CN117511072A - Rubber processing modifier, preparation method and application thereof, tire tread rubber composition, tire tread rubber and preparation method thereof - Google Patents

Rubber processing modifier, preparation method and application thereof, tire tread rubber composition, tire tread rubber and preparation method thereof Download PDF

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Publication number
CN117511072A
CN117511072A CN202210892385.1A CN202210892385A CN117511072A CN 117511072 A CN117511072 A CN 117511072A CN 202210892385 A CN202210892385 A CN 202210892385A CN 117511072 A CN117511072 A CN 117511072A
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Prior art keywords
rubber
weight
parts
processing modifier
tire tread
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CN202210892385.1A
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Inventor
郑方远
王丽丽
唐瀚滢
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Priority to CN202210892385.1A priority Critical patent/CN117511072A/en
Publication of CN117511072A publication Critical patent/CN117511072A/en
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the field of rubber, and discloses a rubber processing modifier, a preparation method and application thereof, a tire tread rubber composition, a tire tread rubber and a preparation method thereof. The rubber processing modifier comprises a mercapto acid monomer, a matrix material and white carbon black; the mercapto acid monomer is provided by at least one of the compounds represented by formula (1):

Description

Rubber processing modifier, preparation method and application thereof, tire tread rubber composition, tire tread rubber and preparation method thereof
Technical Field
The invention relates to the field of rubber, in particular to a rubber processing modifier, a preparation method and application thereof, a tire tread rubber composition, a tire tread rubber and a preparation method thereof.
Background
In recent years, the dynamic hysteresis loss performance of green tires determines the classification of the tires, and also causes the reduction of the strength and wear resistance of the rubber, causing early damage to the tires, and also increases the rolling resistance of the tires, and increases the fuel consumption and the carbon dioxide emission.
CN102382338A discloses an isoprene rubber blend comprising isoprene rubber, trans-1, 4-polyisoprene, reinforcing filler, in situ graft modification aid, compounded rubber and a first additive. The in-situ grafting modification auxiliary agent adopted in the prior art is subjected to grafting reaction with functional groups such as double bonds on a rubber molecular chain while undergoing chemical reaction with the reinforcing filler, so that the interfacial binding force between an organic polymer and the reinforcing filler and the dispersion level of the reinforcing filler in rubber are greatly improved, and the fatigue resistance of the isoprene rubber blend is improved.
CN103881161a discloses a trans-polyisoprene rubber and cis-polyisoprene rubber composition and processing technology thereof, and specifically discloses a rubber composition, wherein the total amount of synthetic trans-polyisoprene and synthetic cis-polyisoprene is 5-60 parts by mass, 40-95 parts by mass of natural rubber, 5-90 parts by mass of white carbon black and 5-90 parts by mass of carbon black, based on 100 parts by mass of rubber; the masterbatch process comprises the following steps: mixing the synthetic trans-polyisoprene or the composition of the synthetic trans-polyisoprene and the synthetic cis-polyisoprene rubber with white carbon black and a coupling agent to obtain white carbon black wood gum; mixing natural rubber and carbon black to obtain carbon black master batch; and (3) final rubber mixing process: and mixing the carbon black master batch, the white carbon black master batch, the anti-aging agent, the active agent, the accelerator and the vulcanizing agent to prepare the rubber composition. The rubber compound prepared by the rubber composition and the process in the prior art has the characteristics of improving wear resistance and reducing heat generation, and can be applied to rubber products, particularly automobile tires, and can reduce rolling resistance and heat generation.
CN103703072a discloses a rubber composition for a tread, which contains a solution polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol, wherein the content of the solution polymerized styrene-butadiene rubber in 100 mass% of the rubber component is 60 mass% or more, the content of the carbon black is 10 mass parts or less, the content of the silica is 50 mass parts or more, and the content of the polyethylene glycol is 0.1 to 3.5 mass parts with respect to 100 mass parts of the rubber component. According to this prior art, a rubber composition containing solution polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol in prescribed amounts, respectively, can provide a pneumatic tire with improved fuel economy and wear resistance in balance when applied to a tire tread. In addition, the vulcanization speed is good when the tire is manufactured, and the appearance of the manufactured tire is good.
CN103087365a discloses a rubber composition for a wet skid and wear resistant balance tire tread, comprising a diene elastomer, an inorganic reinforcing filler, a coupling agent and a plasticizer. In this prior art, when a tire comprising a rubber composition is used, the tread of the tire has excellent wet skid resistance, gives the tire a balance of properties of wet grip and wear resistance, and is used for manufacturing a semi-steel radial car tire.
