CN115651285B - Mixing method of silane coupling agent and rubber composition - Google Patents
Mixing method of silane coupling agent and rubber composition Download PDFInfo
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- 238000002156 mixing Methods 0.000 title claims abstract description 86
- 229920001971 elastomer Polymers 0.000 title claims abstract description 58
- 239000005060 rubber Substances 0.000 title claims abstract description 58
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000006229 carbon black Substances 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 6
- 229920001021 polysulfide Polymers 0.000 claims description 6
- 150000008117 polysulfides Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 241000227425 Pieris rapae crucivora Species 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 22
- 239000006185 dispersion Substances 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 20
- 238000004513 sizing Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000002444 silanisation Methods 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000679 tetrasulfanyl group Chemical group [*]SSSS[H] 0.000 description 1
- IOOGPFMMGKCAGU-UHFFFAOYSA-N tetrasulfur Chemical compound S=S=S=S IOOGPFMMGKCAGU-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- -1 triethoxy, silyl Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the application field of industries such as tires, products and the like, in particular to a mixing method of a silane coupling agent and a rubber composition. According to the method, different silane coupling agents are integrally separated by using a formula, namely, all materials in a mixing stage in the formula are separated according to the proportion of the different silane coupling agents, and the manufacturability problem caused by the combination of the silane coupling agents is fundamentally solved on the premise of not influencing the dispersion degree of the two-stage white carbon black.
Description
Technical Field
The invention relates to the application field of industries such as tires, products and the like, in particular to a mixing method of a silane coupling agent and a rubber composition.
Background
In the rubber tire industry, the main stream reinforcing materials of rubber are divided into two main types, carbon black and white carbon black. White carbon black is widely used in the field of tires with its characteristic low rolling resistance and high wet grip as compared with conventional carbon black. However, since the surface of the white carbon black has a large number of hydroxyl groups, has strong polarity and is not compatible with nonpolar rubber, a substance needs to be introduced to modify the surface of the white carbon black, so that the surface of the white carbon black is changed from polarity to nonpolar, and the white carbon black is well compatible with the rubber. A widely used modifier in the rubber industry is a silane coupling agent.
The molecular structural general formula of the silane coupling agent is as follows,
the two ends of the silica gel are provided with functional groups which can be subjected to chemical reaction, the functional groups (such as triethoxy, silyl and the like) at one end and silicon hydroxyl on the surface of the silica gel are subjected to chemical reaction in a mixing stage, ethanol is removed, and the polar silica gel is changed into nonpolar silica gel. Meanwhile, the functional group (such as tetra-sulfanyl, thiocyanato and the like) at the other end can react with rubber in a vulcanization stage to form a rubber-filler network, so that the problem of incompatibility between white carbon black and rubber is solved, and meanwhile, the rubber and the white carbon black are indirectly and chemically grafted together, thereby achieving the purposes of reducing rolling resistance and improving wet land grip.
In order to better achieve the purpose of modifying the surface of the white carbon black, the usage amount of the silane coupling agent needs to be excessively used, generally 8-12 percent (weight parts) of the usage amount of the white carbon black, and along with the proposal of policies such as European Union labeling method, the usage amount of the white carbon black in a formula is increased to improve the performance of the tire, so that the usage amount of the silane coupling agent is increased. However, if the mercapto alkoxy silane Si363 has high activity, it is easy to cross-link with the rubber molecular chain in the banburying stage, and when the Si363 is used in a large amount, the processing safety of the formulation is greatly reduced. For example, the polysulfide-bond-containing silane Si69 itself has an average number of 3.8 sulfur atoms, and S-S bonds are broken and rearranged in the vulcanization stage, and the excessive sulfur atoms are released to participate in crosslinking. When Si69 is used in large amounts, it affects the cure system of the formulation and thus the formulation properties.
In order to reduce the negative effects caused by the excessive use of certain silane coupling agents, different kinds of methods are used in the rubber tire industry, such as the combination of two silane coupling agents of Si363 and Si 69. The applicant finds that, because the functional groups of different types of silane are different, the optimal reaction temperature is different, for example, the optimal reaction temperature of mercaptosilane Si363 is 130-135 ℃, the optimal reaction temperature of tetrasulfur silane Si69 is 138-143 ℃, and the optimal reaction temperature of disulfide silane Si75 is 143-148 ℃, and because the silane coupling agent can undergo side reactions such as crosslinking after exceeding the optimal reaction temperature, the lower optimal reaction temperature can only be selected for mixing when the different types of silane coupling agents are used together, and the mixing efficiency of the sizing material can be reduced by mixing at low temperature, the dispersion degree of white carbon black can be reduced, and thus adverse effects on the properties of the final sizing material, such as poor physical properties and abrasion performance of the sizing material, can be caused.
