CN107868479B - Protective wax containing trimodal carbon number distribution and application thereof in rubber products - Google Patents
Protective wax containing trimodal carbon number distribution and application thereof in rubber products Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a rubber protective wax containing trimodal carbon number distribution, wherein the trimodal means that three peak values appear on a total carbon number distribution diagram of the protective wax, and the rubber protective wax comprises the following components in percentage by weight: 40-80% of fully refined paraffin, 0-50% of microcrystalline wax, 0-5% of linear polyethylene and 0-20% of Fischer-Tropsch wax. The protective wax of the invention has a broader range of trimodal carbon number distribution, suitable n/isoparaffin content, higher molecular weight, broader molecular weight distribution, and higher congealing point. The protective wax can be used in a tire sizing formula or other rubber products, the ozone protective film formed on the surface has higher stability, better durability and wider ozone protection temperature range, and the appearance quality of the tire or other rubber products can be improved.
Description
Technical Field
The invention belongs to the technical field of rubber, and relates to a rubber composition containing rubber protective wax with a trimodal carbon number distribution and application thereof.
Background
The rubber protective wax commonly used at present is a mixed wax prepared by blending paraffin wax and microcrystalline wax. The rubber protective wax migrates to the surface of a rubber product before ozone molecules in the air react with diene rubber macromolecules, a layer of compact protective film is formed on the surface, direct contact between the ozone and the rubber macromolecules is avoided, so that the rubber protective wax is used for blocking the attack of the ozone to the rubber macromolecules, preventing unsaturated double bonds in the rubber macromolecules from generating addition reaction with the ozone in the air, and preventing aging under the action of light and oxygen, so that the rubber macromolecules are broken and lose elasticity at double bond positions, and cracks (commonly called cracks) are generated on the surface of a tire or other rubber products to finally influence the service life and appearance quality of the tire or other rubber products. In the modern tire industry, particularly for 'green' tires, a new formula needs to be researched to meet higher requirements of low rolling resistance, wet skid resistance, low noise performance and wear resistance improvement of the green tires, and higher requirements are also put forward for rubber protective wax. The anti-aging performance of the rubber protective wax in the tire is closely related to the congealing point, the molecular weight and the distribution, the normal/iso carbon content and the distribution of the rubber protective wax and the content in different carbon number ranges.
The rubber protective wax on the current market has the following problems:
1. the carbon number distribution is often unimodal or bimodal, or the protection temperature range is low, only effective protection can be carried out within the temperature range of-10 ℃ to 40 ℃, and the protection performance is reduced when the temperature is higher than 40 ℃; or the protection temperature is higher, the effective protection can be only carried out within the temperature range of 10 ℃ to 60 ℃, and the protection performance in winter when the temperature is lower than 10 ℃ is reduced;
2. the molecular weight is small, the distribution is narrow, the freezing point is low, the speed of migration or ejection to the surface of a tire or a rubber product is high due to low solubility in a rubber matrix, and an ozone protection film formed on the outer surface of the tire is not compact and stable enough, so that the appearance quality of the surface of the tire is influenced, and the ozone protection effect on the surface of the tire is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a protective wax containing a trimodal carbon number distribution.
In the invention, the protective wax comprises a mixture of four components of fully refined paraffin wax, microcrystalline wax, linear polyethylene and Fischer-Tropsch wax. In the protective wax containing the trimodal carbon number distribution, the total carbon number distribution has three peaks, the first peak appears in C24-C29, the second peak appears in C31-C38, and the third peak appears in C41-C55, so that the protective wax has a wider trimodal carbon number distribution, proper normal/iso carbon content, higher molecular weight, wider molecular weight distribution and higher freezing point.
In the invention, the protective wax specifically comprises: 40-80% of fully refined paraffin; 0-50% microcrystalline wax; 0-5% linear polyethylene; 0-20% Fischer-Tropsch wax.
Preferably, the protective wax specifically comprises: 50% -70% of fully refined paraffin; 25% -40% microcrystalline wax; 0-3% linear polyethylene; 0-10% Fischer-Tropsch wax.