However, the rubber provided by the prior art still cannot meet the requirements of strength, heat generation reduction and wet skid performance improvement of the tread rubber of the tire, and there is a need for providing a rubber with improved performance.
CN107964138A discloses an application of a mercapto acid monomer and an application thereof in tire tread, in which the mercapto acid monomer and a rubber matrix are mixed in the prior art, so that the bridge effect of the matrix modifier mercapto acid monomer in the matrix rubber and white carbon black can be better exerted, the interaction of the white carbon black and the rubber matrix is facilitated, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the heat generation of the vulcanized rubber is reduced, and the wet skid resistance of the vulcanized rubber sizing material is improved. However, the mercapto acid monomer has the disadvantages of bad smell, poor compatibility with a high-viscosity rubber matrix, poor dispersibility, inaccurate feeding and the like, so that the application of the mercapto acid monomer is limited to a certain extent.
Disclosure of Invention
The invention aims to overcome the defect that the compatibility and the dispersibility of a mercapto acid monomer in a high-viscosity rubber matrix are poor in the prior art, and the substrate is high in gel content due to higher local mercapto acid monomer concentration in the in-situ modification process, so that the performances of strength, wear resistance, wet skid resistance, heat generation and the like of a tire tread rubber are affected.
In order to achieve the above object, a first aspect of the present invention provides a rubber processing modifier, characterized in that the rubber processing modifier comprises a mercapto acid monomer, a base material, and white carbon black;
the mercapto acid monomer is provided by at least one of the compounds represented by formula (1):
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
The second aspect of the invention provides a method for preparing a rubber processing modifier, which is characterized in that the method comprises the following steps:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the matrix material to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing modifier;
wherein at least one of the mercapto acid monomer compounds represented by formula (1) provides:
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
In a third aspect, the present invention provides a rubber processing modifier prepared by the above-described preparation method.
The fourth aspect of the invention provides an application of the rubber processing modifier in preparing tire tread rubber.
A fifth aspect of the present invention provides a tire tread rubber composition characterized in that the rubber composition comprises the above-mentioned rubber processing modifier and a base rubber;
wherein the rubber processing modifier is used in an amount of 0.5 to 6 parts by weight, preferably 1 to 3 parts by weight, relative to 100 parts by weight of the base rubber.
The sixth aspect of the invention provides a method for preparing a tread rubber for a tire, which is characterized by comprising the following steps:
mixing all components in a rubber composition containing a rubber processing modifier and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain the tire tread rubber;
wherein the rubber processing modifier is the rubber processing modifier.
The seventh aspect of the present invention provides a tread rubber for a tire produced by the above production method.
Through the technical scheme, the rubber processing modifier, the preparation method and the application thereof, the tire tread rubber composition, the tire tread rubber and the preparation method thereof provided by the invention have the following beneficial effects:
the rubber processing modifier provided by the invention comprises the mercapto acid monomer, the matrix material and the white carbon black, and the mercapto acid monomer, the matrix material and the white carbon black are mixed in advance to prepare the rubber processing modifier, so that the compatibility and the dispersibility of the mercapto acid monomer and the rubber matrix can be obviously improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a rubber processing modifier, characterized in that the rubber processing modifier comprises a mercapto acid monomer, a base material and white carbon black;
the mercapto acid monomer is provided by at least one of the compounds represented by formula (1):
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 Of two MR 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
The rubber processing modifier provided by the invention comprises the mercapto acid monomer, the matrix material and the white carbon black, and the mercapto acid monomer, the matrix material and the white carbon black are mixed in advance to prepare the rubber processing modifier, so that the compatibility and the dispersibility of the mercapto acid monomer and the rubber matrix can be obviously improved, and when the rubber processing modifier is used for preparing the tire tread rubber, the heat generation and the rolling resistance of the tire tread rubber can be obviously reduced on the premise of ensuring that the tire tread rubber has high strength, wear resistance and wet skid resistance.
Furthermore, the sulfhydryl acid monomer is matched with the rubber matrix through the rubber processing modifier provided by the invention, so that the pungent odor generated by the sulfhydryl acid monomer is reduced, the rubber processing modifier is environment-friendly, more importantly, the weighing is convenient, the feeding is accurate, and the batch quality stability is improved.
In one embodiment of the present invention, the mercapto-acid-based monomer is at least one of 3-mercapto-acrylic acid and/or 4-mercapto-butyric acid.
According to the invention, the content of the mercapto acid monomer is 40-60 parts by weight, the content of the matrix material is 20-30 parts by weight, and the content of the white carbon black is 15-25 parts by weight.
