CN113024914A - Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof - Google Patents
Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof Download PDFInfo
- Publication number
- CN113024914A CN113024914A CN202110141154.2A CN202110141154A CN113024914A CN 113024914 A CN113024914 A CN 113024914A CN 202110141154 A CN202110141154 A CN 202110141154A CN 113024914 A CN113024914 A CN 113024914A
- Authority
- CN
- China
- Prior art keywords
- rubber
- carbon black
- parts
- filler
- degree
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005060 rubber Substances 0.000 title claims abstract description 94
- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000006229 carbon black Substances 0.000 title claims abstract description 57
- 230000002787 reinforcement Effects 0.000 title claims abstract description 33
- 238000002156 mixing Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 17
- 238000004073 vulcanization Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008117 stearic acid Substances 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims description 46
- 230000003014 reinforcing effect Effects 0.000 claims description 24
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000004636 vulcanized rubber Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 238000010408 sweeping Methods 0.000 claims description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical group C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 claims 1
- 238000011156 evaluation Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 description 38
- 239000000463 material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- -1 accelerator Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/445—Rubber
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of tire production, in particular to a standard rubber composition system for detecting carbon black reinforcement degree, a mixing method and application thereof. A standard rubber composition system for detecting carbon black reinforcement degree is composed of the following components in parts by weight: 100 parts of rubber, 1.0-5.0 parts of zinc oxide, 0.5-2.0 parts of stearic acid, 0.5-2.0 parts of vulcanization accelerator, 1.0-2.5 parts of sulfur and 0-100 parts of carbon black; the addition amount of the carbon black is increased from 0 part, and the increasing gradient is 10.0-30.0 parts. The rubber composition system is used as a standard formula for testing the reinforcement degree of the carbon black in the rubber, and has scientific and effective reinforcement performance evaluation function due to the extremely simple formula composition and the specific component proportion.
Description
Technical Field
The invention relates to the technical field of tire production, in particular to a standard rubber composition system for detecting carbon black reinforcement degree, a mixing method and application thereof.
Background
"a material or substance having one or more sufficiently uniform and well-defined properties for calibrating measuring devices, evaluating measuring methods or assigning values to materials" according to the definition given to "standard substances (reference substances)" by the ISO and international metrology vocabulary, "standard formulations are standard substances in the rubber industry which serve mainly for rubber property tests, being a necessary condition for ensuring the consistency and comparability of the measurement results.
The rubber material is a multiphase system formed by raw rubber and a plurality of compounding agents, and complex physical and chemical actions exist among all components in the rubber material. A rubber formula at least comprises rubber polymer, vulcanizing agent, accelerator, activator, anti-aging agent, reinforcing filler, softener and other basic components. A reasonable formula comprises five major parts of a polymer system, a vulcanization system, a filling system, a protection system and a softening and plasticizing system.
In the rubber industry, in order to evaluate the actual performance of a material applied in a formulation, it is necessary to mix the material in a specific formulation or a group of formulations for evaluation, and obviously, the more irrelevant components in the formulation, the more factors influencing the data result, and the poorer the accuracy of the data result. On the other hand, due to differences among raw material manufacturers, the performance of materials with the same grade also has certain differences, and all the factors can influence the evaluation result.
Therefore, in some national standards, the components and contents of the formula are clearly defined, and materials with large use amount and large influence weight of test results in the formula are clearly defined, for example, in the national standard "evaluation method of emulsion and solution polymerization type styrene-butadiene rubber (SBR)", the components and the proportion used in the standard test formula used in the test are clearly defined, and the carbon black with the largest use amount in the formula needs to use industrial reference carbon black.
