Rubber protective wax

Abstract

The invention discloses rubber protection wax, raw materials of which comprise a wax material and / or an antioxidant and further comprise a crystal form interference agent, the carbon atom number distribution interval of the wax material is C20-C56, the wax material is selected from paraffin and microcrystalline wax, and the wax material meets the following conditions: the content of non-n-alkane is not lower than 35% by weight, the content of n-alkane is lower than 65% by weight, and along with the increase of the carbon number, the content of the non-n-alkane is not lower than 35% by weight. The percentage of the content of the non-n-alkanes with the carbon number smaller than 34 in the total amount of the alkanes is gradually increased, and the percentage of the content of the n-alkanes with the carbon number smaller than 31 in the total amount of the alkanes is gradually increased along with increasing of the carbon number; the content of non-n-alkanes with the carbon number of 34 accounts for 4-4.1% of the total amount of the alkanes, and the content of n-alkanes with the carbon number of 31 accounts for 7.1-7.2% of the total amount of the alkanes. The rubber additive provided by the invention has the advantages of good carbon distribution state, small lattice gap after being migrated to the surface of rubber, capability of effectively preventing ozone from passing through, stable performance and low cost.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to rubber protective waxes. Background Art

[0002] During the processing, storage, and use of rubber products, especially during dynamic use, rubber products are "attacked" by oxygen and ozone in the air, and are simultaneously affected by a combination of factors such as light, heat, radiation, mechanical force, and other chemical factors, which will cause a series of aging phenomena in rubber products, such as stickiness, hardening, embrittlement, or cracking. Currently, the more popular treatment method in the world is to add a certain proportion of protective wax to rubber products. Rubber protective wax can dynamically form a protective film on the rubber surface, isolating the contact between ozone and the rubber surface, and can effectively delay the oxidation of ozone, thereby extending the service life of rubber.

[0003] This layer of film plays a shielding role in preventing rubber from coming into contact with ozone and prevents the reaction between rubber and ozone. Therefore, people utilize this property of petroleum wax products to meet the protection requirements of rubber products. To effectively protect against ozone cracking, the wax film on the rubber product surface should meet very high requirements: it should have an appropriate wax film thickness, be able to adhere well to the rubber surface, and not be easily shed; the wax film density should be high, dense and void-free, preferably a wax film close to the amorphous state, otherwise ozone will erode the rubber through the voids. To meet these requirements, it is necessary to control the ratio of normal and non-normal paraffins and the carbon number distribution in wax substances. Normal paraffins have a high solubility in various colloids. At the same time, due to their straight-chain molecular structure, their migration resistance is relatively small. When its content exceeds its solubility limit at this temperature, it can migrate to the rubber surface at a relatively fast speed and form a wax film on the surface to achieve the effect of isolating ozone. However, the straight-chain characteristics of normal paraffins result in inevitable weaknesses: the crystal wax film formed by normal paraffins is relatively loose, and the wax film is not dense enough; at the same time, due to its large migration property, within a certain temperature range, in a short period of time, a large amount of normal paraffins migrate to the rubber surface and form large crystal forms on the surface. Eventually, the wax film thickness is relatively large, which will cause shedding, and the crystal gaps are also relatively large, which is not conducive to preventing ozone from passing through, thereby affecting the protection life of the colloid. Non-normal paraffins have a branched molecular structure, forming a crisscrossed microscopic state, with a relatively low solubility in various colloids, and its migration speed is relatively slow compared to straight-chain paraffins. In this way, a reasonable combination ratio of non-normal paraffins and normal paraffins can be used to achieve the purpose of controlling the migration speed. In addition, the wax film formed by non-normal paraffins is very dense, has good adhesion, and is not easily shed.

[0004] All types of rubber protective waxes at home and abroad in the past have had a certain protective effect, but their weaknesses are also inevitable. Taking US Patent 4,877,456 as an example, it is proposed that the total content of normal paraffins in the protective wax for rubber products should reach at least 75%, where C 21 ~C26 The content of n-alkanes within the range is 5% to 25%, and C 36 to C 51 The content of n-alkanes within the range should reach 20% to 45%. Although the carbon number distribution range of this protective wax is wide and it can have a protective effect within a relatively wide temperature range, the content of n-alkanes is too high, and no requirements are put forward for the content of non-n-alkanes. Since n-alkanes migrate relatively fast, it is very difficult to control the migration speed and blooming amount. As a result, at a certain temperature, too much wax seeps out of the rubber surface, affecting the appearance of rubber products and even causing the wax film to fall off. US Patent 5296129 emphasizes the content of n-alkanes with 22 to 44 carbon atoms, and at the same time suggests that the content of non-n-alkanes with 30 to 60 carbon atoms should account for 16% to 30% of the total amount of alkanes. Although this protective wax puts forward requirements for the content of non-n-alkanes, the content of non-n-alkanes is relatively low. A large number of n-alkanes migrate to the surface at a relatively fast speed within a relatively short time. Once lost, it is difficult to maintain the protective effect for a long time. Moreover, this patent only puts forward a rough distribution requirement for the content of non-n-alkanes within the range of C 30 to C 60 It is difficult to avoid the drawback that the distribution of non-n-alkanes with a certain carbon number or several carbon numbers is too concentrated. The maximum migration rates of non-n-alkanes with different carbon numbers correspond to different temperatures respectively, so it is impossible to well control the migration amount of alkanes within each temperature range, and it is very difficult to achieve an ideal protective effect for high-quality rubber products that require a wide protective temperature and a long protective life.