According to the invention, when the dosages of the mercapto acid monomer, the matrix material and the white carbon black are controlled to meet the above range, the load of the mercapto acid monomer of the modifier can be increased, the pungent odor generated when the mercapto acid monomer is added in situ can be reduced, the weighing is convenient and accurate in the preparation process, and the dispersibility of the rubber processing modifier in the rubber matrix is obviously improved.
In one embodiment of the present invention, the mercapto acid monomer is contained in an amount of 60 parts by weight, the matrix material is contained in an amount of 20 parts by weight, and the white carbon black is contained in an amount of 20 parts by weight.
According to the invention, the matrix material comprises ethylene propylene diene monomer and ethylene-vinyl acetate copolymer, wherein the weight ratio of the ethylene propylene diene monomer to the ethylene-vinyl acetate copolymer is 1-2.3:1.
in the invention, ethylene propylene diene monomer and ethylene-vinyl acetate copolymer are selected as matrix materials, and when the weight ratio of the ethylene propylene diene monomer to the ethylene vinyl acetate copolymer is controlled to meet the range, the matrix materials in the rubber processing modifier, the mercapto acid monomer and the white carbon black have excellent coating property, and when the rubber processing modifier is used for tire tread rubber, the compatibility and the dispersibility of the mercapto acid monomer in the rubber matrix can be obviously improved, so that the heat generation and the rolling resistance of the tire tread rubber are further reduced.
In one specific embodiment of the invention, the weight ratio of the ethylene propylene diene monomer to the ethylene-vinyl acetate copolymer is 1:1.
according to the invention, in the ethylene propylene diene monomer, the content of vinyl groups is 50-60wt%, and the content of structural units provided by the third monomer is 5-10wt%.
According to the invention, the Mooney viscosity ML (100 ℃, 1+4min) of the ethylene propylene diene monomer is 55-70.
In the invention, when the content of vinyl, the content of the structural unit provided by the third monomer and the Mooney viscosity of the ethylene propylene diene monomer in the ethylene propylene diene monomer meet the ranges, the rubber processing modifier containing the ethylene propylene diene monomer has excellent processing performance, and when the rubber processing modifier is used for preparing the tire tread rubber, the compatibility and the dispersibility of the mercapto acid monomer in a rubber matrix can be obviously improved, so that the heat generation of the tire tread rubber is further reduced.
In the present invention, the third monomer may be a third monomer of a conventional kind in the art, such as Ethylidene Norbornene (ENB).
According to the invention, in the ethylene-vinyl acetate copolymer, vinyl acetate provides a content of structural units of 10 to 30% by weight.
According to the invention, the ethylene-vinyl acetate copolymer has a melt index of 20-40g/10min at 190℃and a load of 2.16 kg.
In the present invention, when the content of the structural unit provided by Vinyl Acetate (VA) and the melt index of the ethylene-vinyl acetate copolymer in the ethylene-vinyl acetate copolymer (EVA) satisfy the above ranges, the ethylene-vinyl acetate copolymer has excellent processing fluidity, and further the base material comprising the ethylene-vinyl acetate copolymer is more excellent in coating properties of the mercapto acid-based monomer and white carbon black, and when the rubber processing modifier comprising the ethylene-vinyl acetate copolymer is used for preparing a tire tread rubber, the compatibility and dispersibility of the mercapto acid-based monomer in the rubber matrix can be remarkably improved, and further the heat generation and rolling resistance of the tire tread rubber can be further reduced.
In the present invention, the type of the white carbon black is not particularly limited, and may be a white carbon black of a conventional type in the art, for example, a vapor phase white carbon black and/or a precipitation white carbon black, and preferably the white carbon black is a precipitation white carbon black.
The second aspect of the invention provides a method for preparing a rubber processing modifier, which is characterized by comprising the following steps:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the matrix material to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing modifier;
wherein at least one of the mercapto acid monomer compounds represented by formula (1) provides:
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
According to the invention, the rubber processing modifier disclosed by the first aspect of the invention is obtained by mixing the white carbon black and the mercapto acid monomer and then mixing the mixture with the plasticated rubber of the matrix material, so that the mercapto acid monomer, the white carbon black and the matrix material are fully and uniformly mixed in advance, the compatibility and the dispersibility of the mercapto acid monomer and the rubber matrix are obviously improved, and when the rubber processing modifier is used for preparing the tire tread rubber, the heat generation and the rolling resistance of the tire tread rubber can be obviously reduced on the premise of ensuring that the tire tread rubber has high strength, wear resistance and wet skid resistance.
