the present invention include, for example, but are not limited to: linseed oil, walnut oil, sunflower oil, corn oil, avocado oil, hemp oil, grapeseed oil, olive oil, peanut oil, rice oil, sesame oil, soybean oil, rapeseed oil, safflower oil, wheat germ oil, and mixtures thereof.

[0067] In the context of the present invention, the term "vegetable oil derivative" encompasses, for example, at least partially polymerized vegetable oils, partially polymerized oils, dehydrogenated vegetable oils, vegetable oils that have been subjected to an aging treatment, a thermal treatment or a chemical treatment, and mixtures thereof. Thus, vegetable oil derivatives may include stand oils, crude oils and boiled oils.

[0068] Examples of vegetable oil derivatives include, but are not limited to, aged linseed oil, partially polymerized linseed oil, cooked linseed oil, dehydrogenated palm oil, and mixtures thereof.

[0069] Examples of vegetable oil derivatives include linseed oil, walnut oil, sunflower oil, corn oil, avocado oil, hemp oil, and grapeseed oil, olive oil, peanut oil, rice oil, sesame oil, soybean oil, rapeseed oil, safflower oil, wheat germ oil, palm oil, and mixtures thereof.

[0070] The use of vegetable oil or a vegetable oil derivative is advantageous because it is a material of biological origin.

[0071] According to the invention, the vegetable oil or vegetable oil derivative comprises at least 8% by weight, based on the total weight of the vegetable oil or vegetable oil derivative, of at least one fatty acid residue.

[0072] In the context of the present invention, the term "fatty acid residue" has the ordinary meaning known to those skilled in the art. For example, the fatty acid residue may form part of a fat and be at least partially in the form of a triglyceride, a diglyceride and / or a monoglyceride. The fatty acid residue may also be at least partially in the form of a free fatty acid, i.e., not in the form of a glyceride. The free fatty acids may be in a protonated form or in an at least partially deprotonated form.

[0073] The fatty acid residues may be linear or branched.

[0074] Examples of fatty acid residues that can be used include, but are not limited to, linoleic acid, α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid residues.

[0075] According to the present invention, the fatty acid residue comprises at least 2 degrees of unsaturation, preferably at least 3 degrees of unsaturation.

[0076] Surprisingly, the inventors have noticed that the use of the composition (A) of the invention in a vulcanization process allows reducing or in some cases avoiding the release of zinc from the compound (OZ) (or zinc) to the outside of the vulcanized polymer.

[0077] Be not bound by any theory, the inventor believes that at least some of the unsaturation degrees that comprise in described vegetables oil or described vegetables oil derivative will react in the sulfurization process.Therefore, at least some unsaturated fatty acid residues will be incorporated in the sulfurized polymer by crosslinking.When fatty acid residue was with at least two unsaturation degrees, this incorporation was more important or more likely.In addition, after the sulfurization, some unsaturated fatty acid residues seem no longer to exist with the form of glyceride, but exist with the form of fatty acid, and the carboxylic acid functional group (with the form of carboxylate) of this fatty acid is at least partially and zinc complexing.The complexing of the zinc of the fatty acid residue that is caught in the sulfurized polymer matrix will make at least part or all of the zinc in the compound (OZ) be retained.

[0078] Additionally, surprisingly, the properties of the vulcanized polymers were not significantly affected by the presence of vegetable oil.

[0079] Furthermore, the inventors have noticed that the presence of vegetable oil in the composition according to the invention advantageously has a lower angle of repose compared to compositions comprising only OZ compounds, which indicates that the composition flows in a fluid manner.

[0080] The degree of unsaturation of the fatty acid residues may be cis or trans.

[0081] Preferably, the unsaturation of the fatty acid residues is separated by at least one -CH2- functional group, more preferably by only one -CH2- functional group.

[0082] Preferably, the fatty acid residue is C12-C30, more preferably C14-C28, more preferably C14-C26, even more preferably C14-C24, more preferably C16-C24, more preferably C16-C22, more preferably C16-C20, even more preferably C18.

[0083] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least 15 wt.-% of said fatty acid residues, more preferably at least 20 wt.-% of said fatty acid residues, preferably at least 25 wt.-% of said fatty acid residues, more preferably at least 30 wt.-% of said fatty acid residues, more preferably at least 35 wt.-% of said fatty acid residues, even more preferably at least 40 wt.-% of said fatty acid residues, even more preferably at least 50 wt.-% of said fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0084] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at most 80 wt.-% of said fatty acid residues, more preferably at most 75 wt.-% of said fatty acid residues, even more preferably at most 70 wt.-% of said fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0085] In a preferred embodiment, the vegetable oil and / or the vegetable oil derivative comprises at least 15 wt.-% and at most 80 wt.-% of said fatty acid residues, more preferably at least 20 wt.-% and at most 80 wt.-% of said fatty acid residues, even more preferably at least 25 wt.-% and at most 75 wt.-% of said fatty acid residues, more preferably at least 30 wt.-% and at most 70 wt.-% of said fatty acid residues, more preferably at least 35 wt.-% and at most 70 wt.-% of said fatty acid residues, even more preferably at least 40 wt.-% and at most 70 wt.-% of said fatty acid residues, even more preferably at least 50 wt.-% and at most 70 wt.-% of said fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0086] In a preferred embodiment, the vegetable oil and / or the vegetable oil derivative comprises a fatty acid residue (A) containing two degrees of unsaturation and a fatty acid residue (B) containing at least three degrees of unsaturation. The fatty acid residue (A) may be a linoleic acid residue. The fatty acid residue (B) may be a residue of α-linolenic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosapentaenoic acid, or docosahexaenoic acid.