In order to reduce the negative effect of low-temperature mixing on the performance of the formula, some companies have developed mixing processes in which different silane coupling agents are added in different mixing stages according to the optimal reaction temperature from high to low (for example, the applicant filed Chinese patent application No. CN 112847870A), such as adding Si69 with higher optimal reaction temperature in one stage and adding Si363 with lower optimal reaction temperature in the second stage. The process solves the adverse effect caused by mixing the silane coupling agent at low temperature when the silane coupling agent is used, but as the hydroxyl on the surface of the white carbon black is reacted with the silane coupling agent after one-stage mixing, when the silane coupling agent is added again in the second stage, the silane coupling agent with higher optimal reaction temperature is added in the first stage on the surface of the white carbon black, and the steric hindrance effect exists, so that the silanization reaction rate of the silane coupling agent added in the second stage is influenced, and the final performance of the formula sizing material is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a mixing method of a silane coupling agent and a rubber composition, which integrally separates different silane coupling agents and a formula, namely, all materials in a mixing stage in the formula are separated according to the proportion of the different silane coupling agents, and the manufacturability problem caused by the combination of the silane coupling agents is fundamentally solved on the premise of not influencing the dispersion degree of two-stage white carbon black.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a mixing method of a silane coupling agent and a rubber composition comprises the following mixing raw materials in parts by weight based on 100 parts by weight of a rubber component:
100 parts of rubber component
60-100 parts of white carbon black
0-20 parts of carbon black
3.0 to 8.0 parts of polysulfide silane
1.0 to 5.0 portions of sulfhydryl alkoxy silane;
the mixing method comprises the following steps:
and (3) mixing: dividing a rubber component, white carbon black, carbon black and other chemical additives into two parts, and respectively adding polysulfide silane and mercapto alkoxy silane into the two parts to respectively and independently mix to obtain a mixing master batch A and a mixing master batch B; the mixing temperature of the mixing master batch A in one-stage mixing is 138-150 ℃, and the mixing temperature of the mixing master batch B is 130-135 ℃;
two-stage mixing: mixing the master batch A and the master batch B, adding the mixture into two-stage mixing equipment, and carrying out two-stage mixing to obtain a master batch C, wherein the mixing temperature of the two-stage mixing is 130-135 ℃;
three-stage mixing: adding the master batch C, sulfur and an accelerator into three-stage mixing equipment to perform three-stage mixing to obtain the rubber composition.
Preferably, the white carbon black is common white carbon black or high-dispersion white carbon black produced by a precipitation method or a gas phase method, and the surface of the white carbon black needs to have silicon hydroxyl groups such as isolated hydroxyl groups, adjacent hydroxyl groups and gemini hydroxyl groups.
Preferably, the rubber component is one or more of natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and polyisoprene rubber.
As a further preferred aspect, the rubber component is a natural rubber and a solution polymerized styrene-butadiene rubber, wherein the solution polymerized styrene-butadiene rubber is 70-90 parts and the natural rubber is 10-30 parts.
Preferably, the weight ratio of the rubber components in the mixing master batch A to the mixing master batch B is 1:0.5-0.7, and the weight ratio of the white carbon black is 1:0.5-0.7.
Preferably, the polysulfide silane is one or two of Si69 and Si 75; the mercapto alkoxy silane is one or two of Si747 and Si363.
Preferably, the rubber composition further comprises 2.0-5.0 parts of zinc oxide, 1.5-2.5 parts of stearic acid, 3.0-6.0 parts of rubber anti-aging agent, 0.0-10.0 parts of plasticizer, 1.0-2.5 parts of sulfur and 1.5-5.0 parts of accelerator CZ.
Preferably, the method uses a series-type primary internal mixer for primary mixing and secondary mixing, the rotor speed of the internal mixer is controlled to be 40-60rpm, the upper bolt pressure is controlled to be 50-60N/cm < 2 >, the temperature of cooling water of the internal mixer is controlled to be 30-40 ℃, and the method comprises the following steps:
1. the upper auxiliary machine process comprises the following steps:
(1) adding rubber, carbon black, white carbon black, a silane coupling agent and other chemical auxiliaries except sulfur and a vulcanization accelerator, and lowering the top bolt for 20-40 seconds;
(2) lifting the top bolt and keeping for 8-12 seconds;
(3) lowering the upper top bolt to raise the temperature of the sizing material to 90-110 ℃;
(4) adding softening oil by lifting the top bolt, and keeping for 4-6 seconds;
(5) lowering the top bolt to heat the rubber material to a preset temperature, wherein the mixing temperature of the mixing master batch A is 138-150 ℃, and the mixing temperature of the mixing master batch B is 130-135 ℃;
(6) lowering the top bolt to mix the sizing material at the constant temperature of +/-2 ℃ of the preset temperature for 100-150 seconds;
(7) discharging the sizing material to a lower auxiliary machine.