Carbon black (carbon black), also known as carbon black, is an amorphous carbon. Is light, loose and superfine black powder, has very large surface area and ranges from 10 to 3000m2The carbon-containing substance is a product obtained by incomplete combustion or thermal decomposition of a carbon-containing substance (coal, natural gas, heavy oil, fuel oil, etc.) under the condition of insufficient air. Gas black, which is made of natural gas, lamp black, which is made of oils, and acetylene black, which is made of acetylene. In addition, "channel black" and "furnace black" are also included. According to the properties of carbon black, the carbon black is divided into reinforcing carbon black, conductive carbon black, wear-resistant carbon black and the like. Can be used as black dye for manufacturing Chinese ink, printing ink, paint and the like, and also can be used as reinforcing agent of rubber. At present, no published report of a carbon black reinforcement degree detection method exists in the technical field of tires.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a standard rubber composition system for detecting the reinforcing degree of carbon black, which is used as a standard formula for testing the reinforcing degree of the carbon black in rubber, and has a scientific and effective reinforcing performance evaluation effect due to the extremely simple formula and specific component proportion.
In order to achieve the purpose, the invention adopts the following technical scheme:
a standard rubber composition system for detecting carbon black reinforcement degree is composed of the following components in parts by weight: 100 parts of rubber, 1.0-5.0 parts of zinc oxide, 0.5-2.0 parts of stearic acid, 0.5-2.0 parts of vulcanization accelerator, 1.0-2.5 parts of sulfur and 0-100 parts of carbon black; the addition amount of the carbon black is increased from 0 part, and the increasing gradient is 10.0-30.0 parts.
Preferably, the amount of carbon black added is 0 parts, 30 parts, 50 parts or 70 parts.
Preferably, the vulcanization accelerator is TBBS.
Preferably, the rubber is one or a mixture of more of natural rubber, polyisoprene rubber, polybutadiene rubber and styrene-butadiene copolymer rubber.
More preferably, the rubber is solution-polymerized styrene-butadiene rubber eSBR1500 or sSBR 1453.
Preferably, the carbon black is one or a mixture of N234, N375, N550 and N660.
Further, the present invention provides a method for mixing the above rubber composition system, wherein the mixing is carried out in two stages, one stage is a mixing stage and is carried out in a 1.8L intermeshing type internal mixer, the other stage is a final mixing stage and is carried out on a two-roll open mill, and the mixing process of each stage is as follows:
first-stage mixing: the rotor speed is 50 revolutions per minute, the temperature of the temperature control water of the rotor is set to be 60 ℃, and the filling coefficient is as follows: 0.7; when the temperature of the internal mixer chamber reaches 60 ℃, mixing is started. Adding all rubber at 0 second, adding carbon black at 30 seconds, adding operation oil when the temperature of the internal mixer rises to 95 ℃, rising the temperature of the internal mixer to 130 ℃, lifting the top bolt once, sweeping off, rising the temperature of the internal mixer to 150 ℃, and discharging rubber;
and (3) secondary finishing: mixing the master batch uniformly on a roller, adding sulfur and an accelerant, cutting the master batch for 3 times respectively from left to right, manually and alternately rolling and wrapping the master batch for 5 times respectively, then discharging the master batch, standing the master batch at room temperature for 24 hours, and measuring a vulcanization curve by using a rotor-free rheometer at the temperature of 160 ℃; the compound was vulcanized on a 25 ton press at 160 ℃ C. (T)90+2min)。
Further, the present invention also provides the use of the above rubber composition system in the detection of the degree of carbon black reinforcement in rubber.
A method for detecting the reinforcing degree of carbon black in rubber adopts the standard rubber composition system and comprises the following steps:
1) adding different parts of fillers into the same mixed rubber formula system;
2) the swelling index SI of the mixed rubber is measured by using the method for measuring the swelling index of the vulcanized rubber of national standard GB 7763 and 1987;
3) calculating SIfillerTo characterize the crosslink density produced by the filler:
wherein, SIrubberSwelling index, SI, of compounded rubber without fillerpolymerThe swelling index of the mixed rubber filled with different parts of fillers;
the reinforcing factor k of the filler in the rubber is calculated to characterize the degree of reinforcement:
wherein, VfillerIs the volume of the filler, VrubberIs the volume of the rubber, b is the intercept of the fitted curve;
the greater the value of the reinforcing factor k, the poorer the reinforcing degree of this filler in this rubber, and the smaller the value of the reinforcing factor k, the better the reinforcing degree of this filler in this rubber.
