CN110564020A - modified main rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof - Google Patents
modified main rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of tire side materials, and discloses a modified main rubber, a preparation method thereof, a rubber composition, vulcanized rubber, a preparation method thereof and application thereof. The method comprises the following steps: pre-crosslinking the main rubber, the silane coupling agent and the white carbon black, wherein the pre-crosslinking temperature is 130-180 ℃, and the pre-crosslinking time is 1-10 min; the main rubber is high cis-polybutadiene rubber, wherein the cis-1, 4-structure content is more than 98 weight percent. The vulcanized rubber obtained by the method has higher strength, lower heat generation and better flexing resistance, and is suitable for being used as tire sidewall rubber.
Description
Technical Field
The invention relates to the field of tire sidewall materials, in particular to a method for preparing modified main rubber, the modified main rubber prepared by the method, a rubber composition, a method for preparing vulcanized rubber, and application of the vulcanized rubber and the vulcanized rubber prepared by the method as tire sidewall materials.
Background
With the development of the automobile industry, the usage of tires has increased year by year. The tire side wall is a weak part of a tire, and the puncture resistance, high strength, low heat generation, flexing resistance and other performances are key performances of the side rubber, especially the heat generation resistance and flexing resistance of the side rubber of the tire. The excellent heat buildup resistance can reduce tire burst caused by high temperature in the driving process of the automobile, and the excellent flexing resistance can prolong the service life of the tire.
CN102159631B discloses a tire sidewall having a rubber mixture comprising at least one diene elastomer, a reinforcing filler comprising a carbon black, and a vulcanization system, characterized in that the carbon black has a CTAB specific surface area of greater than or equal to 90m2Per g and a proportion of carbon black between 30phr and 40 phr; wherein the rubber mixture comprises 35-55% natural rubber or synthetic polyisoprene and 65-45% diene elastomer selected from the group consisting of polybutadiene, styrene-butadiene copolymer, isoprene-styrene copolymer and isoprene-butadiene-styrene copolymer.
CN102791791B discloses a tire sidewall, at least a portion of which has a rubber composition based on at least one diene elastomer, a crosslinking system and a reinforcing filler, characterized in that the proportion of reinforcing filler in the composition is from 20 to 40 parts by weight per 100 parts of elastomer, phr, the volume fraction of reinforcing filler in the composition is from 8.0 to 3.0%, and in that the reinforcing filler mainly comprises a carbon black or a mixture of carbon blacks, the BET specific surface area of which is from 50 to 69m2/g。
CN104448430A discloses a tire sidewall rubber, which comprises the following components: raw rubber, BR9000 butadiene rubber, reclaimed rubber, N375 carbon black, aromatic oil and small materials; wherein the total weight of the raw rubber, the BR9000 butadiene rubber and the reclaimed rubber is 100 parts, and the total weight of the N375 carbon black, the aromatic oil and the small material is 60-80 parts.
The above patent disclosure is directed to improvements in tire sidewall formulations to enhance sidewall performance. With the increasing demands on tire safety in the automotive industry, there is still a need in the market to provide a vulcanized rubber for tire sidewalls that has high strength, low heat build-up, and high flex resistance.
Disclosure of Invention
The invention aims to improve the performance of the vulcanized rubber for tire side walls in the prior art, and provides a modified main rubber, a preparation method and a rubber composition thereof, the vulcanized rubber, a preparation method and application thereof, and the tire side vulcanized rubber provided has high strength, low heat generation and high flexing resistance.
After research, the inventor of the present invention finds that, by adopting a pre-crosslinking technology, before the main rubber is mixed, the silane coupling agent and the white carbon black are bonded to the rubber molecular chain of the main rubber in a chemical bond manner under certain temperature and time conditions, so that the low heat generation performance of the white carbon black is utilized, the frictional heat generation between the filler and the main rubber during stretching, compression and other processes of the rubber material is reduced, the dispersion uniformity of the white carbon black or other additives in the main rubber can be improved, the vulcanized rubber with excellent comprehensive performance is obtained, and the polarity of the main rubber is increased, thereby completing the present invention.
in order to achieve the above object, a first aspect of the present invention provides a method for producing a modified host rubber, the method comprising: pre-crosslinking the main rubber, the silane coupling agent and the white carbon black, wherein the pre-crosslinking temperature is 130-180 ℃, and the pre-crosslinking time is 1-10 min; the main rubber is high cis-polybutadiene rubber, wherein the cis-1, 4-structure content is more than 98 weight percent.
