CN113462092A - Rubber composition for curing bladder and preparation method thereof - Google Patents
Rubber composition for curing bladder and preparation method thereof Download PDFInfo
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- CN113462092A CN113462092A CN202110803270.6A CN202110803270A CN113462092A CN 113462092 A CN113462092 A CN 113462092A CN 202110803270 A CN202110803270 A CN 202110803270A CN 113462092 A CN113462092 A CN 113462092A
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- 239000005060 rubber Substances 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims abstract description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
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- 239000005011 phenolic resin Substances 0.000 claims description 24
- 229920001568 phenolic resin Polymers 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 18
- 229920005549 butyl rubber Polymers 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- -1 alkyl phenolic resin Chemical compound 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
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- 239000006230 acetylene black Substances 0.000 claims description 8
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
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- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
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- 150000001875 compounds Chemical class 0.000 claims description 4
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- 238000005303 weighing Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920005557 bromobutyl Polymers 0.000 claims description 3
- 229920005556 chlorobutyl Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229920005555 halobutyl Polymers 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002775 capsule Substances 0.000 abstract description 37
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
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- 230000002035 prolonged effect Effects 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 38
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- 238000012360 testing method Methods 0.000 description 17
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- HPTJCEPNQHYWIH-LDADJPATSA-N 3-hydroxy-n-[(e)-4-methylpentan-2-ylideneamino]naphthalene-2-carboxamide Chemical compound C1=CC=C2C=C(O)C(C(=O)N/N=C(C)/CC(C)C)=CC2=C1 HPTJCEPNQHYWIH-LDADJPATSA-N 0.000 description 10
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 9
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- 238000005336 cracking Methods 0.000 description 8
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- 235000019438 castor oil Nutrition 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241001441571 Hiodontidae Species 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
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- 239000004636 vulcanized rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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)
Abstract
The invention discloses a rubber composition for a curing bladder and a preparation method thereof. The rubber composition comprises the following main components: 100 to 120 parts of a rubber mixture containing at least one structural unit derived from isobutylene and a structural unit derived from a conjugated diene, 0.2 to 15 parts of a vulcanizing agent, 0.1 to 3 parts of a hydrazide or hydrazone represented by the formula 1, and 0.1 to 10 parts of a vulcanization accelerator. The hydrazide or hydrazone forms a complex bond with zinc oxide to generate a reversible network structure and play a role of a long-acting anti-aging agent, contributes to enhancing intermolecular acting force at high temperature, generates extra energy dissipation, and can form a complex bond with zinc oxideThe fatigue resistance and the tear resistance of the curing capsule are improved, and the service life of the curing capsule is prolonged. The rubber composition provided by the invention can obviously improve the heat resistance of the vulcanized capsule, improve the fatigue resistance, improve the tear resistance under a high-temperature condition and prolong the service life of the capsule by more than 10%.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber composition for a curing bladder and a preparation method thereof.
Background
The curing bladder is an important tool in the curing process in the production and manufacture of tires and is used as an inner mold for supporting a green tire. Specifically, the green tire is usually sleeved outside a vulcanization bladder, and during the vulcanization process, high-temperature compressed air, inert gas, superheated water and the like are continuously filled into the bladder to expand and extend the bladder, and a tire rubber blank is supported by internal pressure and vulcanized and molded. The service temperature of the capsule is generally 150-210 ℃, and the capsule is subjected to repeated stretching under the working condition, so the service life of the vulcanization capsule is directly influenced by the heat resistance, the high-temperature tearing resistance and the fatigue resistance. During the vulcanization process, the capsule undergoes repeated stretching deformation, the stretching and permanent deformation need to be balanced, if the stretching rate is too low, the service life is damaged, and if the stretching rate is too high, the resilience of the rubber compound can be influenced due to stress relaxation. The permanent deformation relates to the recovery degree of the capsule after repeated stretching, and the capsule can be broken if the permanent deformation is too large. Therefore, the strength and the crosslinking density of the rubber material are required to be considered on the premise of ensuring the elongation, and the capsule is required to be tested for heat-resistant oxidation, so that the quality and the service life of the capsule are always paid extensive attention to by the severe working environment.
At present, the common curing capsule is difficult to meet the market demand in service life, and the fundamental reason is that the formula design cannot well balance multiple performances, and no suitable new material is applied and developed in the curing capsule. To improve the service life of the capsules, the properties of the formulation must satisfy: (1) heat aging resistance; (2) the air tightness is high; (3) excellent flexure resistance; (4) resistance to hot tear; (5) high tensile while maintaining low permanent set.