The invention has the beneficial effects that: the standard formula of the group is optimized, so that the formula has the capability of testing the reinforcing degree of the carbon black in the rubber, and meanwhile, the formula is extremely simple, the influence of irrelevant factors on the test result is greatly reduced, and the test result is more accurate.
Drawings
Fig. 1 is a schematic diagram of the principle of a method for detecting the reinforcing degree of a filler in rubber (the reinforcing coefficient k is 0.6650).
FIG. 2 shows the reinforcement factor of different carbon blacks in eSBR1500 and sSBR 1453.
Detailed Description
The technical solutions in the embodiments of the present invention will be examined and completely described below with reference to the embodiments of the present invention, so as to further explain the invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. Given the embodiments of the present invention, all other embodiments that can be obtained by a person of ordinary skill in the art without any inventive step are within the scope of the present invention.
The invention is realized by the following technical scheme, and is characterized in that:
1. polymer system:
a single target rubber is used as the polymer system.
2. A vulcanization system:
carbon black evaluation system: in order to improve the vulcanization efficiency, a semi-effective vulcanization system, namely a sulfur + accelerator system, is adopted. In order to simplify the formula and reduce experimental errors, common sulfur is used as the sulfur. TBBS (N-tertiary butyl 2-benzothiazole sulfonamide, also known as NS) is selected as an accelerator, and zinc oxide and stearic acid are used as an activation system in a vulcanization system.
3. Filling system: a single evaluation filler was used as the filling system. Meanwhile, in order to test the reinforcing degree of the rubber with different filler filling amounts, the formula needs to be filled with different parts of fillers, namely 0PHR, 30PHR, 50PHR and 70 PHR.
4. A protection system: the protective system in the formula mainly has the effect of preventing performance attenuation caused by thermal oxidation aging in the use process of the rubber product, the experimental period of the reinforcement degree test of the filler in the rubber is short, and the target rubber used in the rubber system has some anti-aging agents, so that the thermal oxidation aging hardly exists in the experimental period, and the protective system is not used in the formula in order to simplify the formula and reduce the experimental error.
5. Softening and plasticizing system: the softening system in the formula is mainly used for improving the processing performance of the formula, and in order to simplify the formula and reduce experimental errors, the softening plasticizing system is not used in the formula.
The reinforcement degree of different carbon blacks in eSBR1500 and sSBR1453 is evaluated in comparison, and the specific formula is shown in Table 1.
TABLE 1 evaluation of different carbon blacks
Table 1 footnotes:
*1: emulsion styrene-butadiene rubber eSBR (styrene-butadiene rubber) 1500, a product of Middling petrochemical Co.
*2: solution polymerized styrene butadiene rubber sSBR1453, a product of Taiwan rubber company Limited, is directed to a carbon black modified product.
*3: carbon black, product of cabot corporation.
*4: environmental protection oil V700, Ningbo Han san chemical Co., Ltd.
*5: zinc oxide, Shizhuangzhiyi Zinc products.
*6: stearic acid, a product of Hangzhou grease chemical Co.
*7: accelerator NS, a product of Shandong Shunhua chemical Co., Ltd.
*8: sulfur, Weifang Jia Macro chemical Co., Ltd.
Preparation of a sample: the mixing of the rubber compound was carried out in two stages, one of which was carried out in a 1.8L intermeshing type internal mixer. The two sections are final mixing sections, and are mixed on a double-roll open mill, and the mixing process of each section is as follows:
first-stage mixing: the rotor speed was 50 revolutions per minute. The temperature-controlled water temperature of the rotor was set to 60 ℃. Filling factor: 0.7 (filling factor refers to the volume of material added to the mixer, in proportion to the volume of the mixing cavity available in the whole mixer). When the temperature of the internal mixer chamber reaches 60 ℃, mixing is started. All rubber was added at 0 second and carbon black was added at 30 seconds. The process oil was added when the internal mixer temperature rose to 95 ℃. The temperature of the internal mixer rises to 130 ℃, and the upper top bolt rises and falls once to sweep. The temperature of the internal mixer rises to 150 ℃, and the rubber is discharged.