Preferably, the white carbon is used in an amount of 5 to 40 parts by weight and the silane coupling agent is used in an amount of 0.7 to 0.9% by weight based on 100 parts by weight of the host rubber.
Preferably, the high cis-polybutadiene rubber is selected from nickel-based butadiene rubber and/or neodymium-based butadiene rubber.
Preferably, the Mooney viscosity of the high cis-polybutadiene rubber is 40 to 60.
In a second aspect, the present invention provides a modified host rubber prepared by the process of the present invention.
The third aspect of the present invention provides a rubber composition containing a modified main rubber, a vulcanizing agent, a vulcanization accelerator, an activator, an antioxidant, a dispersant, a processing oil, and carbon black, wherein the modified main rubber is the modified main rubber of the present invention.
In a fourth aspect, the present invention provides a process for preparing a vulcanized rubber, the process comprising: carrying out first mixing on modified main rubber, an activating agent, an anti-aging agent, a dispersing agent, processing oil and optional carbon black in the rubber composition to obtain a first mixed rubber; then adding a vulcanizing agent and a vulcanization accelerator for second mixing to obtain a second mixed rubber; the second mix is then vulcanized.
a fifth aspect of the invention provides a vulcanizate prepared by the method of the invention.
a sixth aspect of the invention provides the use of the vulcanized rubber of the invention as a tire sidewall material.
The vulcanized rubber provided by the invention has higher strength, lower heat generation and better flexing resistance, and is suitable for being used as tire sidewall rubber.
The rubber composition provided by the invention can be used for preparing vulcanized rubber with excellent comprehensive performance under simple process conditions, and the vulcanized rubber is very suitable for preparing a tire side for a green tire.
additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for preparing a modified host rubber, the process comprising: pre-crosslinking the main rubber, the silane coupling agent and the white carbon black, wherein the pre-crosslinking temperature is 130-180 ℃, and the pre-crosslinking time is 1-10 min; the main rubber is high cis-polybutadiene rubber, wherein the cis-1, 4-structure content is more than 98 weight percent.
The inventor of the invention finds that the modified main rubber can be obtained by pre-crosslinking the main rubber, the silane coupling agent and the white carbon black at a specific temperature for a specific time, and vulcanized rubber formed by using the modified main rubber has higher strength, lower heat generation and better flexing resistance. The inventors of the present invention have also found that, in particular, when the temperature of the pre-crosslinking is 140 ℃ and 170 ℃ and the time of the pre-crosslinking is 2 to 6 minutes, the resulting modified host rubber can make the overall properties of the vulcanized rubber thus prepared more excellent.
Preferably, the white carbon is used in an amount of 5 to 40 parts by weight and the silane coupling agent is used in an amount of 0.7 to 0.9% by weight based on 100 parts by weight of the host rubber. More preferably, the white carbon is used in an amount of 5 to 30 parts by weight, relative to 100 parts by weight of the host rubber.
The inventor of the present invention finds that when the amount of the white carbon is 5 to 30 parts by weight and the amount of the silane coupling agent is 0.7 to 0.9% by weight of the white carbon, relative to 100 parts by weight of the host rubber, the combination of the specific pre-crosslinking temperature and time enables the vulcanized rubber prepared from the modified host rubber thus obtained to have more excellent overall properties.