The amount and kind of raw materials for preparing the rubber processing modifier according to the second aspect of the present invention are exactly the same as those described in the first aspect of the present invention, and the present invention is not repeated in this second aspect, and those skilled in the art should not understand the limitation of the present invention.
In the present invention, the mixing mode of the white carbon black and the mercapto acid monomer is not particularly limited as long as a uniform pre-load mixture of the white carbon black and the mercapto acid monomer can be formed.
According to the invention, the plasticating conditions include: the plasticating temperature is 40-60 ℃, the rotating speed is 40-70rpm, and the plasticating time is 0.5-3min.
In the invention, under the condition, the plasticating is carried out on the base material, so that the processing performance of the base material can be improved, the base material, the mercapto acid monomer and the white carbon black are uniformly mixed, and the compatibility and the dispersibility among the mercapto acid monomer, the base material and the white carbon black in the rubber processing modifier are further improved.
In the present invention, the plastication may be carried out in conventional equipment in the art, preferably an internal mixer.
According to the invention, the mixing conditions include: the mixing time is 2-6min, and the mixing temperature is 50-55 ℃.
In the invention, the plasticated rubber and the pre-loaded mixture are mixed under the conditions, so that the plasticated rubber and the pre-loaded mixture are fully and uniformly mixed, and each component in the prepared rubber processing modifier has excellent dispersibility and compatibility.
In the present invention, the mixing may be carried out in conventional equipment in the art, preferably an internal mixer.
In a third aspect, the present invention provides a rubber processing modifier prepared by the above-described preparation method.
The fourth aspect of the invention provides an application of the rubber processing modifier in preparing tire tread rubber.
A fifth aspect of the present invention provides a tire tread rubber composition characterized in that the rubber composition comprises the above-mentioned rubber processing modifier and a base rubber, wherein the rubber processing modifier is used in an amount of 0.5 to 6 parts by weight relative to 100 parts by weight of the base rubber.
Further, the rubber processing modifier is used in an amount of 1 to 3 parts by weight relative to 100 parts by weight of the base rubber.
In the present invention, the base rubber may be various conventional rubber requiring vulcanization processing for tire tread rubber, and may include, but is not limited to: natural rubber and/or synthetic rubber, which may include, but is not limited to: butadiene rubber and/or styrene-butadiene rubber.
In the invention, the tire tread rubber composition also comprises conventional auxiliary agents of tire tread rubber, such as white carbon black, an active agent, an anti-aging agent, a vulcanizing agent, an accelerator and the like.
In the present invention, the white carbon black may be any of various existing precipitation method white carbon blacks which can be used for reinforcing rubber, and may include, but is not limited to: white carbon black 200MP, 1165MP, 165GR and 115GR, wherein the content of the white carbon black can be selected in a larger range; specifically, the content of the white carbon black may be 40 to 100 parts by weight with respect to 100 parts by weight of the base rubber.
In the present invention, the carbon black may be any of a variety of existing carbon blacks that can be used as rubber additives, including but not limited to: carbon blacks N550, N774 and N330, the content of the carbon black may be selected in a wide range; specifically, the carbon black may be contained in an amount of 0 to 70 parts by weight relative to 100 parts by weight of the base rubber.
The type and amount of the active agent is also well known to those skilled in the art, and the active agent may be zinc oxide and/or stearic acid; specifically, the content of the active agent may be 2 to 10 parts by weight with respect to 100 parts by weight of the base rubber.
In the invention, the softener is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol. Wherein the weight average molecular weight of the polyethylene glycol is 3000-5000, so that the composite material has better processing performance and physical and mechanical properties. The aromatic oil may be, for example, aromatic oil TDAE V500, and the polyethylene glycol may be, for example, polyethylene glycol PEG4000. Specifically, the softener may be contained in an amount of 5 to 15 parts by weight with respect to 100 parts by weight of the base rubber.
In the invention, the anti-aging agent is at least one of amine anti-aging agent, quinoline anti-aging agent and benzimidazole anti-aging agent. For example, the anti-aging agent is anti-aging agent 4020. Specifically, the content of the antioxidant may be 1 to 5 parts by weight with respect to 100 parts by weight of the base rubber.
In the present invention, the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. The accelerator may be N-tert-butyl-2-benzothiazole sulfonamide (TBBS), diphenylguanidine (accelerator D). Specifically, the accelerator may be contained in an amount of 0.5 to 2.5 parts by weight relative to 100 parts by weight of the base rubber.