[0005] Therefore, in view of the above technical problems, it is necessary to provide a rubber protective wax with a suitable migration speed. The content of n-alkanes fully considers the structural characteristics of specific carbon numbers (C 29 to C 33 ) to control its migration behavior. In addition, through the modification of a specific crystal form interfering agent, the wax film migrating to the rubber surface has delicate crystals with small crystal gaps, which can effectively prevent ozone from damaging the rubber.

[0006] The information disclosed in this background art section is only intended to increase the understanding of the overall background of the present invention, and should not be regarded as an admission or any form of suggestion that this information constitutes the prior art already known to those of ordinary skill in the art. Summary of the Invention

[0007] The purpose of the present invention is to provide a rubber protective wax.

[0008] To achieve the above purpose, the technical solution provided by a specific embodiment of the present invention is as follows:

[0009] A rubber protective wax, the raw materials of which include wax materials and / or antioxidants, and the raw materials also include crystal form interfering agents. The carbon atom number distribution range of the wax materials is C 20~C 56 and selected from paraffin wax and microcrystalline wax, wherein the wax material satisfies, wt%:

[0010] The content of non-normal paraffins is not less than 35%, and the content of normal paraffins is less than 65%:

[0011] As the carbon number increases, the percentage of non-normal paraffins with a carbon number less than 34 in the total amount of paraffins shows an increasing trend. As the carbon number increases, the percentage of normal paraffins with a carbon number less than 31 in the total amount of paraffins shows an increasing trend;

[0012] The percentage of non-normal paraffins with a carbon number of 34 in the total amount of paraffins is 4-4.1%, and the percentage of normal paraffins with a carbon number of 31 in the total amount of paraffins is 7.1-7.2%;

[0013] As the carbon number increases, the percentage of non-normal paraffins with a carbon number greater than 34 in the total amount of paraffins shows a decreasing trend, and the percentage of normal paraffins with a carbon number greater than 31 in the total amount of paraffins shows a decreasing trend;

[0014] The crystal form improver is a component with a special designed structure. Its non-polar end has good compatibility with the wax material, while its weakly polar end has the function of strongly interfering with the crystallization of paraffin wax.

[0015] Preferably, the antioxidant accounts for 0-2% of the total amount of raw materials, and the balance in the raw materials is the wax material.

[0016] In one or more embodiments of the present invention, the percentage of non-normal paraffins in the total amount of paraffins in the wax material shows a nearly normal distribution in the range of carbon numbers from 20 to 56.

[0017] In one or more embodiments of the present invention, for the part of the wax material with a carbon number not exceeding 28, the percentage of non-normal paraffins corresponding to each carbon number in the total amount of paraffins does not exceed 0.75%.

[0018] In one or more embodiments of the present invention, the percentage of non-normal paraffins with a carbon number of 29 in the total amount of paraffins in the wax material is 1.25-1.29%.

[0019] In one or more embodiments of the present invention, for the part of the wax material with a carbon number exceeding 40, the percentage of non-normal paraffins corresponding to each carbon number in the total amount of paraffins does not exceed 0.97%.

[0020] In one or more embodiments of the present invention, the percentage of non-normal paraffins with a carbon number of 40 in the total amount of paraffins in the wax material is 1.40-1.43%.

[0021] In one or more embodiments of the present invention, for the part of the wax material with no more than 25 carbon atoms, the percentage of the content of n-alkanes corresponding to each carbon number in the total amount of alkanes does not exceed 0.72%.

[0022] In one or more embodiments of the present invention, the percentage of the content of n-alkanes with 26 carbon atoms in the wax material in the total amount of alkanes is 1.5 - 2.0%.

[0023] In one or more embodiments of the present invention, for the part of the wax material with more than 38 carbon atoms, the percentage of the content of n-alkanes corresponding to each carbon number in the total amount of alkanes does not exceed 0.7%.

[0024] In one or more embodiments of the present invention, the percentage of the content of n-alkanes with 38 carbon atoms in the wax material in the total amount of alkanes is 1.15 - 1.18%.

[0025] In one or more embodiments of the present invention, the melting range of paraffin wax in the wax material is 40 - 70°C, and its content accounts for 20 - 73.5% of the total mass of the wax material. Preferably, the melting range of paraffin wax is 40 - 70°C.

