CN113462092B - Rubber composition for curing capsules and preparation method thereof - Google Patents
Rubber composition for curing capsules and preparation method thereof Download PDFInfo
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- CN113462092B CN113462092B CN202110803270.6A CN202110803270A CN113462092B CN 113462092 B CN113462092 B CN 113462092B CN 202110803270 A CN202110803270 A CN 202110803270A CN 113462092 B CN113462092 B CN 113462092B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 239000002775 capsule Substances 0.000 title abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004073 vulcanization Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 150000007857 hydrazones Chemical class 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229920001568 phenolic resin Polymers 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000006229 carbon black Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229920005549 butyl rubber Polymers 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 10
- 239000004359 castor oil Substances 0.000 claims description 9
- 235000019438 castor oil Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 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 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 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 claims description 3
- MCPSMQGVSYDFLC-UHFFFAOYSA-N formaldehyde;2-octylphenol Chemical group O=C.CCCCCCCCC1=CC=CC=C1O MCPSMQGVSYDFLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 12
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000003712 anti-aging effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 37
- 238000012360 testing method Methods 0.000 description 21
- 239000005011 phenolic resin Substances 0.000 description 19
- 235000019241 carbon black Nutrition 0.000 description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 13
- 150000001993 dienes Chemical class 0.000 description 12
- -1 isoprene hydrocarbon Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000006230 acetylene black Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 10
- 239000004594 Masterbatch (MB) Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006235 reinforcing carbon black Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229920005557 bromobutyl Polymers 0.000 description 2
- 229920005556 chlorobutyl Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance 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
- 239000004215 Carbon black (E152) Substances 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
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007963 capsule composition Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000002955 isolation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 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
- 238000004513 sizing Methods 0.000 description 1
- 241000894007 species Species 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 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
- C08L23/02—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
Abstract
The invention discloses a rubber composition for curing a capsule and a preparation method thereof. The rubber composition mainly comprises the following components: 100-120 parts of a rubber mixture containing at least one structural unit derived from isobutylene, 0.2-15 parts of a vulcanizing agent, 0.1-3 parts of a hydrazide or hydrazone represented by formula 1, and 0.1-10 parts of a vulcanization accelerator. The hydrazide or the hydrazone forms a complex bond with the zinc oxide to generate a reversible network structure and plays a role of a long-acting anti-aging agent, so that the acting force among molecules can be enhanced under the high temperature condition, extra energy dissipation is generated, the fatigue resistance and the tearing resistance of the vulcanized capsule can be improved, and the service life of the vulcanized capsule is prolonged. The rubber composition can obviously improve the heat resistance of the vulcanized capsule, improve the fatigue resistance, improve the tear resistance under the high temperature condition and prolong the service life of the capsule by more than 10 percent.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber composition for curing a capsule and a preparation method thereof.
Background
The curing bladder is an important tool in the curing process in the 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 capsule, high-temperature compressed air, inert gas, superheated water and the like are continuously filled into the capsule in the vulcanization process, so that the green tire is inflated and stretched, and the rubber blank of the tire is propped up by internal pressure, and is vulcanized and molded. The use temperature of the capsule is generally 150-210 ℃, and the working condition is subjected to repeated stretching, so that the heat resistance, the high-temperature tearing resistance and the fatigue resistance directly influence the service life of the vulcanized capsule. The capsule undergoes repeated stretching deformation in the vulcanization process, the stretching and permanent deformation need to be balanced with each other, if the stretching rate is too low, the service life is damaged, and if the stretching rate is too high, the reversion of the rubber material is possibly influenced by stress relaxation. The permanent deformation is related to the recovery degree of the capsule after repeated stretching, and the permanent deformation is too large, so that the capsule is likely to be folded. Therefore, the strength and the crosslinking density of the sizing material are also required to be considered on the premise of ensuring the elongation, and meanwhile, the capsules are required to be subjected to heat and oxidization resistance, so that the quality and the service life of the capsules are always widely focused due to the severe working environment.