In the present invention, the vulcanizing agent is sulfur and/or a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-filled sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-filled insoluble sulfur IS, and the like. Specifically, the vulcanizing agent may be contained in an amount of 0.5 to 2.5 parts by weight relative to 100 parts by weight of the base rubber.
The sixth aspect of the invention provides a method for preparing a tread rubber for a tire, which is characterized by comprising the following steps:
mixing all components in a rubber composition containing a rubber processing modifier and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain the tire tread rubber;
wherein the rubber processing modifier is the rubber processing modifier.
In the invention, each component in the rubber composition is mixed in the presence of the rubber processing modifier provided in the first aspect or the third aspect of the invention to obtain a rubber compound blank, and the rubber compound blank is vulcanized, so that the dispersibility and the compatibility of the mercapto acid monomer in the rubber processing modifier in the base rubber are obviously improved, and the heat generation and the rolling resistance of the tire tread rubber can be obviously reduced on the premise of ensuring that the prepared tire tread rubber has high strength, wear resistance and wet skid resistance.
In the present invention, the specific process and operation of mixing the components in the rubber composition and curing the compound can be carried out with reference to the prior art. Specifically, the tire tread rubber is prepared according to the following method:
s1, carrying out first mixing on base rubber and a rubber processing modifier to obtain first mixed rubber; wherein the conditions of the first kneading include: the mixing time is 1-5min, and the mixing temperature is 60-100 ℃;
s2, carrying out second mixing on the first mixed rubber, white carbon black, an active agent, a softening agent and an anti-aging agent to obtain a second mixed rubber, wherein the second mixing conditions comprise: the mixing time is 5-10min, and the mixing temperature is 80-160 ℃;
s3, standing the second rubber compound, and then carrying out third mixing with a vulcanizing agent and an accelerator to obtain a rubber compound blank, wherein the standing conditions comprise: standing for more than 4 hours at room temperature; the conditions for the third kneading include: the mixing time is 3-7min, and the mixing temperature is not more than 130 ℃;
s4, vulcanizing the rubber compound blank to obtain tire tread rubber, wherein the vulcanization conditions comprise: the vulcanization temperature is 140-170 ℃, the vulcanization time is 30-40min, and the vulcanization pressure is 10-20MPa.
In the present invention, the first mixing, the second mixing, and the third mixing may be performed in mixing equipment conventional in the art, such as an internal mixer.
In the present invention, the vulcanization may be carried out in a vulcanization apparatus conventional in the art, such as a press vulcanizer.
The seventh aspect of the present invention provides a tread rubber for a tire produced by the above production method.
The present invention will be described in detail by examples.
The equipment conditions for preparing vulcanized rubber in the following examples and comparative examples are shown in Table 1.
The test instruments and test conditions of the vulcanized rubbers obtained in examples and comparative examples are shown in Table 2 and Table 3.
The amounts of the components in the following examples and comparative examples were each 1g per part by weight.
TABLE 1
Sequence number Device name Model number Manufacturing factories
1 Banbury mixer BR1600 America Rayleigh Corp
2 Flat vulcanizing machine XLB-D400*400*2 First rubber machinery plant of Shanghai
TABLE 2
Sequence number Test item Model of test instrument Manufacturing factories
1 Tensile Strength Universal pulling machine, SHIMADZU, AG-20KNG Shimadzu corporation of Japan
2 DIN abrasion GT-7012-A High-speed rail detection instruments Co Ltd
3 Dynamic viscoelastometer EPLEXOR 500N German Gaobao Co Ltd
4 Rubber processing analyzer RPA2000 Alpha Co Ltd
5 Dynamic compression fatigue heat generation Compression heat generation experimental machine Y3000E Beijing friend deep electronic instruments Co., ltd
TABLE 3 Table 3
Preparation examples 1 to 5 are for explaining the rubber processing modifier of the present invention and the preparation method thereof.
Preparation example 1
Uniformly stirring 20 parts by weight of precipitation white carbon black (165 GR) and 60 parts by weight of 3-mercaptopropionic acid at room temperature (25 ℃) to obtain a pre-loaded mixture; heating the internal mixer to 40 ℃ at a speed of 70rpm, and putting 10 parts by weight of EPDM (ethylene content 60wt%, content of structural units provided by ENB 10wt%, mooney viscosity 70) and 10 parts by weight of EVA (VA content 30wt%, melt index 40g/10 min) into the internal mixer for plasticating for 1.5min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 4min; and discharging to obtain the rubber processing modifier X1.