[0026] In one or more embodiments of the present invention, the melting range of microcrystalline wax in the wax material is 60 - 90°C, and its content accounts for 26.5 - 80% of the total mass of the wax material.

[0027] In one or more embodiments of the present invention, the wax material further includes the balance of polyethylene wax, and the molecular weight of the polyethylene wax is between 1000 and 10000.

[0028] In one or more embodiments of the present invention, the crystal form interfering agent accounts for 0.5 - 15 wt% of the total amount of raw materials.

[0029] In one or more embodiments of the present invention, the crystal form interfering agent is selected from: EVA, amide, higher fatty acid, higher alkyl polyoxyethylene ether. Preferably, the amide has the following structural formula:

[0030]

[0031] Wherein R is an alkyl or alkenyl group with 11 - 35 carbon atoms, preferably an alkyl or alkenyl group with 15 - 35 carbon atoms; R' and R" are H, alkyl or / and alkenyl group, and the number of carbon atoms of the alkyl or / and alkenyl group is 0 - 12.

[0032] In one or more embodiments of the present invention, the antioxidant in the raw materials is selected from: N-isopropyl-N-phenyl-p-phenylenediamine, dimethyl phthalate, 2,6-di-tert-butyl-p-cresol.

[0033] In one or more embodiments of the present invention, the paraffin wax is 52 - 60 full-refined paraffin wax, and the oil content is less than 1.5%.

[0034] In one or more embodiments of the present invention, the microcrystalline wax is No. 75 - 85 microcrystalline wax, and the oil content is less than 3.6%.

[0035] Compared with the prior art, the composition of the rubber protective wax of the present invention focuses on the performance of n - paraffins in a specific carbon number range. Although the migration rate of n - paraffins is relatively fast, as the carbon number increases, its structure changes, the end groups will fold, showing the performance of pseudo - non - normal structure. When the number of normal carbon atoms is less than 29 (C 29 H 60 ), the end - to - end distance increases with the increase of the n - paraffin molecular size. When it exceeds 29, the end - to - end distance decreases with the increase of the n - paraffin molecular size. From C 30 H 62 to C 32 H 66 , the end - to - end distance is shorter than that of C 29 H 60 . This characteristic helps the migration performance of n - paraffins to be close to that of non - normal paraffins with the same carbon number. Overall, it helps the carbon peak to be maintained at C 31 ~C 33 . For the wax materials on the current market, there are almost no raw materials with a natural non - normal carbon peak at C 31 ~C 33 . Reasonably utilizing the performance of n - paraffins in this carbon number range helps the migration behavior of the final product in rubber. In the descriptions of the current market and existing patents, the dosage of microcrystalline wax is generally high. The carbon number of microcrystalline wax is mostly 40 - 50 carbon atoms, the molecular weight is 560 - 700, and the melting point mostly exceeds 70°C. Too much microcrystalline wax is not conducive to its migration and precipitation protection in winter. In addition, reasonably reducing the amount of microcrystalline wax helps to reduce the cost of the final formulation.

[0036] Compared with the prior art, the composition of the rubber protective wax of the present invention focuses on special crystal form interfering agents. The selected crystal form interfering agents, in addition to having excellent compatibility of the non - polar end with the wax materials, have a polar or weakly polar end at the other end. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0038] Figure 1 It is the carbon number distribution state diagram of the rubber protective wax in an embodiment of the present invention.

[0039] Figure 2 In an embodiment of the present invention, it is a comparative diagram of the crystal structures of the final wax film with and without the addition of a crystal form interfering agent to the rubber protective wax, where a is without the crystal form interfering agent and b is with the crystal form interfering agent. Detailed implementation manners

[0040] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the scope of protection of the present invention.

[0041] Including but not limited to the following embodiments, the measurement of the composition raw materials is in weight percentages.

[0042] In the embodiment solution of the rubber protective wax of the present invention, its composition raw materials include: 0.5-15% of the crystal form interfering agent and / or 0-2% of the antioxidant, and the balance is the wax material. The antioxidant is selected from N-isopropyl-N-phenyl-p-phenylenediamine, dimethyl phthalate, 2,6-di-tert-butyl-p-cresol.

[0043] Among them, the composition of the raw materials of the wax material includes: the melting range of paraffin wax is 40-70°C, and its content accounts for 20-73.5% of the total mass of the wax material; the melting range of microcrystalline wax is 60-90°C, and its content accounts for 26.5-80% of the total mass of the wax material. It may also include that the molecular weight of polyethylene wax is between 1000 and 10000, and its content accounts for 0-8% of the total mass of the wax material.

