CN114714533B - Characterization method and mixing method of mixing process difference of low-rolling-resistance rubber composition - Google Patents
Characterization method and mixing method of mixing process difference of low-rolling-resistance rubber composition Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 122
- 239000005060 rubber Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 230000008569 process Effects 0.000 title claims abstract description 73
- 238000012512 characterization method Methods 0.000 title claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000004513 sizing Methods 0.000 claims abstract description 6
- 239000006229 carbon black Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003814 drug Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010008 shearing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005206 flow analysis Methods 0.000 description 4
- -1 alkyl modified silane Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the application field of the production and manufacturing industries of tires, automobiles and the like, and relates to a characterization method of mixing process difference of a low-rolling-resistance tread rubber composition. The process method comprises the following three steps of two-stage mixing and final mixing: the process condition of the rubber composition after vulcanization is predicted by a sizing material flow analyzer in advance after the rubber composition is mixed, and when the flow value of the rubber composition after two-stage mixing is more than 150 Point, the probability of curling and breaking the rubber composition after vulcanization is extremely low; when the flow value of the rubber composition after two-stage mixing is more than 170 Point, the surface of the rubber composition after vulcanization is smooth and the rubber composition is curled without breaking. The invention can be used for judging the difference of the mixing process of the rubber composition, thereby more effectively further improving and adjusting the mixing process parameters and the formula composition of the rubber composition.
Description
Technical Field
The invention belongs to the application field of the production and manufacturing industries of tires, automobiles and the like, and relates to a characterization method and a mixing method of mixing process differences of a low-rolling-resistance tread rubber composition.
Background
With the implementation of the EU ECE117 regulations, it is imperative to improve the rolling resistance and wet grip performance of tires. The means for reducing rolling resistance and improving wet grip which are commonly used at present mainly comprise: the functionalized solution polymerized styrene-butadiene rubber is used for filling more white carbon black with high specific surface area and mercapto alkoxy or mercapto long-chain alkyl modified silane with higher activity. As in my issued patent (publication number: CN109251379A, publication day: 20190122), a low-filling high-performance tire tread compound and a rubber composition in a tire, comprising the following raw materials in parts by weight: 25.0 to 50.0 parts of natural rubber, 5.0 to 30.0 parts of solution polymerized styrene-butadiene rubber A, 40.0 to 80 parts of solution polymerized styrene-butadiene rubber B, 40.0 to 50.0 parts of high-specific surface white carbon black, 0.5 to 10.0 parts of carbon black, 4.0 to 8.0 parts of mercapto silane coupling agent, 1.0 to 6.0 parts of white carbon black dispersing agent and 2.0 to 10.0 parts of ground-grabbing resin. The tire tread rubber material is prepared from a large amount of natural rubber, is less in filling filler, can provide higher tensile strength and tensile elongation at break, can meet the requirements of low rolling resistance and high wet grip of the tire, and can reach the B level specified by European Union tire label regulation in rolling resistance and wet grip.
However, the functionalized solution polymerized styrene-butadiene rubber adopted in the patent has poor manufacturability due to the modification of a molecular chain segment, and is difficult to form a bulk shape during mixing; the surface of the white carbon black has a large number of hydroxyl groups, flocculation is easy to form during mixing, and the difficulty of dispersing the white carbon black is increased due to the fact that the white carbon black has a high specific surface area (BET is more than 200m 2/g); because of the high activity of the mercapto alkoxy or mercapto long-chain alkyl modified silane, the "pseudo-scorch" condition is easily formed, so that the rubber is easy to break during mixing, and great trouble is brought to production and manufacture.