[0087] Preferably, the unsaturations of the fatty acid residues (A) and (B) are separated by at least one -CH2- functional group, more preferably by only one -CH2- functional group.

[0088] Preferably, each fatty acid residue is a C12-C30 residue, more preferably C14-C28, more preferably C14-C26, even more preferably C14-C24, more preferably C16-C24, more preferably C16-C22, more preferably C16-C20, even more preferably C18.

[0089] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least 8 wt.-%, more preferably at least 10 wt.-% of the fatty acid residues (A), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0090] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at most 30 wt.-%, more preferably at most 25 wt.-%, even more preferably at most 20 wt.-% of said fatty acid residues (A), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0091] In a preferred embodiment, the vegetable oil and / or the vegetable oil derivative comprises at least 8 wt.-% and at most 30 wt.-%, more preferably at least 10 wt.-% and at most 25 wt.-%, even more preferably at least 10 wt.-% and at most 20 wt.-% of said fatty acid residues (A), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0092] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least 30 wt.-%, more preferably at least 35 wt.-%, even more preferably at least 40 wt.-% of said fatty acid residues (B), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0093] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at most 75 wt.-%, more preferably at most 70 wt.-%, even more preferably at most 65 wt.-% of said fatty acid residues (B), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0094] In a preferred embodiment, the vegetable oil and / or the vegetable oil derivative comprises at least 30 wt.-% and at most 75 wt.-%, more preferably at least 35 wt.-% and at most 70 wt.-%, even more preferably at least 10 wt.-% and at most 65 wt.-% of said fatty acid residues (B), based on the total weight of the vegetable oil or the vegetable oil derivative.

[0095] In a preferred embodiment, the vegetable oil and / or the vegetable oil derivative comprises at least 10 wt.-% and at most 20 wt.-% of the fatty acid residues (A), and at least 10 wt.-% and at most 65 wt.-% of the fatty acid residues (B), based on the total weight of the vegetable oil or the vegetable oil derivative; the fatty acid residue (A) is a C16-C22 residue containing at least two unsaturations separated by -CH2- groups; the fatty acid residue (B) is a C16-C22 residue containing at least three unsaturations separated by -CH2- groups.

[0096] In an even more preferred embodiment, the vegetable oil is linseed oil, comprising at least 10% and at most 20% by weight of the fatty acid residues (A), and at least 10% and at most 65% by weight of the fatty acid residues (B); the fatty acid (A) is linoleic acid, and the fatty acid (B) is α-linolenic acid.

[0097] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least one fatty acid residue containing unsaturation.

[0098] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least 5 wt.-%, more preferably at least 10 wt.-%, even more preferably at least 12 wt.-% of the unsaturation-containing fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0099] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at most 35 wt.-%, more preferably at most 30 wt.-%, even more preferably at most 20 wt.-% of the unsaturation-containing fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0100] Preferably, the vegetable oil and / or the vegetable oil derivative comprises at least 5 wt.-% and at most 35 wt.-%, more preferably at least 10 wt.-% and at most 30 wt.-%, even more preferably at least 12 wt.-% and at most 20 wt.-% of the unsaturation-containing fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

[0101] Preferably, the unsaturation-containing fatty acid residue is an oleic acid residue.

[0102] Preferably, the vegetable oil and / or the vegetable oil derivative further comprises other saturated fatty acid residues, such as palmitic acid and stearic acid residues.

[0103] Preferably, the vegetable oil and / or the vegetable oil derivative has an iodine value measured according to standard ISO 3961 of at least 160 g I2, preferably at least 170 g I2, more preferably at least 175 g I2 per gram of the vegetable oil or the vegetable oil derivative.

[0104] Preferably, the vegetable oil and / or the vegetable oil derivative has an acid value measured according to standard ISO 660 of at most 1 mg KOH, more preferably at most 2 mg KOH, more preferably at most 4 mg KOH per gram of the vegetable oil or the vegetable oil derivative.

[0105] Preferably, the viscosity of the vegetable oil and / or the vegetable oil derivative measured at 37.8°C according to the ASTM D445 standard is at least 35 mPa.s, more preferably at least 40 mPa.s. Preferably, the viscosity of the vegetable oil and / or the vegetable oil derivative measured at 37.8°C according to the ASTM D445 standard is at most 65 mPa.s, more preferably at most 60 mPa.s, more preferably at most 55 mPa.s. In a preferred embodiment, the viscosity of the vegetable oil and / or the vegetable oil derivative measured at 37.8°C according to the ASTM D445 standard is at least 35 mPa.s and at most 65 mPa.s, more preferably at least 40 mPa.s and at most 60 mPa.s, more preferably at least 40 mPa.s and at most 55 mPa.s.

[0106] Preferably, the vegetable oil and / or the vegetable oil derivative has a saponification value of at most 200 mg KOH, more preferably at most 195 mg KOH, per gram of the vegetable oil or the vegetable oil derivative, measured according to standard ISO 3657. Preferably, the vegetable oil and / or the vegetable oil derivative has a saponification value of at least 175 mg KOH, more preferably at least 170 mg KOH, per gram of the vegetable oil or the vegetable oil derivative, measured according to standard ISO 3657. Preferably, the vegetable oil and / or the vegetable oil derivative has a saponification value of at least 175 mg KOH and at most 200 mg KOH, more preferably at least 170 mg KOH and at most 195 mg KOH, per gram of the vegetable oil or the vegetable oil derivative, measured according to standard ISO 3657.

[0107] magnesium oxide

[0108] Preferably, the mixing step further comprises mixing at least 0.1 wt% and at most 75 wt% of magnesium oxide based on the total weight of the composition (A), thereby forming composition (A).