[0044] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat to 75-90°C, and after melting, start the stirrer and stir at a low speed of 10-30 rpm for 10-20 minutes. Then paraffin wax can be added and stirred and mixed at 60-100 rpm for 15-30 minutes. Finally, the antioxidant and / or polyethylene wax can be added, the temperature is raised to 95-130°C, and stirred at 150-300 rpm for 20-30 minutes. Then release the molten wax from the reactor and enter the refiner to filter out impurities.

[0045] Group 1

[0046] Example 1

[0047] The rubber protective wax of this embodiment has the following composition raw materials: 0.5% of stearic acid as crystal form interfering agent, and the balance is wax material. The raw materials of the wax material include: paraffin wax with a melting range of 40-70°C, accounting for 20% of the total mass of the wax material; microcrystalline wax with a melting range of 60-90°C, accounting for 80% of the total mass of the wax material.

[0048] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat to 80°C, after melting, start the stirrer, stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Discharge the molten wax from the reactor and enter the refiner to filter out impurities. The samples are tested, and the product performance is shown in Table 01 below.

[0049] Table 01 Performance Test Table of Samples in Example 1

[0050] No. Item Test Value Test Method 1 Freezing Point, °C 71 SH / T0132 2 Drop Melting Point, °C 73 GB / T8026 3 Normal Proportion, % 26 NB / SH / T0653 4 Non-Normal Proportion, % 74 NB / SH / T0653

[0051] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified by various comparative tests on the test colloid:

[0052] Table 02 Composition Table of Samples Applied in Example 1 (in parts by weight)

[0053]

[0054]

[0055] Weigh the raw materials corresponding to the application examples in Table 02. After the raw rubber is kneaded on an open mill, add the remaining raw materials and knead to obtain a uniform mixture, and then mold and vulcanize at 150°C for 65 minutes to obtain the application example samples.

[0056] The performance test of the obtained application samples is shown in Table 03 below

[0057]

[0058] Example 2

[0059] The rubber protective wax of this embodiment has the following composition raw materials: 0.5% of stearic acid as crystal form interfering agent, and the balance is wax material. The raw materials of the wax material include: paraffin wax with a melting range of 40-70°C, accounting for 30% of the total mass of the wax material; microcrystalline wax with a melting range of 60-90°C, accounting for 70% of the total mass of the wax material.

[0060] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat it to 75 °C, and after melting, start the stirrer. Stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Discharge the molten wax from the reactor into a refiner, and filter out the impurities. Test the sample, and the product performance is shown in Table 04 below.

[0061] Table 04 Performance Test Table of the Sample in Example 2

[0062] No. Item Test Value Test Method 1 Freezing Point, °C 69.5 SH / T0132 2 Drop Melting Point, °C 71.3 GB / T8026 3 Normal Proportion, % 34 NB / SH / T0653 4 Non-Normal Proportion, % 66 NB / SH / T0653

[0063] The influence of the product in this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloids:

[0064] Table 05 Application Composition Table of the Sample in Example 2 (in parts by weight)

[0065]

[0066]

[0067] Weigh the raw materials corresponding to the application example in Table 05. After the raw material rubber is kneaded by a kneading mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then perform mold pressing and vulcanization at 150 °C for 65 minutes to obtain the application example sample.

[0068] The performance test of the obtained application sample is shown in Table 06 below

[0069]

[0070] Example 3

[0071] The rubber protective wax in this example includes 0.5% of crystal form interfering agent stearic acid and the balance of wax materials. Among them, the composition of the wax materials includes: paraffin wax with a melting range of 40 - 70 °C, and its content accounts for 73% of the total mass of the wax materials; microcrystalline wax with a melting range of 60 - 90 °C, and its content accounts for 27% of the total mass of the wax materials.

[0072] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat it to 75 °C, and after melting, start the stirrer. Stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Discharge the molten wax from the reactor into a refiner, and filter out the impurities. Test the sample, and the product performance is shown in Table 07 below.

[0073] Table 07 Performance Test Table of the Sample in Example 3

[0074] No. Item Test Value Test Method 1 Freezing Point, °C 60.5 SH / T0132 2 Drop Melting Point, °C 68.4 GB / T8026 3 Normal Proportion, % 42 NB / SH / T0653 4 Non-Normal Proportion, % 58 NB / SH / T0653

[0075] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified through various comparative tests on the test colloid:

[0076] Table 08 Composition Table of Samples in Example 3 (by weight parts)

[0077]

[0078] Weigh the raw materials corresponding to the application examples in Table 08. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example samples.

[0079] The performance detection of the obtained application samples is shown in Table 09 below

[0080]

[0081] Example 4

[0082] The rubber protective wax of this embodiment, its composition raw materials include: 0.5% of stearic acid as crystal form interfering agent, and the balance is wax material. Among them, the composition of the raw materials of the wax material includes: the molecular weight of polyethylene wax is 10,000, and its content accounts for 2% of the total mass of the wax material; the melting range of paraffin wax is 40 - 70 °C, and its content accounts for 70% of the total mass of the wax material; the melting range of microcrystalline wax is 60 - 90 °C, and its content accounts for 28% of the total mass of the wax material.