Disclosure of Invention
In order to improve the manufacturability of the low-rolling-resistance tread rubber composition and improve the production efficiency, the invention provides a mixing process of the low-rolling-resistance tread rubber composition and a difference characterization method thereof, and the mixing process condition of the rubber composition can be predicted in advance by using a sizing material flow analyzer, so that the process problems of breakage, non-agglomeration, curling fracture, surface roughness and the like in mixing are reduced, and the method can be used for judging the difference of the mixing process of the rubber composition, thereby more effectively further improving and adjusting the mixing process parameters, the formula composition of the rubber composition and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
A characterization method of mixing process difference of a low rolling resistance rubber composition comprises two-stage mixing and final mixing processes; the process condition of the rubber composition after vulcanization is predicted by a sizing material flow analyzer in advance after the rubber composition is mixed, and when the flow value of the rubber composition after two-stage mixing is more than 150 Point, the probability of curling and breaking the rubber composition after vulcanization is extremely low; when the flow value of the rubber composition after two-stage mixing is more than 170Point, the surface of the rubber composition after vulcanization is smooth and the rubber composition is curled without breaking.
Further, the application also provides a mixing process of the low-rolling-resistance rubber composition, and the mixing process method comprises two-stage mixing and final mixing three-stage processes; the rubber composition predicts the technological condition after vulcanization by a rubber material flow analyzer in advance after mixing, and adjusts mixing technological parameters or raw materials affecting rubber material fluidity in a rubber composition formula in advance according to rubber material fluidity test data.
When the flow value of the rubber composition after two-stage mixing is more than 150 Point, the probability of curling and breaking the rubber composition after vulcanization is very small; when the flow value of the rubber composition after two-stage mixing is more than 170 Point, the surface of the rubber composition after vulcanization is smooth and the rubber composition is curled without breaking.
Preferably, the first-stage mixing is carried out in a GK320-E550 series internal mixer of German HF, the second-stage air-drop stage is carried out in a F370 internal mixer of Dalian rubber and plastic machinery, and the third-stage mixing is carried out in a F370 internal mixer of Dalian rubber and plastic machinery.
Preferably, in the process method, the mixing filling rate of a section of internal mixer in series is 60-70%.
Preferably, in the process method, the key mixing process of the one-stage series internal mixer is that the constant temperature is 130-135 ℃, the constant temperature time is 80-100 seconds, and the relatively low-temperature mixing process is adopted.
Preferably, the rubber composition comprises a functionalized solution polymerized styrene-butadiene rubber; one or two of natural rubber and butadiene rubber are mixed.
Preferably, the rubber composition comprises 25.0-50.0 parts of natural rubber, 5.0-30.0 parts of non-oil-extended solution polymerized styrene-butadiene rubber A, 40.0-80.0 parts of oil-extended 20% solution polymerized styrene-butadiene rubber B, 40.0-60.0 parts of high-ratio surface white carbon black, 0.5-10.0 parts of carbon black, 1.0-6.0 parts of white carbon black dispersing agent, 2.0-10.0 parts of ground-gripping resin, 1.0-5.0 parts of mercaptosilane coupling agent and 0.1-3 parts of dialkyl zinc dithiophosphate, wherein the mass of styrene in the non-oil-extended solution polymerized styrene-butadiene rubber A accounts for 20-30% of the total weight of the polymer, and the mass of vinyl accounts for 50-60% of the total weight of butadiene; the mass of styrene in the oil-extended 20% solution polymerized styrene-butadiene rubber B accounts for 40-50% of the total weight of the polymer, and the mass of vinyl accounts for 20-40% of the total weight of butadiene; the nitrogen adsorption specific surface area (BET) of the high-ratio surface white carbon black is more than 200m 2/g; wherein the zinc dialkyldithiophosphate has the formula:
。
Preferably, the rubber composition comprises 30-40 parts of non-oil extended emulsion polymerized styrene-butadiene rubber; 60-80 parts of emulsion polymerized styrene-butadiene rubber with the oil filled of 37.5 percent; 5-20 parts of butadiene rubber and 70-90 parts of carbon black.