At present, the capsule production basically uses butyl rubber, and the butyl rubber has high gas and steam barrier property and moisture tightness, so that the butyl rubber is suitable for repeatedly withstanding the severe conditions of continuous exchange of hot water, steam, compressed air and inert gas in the use process of the capsule, but the heat and aging resistance is influenced because unsaturated olefin still exists in the chemical structure of the butyl rubber. The traditional capsule adopts carbon black as a reinforcing material, which is not beneficial to high-temperature heat conduction and has long vulcanization time. In order to effectively shorten the vulcanization time of tire production and improve the productivity, the method generally adopts the method of reducing the thickness of the bladder but shortening the service life of the bladder; another feasible method is to blend materials with high thermal conductivity (such as acetylene black, graphene, carbon nanotubes, etc.) to replace part of carbon black, so as to improve the thermal conductivity of the composite material, but due to poor dispersibility, the formula of the curing capsule is difficult to balance, and the good service life can be maintained while the thermal conductivity is improved.
Disclosure of Invention
Based on the above background, in order to solve the problems of the prior art, the present invention discloses a rubber composition for a curing bladder and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a rubber composition for a curing bladder is prepared from the following raw materials: a rubber compound containing at least one structural unit derived from isobutylene and a structural unit derived from a conjugated diene, a vulcanizing agent, a hydrazide or hydrazone, a vulcanization accelerator;
the vulcanization accelerator is zinc oxide;
the hydrazide or hydrazone is represented by formula 1:
wherein R1 is independently selected from: an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an alkane group having 6 to 30 carbon atoms; r2 is independently selected from: hydrogen, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an alkane group having 6 to 30 carbon atoms; the aromatic hydrocarbon is optionally substituted with an alkyl group of 1 to 20 carbon atoms, a hydroxyl group or an amino group. The rubber mixture at least containing a structural unit derived from isobutene and a structural unit derived from conjugated diene has extremely low structural unsaturation degree, so that the rubber mixture has the properties of low air permeability, good moisture sealing performance and the like, and is beneficial to the good air tightness and steam resistance of the prepared vulcanized capsule.
Preferably, the rubber composition is prepared from the following raw materials in parts by mass: 100-120 parts of a rubber mixture containing at least one structural unit derived from isobutylene and a structural unit derived from a conjugated diene, 0.2-15 parts of a vulcanizing agent, 0.1-3 parts of a hydrazide or hydrazone, and 0.1-10 parts of a vulcanization accelerator.
The hydrazide or hydrazone is preferably (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide.
Preferably, the raw materials also comprise 30 to 150 parts of filler, 0 to 50 parts of softener and 0.1 to 20 parts of halogen donor;
more preferably, the raw materials comprise: 100-110 parts of rubber mixture at least containing one structural unit derived from isobutene and a structural unit derived from conjugated diene, 1-10 parts of vulcanizing agent, 0.2-2 parts of hydrazide or hydrazone, 1-8 parts of vulcanization accelerator, 40-120 parts of filler, 2-30 parts of softener and 1-15 parts of halogen donor.
Preferably, the structural unit derived from conjugated diene is isoprene, and the isoprene structural unit is a graft chain, and the other structural units of the rubber mixture are linear chains; the rubber mixture is more preferably at least one of butyl rubber and halogenated butyl rubber.
Further, the rubber mixture contains a structural unit derived from isobutylene and a structural unit derived from conjugated diene, at least part of the conjugated diene is isoprene, a molecular chain of the structural unit is a graft chain, and the rest of the molecular chain is a linear chain. In the present invention, "a structural unit derived from isobutylene" means that the structural unit is formed of isobutylene, and the atomic species and the number of each atom are the same as compared with isobutylene except that the electronic structure is changed. The structural unit derived from a conjugated diene "means that the structural unit is formed of a conjugated diene, and the species of atoms and the number of atoms are the same as compared with the conjugated diene except that the electronic structure is changed, and the conjugated diene means a compound having a conjugated double bond in the molecular structure.
Specific examples may include, but are not limited to, butadiene and/or isoprene. Further, one or more kinds of butyl rubbers are preferably mixed. In the rubber composition according to the present invention, in the butyl rubber, the structural unit derived from the conjugated diene may be a structural unit derived from isoprene or a combination of a structural unit derived from isoprene and a structural unit derived from other conjugated diene (such as butadiene) than isoprene.
Preferably, the vulcanizing agent is a phenolic resin vulcanizing agent, preferably an alkyl phenolic resin vulcanizing agent and/or a halogenated alkyl phenolic resin vulcanizing agent, and more preferably one of octyl phenolic resin and halogenated p-octyl phenolic resin or a mixture thereof.