Preferably, the high cis-polybutadiene rubber is selected from nickel-based butadiene rubber and/or neodymium-based butadiene rubber.
preferably, the Mooney viscosity of the high cis-polybutadiene rubber is 40 to 60. Can be commercially available, for example, nickel-based butadiene rubber BR9000 is commercially available from medium petrochemical Yanshan petrochemical company with a Mooney viscosity of 46. Neodymium-based butadiene rubber Nd40 was commercially available from Mimosite Yanshan petrochemical company and had a Mooney viscosity of 43.
in the invention, the specific surface area of the white carbon black is 100-200m2Per g, preferably 165-185m2(ii) in terms of/g. The white carbon black can be selected from one white carbon black or a mixture of at least two white carbon blacks. The inventor of the invention finds that when the specific surface area of the white carbon black meets 165-185m2when the specific pre-crosslinking temperature and time are matched, the comprehensive performance of the vulcanized rubber prepared from the obtained modified main rubber is more excellent. White carbon black satisfying this specific surface area condition is commercially available, for example, 165GR (specific surface area of 165 m) from Rodiya (Qingdao) Co., Ltd2,/g), 175GR (specific surface area 185 m)2,/g) and 185GR (specific surface area 195 m)2/g)。
in the present invention, the silane coupling agent which can cooperate with the host rubber to achieve the pre-crosslinking is preferably a silane coupling agent containing an alkoxy group and containing a sulfur atom or an amino group; more preferably, the silane coupling agent is at least one of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide, gamma-aminopropyltriethoxysilane, and bis- [ gamma- (triethoxysilyl) propyl ] -disulfide. The silane coupling agent is commercially available, for example, Si69 (bis- [ γ - (triethoxysilyl) propyl ] -tetrasulfide), Si75 (bis- [ γ - (triethoxysilyl) propyl ] -disulfide) available from chemical technology, Inc. of Shanghai Rui.
In a second aspect, the present invention provides a modified host rubber prepared by the process of the present invention.
In a second aspect of the invention, there is provided a modified host rubber prepared by the process provided in the first aspect of the invention.
The present invention can also provide a modified host rubber having the same properties as the modified host rubber described in the second aspect. In the present invention, there is no particular limitation on the method for producing the modified host rubber having the same properties as the modified host rubber described in the second aspect, and the present invention claims the modified host rubber having the same properties as the modified host rubber described in the second aspect of the present invention.
The third aspect of the present invention provides a rubber composition containing a modified main rubber, a vulcanizing agent, a vulcanization accelerator, an activator, an antioxidant, a dispersant, a processing oil, and optionally carbon black, wherein the modified main rubber is the modified main rubber of the present invention.
the modified main rubber contains main rubber, white carbon black and a silane coupling agent.
In the invention, for the convenience of material metering, the dosage of the main rubber relative to the modified main rubber is taken as a reference. Preferably, the vulcanizing agent is 0.5-4 parts by weight, the vulcanization accelerator is 0.5-5 parts by weight, the activator is 2-8 parts by weight, the anti-aging agent is 1-8 parts by weight, the dispersant is 1-6 parts by weight, and the processing oil is 5-30 parts by weight, relative to 100 parts by weight of the main rubber in the modified main rubber; more preferably, the vulcanizing agent is 1-2 parts by weight, the vulcanization accelerator is 1-3 parts by weight, the activator is 3-5 parts by weight, the anti-aging agent is 3-5 parts by weight, the dispersant is 2-4 parts by weight, and the processing oil is 10-20 parts by weight.
preferably, the vulcanizing agent is at least one of sulfur, dithiomorphine and dimorpholine tetrasulfide. More preferably, the vulcanizing agent is sulfur. The sulfur may be, for example, at least one of ordinary sulfur, insoluble sulfur IS60-10, and pre-dispersed sulfur S-80. The vulcanizing agents are commercially available.
Preferably, the vulcanization accelerator is a sulfenamide vulcanization accelerator and/or a guanidine vulcanization accelerator. More preferably, the vulcanization accelerator is at least one of diphenylguanidine (accelerator D), N-tert-butyl-2-benzothiazylsulfenamide (accelerator TBBS), 2' -dibenzothiazyl disulfide (accelerator DM), N-tert-butyl-bis (2-benzothiazole) sulfenimide (accelerator TBSI) and N-cyclohexyl-bis (2-mercaptobenzothiazole) sulfenamide (accelerator CZ). The vulcanization accelerator is commercially available.
Preferably, the activator is selected from at least one of zinc oxide, magnesium oxide and stearic acid. More preferably, the activators are zinc oxide and stearic acid. The activators are commercially available.