At present, the common curing bladder has difficulty in meeting the market demand in terms of service life, and the root cause is that the formula design cannot well balance a plurality of performances, and no suitable new material is applied and developed in the curing bladder. To increase the life of the capsule the performance of the formulation must be: (1) heat aging resistance; (2) higher gas tightness; (3) excellent flexure resistance; (4) hot tear resistance; (5) high stretch while maintaining low permanent set.
At present, butyl rubber is basically used in capsule production, and the butyl rubber has the characteristics of higher gas and steam isolation and moisture tightness, is suitable for severe conditions of repeated hot water, steam, compressed air and inert gas exchange in the capsule use process, but the heat aging resistance can be influenced due to unsaturated olefin in the chemical structure. And the traditional capsule adopts carbon black as a reinforcing material, which is unfavorable for high-temperature heat conduction and has long vulcanization time. In order to effectively shorten the vulcanization time of tire production and improve productivity, the method generally adopted is to reduce the thickness of the capsule, but shorten the service life of the capsule; another possible method is to blend a material with a high thermal conductivity (e.g., acetylene black, graphene, carbon nanotubes, etc.) to replace a portion of the carbon black, thereby improving the thermal conductivity of the composite material, but due to its poor dispersibility, it is difficult to balance the vulcanization capsule formulation while improving the thermal conductivity and maintaining a good service life.
Disclosure of Invention
Based on the background, the invention discloses a rubber composition for curing a capsule and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a rubber composition for curing a bladder is prepared from the following raw materials: a rubber mixture comprising 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 shown in 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 comprises a structural unit derived from isobutene and a structural unit derived from conjugated diene, has extremely low structural unsaturation, has the properties of low air permeability, good moisture tightness 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 weight: 100-120 parts of a rubber mixture containing at least one structural unit derived from isobutylene and a structural unit derived from 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-methylpentan-2-ylidene) -2-naphthalic hydrazide.
Preferably, the raw materials further comprise 30-150 parts of filler, 0-50 parts of softener and 0.1-20 parts of halogen donor;
more preferably, the raw materials include: 100-110 parts of a rubber mixture containing at least one structural unit derived from isobutylene and a structural unit derived from conjugated diene, 1-10 parts of a vulcanizing agent, 0.2-2 parts of a hydrazide or hydrazone, 1-8 parts of a vulcanization accelerator, 40-120 parts of a filler, 2-30 parts of a softener and 1-15 parts of a 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 a conjugated diene, at least a part of the conjugated diene is isoprene, a molecular chain of the structural unit is a graft chain, and the remaining part of the molecular chain is a linear chain. In the present invention, the term "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 except that the electronic structure of the structural unit is changed as compared with isobutylene. The term "structural unit derived from conjugated diene" means that the structural unit is formed of conjugated diene, and the conjugated diene means a compound having a conjugated double bond in its molecular structure, except that the electron structure is changed, and the number of atoms is the same.
Specific examples may include, but are not limited to, butadiene and/or isoprene. Further, it is preferable that one or more of butyl rubber are mixed. In the rubber composition according to the present invention, the structural unit derived from the conjugated diene may be structural units derived from isoprene hydrocarbon or may be a combination of structural units derived from isoprene and structural units derived from other conjugated dienes (e.g., butadiene) other 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, more preferably one of octyl phenolic resin, 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 a butyl rubber to undergo a crosslinking reaction to form a three-dimensional network structure. The vulcanizing agent is preferably a phenolic resin vulcanizing agent, and phenolic resin is more suitable than sulfur system as an effective vulcanizing agent for a rubber composition having extremely low unsaturation. Meanwhile, the resin vulcanization system can improve the heat aging resistance, the superheated steam resistance and the compression deformation resistance of the rubber. The phenolic resin vulcanizing agent is preferably an alkyl phenolic resin (alkyl group is located on benzene ring of phenol) vulcanizing agent and/or a halogenated alkyl phenolic resin vulcanizing agent, more preferably a para-alkyl phenolic resin vulcanizing agent and/or a halogenated para-alkyl phenolic resin vulcanizing agent, further preferably one or more of a para-octyl phenolic resin, a para-butyl phenolic resin, a halogenated para-octyl phenolic resin and a halogenated para-butyl phenolic resin, such as one or more of a para-tert-octyl phenolic resin, a para-tert-butyl phenolic resin and a brominated para-tert-octyl phenolic resin.