Wherein the freezing point of the fully refined paraffin is 52-70 ℃.
Wherein the melting point of the microcrystalline wax drops is 70-90 ℃; preferably, it is from 70 ℃ to 85 ℃.
Wherein the melting point of the linear polyethylene is 80-120 ℃; preferably, it is 90 ℃ or 110 ℃.
Wherein the Fischer-Tropsch wax is a high-purity synthetic wax with a medium or high drop melting point, which is synthesized by adopting a Fischer-Tropsch method, and the drop melting point is 80-110 ℃; preferably, from 85 ℃ to 110 ℃.
Wherein the molecular weight includes a number average molecular weight Mn and a weight average molecular weight Mw. The number average molecular weight Mn is between 700 and 1000, preferably between 712 and 994; the weight average molecular weight Mw is between 1000 and 2200, preferably between 1096 and 2156.
Wherein said molecular weight size and distribution are determined by gel chromatography.
Wherein the freezing point of the protective wax is 70-80 ℃; preferably, it is from 70 ℃ to 76 ℃.
Wherein the freezing point is determined according to SH/T0132-2004 standard.
Wherein, the melting point is determined according to GB/T8026-2014 standard, the product grade of the fully refined paraffin corresponds to the range of the freezing point by referring to the fully refined paraffin GB/T446-2010, such as national standard No. 62, the corresponding freezing point is 60-62 ℃, national standard No. 64, the corresponding freezing point is 62-64 ℃; the product grades of the microcrystalline wax and the Fischer-Tropsch wax correspond to the drop melting point index.
Wherein said normal and iso carbons are normal and non-normal (iso) alkanes and the carbon number content and distribution are determined according to SH/T0653-1998 standard.
Wherein the protective wax contains 50-80% of a positive carbon structure, 0.5-1.5% of a positive carbon content between C16 and C20, 2.4-5% of a positive carbon content between C21 and C23, 4.5-8.5% of a positive carbon content between C24 and C26, 3.4-5% of a positive carbon content between C27 and C28, 5-8% of a positive carbon content between C29 and C30, 10-15% of a positive carbon content between C31 and C33, 6-9% of a positive carbon content between C34 and C6329, 6-9% of a positive carbon content between C37 and C68642, 6-8% of a positive carbon content between C41 and C43, 2-4% of a positive carbon content between C44 and C465, and 2-584.5% of a positive carbon content between C46 and C584.4%, the positive carbon content between C53 and C62 is 1.3% -3%.
Preferably, the protective wax has a positive carbon structure content of 52% -76.6%, wherein the positive carbon content between C16 and C20 is 0.7% -1.4%, the positive carbon content between C21 and C23 is 2.4% -4.8%, the positive carbon content between C24 and C26 is 4.8% -8.4%, the positive carbon content between C27 and C28 is 3.4% -4.7%, the positive carbon content between C29 and C30 is 5.1% -7.8%, the positive carbon content between C31 and C33 is 10.3% -14.8%, the positive carbon content between C34 and C36 is 6.2% -8.9%, the positive carbon content between C37 and C40 is 6.3% -8.8%, the positive carbon content between C41 and C43 is 6.1% -7.8.9%, the positive carbon content between C37 and C40 is 6.3% -8.8%, the positive carbon content between C463% and C582% is 3.5732-C584.3%, and C5732% is 3.8%, the positive carbon content between C53 and C62 is 1.3% -2.3%.
Wherein the protective wax contains 20-50% of iso-carbon structure, 0-0.5% of iso-carbon between C16 and C20, 0.5-1% of iso-carbon between C21 and C23, 1-2.5% of iso-carbon between C24 and C26, 0.5-1% of iso-carbon between C27 and C28, 1-2% of iso-carbon between C29 and C30, 3-7% of iso-carbon between C31 and C33, 2-6% of iso-carbon between C34 and C36, 4.5-10% of iso-carbon between C37 and C40, 4-8% of iso-carbon between C41 and C43, 1-4% of iso-carbon between C44 and C5, and 1-4% of iso-carbon between C46 and C52, the content of the carbon atoms between C53 and C62 is 0.5 to 2 percent.
