CN110878150B - Rubber composition containing phenolic resin with polysulfide structure, application and tire - Google Patents
Rubber composition containing phenolic resin with polysulfide structure, application and tire Download PDFInfo
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- CN110878150B CN110878150B CN201911216251.2A CN201911216251A CN110878150B CN 110878150 B CN110878150 B CN 110878150B CN 201911216251 A CN201911216251 A CN 201911216251A CN 110878150 B CN110878150 B CN 110878150B
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The application relates to the technical field of rubber products, in particular to a rubber composition containing a phenolic resin with a polysulfide structure, application of the rubber composition and a tire prepared by using the rubber composition. The rubber composition comprises 100 parts by weight of a rubber component, 1.0-20.0 parts by weight of phenolic resin containing a polysulfide structure and a methylene donor accounting for 3.0-25 wt% of the mass content of the phenolic resin containing the polysulfide structure. The rubber composition containing the phenolic resin with the polysulfide structure can effectively improve the mechanical property, the tear resistance, the cutting resistance and the puncture resistance of a rubber material under the same processing condition, simultaneously can reduce dynamic heat generation and improve the flexibility of a rubber compound, and is particularly suitable for the side wall of a tire.
Description
Technical Field
The application relates to the technical field of rubber products, in particular to a rubber composition containing a phenolic resin with a polysulfide structure, application of the rubber composition and a tire prepared by using the rubber composition.
Background
Along with the rapid development of the mining industry, the engineering mechanical tire is developed in a specialized direction, the requirement of the engineering mechanical tire in China is large, the coverage area is wide, the engineering mechanical tire is mainly operated in severe environments such as mountainous areas and mining areas and is easy to be cut by stones, the phenomena of chipping and chipping occur, the tire quality is influenced, and the service life of the tire is shortened.
The side wall of the tire is one of the main stressed and heated components of the engineering machinery tire, so that the side wall of the engineering tire is required to have good flexing resistance, tearing resistance and cutting resistance, and strict requirements are provided for the quality of the tire. At present, the commonly used method is to add an anti-reversion agent into a sidewall rubber to solve the problem of rubber over-vulcanization, the commonly used anti-reversion agent is HTS, PK900 and the like, but the price is high, and a rigid resin network is formed by adding phenolic resin and a methylene donor to improve the problems of cutting resistance, tearing resistance, puncture resistance and the like of a tire, but the resin network and a rubber cross-linked network are not connected with each other through chemical bonds, but only through the physical winding interaction between the networks, the networks are easy to break, the heat generation is high, and the contribution to the tread performance is limited.
Chinese patent CN106397865B provides a rubber composition for a tread, which contains a sulfur-containing phenolic resin, the structure of the sulfur-containing phenolic resin is characterized in that the resin contains structural segments of the phenolic resin, and the structural segments of the phenolic resin are connected by a single-sulfur bond or a double-sulfur bond. The molecular chain of the phenolic resin is introduced with reactive sulfur atoms, so that the resin has the characteristics of the phenolic resin and can react with rubber through sulfur, and the phenolic resin and the rubber are chemically crosslinked. However, the single-sulfur bond or the double-sulfur bond in the sulfur-containing phenolic resin structure is directly connected with the benzene ring in the phenolic resin structure, which is a rigid structure, so that the cross-linking bond lacks flexibility, which results in poor flexing property and high dynamic heat generation of the rubber compound.
Disclosure of Invention
In order to solve the above-described technical problems, it is desired to obtain a rubber composition and a tire including a sidewall obtained by the rubber composition, which can improve the flexing characteristics of the sidewall.
In order to achieve the above object, according to one aspect of the present application, there is provided a rubber composition having a phenolic resin containing a polysulfide structure.
