CN111961290B - Low-zinc tire inner liner rubber and preparation method thereof - Google Patents
Low-zinc tire inner liner rubber and preparation method thereof Download PDFInfo
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- CN111961290B CN111961290B CN202010756194.3A CN202010756194A CN111961290B CN 111961290 B CN111961290 B CN 111961290B CN 202010756194 A CN202010756194 A CN 202010756194A CN 111961290 B CN111961290 B CN 111961290B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 150
- 239000011701 zinc Substances 0.000 title claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000011787 zinc oxide Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000006229 carbon black Substances 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229920005555 halobutyl Polymers 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 43
- 238000007599 discharging Methods 0.000 claims description 39
- 238000003825 pressing Methods 0.000 claims description 35
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 229920005557 bromobutyl Polymers 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical group NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010734 process oil Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 11
- 230000020169 heat generation Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 230000035699 permeability Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 208000035967 Long Term Adverse Effects Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- WGLYADVYCJUFAY-UHFFFAOYSA-N cloran Chemical compound C12CC3C(=O)OC(=O)C3CC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl WGLYADVYCJUFAY-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- -1 flexibility Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
- C08L23/283—Iso-olefin halogenated homopolymers or copolymers
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a low-zinc tire inner liner rubber and a preparation method thereof, wherein the inner liner rubber is prepared from the following raw materials in parts by weight: 100.00 parts of halogenated butyl rubber, 0.2-4.0 parts of rubber modifier, 40.0-70.0 parts of filler, 0-1.0 part of magnesium oxide, 0.2-1.0 part of zinc oxide, 0.5-2.5 parts of stearic acid, 4.0-12.0 parts of homogenizing agent, 2.0-6.0 parts of tackifying resin, 4.0-12.0 parts of rubber operating oil, 0.8-2.0 parts of accelerator DM and 0.5-1.5 parts of sulfur. The low-zinc tire inner liner rubber and the preparation method thereof provided by the invention have the characteristics of low zinc and environmental protection, and the usage amount of zinc oxide in the rubber material formula is reduced; and the rubber modifier is added in the formula, so that the interaction between the rubber and the filler is enhanced, the crosslinking density and the tensile strength of the rubber are improved, the dispersity of the carbon black is improved, and the hysteresis loss and the heat generation of the rubber compound are reduced. The tire inner liner rubber prepared by the method not only meets the requirement of low zinc and environmental protection, but also has excellent air tightness, flexibility and ageing resistance.
Description
Technical Field
The invention relates to the technical field of tire manufacturing, in particular to low-zinc tire inner liner rubber and a preparation method thereof.
Background
At present, zinc compounds, in particular zinc oxide, are used in the production of virtually all rubber articles. In the European Union, about 10 million tons of zinc oxide and a little other zinc compounds are used in the rubber industry every year, accounting for about 40% of the total zinc oxide consumption, and the annual zinc oxide consumption in China is about 18-30 million tons. Although zinc is used in a wide variety of applications, certain alloys of zinc are toxic to microorganisms and aquatic organisms when released into the environment, into streams, rivers and oceans. In 1995, zinc and zinc compounds were listed as the main substances in the list of rubber compounds compiled by the swedish environmental protection agency, and were suggested to be used instead or limited. In the same year, zinc and zinc oxide are listed again in the second category of hazardous substances in the risk assessment program of the european union. In 4 months 2004, the EU directive 2004/73/EC formally classified zinc oxide as "harmful to the environment" with a hazard level of R50/53 "which is very harmful to aquatic organisms and can have a long-term adverse effect on the aquatic ecosystem and should be" prevented from being discharged into the ecological environment ". By the end of 2016 at 3 months, a law SB1260 was proposed by california in the united states that restricted the use of zinc or zinc oxide in tires, and that may prohibit the sale of tire products containing certain amounts of zinc, creating a high level of concern for zinc oxide and tire manufacturing companies. The act also considers rubber materials outdoors as a major source of zinc contamination in the environment. In overview, the proposal of the act is a warning in the current environment to the tire manufacturing industry to accelerate the upgrade of green products. Zinc pollution is a real existence, and as the requirement of the global rubber industry on environmental protection is continuously improved, the active search and development of zinc oxide substitute products are more and more emphasized, and the research on zinc reduction in the formula of tire rubber is a trend. Therefore, the research and development of the low-zinc tire rubber formula have important strategic significance for realizing energy conservation, emission reduction and environmental protection.