Preferably, the protective wax contains 23.4% -48% of iso-carbon structure, wherein the iso-carbon content between C16 and C20 is 0% -0.4%, the iso-carbon content between C21 and C23 is 0.5% -0.9%, the iso-carbon content between C24 and C26 is 1.3% -2.3%, the iso-carbon content between C27 and C28 is 0.7% -0.9%, the iso-carbon content between C29 and C638 is 1.4% -1.9%, the iso-carbon content between C31 and C33 is 3.1% -6.7%, the iso-carbon content between C34 and C36 is 2.2% -5.9%, the iso-carbon content between C37 and C40 is 4.9% -9.7%, the iso-carbon content between C41 and C43 is 4.4% -7.468%, the iso-carbon content between C375% and C583. 45% is 3.3% -3% and C583.7%, the content of the carbon atoms between C53 and C62 is 0.7 to 2 percent.
Compared with the rubber protective wax on the market, the protective wax has wider trimodal carbon number distribution, proper n/isoparaffin content, higher molecular weight, wider molecular weight distribution and higher congealing point. The protective wax can be used in a tire sizing formula or other rubber products, the ozone protective film formed on the surface has higher stability, better durability and wider ozone protection temperature range, and the appearance quality of the tire or other rubber products can be improved.
The invention also provides a preparation method of the protective wax containing the trimodal carbon number distribution, which comprises the following specific steps:
(1) weighing fully refined paraffin, microcrystalline wax, Fischer-Tropsch wax and linear polyethylene according to the proportion;
(2) adding weighed fully refined paraffin, microcrystalline wax, Fischer-Tropsch wax and linear polyethylene into a melting tank, heating to 80-140 ℃, melting for 10-60 minutes, after complete melting, entering a stirring tank, heating to 80-120 ℃, and stirring at constant temperature for 10-60 minutes; and filtering, cooling and forming the obtained product to obtain the protective wax.
Wherein in the step (1), the proportion of the fully refined paraffin, the microcrystalline wax, the Fischer-Tropsch wax and the linear polyethylene is as follows: 40-80% of fully refined paraffin; 20% -50% microcrystalline wax; 0-5% linear polyethylene; 0-20% Fischer-Tropsch wax. Preferably, the method comprises the following steps: 50% -70% of fully refined paraffin; 25% -40% microcrystalline wax; 0-3% linear polyethylene; 0-10% Fischer-Tropsch wax.
Wherein, in the step (2), after the addition to the melting tank, the temperature is preferably raised to 80 ℃, 100 ℃, 110 ℃ or 140 ℃, and the melting time is preferably 10 minutes, 20 minutes, 30 minutes or 60 minutes.
In the step (2), after entering the stirring tank, the temperature is preferably raised to 70.2 ℃, 100 ℃ or 120 ℃, and the stirring time is preferably 10 minutes, 20 minutes, 30 minutes or 60 minutes.
The invention also provides the protective wax containing the trimodal carbon number distribution, which is prepared by the method.
The invention also provides the application of the protective wax containing the trimodal carbon number distribution in rubber products; the rubber products comprise rubber products such as tire treads and sidewall rubber materials, conveying belts, driving belts, automobiles, bridges, building damping parts, rubber shoes and the like.
The invention also provides a rubber composition containing the protective wax with the trimodal carbon number distribution, which comprises the following components in percentage by weight: 100 parts of rubber component, 40.0-60.0 parts of carbon black, 1.0-10.0 parts of process oil, 1.5-5.0 parts of anti-aging agent, 1.0-5.0 parts of protective wax with a trimodal carbon number distribution, 1.0-5.0 parts of sulfur and 0.5-3.0 parts of accelerator.
Preferably, the rubber composition comprises: 100 parts of rubber component, 45-55 parts of carbon black, 2-8 parts of process oil, 2-4 parts of anti-aging agent, 2-4 parts of protective wax with trimodal carbon number distribution, 2-4 parts of sulfur and 1-2 parts of accelerator.