According to the embodiment of the application, the rubber composition with the phenolic resin containing the polysulfide structure comprises 100 parts by weight of rubber component, 1.0-20.0 parts by mass of phenolic resin containing the methylene polysulfide structure and 3.0-25 wt% of methylene donor in the mass content of the phenolic resin containing the polysulfide structure
Wherein:
—R1-R3identical or different, are each selected from hydrogen, linear or branched C1-C20Alkyl of (C)6-C30Aryl of (C)6-C30Alkylaryl and C of6-C30At least one of aralkyl groups of (a);
—R4-R8same or different, are each selected from hydrogen and C1-C3At least one of alkyl groups of (a);
-x is an integer from 2 to 6;
-m is an integer from 1 to 10;
-n is an integer from 0 to 30.
Further, in the rubber composition,
—R1-R3selected from hydrogen, straight or branched C1-C15Alkyl of (C)6-C18Aryl of (C)6-C18Alkylaryl and C of6-C18At least one of aralkyl groups of (a);
—R4-R8at least one selected from hydrogen and methyl;
-x is an integer from 2 to 4;
-m is an integer from 1 to 7;
-n is an integer from 0 to 20.
Further, in the rubber composition,
—R1-R3selected from hydrogen, straight or branched C1-C10Alkyl of (C)6-C12Aryl of (C)6-C12Alkylaryl and C of6-C12At least one of aralkyl groups of (a);
-m is an integer from 1 to 3;
-n is an integer from 0 to 10.
Further, the methylene donor is at least one selected from hexamethylenetetramine and hexamethoxymelamine.
Further, the rubber component is at least one selected from the group consisting of Natural Rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR) and polybutadiene-styrene rubber (SBR).
Further, the rubber composition also comprises 30.0 to 80.0 weight parts of carbon black, 3.0 to 10.0 weight parts of sulfur, 0.5 to 2.5 weight parts of vulcanization accelerator and 5.0 to 10.0 weight parts of process oil.
Further, the carbon black has a nitrogen adsorption specific surface area of 30 to 150m2/g。
Further, the rubber composition also comprises a vulcanization activator, an anti-aging agent and tackifying resin.
In order to achieve the above object, according to a second aspect of the present application, there is also provided a use of the rubber composition having a phenol resin containing a polysulfide structure of the first aspect for producing a sidewall of a tire.
In order to achieve the above object, according to a third aspect of the present application, there is also provided a tire having a sidewall using the rubber composition provided in the first aspect of the present application.
Compared with the prior art, the rubber composition containing the phenolic resin with the polysulfide structure can effectively improve the mechanical property, the tear resistance, the cut resistance and the puncture resistance of a rubber material under the condition of the same processing conditions, can reduce dynamic heat generation and improve the flexing property of a rubber compound, and is particularly suitable for the tire side of a tire.
Detailed Description
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this application, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The rubber composition provided by the invention at least comprises three components of a rubber component, a phenolic resin and a methylene donor. In addition to the above components, the rubber composition may further contain carbon black, sulfur, a vulcanization accelerator, process oil, and other necessary additives which are generally used in the rubber industry.
The rubber component of the above ingredients includes, but is not limited to, Natural Rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), polybutadiene-styrene rubber (SBR), and any combination thereof. The various indexes related to the various rubber components can be referred to those generally used in the rubber industry, and the present invention is not particularly limited, for example, polybutadiene rubber can be high cis-content polybutadiene rubber, modified polybutadiene rubber, etc., and when modified rubber is used, the specific modification method can also be a process method commonly used in the rubber industry.
The methylene donor in the above components is selected from Hexamethoxymethylmelamine (HMMM) or Hexamethylenetetramine (HMT). The weight percentage of methylene donor in the phenolic resin containing polysulfide structure is 3.0-25 wt%.
In the rubber composition of the present invention, the carbon black is 30.0 to 80.0 parts by weight, the sulfur is 3.0 to 10.0 parts by weight, the vulcanization accelerator is 0.5 to 2.5 parts by weight, and the process oil is 5.0 to 10.0 parts by weight, relative to 100 parts by weight of the rubber component.
The carbon black may be any carbon black used in the prior art for tires or any other applications, and preferably, the carbon black has a nitrogen adsorption specific surface area of 30m2/g-150m2The amount thereof is preferably 40.0 to 70.0 parts by mass per g.