Preferably, the anti-aging agent is selected from at least one of amine anti-aging agents, quinoline anti-aging agents and microcrystalline wax; the amine antioxidant can be at least one of N-isopropyl-N ' -phenyl-p-phenylenediamine (antioxidant 4010A), N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine (antioxidant 4020) and N, N ' -bis (1, 4-dimethylpentyl) p-phenylenediamine (antioxidant 77 PD). And the quinoline antioxidant can be 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD) and/or 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline (antioxidant AW). The antioxidant is commercially available.
According to a preferred embodiment, the antioxidant is a mixture of microcrystalline wax and at least one substance selected from the group consisting of amine antioxidants and quinoline antioxidants.
preferably, the microcrystalline wax has a melting point of 60-95 ℃ and a molecular weight of 580-700. In particular, the microcrystalline wax consists essentially of C20-60And a small amount of n-alkane and isoparaffin.
Preferably, the dispersant is polyethylene glycol having a molecular weight of 1000-. Commercially available, for example, PEG4000 from England chemical Co., Ltd, Nanjing, and having a weight average molecular weight of 4000.
Preferably, the processing oil is an aromatic oil and/or a naphthenic oil; for example, the process oil may be at least one of TDAE (Treated Aromatic oil), RAE (residual Aromatic Extract), and NAP (naphthenic oil (naptttenics)). The rubber composition of the present invention is not particularly limited in the nature of the aromatic oil and the naphthenic oil, and may be various aromatic oils and naphthenic oils as generally used in the art. Are commercially available.
In the present invention, the sum of the carbon black and the white carbon black in the modified main rubber is used as a reinforcing agent. Except that the white carbon black is first mixed with the main rubber and the silane coupling agent through the pre-crosslinking to form the modified main rubber, so that the further obtained vulcanized rubber has higher strength, lower heat generation and better flexibility resistance. Preferably, the reinforcing agent is 40 to 80 parts by weight, preferably 50 to 70 parts by weight, based on 100 parts by weight of the main rubber in the modified main rubber.
According to the invention, carbon black may or may not be added to the rubber composition. The carbon black is 50 to 90% by weight, preferably 60 to 90% by weight, of the reinforcing agent. For example, when the amount of white carbon black in the modified host rubber contained in the rubber composition is sufficient to meet the index requirements of the vulcanized rubber to be further prepared, the amount of the reinforcing agent is equal to the amount of white carbon black. When carbon black is added, the adding amount of the carbon black meets the range under the condition of meeting the requirement of the using amount of the white carbon black; meanwhile, the total amount of the white carbon black and the carbon black is 40 to 80 parts by weight, preferably 50 to 70 parts by weight, of the reinforcing agent relative to 100 parts by weight of the main rubber in the modified main rubber.
preferably, the carbon black is 8# reference carbon black and/or carbon black N330. Are all commercially available. For example, the reference carbon black # 8 can be IRB8# available from continental U.S. carbon black.
In a fourth aspect, the present invention provides a process for preparing a vulcanized rubber, the process comprising: carrying out first mixing on modified main rubber, an activating agent, an anti-aging agent, a dispersing agent, processing oil and carbon black in the rubber composition to obtain first mixed rubber; then adding a vulcanizing agent and a vulcanization accelerator for second mixing to obtain a second mixed rubber; the second mix is then vulcanized.
In the method for producing a vulcanized rubber provided by the present invention, the method and conditions of the first mixing and the second mixing may be conventionally selected in the art. Generally, the mixing may be carried out in an open mill or an internal mixer, and the mixing sequence between the respective substances in the first mixing process may be carried out simultaneously or stepwise, preferably stepwise.
According to a particular embodiment of the invention, the process for preparing a vulcanized rubber can be carried out as follows: in an internal mixer, the components other than the vulcanizing agent and the vulcanization accelerator in the aforementioned rubber composition of the invention are added to carry out first mixing; then, passing the mixture on an open mill for at least three times to obtain a first rubber compound; and (3) allowing the first mixed rubber to pass through a mixing roll for at least one time with a vulcanizing agent and a vulcanization accelerator to obtain a second mixed rubber, and vulcanizing the second mixed rubber to obtain vulcanized rubber.