Wherein, the rubber component comprises natural rubber and styrene butadiene rubber; the preferred ratio between the two is 0.5-2.
Wherein, the carbon black can be various grades on the market, and is preferably N375.
The operating oil can be various brands on the market, and is preferably environment-friendly aromatic oil.
The anti-aging agent can be various brands on the market, and preferably TMQ, DTPD and 6 PPD.
Wherein the protective wax has a trimodal carbon number distribution.
Wherein the accelerant can be various brands on the market, and zinc oxide is preferred
Wherein, the sulfur can be selected from various brands on the market, and is preferably common sulfur.
Compared with the prior art, the invention has the beneficial effects that:
(1) the protective wax adopted by the invention has a wider range of trimodal carbon number distribution and wider molecular weight distribution, and can effectively protect the tires from ozone for a long time at the temperature of-10 ℃ to 60 ℃ within a wider range of high and low temperatures;
(2) the protective wax adopted by the invention has higher molecular weight, proper normal/different carbon content, higher intermiscibility in a tire rubber material, slower speed of transferring or spraying to the surface, no whitening of a wax film transferred to the surface of the tire and good appearance quality of the surface of the tire;
(3) the protective wax adopted by the invention has a higher freezing point (70-80 ℃), and an ozone protective film formed on the outer surface of the tire is stable and is not easy to break even reaching 70 ℃, so that the tire has more effective ozone protection in a higher temperature range;
(4) the rubber composition provided by the invention has excellent high-temperature ozone aging resistance and sunlight aging resistance, the protective wax can form a protective film after being used for a long time, the service life of a rubber product can be prolonged, the ozone protective film formed on the surface has higher stability and better durability, the temperature range of ozone protection is wider, and the appearance quality of a tire or other rubber products can be improved.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
In the description of the specific examples which follow, the components are measured in percent by weight.
Example 1
6% of fully refined paraffin (national standard No. 52), 8% of fully refined paraffin (national standard No. 62), 12% of fully refined paraffin (national standard No. 64), 26% of fully refined paraffin (national standard No. 66), 10% of fully refined paraffin (national standard No. 68), 20% of fully refined paraffin (national standard No. 70), 15% of microcrystalline wax (melting point drop 75 ℃) and 5% of microcrystalline wax (melting point drop 90 ℃).
Adding the weighed microcrystalline wax and fully refined paraffin into a melting tank, heating to 80 ℃, maintaining for 60min, completely melting, entering a stirring tank, and stirring and mixing for 60min at 80 ℃; and filtering, cooling and forming the obtained product to obtain the product. The freezing point of the product is 70.2 ℃, the content of a normal carbon structure is 76.6%, wherein the content of the normal carbon between C16 and C20 is 1.4%, the content of the normal carbon between C21 and C23 is 4.8%, the content of the normal carbon between C24 and C26 is 8.4%, the content of the normal carbon between C27 and C28 is 4.7%, the content of the normal carbon between C29 and C30 is 7.8%, the content of the normal carbon between C31 and C33 is 14.8%, the content of the normal carbon between C34 and C36 is 8.9%, the content of the normal carbon between C37 and C40 is 8.8%, the content of the normal carbon between C41 and C43 is 7.8%, the content of the normal carbon between C44 and C45 is 3.4%, the content of the normal carbon between C2 and C52 is 3.5%, and the content of the normal carbon between C863.3.3%.
The iso-carbon structure content is 23.4%, wherein the iso-carbon content between C16 and C20 is 0%, the iso-carbon content between C21 and C23 is 0.7%, the iso-carbon content between C24 and C26 is 1.3%, the iso-carbon content between C27 and C28 is 0.7%, the iso-carbon content between C29 and C30 is 1.6%, the iso-carbon content between C31 and C33 is 3.1%, the iso-carbon content between C34 and C36 is 2.2%, the iso-carbon content between C37 and C40 is 4.9%, the iso-carbon content between C41 and C43 is 4.4%, the iso-carbon content between C44 and C45 is 1.5%, the iso-carbon content between C46 and C52 is 2.3%, and the iso-carbon content between C53 and C62 is 0.7%. The number average molecular weight Mn was 712 and the weight average molecular weight Mw was 1096.