Preferably, the specific operation steps of one-stage mixing in the process method are as follows: GK320 upper computer mixing process: adding rubber and medicines, adding white carbon black, a mercapto silane coupling agent and the like, lowering an upper ram, mixing for 15 seconds, lifting a lump, lowering the upper ram, mixing and heating to 105 ℃, raising the upper ram, mixing and heating to 145 ℃, and mixing for 60 seconds at constant temperature for rubber discharge; e550 lower machine mixing process: feeding, mixing and heating to 145 ℃, mixing at constant temperature for 250 seconds, and discharging rubber; the specific operation steps of the two-stage mixing are as follows: adding a section of master batch for mixing; lowering the upper top bolt for 15 seconds, lifting the upper top bolt for 8 seconds, raising the temperature of the upper top bolt to 110 ℃, lifting the upper top bolt for 5 seconds, raising the temperature of the upper top bolt to 140 ℃, and discharging glue; the specific operation steps of the three-section final refining are as follows: adding the mixed two-stage masterbatch, sulfur and an accelerator; lowering the top plug for 20 seconds; lifting the bolt for 8 seconds; lowering the top plug for 15 seconds; lifting the top plug for 5 seconds; lowering the upper top bolt to raise the temperature to 102 ℃ and discharging glue.
The invention has the beneficial effects that: by the method and the mixing process, the process problems of curling fracture, rough surface and the like existing in the mixing process of the low-rolling-resistance rubber composition are basically avoided, and the production efficiency is improved. In addition, the invention judges the difference of the mixing process of the rubber composition by using a sizing material flow analyzer, and plays a more visual and more effective characterization mode for the adjustment of the mixing process.
Detailed Description
Specific examples are given in table 1 below:
Table 1 formulation tables for comparative examples 1-4 and examples 1-4
Note that: the other components are specifically composed of white carbon black dispersant, ground-grabbing resin, anti-aging agent 6PPD, microcrystalline wax, stearic acid, zinc oxide, accelerator DPG, sulfur, accelerator CZ and accelerator TBzTD.
The process of comparative example 1 is specifically as follows: adopting a two-stage mixing and final mixing three-stage process;
Comparative example 1 mixing a section: mixing by adopting a German Krupp GK320-E550 type series internal mixer, wherein the mixing process of the GK320 upper computer comprises the following specific process steps: adding rubber and medicines, adding white carbon black, a silane coupling agent and the like, lowering an upper top bolt, mixing for 15 seconds, lifting a lump, lowering the upper top bolt, mixing and heating to 105 ℃, raising the upper top bolt, mixing and heating to 145 ℃, and mixing for 60 seconds at constant temperature, and discharging rubber; e550 lower computer mixing process comprises the following specific process steps: feeding, mixing and heating to 145 ℃, mixing at constant temperature for 250 seconds, and discharging rubber; the medicine consists of a white carbon black dispersing agent, ground-grabbing resin, an anti-aging agent 6PPD, microcrystalline wax, stearic acid, zinc oxide, an accelerator DPG, sulfur, an accelerator CZ and an accelerator TBzTD.
Comparative example 1 two stage mixing process: mixing by using a shearing type internal mixer of F370 of Dalian rubber plastic machinery Co., ltd.: adding a section of master batch for mixing; lowering the upper top bolt for 15 seconds, lifting the upper top bolt for 8 seconds, raising the temperature of the upper top bolt to 110 ℃, lifting the upper top bolt for 5 seconds, raising the temperature of the upper top bolt to 140 ℃, and discharging glue;
Comparative example 1 final stage process: mixing by using a shearing type internal mixer of F370 of Dalian rubber plastic machinery Co., ltd.: adding the mixed two-stage masterbatch, sulfur and an accelerator; lowering the top plug for 20 seconds; lifting the bolt for 8 seconds; lowering the top plug for 15 seconds; lifting the top plug for 5 seconds; lowering the upper top bolt to raise the temperature to 102 ℃ and discharging glue.
The processes of comparative examples 2-4 and examples 1-4 are specifically as follows: two-stage mixing and final mixing three-stage process is adopted.