The sulfur may be any of those used in the prior art for tires or any other applications, and is preferably used in an amount of 3 to 7 parts by weight.
The vulcanization accelerator may be any vulcanization accelerator used in the prior art for tires or any other application, including, but not limited to, sulfenamide-based vulcanization accelerators or thiazole-based vulcanization accelerators, and is preferably used in an amount of 0.5 to 2.5 parts by weight.
The rubber composition of the present invention may be compounded with additives usually used in the rubber industry, such as a vulcanization activator, an antioxidant, and a tackifier resin, as necessary, in addition to the above rubber component, phenol resin, carbon black, methylene donor, sulfur, and process oil. The amount of these additives to be mixed may be set within a range not impairing the effects of the present invention by the rubber component, the phenol resin containing a polysulfide structure, the methylene donor, and the like. The vulcanization activator can be zinc oxide and stearic acid, and can increase the activity of the accelerator and improve the performance of vulcanized rubber. The anti-aging agent can be p-phenylenediamine and/or ketoamine rubber anti-aging agent, the anti-aging agent can prevent or inhibit factors such as oxygen, heat, light, ozone, mechanical stress, heavy metal ions and the like from damaging the rubber performance and prolong the service life of the rubber, and the tackifying resin can be p-tert-octyl phenol formaldehyde resin and is used for increasing the viscosity of rubber materials and convenient to process.
In the present invention, the rubber composition to be applied to the sidewall can be obtained by using the phenol resin containing a polysulfide structure among the above-mentioned components. The structure of the phenolic resin is shown as a formula (I), the structure of the phenolic resin contains a phenolic resin structural fragment, a poly (bi) sulfur bond and a methylene structure, and the methylene is positioned between the poly (bi) sulfur bond and a benzene ring. In a first aspect, structural fragments of the phenolic resin can react with methylene donors to form a rigid resin network structure that can improve the cut, tear, puncture resistance of the rubber compound; in the second aspect, the phenolic resin containing the polysulfide structure has a multi (dual) sulfur bond structural unit, the multi (dual) sulfur bond structure is easier to participate in the vulcanization reaction of rubber, so that the resin and the rubber are connected together through a sulfur chain, a formed rigid resin network structure can move along with the movement of the rubber chain, the friction between the rubber molecular chain and the resin network is reduced, the dynamic heat generation is reduced, and the polysulfide bond is preferably a tetrasulfide bond; in the third aspect, the poly (bi) sulfide bond is connected with the benzene ring in the phenolic resin structure through a methylene or methine, the methylene or methine can increase the flexibility of the crosslink bond, thereby improving the flex performance of the rubber compound, because the benzene ring is a rigid structure and the benzene ring is an electron-withdrawing group, if the benzene ring of the rigid structure is directly crosslinked to the rubber chain through sulfur, the sulfur-carbon bond is easy to break when the rubber main chain moves, and the methylene structure is introduced between the benzene ring and the sulfur, so that the flexibility of the crosslink bond is increased, the electron-withdrawing property of the benzene ring is reduced, and the sulfur-carbon bond is not easy to break; in the fourth aspect, the objective of using the phenolic resin containing polysulfide structure in the rubber composition applied to the sidewall is to build a resin crosslinked network on the basis of the conventional sulfur crosslinked network, and the resin crosslinked network can be linked to the rubber main chain through sulfur, thereby increasing the dispersibility of the resin network and the compatibility of the resin network and the rubber network. Even if the cross-linking bonds between the resin network and the rubber network are broken during the aging of the rubber composition, the resin network is uniformly dispersed and interpenetrated in the rubber network, and the rubber network is reinforced.
In the phenolic resin containing methylene polysulfide structure shown in formula (I) provided by the invention, R1-R3Identical or different, are each selected from hydrogen, linear or branched C1-C20Alkyl of (C)6-C30Aryl of (C)6-C30Alkylaryl and C of6-C30At least one of aralkyl groups of (a); r4-R8Same or different, are each selected from hydrogen and C1-C3At least one of alkyl groups of (a).