According to the rubber composition of the present invention, the vulcanizing agent may be a substance capable of causing the butyl rubber to undergo a crosslinking reaction to form a three-dimensional network structure. According to the rubber composition of the present invention, the vulcanizing agent is preferably a phenol resin vulcanizing agent, and phenol resin is more suitable than a sulfur system as an effective vulcanizing agent for a rubber composition having extremely low unsaturation degree. Meanwhile, the heat aging resistance, the superheated steam resistance and the compression deformation resistance of the rubber can be improved by adopting a resin vulcanization system. The phenolic resin vulcanizing agent is preferably an alkyl phenolic resin (alkyl is positioned on a benzene ring of phenol) vulcanizing agent and/or a halogenated alkyl phenolic resin vulcanizing agent, more preferably a p-alkyl phenolic resin vulcanizing agent and/or a halogenated p-alkyl phenolic resin vulcanizing agent, and further preferably one or more than two of p-octyl phenolic resin, p-butyl phenolic resin, halogenated p-octyl phenolic resin and halogenated p-butyl phenolic resin, such as one or more than two of p-tert-octyl phenolic resin, p-tert-butyl phenolic resin and brominated p-tert-octyl phenolic resin.
Preferably, the vulcanization accelerator is zinc oxide.
Preferably, the raw material further comprises a filler; the filler is at least one of carbon black, acetylene black, carbon nanotubes, graphite and graphene;
preferably, the raw material further comprises a halogen donor; the halogen donor is preferably a halogen-containing polymer, and more preferably one or more of chloroprene rubber, vinyl chloride elastomer, chlorinated butyl rubber, and brominated butyl rubber.
The filler is at least one of carbon black, acetylene black, carbon nanotubes, graphite and graphene. The carbon black serving as an inorganic reinforcing filler is beneficial to maintaining the mechanical property of the processed and vulcanized rubber, has higher wear resistance and is beneficial to improving the quality of the vulcanized rubber capsule; acetylene black, carbon nanotubes, graphite and graphene are used for improving the heat conduction efficiency of the curing bladder.
Typical carbon blacks are N110, N115, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, N991. These carbon blacks have iodine absorptions of 5 to 150g/kg and DBP absorptions of 30 to 150cm3Characteristic of/100 g.
Further, carbon black having an average particle diameter of 20 to 30nm is preferable, and the carbon black may be one or two or more of high-reinforcing type carbon black and high-reinforcing type carbon black. Specific examples of the high-reinforcement type carbon black may include, but are not limited to, one or more of N110, N115, N121, N134, N220, N231, N234, and N242, and specific examples of the high-reinforcement type carbon black may include, but are not limited to, one or more of N326, N330, N339, N343, N347, N351, N358, and N375. In a preferred embodiment, the mass ratio of carbon black to acetylene black is (1-2): (0.5-1). Further, the mass of the mixture of carbon black and acetylene black is preferably 50 to 70 parts per 100 parts by mass of the butyl rubber.
The rubber composition according to the invention preferably further contains at least one softening agent to improve processability. The softener is one or a mixture of more of vegetable oil; castor oil is preferred, and the mass is preferably 2 to 20 parts. The castor oil of the invention is used as a softening agent, can improve the service life of the capsule, and the high boiling point (bp 226.8 ℃) of the castor oil is beneficial to keeping elongation under the condition of increasing temperature.
The rubber composition also contains a halogen donor to promote resin vulcanization and shorten the vulcanization time. The halogen donor may be a halogen-containing polymer, and specific examples thereof may include, but are not limited to: one or a combination of two or more of chloroprene rubber, vinyl chloride elastomer, chlorinated butyl rubber and brominated butyl rubber, and chloroprene rubber is preferable. The chloroprene rubber has good physical and mechanical properties, oil resistance, heat resistance, flame resistance, sunlight resistance, ozone resistance, acid and alkali resistance and chemical reagent resistance, and can be used as a catalyst in the crosslinking process of resin and rubber compositions.
The dosage of the halogen donor can be selected according to the dosage of the butyl rubber, so that the vulcanization speed of the butyl rubber can meet the requirement. Further, the amount by mass is preferably 2 to 12 parts per 100 parts by mass of the butyl rubber.
The invention also provides a preparation method of the rubber composition for the curing bladder, which comprises the following steps:
step (1): weighing the raw materials according to the raw material composition of the rubber composition for a curing bladder as defined in any one of claims 1 to 8;
step (2): mixing a rubber mixture, a halogen donor, hydrazide or hydrazone, a filler, a softener and a vulcanization accelerator in an internal mixer, and discharging to obtain a material A;
and (3): mixing the material A, the rest hydrazide or hydrazone, the filler, the softener and the vulcanization accelerator in an internal mixer, and discharging to obtain a material B;
and (4): after cooling the material B in the step (3), standing, adding a vulcanizing agent, the rest hydrazide or hydrazone and a vulcanization accelerator, mixing again, and discharging to obtain a material C;
and (5): and (4) vulcanizing the material C in the step (4) to obtain a rubber composition product.