2. The process of the auxiliary machine comprises the following steps:
(1) heating the sizing material to 130-135 ℃;
(2) mixing for 280-350 seconds at the constant temperature of +/-2 ℃ of the preset temperature;
(3) discharging glue to an open mill: turning over the cooled sizing material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill for uniform dispersion, and cooling the lower piece to room temperature.
Further, the invention also discloses a rubber composition obtained by the mixing method.
The invention further discloses a tire, and the tread of the tire is prepared by vulcanizing the rubber composition.
According to the technical scheme, different silane coupling agents are integrally separated by the formula, namely all materials in a first section of mixing stage in the formula are proportionally separated according to the proportion of the different silane coupling agents, the separated formulas are respectively and independently mixed, each independent mixing formula in the first section can be mixed according to the optimal mixing temperature of the used silane coupling agent, and meanwhile, the white carbon black dispersion medium in each independent mixing formula in the first section is pure rubber with lower modulus, so that the dispersion degree of the white carbon black is greatly improved. The two-stage mixing process mainly aims at combining the rubber materials of the two-stage mixing process without involving the dispersion and the silanization reaction of the white carbon black, and therefore the two-stage mixing process cannot influence the final performance of the formula due to the fact that the setting of low-temperature mixing according to different silane coupling agents used.
The beneficial effects of adopting above-mentioned technical scheme are: the invention provides a novel formula mixing process aiming at a white carbon black formula used by a silane coupling agent. Compared with the traditional mixing process, the white carbon black formula sizing material mixed by the process has the advantages that the physical property, the abrasion performance and the dynamic performance of the formula are improved to a certain extent.
Detailed Description
The technical scheme in the embodiment of the invention is checked and fully described in combination with the embodiment of the invention, and the invention is further explained. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. Given the embodiments of the present invention, all other embodiments that would be obvious to one of ordinary skill in the art without making any inventive effort are within the scope of the present invention.
Examples of the present invention and comparative examples are specifically shown in table 1 (parts by weight).
Table 1 details of the formulations of comparative examples 1-5 and example 1
Table 1 footnotes
*1: m2520, 25% of the total weight of styrene mass station polymer, vinyl 25% of the total weight of butadiene, LG chemical product;
*2: svr10#, vietnam product;
*3:1165MP, cetyl trimethylammonium bromide (CTAB) =160m2/g, solvay chemical product;
*4: n134, cabot chemical products;
*5: si69, jiangxi Hongbai New Material Co., ltd;
*6: si747, jiangsu Qi Gao New Material Co., ltd;
the rest raw materials are all commercial industrial grade products.
Preparation of first-stage and second-stage samples: (the process uses a series-type internal mixer
Controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 The temperature of cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
1. the upper auxiliary machine process comprises the following steps:
(1) adding rubber, carbon black, white carbon black, a silane coupling agent and other chemical additives, and lowering the top plug and keeping for 30 seconds;
(2) lifting the top plug and keeping for 10 seconds;
(3) lowering the upper top bolt to heat the sizing material to 100 ℃;
(4) adding softening oil by lifting the top plug, and keeping for 5 seconds;
(5) lowering the upper top bolt to heat the sizing material to a preset temperature;
(6) lowering the top bolt to mix the sizing material at the constant temperature of +/-2 ℃ for 120 seconds;
(7) discharging the sizing material to a lower auxiliary machine.
2. The process of the auxiliary machine comprises the following steps:
(1) heating the sizing material to a preset temperature;
(2) constant-temperature mixing at preset temperature +/-2 ℃ for 300 seconds;
(3) discharging glue to an open mill: turning over the cooled sizing material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill for uniform dispersion, and cooling the lower piece to room temperature.
The constant temperature preset temperature of each example is shown in Table 2
TABLE 2 comparative examples 1-5, example 1 preset isothermal temperatures
The rubber composition obtained by mixing was vulcanized in a mould prepared in advance, the vulcanization conditions being 160 ℃ for 15min and the pressure being 15 MPa. The properties of the vulcanized rubber were then measured by the following test methods, and the measurement results are shown in Table 3.