[0109] Therefore, preferably, the method according to the invention comprises at least one mixing step of:

[0110] Based on the total weight of the composition (A)

[0111] 5% by weight and up to 75% by weight of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and

[0112] at least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative,

[0113] • At least 0.1 wt% and at most 75 wt% magnesium oxide, thereby forming composition (A).

[0114] Preferably, at least 0.5 wt. %, more preferably at least 0.8 wt. %, even more preferably at least 1 wt. % of magnesium oxide is mixed in the mixing step.

[0115] If desired, at least 5 wt%, or at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt% of magnesium oxide is mixed in the mixing step.

[0116] Preferably, at most 75 wt.-%, more preferably at most 70 wt.-%, even more preferably at most 60 wt.-%, even more preferably at most 50 wt.-%, even more preferably at most 40 wt.-%, even more preferably at most 30 wt.-%, even more preferably at most 20 wt.-%, even more preferably at most 10 wt.-% of magnesium oxide is mixed in the mixing step.

[0117] Preferably, at least 0.5 wt% and at most 7 wt% magnesium oxide is mixed in the mixing step, more preferably at least 0.5 wt% and at most 5 wt%, even more preferably at least 1 wt% and at most 3 wt%.

[0118] calcium carbonate

[0119] Preferably, the mixing step further comprises mixing at least 10 wt% and at most 80 wt% of at least one inorganic base, based on the total weight of the composition (A), thereby forming composition (A).

[0120] The inventors have noticed that the compositions according to the invention in which an inorganic base is present advantageously have a low angle of repose, which indicates that the composition flows fluidly.

[0121] Preferably, the composition according to the invention has an angle of repose of at most 42°, more preferably at most 40°, even more preferably at most 39°, even more preferably at most 38°, even more preferably at most 37°.

[0122] Therefore, preferably, the method according to the invention comprises at least one mixing step of:

[0123] Based on the total weight of the composition (A),

[0124] at least 5% by weight and at most 75% by weight of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and

[0125] at least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative,

[0126] • At least 10% and at most 80% by weight of at least one inorganic base, thereby forming composition (A).

[0127] In a preferred embodiment, the method according to the invention comprises at least one mixing step of:

[0128] Based on the total weight of the composition (A),

[0129] at least 5% by weight and at most 75% by weight of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and

[0130] at least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative,

[0131] at least 10% by weight and at most 80% by weight of at least one inorganic base,

[0132] • At least 0.1 wt% and at most 75 wt% magnesium oxide, thereby forming composition (A).

[0133] If desired, the at least one inorganic base comprises at least one alkali metal or alkaline earth metal cation M and at least one anion A, the alkali metal or alkaline earth metal cation M preferably being selected from the group consisting of: Li + 、Na + , K + , Ca 2+ Mg 2+ and combinations thereof, the at least one anion A is preferably selected from the group consisting of: 2- OH - 、CO3 2- 、HCO3 - and combinations thereof.

[0134] Preferably, the at least one inorganic base has the formula [M] x [A] y , wherein M is an alkali metal or alkaline earth metal cation, preferably selected from the group consisting of: Li + 、Na + , K + , Ca 2+ Mg 2+ and combinations thereof, and A is an anion, preferably selected from the group consisting of: O 2- OH - 、CO3 2- 、HCO3 - The coefficients x and y can take values ​​of 1 or 2, or values ​​between 1 and 2. The values ​​of the coefficients x and y depend on the cation and anion.

[0135] More preferably, the at least one inorganic base is selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, MgO, Li2CO3, Na2CO3, K2CO3, CaCO3, CaO, MgCO3, LiHCO3, NaHCO3, KHCO3, Ca(HCO3)2, Mg(HCO3)2, MgO.CaO, and mixtures and / or combinations thereof.

[0136] Preferably, the inorganic base is a carbonate.

[0137] In the framework of the present invention, the term "carbonate" includes 2- Anions and HCO3 - Anionic compounds therefore also include bicarbonates and hydroxycarbonates.

[0138] The carbonate may be, for example, CaCO3, Na2CO3, MgCO3, Al2(CO3)3, or NaHCO3.

[0139] Preferably, the carbonate is CaCO3.

[0140] Preferably, at least 13 wt. %, more preferably at least 15 wt. %, even more preferably at least 17 wt. % of the inorganic base is mixed in the mixing step.

[0141] Preferably, not more than 75 wt%, more preferably not more than 70 wt%, even more preferably not more than 65 wt% of the inorganic base is mixed in the mixing step.

[0142] Preferably, at least 13 wt% and at most 75 wt%, more preferably at least 15 wt% and at most 70 wt%, even more preferably at least 17 wt% and at most 65 wt% of the inorganic base are mixed in the mixing step.

[0143] Other additives / fillers

[0144] If necessary, the mixing step may include further mixing at least 10 wt% and at most 80 wt% of at least one filler based on the total weight of the composition (A), thereby forming composition (A).

[0145] In the context of the present invention, the filler (I) may be any filler that can be used in the vulcanization process. However, the term "filler" does not mean that the filler (I) is inert; in fact, the filler (I) may be, for example, a base. The filler (I) may or may not play a role in the vulcanization process.

[0146] The filler (I) includes, but is not limited to, alumina, silica, hydroxide, silicate, and mixtures thereof.

[0147] Silica may include, but is not limited to, silica fume or precipitated silica.

[0148] Use in vulcanization processes

[0149] As mentioned above, the present invention also relates to a method for vulcanizing a vulcanizable composition [composition (C)], comprising the following steps relative to the total weight of composition (C):

[0150] Provided is the composition (C), comprising:

[0151] at least one vulcanizable polymer [polymer (V)] and between 2 and 10 parts by weight of the composition (A) according to the present invention, relative to 100 parts by weight of the polymer (V), and between 0.2 and 15 parts by weight of at least one vulcanizing agent [vulcanizing agent (V)], relative to 100 parts by weight of the polymer (V), to form the composition (C).