Comparative examples 2-4 and examples 1-4 were compounded in a series of internal mixers in which the key steps are shown in the following table, the remaining steps being identical to the compounding step of comparative example 1.
Table 2 comparison of critical compounding processes for comparative examples 1-4 and examples 1-4
| Key mixing process | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Examples 1 to 4 |
| One-stage mixing volume (kg) | 243 | 215 | 243 | 215 | 215 |
| Filling ratio (%) | 71.8 | 63.4 | 71.8 | 63.4 | 63.4 |
| Constant temperature (DEG C) of upper and lower computers | 145 | 145 | 135 | 135 | 135 |
| Total constant temperature time(s) of upper and lower computers | 310 | 310 | 120 | 120 | 120 |
Comparative examples 2-4 and examples 1-4 were kneaded in a two-stage process: mixing by using a large-continuous rubber plastic mechanical Co.Ltd F370 shearing type internal mixer, wherein the key step of the mixing process is that the upper top bolt is heated to 130 ℃, rubber is discharged, and the rest mixing steps are consistent with those of comparative example 1.
Comparative examples 2-4 and examples 1-4 final vulcanization process: the rubber and plastic materials were kneaded by using a shearing type internal mixer F370 (manufactured by Dalian rubber and plastic machines Co., ltd.) in the same manner as in comparative example 1.
All comparative examples and examples were conducted in comparison with each other in terms of rheological properties, physical mechanical properties, dynamic properties, processability, in particular, the two-stage compounded rubber composition was examined and analyzed by a compound flow analyzer, and all data were calculated in comparison with comparative example 1 as 100.
TABLE 3 rheological vs. physical Properties comparison of comparative examples 1-4 and examples 1-4
| Rheology and processability of the compositions | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Example 1 | Example 2 | Example 3 | Example 4 |
| MH | 100 | 98 | 110 | 96.7 | 103 | 101 | 115 | 113 |
| T10 | 100 | 96 | 110 | 121 | 111 | 105 | 109 | 108 |
| Scorch time T5 @127 DEG C | 100 | 105 | 98 | 115 | 116 | 110 | 105 | 113 |
| Elongation at break | 100 | 104 | 98 | 102 | 107 | 100 | 106 | 112 |
| Tear strength | 100 | 104 | 106 | 94 | 109 | 101 | 121 | 113 |
| Hardness of | 100 | 98 | 102 | 100 | 100 | 101 | 101 | 103 |
| Tan at 0℃ | 100 | 99 | 102 | 95 | 102 | 98 | 100 | 114 |
| Tan at 60℃ | 100 | 95 | 112 | 106 | 105 | 96 | 98 | 97 |
As can be seen from the data in Table 3, the rheological, processing, physical and dynamic properties of comparative examples 2-4 and examples 1-4 are slightly improved or reduced, and particularly the properties of examples 1-4 are greatly improved, as compared with comparative example 1.
Table 4 comparative examples 1-4 and comparative compound flow analysis test to example 1
| Sizing material flow analysis test (mixing two-stage) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Example 1 | Example 2 | Example 3 | Example 4 |
| Test pressure (Mpa) | 9.45 | 9.45 | 9.45 | 9.45 | 9.45 | 9.45 | 9.45 | 9.45 |
| Flow value (Point) | 136 | 138 | 153 | 168 | 179 | 172 | 181 | 180 |
From the compound flow analysis test data in Table 4, it is seen that the flow values of comparative examples 2-4 and example 1 are each improved to a different extent than comparative example 1, especially for example 1, with a greater improvement in flow value.
Table 5 comparative examples 1-4 and surface condition of compounds after vulcanization compared with example 1
From a combination of the data in tables 4 and 5, it can be seen that the difference in processability of the rubber composition after vulcanization can be determined or predicted by a compound flow analyzer in advance. The inventor of the present patent finds out through multiple experimental summary: taking the rubber composition of the invention as an example, when the flow value of the rubber composition after two-stage mixing is more than 150Point, the probability of curling and breaking of the rubber composition after vulcanization is very small, and when the flow value of the rubber composition after two-stage mixing is more than 170Point, the surface of the rubber composition after vulcanization is smooth and curling can not be broken. After the rubber composition is mixed, the technological condition after vulcanization can be predicted by a rubber material flow analyzer in advance, and according to the rubber material fluidity test data, mixing technological parameters or raw materials affecting the rubber material fluidity in the formula of the rubber composition can be adjusted in advance.