Preferably, the filler and the softener are added in part or in whole in step (2) or step (3), and more preferably, the filler and the softener are added in whole in step (2).
Preferably, the hydrazide or hydrazone, the vulcanization accelerator may be added partially or completely in step (2) or step (3) or step (4); more preferably, the hydrazide or hydrazone is added in its entirety in step (3).
Preferably, the mixing time in the step (2) is 2-10 minutes, preferably 4-8 minutes, and the temperature during discharging is 130-190 ℃, preferably 150-170 ℃.
Preferably, the mixing time in the step (3) is 2-10 minutes, preferably 4-8 minutes, and the temperature during discharging is 130-190 ℃, preferably 150-170 ℃.
Preferably, the re-kneading time in the step (4) is 2 to 10 minutes, preferably 4 to 8 minutes, and the temperature at the time of discharging is 80 to 150 ℃, preferably 90 to 120 ℃.
Preferably, the vulcanization temperature in the step (5) is 130-220 ℃, preferably 160-200 ℃, and the vulcanization time is 10-100 minutes, preferably 30-80 minutes.
The preparation method of the rubber composition comprises the following steps: adding a rubber mixture of a structural unit derived from isobutene and a structural unit derived from conjugated diene, hydrazide or hydrazone, a filler, a vulcanization accelerator and other additives into an internal mixer, mixing, discharging, cooling, standing, adding a vulcanizing agent and the rest of the vulcanization accelerator, mixing again, discharging, and vulcanizing to obtain the rubber composition product.
The invention has the beneficial effects that: the rubber composition for the curing bladder can remarkably improve the heat resistance of the curing bladder, and is particularly beneficial to prolonging the service life of the curing bladder under high-temperature conditions. The hydrazide or hydrazone forms a complex bond with zinc oxide to generate a reversible network structure and play a role in long-acting anti-aging, contributes to enhancing intermolecular acting force at high temperature, generates extra energy dissipation, can improve the heat resistance, the fatigue resistance and the tear resistance at high temperature of the vulcanized capsule, and prolongs the service life of the vulcanized capsule.
Drawings
FIG. 1 is a schematic representation of a high temperature slow tear specimen.
Detailed Description
Hereinafter, the present invention will be described in more detail and specifically with reference to examples, but the following examples are not intended to limit the present invention.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The invention provides a rubber composition for a curing capsule, which is prepared from the following raw materials in parts by weight: 100 portions and 120 portions of butyl rubber; 8-12 parts of chloroprene rubber; 50-70 parts of carbon black (the carbon black is a mixture of carbon black N220 and acetylene carbon black in a mass ratio of (1-2): 0.5-1), 4-6 parts of castor oil, 1-2 parts of stearic acid, 1-6 parts of zinc oxide, 10-15 parts of vulcanized resin (the vulcanized resin is octylphenol formaldehyde resin), and 0.1-1 part of hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide).
Butyl rubber IIR268, IIR 301: asarundico family
Chloroprene rubber: electric chemistry of Japan
Carbon black N220: cabot
Acetylene black: hebei Xinrong carbon Black Co Ltd
Castor oil: hualong pharmaceutical Co Ltd, Henan province
Stearic acid: sichuan Tianyu oleochemical Co., Ltd
Zinc oxide: dalian Zinc oxide Co Ltd
Curing resin: huaqi chemical Co., Ltd
Hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide: otsuka chemical society
The sample preparation procedure of comparative example 1 and examples 1 and 2, comprising the following steps:
(1) weighing the raw materials according to the parts by weight of the rubber composition for the curing bladder.
(2) Premixing butyl rubber and chloroprene rubber in an internal mixer for 30s at 70 ℃ in advance according to the formula proportion, adding (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide, a mixture of carbon black N220 and acetylene carbon black, stearic acid and zinc oxide into the internal mixer for mixing, adding castor oil when the temperature reaches 120 ℃ in the process, mixing for 4 minutes, and discharging rubber when the temperature reaches above 160 ℃ to obtain the master batch.
(3) And (3) cooling the master batch, standing for 8 hours, adding half of the master batch into the internal mixer, mixing for 30 seconds, adding the other half of the master batch, and mixing for 4 minutes to discharge the master batch at the temperature of over 160 ℃.
(4) Cooling for 8 hours, adding the vulcanized resin for mixing again, quickly discharging rubber at about 110 ℃ for 4 minutes, tabletting, cooling, and naturally cooling to room temperature.
(5) The rubber composition product was obtained after vulcanization at 190 ℃ for 40 minutes, and then tested for relevant physical properties.
The sample preparation procedure of comparative example 2 and examples 3 and 4, comprising the following steps:
(1) weighing the raw materials according to the parts by weight of the rubber composition for the curing bladder.