Preferably, the vulcanization accelerator is zinc oxide.
Preferably, the raw materials further comprise 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, more preferably one or more of chloroprene rubber, a vinyl chloride elastomer, chlorinated butyl rubber and brominated butyl rubber.
The filler provided by the invention is at least one of carbon black, acetylene black, carbon nanotubes, graphite and graphene. The carbon black as an inorganic reinforcing filler is beneficial to maintaining the mechanical properties of the processed and vulcanized rubber, has higher wear resistance and is beneficial to improving the quality of vulcanized capsules; acetylene black, carbon nanotubes, graphite and graphene are used for improving the heat conduction efficiency of the vulcanization capsule.
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. This isThe carbon blacks have iodine absorption values of 5-150g/kg and DBP absorption values of 30-150cm 3 100 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 highly reinforcing carbon black and medium and highly reinforcing carbon black. Specific examples of the highly reinforcing carbon black may include, but are not limited to, one or two or more of N110, N115, N121, N134, N220, N231, N234, N242, and specific examples of the medium highly reinforcing carbon black may include, but are not limited to, one or two 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 carbon black and acetylene black mixture is preferably 50 to 70 parts with respect to 100 parts by mass of the butyl rubber.
The rubber composition according to the invention preferably further comprises at least one softener to improve processability. The softener is one or more of vegetable oil; preferably castor oil, preferably 2-20 parts by mass. The castor oil provided by the invention is used as a softener, so that the service life of the capsule can be prolonged, and the high boiling point (bp 226.8 ℃) of the castor oil is favorable for keeping elongation under the condition of temperature rise.
The rubber composition further contains a halogen donor to promote vulcanization of the resin and shorten the vulcanization time. The halogen donor may be a halogen-containing polymer, specific examples of which may include, but are not limited to: one or a combination of two or more of neoprene, vinyl chloride elastomer, chlorinated butyl rubber and brominated butyl rubber, preferably neoprene. The neoprene 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 amount of halogen donor may be selected according to the amount of butyl rubber so that the vulcanization rate of butyl rubber meets the requirements. Further, the mass is preferably 2 to 12 parts with respect to 100 parts by mass of butyl rubber.
The invention also provides a preparation method of the rubber composition for curing the capsule, which comprises the following steps:
step (1): weighing raw materials for the raw material composition of the rubber composition for a vulcanization bladder according to any one of claims 1 to 8;
step (2): mixing the rubber mixture, the halogen donor, the hydrazide or hydrazone, the filler, the softener and the vulcanization accelerator in an internal mixer, and discharging to obtain a material A;
step (3): mixing the material A, the rest of hydrazide or hydrazone, a filler, a softener and a vulcanization accelerator in an internal mixer, and discharging to obtain a material B;
step (4): cooling the material B in the step (3), standing, adding a vulcanizing agent and the rest of hydrazide or hydrazone, and discharging after mixing again to obtain a material C;
step (5): and (3) vulcanizing the material C in the step (4) to obtain a rubber composition product.
Preferably, the filler and the softener may be 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 and the vulcanization accelerator are added in part or in whole in the step (2) or the step (3) or the step (4); more preferably, the hydrazide or hydrazone is added in step (3) in its entirety.
Preferably, the mixing time in the step (2) is 2-10 minutes, preferably 4-8 minutes, and the temperature at the time of 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 at the time of discharging is 130-190 ℃, preferably 150-170 ℃.
Preferably, the re-mixing 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 vulcanizing temperature of the step (5) is 130-220 ℃, preferably 160-200 ℃, and the vulcanizing 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 structural units derived from isobutene, hydrazide or hydrazone, a filler, a vulcanization accelerator and other additives into an internal mixer, mixing and discharging, cooling and standing, adding a vulcanizing agent and the rest vulcanization accelerator, mixing again, discharging, and vulcanizing to obtain a rubber composition product.