Final mixing: mixing the master batch uniformly on a roller, adding sulfur and an accelerant, cutting for 3 times respectively from left to right, and manually and alternately rolling and triangularlyAnd packaging for 5 times, taking out the slices, standing at room temperature for 24 hours, and measuring a vulcanization curve by using a rotor-free rheometer at the temperature of 160 ℃. The compound was vulcanized on a 25 ton press at 160 ℃ C. (T)90+2min)。
Swelling index SI of unfilled filler measured by national standard GB 7763-1987 method for measuring swelling index of vulcanized rubberrubberThe swell index is characterized by the crosslink density of the rubber in the absence of filler in the formulated system.
The swelling index SI of the fillers with different filling fractions is obtained by using the same test methodpolymerThe swelling index is characterized by the crosslink density of the rubber and filler in the presence of the filler in the formulated system.
The data results were calculated according to equation 2.
SIfillerThe cross-link density of the filler is characterized after the cross-link density generated by the rubber is removed under the formula system.
The volume V of the filler in the formulafillerVolume V with rubberrubberThe ratio is taken as the abscissa, 1/SIfillerAs ordinate, make Vfiller/Vrubber—1/SIfillerThe slope k of the curve, which characterizes the degree of reinforcement of the filler in the rubber, is defined as the reinforcement factor, the greater the value of the reinforcement factor k, the less the degree of reinforcement of the filler in the rubber, the smaller the value of the reinforcement factor k, the better the degree of reinforcement of the filler in the rubber.
The concrete principle is shown in figure 1, and the quality of the reinforcing performance of the filler can be accurately compared by measuring the reinforcing degree of the filler in the rubber by the method.
The swelling index SI of different schemes measured by national standard GB 7763-fillerVolume V with rubberrubberThe ratio is taken as the abscissa, 1/SIfillerAs ordinate, make Vfiller/Vrubber—1/SIfillerThe slope k of the curve, i.e., the value of the carbon black reinforcing coefficient k, was obtained, and the specific results are shown in FIG. 2.
Comparing the values of the reinforcing coefficients k of different carbon blacks shows that the reinforcing coefficient k of the carbon black becomes larger and the degree of reinforcement becomes lower as the particle size of the carbon black becomes larger and the degree of structure becomes lower. This is because the carbon black has a large particle diameter and a low structure degree, and the specific surface area of the carbon black is small, and the effective action area with the rubber is small, thereby reducing the degree of reinforcement.
As can be seen by comparing the values of the coefficient of reinforcement k in eSBR1500 and sSBR1453 for the same carbon black, the value of the coefficient of reinforcement k in eSBR1500 is greater than the value of the coefficient of reinforcement k in sSBR1453, i.e. the carbon black is less reinforced in eSBR1500 than sSBR 1453. This is because sbbr 1453 is a modified solution-polymerized styrene-butadiene rubber, which has a better affinity for carbon black than eSBR 1500.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in 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 (9)
1. A standard rubber composition system for detecting carbon black reinforcement degree is composed of the following components in parts by weight: 100 parts of rubber, 1.0-5.0 parts of zinc oxide, 0.5-2.0 parts of stearic acid, 0.5-2.0 parts of vulcanization accelerator, 1.0-2.5 parts of sulfur and 0-100 parts of carbon black; the addition amount of the carbon black is increased from 0 part, and the increasing gradient is 10.0-30.0 parts.
2. The standard rubber composition system for testing the reinforcing degree of the carbon black according to claim 1, wherein the addition amount of the carbon black is 0 part, 30 parts, 50 parts or 70 parts.
3. The standard rubber composition system for testing the reinforcement degree of carbon black of claim 1, wherein the vulcanization accelerator is TBBS.