The inner liner of the tire is a key component of the tubeless tire and determines the dissolving and diffusing speed of air and water vapor in the tire. With the enhancement of green environmental awareness, the reduction of zinc oxide in the formulation of the inner liner rubber is receiving more and more attention. The application of different amounts of nano zinc oxide in the inner liner of the all-steel truck radial tire is researched by the chloran and the like, the common zinc oxide is replaced by 0.7 part, 1.4 parts, 2.1 parts, 2.8 parts and 3.5 parts of nano zinc oxide, and when the amount of the nano zinc oxide is 0.7 part, the tensile strength of the inner liner rubber is obviously reduced. This is because zinc oxide is mainly used as a vulcanization activator in rubber, and when zinc oxide participates in vulcanization, a chemical reaction occurs on the surface of zinc oxide particles. In the reaction process, the surfaces of the zinc oxide particles are continuously reacted, the particle size is continuously reduced, and the zinc oxide is consumed until the rubber material is fully vulcanized. Thus, the factors that determine the reactivity and amount of zinc oxide are the microstructure of the zinc oxide and the effective specific surface area. The microstructure of the indirect method zinc oxide is solid powder particles, the particle size is large, the effective specific surface area is small, and the reaction activity is low; the nano zinc oxide and the like are irregular porous powder particles, have small particle size, can be agglomerated, have small effective specific surface area, are not easy to disperse in rubber materials, and cause low reaction activity. Therefore, in the existing rubber formula system, the usage amount of zinc oxide is large, the weight part of zinc oxide in the rubber formula system is generally more than 1 part, otherwise, the performances such as crosslinking density, tensile strength and ageing resistance are reduced, the air retention performance and the flexibility of the tire are reduced, and the normal use of the tire is influenced.
Therefore, the formula of the inner liner with low zinc content, excellent air retention performance and excellent flexibility is developed, the requirement of the high-performance environment-friendly tire is met, and the method has important practical significance.
Disclosure of Invention
In order to solve the problems, the invention provides the low-zinc tire inner liner rubber and the preparation method thereof, which greatly reduce the dosage of zinc oxide in the formula of the inner liner rubber, meet the environmental protection of tires and have excellent air retention performance and flexibility.
The technical scheme adopted by the invention is as follows:
the low-zinc tire inner liner rubber is prepared from the following raw materials in parts by weight: 100.00 parts of halogenated butyl rubber, 0.2-4.0 parts of rubber modifier, 40.0-70.0 parts of filler, 0-1.0 part of magnesium oxide, 0.2-1.0 part of zinc oxide, 0.5-2.5 parts of stearic acid, 4.0-12.0 parts of homogenizing agent, 2.0-6.0 parts of tackifying resin, 4.0-12.0 parts of rubber operating oil, 0.8-2.0 parts of accelerator DM and 0.5-1.5 parts of sulfur.
Preferably, the feed additive is prepared from the following raw materials in parts by weight: 100.00 parts of halogenated butyl rubber, 1.0-3.0 parts of rubber modifier, 40.0-65.0 parts of filler, 0.3-0.7 part of magnesium oxide, 0.6-1.0 part of zinc oxide, 1.0-2.0 parts of stearic acid, 6.0-10.0 parts of homogenizing agent, 2.0-4.0 parts of tackifying resin, 6.0-10.0 parts of rubber operating oil, 1.2-1.6 parts of accelerator DM and 0.5-1.2 parts of sulfur.
Preferably, the rubber modifier is a dihydrazide compound, and the structure of the dihydrazide compound is as follows:
wherein R is selected from a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a linear or branched, saturated or unsaturated aliphatic group having 2 to 20 carbon atoms.