From the viewpoint of improving the dispersibility of the phenol resin containing a polysulfide structure in the rubber component, R1-R8With the greatest possible choice of hydrogen or radicals having a lower carbon number, preferably, R1-R3Selected from hydrogen, straight or branched C1-C15Alkyl of (C)6-C18Aryl of (C)6-C18Alkylaryl and C of6-C18At least one of aralkyl groups of (1), R4-R8At least one selected from hydrogen and methyl; most preferably, R1-R3Selected from hydrogen, straight or branched C1-C10Alkyl of (C)6-C12Aryl of (C)6-C12Alkylaryl and C of6-C12At least one of aralkyl groups of (a). In addition, the non-hydrogen substituent on the benzene ring can increase the compatibility of the resin and rubber, and the prepared resin is of a linear structure, but cannot be further crosslinked into a resin network by using a curing agent (such as methylene donors HMT and HMMM). When the benzene ring has no substituent (hydrogen), the resin can be crosslinked with a curing agent (such as methylene donor HMT and HMMM) to form a resin network, so as to reinforce the rubber. The choice of each substituent may be determined according to production requirements.
In order to preserve a relatively complete phenolic resin structure in the rubber, the number m of repeating units in the polycondensate is an integer from 1 to 10, preferably an integer from 1 to 7, most preferably an integer from 1 to 3; n is an integer from 0 to 30, preferably from 0 to 20, most preferably from 0 to 10. If the resin has a large number of sulfur-containing structural units in the structure, the resin is broken into fragments by the cleavage of the sulfur bond in the vulcanization of the rubber, and the rubber-reinforcing effect is not good even if a further network of the resin is formed. The structure of sulfur-containing phenol and phenolic resin blocks is prepared, n is larger than m, the structural units of the phenolic resin can be reserved in the resin, and the rubber can be reinforced after further curing and crosslinking.
In order to increase the efficiency of the resin-rubber vulcanization reaction, x is an integer of 2 to 6, preferably an integer of 2 to 4.
The phenolic resin containing a methylene polysulfide represented by the formula (I) mentioned in the present invention can be prepared by a general method in the prior art, and an alternative preparation method is exemplified below, and the preparation method of the phenolic resin specifically comprises the following steps:
step 1, adding sodium hydroxide or sodium sulfide, sulfur and water into a reactor with a stirring device, a thermometer and a reflux device, heating to 80-100 ℃, and reacting for 2-6 hours to obtain an aqueous solution of a product A;
and 2, adding the product A water solution with the mass percentage concentration of 10-50% and phenol or alkylphenol into a reactor with a stirring device, a thermometer and a reflux device, heating to 60-100 ℃, adding aldehyde, stirring at 60-100 ℃ for reaction for 2-6 hours, neutralizing the reaction liquid to be neutral by using acid after the reaction is finished, adding a solvent for liquid separation, extracting a water phase by using a peristaltic pump, washing an organic phase by using water, distilling by using a distilling device, distilling under reduced pressure when the distilling temperature is increased to 140-180 ℃, and distilling under reduced pressure at-0.1 Mpa-0.1 Mp for 10-60 minutes. Finally, the reaction was stopped and the resin was poured out.
In step 1, the product a has the formula: na (Na)2SxX is an integer of 2-6; preferably, x is an integer of 2-4;
in the step 2, the structure of the phenol or the alkylphenol is shown as the formula (II):
in the formula (II), R is selected from hydrogen, straight chain or branched chain C1-C20Alkyl of (C)6-C30Aryl of (C)6-C30Alkylaryl of, C6-C30At least one of aralkyl groups of (a).
