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CN-119371750-B - Tire inner liner rubber composite material with high biobased content and excellent air tightness and preparation method thereof

CN119371750BCN 119371750 BCN119371750 BCN 119371750BCN-119371750-B

Abstract

The invention provides a rubber composite material, which comprises, by mass, 100 parts of raw rubber, 40-100 parts of reinforcing filler, 2-10 parts of activating agent, 4-10 parts of plasticizer, 2-15 parts of homogenizing agent, 2-15 parts of tackifying resin, 0.05-0.5 part of magnesium oxide, 1.0-6.0 parts of accelerator and 0.5-3 parts of vulcanizing agent, wherein the raw rubber comprises itaconate rubber and halogenated butyl rubber. The air-tight layer rubber provided by the invention comprises the environment-friendly bio-based itaconate rubber, is favorable for energy conservation and carbon reduction, is compact in arrangement and has certain gas barrier property due to the fact that the itaconate rubber has certain side groups, and has better air tightness and ageing resistance than natural rubber when being compounded with butyl rubber.

Inventors

  • GAO SONG
  • HAO FULAN
  • ZONG XIN
  • CUI HONGHONG
  • ZHANG SHUHUA
  • LIU QINGCHUN

Assignees

  • 山东京博中聚新材料有限公司

Dates

Publication Date
20260508
Application Date
20240902

Claims (10)

  1. 1. The rubber composite material is characterized by comprising the following raw materials in parts by weight: 100 parts by weight of raw rubber; the raw rubber comprises itaconate rubber and halogenated butyl rubber; 40-100 parts by weight of a reinforcing filler; 2-10 parts of an activating agent; 4-10 parts of plasticizer; 2-15 parts of a homogenizing agent; 2-15 parts of tackifying resin; 0.05-0.5 parts by weight of magnesium oxide; 1.0-6.0 parts by weight of an accelerator; 0.5-3 parts by weight of vulcanizing agent; in the raw rubber, the mass ratio of the halogenated butyl rubber to the itaconate rubber is (1-9) 1; The itaconate rubber is a binary, ternary or quaternary copolymer containing itaconate and bio-based diene or petroleum-based conjugated diene; The itaconate rubber is a copolymer obtained by low-temperature emulsion polymerization of a raw material comprising dibutyl itaconate units and butadiene units; the polymerization temperature of the low-temperature emulsion polymerization is 1-20 ℃.
  2. 2. The rubber composite of claim 1, wherein the itaconate is selected from one or more of dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, diisopropyl itaconate, diisobutyl itaconate, di-n-pentyl itaconate, and diisoamyl itaconate; the bio-based diene is a diene produced by microbial fermentation or a terpene derived from a plant.
  3. 3. The rubber composite according to claim 1, wherein the petroleum-based conjugated diene is isoprene and/or butadiene; The rubber composite is a rubber composite for an inner liner of a tire.
  4. 4. The rubber composite of claim 1, wherein the itaconate rubber further comprises a third component and/or a fourth component; The third component and the fourth component are respectively and independently selected from one or more of glycidyl methacrylate, styrene, vinyl chloride acetate, acrylamide, cyclopentadiene, ethylidene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; The reinforcing filler is one or more of carbon black, calcium carbonate, calcium sulfate, dolomite powder, clay, montmorillonite, barium sulfate, talcum powder, magnesium carbonate, magnesium silicate, graphene and cellulose bio-based filler; the vulcanizing agent is sulfur.
  5. 5. The rubber composite of claim 1, wherein the activator is one or more of zinc oxide, stearic acid, and magnesium oxide; the plasticizer is one or more of naphthenic oil, aromatic oil, petroleum resin, epoxidized soybean oil and palm oil; the homogenizing agent is an aromatic hydrocarbon resin mixture; The tackifying resin is phenolic resin and/or petroleum resin; The accelerator is one or more of thiazole accelerators, thiuram accelerators, dithiocarbamic acid salt accelerators, xanthate accelerators, guanidine accelerators, aldehyde amine accelerators, sulfenamide accelerators and thiourea accelerators.
  6. 6. A method for preparing the rubber composite material according to any one of claims 1 to 5, comprising the steps of: 1) Plasticating the raw rubber in an internal mixer to obtain plasticated rubber; 2) Adding a reinforcing filler, a plasticizer, magnesium oxide, a homogenizing agent and tackifying resin into the plasticated rubber obtained in the steps, mixing, and discharging the rubber to obtain a section of masterbatch; 3) Cooling the primary masterbatch obtained in the step, and then continuously banburying the primary masterbatch, the vulcanizing agent, the activating agent and the accelerator, and discharging the masterbatch to obtain a secondary final masterbatch; 4) And (3) carrying out thin pass on the two-stage final rubber mixture obtained in the steps on an open mill to obtain rubber compound, and vulcanizing to obtain the rubber composite material.
  7. 7. The method according to claim 6, wherein the plasticating time is 0.5 to 1.5 minutes; the plasticating temperature is 40-80 ℃; The rotating speed of the internal mixer during plasticating is 40-80 rpm; the mixing temperature is 110-150 ℃; the mixing time is 4-8 min.
  8. 8. The method according to claim 6, wherein the temperature after cooling is 80 ℃ or lower; the temperature of the continuous banburying is 90-130 ℃; the continuous banburying time is 1-3 min; The number of times of thin pass is 3-12 times; The roll gap of the thin pass is 0.5-4.0 mm.
  9. 9. The method of claim 6, wherein the post-thin-pass further comprises a parking step; the parking time is 18-24 hours; The vulcanization temperature is 130-180 ℃; the vulcanizing time is 5-60 min; the vulcanizing pressure is 20-40 tons.
  10. 10. Use of the rubber composite material according to any one of claims 1 to 5 or the rubber composite material prepared by the preparation method according to any one of claims 6 to 9 in a tire.