In a preferred embodiment of the present invention, the process for preparing a vulcanized rubber can be carried out as follows:
(1) pre-crosslinking: in an internal mixer, high cis-polybutadiene rubber (cis 1, 4-structure content is more than 98 wt%, Mooney viscosity is 40-60), silane coupling agent and white carbon black (specific surface area is 100-2Per g, preferably 165-185m2/g) carrying out pre-crosslinking at the temperature of 130-180 ℃ for 1-10min to obtain modified main rubber;
(2) first mixing: mixing the modified main body rubber and an activating agent in an internal mixer, adding an anti-aging agent, carbon black, a dispersing agent and processing oil, and carrying out internal mixing at the temperature of 150-160 ℃ for 5-7min after the temperature of the rubber material reaches the temperature; passing the rubber material on an open mill with a roll spacing of 3-7mm and a roll temperature of 50 +/-5 ℃ for at least three times to obtain a first rubber compound, and standing for 3-5 hours;
(3) and (3) second mixing: carrying out second mixing on the first mixed rubber, the vulcanizing agent and the vulcanization accelerator obtained in the step (2) at the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the rubber material temperature reaches 100-120 ℃ and banburying is carried out for 2-4min at the temperature; passing the rubber material on an open mill with a roll spacing of 0.4-0.6mm and a roll temperature of 50 +/-5 ℃ for at least one time, adjusting the roll spacing to 2-4mm, and passing for at least two times to obtain a second rubber compound and standing for 18-30 hours;
(4) And (3) vulcanization: and (4) vulcanizing the second rubber compound obtained in the step (3) at the temperature of 140 ℃ and 160 ℃ and under the pressure of 5-15MPa for 10-50 minutes to obtain the vulcanized rubber.
A fifth aspect of the invention provides a vulcanizate prepared by the method of the invention. The tensile strength of the vulcanized rubber is more than 16MPa, preferably 16.1-17.3 MPa; the tear strength is more than 27kN/m, preferably 27-28.6 kN/m; the heat generation of compression is less than 31 ℃; the fatigue life is more than 7.8 ten thousand times.
A sixth aspect of the invention provides the use of the vulcanized rubber of the invention as a tire sidewall material.
The process for preparing the tire sidewall material by using the vulcanized rubber of the present invention can be various processes conventionally used in the art, and the present invention is not particularly limited to a specific application process.
the present invention will be described in detail below by way of examples.
The materials used below are described as follows:
The nickel-based butadiene rubber BR9000 is a commercial product available from the medium petrochemical yanshan petrochemical company, and has a mooney viscosity of 46.
Neodymium-based butadiene rubber Nd40 was a commercial product from the Chinese petrochemical Yanshan petrochemical company, Mooney viscosity 43
The white carbon black is purchased from Rodiya (Qingdao) Co Ltd and is respectively 165GR (the specific surface area is 165 m)2,/g), 175GR (specific surface area 185 m)2,/g) and 185GR (specific surface area 195 m)2commercial product of/g).
reference carbon black # 8 (carbon black) is a commercial product available from continental carbon black corporation under the trademark IRB8 #.
TDAE (process oil) is a commercial product from olympic rubber ltd, nju.
ASTM 103# naphthenic oils (process oils) are products of Ningbo Co.Chemie Ltd.
Si69 and Si75 (coupling agents) are commercially available from chemical technology, Inc., Shanghai Rui.
Zinc oxide and stearic acid (activator) are commercial products available from the national pharmaceutical group chemicals limited.
anti-aging agent 4010A (anti-aging agent) is a commercial product available from gayue county li and chemical ltd.
Accelerator D (vulcanization accelerator) is a commercial product from morning chemical ltd, shijiazhuan.
The accelerator TBBS (vulcanization accelerator) is a commercial product from the new materials science ltd, guangdong.
Sulfur (vulcanizing agent) is a commercial product available from Chemicals, Inc., national drug group.
The microcrystalline wax is a commodity which is purchased from Tianjin Hengshengxin international trade company Limited and has the brand number of W-445, and the number of carbon atoms is 20-50.