Example 2
6% of fully refined paraffin (national standard No. 62), 10% of fully refined paraffin (national standard No. 64), 6% of fully refined paraffin (national standard No. 66), 18% of fully refined paraffin (national standard No. 68), 15% of microcrystalline wax (national standard No. 75), 5% of microcrystalline wax (drop melting point 80 ℃), 9% of Fischer-Tropsch wax (drop melting point 85 ℃), 7% of Fischer-Tropsch wax (drop melting point 95 ℃), 1.5% of Fischer-Tropsch wax (drop melting point 110 ℃), and 2.5% of linear polyethylene (melting point 120 ℃).
Adding the weighed microcrystalline wax, fully refined paraffin, linear polyethylene and Fischer-Tropsch wax into a melting tank, heating to 140 ℃, maintaining for 10min, completely melting, entering a stirring tank, and stirring for 10min at 120 ℃; and filtering, cooling and forming the obtained product to obtain the product. The freezing point of the product is 79.6 ℃, the content of a normal carbon structure is 52%, wherein the content of the normal carbon between C16 and C20 is 0.7%, the content of the normal carbon between C21 and C23 is 2.6%, the content of the normal carbon between C24 and C26 is 4.8%, the content of the normal carbon between C27 and C28 is 3.7%, the content of the normal carbon between C29 and C30 is 5.1%, the content of the normal carbon between C31 and C33 is 10.3%, the content of the normal carbon between C34 and C36 is 6.2%, the content of the normal carbon between C37 and C40 is 6.3%, the content of the normal carbon between C41 and C43 is 6.1%, the content of the normal carbon between C44 and C45 is 2.2%, the content of the normal carbon between C46 and C52 is 2.5%, and the content of the normal carbon between C6327 and C845 is 865%.
The rubber protective wax contains 48% of an iso-carbon structure, wherein the iso-carbon content between C16 and C20 is 0.4%, the iso-carbon content between C21 and C23 is 0.9%, the iso-carbon content between C24 and C26 is 2.3%, the iso-carbon content between C27 and C28 is 0.9%, the iso-carbon content between C29 and C30 is 1.8%, the iso-carbon content between C31 and C33 is 6.7%, the iso-carbon content between C34 and C36 is 5.9%, the iso-carbon content between C37 and C40 is 9.7%, the iso-carbon content between C41 and C43 is 7.8%, the iso-carbon content between C44 and C45 is 3.8%, the iso-carbon content between C46 and C52 is 5.8%, and the iso-carbon content between C8427 and C862% is 8427%. The number average molecular weight Mn was 994 and the weight average molecular weight Mw was 2156.
Example 3
10% of fully refined paraffin (national standard No. 64), 22% of fully refined paraffin (national standard No. 66), 23% of fully refined paraffin (national standard No. 68), 5% of microcrystalline wax (national standard No. 70), 15% of microcrystalline wax (national standard No. 80), 10% of Fischer-Tropsch wax (melting point 85 ℃), 8% of Fischer-Tropsch wax (melting point 95 ℃), 2% of Fischer-Tropsch wax (melting point 110 ℃), and 5% of linear polyethylene (melting point 105 ℃).
Adding the weighed microcrystalline wax, fully refined paraffin, linear polyethylene and Fischer-Tropsch wax into a melting tank, heating to 110 ℃, maintaining for 20min, completely melting, entering a stirring tank, and stirring for 20min at 100 ℃; and filtering, cooling and forming the obtained product to obtain the product. The freezing point of the product is 74 ℃, the content of a positive carbon structure is 55.8%, wherein the content of the positive carbon between C16 and C20 is 0.8%, the content of the positive carbon between C21 and C23 is 2.4%, the content of the positive carbon between C24 and C26 is 5.5%, the content of the positive carbon between C27 and C28 is 3.4%, the content of the positive carbon between C29 and C30 is 6.1%, the content of the positive carbon between C31 and C33 is 11.3%, the content of the positive carbon between C34 and C36 is 6.9%, the content of the positive carbon between C37 and C40 is 6.7%, the content of the positive carbon between C41 and C43 is 6.8%, the content of the positive carbon between C44 and C45 is 2.2%, the content of the positive carbon between C46 and C52 is 2.4%, and the content of the positive carbon between C6327 and C863 is 1.3%.
