CN-122011573-A - Rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy, preparation method thereof and tire inner liner

CN122011573ACN 122011573 ACN122011573 ACN 122011573ACN-122011573-A

Abstract

The application relates to the field of high polymer materials, and particularly discloses a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy, and a preparation method and application thereof. A process for preparing the dual-continuous heterogeneous cross-linked dynamic sulfurized alloy of rubber and plastics includes such steps as high-temp mixing of dispersed phase halogenated butyl rubber with gas-isolating resin, compatibilizer and heat-resistant oxidizing agent, cooling, mixing with liquid rubber, dynamic sulfurizing agent and stannous chloride, dynamic sulfurizing to obtain thermoplastic sulfurized halogenated butyl rubber, high-temp mixing with continuous phase halogenated butyl rubber and heat-resistant oxidizing agent, cooling, sequentially adding zinc oxide, stearic acid, antiager, carbon black, inorganic filler, liquid rubber, protecting wax, sulfurizing agent and assistant, and pugging. The dynamic vulcanized alloy prepared by the application has excellent gas barrier property, good ductility and adhesion property, can be applied to the existing rubber calendering equipment and process, and can form a novel DVA tire inner liner with the thickness as low as 0.3 millimeter.

Inventors

ZHANG SHIJIA
TIAN MING
NING NANYING
LI KUNPENG
DONG RUN
ZHANG LIQUN
CHEN WENQUAN
TIAN HONGCHI
Luan Haowo
WANG FANGHE
ZOU FANG
JIANG JIAN
GUO HUA
LIU JUN

Assignees

道恩高材(北京)科技有限公司
山东道恩高分子材料股份有限公司

Dates

Publication Date: 20260512
Application Date: 20251211

Claims (10)

1. A rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy is characterized by comprising the following steps of; S1, uniformly mixing disperse phase halogenated butyl rubber, gas barrier resin, compatibilizer and high-temperature rubber and plastic of a first heat-resistant agent to prepare high-temperature mixed rubber, wherein the banburying temperature is 10-20 ℃ higher than the melting point of the gas barrier resin; s2, mixing the high-temperature mixed rubber obtained in the step S1 with the first liquid rubber, the dynamic vulcanizing agent and stannous chloride uniformly after open mill cooling to obtain a mixed rubber; s3, dynamically vulcanizing the mixed rubber obtained in the step S2 to obtain thermoplastic vulcanized halogenated butyl rubber; S4, directly and uniformly mixing the thermoplastic vulcanized halogenated butyl rubber obtained in the step S3 with continuous phase halogenated butyl rubber and a second anti-heat-oxidizing agent at a high temperature, wherein the banburying temperature is 10-20 ℃ higher than the melting point of the gas barrier resin; S5, after the high-temperature mixed material obtained in the step S4 is subjected to open mill cooling, zinc oxide, stearic acid, an anti-aging agent, carbon black, lamellar inorganic filler, second liquid rubber, protective wax, a vulcanizing agent and a vulcanizing aid are sequentially added in stages, and the mixing is uniform, so that the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy is obtained.
2. The preparation method of the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy as set forth in claim 1, wherein the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy is characterized by comprising the following raw materials in parts by weight: 50-70 parts of disperse phase halogenated butyl rubber, 30-50 parts of gas barrier resin, 2-10 parts of compatibilizer, 0.4-1 part of first thermal antioxidant, 2-10 parts of first liquid rubber, 3-8 parts of dynamic vulcanizing agent, 1-4 parts of stannous chloride, 80-100 parts of continuous phase halogenated butyl rubber, 0.4-1 part of second thermo-oxidative agent, 2-6 parts of zinc oxide, 2-4 parts of stearic acid, 5-50 parts of carbon black, 5-40 parts of lamellar inorganic filler, 2-10 parts of second liquid rubber, 1-6 parts of anti-aging agent, 2-4 parts of protective wax, 2-5 parts of vulcanizing agent and 2-5 parts of vulcanization aid.
3. The method for preparing the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy according to claim 1, wherein the halogen content of the disperse phase halogenated butyl rubber and the halogen content of the continuous phase halogenated butyl rubber are respectively 0.3-1.8wt%, and the disperse phase halogenated butyl rubber and the continuous phase halogenated butyl rubber are respectively at least one selected from brominated butyl rubber, chlorinated butyl rubber and brominated polyisobutylene-p-methylstyrene rubber; the gas barrier resin is at least one selected from PA6, PA6/PA66 binary copolymer and EVOH.
4. The method for preparing a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy according to claim 1, wherein the compatibilizer is at least one selected from ethylene-methyl acrylate copolymer grafted glycidyl acrylate, polypropylene-maleic anhydride copolymer, styrene elastomer-maleic anhydride copolymer and maleic anhydride grafted polyolefin elastomer.
5. The method for preparing a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy according to claim 1, wherein the first liquid rubber and the second liquid rubber are at least one selected from the group consisting of liquid polyisobutylene rubber and liquid butyl rubber with viscosity average molecular weight of 10000-100000.
6. The method for preparing a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy according to claim 1, wherein the dynamic vulcanizing agent is at least one selected from the group consisting of thermal reaction type phenolic resin and brominated phenolic resin.
7. The preparation method of the rubber and plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy according to claim 1, wherein the first heat-resistant oxidizing agent and the second heat-resistant oxidizing agent are prepared by compounding a main antioxidant or a main antioxidant and an auxiliary antioxidant according to any proportion, wherein the main antioxidant is at least one selected from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester, 2' -sulfinyl ethylene glycol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 2H, 5H) -trione, and the auxiliary antioxidant is at least one selected from tri (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) diphosphite, bis (3-octadecyl) dithio) propionate, pentaerythritol dithio (3-dodecyl) dipropionate; The anti-aging agent is at least one selected from N-isopropyl-N '-phenyl p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl p-phenylenediamine, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid N-stearyl alcohol ester, 2, 4-trimethyl-1, 2-dihydroquinoline polymer and 2-mercaptobenzimidazole; the lamellar inorganic filler is at least one selected from double isopropyl oxide lamellar carbon, talcum powder, modified aluminum-magnesium hydrotalcite, modified clay and modified montmorillonite; The protective wax is selected from at least one of paraffin wax and microcrystalline wax.
8. A rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy, which is characterized by being prepared by adopting the preparation method of the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy as defined in any one of claims 1-7.
9. The tyre inner liner is characterized in that the rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy prepared by the method of any one of claims 1-7 is used as a raw material, and is prepared by extrusion into a sheet and calendaring.
10. The tire inner liner according to claim 9, wherein the tire inner liner is compounded with a transition layer or used alone as an inner liner, and is vulcanized with a belt layer, a ply layer, a bead, a sidewall rubber, a tread rubber, and an inter-tire rubber after tire molding to obtain a tire.