PEG4000 (polyethylene glycol) is a commercial product from Nanjing England chemical Co., Ltd. and has a molecular weight of 4000.
The internal mixer is of a model XSM-1/10-120 of Shanghai Kechu rubber and plastic mechanical equipment Limited, the volume of a die cavity is 1L, and a heating system is electrically heated and has a cooling function.
The plate vulcanizing machine is produced by Pan stone oil pressure industry (Anhui) and has the model of P-50-PCD-3L.
The total amount of the rubber compositions in each of the following examples was the same and 1200 g.
Examples 1-7 are intended to illustrate the preparation of vulcanizates according to the invention.
Example 1
(1) Pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm for 3min at the temperature of 160 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) and (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: and vulcanizing the second rubber compound at 160 ℃ and under the pressure of 15MPa for 35min to obtain vulcanized rubber S1.
the kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 2
(1) pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm for 2min at the temperature of 170 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain a first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, and passing twice; obtaining a second rubber compound and standing for 24 hours;
(4) and (3) vulcanization: the second rubber compound was vulcanized at 155 ℃ under a pressure of 10MPa for 40 minutes to obtain vulcanized rubber S2.
the kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 3
(1) Pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm at the temperature of 150 ℃ for 4.5 min; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, and passing twice; obtaining a second mixed rubber and standing for 24 hours;
(4) And (3) vulcanization: and vulcanizing the second mixed rubber for 50min at the temperature of 150 ℃ and under the pressure of 8MPa to obtain vulcanized rubber S3.
The kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 4
(1) Pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm for 2.2min at the temperature of 170 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) and (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: the second rubber compound was vulcanized at 160 ℃ under a pressure of 13MPa for 35min to obtain vulcanized rubber S4.
the kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 5
(1) pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm at the temperature of 165 ℃ for 2.8 min; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: the second rubber compound was vulcanized at 145 ℃ under a pressure of 6MPa for 60 minutes to obtain vulcanized rubber S5.
The kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 6
(1) Pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm for 6min at the temperature of 140 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: the second rubber compound was vulcanized at 155 ℃ under a pressure of 13MPa for 53min to obtain vulcanized rubber S6.
The kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
Example 7
(1) Pre-crosslinking: mixing the main body rubber, the silane coupling agent and the white carbon black in an internal mixer at the rotating speed of 80rpm for 3min at the temperature of 165 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: and vulcanizing the second rubber compound at 160 ℃ and under the pressure of 15MPa for 35min to obtain vulcanized rubber S7.
The kind of substances in the pre-crosslinking process for preparing the modified main rubber and the kinds and amounts of the respective components in the rubber composition in the kneading process in this example are shown in Table 1.
comparative example 1
(1) First mixing: mixing the main body rubber, the activating agent, the white carbon black and the silane coupling agent in an internal mixer for 2.5min at the rotating speed of 80 rpm; then adding an anti-aging agent, carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain first rubber compound, and standing for 4 hours;
(2) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, passing twice to obtain second rubber compound and standing for 24 hours;
(3) And (3) vulcanization: and vulcanizing the second mixed rubber for 35min at 160 ℃ and under the pressure of 15MPa to obtain vulcanized rubber DS 1.
The total amount and kind of each substance involved in this comparative example were the same as those in example 1.
Comparative example 2
(1) pre-crosslinking: mixing the main rubber and the silane coupling agent in an internal mixer at the rotating speed of 80rpm for 2min at the temperature of 120 ℃; starting a cooling system of the internal mixer, and reducing the temperature of materials in the internal mixer to 80 ℃; obtaining modified main rubber;
(2) First mixing: adding an activating agent into the modified main rubber in an internal mixer at the rotating speed of 80rpm for mixing for 2.5 min; then adding an anti-aging agent, carbon black, white carbon black, a dispersing agent and processing oil, mixing for 6min at the temperature after the temperature of the rubber material reaches 150 ℃, and unloading the rubber material; passing the rubber material on an open mill with the roller spacing of 5mm and the roller temperature of 50 +/-5 ℃ for three times to obtain a first rubber compound, and standing for 4 hours;
(3) And (3) second mixing: carrying out second mixing on the first mixed rubber, a vulcanizing agent and a vulcanization accelerator at the rotation speed of 40rpm and the initial temperature of 40 +/-5 ℃, and unloading the rubber material when the temperature of the rubber material reaches 100 ℃ and mixing for 4min at the temperature; passing the rubber material once on an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃, adjusting the roller spacing to 3mm, and passing twice; obtaining a second rubber compound and standing for 24 hours;
(4) And (3) vulcanization: the second rubber compound was vulcanized at 155 ℃ under a pressure of 10MPa for 40 minutes to obtain a vulcanized rubber DS 2.