Preferably, the rubber modifier is terephthalic acid dihydrazide, and the structural formula is as follows:
preferably, the filler includes, but is not limited to, carbon black, inorganic fillers; 40.0 to 65.0 portions of carbon black and 0 to 20 portions of inorganic filler; the carbon black is preferably one or more of N660 carbon black and N762 carbon black; the inorganic filler is preferably one or more of kaolin, carbon, mica powder, modified kaolin and modified calcium carbonate.
According to the low-zinc tire inner liner rubber provided by the invention, the zinc oxide accounts for only 0.2-1.0 part by weight in the rubber material formula, so that compared with the prior art, the using amount of the zinc oxide is greatly reduced, and the environmental protection property of a tire is ensured; meanwhile, in order to prevent the reduction of cross-linking density, mechanical property, air retention property and the like of vulcanized rubber possibly caused by zinc oxide reduction, a rubber modifier is added in a rubber material formula, one end of an amino group at the tail end of the rubber modifier can react with halogenated butyl rubber, and the other end of the amino group can react with carboxyl and other oxidizing groups on the surface of carbon black, so that the interaction between the rubber and a filler is tighter, the cross-linking density and the tensile strength of the rubber are improved, the dispersibility of the carbon black is improved, the hysteresis loss and the heat generation of the rubber material are reduced, the mechanical property and the air tightness of a tire are ensured, and the flexing property, the aging resistance and the like are considered at the same time.
Preferably, the halogenated butyl rubber is preferably brominated butyl rubber, the brominated butyl rubber has a main chain of which the butyl rubber is basically saturated, and has high activity, high vulcanization speed, low permeability and good aging resistance, and the brominated butyl rubber adopted in the formula of the tire inner liner rubber material can improve the air retention of the tire, and can also improve the adhesion performance between the inner liner and the tire body and the durability of the tire.
Preferably, the tackifying resin is one or two of octyl phenolic tackifying resin and C5 petroleum resin.
Preferably, the rubber process oil is a naphthenic oil.
Preferably, the sulphur is preferably insoluble sulphur HD OT 20.
A method for preparing the low-zinc tire inner liner rubber according to any one of the above steps, comprising the following steps:
s1, first-stage rubber compound: adjusting the rotation speed of an internal mixer to 30-40 rpm, adding halogenated butyl rubber, filler, stearic acid, tackifying resin, homogenizing agent and magnesium oxide into the internal mixer, pressing a top bolt for mixing for 20-50 seconds, lifting the top bolt, injecting rubber operation oil, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt, pressing the top bolt for mixing for 20-50 seconds, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to 130-135 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of master batch;
s2, final mixing: adjusting the rotating speed of an internal mixer to 15-25 rpm, adding a section of master batch, sulfur, an accelerator, zinc oxide and a rubber modifier, pressing a top bolt for mixing for 20-50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 95-105 ℃; and (5) discharging pieces by using an open mill, cooling and stacking to obtain the final rubber compound.
Compared with the prior art, the low-zinc tire inner liner rubber and the preparation method thereof provided by the invention have the characteristics of low zinc and environmental friendliness, and the usage amount of zinc oxide in the rubber material formula is reduced; and the rubber modifier is added in the formula, so that the interaction between the rubber and the filler is enhanced, the crosslinking density and the tensile strength of the rubber are improved, the dispersity of the carbon black is improved, and the hysteresis loss and the heat generation of the rubber compound are reduced. The tire inner liner rubber prepared by the method not only meets the requirement of low zinc and environmental protection, but also has excellent air tightness, flexibility and ageing resistance.
Detailed Description
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
The low-zinc tire inner liner rubber disclosed by the invention comprises the following components in parts by weight in each example and comparative example as shown in table 1:
TABLE 1 parts by weight of components in each of examples and comparative examples of the low-zinc tire inner liner rubber disclosed in the present invention
The preparation process of the low-zinc tire inner liner rubber of the embodiments 1 to 4 is as follows:
s1, first-stage rubber compound: adjusting the rotating speed of an internal mixer to 35 r/min, adding 100 parts of brominated butyl rubber, carbon black N660, carbon black N762, stearic acid, tackifying resin, a homogenizing agent and magnesium oxide into the internal mixer, pressing a top bolt for mixing for 35 seconds, lifting the top bolt, injecting naphthenic oil, pressing the top bolt for mixing for 35 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 35 seconds, lifting the top bolt, pressing the top bolt for mixing for 35 seconds, opening a discharge door for discharging rubber, and controlling the rubber discharging temperature to 133 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of masterbatch;
s2, final mixing: adjusting the rotating speed of an internal mixer to 20 r/min, adding a section of master batch, insoluble sulfur HD OT 20, an accelerator DM, zinc oxide and a rubber modifier, pressing a top bolt for mixing for 35 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 35 seconds, lifting the top bolt, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 100 ℃; and (5) discharging pieces by using an open mill, cooling and stacking to obtain the final rubber compound.