[0152] Preferably, the composition (C) is heated to a temperature and for a time sufficient to obtain a vulcanized composition.

[0153] According to the present invention, the term "vulcanizable composition" refers to a composition suitable for undergoing a vulcanization reaction as described above.

[0154] The mixture of at least one polymer (V) and the composition (A) may comprise other compounds, and therefore the composition (C) may also comprise other compounds.

[0155] The step of heating the composition (C) can be performed by equipment known to those skilled in the art, such as a hot press and the like.

[0156] Preferably, the composition (C) can be heated to a temperature of at least 120° C., preferably at least 140° C., more preferably at least 150° C., more preferably at least 165° C. If necessary, the composition (C) can be heated to a temperature of at most 220° C., preferably at most 200° C., more preferably at most 180° C.

[0157] In a preferred embodiment, the composition (C) is heated to a temperature between 120 and 220°C, more preferably between 160 and 200°C, even more preferably between 165 and 180°C.

[0158] The heating time of the composition (C) must be sufficient to obtain a vulcanized composition. A person skilled in the art can apply the heating time generally used in the prior art.

[0159] Polymer (V)

[0160] The term "vulcanizable polymer" [hereinafter referred to as polymer (V)] relates to any type of polymer that is capable of undergoing a vulcanization reaction, ie capable of chemically crosslinking during this reaction.

[0161] The polymer (V) according to the invention preferably comprises at least one monomer unit having at least one degree of unsaturation. This monomer unit then acts as an active site during the crosslinking process. Preferably, polymer (V) comprises multiple degrees of unsaturation.

[0162] The polymer (V) may be, for example, a homopolymer, a copolymer or a terpolymer and may be obtained by polymerization processes of the Ziegler-Natta or metallocene type, without however being limited to the above-mentioned polymerization processes.

[0163] Preferably, polymer (V) may be an elastomer. For example, polymer (V) includes, but is not limited to, natural rubber, polyisoprene, styrene butadiene (SBR), polybutadiene, isoprene butadiene (IBR), styrene isoprene butadiene (SIBR), ethylene propylene / ethylene propylene diene (EPDM), nitrile elastomers, polymers of propylene oxide polymers, star-branched butyl elastomers, halogenated star-branched butyl elastomers, brominated butyl rubber, chlorinated butyl rubber, cross-linked star-branched polyisobutylene rubber, brominated star-branched butyl polyisobutylene / isoprene copolymer rubber), poly(isobutylene-co-alkylstyrene), preferably isobutylene / methylstyrene copolymers, such as isobutylene / m-bromomethylstyrene copolymers, isobutylene / bromomethylstyrene copolymers, isobutylene / chloromethylstyrene copolymers, isobutylene cyclopentadiene copolymers, and isobutylene / chloromethylene copolymers.

[0164] Preferably, polymer (V) comprises ethylene repeating units. Said polymer (V) preferably comprises at least 20 wt.-%, preferably at least 30 wt.-%, more preferably at least 40 wt.-%, even more preferably at least 50 wt.-% of said ethylene repeating units relative to the total weight of said polymer (V). Said polymer (V) may preferably comprise at most 95 wt.-%, more preferably at most 90 wt.-%, even more preferably at most 85 wt.-%, even more preferably at most 80 wt.-% of said ethylene repeating units relative to the total weight of said polymer (V).

[0165] In a preferred embodiment, the polymer (V) comprises from 20% to 95% by weight, preferably from 30% to 90% by weight, more preferably from 40% to 85% by weight, even more preferably from 50% to 80% by weight of the ethylene repeating units, relative to the total weight of the polymer (V).

[0166] More preferably, the polymer (V) further comprises diene repeating units, including, for example but not limited to, isoprene, butadiene, ethylidene norbornene, dicyclopentadiene, vinyl norbornene, and mixtures thereof.

[0167] Preferably, polymer (V) comprises diene repeating units. The polymer (V) preferably comprises at least 0.1 wt.-%, preferably at least 0.2 wt.-%, more preferably at least 0.3 wt.-%, even more preferably at least 0.4 wt.-%, even more preferably at least 0.5 wt.-% of said diene repeating units relative to the total weight of the polymer (V). The polymer (V) may preferably comprise at most 25 wt.-%, more preferably at most 20 wt.-%, even more preferably at most 15 wt.-%, even more preferably at most 12 wt.-% of said diene repeating units relative to the total weight of the polymer (V).

[0168] In a preferred embodiment, the polymer (V) comprises between 0.1 and 25 wt.-% of said diene repeat units, preferably between 0.2 and 20 wt.-%, more preferably between 0.3 and 15 wt.-%, even more preferably between 0.5 and 12 wt.-%.

[0169] In another specific embodiment, polymer (V) is a terpolymer and comprises between 50 and 80 wt.-% of said ethylene repeating units and between 0.1 and 25 wt.-%, preferably between 0.2 and 20 wt.-%, more preferably between 0.3 and 15 wt.-%, even more preferably between 0.5 and 12 wt.-% of said diene repeating units chosen from the group consisting of ethylidene norbornene, dicyclopentadiene, vinyl norbornene and mixtures thereof, relative to the total weight of said polymer (V).

[0170] In another alternative embodiment, polymer (V) may need to have a lower weight percentage of diene, in which case polymer (V) comprises between 0.1% and 10% by weight, preferably between 0.2% and 9% by weight, more preferably between 0.3% and 8% by weight, even more preferably between 0.5% and 7.5% by weight of said diene repeating units, relative to the total weight of said polymer (V). In this case, polymer (V) preferably also comprises between 20% and 95% by weight, more preferably between 30% and 90% by weight, more preferably between 40% and 85% by weight, still more preferably between 50% and 80% by weight of said ethylene repeating units, said diene repeating units being selected from the group consisting of ethylidene norbornene, dicyclopentadiene, vinyl norbornene, and mixtures thereof.