The beneficial effects of the invention are as follows: 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 the zinc oxide to generate a reversible network structure and plays a role in long-acting aging prevention, so that the acting force among molecules can be enhanced under the high temperature condition, extra energy dissipation is generated, the heat resistance, fatigue resistance and tear resistance of the vulcanized capsule under the high temperature can be improved, and the service life of the vulcanized capsule is prolonged.
Drawings
FIG. 1 is a schematic illustration of a high temperature slow tear specimen.
Detailed Description
Hereinafter, the present invention will be described in more detail and in detail with reference to examples, but the following examples are not intended to limit the present invention.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
The invention provides a rubber composition for curing capsules, which is prepared from the following raw materials in parts by weight: 100-120 parts 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 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 octyl phenol formaldehyde resin), and 0.1-1 part of hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentane-2-subunit) -2-naphthalic hydrazide.
Butyl rubber IIR268, IIR301: araneaceae (Araneceae)
Neoprene: japanese electric chemistry
Carbon black N220: kabote
Acetylene black: hebei Xin Rong Tanhei Co., ltd
Castor oil: henan Hualong pharmaceutical Co., ltd
Stearic acid: sichuan Tianyu oil chemistry Co., ltd
Zinc oxide: dalian Zinc oxide Co Ltd
Vulcanized resin: hua Ji chemical Co., ltd
Hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentan-2-ylidene) -2-naphthalic hydrazide: otsuka chemical Co., ltd
The sample preparation schemes of comparative example 1 and examples 1,2 include the following steps:
(1) The respective raw materials were weighed in parts by weight of a rubber composition for curing a bladder.
(2) Pre-mixing 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-subunit) -2-naphthalic hydrazide, a mixture of carbon black N220 and acetylene 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 more than 160 ℃ to obtain the master batch.
(3) After the masterbatch is cooled and stood for 8 hours, half of the masterbatch is put into an internal mixer, mixed for 30 seconds, and the other half of the masterbatch is put into the internal mixer for banburying for 4 minutes, and the temperature reaches more than 160 ℃ for discharging.
(4) Cooling for 8 hours, adding vulcanized resin, mixing again, discharging glue rapidly at about 110 ℃ for 4 minutes, tabletting, cooling, and naturally cooling to room temperature.
(5) After curing at 190℃for 40 minutes, a rubber composition product was obtained, which was then tested for relevant physical properties.
Comparative example 2 and example 3,4 sample preparation procedure comprising the steps of:
(1) The respective raw materials were weighed in parts by weight of a rubber composition for curing a bladder.
(2) Pre-mixing 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-subunit) -2-naphthalic hydrazide, a mixture of carbon black N220 and acetylene 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 more than 160 ℃ to obtain the master batch.
(3) After the masterbatch is cooled and stood for 8 hours, putting half of the masterbatch and zinc oxide into an internal mixer, mixing for 30 seconds, putting the other half of the masterbatch into the internal mixer, and carrying out internal mixing for 4 minutes until the temperature reaches 160 ℃ or above, and discharging the masterbatch.
(4) Cooling for 8 hours, adding vulcanized resin, mixing again, discharging glue rapidly at about 110 ℃ for 4 minutes, tabletting, cooling, and naturally cooling to room temperature.
(5) After curing at 190℃for 40 minutes, a rubber composition product was obtained, which was then tested for relevant physical properties.
The standards and methods for testing the rubber compositions of the present invention in the following examples are as follows, and the test results are all expressed in an exponential form:
1) Mooney viscosity: referring to ASTM D1646-2007, test conditions are ML (1+4) 100deg.C. (example Mooney viscosity/comparative Mooney viscosity) x100%, the greater the index the higher the Mooney viscosity.
2) Mooney scorch: with reference to ASTM D1646-2007, the test temperature is 130 ℃. (example mooney scorch/comparative mooney scorch) x100%, the greater the index the longer the scorch time.
3) Shore A hardness: shore hardness test, referring to ASTM D2240-2010, the test ambient temperature is 23.+ -. 2 ℃. (example hardness/comparative example hardness) x100%, the greater the index the higher the hardness.