The iso-carbon structure content is 44.2%, wherein the iso-carbon content between C16 and C20 is 0.4%, the iso-carbon content between C21 and C23 is 0.9%, the iso-carbon content between C24 and C26 is 2.3%, the iso-carbon content between C27 and C28 is 0.8%, the iso-carbon content between C29 and C30 is 1.9%, the iso-carbon content between C31 and C33 is 6.7%, the iso-carbon content between C34 and C36 is 4.5%, the iso-carbon content between C37 and C40 is 8.5%, the iso-carbon content between C41 and C43 is 7.6%, the iso-carbon content between C44 and C45 is 3.9%, the iso-carbon content between C46 and C52 is 5.2%, and the iso-carbon content between C53 and C62 is 1.5%. The number-average molecular weight Mn is 812 and the weight-average molecular weight Mw is 1696.
Example 4
8% of fully refined paraffin wax (national standard No. 62), 13% of fully refined paraffin wax (national standard No. 64), 39% of fully refined paraffin wax (national standard No. 68), 25% of microcrystalline wax (national standard No. 70), 10% of microcrystalline wax (drop melting point 90 ℃) and 5% of Fischer-Tropsch wax (drop melting point 110 ℃).
Adding the weighed microcrystalline wax, fully refined paraffin, linear polyethylene and Fischer-Tropsch wax into a melting tank, heating to 100 ℃, maintaining for 30min, completely melting, entering a stirring tank, and stirring for 30min at 100 ℃; and filtering, cooling and forming the obtained product to obtain the product. The freezing point of the product is 70.8 ℃, the positive carbon structure content is 59.9%, the positive carbon content between C16 and C20 is 0.9%, the positive carbon content between C21 and C23 is 2.9%, the positive carbon content between C24 and C26 is 5.9%, the positive carbon content between C27 and C28 is 3.8%, the positive carbon content between C29 and C30 is 6.7%, the positive carbon content between C31 and C33 is 11.8%, the positive carbon content between C34 and C36 is 7.9%, the positive carbon content between C37 and C40 is 7.2%, the positive carbon content between C41 and C43 is 6%, the positive carbon content between C44 and C45 is 2.8%, the positive carbon content between C46 and C52 is 2.6%, and the positive carbon content between C62 and C53 is 1.82%.
The iso-carbon structure content is 40.1%, wherein the iso-carbon content between the carbon numbers C16 and C20 is 0.3%, the iso-carbon content between the carbon numbers C21 and C23 is 0.5%, the iso-carbon content between the carbon numbers C24 and C26 is 2.1%, the iso-carbon content between the carbon numbers C27 and C28 is 0.8%, the iso-carbon content between the carbon numbers C29 and C30 is 1.4%, the iso-carbon content between the carbon numbers C31 and C33 is 5.7%, the iso-carbon content between the carbon numbers C34 and C36 is 4.1%, the iso-carbon content between the carbon numbers C37 and C40 is 7.9%, the iso-carbon content between the carbon numbers C41 and C43 is 7.3%, the iso-carbon content between the carbon numbers C44 and C45 is 3.3%, the iso-carbon content between the carbon numbers C46 and C52 is 4.9%, and the iso-carbon numbers C8427-848% are 861%. The number-average molecular weight Mn is 735 and the weight-average molecular weight Mw is 1196.
The above 4 examples are preferred embodiments of the present invention, and for illustrating the advantages of the present invention, 3 major brands of rubber protective wax are purchased from the market, and the A/B/C is used as a code number, and compared with the rubber protective wax obtained in the examples, see Table 1 below.