Test method for evaluating rubber properties
Physical properties:
the hardness at room temperature was measured based on GB/T531.1-2008, and the results are shown in Table 3, the higher the value, the higher the hardness.
The tensile strength measured based on GB/T528-2009 is shown as "tensile strength". In addition, the elongation at break during the same test is shown as "elongation at break". The product of tensile strength and elongation at break is shown as the "tensile product" as shown in table 3. The larger the value, the higher the reinforcing property, and the better the physical properties. The aging condition of the physical properties after aging is 100 ℃ for 48 hours, the ratio of the tensile product after aging to the tensile product before aging is the thermal aging retention rate, and the larger the value is, the better the aging resistance is.
Abrasion resistance-Akron abrasion:
the acle abrasion measured based on GB/T1689-2014 was shown to be "acle abrasion". The smaller the value, the less wear and the better the wear resistance.
Dynamic performance-dynamic thermo-mechanical analysis (Dynamic thermomechanical analysis, DMA):
measured using a dynamic thermo-mechanical analyzer of the VR-7120 type manufactured by UESHIMA corporation, japan. The test conditions were: a stretch mode; frequency, 12Hz; strain, 7% ± 0.25%; temperature rise is 2 ℃/min. The results are shown in Table 3. The tan delta value at 0 ℃ characterizes the wet grip of the vulcanized rubber, the greater the value, the better the wet grip of the vulcanized rubber to make a tire; the tan delta value at 60 ℃ characterizes the hysteresis loss of the vulcanized rubber, the smaller the value, the lower the hysteresis loss of the vulcanized rubber, and the lower the rolling resistance of the resulting tire.
TABLE 3 comparative examples 1-5, example 1 test results
As can be seen from the comparison of examples 1 and 2, when the mercaptosilane Si747 is added to the two stages separately, the physical properties and dynamic properties of the formulation are reduced to some extent, because the Si747 added to the two stages is liquid, and the addition of the pure liquid and the mixing of the solid rubber are difficult during the mixing with the rubber, which causes problems such as slipping of the rotor and volatilization loss of the Si 747. Meanwhile, when the mercaptosilane Si747 is added in the second stage, the sulfur-containing silane Si69 added in the first stage exists on the surface of the white carbon black, and the steric hindrance effect exists, so that the silanization reaction rate of the mercaptosilane Si747 added in the second stage is influenced, and the final performance of the formula sizing material is influenced.
As can be seen from comparison of comparative examples 2 and 3, when mercaptosilane Si747 is moved to two stages and added together with carbon black, both the physical properties and dynamic properties of the formulation are improved to some extent, since liquid Si747 has already been impregnated into carbon black, no loss of Si747 will occur during mixing, but the properties of comparative example 3 are reduced to some extent compared with comparative example 1, because mercaptosilane Si747 has not been able to react well with the hydroxyl groups on the surface of white carbon black for the reason of steric hindrance, resulting in reduced properties of the formulation.
As can be seen from comparison of comparative examples 1 and comparative examples 4 and 5, when mercaptosilane Si747 is added to the second stage and added together with a small amount of white carbon black, both the physical properties and dynamic properties of the formulation are improved to some extent, because the overall mixing thermal history of comparative examples 4 and 5 is higher than that of comparative example 1, the dispersion of white carbon black is improved, and simultaneously, the addition of white carbon black in batches together with the silane coupling agent eliminates the steric hindrance effect between the silane coupling agents, so that the properties of comparative examples 4 and 5 are superior to those of comparative example 1. Meanwhile, the performance of the comparative example 5 is found to be superior to that of the comparative example 4, because the two-stage dispersion medium is a high modulus medium of a rubber+filler mixture, and the white carbon black is difficult to disperse, so that the smaller the amount of the white carbon black added in the two stages is, the more excellent the performance of the formula is, but the smaller the amount is, provided that the amount required by the silylation reaction of the silane coupling agent used can be satisfied.
As can be seen from the test data of example 1, the performance is most excellent in all the schemes, because the process scheme of example 1 has high thermal history at the same time, and the dispersion medium of the white carbon black is always a pure rubber medium with lower modulus in the first and second mixing processes, so that the dispersion degree of the white carbon black is better, and the silylation reaction between the white carbon black and the silane coupling agent is more complete without the influence of steric hindrance.
A batch of 235/45R18 gauge tires was prepared using the compounds of comparative example 1 and example 1, and tire full-length tests were performed with the test results shown in Table 4.
Table 4 comparative example 1, example 1 compound test tire machine tool performance data
From the data in Table 4, it can be seen that the high speed and durability of the tire of the present invention meets the requirements of the regulations, and the grade of the label of the tire is improved to some extent although the grade is unchanged.