4) MA100:100% tensile modulus test, modulus at 100% elongation was taken and the test environment temperature was 23.+ -. 2 ℃ with reference to ASTM D412-2006. (example MA 100/comparative example MA 100) x100%, the greater the index the higher the tensile modulus.
5) Tensile strength and elongation at break: referring to ASTM D412-2006, the samples were dumbbell-shaped with a test speed of 500mm/min and a test ambient temperature of 23.+ -. 2 ℃. (example tensile strength and elongation at break/comparative tensile strength and elongation at break) x100%, the greater the index the higher the tensile strength and elongation at break.
6) Tear strength: referring to ASTM D624-2007, a square specimen was used at a test speed of 500mm/min and a test environment temperature of 23.+ -. 2 ℃. (example tear strength/comparative example tear strength) x100%, the greater the index the higher the tear strength.
7) Permanent deformation: reference is made to ISO 2285:2013, adopting a dumbbell-shaped sample, wherein the test speed is 500mm/min, and the test environment temperature is 23+/-2 ℃. (example permanent set/comparative example permanent set) x100%, the smaller the index, the lower the degree of permanent set.
8) Air tightness: referring to GB/T7755-2003, a round sample of the required size is cut, the experimental pressure is 0.1MPa, and the test environment temperature is 40+ -2 ℃. (example air tightness/comparative example air tightness) x100%, the smaller the index, the better the air tightness.
9) Determination of flex crack and tear propagation (de moxiya type): referring to GB/T13934-2006, the test sample is a bar with a semicircular cross section with molded grooves, and the test environment temperature is 23+ -2deg.C. The number of cracks was compared and classified according to the GB/T13934-2006 standard. (number of kilocycles required for example to reach 6-stage crack grade/number of kilocycles required for comparative example to reach 6-stage crack grade) x100%, the greater the index, the better the flex crack resistance.
10 High temperature slow tear energy): a test specimen (see FIG. 1) with a width of 40mm, a height of 65mm and a notch of 10mm was used, the test speed was 50mm/min, and the test environment temperature was 180.+ -. 5 ℃. (example high temperature slow tear energy/comparative example high temperature slow tear energy) x100%, the higher the index the higher the high temperature tear energy.
11 Cross-link density): the equilibrium swelling process is carried out at room temperature using toluene as solvent. (example crosslink density/comparative example crosslink density) x100%, the greater the index the higher the crosslink density.
And calculating the crosslink density gamma (mol/cm) according to Flory-Rehner equation (1) 3 )：
Wherein Vr is the volume fraction of the rubber phase in the swelling rubber; vs is the molar volume of solvent (mL/mol); λ is the interaction parameter of the solvent and the polymer, 0.314; gamma is the crosslink density of the vulcanizate.
Calculating Vr according to equation 2:
wherein W is d The mass (g) of the swollen sample after drying; w (W) s The mass (g) of the sample after swelling; w (W) 0 The initial mass (g) of the sample; b is the mass fraction of the filler in the formula; ρr is rubber density (g/mL); ρs is the solvent density (g/mL).
12 Average life index of the capsules (number of normally vulcanizable): tire curing conditions (internal temperature 210 ℃ C., curing time 20 min). (example actual plant capsule average life/comparative example actual plant capsule average life) x100%, the greater the index the higher the actual plant 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 the following table 1, each in mass:
table 1: raw materials of comparative examples 1,2 and examples 1 to 4
Example 1 increased 0.6 parts of (E) -3-hydroxy-N '- (4-methylpentan-2-ylidene) -2-naphthalenazide as compared to comparative example 1, and example 2 increased 1 part of (E) -3-hydroxy-N' - (4-methylpentan-2-ylidene) -2-naphthalenazide as compared to comparative example 1. Example 3 increased 0.6 parts of (E) -3-hydroxy-N '- (4-methylpentan-2-ylidene) -2-naphthalenazide as compared to comparative example 2, and example 4 increased 1 part of (E) -3-hydroxy-N' - (4-methylpentan-2-ylidene) -2-naphthalenazide as compared to comparative example 2. And comparative example 2 and examples 3 and 4 changed the order of zinc oxide addition as compared with comparative example 1 and examples 1 and 2.