Description

Tire inner liner rubber composite material with high biobased content and excellent air tightness and preparation method thereof Technical Field The invention belongs to the technical field of tire inner liner rubber composite materials, relates to a rubber composite material and a preparation method and application thereof, and in particular relates to a tire inner liner rubber composite material with high bio-based content and excellent air tightness, and a preparation method and application thereof. Background With the popularization of new energy automobiles, higher requirements are put forward on the bearing and instantaneous torque of the tire, and further higher requirements are put forward on the air tightness of the tire. The insufficient inflation of the tire causes problems such as an increase in rolling resistance of the tire, a slow steering reaction, a long braking distance, uneven wear of the tire, and a burst of the tire due to an increase in stress of internal parts of the tire. The air tightness of the tire is mainly determined by the rubber layer of the innermost layer of the tire, that is, the inner liner. The high-air-tightness composite material provides an application scheme for new energy automobiles, the thickness of the air-tightness layer is reduced, and the rolling resistance of the tire is reduced. In the prior art, the base rubber of the inner liner of the tire is mostly a composition of natural rubber and halogenated butyl rubber, and the problem of the combination is mainly that the air permeability coefficient of the inner liner is increased along with the increase of the use amount of the natural rubber, so that the air retention performance of the tire is reduced, and the service life and the driving operability of the tire are influenced. On the other hand, the main raw materials of butyl rubber used in the tire industry, such as isobutylene and isoprene, are derived from non-renewable petrochemical resources. The rubber industry is a consumer of petrochemical resources, a large amount of waste water and waste gas are generated, and development of biomass energy and bio-based chemicals is gradually valued by all countries in the world, and the reserves are large and are carbon neutral. The development of bio-based synthetic elastomer composites based on bio-based chemicals is of great importance for sustainable development. Under the influence of related policies, full utilization of low-carbon and renewable resources has been paid attention to all countries around the world. Among the raw materials used in the production of tires, most of the raw materials are seriously dependent on rubber materials synthesized by fossil resources, and have high carbon emission, which is very unfavorable for the sustainable development of the tire industry. Although compared with the traditional petroleum-based materials, the biomass-based materials have the advantages of large reserves, neutral carbon, reduced raw material cost and the like, various attempts are gradually made in the prior researches by adopting the biomass-based materials, but the product performance is still not ideal. Along with the accelerated implementation of the green transformation and upgrading of the rubber auxiliary agent industry and the increase of environmental protection pressure, various environment-friendly auxiliary agents are applied to various rubber products, and the adoption of novel environment-friendly and nontoxic natural materials, green auxiliary agents and other safe and environment-friendly materials to replace traditional various additives has great significance for the sustainable development of the transmission belt industry and is also a main direction of technical development. Therefore, how to obtain a proper production process and rubber composite material solves the problems existing in the prior process and rubber products, particularly the rubber material of the inner liner of the tire, further improves the green environmental protection degree, and becomes an important problem to be solved urgently by a plurality of first-line production research personnel and industry manufacturers in the industry. Disclosure of Invention In view of the above, the technical problem to be solved by the invention is to provide a rubber composite material, a preparation method and application thereof, in particular to a tire inner liner rubber composite material with high bio-based content and excellent air tightness. The air-tight layer rubber provided by the invention comprises the environment-friendly bio-based itaconate rubber, is favorable for energy conservation and carbon reduction, is compact in arrangement and has a certain gas barrier property due to the fact that the itaconate rubber has a certain side group, and has better air tightness and ageing resistance than natural rubber when being compounded with butyl rubber. In addition, the airtight layer adhesive has the advantages of simple