Industrial applicability
According to the invention, the performance of the white carbon black formula used by the silane coupling agent can be improved to a certain extent by optimizing the process on the premise of not changing the components of the formula.
The previous description of the disclosed comparative examples is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these comparative examples will be readily apparent to those skilled in the art. The general principles defined herein may be applied to other comparative examples without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A mixing method of a silane coupling agent and a rubber composition is characterized in that the rubber composition comprises the following raw materials in parts by weight based on 100 parts by weight of the rubber composition:
100 parts of rubber component
60-100 parts of white carbon black
0-20 parts of carbon black
3.0 to 8.0 parts of polysulfide silane
1.0 to 5.0 portions of sulfhydryl alkoxy silane;
the mixing method comprises the following steps:
and (3) mixing: dividing a rubber component, white carbon black, carbon black and other chemical additives into two parts, and respectively adding polysulfide silane and mercapto alkoxy silane into the two parts to respectively and independently mix to obtain a mixing master batch A and a mixing master batch B; the mixing temperature of the mixing master batch A in one-stage mixing is 138-150 ℃, and the mixing temperature of the mixing master batch B is 130-135 ℃; the weight ratio of the rubber components in the mixing master batch A to the mixing master batch B is 1:0.5-0.7, and the weight ratio of the white carbon black is 1:0.5-0.7;
two-stage mixing: mixing the master batch A and the master batch B, adding the mixture into two-stage mixing equipment, and carrying out two-stage mixing to obtain a master batch C, wherein the mixing temperature of the two-stage mixing is 130-135 ℃;
three-stage mixing: adding the master batch C, sulfur and an accelerator into three-stage mixing equipment to perform three-stage mixing to obtain the rubber composition.
2. The method for mixing a silane coupling agent and a rubber composition according to claim 1, wherein the white carbon black is a common white carbon black or a highly dispersed white carbon black produced by a precipitation method or a gas phase method, and the surface of the white carbon black is required to have a silicon hydroxyl group.
3. The method for kneading a silane coupling agent and a rubber composition according to claim 1, wherein the rubber component is one or more of natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and polyisoprene rubber.
4. The method for kneading a silane coupling agent and a rubber composition according to claim 3, wherein the rubber component comprises a natural rubber and a solution polymerized styrene-butadiene rubber, the solution polymerized styrene-butadiene rubber is 70 to 90 parts, and the natural rubber is 10 to 30 parts.
5. The method for kneading a silane coupling agent and a rubber composition according to claim 1, wherein the polysulfide silane is one or both of Si69 and Si 75; the mercapto alkoxy silane is one or two of Si747 and Si363.
6. The method for mixing a silane coupling agent and a rubber composition according to claim 1, wherein the rubber composition further comprises 2.0-5.0 parts of zinc oxide, 1.5-2.5 parts of stearic acid, 3.0-6.0 parts of rubber anti-aging agent, 0.0-10.0 parts of plasticizer, 1.0-2.5 parts of sulfur and 1.5-5.0 parts of accelerator CZ.
7. A rubber composition obtained by the kneading method according to any one of claims 1 to 6.
8. A tire, wherein the tread of the tire is prepared by vulcanizing the rubber composition according to claim 7.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111136816A (en) * | 2020-01-10 | 2020-05-12 | 怡维怡橡胶研究院有限公司 | Processing technology of tread rubber compound for improving wet skid resistance of tire |
| CN114230884A (en) * | 2021-12-28 | 2022-03-25 | 中策橡胶集团股份有限公司 | High-performance car tire tread rubber composition, mixing method thereof and car tire |
| CN114752125A (en) * | 2022-04-11 | 2022-07-15 | 中策橡胶集团股份有限公司 | Tread rubber composition with good low-temperature ground gripping performance, mixing method thereof and tire |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111136816A (en) * | 2020-01-10 | 2020-05-12 | 怡维怡橡胶研究院有限公司 | Processing technology of tread rubber compound for improving wet skid resistance of tire |
| CN114230884A (en) * | 2021-12-28 | 2022-03-25 | 中策橡胶集团股份有限公司 | High-performance car tire tread rubber composition, mixing method thereof and car tire |
| CN114752125A (en) * | 2022-04-11 | 2022-07-15 | 中策橡胶集团股份有限公司 | Tread rubber composition with good low-temperature ground gripping performance, mixing method thereof and tire |
Non-Patent Citations (1)
| Title |
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| 天然橡胶轮胎胶料中硅烷偶联剂种类对白炭黑增强效率的影响;杨英等;《世界橡胶工业》;第44卷(第8期);第9-20页 * |
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