For comparative examples 1 and 2 and examples 1 to 4, the performance test was conducted after aging at 100℃for x48 hours and at 180℃for x48 hours, respectively, and the results were shown in Table 2 below.
Table 2: comparison of the performance results of comparative examples 1 and 2 and examples 1 to 4
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* The test results of the rubber compositions are expressed in the form of an index
In examples 1 and 2, the crosslinking density slightly decreased, but the air tightness was improved and the permanent set slightly increased, when the hardness was not greatly changed, as compared with comparative example 1; modulus, tensile strength, elongation at break and tearing strength are all improved, the increase and the improvement amplitude of flex cracking and cracking are more than 20%, and the high-temperature slow tearing can be improved by more than 30%. In addition, in example 2, the modulus was slightly reduced, the flex crack and tear growth and the high temperature slow tear improvement were more pronounced than in example 1, and 45% and 5% were achieved based on example 1, respectively. After aging, examples 1 and 2 still maintained good mechanical properties and air tightness, and the increase in flex cracking and cracking was more remarkable than comparative example 1. Especially, after aging for 48 hours at 180 ℃, the fatigue property of the embodiment 2 is improved by nearly 10 times, mainly because of the complex bond formed by (E) -3-hydroxy-N' - (4-methylpentane-2-subunit) -2-naphthalic hydrazide and zinc oxide, a reversible network structure is generated, which is helpful for enhancing the acting force between molecules at high temperature, generating additional energy dissipation, remarkably improving the fatigue resistance and prolonging the service life of the vulcanized capsule.
When the order of zinc oxide addition was changed, the hardness, modulus and permanent set were decreased and the tensile strength and elongation at break were improved in comparative example 2 and examples 3 and 4, as compared with comparative example 1 and examples 1 and 2. Examples 3 and 4 had slightly lower crosslink density, lower air tightness, and improved modulus, tensile strength, elongation at break, flex crack and tear strength and high temperature slow tear energy, as compared to comparative example 2. After aging, the flex crack and tear growth increases more significantly in examples 3 and 4 than in comparative example 2. With more severe high-temperature aging conditions and increased addition of (E) -3-hydroxy-N '- (4-methylpentane-2-subunit) -2-naphthalic hydrazide, the fatigue characteristics of examples 3 and 4 are more excellent, mainly because zinc oxide and (E) -3-hydroxy-N' - (4-methylpentane-2-subunit) -2-naphthalic hydrazide form complex bonds to generate a reversible network structure, which is helpful for enhancing intermolecular acting force at high temperature, generating additional energy dissipation, playing a long-acting anti-aging role and remarkably improving 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, the tear resistance under the high-temperature condition and prolong the service life of the vulcanized capsule.
The cured capsules prepared in comparative examples 1,2 and examples 1 to 4 were tested for service life under the same conditions, and the results are shown in Table 3 below:
table 3: comparison of the service lives of the vulcanizates of comparative examples 1,2 and examples 1 to 4
The life of the example 1 was improved by 8% compared with the average life of the curing bladder made in comparative example 1, the life of the example 2 was improved by 14% compared with the average life of the curing bladder made in comparative example 1, the life of the example 3 was improved by 10% compared with the average life of the curing bladder made in comparative example 2, and the life of the example 4 was improved by 15% compared with the average life of the curing bladder made in comparative example 2. Thus, rubber compositions containing (E) -3-hydroxy-N' - (4-methylpentane-2-ylidene) -2-naphthalhydrazide are particularly useful for extending the useful life of cured capsules under high temperature conditions.