[0083] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat to 75 °C, after melting, start the stirrer, stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Finally, add polyethylene wax, raise the temperature to 95 °C, and stir at 150 rpm for 20 minutes. Discharge the molten wax from the reactor and enter the refiner to filter out impurities. The samples are tested, and the product performance is shown in Table 010 below.

[0084] Table 010 Performance Detection Table of Samples in Example 4

[0085] No. Item Test Value Test Method 1 Freezing Point, °C 74.3 SH / T0132 2 Drop Melting Point, °C 78.4 GB / T8026 3 Normal Proportion, % 42.9 NB / SH / T0653 4 Non-Normal Proportion, % 57.1 NB / SH / T0653

[0086] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified through various comparative tests on the test colloid:

[0087] Table 011 Composition Table of Samples in Example 4 (by weight parts)

[0088]

[0089] Weigh the raw materials corresponding to Application Example in Table 011. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then perform mold pressing and vulcanization at 150 °C for 65 min to obtain the sample of the application example.

[0090] The performance detection of the obtained application sample is shown in Table 012 as follows

[0091]

[0092]

[0093] Example 5

[0094] The rubber protective wax of this example, its composition raw materials include 0.5% of stearic acid as crystal form interfering agent and the balance of wax materials. Among them, the composition of the raw materials of the wax materials includes: the molecular weight of polyethylene wax is 10,000, and its content accounts for 1% of the total mass of the wax materials; the melting range of paraffin wax is 40 - 70 °C, and its content accounts for 71% of the total mass of the wax materials; the melting range of microcrystalline wax is 60 - 90 °C, and its content accounts for 28% of the total mass of the wax materials.

[0095] Weigh the raw materials according to the ratio: add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat to 75 °C, after melting, start the stirrer, stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Finally, add polyethylene wax, raise the temperature to 95 °C, and stir at 150 rpm for 20 minutes. Then discharge the molten wax from the reactor into the refiner to filter out impurities. The sample is tested, and the product performance is shown in Table 013 as follows.

[0096] Table 013 Performance Detection Table of Example 5 Sample

[0097] No. Item Test Value Test Method 1 Freezing Point, °C 71.1 SH / T0132 2 Drop Melting Point, °C 74.6 GB / T8026 3 Normal Proportion, % 43 NB / SH / T0653 4 Non-Normal Proportion, % 57 NB / SH / T0653

[0098] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0099] Table 014 Application Composition Table of Example 5 Sample (by weight parts)

[0100]

[0101]

[0102] Weigh the raw materials corresponding to the application example in Table 014. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then perform mold pressing and vulcanization at 150 °C for 65 min to obtain the sample of the application example.

[0103] The performance detection of the obtained application sample is shown in Table 015 as follows

[0104]

[0105] Example 6

[0106] The rubber protective wax of this example has its composition raw materials including 0.5% of stearic acid as crystal form interfering agent and the balance of wax materials. Among them, the composition of the raw materials of the wax materials includes: the molecular weight of polyethylene wax is 10,000, and its content accounts for 0.5% of the total mass of the wax materials; the melting range of paraffin wax is 40 - 70 °C, and its content accounts for 71.5% of the total mass of the wax materials; the melting range of microcrystalline wax is 60 - 90 °C, and its content accounts for 28% of the total mass of the wax materials.

[0107] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat to 75 °C, after melting, start the stirrer, stir at a low speed of 10 rpm for 10 minutes at a constant temperature, then add paraffin wax, and stir and mix at 60 rpm for 15 minutes. Finally, add polyethylene wax, raise the temperature to 95 °C, and stir at 150 rpm for 20 minutes. Then release the molten wax from the reactor and enter the refiner to filter out impurities. The sample is tested, and the product performance is shown in Table 016 below.

[0108] Table 016 Performance Test Table of Example 6 Samples

[0109] No. Item Test Value Test Method 1 Freezing Point, °C 62.1 SH / T0132 2 Drop Melting Point, °C 68.6 GB / T8026 3 Normal Proportion, % 43 NB / SH / T0653 4 Non-Normal Proportion, % 57 NB / SH / T0653

[0110] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified through various comparative tests on the test colloid:

[0111] Table 017 Composition Table of Example 6 Samples for Application (in parts by weight)

[0112]

[0113]

[0114] Weigh the raw materials corresponding to the application examples in Table 017. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then press and vulcanize at 150 °C for 65 min to obtain the application example samples.

[0115] The performance test of the obtained application samples is shown in Table 018 below

[0116]

[0117] Group Two

[0118] Example 11

[0119] The difference between the rubber protective wax of this embodiment and that of Embodiment 1 is only that its composition raw materials include: antioxidant 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent stearic acid 0.5%, and the balance is wax material.

[0120] The samples were tested, and the product performances are shown in Table 11 below.

