WO2021120085A1 - Procédé de fabrication d'une vessie de vulcanisation de pneu à haute résistance - Google Patents

Procédé de fabrication d'une vessie de vulcanisation de pneu à haute résistance Download PDF

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Publication number
WO2021120085A1
WO2021120085A1 PCT/CN2019/126523 CN2019126523W WO2021120085A1 WO 2021120085 A1 WO2021120085 A1 WO 2021120085A1 CN 2019126523 W CN2019126523 W CN 2019126523W WO 2021120085 A1 WO2021120085 A1 WO 2021120085A1
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WO
WIPO (PCT)
Prior art keywords
rubber
parts
mixing
temperature
tire curing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/126523
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English (en)
Chinese (zh)
Inventor
赵会岩
赵海林
范屏
张学永
刘涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yongyi Rubber Co Ltd
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Yongyi Rubber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Publication of WO2021120085A1 publication Critical patent/WO2021120085A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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; Homopolymers or copolymers of other iso-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/18—Polymers of hydrocarbons having four or more carbon atoms, e.g. polymers of butylene, e.g. PB, i.e. polybutylene
    • B29K2023/22—Copolymers of isobutene, e.g. butyl rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/757—Moulds, cores, dies
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to the technical field of production and processing of tire curing bladder, in particular to a method for preparing a high-strength tire curing bladder.
  • the tire vulcanizing bladder is a hollow thin-walled rubber product. It is installed in the tire vulcanizer and used as an inner mold for tire shaping during the vulcanization and molding process of the tire. Fill the tire vulcanizing bladder with superheated water or compressed air and other media to stretch the tire vulcanizing bladder to support the tire rubber blank, which fits the tire lining, and uses the flow and heat transfer characteristics of the medium fluid inside the tire vulcanizing bladder to maintain the tire The temperature during the vulcanization process is relatively balanced, achieving the effect of uniform vulcanization of the tire and improving the balance performance of the tire.
  • tire curing bladder heating medium requires good air tightness, so butyl rubber is usually used as the base rubber; the air tightness of butyl rubber is related to its own degree of unsaturation. Generally, the lower the degree of unsaturation, the lower the air tightness. The better the tightness; the lower the degree of unsaturation, the excellent aging resistance; however, the low degree of unsaturation, poor processability, slow curing speed, and low elasticity are unfavorable factors for the production and repeated use of tire curing bladder. As tire curing bladder requires more characteristics, research on its preparation process has been going on.
  • CN105647038B discloses "a method for preparing a high-strength tire curing bladder", which includes the following steps: the first step, the modified chlorinated butyl rubber: the second step, by weight, the modified chlorinated butyl rubber, Natural rubber, N330 carbon black, N660 carbon black, sulfur, zinc oxide, vulcanized resin, stearic acid, vulcanized cottonseed oil, nano silica and stannous chloride, put them in an open mill for mixing, and mixing temperature 90°C-95°C, time 20-30min, after mixing, use an extruder to extrude the film; the third step, injection vulcanization process, vulcanization time 46-55min.
  • the technical solution in the patent improves the strength, the processing time is long.
  • the present invention provides a method for preparing a high-strength tire curing bladder, which is improved in terms of raw materials, formula design, production technology, etc., to manufacture a high-strength tire curing bladder.
  • the raw materials for tire curing bladder include: raw rubber, fillers, active agents, processing aids, and vulcanizing agents.
  • the raw rubber includes: butyl rubber and bromobutyl rubber
  • the filler includes: high-structure wear-resistant carbon black, acetylene carbon black, graphite and aluminum oxide
  • the active agent is Zinc oxide masterbatch
  • processing aids include: stearic acid, paraffin wax
  • vulcanizing agents include vulcanized resin and sulfur
  • the degree of unsaturation of butyl rubber is 0.5-2%, and bromobutyl rubber contains 1.5-2.5% bromine.