The kind of substances in the pre-crosslinking process for preparing the modified main rubber in this comparative example and the kinds and amounts of the respective components in the rubber composition in the kneading process are shown in Table 1.
TABLE 1
TABLE 1
Test example
The properties of the vulcanizates prepared in the above examples and comparative examples were tested as follows.
(1) mooney viscosity
Testing according to GB/T1232.1-2000 standard. Preheating at 100 + -0.5 deg.C for 1min, and testing for 4 min.
(2) and (3) testing tensile property: testing according to the method in the national standard GB/T1040-92 Plastic tensile Property test method, wherein the model of the tensile machine is AG-20KNG produced by Shimadzu corporation; the tensile rate was 500mm/min and the test temperature was 23 ℃. The effective portion of the sample had a length of 25mm and a width of 6 mm. For each set of samples, 10 replicates were run and the results averaged.
The results obtained are shown in Table 2. (data of "tensile strength/MPa", "100% set elongation/MPa", "elongation/%" and "tear strength/kN/m" in Table 2).
(3) Dynamic mechanical properties:
Temperature scanning the samples were tested for viscoelastic behavior on a dynamic thermomechanical analyzer eplex-500N, GABO, germany. The sample had a length of 35mm, a width of 8mm and a thickness of 1.0 mm. The test adopts a tensile mode, the test frequency is 11Hz, the temperature range is-80 ℃ to 80 ℃, the heating rate is 3 ℃/min, the static strain is 1 percent, and the dynamic strain is 0.25 percent. The results obtained are shown in Table 2 (data of "tan. delta./0 ℃", "tan. delta./60 ℃" and "Tg/. degree. C.", in Table 2).
(4) Flexural Property
The method is characterized in that a GT-7011-GLH type flexion testing machine of Taiwan high-speed rail company is adopted to measure the flexion performance according to the determination of extension fatigue of vulcanized rubber of GB/T1688-2008 of the national standard, and the fatigue life is represented. The test specimens were dumbbell-shaped, 2mm in thickness, 75% strain elongation, 4Hz in cycle frequency and 23 ℃.
(5) Heat generation by compression
The instrument comprises the following steps: Y3000E compression thermogenesis tester, beijing friend deep electronics ltd. The sample is preheated at 55 ℃ for 30min, and the sample is cylindrical, has the diameter of 17.8 +/-0.15 mm and the height of 25 +/-0.25 mm. Stroke 4.45 + -0.03 mm, compression frequency 30 + -0.3 Hz, test 25 min.
TABLE 2
the results in table 1 show that, by using the method of pre-crosslinking the main rubber and the silane coupling agent, the sulfur-sulfur bond of the silane coupling agent is broken at high temperature and chemically reacts with the molecular chain of the main rubber, and siloxane groups are introduced into the molecular chain of the main rubber, so that the dispersibility of the main rubber to the white carbon black and other additives is greatly improved, and the frictional heat generation of the filler and the molecular chain is greatly reduced, thereby improving the tensile strength, tear strength, heat generation performance and yield resistance of the vulcanized rubber.
the preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method of preparing a modified host rubber, the method comprising: pre-crosslinking the main rubber, the silane coupling agent and the white carbon black, wherein the pre-crosslinking temperature is 130-180 ℃, and the pre-crosslinking time is 1-10 min; the main rubber is high cis-polybutadiene rubber, wherein the cis-1, 4-structure content is more than 98 weight percent.
2. The method as claimed in claim 1, wherein the pre-crosslinking temperature is 140-170 ℃ and the pre-crosslinking time is 2-6 min.