TABLE 1 Performance test index of the product of the example
As is clear from the data in Table 1, the rubber protective waxes of examples 1, 2, 3, and 4 all had a trimodal carbon number distribution, a high weight average molecular weight, and a high congealing point as compared with the comparative A/B/C.
The influence of the product of the invention on the physical properties and the protection effect of the tire are verified by comparing each item through an application experiment, and the experimental results are shown in the following table 2.
The specific sample preparation and the specific experimental procedure were as follows:
the preparation of the sample is strictly in accordance with GB/T6038-
1. Preparation of formula and sample:
NR (SCR 10): 48; BR 9000: 52; carbon black N550: 52; a process oil 8; chemical anti-aging agent: 3.5; protective wax: 2.5; and (3) sulfur: 1.6; other accelerators, etc.: 2.
2. experimental equipment and methods:
the 3L kneader, 6 inch open mill, Alpha rubber rotorless sulfur variation apparatus MDR2000, Alpha Mooney viscometer MV2000, Instron tensile machine 3365, and other equipment were used normally.
3. Mixing process:
7 different rubber protective waxes are subjected to the same-quantity variety-changing test of the formula. The same 2-stage mixing process was used, and mixing was carried out in a 3L kneader at 45r/min for one stage. The sulfur and accelerator were added at 25r/min in the second stage using the same equipment, and the sheet was taken off on a 6-inch open mill.
4. Ozone aging static and dynamic test method:
adopting ASTM D1149GB7762 standard
Sample conditioning:
stretching 10%, or 20%, or 35%, or 50%, or others, standing at room temperature 23 ℃ for 0 hour, 24 hours, 48 hours, 72 hours, or more, standing for conditioning in the stretched state to allow the "wax film" that has broken in the stretched state to reform, the higher the congealing point, or the higher the iso-carbon content, or the higher the molecular weight of the protective wax, the longer the standing conditioning time is required to form a stable "protective film".
Ozone aging conditions
Ozone concentration: 50pphm, 100pphm, 200pphm, 300pphm, or others, one of which is selected
Aging temperature: 40 + -2 deg.C, 0 + -2 deg.C, 20 + -2 deg.C, 50 + -2 deg.C or others
Aging time: 24 hours, 36 hours, 48 hours, 60 hours, 72 hours, 96 hours, or others, selected from one of them
5. And (4) evaluating the result:
observation under stretched condition
Crack rating 0 (no cracks), 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 cracks
TABLE 2 comparison of physical Properties of seven protective waxes in the same formulation
The seven rubber protective waxes have no obvious influence on the physical and mechanical properties of the rubber material, and the physical and mechanical properties are relatively close.
Ozone aging according to GB7762 under the experimental conditions of 100pphm ozone concentration and 50 + -2 deg.C temperature, the experimental results are shown in the following table 3:
TABLE 3 comparison results of ozone accelerated tests in seven protective wax laboratories
The weather-resistant solar aging test results are shown in the following table 4:
TABLE 4 weather-aging resistance comparison results of seven protective waxes
As can be seen from the comparison of the experimental results in tables 3 and 4, the rubber protective wax prepared according to examples 1 to 4 of the present invention has superior high-temperature ozone aging performance and sunlight aging performance to those of other similar products.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (5)
1. The protective wax containing the trimodal carbon number distribution is characterized by comprising fully refined paraffin, microcrystalline wax, linear polyethylene and Fischer-Tropsch wax, wherein the weight percentage of each component is as follows: 40-80% of fully refined paraffin; 0% -50% microcrystalline wax; 0-5% linear polyethylene; 0-20% fischer-tropsch wax;