4. The standard rubber composition system for testing carbon black reinforcement degree according to claim 1, wherein the rubber is one or more of natural rubber, polyisoprene rubber, polybutadiene rubber and styrene-butadiene copolymer rubber.
5. The standard rubber composition system for testing carbon black reinforcement degree according to claim 1, wherein the rubber is solution polymerized styrene butadiene rubber (eSBR) eSBR1500 or sSBR 1453.
6. The standard rubber composition system for testing carbon black reinforcement degree according to claim 1, wherein the carbon black is one or more of N234, N375, N550 and N660.
7. A method of mixing a standard rubber composition system according to any one of claims 1 to 6, wherein the mixing is carried out in two stages, one of which is a mixing stage in a 1.8L intermeshing type internal mixer and the other of which is a final mixing stage, on a two roll mill, the mixing process in each stage being as follows:
first-stage mixing: the rotor speed is 50 revolutions per minute, the temperature of the temperature control water of the rotor is set to be 60 ℃, and the filling coefficient is as follows: 0.7; when the temperature of the internal mixer chamber reaches 60 ℃, mixing is started. Adding all rubber at 0 second, adding carbon black at 30 seconds, adding operation oil when the temperature of the internal mixer rises to 95 ℃, rising the temperature of the internal mixer to 130 ℃, lifting the top bolt once, sweeping off, rising the temperature of the internal mixer to 150 ℃, and discharging rubber;
and (3) secondary finishing: mixing the master batch uniformly on a roller, adding sulfur and an accelerant, cutting the master batch for 3 times respectively from left to right, manually and alternately rolling and wrapping the master batch for 5 times respectively, then discharging the master batch, standing the master batch at room temperature for 24 hours, and measuring a vulcanization curve by using a rotor-free rheometer at the temperature of 160 ℃; the compound was vulcanized on a 25 ton press at 160 ℃ C. (T)90+2min)。
8. Use of the rubber composition system of any one of claims 1 to 6 for the detection of the degree of reinforcement of carbon black in rubber.
9. A method for testing the reinforcement of carbon black in rubber, which comprises the steps of:
1) adding different parts of fillers into the same mixed rubber formula system;
2) the swelling index SI of the mixed rubber is measured by using the method for measuring the swelling index of the vulcanized rubber of national standard GB 7763 and 1987;
3) calculating SIfillerTo characterize the crosslink density produced by the filler:
wherein, SIrubberSwelling index, SI, of compounded rubber without fillerpolymerThe swelling index of the mixed rubber filled with different parts of fillers;
4) the reinforcing factor k of the filler in the rubber is calculated to characterize the degree of reinforcement:
wherein, VfillerIs the volume of the filler, VrubberIs the volume of rubber, b isThe intercept of the resultant curve; the greater the value of the reinforcing factor k, the poorer the reinforcing degree of this filler in this rubber, and the smaller the value of the reinforcing factor k, the better the reinforcing degree of this filler in this rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110141154.2A CN113024914A (en) | 2021-02-02 | 2021-02-02 | Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110141154.2A CN113024914A (en) | 2021-02-02 | 2021-02-02 | Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113024914A true CN113024914A (en) | 2021-06-25 |
Family
ID=76459774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110141154.2A Pending CN113024914A (en) | 2021-02-02 | 2021-02-02 | Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113024914A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179479A (en) * | 2003-12-18 | 2005-07-07 | Mitsui Chemicals Inc | Method for determining degree of dispersion of carbon black in rubber composition and method for producing the rubber composition |
| CN105175829A (en) * | 2014-06-23 | 2015-12-23 | 北京橡胶工业研究设计院 | Rubber composition with low rolling resistance and good wet slippery and wear resistance |