In the step 1, the usage amount of the sulfur is 60 to 240 percent of the usage amount of the sodium hydroxide based on the mole number of the sodium hydroxide. The proportional relationship is based on the equation of the reaction between sodium hydroxide and sulfur and the molecular formula Na of the product A2Sx(x is an integer of 2 to 6); based on the mole number of the sodium sulfide, the dosage of the sulfur is 0 to 500 percent of the dosage of the sodium hydroxide. The proportional relationship is based on the equation of the reaction between sodium sulfide and sulfur and the molecular formula Na of the product A2Sx(x is an integer of 2 to 6); the amount of water is 50-500% of the amount of sodium hydroxide or sodium sulfide based on the mass of sodium hydroxide (or sodium sulfide).
Sodium polysulfide can be prepared by the above method. Wherein, the reaction of the sodium hexasulfide and the sulfur has no reaction by-product, the by-product of the reaction of the sodium hydroxide and the sulfur is sodium thiosulfate, and the sodium thiosulfate has no influence on the subsequent reaction.
In the step 2, the dosage of the product A is 10-100% of the dosage of phenol or alkylphenol based on the mole number of phenol or alkylphenol. By varying the amounts of phenol or alkylphenol and product a, resins of different sulfur contents can be prepared.
The aldehyde is selected from at least one of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; preferably, the aldehyde is selected from at least one of formaldehyde and acetaldehyde. Based on the mole number of the phenol or the alkylphenol, the dosage of the aldehyde is 100 to 400 percent of the dosage of the phenol or the alkylphenol. The aldehyde can be solid aldehyde (such as paraformaldehyde) or liquid aldehyde, and the aldehyde concentration is 30-50%. The acid is at least one selected from hydrochloric acid, sulfuric acid, oxalic acid and sulfonic acid; preferably, the acid is at least one selected from hydrochloric acid, sulfuric acid, and oxalic acid. After the phenolic resin reaction is finished, the solution is alkaline and needs to be neutralized to be neutral by acid. The amount of the acid added is adjusted to 6.0-7.0 of the pH value of the reaction solution. The solvent is at least one selected from toluene and xylene. Based on the mass of phenol or alkylphenol, the dosage of the solvent is 50-200% of the dosage of phenol or alkylphenol. The solvent is added for the purpose of dissolving the resin in the solvent and separating from water in the reaction liquid.
The following is a specific process for preparing a p-tertiary phenol (PTOP) polythiophenol-containing resin:
adding 12.0g (0.3mol) of sodium hydroxide and 16.0g (0.5mol) of sulfur into a 250ml four-neck flask with a temperature control device, a stirring device and a reflux device, adding 25.0g of water, installing a temperature control probe and a spherical condenser tube, stirring until the sulfur is dissolved and added, raising the reaction temperature to reflux, and carrying out reflux reaction for 4 hours to obtain a dark red transparent clear sodium polysulfide aqueous solution. 41.3g (0.2mol) of PTOP was placed in a 250ml four-necked flask containing an aqueous solution of sodium polysulfide, and the atmosphere in the reactor was replaced with nitrogen gas, and the temperature was raised to melt the PTOP. The reaction liquid is transparent and clear at 80 ℃, 48.6g (0.6mol) of 37 percent liquid formaldehyde is dripped, and the reaction is carried out for 4 hours at 80 ℃ after the dripping is finished. And adding oxalic acid to neutralize the reaction solution with the pH value of 6.0-7.0 after the reaction is finished, and adding 50.0g of solvent toluene for liquid separation. The lower aqueous phase was extracted at 80 ℃ with a peristaltic pump and the toluene layer was washed 3 times with water. And (3) raising the reaction temperature in a distillation state for distillation, and carrying out reduced pressure distillation for 30min when the temperature is raised to 150 ℃, wherein the vacuum degree is 0.09MPa, so as to obtain the final resin. The softening point of the resin was 80.4 ℃ as measured by a calorific value analyzer; the hydroxymethyl content is 4.5%; the content of PTOP in the liquid chromatography test product is 1.03 percent, and the content of elemental sulfur is 0 percent (indicating that all sulfur is connected into the resin); resin molecular weight Mn-1038, Mw-2317, Mz-3674, polydispersity 2.23; the sulfur content in the resin measured by the elemental analyzer was 17.33%. The structural formula of the obtained resin is shown as the formula (III)