3. The method according to claim 1 or 2, wherein the white carbon is used in an amount of 5 to 40 parts by weight and the silane coupling agent is used in an amount of 0.7 to 0.9% by weight, relative to 100 parts by weight of the host rubber; preferably, the white carbon is used in an amount of 5 to 30 parts by weight, relative to 100 parts by weight of the host rubber.
4. The method according to any one of claims 1 to 3, wherein the high cis polybutadiene rubber is selected from nickel-based butadiene rubber and/or neodymium-based butadiene rubber; preferably, the first and second electrodes are formed of a metal,
The Mooney viscosity of the high-cis polybutadiene rubber is 40-60.
5. The method as claimed in any one of claims 1 to 5, wherein the silica has a specific surface area of 100-200m2Per g, preferably 165-185m2(ii)/g; preferably, the first and second electrodes are formed of a metal,
The silane coupling agent is a silane coupling agent containing alkoxy and containing sulfur atoms or amino groups, and preferably, the silane coupling agent is at least one of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide, gamma-aminopropyltriethoxysilane and bis- [ gamma- (triethoxysilyl) propyl ] -disulfide.
6. A modified host rubber prepared by the process of any one of claims 1 to 5.
7. A rubber composition comprising a modified body rubber, a vulcanizing agent, a vulcanization accelerator, an activator, an antioxidant, a dispersant, a processing oil and optionally carbon black, wherein the modified body rubber is the modified body rubber according to claim 6.
8. The rubber composition according to claim 7, wherein the vulcanizing agent is 0.5 to 4 parts by weight, the vulcanization accelerator is 0.5 to 5 parts by weight, the activator is 2 to 8 parts by weight, the antioxidant is 1 to 8 parts by weight, the dispersant is 1 to 6 parts by weight, and the processing oil is 5 to 30 parts by weight, relative to 100 parts by weight of the host rubber in the modified host rubber; preferably, the first and second electrodes are formed of a metal,
1-2 parts of vulcanizing agent, 1-3 parts of vulcanization accelerator, 3-5 parts of activating agent, 3-5 parts of anti-aging agent, 2-4 parts of dispersing agent and 10-20 parts of processing oil.
9. The rubber composition according to claim 7 or 8, wherein the sum of the carbon black and the white carbon black in the modified host rubber is used as a reinforcing agent; preferably, the first and second electrodes are formed of a metal,
the reinforcing agent is 40 to 80 parts by weight, preferably 50 to 70 parts by weight, based on 100 parts by weight of the host rubber in the modified host rubber.
10. the rubber composition of any of claims 7-9, wherein the vulcanizing agent is at least one of sulfur, dithiomorphine, and dimorpholine tetrasulfide;
The vulcanization accelerator is sulfenamide vulcanization accelerator and/or guanidine vulcanization accelerator;
The activator is selected from at least one of zinc oxide, magnesium oxide and stearic acid;
The dispersant is polyethylene glycol with the molecular weight of 1000-10000;
The processing oil is aromatic oil and/or naphthenic oil;
The anti-aging agent is selected from at least one of amine anti-aging agents, quinoline anti-aging agents and microcrystalline wax; preferably, the melting point of the microcrystalline wax is 60-95 ℃, and the molecular weight is 580-700;
preferably, the carbon black is 8# reference carbon black and/or carbon black N330.
11. A method of preparing a vulcanized rubber, the method comprising: first mixing the modified main rubber, the activator, the antioxidant, the dispersant, the processing oil and the carbon black in the rubber composition according to any one of claims 7 to 10 to obtain a first mixed rubber;
then adding a vulcanizing agent and a vulcanization accelerator for second mixing to obtain a second mixed rubber;
The second mix is then vulcanized.
12. The method as claimed in claim 11, wherein the vulcanization conditions include a vulcanization temperature of 140 ℃ and 160 ℃, a vulcanization pressure of 5-15MPa, and a vulcanization time of 10-50 min.
13. A vulcanized rubber produced by the method of claim 11 or 12.
14. Use of the vulcanizate of claim 13 as a tire sidewall material.
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