Preparation example 2
Uniformly stirring 20 parts by weight of precipitation white carbon black (165 GR) and 60 parts by weight of 3-mercaptopropionic acid at room temperature (25 ℃) to obtain a pre-loaded mixture; heating the internal mixer to 60 ℃ at 40rpm, and putting 10 parts by weight of EPDM (ethylene content 50wt%, content 8wt% of structural units provided by ENB, mooney viscosity 55) and 10 parts by weight of EVA (VA content 10wt%, melt index 20g/10 min) into the internal mixer for plasticating for 0.5min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 6min; and discharging to obtain the rubber processing modifier X2.
Preparation example 3
Uniformly stirring 20 parts by weight of precipitation white carbon black (165 GR) and 60 parts by weight of 4-mercaptobutyric acid at room temperature (25 ℃) to obtain a pre-loaded mixture; heating the internal mixer to 50 ℃ at a speed of 50rpm, and putting 10 parts by weight of EPDM (ethylene content 55wt%, content of structural units provided by ENB 5wt%, mooney viscosity 65) and 10 parts by weight of EVA (VA content 20wt%, melt index 30g/10 min) into the internal mixer for plasticating for 3min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 2min; and discharging to obtain the rubber processing modifier X3.
Preparation example 4
Uniformly stirring 20 parts by weight of precipitation white carbon black (165 GR) and 60 parts by weight of 4-mercaptobutyric acid at room temperature (25 ℃) to obtain a pre-loaded mixture; heating the internal mixer to 40 ℃ at the speed of 70rpm, and putting 10 parts by weight of EPDM (ethylene content 59wt%, ENB content 1.5wt%, mooney viscosity 38) and 10 parts by weight of EVA (VA content 10wt%, melt index 8g/10 min) into the internal mixer for plasticating for 1.5min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 4min; and discharging to obtain the rubber processing modifier X4.
Preparation example 5
Uniformly stirring 15 parts by weight of precipitation white carbon black (165 GR) and 40 parts by weight of 3-mercaptopropionic acid at room temperature (25 ℃) to obtain a pre-loaded mixture; heating the internal mixer to 40 ℃ at the speed of 70rpm, and putting 20 parts by weight of EPDM (ethylene content 60wt%, ENB content 10wt%, mooney viscosity 70) and 10 parts by weight of EVA (VA content 30wt%, melt index 40g/10 min) into the internal mixer for plasticating for 1.5min; then adding the pre-loaded mixture into an internal mixer, and mixing with the plasticated matrix for 4min; and discharging to obtain the rubber processing modifier X5.
Examples 1-6 are provided to illustrate the tire tread rubber provided by the present invention and a method of making the same.
Example 1
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 3 parts by weight of rubber processing modifier X1, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, a company of rotunda, france), 15 parts by weight of carbon black (Ji Deli chemical engineering, N330, a company of doku city), 3 parts by weight of zinc oxide (a company of fang Hengfeng chemical, a company of doku constant), 2 parts by weight of stearic acid (a company of miku constant ), 10 parts by weight of aromatic hydrocarbon oil (a company of Santa Clara, TDAE V500), 3 parts by weight of an antioxidant (a company of Jiangsu san-o chemical, 4020) were added to an internal mixer to mix them, the mixture was allowed to stand at room temperature for 5 hours after the mixing was completed, then 2 parts by weight of sulfur (a company of Hengfu chemical, a company of Dongfu Co., ltd.) and 3 parts by weight of TBBS (N-t-butyl-2-benzothiazole sulfenamide) were added, and the obtained mixture was kneaded at 60 ℃ for 5 minutes to obtain a rubber compound, and then the obtained compound was subjected to press vulcanization at 160 ℃ under a vulcanization pressure of 10MPa and a vulcanization time of 40min, to obtain a vulcanized rubber sample S1.
The vulcanized rubber sample S1 was subjected to a performance test, and the results are shown in Table 4.
Example 2
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 1 part by weight of rubber processing modifier X2, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, a company of rotunda, france), 15 parts by weight of carbon black (Ji Deli chemical engineering, N330, a company of doku city), 3 parts by weight of zinc oxide (a company of fang Hengfeng chemical, a company of doku constant), 2 parts by weight of stearic acid (a company of miku constant, a company of doku constant), 10 parts by weight of aromatic hydrocarbon oil (a company of Xinda (Ningbo), TDAE V500), 3 parts by weight of an anti-aging agent (a company of Jiangsu san chemical, 4020) were added to an internal mixer to mix them, and after mixing was completed, the mixture was left to stand at room temperature for 5 hours, then 2 parts by weight of sulfur (a company of Hengfang chemical, a company of doku constant), 3 parts by weight of TBBS (N-t-butyl-2-benzothiazole sulfenamide) were added, and then a rubber mix was obtained at 60 ℃ for 5 minutes, and then the obtained rubber mix was subjected to press vulcanization at 160 ℃ under a vulcanization pressure of 10MPa for 40 minutes, so as to obtain a vulcanized rubber sample S2.