The following is another specific process for preparing phenol polysulfide-containing phenolic resin:
adding 12.0g (0.3mol) of sodium hydroxide and 16.0g (0.5mol) of sulfur into a 250ml four-neck flask with a temperature control device, a stirring device and a reflux device, adding 25.0g of water, installing a temperature control probe and a spherical condenser tube, stirring until the sulfur is dissolved and added, raising the reaction temperature to reflux, and carrying out reflux reaction for 4 hours to obtain a dark red transparent clear sodium polysulfide aqueous solution. To a 250ml four-necked flask containing an aqueous solution of sodium polysulfide (80 to 90 ℃ C.), 18.8g (0.2mol) of phenol in a molten state was charged, and the atmosphere in the reactor was purged with nitrogen. 48.6g (0.6mol) of 37% liquid formaldehyde are added dropwise with stirring at 90 ℃ and reacted for 4 hours at 90 ℃. And adding oxalic acid to neutralize the reaction solution with the pH value of 6.0-7.0 after the reaction is finished, and adding 50.0g of solvent toluene for liquid separation. The lower aqueous phase was extracted at 80 ℃ with a peristaltic pump and the toluene layer was washed 3 times with water. And (3) raising the reaction temperature in a distillation state for distillation, and carrying out reduced pressure distillation for 30min when the temperature is raised to 150 ℃, wherein the vacuum degree is 0.09MPa, so as to obtain the final resin. The softening point of the resin was tested to be 92.6 ℃ with a calorific value analyzer; the hydroxymethyl content is 5.2%; the phenol content in the liquid chromatography test product was 1.63%, the elemental sulfur content was 0% (indicating that all sulfur was incorporated into the resin); resin molecular weight Mn of 1147, Mw of 2472, Mz of 3592, polydispersity of 2.05; the sulfur content in the resin was 20.52% as measured by elemental analyzer. The structural formula of the obtained resin is shown as the formula (IV)
The exemplary preparation methods provided above use phenol or alkyl phenol, aldehyde, sodium sulfide or sodium polysulfide as the starting material and, since sodium sulfide or sodium polysulfide is basic, there is no need to add a basic catalyst in the present preparation method. In addition, the aqueous solution of sodium sulfide or sodium polysulfide has low volatility, and thioether or mercaptan byproducts cannot be generated in the reaction process, so that environmental pollution cannot be caused.
The rubber composition of the present invention can be produced by a conventional method in the art, and the above-mentioned various components are mixed and then vulcanized to give a rubber composition. The manufacturing apparatus used may be an internal mixer, a kneader, an open mill, etc. which are generally used in the art.
The rubber composition of the present invention is particularly suitable for a sidewall of a tire because it has excellent tear resistance, cut resistance and puncture resistance, while reducing dynamic heat generation and improving the flex characteristics of a rubber compound, and thus can be used for manufacturing a sidewall of a tire.
The side wall of the tire of the present invention can be produced by a usual method using the rubber composition of the present invention, that is, the components of the rubber composition to be mixed as needed are extruded in accordance with the shape of the side wall of the tire before the unvulcanized step, molded on a tire molding machine, and then the unvulcanized tire is heated and pressurized in a vulcanizer to obtain the tire.
The invention will be further explained below with reference to examples. The rubber compositions of examples 1 to 6 and comparative examples 1 to 3 were prepared by using the raw material components and the amounts shown in tables 1 and 2, wherein the amounts shown in the tables are parts by weight.