[0171] In yet another alternative embodiment, polymer (V) may need to have a greater weight percentage of diene, in which case polymer (V) comprises between 1 and 20 weight-% of said diene repeat units, preferably between 2.5 and 17 weight-%, more preferably between 5 and 15 weight-%, even more preferably between 7 and 12 weight-% relative to the total weight of said polymer (V). In this case, polymer (V) preferably further comprises between 20 and 95 wt.-%, more preferably between 30 and 90 wt.-%, more preferably between 40 and 85 wt.-%, even more preferably between 50 and 80 wt.-%, even more preferably between 50 and 70 wt.-%, even more preferably between 50 and 75 wt.-%, still more preferably between 50 and 70 wt.-%, still more preferably between 50 and 65 wt.-%, of said ethylene repeating units, relative to the total weight of said polymer (V), and said diene repeating units are chosen from the group consisting of ethylidene norbornene, dicyclopentadiene, vinyl norbornene and mixtures thereof.

[0172] Polymer (V) may also contain propylene repeating units.

[0173] The composition (C) provided comprises a mixture of at least one vulcanizable polymer [polymer (V)] and the composition (A), wherein the composition (A) is between 2 and 10 parts by weight relative to 100 parts by weight of the polymer (V). Preferably, the composition (C) provided may comprise a mixture of at least one polymer (V) and the composition (A), wherein the composition (A) is preferably between 2 and 8 parts by weight, more preferably between 3 and 7 parts by weight, and even more preferably between 4 and 6 parts by weight relative to 100 parts by weight of the polymer (V).

[0174] Additional components

[0175] Preferably, the step of supplying the composition (C) may comprise the step of adding at least one additional component to the polymer (V), wherein the at least one additional component is selected from the group consisting of diatomaceous earth, quartz, talc, glass wool, graphite, carbon black, carbon nanotubes and mixtures thereof.

[0176] In a preferred embodiment, the at least one additional component is carbon black.

[0177] oil phase

[0178] Preferably, the step of providing said composition (C) may comprise the step of adding an oily phase to said polymer (V).

[0179] The oil phase is liquid at room temperature. Preferably, the oil phase is liquid at a temperature of -20°C, preferably -10°C, preferably -5°C, more preferably 0°C, even more preferably 5°C, even more preferably 10°C, even more preferably 15°C.

[0180] If desired, the step of adding the oil phase to the polymer may be performed before or after the step of adding at least one additional component. Alternatively, the step of adding the oil phase to the polymer may be performed simultaneously or at least partially simultaneously with the step of adding at least one additional component.

[0181] vulcanization accelerator

[0182] Preferably, the step of supplying the composition (C) may further include adding a vulcanization accelerator [accelerator (V)].

[0183] Any accelerator (V) commonly used in vulcanization processes can be used. Generally, the accelerator (V) is selected from compounds capable of interacting with the activator (V) in order to reduce the vulcanization time and / or temperature. Preferably, the accelerator is selected from the group consisting of aminoaldehydes, guanidines, thiazoles, thiophosphates, sulfenamides, thioureas, thiurams, dithiocarbamates, xanthates, and mixtures thereof.

[0184] Examples of aminoaldehydes include, but are not limited to, hexamethylenetetramine, heptanal-aniline condensation products, and mixtures thereof.Examples of guanidines include, but are not limited to, diphenylguanidine, N,N'-diorthotolylguanidine, and mixtures thereof.

[0185] Examples of thiazoles include, but are not limited to, 2-mercaptobenzothiazole, 2-2'-dithiobis(benzothiazole), zinc-2-mercaptobenzothiazole, and mixtures thereof. Thiophosphates may be, for example, zinc-O,O-di-N-dithiophosphate. Sulfenamides include, but are not limited to, N-cyclohexyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, 2-(4-morpholinothio)-benzothiazole, N,N'-dicyclohexyl-2-benzothiazolesulfenamide, and mixtures thereof. Thioureas include, but are not limited to, ethylenethiourea, dicyclopentanethiourea, dibutylthiourea, and mixtures thereof. Thiurams include, but are not limited to, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetrabenzylthiuram disulfide, and mixtures thereof. The dithiocarbamate includes, but is not limited to, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, and mixtures thereof. The xanthate may be, for example, zinc isopropyl xanthate.

[0186] In a preferred embodiment, the accelerator (V) is selected from the group consisting of mercaptobenzothiazole, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazolesulfenamide, zinc dibutyldithiocarbamate, and mixtures thereof.

[0187] In a more preferred embodiment, the accelerator (V) is a mixture of mercaptobenzothiazole, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazolesulfenamide and zinc dibutyldithiocarbamate.

[0188] Preferably, at least 0.2 parts by weight, more preferably at least 0.5 parts by weight, even more preferably at least 1 part by weight, even more preferably at least 1.5 parts by weight of the accelerator (V) may be added relative to 100 parts by weight of the polymer (V). If necessary, up to 15 parts by weight, more preferably up to 12 parts by weight, still more preferably up to 10 parts by weight of the accelerator (V) may be added relative to 100 parts by weight of the polymer (V).

[0189] In one embodiment, the accelerator (V) may be added in an amount between 0.2 and 15 parts by weight, preferably between 0.5 and 12 parts by weight, more preferably between 1 and 10 parts by weight, even more preferably between 1.5 and 10 parts by weight, relative to 100 parts by weight of the polymer (V).