From the above data of the comparative examples and examples, it is understood that in the low rolling resistance tread rubber composition of the present invention, the process condition of the rubber composition can be predicted in advance by using the stock flow analyzer, and the production efficiency can be improved. Meanwhile, the invention also provides a method for effectively improving the manufacturability of the low-rolling-resistance tread rubber composition, which can improve the dispersibility of the rubber composition and improve the physical property and dynamic property of the rubber composition to a certain extent.
In order to further illustrate the invention, by using a rubber material flow analyzer to judge the difference of the mixing process of the rubber composition in advance, the adjustment of the mixing process is intuitively and effectively characterized, and the following provides further examples, namely the rubber compositions of examples 5, 6, 7, 8 and 9, mainly comprising the following raw materials in parts by weight: 35 parts of non-oil-extended emulsion polymerized styrene-butadiene rubber; 68.75 parts of emulsion polymerized styrene-butadiene rubber with the oil filled of 37.5 percent; 15 parts of butadiene rubber and 80 parts of carbon black. The two-stage mixing and final mixing processes are adopted, the two-stage mixing is carried out by adopting a large-continuous rubber plastic mechanical Co-Ltd F370 shearing internal mixer, the final mixing processes of examples 5, 6, 7, 8 and 9 are consistent, the difference is that the key process of the one-stage mixing is different, and the specific difference is shown in the following table 6:
TABLE 6 examples 5, 6, 7, 8 mixing one stage of key process, detection results by a rubber flow analyzer, comparison of rubber surface states after vulcanization
| Critical process/flow meter analytical testing | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| Glue discharging temperature (DEG C) | 150 | 150 | 150 | 140 | 130 |
| Total time of kneading(s) | 200 | 150 | 100 | 200 | 200 |
| Test pressure (Mpa) | 9.45 | 9.45 | 9.45 | 9.45 | 9.45 |
| Flow value (Point) | 181 | 173 | 162 | 164 | 147 |
| Surface state of rubber after vulcanization | Smooth and glossy | Smooth and matt | Slightly smooth | Slightly smooth | Slightly rough |
From the compound flow analysis test data in Table 6, the flow values of examples 6, 7, 8, and 9 were each reduced to a different extent than example 5, and in particular example 9, the flow values were greatly reduced. The surface state of the rubber after vulcanization also showed that example 9 was slightly rough. Since examples 5,6, 7, 8 and 9 are all carbon black formulations, the fluidity itself is superior to that of the white carbon black formulation, and from the test data, the surface of the rubber composition after vulcanization is smooth when the flow value of the rubber composition after kneading for a period of time is > 160 Point. From the data of examples 5,6, 7, 8 and 9, the whole carbon black formula can also detect the fluidity of the rubber composition in the mixing section in advance by using a rubber material flow analyzer, predict the technological condition after vulcanization, and can carry out the supplement processing or other adjustment on the rubber composition in the mixing section in advance according to the rubber material fluidity test data in the mixing section, thereby improving the production efficiency and reducing the possible technological problems during vulcanization.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A characterization method of mixing process difference of a low rolling resistance rubber composition comprises two-stage mixing and final mixing processes; the method is characterized in that the process condition of the rubber composition after vulcanization is predicted by a sizing material flow analyzer in advance after the rubber composition is mixed, and when the flow value of the rubber composition after two-stage mixing is more than 150Point, the probability of curling and breaking the rubber composition after vulcanization is extremely low; when the flow value of the rubber composition after two-stage mixing is more than 170Point, the surface of the rubber composition after vulcanization is smooth and the rubber composition is curled without breaking;