Some of the components and sources thereof in the rubber compositions of the examples and comparative examples are as follows:
natural Rubber (NR), SMR20, malaysia products;
styrene Butadiene Rubber (ESBR), ESBR1502, shenhua chemical industry ltd;
carbon black N330, cabot (china) investment ltd;
carbon black N660, cabot (china) investment limited;
zinc oxide, a large continuous zinc oxide plant;
browning stearic acid and lithocarpus tikoua;
HMT, tokinan herboria chemical ltd;
plasticizer WB222, product of Struktol, USA;
reinforcing resin SL-2005, Huaqi (China) chemical Co., Ltd;
anti-aging agent 4020, saint ao chemical ltd of Jiangsu;
anti-aging agent RD, Jiangsu saint ao chemical Co., Ltd;
operating oil P50, dadall;
tear resistant resin SL-6903, Huaqi (China) chemical Co., Ltd;
anti-reversion agent HTS, american fulex product;
rubber protective wax OK1987, product of Paramelt;
sulfur, fuhua chemical limited in phoenix city;
accelerator CZ, celadon Huaheng auxiliary agent factory.
In comparative example 3, the structural formula of the sulfur-containing phenol resin used is shown by the formula (V),
it is prepared by laboratory, wherein m is 2-4 and n is 4-6.
The phenolic resin containing polysulfide structure in examples 1, 4-6 is shown in formula (IV),
wherein m is 2-4 and n is 4-6.
The phenolic resin containing polysulfide structure in example 2 is shown in formula (VI),
wherein m is 2-4 and n is 4-6.
The phenolic resin containing polysulfide structure in example 3 is shown in formula (VII),
wherein m is 2-4 and n is 4-6.
The equipment used in each example and comparative example was as follows:
1.6LBR1600 internal mixer, product of Farrel company, USA;
XK-160 type open mill, product of machinery plant of Qingdao Xincheng Yiming;
XLB-D600X 600 type plate vulcanizer, product of Zhejiang Huzhou Hongqiao machinery factory;
model 3365 tensile machine, product of instron corporation, usa;
dynamic cutting test machine, a product of Taipu USA;
compression thermogenesis instrument, product of Alpha company, usa.
TABLE 1 comparative examples and examples 1-3 formulation tables
Table 2 examples 4-6 formulation table
According to the formulations shown in tables 1 and 2, rubber, carbon black, white carbon, and other compounds except sulfur, a methylene donor, and a vulcanization accelerator were mixed for 6 minutes with a 1.6-liter Banbury mixer to obtain a master batch, and then a vulcanization accelerator, a methylene donor, and sulfur were mixed in the master batch using an open mill to obtain rubber compositions, and each of the thus-obtained rubber compositions was vulcanized at a temperature of 150 ℃ for 30 minutes to obtain vulcanized rubbers, and each of the thus-obtained rubber compositions was vulcanized at a temperature of 150 ℃ for 60 minutes to obtain high-temperature long-time vulcanized rubbers.
The operations and performance index tests for each example and comparative example were performed using the following standard methods, and the results of the performance index tests are shown in Table 3.
Rubber test compound material batching, mixing and vulcanizing equipment and operation procedures are disclosed in GB/T6038-2006;
the general procedures for preparing and adjusting the samples in the rubber physical test method are disclosed in GB/T2914-2006;
the determination of the tensile stress strain performance of vulcanized rubber or thermoplastic rubber is disclosed in GB/T528-2009;
the vulcanized rubber or thermoplastic rubber indentation hardness test method (Shore durometer method) is disclosed in GB/T531.1-2008;
the tear strength of vulcanized or thermoplastic rubbers is determined (square specimens) in GB/T529-2008;
the temperature rise and fatigue resistance of the vulcanized rubber in a flexing test are measured and are shown in GB/T1687-93.
TABLE 3 formula Performance test Table
As can be seen from Table 3, the mechanical properties of examples 1-6 are comparable and significantly better than those of the comparative example. In comparison with comparative example 1, in examples 1 to 6 of the present invention using the rubber composition having a phenolic resin containing a polysulfide structure, the 50% stress at definite elongation is improved and the tensile strength at break is increased, the flex crack property, the tear strength and the cut resistance are remarkably improved, and the heat generation by compression is reduced. In examples 1 to 6 of the present invention using the rubber composition having a phenol resin containing a polysulfide structure, the 50% stress at definite elongation is improved and the tensile strength is increased, the flex crack property, the tear strength and the cut resistance are remarkably improved, and the heat generation by compression is reduced, as compared with the composition of comparative example 2 in which a conventional phenol resin (SL-2005) is added. Examples 1 to 6 use the rubber composition having a phenol resin containing a polysulfide structure, and the flexural tear growth length was reduced and the heat generation in compression was reduced, as compared with the composition of comparative example 3 in which the sulfur-containing phenol resin (V) was added.