The vulcanized rubber sample S2 was subjected to a performance test, and the results are shown in Table 4.
Example 3
70 parts by weight of solution polymerized styrene-butadiene rubber (Yanshan petrochemical product, SSBR 2636) and 30 parts by weight of butadiene rubber (Yanshan petrochemical product, BR 9000) were added to an internal mixer together with 2 parts by weight of rubber processing modifier X3, and mixed for 3 minutes at 70 ℃; then 60 parts by weight of white carbon black (165 GR, a company of rotunda, france), 15 parts by weight of carbon black (Ji Deli chemical engineering, N330, a company of doku city), 3 parts by weight of zinc oxide (a company of fang Hengfeng chemical, a company of doku constant), 2 parts by weight of stearic acid (a company of miku constant, a company of doku constant), 10 parts by weight of aromatic oil (a company of Xinda (Ningbo), TDAE V500), 3 parts by weight of an anti-aging agent (a company of Jiangsu san chemical, 4020) were added into an internal mixer to mix them, after mixing was completed, the mixture was left to stand at room temperature for 5 hours, then 2 parts by weight of sulfur (a company of Hengfu chemical, a company of N330) and 3 parts by weight of TBBS (N-t-butyl-2-benzothiazole sulfenamide) were added, and then a rubber mix was obtained at 60 ℃ for 5 minutes, and then the obtained rubber mix was subjected to press vulcanization at 160 ℃ under a vulcanization pressure of 10MPa for 40 minutes, thereby obtaining a vulcanized rubber sample S3.
The vulcanized rubber sample S3 was subjected to a performance test, and the results are shown in Table 4.
Example 4
A rubber was prepared in the same manner as in example 1 except that the rubber processing modifier X1 was added in an amount of 5 parts by weight, to prepare a vulcanized rubber sample S4.
The vulcanized rubber sample S4 was subjected to a performance test, and the results are shown in Table 4.
Example 5
A rubber was prepared in the same manner as in example 1 except that the rubber processing modifier was added in an amount of 3 parts by weight of X4 to prepare a vulcanized rubber sample S5.
The vulcanized rubber sample S5 was subjected to a performance test, and the results are shown in Table 4.
Example 6
A rubber was prepared in the same manner as in example 1 except that the rubber processing modifier X1 was replaced with the rubber processing modifier X5, to prepare a vulcanized rubber sample S6.
The vulcanized rubber sample S6 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 1
A rubber was prepared in the same manner as in example 1 except that the rubber processing modifier X1 was added in an amount of 8 parts by weight to prepare a vulcanized rubber sample DS1.
The vulcanized rubber sample DS1 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 2
A rubber was prepared in the same manner as in example 1, except that the same added parts of pure 3-mercaptopropionic acid (1.8 parts by weight) were used in place of the rubber processing modifier X1 during the preparation, and vulcanized to give vulcanized rubber DS2.
The vulcanized rubber sample DS2 was subjected to a performance test, and the results are shown in Table 4.
Comparative example 3
A rubber was prepared in the same manner as in example 1 except that the rubber processing modifier was not added during the preparation, and vulcanized to give vulcanized rubber DS3.
The vulcanized rubber sample DS3 was subjected to a performance test, and the results are shown in Table 4.
TABLE 4 Table 4
From the above results, the rubber processing modifier provided by the invention can enable the white carbon black to have better dispersibility in the rubber matrix, and the interaction between the white carbon black and the rubber matrix is stronger, so that the strength of the vulcanized rubber can be better improved, the heat generation of the vulcanized rubber can be reduced, and the wet skid resistance can be improved.
Further, as can be seen from the data of comparative examples 1 and 2, when the same rubber composition formulation as in example 1 is employed, but the mercapto acid-based monomer is added in a different manner, the further prepared vulcanized rubber DS2 is significantly inferior in performance to the vulcanized rubber S1, such as a tear strength lower than S1, a compression temperature higher than S1, and DIN abrasion higher than S1; the dynamic mechanical properties of the vulcanizate of example 1 show less rolling resistance, better wet skid resistance, and the pecies effect data also demonstrate that the carbon black dispersion of the vulcanizate S1 of example 1 is significantly better than DS2.