(2) Premixing butyl rubber and chloroprene rubber in an internal mixer for 30s at 70 ℃ in advance according to the formula proportion, adding (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide, a mixture of carbon black N220 and acetylene carbon black and stearic acid into the internal mixer for mixing, adding castor oil when the temperature reaches 120 ℃ in the process, mixing for 4 minutes, and discharging rubber when the temperature reaches above 160 ℃ to obtain the master batch.
(3) And (3) cooling the master batch, standing for 8 hours, then putting half of the master batch and zinc oxide into an internal mixer, mixing for 30 seconds, then putting the other half of the master batch, and carrying out internal mixing for 4 minutes to achieve rubber discharge at the temperature of more than 160 ℃.
(4) Cooling for 8 hours, adding the vulcanized resin for mixing again, quickly discharging rubber at about 110 ℃ for 4 minutes, tabletting, cooling, and naturally cooling to room temperature.
(5) The rubber composition product was obtained after vulcanization at 190 ℃ for 40 minutes, and then tested for relevant physical properties.
The following examples are given for the standard and method of testing the rubber compositions of the present invention, and the test results are expressed in terms of indices:
1) mooney viscosity: referring to ASTM D1646-2007, the test conditions were ML (1+4)100 ℃. (example Mooney viscosity/comparative Mooney viscosity) x 100%, the larger the index the higher the Mooney viscosity.
2) Mooney scorching: with reference to ASTM D1646-2007, the test temperature was 130 ℃. (example Mooney scorch/comparative Mooney scorch) x 100%, the larger the index the longer the scorch time.
3) Shore A hardness: shore hardness test, according to ASTM D2240-2010, the test environment temperature is 23 +/-2 ℃. (example hardness/comparative hardness) x 100%, the higher the index the higher the hardness.
4) MA 100: the 100% tensile modulus was measured according to ASTM D412-2006, and the test environment temperature was 23. + -. 2 ℃ when the modulus was taken at a tensile ratio of 100%. (example MA 100/comparative example MA 100). times.100%, the higher the index the higher the tensile modulus.
5) Tensile strength and elongation at break: referring to ASTM D412-2006, the samples were dumbbell-shaped, testing speed 500mm/min, and testing ambient temperature 23 + -2 deg.C. (tensile strength and elongation at break of examples/tensile strength and elongation at break of comparative examples) x 100%, the larger the index the higher the tensile strength and elongation at break.
6) Tear strength: referring to ASTM D624-2007, a right-angle shaped test specimen is adopted, the test speed is 500mm/min, and the test environment temperature is 23 +/-2 ℃. (example tear strength/comparative example tear strength) x 100%, the larger the index the higher the tear strength.
7) Permanent deformation: with reference to ISO 2285: 2013, adopting a dumbbell-shaped sample, and testing at a speed of 500mm/min and at a test environment temperature of 23 +/-2 ℃. (example permanent set/comparative example permanent set) x 100%, the smaller the index the lower the degree of permanent set.
8) Airtightness: referring to GB/T7755-2003, a round sample with required size is cut, the experimental pressure is 0.1MPa, and the test environment temperature is 40 +/-2 ℃. (example airtightness/comparative example airtightness) x 100%, the smaller the index, the better the airtightness.
9) Determination of flex-cracking and crack growth (dermaska subtype): referring to GB/T13934-. The number of cracks is compared and graded according to the standard GB/T13934-2006. (number of thousand cycles required for the example to achieve a grade 6 crack rating/number of thousand cycles required for the comparative example to achieve a grade 6 crack rating) x 100%, the greater the index the better the flex crack resistance.
10) High temperature slow tear energy: a specimen having a width of 40mm, a height of 65mm and a notch of 10mm (see FIG. 1) was used, the test speed was 50mm/min, and the test environment temperature was 180. + -. 5 ℃. (high temperature slow tear energy for example/high temperature slow tear energy for comparative example) x 100%, the higher the index the higher the high temperature tear energy.
11) Crosslinking density: the equilibrium swelling method is carried out at room temperature, and the solvent is toluene. (example crosslink Density/comparative example crosslink Density) x 100%, the greater the index the higher the crosslink density.
And the crosslinking density gamma (mol/cm) was calculated according to the Flory-Rehner equation (formula 1)3)：
Wherein Vr is the volume fraction of the rubber phase in the swollen rubber; vs is the molar volume of solvent (mL/mol); λ is the interaction parameter of the solvent and polymer, 0.314; gamma is the crosslink density of the vulcanizate.
Calculating Vr according to equation 2:
wherein WdMass (g) of the swollen sample after drying; wsMass (g) after swelling of the sample; w0Is the initial mass (g) of the sample; b is the mass fraction of the filler in the formula; ρ r is rubber density (g/mL); ρ s is the solvent density (g/mL).