wherein the protective wax contains 50-80% of a positive carbon structure, 0.5-1.5% of positive carbon between C16 and C20, 2.4-5% of positive carbon between C21 and C23, 4.5-8.5% of positive carbon between C24 and C26, 3.4-5% of positive carbon between C27 and C28, 5-8% of positive carbon between C29 and C30, 10-15% of positive carbon between C31 and C33, 6-9% of positive carbon between C34 and C36, 6-9% of positive carbon between C37 and C40, 6-8% of positive carbon between C41 and C43, 2-4% of positive carbon between C44 and C45, and 2-584% of positive carbon between C46 and C52, the positive carbon content between C53 and C62 is 1.3% -3%;
wherein the protective wax contains 20-50% of iso-carbon structure, wherein the iso-carbon content between C16 and C20 is 0-0.5%, the iso-carbon content between C21 and C23 is 0.5-1%, the iso-carbon content between C24 and C26 is 1-2.5%, the iso-carbon content between C27 and C28 is 0.5-1%, the iso-carbon content between C29 and C30 is 1-2%, the iso-carbon content between C31 and C33 is 3-7%, the iso-carbon content between C34 and C36 is 2-6%, the iso-carbon content between C37 and C40 is 4.5-10%, the iso-carbon content between C41 and C43 is 4-8%, the iso-carbon content between C44 and C5 is 1-4%, and the iso-carbon content between C46 and C52 is 2-5736%, the content of iso-carbon between C53 and C62 is 0.5 to 2 percent;
the total carbon number distribution of the protective wax has three peaks, wherein the first peak appears in C24-C29, the second peak appears in C31-C38, and the third peak appears in C41-C55.
2. The protective wax having a trimodal carbon number distribution according to claim 1, wherein the fully refined paraffin wax has a congealing point of 52 ℃ to 70 ℃; the melting point of the microcrystalline wax drops is 70-90 ℃; the melting point of the linear polyethylene is 80-120 ℃; the melting point of the Fischer-Tropsch wax drops is 80-110 ℃.
3. The protective wax having a trimodal carbon number distribution as claimed in claim 1, wherein the protective wax has a congealing point of 70 ℃ to 80 ℃, a number average molecular weight Mn of 700-1000 and a weight average molecular weight Mw of 1000-2200.
4. Use of the protective wax comprising a trimodal carbon number distribution as claimed in any one of claims 1 to 3 for the preparation of rubber articles.
5. The use of claim 4, wherein the rubber article comprises a tire tread, sidewall compound, conveyor belt, power transmission belt, automobile, bridge, building bumper, rubber shoe.
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| WO2019244578A1 (en) * | 2018-06-18 | 2019-12-26 | 横浜ゴム株式会社 | Pneumatic tire |
| CN109777128B (en) * | 2019-01-31 | 2021-04-06 | 青岛福凯橡塑新材料有限公司 | High-isoparaffin rubber protective wax and preparation method thereof |
| CN113004586B (en) * | 2019-12-19 | 2023-01-03 | 彤程化学（中国）有限公司 | Tire side wall rubber composition with low hysteresis loss and improved appearance and preparation method thereof |
| CN113045988B (en) * | 2021-03-04 | 2022-04-19 | 中国石油化工股份有限公司 | All-weather special protective wax based on soft microcrystalline wax and preparation method thereof |
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| CN1362453A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Rubber protecting wax |
| CN1760278A (en) * | 2004-10-12 | 2006-04-19 | 中国石油天然气股份有限公司 | Wax-for preventing rubber |
| CN101649119A (en) * | 2009-03-20 | 2010-02-17 | 上海绿菱特种蜡制品厂 | Novel rubber protective wax |
| CN106715594A (en) * | 2014-10-10 | 2017-05-24 | 日油株式会社 | Surface physical property modifier composition, thermoplastic resin composition containing same, and resin molded article therefrom |
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| CN1362453A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Rubber protecting wax |
| CN1760278A (en) * | 2004-10-12 | 2006-04-19 | 中国石油天然气股份有限公司 | Wax-for preventing rubber |
| CN101649119A (en) * | 2009-03-20 | 2010-02-17 | 上海绿菱特种蜡制品厂 | Novel rubber protective wax |
| CN106715594A (en) * | 2014-10-10 | 2017-05-24 | 日油株式会社 | Surface physical property modifier composition, thermoplastic resin composition containing same, and resin molded article therefrom |
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