The rubber processing modifier and the preparation method can enable the obtained vulcanized rubber to have better performance, so that the fuel economy of an automobile can be improved when the vulcanized rubber is applied to the tread of the automobile tire.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. A rubber processing modifier, characterized in that the rubber processing modifier comprises a mercapto acid monomer, a matrix material and white carbon black;
the mercapto acid monomer is provided by at least one of the compounds represented by formula (1):
wherein x is 0 and R 2 is-SH; or,
x is 1, M is represented by formula (2)R is of the structure of 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
2. The rubber processing modifier according to claim 1, wherein the mercapto acid monomer is contained in an amount of 40 to 60 parts by weight, the base material is contained in an amount of 20 to 30 parts by weight, and the white carbon black is contained in an amount of 15 to 25 parts by weight;
preferably, the matrix material comprises ethylene propylene diene monomer and ethylene-vinyl acetate copolymer, wherein the weight ratio of the ethylene propylene diene monomer to the ethylene-vinyl acetate copolymer is 1-2.3:1.
3. the rubber processing modifier according to claim 2, wherein the ethylene propylene diene monomer has a vinyl content of 50 to 60wt% and the third monomer provides a structural unit content of 5 to 10wt%;
preferably, the Mooney viscosity ML of the ethylene propylene diene monomer rubber is 55-70;
preferably, in the ethylene-vinyl acetate copolymer, vinyl acetate provides a content of structural units of 10 to 30wt%;
preferably, the ethylene-vinyl acetate copolymer has a melt index of 20-40g/10min at 190℃under a load of 2.16 kg.
4. A method for preparing a rubber processing modifier, the method comprising the steps of:
(1) Stirring white carbon black and a mercapto acid monomer until the white carbon black and the mercapto acid monomer are uniformly mixed to obtain a pre-loaded mixture;
(2) Plasticating the matrix material to obtain plasticated rubber;
(3) Mixing the pre-loaded mixture with the plasticated rubber to obtain the rubber processing modifier;
wherein at least one of the mercapto acid monomer compounds represented by formula (1) provides:
wherein x is 0 and R 2 is-SH; or,
x is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or,
x is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or,
x is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 And not H at the same time.
5. The preparation method according to claim 4, wherein the mercapto acid monomer is used in an amount of 40 to 60 parts by weight, the matrix material is used in an amount of 20 to 30 parts by weight, and the white carbon black is used in an amount of 15 to 25 parts by weight;
preferably, the matrix material comprises ethylene propylene diene monomer and ethylene-vinyl acetate copolymer, wherein the weight ratio of the ethylene propylene diene monomer to the ethylene-vinyl acetate copolymer is 1-2.3:1.
6. the preparation method according to claim 5, wherein the ethylene propylene diene monomer has a vinyl group content of 50 to 60wt% and the third monomer provides a structural unit content of 5 to 10wt%;
preferably, the Mooney viscosity ML of the ethylene propylene diene monomer rubber is 55-70;
preferably, the ethylene-vinyl acetate copolymer has a content of structural units derived from vinyl acetate of 10 to 30wt%;
preferably, the ethylene-vinyl acetate copolymer has a melt index of 20-40g/10min at 190℃under a load of 2.16 kg.
7. The preparation method according to any one of claims 4 to 6, wherein the plasticating conditions include: the plasticating temperature is 40-60 ℃, the rotating speed is 40-70rpm, and the plasticating time is 0.5-3min;
preferably, the plastication is carried out in an internal mixer;
preferably, the mixing conditions include: the mixing time is 2-6min, and the mixing temperature is 50-55 ℃.
8. A rubber processing modifier produced by the production process according to any one of claims 4 to 7.
9. Use of the rubber processing modifier of any one of claims 1-3 and 8 in the preparation of a tire tread stock.
10. A tire tread rubber composition comprising the rubber processing modifier of any one of claims 1-3 and 8 and a base rubber;
wherein the rubber processing modifier is used in an amount of 0.5 to 6 parts by weight, preferably 1 to 3 parts by weight, relative to 100 parts by weight of the base rubber.
11. A method of preparing a tire tread stock, the method comprising:
mixing a rubber composition containing a rubber processing modifier and base rubber to obtain a rubber compound blank, and vulcanizing the rubber compound blank to obtain the tire tread rubber;
wherein the rubber processing modifier is the rubber processing modifier according to any one of claims 1 to 3 and 8.
12. A tire tread band made by the method of making of claim 11.
CN202210892385.1A 2022-07-27 2022-07-27 Rubber processing modifier, preparation method and application thereof, tire tread rubber composition, tire tread rubber and preparation method thereof Pending CN117511072A (en)

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