12) Average life index of capsule (number of possible normal cures): tire vulcanization conditions (internal temperature 210 ℃ C., vulcanization time 20 min). (example actual factory capsule average life/comparative actual factory capsule average life) x 100%, the larger the index the higher the actual factory capsule average life index.
The raw materials used in comparative examples 1 and 2 and examples 1 to 4 of the present invention are shown in table 1 below, all by mass:
table 1: raw materials of comparative examples 1 and 2 and examples 1 to 4
Example 1 increased (E) -3-hydroxy-N '- (4-methylpentane-2-ylidene) -2-naphthohydrazide by 0.6 parts compared to comparative example 1, and example 2 increased (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide by 1 part compared to comparative example 1. Example 3 increased 0.6 part of (E) -3-hydroxy-N '- (4-methylpentane-2-ylidene) -2-naphthohydrazide compared to comparative example 2, and example 4 increased 1 part of (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide compared to comparative example 2. And compared with the comparative example 1 and the examples 1 and 2, the feeding sequence of the zinc oxide is changed in the comparative example 2 and the examples 3 and 4.
For comparative examples 1 and 2 and examples 1 to 4, performance tests were performed without aging, after aging at 100 ℃ x48h, and after aging at 180 ℃ x48h, respectively, and the results are shown in table 2 below.
Table 2: comparison of Performance results for comparative examples 1, 2 and examples 1-4
The test results of the rubber composition are expressed in the form of indexes
Compared with comparative example 1, in the case of the examples 1 and 2, the hardness change is not large, the crosslinking density is slightly reduced, but the air tightness is improved, and the permanent deformation is slightly increased; modulus, tensile strength, elongation at break and tearing strength are all improved, the increasing amplitude of flex cracking and cracking is over 20%, and the increasing amplitude of high-temperature slow tearing is over 30%. And compared with example 1, in example 2, except that the modulus is slightly reduced, the flex cracking and the cracking are increased, and the high-temperature slow tearing energy is increased by more remarkably 45% and 5% on the basis of example 1 respectively. After aging, the examples 1 and 2 still maintain good mechanical properties and air tightness, and the increase of flex cracking and cracks is more remarkable compared with the comparative example 1. Especially after the curing at 180 ℃ and 48 times 48h, the fatigue property of the example 2 is improved by nearly 10 times, which is mainly because the complex bond formed by the (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide and the zinc oxide generates a reversible network structure which is helpful for enhancing intermolecular acting force under the condition of high temperature, generates additional energy dissipation, remarkably improves the fatigue resistance and prolongs the service life of the vulcanized capsule.
After the feeding sequence of zinc oxide is changed, compared with comparative example 1 and examples 1 and 2, the hardness, modulus and permanent deformation of comparative example 2 and examples 3 and 4 are reduced, and the tensile strength and elongation at break are improved. Compared with comparative example 2, examples 3 and 4 have increased hardness, slightly decreased crosslinking density, decreased air tightness, increased modulus, tensile strength, elongation at break, increased flexural cracking and tearing of tearing strength, and improved high-temperature and slow-speed tearing performance. After aging, the increase in flex cracking and crack growth was more significant for examples 3 and 4 compared to comparative example 2. Along with harsher high-temperature aging conditions, the addition amount of the (E) -3-hydroxy-N '- (4-methylpentane-2-ylidene) -2-naphthoyl hydrazide is increased, and the fatigue characteristics of the examples 3 and 4 are more excellent, mainly because the zinc oxide and the (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthoyl hydrazine form a complex bond to generate a reversible network structure, which is beneficial to enhancing the acting force between molecules at high temperature, generating extra energy dissipation, playing a role in long-acting aging prevention and obviously improving the heat resistance; the addition of zinc oxide in the second rubber mixing stage is more beneficial to improving the permanent deformation after high-temperature aging, and the network structures can obviously improve the fatigue resistance and the tear resistance under the high-temperature condition and prolong the service life of the curing capsule.
The service life of the vulcanized capsules manufactured in comparative examples 1 and 2 and examples 1 to 4 was tested under the same conditions, and the results are shown in the following table 3:
table 3: comparative examples 1 and 2 and comparative examples 1 to 4 for service life of curing bladder
The life of example 1 was 8% longer than the average life of the curing bladder prepared in comparative example 1, the life of example 2 was 14% longer than the average life of the curing bladder prepared in comparative example 1, the life of example 3 was 10% longer than the average life of the curing bladder prepared in comparative example 2, and the life of example 4 was 15% longer than the average life of the curing bladder prepared in comparative example 2. Thus, rubber compositions containing (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthohydrazide are particularly useful for extending the service life of the curing bladder under high temperature conditions.