[0121] Table 11 Performance Test Table of Samples in Embodiment 11

[0122]

[0123]

[0124] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloids:

[0125] Table 12 Application Composition Table of Samples in Embodiment 11 (by weight parts)

[0126]

[0127] Weigh the raw materials corresponding to the application examples in Table 12. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example samples.

[0128] The performance test of the obtained application samples is shown in Table 13 below

[0129]

[0130]

[0131] Embodiment 12

[0132] The difference between the rubber protective wax of this embodiment and that of Embodiment 2 is only that: antioxidant 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent stearic acid 0.5%, and the balance is wax material.

[0133] The samples were tested, and the product performances are shown in Table 14 below.

[0134] Table 14 Performance Test Table of Samples in Embodiment 12

[0135] No. Item Test Value Test Method 1 Freezing Point, °C 69.3 SH / T0132 2 Drop Melting Point, °C 71.1 GB / T8026 3 Normal Proportion, % 34 NB / SH / T0653 4 Non-Normal Proportion, % 66 NB / SH / T0653

[0136] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloids:

[0137] Table 15 Application Composition Table of Samples in Embodiment 12 (by weight parts)

[0138]

[0139]

[0140] Weigh the raw materials of the corresponding application example in Table 15. After the raw material rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example sample.

[0141] The performance detection of the obtained application sample is shown in Table 16 below

[0142]

[0143] Example 13

[0144] The difference between the rubber protective wax of this example and that of Example 3 is only that its composition raw materials include: 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent stearic acid 0.5%, and the balance is wax material.

[0145] The sample is tested, and the product performance is shown in Table 17 below.

[0146] Table 17 Performance Detection Table of Example 13 Sample

[0147] No. Item Test Value Test Method 1 Freezing Point, °C 60.8 SH / T0132 2 Drop Melting Point, °C 68.6 GB / T8026 3 Normal Proportion, % 42 NB / SH / T0653 4 Non-Normal Proportion, % 58 NB / SH / T0653

[0148] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0149] Table 18 Application Composition Table of Example 13 Sample (by weight parts)

[0150]

[0151] Weigh the raw materials of the corresponding application example in Table 18. After the raw material rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example sample.

[0152] The performance detection of the obtained application sample is shown in Table 19 below

[0153]

[0154] Example 14

[0155] The difference between the rubber protective wax of this example and that of Example 4 is only that its composition raw materials include: antioxidant 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent stearic acid 0.5%, and the balance is wax material.

[0156] The sample is tested, and the product performance is shown in Table 110 below.

[0157] Table 110 Performance Detection Table of Samples in Example 14

[0158] No. Item Test Value Test Method 1 Freezing Point, °C 74.0 SH / T0132 2 Drop Melting Point, °C 78.2 GB / T8026 3 Normal Proportion, % 42.9 NB / SH / T0653 4 Non-Normal Proportion, % 57.1 NB / SH / T0653

[0159] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0160] Table 111 Application Composition Table of Samples in Example 14 (by weight parts)

[0161]

[0162]

[0163] Weigh the raw materials corresponding to the application examples in Table 111. After the raw material rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example samples.

[0164] The performance detection of the obtained application samples is shown in Table 112 below

[0165]

[0166] Example 15

[0167] The difference between the rubber protection wax in this example and that in Example 5 is only: antioxidant 2,6 - di - tert - butyl - p - cresol 2%, crystal form interference agent stearic acid 0.5%, and the balance is wax material.

[0168] The samples are tested, and the product performance is shown in Table 113 below.

[0169] Table 113 Performance Detection Table of Samples in Example 15

[0170] No. Item Test Value Test Method 1 Freezing Point, °C 71.1 SH / T0132 2 Drop Melting Point, °C 74.3 GB / T8026 3 Normal Proportion, % 43 NB / SH / T0653 4 Non-Normal Proportion, % 57 NB / SH / T0653

[0171] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0172] Table 114 Application Composition Table of Samples in Example 15 (by weight parts)

[0173]

[0174] Weigh the raw materials corresponding to the application examples in Table 114. After the raw material rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then carry out mold pressing and vulcanization at 150 °C for 65 min to obtain the application example samples.

[0175] The performance detection of the obtained application samples is shown in Table 115 below

[0176]

[0177] Example 16

[0178] The difference between the rubber protective wax of this example and that of Example 6 is only that its composition raw materials include: 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent stearic acid 0.5%, and the balance is wax material.

[0179] The samples were tested, and the product performance is shown in Table 116 below.