[0190] Reagent (V)

[0191] According to the invention, agent (V) is an agent for the vulcanization of polymer (V). Preferably, agent (V) is suitable for reacting with at least one unsaturation of polymer (V) so as to induce crosslinking of the latter.

[0192] Examples of the reagent (V) include, but are not limited to, sulfur, polysulfides, sulfur monochloride, sulfur dichloride, tellurium, selenium, thiuram, disulfides (such as p-benzoquinonedioxime, etc.), organic peroxides, and diisocyanates.

[0193] Preferably, reagent (V) is a sulfur compound, and more preferably comprises at least one disulfide bond (SS). More preferably, reagent (V) is a sulfur compound selected from the group consisting of sulfur, sulfur chloride, polysulfides, and mixtures thereof.

[0194] The inventors have demonstrated that, in order to obtain a vulcanizable composition, composition (C) must contain at least 0.2 parts by weight of agent (V) relative to 100 parts by weight of polymer (V). Preferably, composition (C) contains at least 0.3 parts by weight, more preferably at least 0.5 parts by weight of agent (V) relative to 100 parts by weight of polymer (V).

[0195] The method according to the present invention comprises the step of adding 0.2 to 15 parts by weight of at least one vulcanizing agent [agent (V)] relative to 100 parts by weight of the polymer (V) to form the composition (C).

[0196] In a preferred embodiment, the method according to the present invention comprises the step of adding 0.2 to 4 parts by weight, preferably 0.3 to 3 parts by weight, more preferably 0.5 to 3 parts by weight of said agent (V) relative to 100 parts by weight of said polymer (V).

[0197] Advantageously, agent (V) is added to composition (C) in pulverulent form.

[0198] A final aspect of the present invention relates to the vulcanized composition obtained by the vulcanization process according to the invention.

[0199] Example - Preparation of Vulcanization Activation Composition

[0200] ZnO, CaCO₃, linseed oil, and MgO were mixed in a mixer equipped with a thermocouple to measure temperature. All ingredients were added simultaneously in the proportions specified in Table 1. The maximum temperature and mixing time during mixing were also specified in Table 1.

[0201] The unsaturated fatty acid residue composition of the linseed oil used is summarized in Table 2. Furthermore, the linseed oil used contained between 5% and 18% by weight of saturated fatty acids, relative to the total weight of the linseed oil. The percentage of the various fatty acid residues can be measured using ISO 12966 or any other equivalent standard. The D50 of the ZnO was between 1 μm and 100 μm.

[0202] Table 1

[0203]

[0204] The BET specific surface area of ​​the final composition (A) was measured. The specific surface area was close to 0, which tends to indicate that the core of ZnO (and CaCO3 and MgO) was completely or almost completely covered by linseed oil.

[0205] Table 2

[0206] Unsaturated fatty acid residues in linseed oil Weight % of total linseed oil weight Oleic acid 16 to 23 Linoleic acid 12 to 16 α-linolenic acid 51 to 61

[0207] Unlike the other compositions obtained in Examples 1, 2, 3 and 5, the composition obtained in Example 4 did not generate dust.

[0208] The compositions of Examples 1 to 5 and 7 are powdery compositions in which ZnO, CaCO3 and MgO are the main components of a core at least partially covered with a layer of linseed oil. The composition of Example 6 is a pasty composition.

[0209] The composition according to Example 8 is a powdery composition wherein ZnO and MgO are the main components of a core at least partially covered by a layer of linseed oil.

[0210] The angle of repose of Example 7 is smaller than that of Example 8. The angle of repose of Example 8 is smaller than that of Comparative Example 1.

[0211] Those skilled in the art know how to measure the angle of repose. For example, a defined volume (e.g., 150 ml) of the composition whose angle of repose is to be measured is taken and placed in a funnel located above and centered on a flat-bottomed cylinder. For example, the funnel outlet can be 7.5 cm from the top of the cylinder. The entire defined volume is allowed to flow. Once the entire product is used up, the height of the resulting pyramid is measured (in millimeters). The angle at the base of the pyramid, called the angle of repose, is measured using trigonometric formulas.

[0212] Example - Use of the composition of composition (A) in a vulcanization process

[0213] Each of the compositions (A) obtained in Examples 2, 3, 4 and 6 was mixed together with the ingredients having the properties and proportions listed in Table 3 in a mixer.

[0214] Table 3

[0215]

[0216] The mechanical properties of the vulcanized rubber are shown in Table 4. The same process was repeated except that ZnO was substituted for the composition (A) of Examples 2, 3, 4 and 6. These are "ZnO" Examples (Comparative Examples).

[0217] Table 4

[0218] Example ZnO 2 3 4 6 Cmin(dNm) 2,72 2,4 2,4 2,6 2,59 Cmax(dNm) 21,40 18,4 19,1 18,3 17,77 TR (minutes) 18,69 16,1 16,7 15,8 15,18 Ts2 (minutes) 1,00 0.87 0,91 0,96 1,10 Ts2 (minutes) 1,55 1.35 1,42 1,47 1,58 T90 (minutes) 2,80 2,31 2,41 2,47 2,63 R / R(Mpa) 19,2 19,7 20,7 20.5 20.5 Hardness (Sh-A) 65 61 60,5 59 59 Tear strength (KN / m) 202 205 181 206 206

[0219] The vulcanization duration can be determined using an oscillating disc rheometer by measuring the vulcanization start time (Ts2) and the time associated with the end of vulcanization (t90). The maximum torque (Cmax) measured during the rheological test can be used to determine the ts2 and t90 values. The change in torque can indicate the degree of crosslinking of the product obtained after vulcanization. All rheological measurements were carried out at a temperature of 170°C.