The rubber composition comprises 25.0-50.0 parts of natural rubber, 5.0-30.0 parts of non-oil-extended solution polymerized styrene-butadiene rubber A, 40.0-80.0 parts of oil-extended 20% solution polymerized styrene-butadiene rubber B, 40.0-60.0 parts of high-ratio surface white carbon black, 1.0-6.0 parts of white carbon black dispersing agent, 2.0-10.0 parts of ground-grabbing resin, 1.0-5.0 parts of mercaptosilane coupling agent and 0.1-3 parts of zinc dialkyl dithiophosphate, wherein the mass of styrene in the non-oil-extended solution polymerized styrene-butadiene rubber A accounts for 20-30% of the total weight of the polymer, and the mass of vinyl accounts for 50-60% of the total weight of butadiene; the mass of styrene in the oil-extended 20% solution polymerized styrene-butadiene rubber B accounts for 40-50% of the total weight of the polymer, and the mass of vinyl accounts for 20-40% of the total weight of butadiene; the nitrogen adsorption specific surface area (BET) of the high-ratio surface white carbon black is more than 200m 2/g; wherein the zinc dialkyldithiophosphate has the formula:
；
the specific operation steps of one-stage mixing in the process method are as follows:
GK320 upper computer mixing process: adding rubber and medicines, adding white carbon black, a silane coupling agent and the like, lowering an upper top bolt, mixing for 15 seconds, lifting a lump, lowering the upper top bolt, mixing and heating to 105 ℃, raising the upper top bolt, mixing and heating to 145 ℃, and mixing for 60 seconds at constant temperature, and discharging rubber;
E550 lower machine mixing process: feeding, mixing and heating to 145 ℃, mixing at constant temperature for 250 seconds, and discharging rubber;
The specific operation steps of the two-stage mixing are as follows: adding a section of master batch for mixing; lowering the upper top bolt for 15 seconds, lifting the upper top bolt for 8 seconds, raising the temperature of the upper top bolt to 110 ℃, lifting the upper top bolt for 5 seconds, raising the temperature of the upper top bolt to 140 ℃, and discharging glue;
The specific operation steps of the three-section final refining are as follows: adding the mixed two-stage masterbatch, sulfur and an accelerator; lowering the top plug for 20 seconds; lifting the bolt for 8 seconds; lowering the top plug for 15 seconds; lifting the top plug for 5 seconds; lowering the upper top bolt to raise the temperature to 102 ℃ and discharging glue.
2. A mixing process of a low-rolling-resistance rubber composition comprises a two-stage mixing process and a final mixing process; the method is characterized in that the process condition of the rubber composition after being vulcanized is predicted by a rubber material flow analyzer in advance after the rubber composition is mixed, and mixing process parameters or raw materials affecting the rubber material fluidity in a formula of the rubber composition are adjusted in advance according to rubber material fluidity test data; when the flow value of the rubber composition after two-stage mixing is more than 150Point, the probability of curling and breaking the rubber composition after vulcanization is very small; when the flow value of the rubber composition after two-stage mixing is more than 170Point, the surface of the rubber composition after vulcanization is smooth and the rubber composition is curled without breaking;
The rubber composition comprises 25.0-50.0 parts of natural rubber, 5.0-30.0 parts of non-oil-extended solution polymerized styrene-butadiene rubber A, 40.0-80.0 parts of oil-extended 20% solution polymerized styrene-butadiene rubber B, 40.0-60.0 parts of high-ratio surface white carbon black, 1.0-6.0 parts of white carbon black dispersing agent, 2.0-10.0 parts of ground-grabbing resin, 1.0-5.0 parts of mercaptosilane coupling agent and 0.1-3 parts of zinc dialkyl dithiophosphate, wherein the mass of styrene in the non-oil-extended solution polymerized styrene-butadiene rubber A accounts for 20-30% of the total weight of the polymer, and the mass of vinyl accounts for 50-60% of the total weight of butadiene; the mass of styrene in the oil-extended 20% solution polymerized styrene-butadiene rubber B accounts for 40-50% of the total weight of the polymer, and the mass of vinyl accounts for 20-40% of the total weight of butadiene; the nitrogen adsorption specific surface area (BET) of the high-ratio surface white carbon black is more than 200m 2/g; wherein the zinc dialkyldithiophosphate has the formula:
；
the specific operation steps of one-stage mixing in the process method are as follows:
GK320 upper computer mixing process: adding rubber and medicines, adding white carbon black, a silane coupling agent and the like, lowering an upper top bolt, mixing for 15 seconds, lifting a lump, lowering the upper top bolt, mixing and heating to 105 ℃, raising the upper top bolt, mixing and heating to 145 ℃, and mixing for 60 seconds at constant temperature, and discharging rubber;
E550 lower machine mixing process: feeding, mixing and heating to 145 ℃, mixing at constant temperature for 250 seconds, and discharging rubber;
The specific operation steps of the two-stage mixing are as follows: adding a section of master batch for mixing; lowering the upper top bolt for 15 seconds, lifting the upper top bolt for 8 seconds, raising the temperature of the upper top bolt to 110 ℃, lifting the upper top bolt for 5 seconds, raising the temperature of the upper top bolt to 140 ℃, and discharging glue;
The specific operation steps of the three-section final refining are as follows: adding the mixed two-stage masterbatch, sulfur and an accelerator; lowering the top plug for 20 seconds; lifting the bolt for 8 seconds; lowering the top plug for 15 seconds; lifting the top plug for 5 seconds; lowering the upper top bolt to raise the temperature to 102 ℃ and discharging glue.
3. The mixing process according to claim 2, wherein the first mixing stage is carried out in a GK320-E550 series internal mixer from HF, inc., the second air drop stage is carried out in a F370 internal mixer from Dalian rubber and plastics, inc., and the third mixing stage is carried out in a F370 internal mixer from Dalian rubber and plastics, inc.
4. The mixing process according to claim 2, wherein the mixing filling rate of the one-stage internal mixer in the process method is 60-70%.
5. The mixing process according to claim 2, wherein the key mixing process of the one-stage internal mixer in the process method is a constant temperature of 130-135 ℃ and a constant temperature time of 80-100 seconds, and a relatively low-temperature mixing process is adopted.
6. The compounding process of claim 2, wherein the rubber composition comprises one or a mixture of two of functionalized solution polymerized styrene-butadiene rubber, natural rubber, and butadiene rubber.
7. A low rolling resistance tyre, the tread of which is vulcanized by obtaining a low rolling resistance rubber composition according to the method of any one of claims 2 to 6.
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| CN104292796A (en) * | 2014-09-30 | 2015-01-21 | 山东阳谷华泰化工股份有限公司 | Application of zinc isoocatanoate in reduction on agglomeration of white carbon black, white carbon black dispersing agent containing zinc isoocatanoate and preparation method thereof |
| CN106239758A (en) * | 2016-08-25 | 2016-12-21 | 特拓(青岛)轮胎技术有限公司 | A kind of method improving rubber mobility precision |
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| JP6362584B2 (en) * | 2015-12-15 | 2018-07-25 | 住友ゴム工業株式会社 | Method for producing rubber composition and tire |
| CN109251379B (en) * | 2018-08-15 | 2020-12-04 | 中策橡胶集团有限公司 | Low-filling high-performance tire tread rubber material and tire |
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| CN104292796A (en) * | 2014-09-30 | 2015-01-21 | 山东阳谷华泰化工股份有限公司 | Application of zinc isoocatanoate in reduction on agglomeration of white carbon black, white carbon black dispersing agent containing zinc isoocatanoate and preparation method thereof |
| CN106239758A (en) * | 2016-08-25 | 2016-12-21 | 特拓(青岛)轮胎技术有限公司 | A kind of method improving rubber mobility precision |
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