[0180] Table 116 Performance Test Table of Samples in Example 16

[0181] No. Item Test Value Test Method 1 Freezing Point, °C 62.2 SH / T0132 2 Drop Melting Point, °C 68.5 GB / T8026 3 Normal Proportion, % 43 NB / SH / T0653 4 Non-Normal Proportion, % 57 NB / SH / T0653

[0182] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by various comparative tests on the test colloid:

[0183] Table 117 Application Composition Table of Samples in Example 16 (by weight parts)

[0184]

[0185] Weigh the raw materials corresponding to the application examples in Table 117. After the raw rubber is kneaded by an open mill, the remaining raw materials are added for mixing to obtain a uniform mixture, and then it is molded and vulcanized at 150°C for 65 min to obtain the application example samples.

[0186] The performance test of the obtained application samples is shown in Table 118 below

[0187]

[0188] Group Three

[0189] Example 21

[0190] The rubber protective wax of this example, its composition raw materials include: N-isopropyl-N-phenyl-p-phenylenediamine 0.5%, crystal form interfering agent EVA 5%, and the balance is wax material. Among them, the composition of the raw materials of the wax material includes: the molecular weight of polyethylene wax is 10,000, and its content accounts for 4% of the total mass of the wax material; the melting range of paraffin wax is 40 - 70°C, and its content accounts for 26% of the total mass of the wax material; the melting range of microcrystalline wax is 60 - 90°C, and its content accounts for 70% of the total mass of the wax material.

[0191] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat it to 90 °C, after melting, start the stirrer, stir at a low speed of 30 rpm for 20 minutes at a constant temperature, then add paraffin wax, and stir and mix at 100 rpm for 30 minutes. Finally, add polyethylene wax and antioxidant, raise the temperature to 105 °C, and stir at 300 rpm for 30 minutes. Then discharge the molten wax from the reactor and enter the refiner to filter out impurities. The sample is tested, and the product performance is shown in Table 21 below.

[0192] Table 21 Performance Test Table of the Sample in Example 21

[0193] No. Item Test Value Test Method 1 Freezing Point, °C 75.6 SH / T0132 2 Drop Melting Point, °C 79.8 GB / T8026 3 Normal Proportion, % 32 NB / SH / T0653 4 Non-Normal Proportion, % 68 NB / SH / T0653

[0194] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0195] Table 22 Application Composition Table of the Sample in Example 21 (in parts by weight)

[0196]

[0197]

[0198] Weigh the raw materials corresponding to the application examples in Table 22. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then press and vulcanize at 150 °C for 65 minutes to obtain the application example samples.

[0199] The performance test of the obtained application samples is shown in Table 23 below

[0200]

[0201] Example 22

[0202] The rubber protective wax of this example has the following composition raw materials: dimethyl phthalate 0.5%, crystal form interfering agent octadecyl polyoxyethylene ether 15%, and the balance is wax material. Among them, the composition of the raw materials of the wax material includes: polyethylene wax with a molecular weight of 10,000, and its content accounts for 2% of the total mass of the wax material; paraffin wax has a melting range of 40 - 70 °C, and its content accounts for 50% of the total mass of the wax material; microcrystalline wax has a melting range of 60 - 90 °C, and its content accounts for 48% of the total mass of the wax material.

[0203] Weigh the raw materials according to the ratio: Add the weighed microcrystalline wax and crystal form interfering agent into a stainless steel kettle, slowly heat it to 80 °C, and after melting, start the stirrer. After stirring at a low speed of 20 rpm for 15 minutes at a constant temperature, add paraffin wax, and stir and mix at 80 rpm for 20 minutes. Finally, add polyethylene wax and antioxidant, raise the temperature to 100 °C, and stir at 250 rpm for 28 minutes. Then discharge the molten wax from the reactor into the finisher and filter out the impurities. Test the sample, and the product performance is shown in Table 24 below.

[0204] Table 24 Performance Test Table of the Sample in Example 22

[0205] No. Item Test Value Test Method 1 Freezing Point, °C 74.3 SH / T0132 2 Drop Melting Point, °C 77.1 GB / T8026 3 Normal Proportion, % 37 NB / SH / T0653 4 Non-Normal Proportion, % 63 NB / SH / T0653

[0206] The influence of the product of this example on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloid:

[0207] Table 25 Application Composition Table of the Sample in Example 22 (by weight parts)

[0208]

[0209]

[0210] Weigh the raw materials corresponding to the application examples in Table 25. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then perform mold pressing and vulcanization at 150 °C for 65 min to obtain the application example samples.

[0211] The performance test of the obtained application samples is shown in Table 26 below

[0212]

[0213] Group Four

[0214] Example 31

[0215] The difference between the rubber protective wax in this example and that in Example 1 is only that its composition raw materials include: antioxidant 2,6-di-tert-butyl-p-cresol 2%, crystal form interfering agent C 22 H 45 CON(CH3)(C2H5) 0.5 wt%, the molecular weight of polyethylene wax is 10,000, and its content accounts for 0.5% of the total mass (equivalently, polyethylene wax accounts for 0.5% of the total mass of the wax material); the melting range of paraffin wax is 40 - 70 °C, and its content accounts for 71% of the total mass (equivalently, paraffin wax accounts for 72.8% of the total mass of the wax material); the melting range of microcrystalline wax is 60 - 90 °C, and its content accounts for 26% of the total mass (equivalently, microcrystalline wax accounts for 26.7% of the total mass of the wax material).