The preparation process of comparative examples 1 to 2 was as follows:
s1, first-stage rubber compound: adjusting the rotating speed of an internal mixer to 35 r/min, adding 100 parts of brominated butyl rubber, carbon black N660, carbon black N762, stearic acid, tackifying resin, a homogenizing agent and magnesium oxide into the internal mixer, pressing a top bolt for mixing for 35 seconds, lifting the top bolt, injecting naphthenic oil, pressing the top bolt for mixing for 35 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 35 seconds, lifting the top bolt, pressing the top bolt for mixing for 35 seconds, opening a discharge door for discharging rubber, and controlling the rubber discharging temperature to 133 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of masterbatch;
s2, final mixing: adjusting the rotating speed of an internal mixer to 20 r/min, adding a section of master batch, insoluble sulfur HD OT 20, an accelerant DM and zinc oxide, pressing a top bolt for mixing for 35 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 35 seconds, lifting the top bolt, opening a discharge door for discharging rubber, and controlling the rubber discharging temperature to be 100 ℃; and (5) discharging pieces by using an open mill, cooling and stacking to obtain the final rubber compound.
The results of the performance tests on the compounds obtained in examples 1 to 4 and comparative examples 1 to 2 are shown in Table 2.
TABLE 2 basic physical Properties of the compounds obtained in examples 1 to 4 and comparative examples 1 to 2
The minimum torque ML of the rubber depends on the rigidity and viscosity of the rubber compound at a low shear rate, and reflects the flowability of the rubber compound at a certain temperature; the maximum torque MH of the rubber is a measure of the stiffness of the fully vulcanized vulcanizate at the test temperature, reflecting the modulus of the rubber after vulcanization; the MH-ML difference can reflect the crosslinking degree of the vulcanized rubber; tan delta @60 ℃ is a measurement result of a dynamic thermal mechanical analyzer for GABO, the rolling resistance of the vulcanized rubber has a good correlation with a loss factor tan delta of the rubber at 60 ℃, and the smaller the value of tan delta at around 60 ℃, the lower the heat generation of the vulcanized rubber and the smaller the rolling resistance.
As can be seen from tables 1-2, comparative example 1 is the formulation of the inner liner rubber in the prior art, compared with comparative example 1, the amount of zinc oxide in the formulation of the rubber material in comparative example 2 is significantly reduced, the difference between MH-ML of the prepared rubber material after vulcanization is significantly reduced compared with comparative example 1, which shows that the cross-linking density of the rubber material after vulcanization in comparative example 2 is reduced, and the tensile strength is reduced, the air permeability coefficient at 23 ℃ and the air permeability coefficient at 23 ℃ are significantly increased, thereby demonstrating that simply reducing the amount of zinc oxide in the formulation of the inner liner rubber will result in the reduction of the tensile strength and air tightness of the inner liner rubber.