| CN105424735A (en) * | 2014-09-11 | 2016-03-23 | 住友橡胶工业株式会社 | Method of measuring crosslink densities in sulfur-containing polymer composite material |
| JP2018132363A (en) * | 2017-02-14 | 2018-08-23 | 住友ゴム工業株式会社 | Method for measuring gel content, rubber composition and pneumatic tire |
-
2021
- 2021-02-02 CN CN202110141154.2A patent/CN113024914A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179479A (en) * | 2003-12-18 | 2005-07-07 | Mitsui Chemicals Inc | Method for determining degree of dispersion of carbon black in rubber composition and method for producing the rubber composition |
| CN105175829A (en) * | 2014-06-23 | 2015-12-23 | 北京橡胶工业研究设计院 | Rubber composition with low rolling resistance and good wet slippery and wear resistance |
| CN105424735A (en) * | 2014-09-11 | 2016-03-23 | 住友橡胶工业株式会社 | Method of measuring crosslink densities in sulfur-containing polymer composite material |
| JP2018132363A (en) * | 2017-02-14 | 2018-08-23 | 住友ゴム工業株式会社 | Method for measuring gel content, rubber composition and pneumatic tire |
Non-Patent Citations (1)
| Title |
|---|
| MERCKEL ET AL: "Effects of the Amount of Fillers and of the Crosslink Density on the Mechanical Behavior of Carbon-Black Filled Styrene Butadiene Rubbers", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112789315B (en) | Rubber composition | |
| Sirisinha et al. | Properties of tire tread compounds based on functionalized styrene butadiene rubber and functionalized natural rubber | |
| CA1120179A (en) | Rubber compositions and method therefor | |
| Sae-Oui et al. | Effects of blend ratio and SBR type on properties of carbon black‐filled and silica‐filled SBR/BR tire tread compounds | |
| EP2772513B1 (en) | Modified rubber masterbatch, rubber composition prepared therewith and vulcanized rubber and preparation method thereof | |
| US20200392314A1 (en) | Civil engineering vehicle tire | |
| KR930002555B1 (en) | Carbon black for blending of tire tread rubber | |
| Pal et al. | Impact of α‐cellulose as a green filler on physico‐mechanical properties of a solution grade styrene‐butadiene rubber based tire‐tread compound | |
| CN109575372B (en) | Ultra-low rolling resistance all-steel radial tire tread rubber composition | |
| CN106536621B (en) | Rubber composition comprising an elastomer containing methacrylate units | |
| US20080095696A1 (en) | Carbon black for functional rubber component | |
| US5484836A (en) | Rubber composition for tire tread | |
| CN113024914A (en) | Standard rubber composition system for detecting carbon black reinforcement degree and mixing method and application thereof | |
| AU738877B2 (en) | Pneumatic tire for heavy duty use | |
| Wang et al. | Liquid 3, 4-polyisoprene: a novel processing aid to achieve tire tread SBR composites with high wet grip and low energy consumption | |
| Thaptong et al. | Optimization of highly dispersible silica/carbon black hybrid filler ratio for tire tread based on solution‐and emulsion‐styrene butadiene rubber | |
| CN112847870B (en) | White carbon black-containing rubber composition and mixing method thereof | |
| CN113024913B (en) | Rubber composition system for detecting white carbon black reinforcing degree and mixing method and application thereof | |
| CN108017814B (en) | Rubber composition, vulcanized rubber, and preparation method and application thereof | |
| CN115594902A (en) | Tread rubber composition and preparation method and application thereof | |
| US5985978A (en) | Rubber composition for tire tread | |
| CN112881662A (en) | Method for detecting reinforcing degree of filler in rubber and application of filler | |
| Railsback et al. | Cis-polybutadiene-natural rubber blends | |
| JP2017223586A (en) | Method for evaluating deterioration of vulcanized rubber composition | |
| US20220010101A1 (en) | Rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 310008 No. 1, No. 1 Street, Qiantang District, Hangzhou, Zhejiang Applicant after: Zhongce Rubber Group Co.,Ltd. Address before: 310008 No.1 Baiyang street, Qiantang New District, Hangzhou City, Zhejiang Province Applicant before: ZHONGCE RUBBER GROUP Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210625 |
|
| RJ01 | Rejection of invention patent application after publication |