From the comparison of the test results, it can be concluded that: according to the invention, the hydrazide or hydrazone (E) -3-hydroxy-N' - (4-methylpentane-2-subunit) -2-naphthalic hydrazide forms a complex bond with zinc oxide to generate a reversible network structure and plays a role of a long-acting anti-aging agent, so that the acting force among molecules can be enhanced under the high temperature condition, extra energy dissipation is generated, the heat resistance, fatigue resistance and tear resistance of the vulcanized capsule can be improved, and the service life of the vulcanized capsule is prolonged. Compared with the comparative example, the service life of the capsule can be prolonged by more than 10%, the embodiment has good economic benefit, and the production efficiency and the yield of a tire factory are improved. The hydrazide or hydrazone is particularly suitable for curing capsules used under high temperature conditions, and the service life of the hydrazide or hydrazone is prolonged under severe high temperature conditions.
Furthermore, the technical scope of the present invention is not limited to the matters described in the specification, and although the present specification describes embodiments, each embodiment does not include only a separate technical solution, and the description is only for the sake of clarity. Various changes and modifications may be made by one skilled in the relevant art without departing from the scope of the technical idea of the invention, and the technical solutions in the embodiments may be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims (10)
1. A rubber composition for curing a bladder, characterized by being prepared by the steps of:
step 1): weighing raw materials; the raw materials comprise a rubber mixture, a halogen donor, hydrazide, filler, a softener, a vulcanization accelerator and a vulcanizing agent;
step 2): mixing the rubber mixture, the halogen donor, the hydrazide, the filler, the softener and the vulcanization accelerator in an internal mixer, and discharging to obtain a material A;
step 3): mixing the material A, the rest of hydrazide, the filler, the softener and the vulcanization accelerator in an internal mixer, and discharging to obtain a material B;
step 4): cooling the material B in the step 3), standing, adding a vulcanizing agent, and mixing the rest hydrazide and a vulcanization accelerator again, and discharging to obtain a material C;
step 5): vulcanizing the material C in the step 4) to obtain a rubber composition product;
the rubber mixture is butyl rubber; the halogen donor is neoprene; the hydrazide is (E) -3-hydroxy-N' - (4-methylpentan-2-subunit) -2-naphthalic hydrazide; the filler is carbon black; the softener is castor oil and stearic acid; the vulcanization accelerator is zinc oxide; the vulcanizing agent is octyl phenol formaldehyde resin;
the weight portions of the raw materials are as follows:
100-120 parts of butyl rubber; 8-12 parts of chloroprene rubber; 50-70 parts of carbon black; 4-6 parts of castor oil; 1-2 parts of stearic acid; 1-6 parts of zinc oxide; 10-15 parts of octyl phenol formaldehyde resin; (E) -3-hydroxy-N' - (4-methylpentan-2-ylidene) -2-naphthalic hydrazide 0.1-1 parts;
the carbon black is carbon black N220 and acetylene carbon black in a mass ratio of (1-2): (0.5-1).
2. The rubber composition according to claim 1, wherein the kneading time in the step 2) and the step 3) is 2 to 10 minutes, and the temperature at the time of discharging is 130 to 190 ℃; the filler and the softener can be added in the step (2) or the step (3) partially or completely; the hydrazide or hydrazone, and the vulcanization accelerator may be added in part or in whole in step (2) or step (3) or step (4).
3. The rubber composition according to claim 2, wherein the kneading time in step 2) and step 3) is 4 to 8 minutes.
4. The rubber composition according to claim 2, wherein the temperature at the time of discharging in step 2) and step 3) is 150 to 170 ℃.
5. The rubber composition according to claim 1, wherein the rehing time in the step 4) is 2 to 10 minutes and the temperature at the time of discharging is 80 to 150 ℃.
6. The rubber composition according to claim 5, wherein the rehing time in step 4) is 4 to 8 minutes.
7. The rubber composition according to claim 5, wherein the temperature at the time of discharging in the step 4) is 90 to 120 ℃.
8. The rubber composition according to claim 1, wherein the vulcanization temperature in the step 5) is 130 to 220℃and the vulcanization time is 10 to 100 minutes.
9. The rubber composition according to claim 8, wherein the vulcanization temperature of step 5) is 160 to 200 ℃.
10. The rubber composition according to claim 8, wherein the vulcanization time of step 5) is 30 to 80 minutes.
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