Example 1 a rubber modifier was added based on the compound formulation of comparative example 2, and the MH-ML difference of the inner liner rubber prepared from the compound formulation of example 1 was significantly improved, the tensile strength and the carbon black dispersion grade were significantly improved, and the air permeability coefficient at 23 ℃, the percentage of air permeability coefficient at 23 ℃, and the value of tan σ @60 ℃ were significantly reduced, as a result, it was found that the cross-linking density, tensile strength, air impermeability, and low heat build-up of the inner liner rubber of example 1 were significantly improved as compared to those of comparative example 2; furthermore, the MH-ML difference, the tensile strength, the carbon black dispersion grade and the 300 ten thousand flex grade of the inner liner rubber of the example 1 are all higher than those of the comparative example 1, the air permeability coefficient at 23 ℃, the percentage of the air permeability coefficient at 23 ℃ and the tan σ @60 ℃ are significantly lower than those of the comparative example 1, so that the inner liner rubber of the example 1 has higher crosslinking density, tensile strength, carbon black dispersion, flexibility, air permeability and low heat generation performance than those of the comparative example 1, namely the inner liner rubber in the prior art, and the amino group at the tail end of the rubber modifier can react with the halogenated butyl rubber at one end and react with the carboxyl group and other oxidizing group on the surface of the carbon black at the other end, so that the interaction between the rubber and the filler is tighter, the crosslinking density and the tensile strength of the rubber are improved, the dispersion of the carbon black is improved, and the hysteresis loss and the heat generation of the rubber are reduced. Compared with the comparative example 1, after the rubber modifier is used, the air tightness of the rubber material is improved by 7-9%, and the heat generation performance is reduced by 5-8%. By calculation, the zinc content in the rubber compound formula of the comparative example 1 is 1.28%, the zinc contents in the rubber compound formulas of the examples 1 and 2 are 0.26% and 0.17% respectively, and the zinc contents are respectively reduced by 80% and 87%, so that the use amount of zinc in the inner liner rubber is greatly reduced, and the requirements of low-zinc environment-friendly tires are met. While the comparative example 2 reduces the amount of zinc oxide, the yield performance is not reduced, but the use of less zinc oxide results in insufficient crosslinking density of the rubber, large air permeability and loss factor of vulcanized rubber, and reduced performance.
In conclusion, the tire inner liner rubber prepared by the method not only meets the requirement of low zinc environmental protection, but also has excellent air tightness, flexibility and ageing resistance.
Example 5
The preparation method of the low-zinc tire inner liner rubber comprises the following steps:
s1, mixing rubber: adjusting the rotation speed of an internal mixer to 30 rpm, adding 100 parts of brominated butyl rubber, 52 parts of carbon black N660, 5 parts of kaolin, 5 parts of carbon, 1.3 parts of stearic acid, 4 parts of octyl phenolic tackifying resin and 8 parts of homogenizing agent into the internal mixer, pressing a top bolt for mixing for 20 seconds, lifting the top bolt, injecting 10 parts of naphthenic oil, pressing the top bolt for mixing for 20 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20 seconds, lifting the top bolt, pressing the top bolt for mixing for 20 seconds, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 130 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of masterbatch;
s2, final mixing: adjusting the rotating speed of an internal mixer to 15 r/min, adding a section of master batch, 1 part of insoluble sulfur HD OT 20, 1.6 parts of accelerator DM, 0.7 part of zinc oxide and 2.1 parts of rubber modifier, pressing a top bolt for mixing for 20 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20 seconds, lifting the top bolt, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 95 ℃; and (5) discharging pieces by using an open mill, cooling and stacking to obtain the final rubber compound.
Example 6
The preparation method of the low-zinc tire inner liner rubber comprises the following steps:
s1, first-stage rubber compound: adjusting the rotating speed of an internal mixer to 40 r/min, adding 100 parts of butyl bromide rubber, 50 parts of carbon black N762, 10 parts of mica powder, 10 parts of modified calcium carbonate, 2.0 parts of stearic acid, 4 parts of C5 petroleum resin, 10 parts of a homogenizing agent and 0.3 part of magnesium oxide into the internal mixer, pressing a top bolt for mixing for 50 seconds, lifting the top bolt, injecting 6 parts of naphthenic oil, pressing the top bolt for mixing for 50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 50 seconds, lifting the top bolt for mixing for 50 seconds, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 135 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of masterbatch;
s2, final mixing: adjusting the rotation speed of an internal mixer to 25 rpm, adding a section of master batch, 1.2 parts of insoluble sulfur HD OT 20, 1.2 parts of accelerator DM, 0.6 part of zinc oxide and 3 parts of rubber modifier, pressing a top bolt for mixing for 50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 50 seconds, lifting the top bolt, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 105 ℃; and (5) discharging pieces by using an open mill, cooling and stacking to obtain the final rubber compound.