The comparison of the test results can lead to the conclusion that: the hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthoyl hydrazine forms a complex bond with zinc oxide to generate a reversible network structure and play a role of a long-acting anti-aging agent, contributes to enhancing intermolecular acting force at high temperature, generates extra energy dissipation, can improve the heat resistance, fatigue resistance and tear resistance of the vulcanized capsule, and prolongs the service life of the vulcanized capsule. Compared with the comparative example, the service life of the capsule can be prolonged by more than 10%, so that the method has good economic benefit and improves the production efficiency and yield of tire factories. The hydrazide or hydrazone is particularly suitable for curing capsules used under high-temperature conditions, and prolongs the service life of the capsules under severe high-temperature conditions.
In addition, the technical scope of the present invention is not limited to the content of the specification, and although the specification describes the embodiments, not every embodiment includes only one independent technical solution, and such description of the specification is only for clarity. Various changes and modifications can be made by those skilled in the relevant art without departing from the scope of the technical idea of the present invention, and the technical solutions in the embodiments are appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims (10)
1. A rubber composition for a curing bladder is characterized by being prepared from the following raw materials: a rubber compound containing at least one structural unit derived from isobutylene and a structural unit derived from a conjugated diene, a vulcanizing agent, a hydrazide or hydrazone, a vulcanization accelerator;
the vulcanization accelerator is zinc oxide;
the hydrazide or hydrazone is represented by formula 1:
wherein R1 is independently selected from: an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an alkane group having 6 to 30 carbon atoms; r2 is independently selected from: hydrogen, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an alkane group having 6 to 30 carbon atoms; the aromatic hydrocarbon is optionally substituted with an alkyl group of 1 to 20 carbon atoms, a hydroxyl group or an amino group.
2. The rubber composition according to claim 1, which is prepared from the following raw materials in parts by mass: 100-120 parts of a rubber mixture containing at least one structural unit derived from isobutylene and a structural unit derived from a conjugated diene, 0.2-15 parts of a vulcanizing agent, 0.1-3 parts of a hydrazide or hydrazone, and 0.1-10 parts of a vulcanization accelerator.
3. The rubber composition according to claim 2, wherein the raw material further comprises 30 to 150 parts of a filler, 0 to 50 parts of a softener, 0.1 to 20 parts of a halogen donor;
more preferably, the raw materials comprise: 100-110 parts of rubber mixture at least containing one structural unit derived from isobutene and a structural unit derived from conjugated diene, 1-10 parts of vulcanizing agent, 0.2-2 parts of hydrazide or hydrazone, 1-8 parts of vulcanization accelerator, 40-120 parts of filler, 2-30 parts of softener and 1-15 parts of halogen donor.
4. The rubber composition according to any one of claims 1 to 3, wherein the structural unit derived from a conjugated diene is isoprene, and the isoprene structural unit is a graft chain, and the other structural units of the rubber mixture are linear chains; the rubber mixture is more preferably at least one of butyl rubber and halogenated butyl rubber.
5. The rubber composition according to any one of claims 1 to 3, wherein: the vulcanizing agent is a phenolic resin vulcanizing agent, preferably an alkyl phenolic resin vulcanizing agent and/or a halogenated alkyl phenolic resin vulcanizing agent, and more preferably one or a mixture of octyl phenolic resin and halogenated p-octyl phenolic resin.
6. The rubber composition according to any one of claims 1 to 3, wherein:
the raw materials also comprise a filler; the filler is at least one of carbon black, acetylene black, carbon nanotubes, graphite and graphene;
the feedstock further comprises a halogen donor; the halogen donor is preferably a halogen-containing polymer, and more preferably one or more of chloroprene rubber, vinyl chloride elastomer, chlorinated butyl rubber, and brominated butyl rubber.
7. A method for preparing a rubber composition for a curing bladder, comprising the steps of:
step (1): weighing the raw materials according to the raw material composition of the rubber composition for a curing bladder as defined in any one of claims 1 to 8;
step (2): mixing a rubber mixture, a halogen donor, hydrazide or hydrazone, a filler, a softener and a vulcanization accelerator in an internal mixer, and discharging to obtain a material A;
and (3): mixing the material A, the rest hydrazide or hydrazone, the filler, the softener and the vulcanization accelerator in an internal mixer, and discharging to obtain a material B;
and (4): after cooling the material B in the step (3), standing, adding a vulcanizing agent, the rest hydrazide or hydrazone and a vulcanization accelerator, mixing again, and discharging to obtain a material C;
and (5): and (4) vulcanizing the material C in the step (4) to obtain a rubber composition product.
8. The preparation method according to claim 7, wherein the mixing time in the step (2) and the step (3) is 2-10 minutes, preferably 4-8 minutes, and the temperature at the time of discharging is 130-190 ℃, preferably 150-170 ℃; the filler and the softener can be partially or completely added in the step (2) or the step (3); the hydrazide or hydrazone, the vulcanization accelerator may be added partially or entirely in step (2) or step (3) or step (4).