Description

Rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy, preparation method thereof and tire inner liner Technical Field The application relates to the technical field of high polymer materials, in particular to a rubber-plastic bicontinuous heterogeneous cross-linked dynamic vulcanized alloy, a preparation method thereof and an airtight layer of a tire. Background With the rapid development of the automobile industry, particularly new energy automobiles, higher requirements are also put forward on low rolling resistance, self-repairing technology, intelligent monitoring and other tire new technologies, the running of an electric automobile can be increased by 5% -8% when the rolling resistance of the tire is reduced by 10%, the rolling resistance can be reduced by structural optimization designs such as flattening of the tire, rim width and the like, and the rolling resistance of the tire can be reduced by improving the production process of the tire material, such as reducing molecular chain entanglement by a chemical rubber mixing process, and realizing the reduction of the rolling resistance of the tire by adopting measures such as matching of modified solution polymerized styrene-butadiene rubber and white carbon black. The inner liner of the tire is an air barrier layer provided on the inner surface of the tire to maintain the inner pressure of the tire, and a rubber composition made of butyl rubber or halogenated butyl rubber is generally used to provide the mechanical properties required for the inner liner of the tire and better gas barrier properties, but the conventional vulcanized halogenated butyl rubber technology has difficulty in improving the gas barrier properties, thinning the inner liner, and ensuring the pressure maintaining properties of the tire. The new inner liner material of dynamic vulcanized alloy material (DVA, dynamicallyVulcanizedAlloy) prepared by dynamic vulcanization of nylon resin and butyl rubber is firstly prepared by the Ekken Mobil company in the United states, halogenated butyl rubber is adopted as a material continuous phase, the nylon with the most dispersed phase is processed into a thinner inner liner according to the extrusion, casting or blow molding process of plastics, meanwhile, the material has high gas barrier property, the thinning and weight reduction design of the tire is realized, and the technology is initially applied to Japanese cross-shore tire company. Ethylene-vinyl alcohol copolymer (EVOH) has excellent gas barrier properties, and in the prior art, chinese patent application No. CN201180068893.8 discloses an ethylene-vinyl alcohol-based thermoplastic elastomer and vulcanized rubber, which are made of EVOH and butyl rubber or halogenated butyl rubber, etc. Although both the halogenated butyl rubber and the ethylene-vinyl alcohol copolymer are very excellent in air tightness, the thermoplastic vulcanizate prepared by the dynamic vulcanization process of the two is more excellent in air tightness. However, halogenated butyl rubber is less compatible with ethylene-vinyl alcohol copolymers, and thus, it is difficult for the halogenated butyl rubber/ethylene-vinyl alcohol copolymer system to improve the compatibility of the two and reduce the hardness. In the preparation of butyl rubber/ethylene vinyl alcohol TPV, compatibilizers are often added to improve both compatibility to obtain good performing articles. In the prior art, the Chinese patent application number CN201210509704.2 discloses a gas-blocking and steam-resistant EPDM/EVOH-MAA dynamic vulcanization thermoplastic elastomer, which is prepared by dynamically vulcanizing EPDM and EVOH-MAA, grafting ethylene propylene diene monomer rubber with maleic anhydride as a compatibilizer, improving the compatibility and preparing the DVA of an EVOH system. The DVA material which takes the barrier resin as a continuous phase and the vulcanized rubber as a disperse phase is prepared by using the butyl rubber and the barrier resin as main raw materials through compatibilizer optimization and dynamic vulcanization technology, and compared with the traditional halogenated butyl rubber, the DVA material has obvious advantages of gas barrier performance. Thinner film articles can be made by casting or blown film forming of plastics. However, such dynamically vulcanized thermoplastic elastomers having a single thermoplastic resin as the continuous phase are not compatible with existing tire building processes and equipment. According to the feeding, cutting and attaching modes of the coiled materials of the existing tire building machine, the butt joint and joint crimping adhesion of the traditional vulcanized halogenated butyl rubber inner liner material can be better realized due to unvulcanized rubber compound under normal temperature, the rubber compound flows under high pressure, and the joint is completely integrally formed after high-temperature vulcanization. The dynamic vulcani