Therefore, the rubber composition containing the phenolic resin with the polysulfide structure has high tearing strength and better cutting resistance, and meanwhile, the flex cracking performance of the rubber compound is obviously improved, and the compression heat generation is lower. After high-temperature long-time vulcanization (150 ℃, 60min), the tensile strength at break, the stress at definite elongation and the tearing strength of the rubber formula containing the phenolic resin with the polysulfide structure are obviously higher than those of the rubber formula containing the common phenolic resin, and the mechanical property of the rubber formula containing the phenolic resin with the polysulfide structure is obvious.
It should be noted that the rubber composition with the phenolic resin containing polysulfide structure and the other components and operations of the preparation method thereof provided by the present application are known to those skilled in the art, and the operations, steps, parameters and working principles which are not described are known to those skilled in the art, and those skilled in the art can refer to the rubber product and the preparation process thereof in the prior art, and will not be described in detail herein.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments 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 (10)
1. A rubber composition containing phenolic resin with a polysulfide structure is characterized by comprising 100 parts by weight of rubber component, 1.0-20.0 parts by weight of phenolic resin with the polysulfide structure and a methylene donor accounting for 3.0-25 wt% of the phenolic resin with the polysulfide structure, wherein the phenolic resin with the polysulfide structure has a structural formula shown in a formula (I),
wherein:
—R1-R3identical or different, are each selected from hydrogen, linear or branched C1-C20Alkyl of (C)6-C30Aryl of (C)6-C30Alkylaryl and C of6-C30At least one of aralkyl groups of (a);
—R4-R8same or different, are each selected from hydrogen and C1-C3At least one of alkyl groups of (a);
-x is an integer from 4 to 6;
-m is an integer from 2 to 4;
-n is an integer from 4 to 6.
2. The rubber composition according to claim 1,
—R1-R3selected from hydrogen, straight or branched C1-C15Alkyl of (C)6-C18Aryl of (C)6-C18Alkylaryl and C of6-C18At least one of aralkyl groups of (a);
—R4-R8at least one selected from hydrogen and methyl;
-x is 4;
-m is an integer from 1 to 7;
-n is an integer from 0 to 20.
3. The rubber composition according to claim 2,
—R1-R3selected from hydrogen, straight or branched C1-C10Alkyl of (C)6-C12Aryl of (C)6-C12Alkylaryl and C of6-C12At least one of aralkyl groups of (a);
-m is an integer from 1 to 3;
-n is an integer from 0 to 10.
4. The rubber composition according to claim 1, wherein the methylene donor is at least one selected from hexamethylenetetramine and hexamethoxymelamine.
5. The rubber composition of claim 1, wherein the rubber component is at least one selected from the group consisting of Natural Rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), and polybutadiene-styrene rubber (SBR).
6. The rubber composition according to claim 1, further comprising 30.0 to 80.0 parts by weight of carbon black, 3.0 to 10.0 parts by weight of sulfur, 0.5 to 2.5 parts by weight of a vulcanization accelerator, and 5.0 to 10.0 parts by weight of a process oil.
7. The rubber composition according to claim 6, wherein the carbon black has a nitrogen adsorption specific surface area of 30 to 150m2/g。
8. The rubber composition according to claim 6, further comprising a vulcanization activator, an antioxidant and a tackifier resin.
9. Use of the rubber composition with a phenolic resin containing polysulfur structure according to any one of claims 1 to 8 for the preparation of a tyre sidewall.
10. A tire having a sidewall using the rubber composition according to any one of claims 1 to 8.
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