[0216] The sample is tested, and the distribution of n-alkanes and non-n-alkanes is asFigure 1 As shown, the product performance is as shown in Table 31 below. The comparison of the crystal structures of the samples in this embodiment and this scheme without adding crystal form interfering agents is as follows Figure 2 shown.

[0217] Table 31 Performance Detection Table of Samples in Example 31

[0218] No. Item Test Value Test Method 1 Freezing Point, °C 62.1 SH / T0132 2 Drop Melting Point, °C 66.4 GB / T8026 3 Normal proportion, % 56.26 NB / SH / T0653 4 Non-normal proportion, % 43.74 NB / SH / T0653 5 Carbon peak <![CDATA[C 31 ~C 32 > NB / SH / T0653

[0219] The influence of the product of this embodiment on the physical properties of rubber products and its protective effect can be verified by conducting various comparative tests on the test colloids:

[0220] Table 32 Application Composition Table of Samples in Example 31 (by weight parts)

[0221]

[0222] Weigh the raw materials corresponding to the application examples in Table 32. After the raw rubber is kneaded by an open mill, add the remaining raw materials for mixing to obtain a uniform mixture, and then press and vulcanize at 150 °C for 65 min to obtain the application example samples.

[0223] The performance detection of the obtained application samples is as shown in Table 33 below

[0224]

[0225] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, in any regard, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to encompass all changes falling within the meaning and scope of the equivalent elements of the claims in the present invention.

[0226] In addition, it should be understood that although this specification is described according to the embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A rubber protective wax, the raw materials of which include wax materials and / or antioxidants, characterized in that: The raw materials further include a crystal form interfering agent, and the carbon atom number distribution range of the wax material is C 20 ~C 56 and it is selected from paraffin wax and microcrystalline wax, and the wax material satisfies, wt%: The content of non-normal paraffins is not less than 35%, and the content of normal paraffins is less than 65%: With the increase of carbon number, the percentage of non-normal paraffins with carbon number less than 34 in the total amount of paraffins shows an increasing trend, and with the increase of carbon number, the percentage of normal paraffins with carbon number less than 31 in the total amount of paraffins shows an increasing trend; The percentage of non-normal paraffins with carbon number 34 in the total amount of paraffins is 4-4.1%, and the percentage of normal paraffins with carbon number 31 in the total amount of paraffins is 7.1-7.2%; With the increase of carbon number, the percentage of non-normal paraffins with carbon number greater than 34 in the total amount of paraffins shows a decreasing trend, and the percentage of normal paraffins with carbon number greater than 31 in the total amount of paraffins shows a decreasing trend; The crystal form interfering agent has a non-polar end and a weakly polar end with good compatibility with waxy paraffin materials.

2. The rubber protective wax according to claim 1, wherein In the range of carbon number from 20 to 56 of the wax material, the percentage of non-normal paraffins in the total amount of paraffins shows a nearly normal distribution.

3. The rubber protective wax according to claim 2, wherein For the part of the wax material with carbon number not exceeding 28, the percentage of non-normal paraffins corresponding to each carbon number in the total amount of paraffins does not exceed 0.75%.

4. The rubber protective wax according to claim 3, wherein The percentage of non-normal paraffins with carbon number 29 in the total amount of paraffins of the wax material is 1.25-1.29%.

5. The rubber protective wax according to claim 2, wherein, For the part of the wax material with carbon number exceeding 40, the percentage of non-normal paraffins corresponding to each carbon number in the total amount of paraffins does not exceed 0.97%.

6. The rubber protective wax according to claim 5, characterized in that, The percentage of non-normal paraffins with carbon number 40 in the total amount of paraffins of the wax material is 1.40-1.43%.

7. The rubber protective wax according to claim 1, wherein, The melting range of paraffin in the wax material is 40-70°C, and its content accounts for 20-73.5% of the total mass of the wax material.

8. The rubber protective wax according to claim 1, wherein The melting range of microcrystalline wax in the wax material is 60-90°C, and its content accounts for 26.5-80% of the total mass of the wax material.

9. The rubber protective wax according to any one of claims 1 to 8, characterized in that The wax material also includes the balance of polyethylene wax, and the molecular weight of the polyethylene wax is between 1000 and 10000.

10. The rubber protective wax according to claim 1, characterized in that, The antioxidant in the raw material is selected from: N-isopropyl-N-phenyl-p-phenylenediamine, dimethyl phthalate, 2,6-di-tert-butyl-p-cresol.

11. The rubber protective wax according to claim 1, wherein The crystal form interfering agent is selected from: EVA, amide, higher fatty acid, higher alkyl polyoxyethylene ether.

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