[0220] The maximum torque corresponds to the value measured for the vulcanized (cured) product. To maintain a constant vibration of the rheometer disc in both frequency and amplitude, the device's motor provides a so-called variable torque. This variable torque depends on the elasticity / viscosity of the test product. Therefore, the more viscous or elastic the product, the higher the torque.

[0221] Cmin, Cmax, TR, Ts2, T50, and T90 were measured using an oscillating disk rheometer at 170°C according to ASTM D5289.

[0222] R / R (breaking strength) is measured according to NF T 46-002 standard.

[0223] Hardness measurement (SH-A hardness) was performed in accordance with ISO 7619-1 2010.

[0224] The tear resistance was measured according to NF T 46-007.

[0225] It can be seen that the mechanical properties of the different examples are similar, which tends to indicate that the presence of vegetable oil has no or negligible effect on the mechanical properties of the vulcanized polymer.

[0226] Zinc release test

[0227] The rubber obtained after vulcanization using the composition (a) of Example 6 and ZnO (comparative example) was tested for zinc release.

[0228] For each rubber sample, cut a rubber piece measuring 10 cm x 8 cm. Each piece of rubber was split and cut into approximately 20 small cubes measuring 2 cm x 2 cm. Each cube was weighed. Each cube was rinsed three times in three aluminum pans containing ultrapure water (milli-Q).

[0229] After rinsing, the cubes were placed directly into a 250 ml glass bottle and covered with 200 ml of milli-Q water. The bottle was sealed with a stopper. The bottle was filled with milli-Q water for reference.

[0230] Each bottle was placed in an oven at 35°C and shaken daily for 4 weeks. Samples were taken from each bottle periodically and analyzed by atomic absorption according to standard FD T90-112. The results of the bottled water analysis are shown in Table 5.

[0231] Table 5

[0232] Zinc content in water ZnO (Comparative Example) Composition (A) Example 6 1 week later 1,74mg / L 0,17mg / L 2 weeks later 2.8mg / L 0,13mg / L 4 weeks later 3,22mg / L 0,15mg / L

[0233] It can be seen that the amount of ZnO released from the rubber obtained after vulcanization using composition (A) of Example 6 is very small and the amount of ZnO released does not seem to change over time. The opposite results were observed when standard ZnO was used for vulcanization.

Claims

1. A method for preparing a vulcanization-activated composition [hereinafter referred to as composition (A)], said method comprising at least one mixing step: at least 5% and at most 95% by weight, preferably at least 5% and at most 75% by weight, of particles of an oxygen-containing zinc compound [hereinafter referred to as compound (OZ)], and at least 1% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative, forming the composition (A), the % by weight being based on the total weight of the composition (A); in, The vegetable oil or vegetable oil derivative comprises, based on the total weight of the vegetable oil or vegetable oil derivative: at least 8 wt. % of at least one fatty acid residue; the fatty acid residue comprises at least two degrees of unsaturation.

2. The method according to claim 1, wherein The mixing step further comprises mixing at least 0.1 wt% and at most 75 wt% of magnesium oxide based on the total weight of the composition (A).

3. A method according to any one of the preceding claims, wherein The mixing step additionally comprises mixing at least 10% by weight and at most 80% by weight of at least one inorganic base, based on the total weight of the composition (A).

4. A method according to any one of the preceding claims, wherein The vegetable oil is selected from the group consisting of linseed oil, walnut oil, sunflower oil, corn oil, avocado oil, sesame oil, grapeseed oil, olive oil, peanut oil, rice oil, sesame oil, soybean oil, rapeseed oil, safflower oil, wheat germ oil, and mixtures thereof.

5. A method according to any one of the preceding claims, wherein The vegetable oil derivative is a derivative of an oil selected from the group consisting of linseed oil, walnut oil, sunflower oil, corn oil, avocado oil, hemp oil, grapeseed oil, olive oil, peanut oil, rice oil, sesame oil, soybean oil, rapeseed oil, safflower oil, wheat germ oil, palm oil and mixtures thereof.

6. A method according to any one of the preceding claims, wherein The fatty acid residues are C12-C30 residues, more preferably C14-C28, more preferably C14-C26, even more preferably C14-C24, more preferably C16-C24, more preferably C16-C22, more preferably C16-C20, even more preferably C18.

7. A method according to any one of the preceding claims, wherein The vegetable oil and / or the vegetable oil derivative comprises at least 15 wt.-% of the fatty acid residues, more preferably at least 20 wt.-% of the fatty acid residues, more preferably at least 25 wt.-% of the fatty acid residues, more preferably at least 30 wt.-% of the fatty acid residues, more preferably at least 35 wt.-% of the fatty acid residues, even more preferably at least 40 wt.-% of the fatty acid residues, even more preferably at least 50 wt.-% of the fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

8. A method according to any one of the preceding claims, wherein The vegetable oil and / or the vegetable oil derivative comprises at most 80 wt.-% of said fatty acid residues, more preferably at most 75 wt.-% of said fatty acid residues, even more preferably at most 70 wt.-% of said fatty acid residues, based on the total weight of the vegetable oil or the vegetable oil derivative.

9. A method according to any one of the preceding claims, wherein The fatty acid residue is a residue selected from the group consisting of an α-linolenic acid residue, a γ-linolenic acid residue, a dihomo-γ-linolenic acid residue, an arachidonic acid residue, an eicosapentaenoic acid residue, a docosahexaenoic acid residue and a linoleic acid residue.

10. A method according to any one of the preceding claims, wherein The fatty acid residue is a fatty acid residue containing two degrees of unsaturation (A), and the vegetable oil and / or the vegetable oil derivative further comprises a fatty acid residue containing at least three degrees of unsaturation (B).