9. The method according to claim 7, wherein the remixing time in the step (4) is 2 to 10 minutes, preferably 4 to 8 minutes, and the temperature at the time of discharging is 80 to 150 ℃, preferably 90 to 120 ℃.
10. The preparation method according to claim 7, wherein the vulcanization temperature in step (5) is 130-220 ℃, preferably 160-200 ℃, and the vulcanization time is 10-100 minutes, preferably 30-80 minutes.
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|---|---|---|---|---|
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029814A1 (en) * | 2006-09-04 | 2008-03-13 | Bridgestone Corporation | Rubber composition and pneumatic tire using the same |
| CN102942744A (en) * | 2012-10-12 | 2013-02-27 | 天津鹏翎胶管股份有限公司 | Ethylene-propylene-diene monomer mould pressing abnormal shape sponge sheath rubber composition |
| CN103261300A (en) * | 2010-12-21 | 2013-08-21 | 米其林集团总公司 | Composition based on natural rubber and carbon black comprising hydrazide, hydrazone and polyamine |
| CN103333416A (en) * | 2013-07-30 | 2013-10-02 | 广州市骏怡汇汽车科技有限公司 | Environment-friendly sulfur-free foaming material as well as preparation method and application of environment-friendly sulfur-free foaming material |
| CN104558713A (en) * | 2013-10-25 | 2015-04-29 | 东洋橡胶工业株式会社 | Rubber composition |
| CN105073844A (en) * | 2013-03-28 | 2015-11-18 | 株式会社普利司通 | Method for producing rubber composition, and rubber composition |
| CN105400087A (en) * | 2015-12-08 | 2016-03-16 | 南京亚通橡塑有限公司 | Long-service-life tire curing bladder and production technology thereof |
| WO2018045987A1 (en) * | 2016-09-07 | 2018-03-15 | 中国石油化工股份有限公司 | Butyl rubber, preparation method therefor, and rubber product, composition and application thereof, and automobile tire inner liner, tube and curing bladder |
| CN110240761A (en) * | 2018-03-08 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of rubber composition and its application and a kind of curing bag and preparation method thereof |
| CN110283364A (en) * | 2019-07-03 | 2019-09-27 | 大冢材料科技（上海）有限公司 | A kind of rubber composition and preparation method thereof for safety tread sidewall |
| CN111961290A (en) * | 2020-07-31 | 2020-11-20 | 赛轮集团股份有限公司 | Low-zinc tire inner liner rubber and preparation method thereof |
-
2021
- 2021-07-15 CN CN202110803270.6A patent/CN113462092B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029814A1 (en) * | 2006-09-04 | 2008-03-13 | Bridgestone Corporation | Rubber composition and pneumatic tire using the same |
| CN103261300A (en) * | 2010-12-21 | 2013-08-21 | 米其林集团总公司 | Composition based on natural rubber and carbon black comprising hydrazide, hydrazone and polyamine |
| CN102942744A (en) * | 2012-10-12 | 2013-02-27 | 天津鹏翎胶管股份有限公司 | Ethylene-propylene-diene monomer mould pressing abnormal shape sponge sheath rubber composition |
| CN105073844A (en) * | 2013-03-28 | 2015-11-18 | 株式会社普利司通 | Method for producing rubber composition, and rubber composition |
| CN103333416A (en) * | 2013-07-30 | 2013-10-02 | 广州市骏怡汇汽车科技有限公司 | Environment-friendly sulfur-free foaming material as well as preparation method and application of environment-friendly sulfur-free foaming material |
| CN104558713A (en) * | 2013-10-25 | 2015-04-29 | 东洋橡胶工业株式会社 | Rubber composition |
| CN105400087A (en) * | 2015-12-08 | 2016-03-16 | 南京亚通橡塑有限公司 | Long-service-life tire curing bladder and production technology thereof |
| WO2018045987A1 (en) * | 2016-09-07 | 2018-03-15 | 中国石油化工股份有限公司 | Butyl rubber, preparation method therefor, and rubber product, composition and application thereof, and automobile tire inner liner, tube and curing bladder |
| CN110240761A (en) * | 2018-03-08 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of rubber composition and its application and a kind of curing bag and preparation method thereof |
| CN110283364A (en) * | 2019-07-03 | 2019-09-27 | 大冢材料科技（上海）有限公司 | A kind of rubber composition and preparation method thereof for safety tread sidewall |
| CN111961290A (en) * | 2020-07-31 | 2020-11-20 | 赛轮集团股份有限公司 | Low-zinc tire inner liner rubber and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230870A (en) * | 2021-12-22 | 2022-03-25 | 赛轮(沈阳)轮胎有限公司 | Formula for prolonging service life of capsule of forming machine |
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