The low-zinc tire inner liner rubber and the preparation method thereof provided by the invention are introduced in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and central concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. The low-zinc tire inner liner rubber is characterized by being prepared from the following raw materials in parts by weight: 100.00 parts of halogenated butyl rubber, 0.2-4.0 parts of rubber modifier, 40.0-70.0 parts of filler, 0-1.0 part of magnesium oxide, 0.2-1.0 part of zinc oxide, 0.5-2.5 parts of stearic acid, 4.0-12.0 parts of homogenizing agent, 2.0-6.0 parts of tackifying resin, 4.0-12.0 parts of rubber operating oil, 0.8-2.0 parts of accelerator DM and 0.5-1.5 parts of sulfur;
the rubber modifier is a dihydrazide compound, and the dihydrazide compound has the following structural formula:
wherein R is selected from a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms or a linear or branched, saturated or unsaturated aliphatic group having 2 to 20 carbon atoms.
2. The low-zinc tire inner liner rubber as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 100.00 parts of halogenated butyl rubber, 1.0-3.0 parts of rubber modifier, 40.0-65.0 parts of filler, 0.3-0.7 part of magnesium oxide, 0.6-1.0 part of zinc oxide, 1.0-2.0 parts of stearic acid, 6.0-10.0 parts of homogenizing agent, 2.0-4.0 parts of tackifying resin, 6.0-10.0 parts of rubber operating oil, 1.2-1.6 parts of accelerator DM and 0.5-1.2 parts of sulfur.
3. The low zinc tire inner liner rubber as claimed in claim 1, wherein the rubber modifier is terephthalic acid dihydrazide, and the structural formula is as follows:
4. the low zinc tire inner liner rubber according to claim 1, wherein the filler includes, but is not limited to, carbon black, inorganic filler; 40.0 to 65.0 portions of carbon black and 0 to 20 portions of inorganic filler; the carbon black is selected from one or more of N660 carbon black and N762 carbon black; the inorganic filler is selected from one or more of kaolin, carbon, mica powder, modified kaolin and modified calcium carbonate.
5. The low zinc tire inner liner rubber as claimed in claim 1, wherein the halogenated butyl rubber is selected from brominated butyl rubber.
6. The low-zinc tire inner liner rubber as claimed in claim 1, wherein the tackifying resin is one or two of octyl phenolic tackifying resin and C5 petroleum resin.
7. The low zinc tire inner liner rubber according to claim 1, wherein the rubber process oil is naphthenic oil.
8. The low zinc tire inner liner rubber according to claim 1, wherein the sulfur is selected from insoluble sulfur HD OT 20.
9. A method for preparing a low zinc tire inner liner rubber according to any one of claims 1 to 8, comprising the following steps:
s1, first-stage rubber compound: adjusting the rotation speed of an internal mixer to 30-40 rpm, adding halogenated butyl rubber, filler, stearic acid, tackifying resin, homogenizing agent and magnesium oxide into the internal mixer, pressing a top bolt for mixing for 20-50 seconds, lifting the top bolt, injecting rubber operating oil, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt, pressing the top bolt for mixing for 20-50 seconds, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to 130-135 ℃; sheet feeding of an open mill, cooling and stacking to obtain a section of master batch;
s2, final mixing: adjusting the rotating speed of an internal mixer to 15-25 rpm, adding a section of master batch, sulfur, an accelerator, zinc oxide and a rubber modifier, pressing a top bolt for mixing for 20-50 seconds, lifting the top bolt for cleaning, pressing the top bolt for mixing for 20-50 seconds, lifting the top bolt, opening a discharging door for discharging rubber, and controlling the rubber discharging temperature to be 95-105 ℃; and (4) discharging pieces from the open mill, cooling and building stacks to obtain the final rubber compound.
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| CN114031862B (en) * | 2021-12-17 | 2023-10-27 | 青岛沃瑞轮胎有限公司 | Novel low-carbon energy-saving environment-friendly tire inner liner for automobile and preparation method thereof |
| CN114989539B (en) * | 2022-06-06 | 2023-04-18 | 中策橡胶集团股份有限公司 | Inner liner rubber composition of high-airtightness tire, preparation method and application thereof, and tire |
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