11. A method according to any one of the preceding claims, wherein The fatty acid residue (A) is a linoleic acid residue, and the fatty acid residue (B) is a residue selected from the group consisting of an α-linolenic acid residue, a γ-linolenic acid residue, a dihomo-γ-linolenic acid residue, an arachidonic acid residue, an eicosapentaenoic acid residue, and a docosahexaenoic acid residue, and linoleic acid.

12. A method according to any one of the preceding claims, wherein In the mixing step at least 10 wt.-% of the compound (OZ), more preferably at least 12 wt.-%, more preferably at least 15 wt.-%, more preferably at least 20 wt.-%, more preferably at least 25 wt.-%, more preferably at least 30 wt.-%, more preferably at least 40 wt.-%, more preferably at least 50 wt.-%, more preferably at least 60 wt.-% of the compound (OZ), based on the total weight of the composition (A) is mixed.

13. A method according to any one of the preceding claims, wherein In the mixing step, at most 70 wt.-% of the compound (OZ), based on the total weight of the composition (A), more preferably at most 65 wt.-%, more preferably at most 55 wt.-%, more preferably at most 50 wt.-%, more preferably at most 45 wt.-%, more preferably at most 40 wt.-%, more preferably at most 35 wt.-% of the compound (OZ) is mixed.

14. A method according to any one of the preceding claims, wherein The D50 of compound (OZ) is at least 100 nm, more preferably at least 200 nm, even more preferably at least 300 nm, even more preferably at least 400 nm, even more preferably at least 500 nm, even more preferably at least 600 nm, even more preferably at least 700 nm, even more preferably at least 800 nm, even more preferably at least 1 μm, even more preferably at least 2 μm, as measured by a laser particle size analyzer in water.

15. A method according to any one of the preceding claims, wherein The D50 of the compound (OZ) can be at most 500 μm, or at most 100 μm, or at most 20 μm, or at most 15 μm, as measured by a laser particle size analyzer in water.

16. A method according to any one of the preceding claims, wherein The compound (OZ) is selected from the group consisting of zinc oxide, zinc hydroxide, zinc carbonate, zinc hydroxycarbonate and mixtures thereof.

17. A method according to any one of the preceding claims, wherein The composition (A) is a pasty composition or a liquid composition, and the method comprises at least one mixing step: Based on the total weight of the composition (A), at least 20% and at most 60% by weight of particles of compound (OZ), and • At least 15% and at most 75% by weight of at least one vegetable oil or at least one vegetable oil derivative, forming the composition (A).

18. The method according to any one of claims 1 to 16, wherein The composition (A) is a powder composition of at least partially coated OZ compound particles, and the method comprises at least one mixing step: Based on the total weight of the composition (A), at least 20% and at most 60% by weight of particles of compound (OZ), and • At least 1% and at most 35% by weight of at least one vegetable oil or at least one vegetable oil derivative, forming the composition (A).

19. The method according to any one of claims 2 to 18, wherein At least 0.5 wt%, more preferably at least 0.8 wt%, even more preferably at least 1 wt% of magnesium oxide is mixed in the mixing step.

20. The method according to any one of claims 2 to 19, wherein At most 75 wt. %, more preferably at most 70 wt. %, even more preferably at most 60 wt. %, even more preferably at most 50 wt. %, even more preferably at most 40 wt. %, even more preferably at most 30 wt. %, even more preferably at most 20 wt. %, even more preferably at most 10 wt. % of magnesium oxide is mixed in said mixing step.

21. The method according to any one of claims 3 to 20, wherein The at least one inorganic base is selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, MgO Li2CO3, Na2CO3, K2CO3, CaCO3, CaO, MgCO3, LiHCO3, NaHCO3, KHCO3, Ca(HCO3)2, Mg(HCO3)2, MgO.CaO, and mixtures and / or combinations thereof.

22. The method according to any one of claims 3 to 21, wherein At least 13 wt%, more preferably at least 15 wt%, even more preferably at least 17 wt% of the inorganic base is mixed in the mixing step.

23. The method according to any one of claims 3 to 22, wherein Up to 75 wt. %, more preferably up to 70 wt. %, even more preferably up to 65 wt. % of the inorganic base is mixed in the mixing step.

24. A method according to any one of the preceding claims, wherein The mixing step is performed at a temperature of at most 100°C, preferably at most 80°C, more preferably at most 70°C, even more preferably at most 60°C, even more preferably at most 50°C, even more preferably at most 40°C.

25. A method according to any one of the preceding claims, wherein The mixing step is carried out at a temperature of at least 10°C, more preferably at least 15°C, more preferably at least 17°C, more preferably at least 20°C.

26. A method according to any one of the preceding claims, wherein The mixing is performed for at most 30 minutes, or at most 20 minutes, or at most 10 minutes, or at most 5 minutes, or at most 1 minute, or at most 30 seconds.

27. A method according to any one of the preceding claims, wherein The mixing is performed for at least 10 seconds.

28. A vulcanization activated composition obtainable by a process according to any one of the preceding claims.

29. Use of a composition according to claim 28 or a composition obtained by a method according to any one of claims 1 to 27 in a vulcanization process.

30. A method for vulcanizing a vulcanizable composition [composition (C)], comprising the following steps, relative to the total weight of the composition (C): Provided is the composition (C), comprising: at least one vulcanizable polymer [polymer (V)] and between 2 and 10 parts by weight of the composition (A) according to claim 28 or the composition (A) obtained by the process according to any one of claims 1 to 27, relative to 100 parts by weight of the polymer (V), and between 0.2 and 15 parts by weight of at least one vulcanizing agent [vulcanizing agent (V)] relative to 100 parts by weight of the polymer (V) to form the composition (C).

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