  • the formula is as follows: 100 parts of raw rubber, 30-60 parts of fillers, 3-5 parts of active agents, 3-5 parts of processing aids, 2-6 parts of vulcanizing agents ;
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 70-80°C, the pressure is controlled at 16-18MPa; the injection vulcanization temperature is 180-200°C, and the vulcanization time is 30-42min; vulcanization After the end, the injection vulcanizer pushes the tire bladder out of the mold cavity to prepare a high-strength tire vulcanizing bladder.
  • butyl rubber accounts for 60-80% of the raw rubber by mass fraction
  • bromobutyl rubber accounts for 20-40% of the raw rubber by mass fraction.
  • Mainly butyl rubber, bromobutyl rubber is used to modify butyl rubber, bromobutyl rubber and the unsaturated part of butyl rubber have good adhesion, and the ratio setting is consistent with the unsaturation of butyl rubber Degree and bromine content of bromobutyl rubber are related.
  • the mass fraction ratio between high-structure wear-resistant carbon black, acetylene carbon black, graphite and aluminum oxide is (1-2): (2-4): (1-2):1 .
  • the mass fraction ratio between stearic acid and paraffin wax is 1: (1-2).
  • the mass fraction ratio between vulcanized resin and sulfur is (1-3):1.
  • bromobutyl rubber accounts for 20-40% of the raw rubber. Studies have found that bromobutyl rubber is superior to butyl rubber in terms of heat resistance and self-adhesiveness, and can be used to modify butyl rubber. Compared with chlorinated butyl rubber, the solid vulcanization point on the polymer chain of bromobutyl rubber is more reactive, so bromobutyl rubber has stronger adhesion to the unsaturated part of butyl rubber , The vulcanization speed is also faster than chlorinated butyl rubber.
  • the vulcanization time of bromobutyl rubber is half of the vulcanization time of chlorobutyl rubber.
  • bromobutyl rubber is equivalent to chlorobutyl rubber.
  • Zinc oxide masterbatch can effectively solve the problem of inaccurate measurement of zinc oxide and uneven dispersion in the raw rubber; to improve the uniformity of the processed film.
  • the specific preparation steps of the zinc oxide masterbatch used in the present invention are as follows: first put the carrier rubber and zinc stearate into an open mill according to the proportions, and masticate uniformly; then combine the above products with zinc oxide powder and naphthenic minerals The oil is put into the internal mixer in proportion to mix and banbury; finally, the materials obtained from the mixing and banburying are thrown into the transport hopper, transported to the conical twin-screw forced kneader, and transported to the single-screw cold feed extruder after kneading. Pelletizing and discharging.
  • the solid vulcanization point on the polymer chain of bromobutyl rubber has stronger reactivity, and the mixing time should not be too long at a higher temperature.
  • the rubber extruder is used as the three-stage rubber mixing equipment to shorten the higher temperature. Mixing time, while maintaining the stability of bromobutyl rubber, achieve the purpose of uniform mixing;
  • Zinc oxide masterbatch can effectively solve the problems of inaccurate measurement of zinc oxide and uneven dispersion in the raw rubber, so as to improve the uniformity of the processed film.
  • the rubber formula of the tire curing bladder is based on parts by weight, 60-80 parts of butyl rubber, 20-40 parts of bromobutyl rubber, 6-13 parts of high-structure wear-resistant carbon black, and 12-27 parts of acetylene carbon black. 6-13 parts of graphite, 3-12 parts of aluminum oxide, 1-2.5 parts of stearic acid, 1.5-3.4 parts of paraffin wax, 1-4.5 parts of vulcanized resin, 0.5-3 parts of sulfur, 3-5 parts of zinc oxide masterbatch Copies
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 70-80°C, the pressure is controlled at 16-18MPa; the injection vulcanization temperature is 180-200°C, and the vulcanization time is 30-42min; vulcanization After the end, the injection vulcanizer pushes the tire bladder out of the mold cavity to prepare a high-strength tire vulcanizing bladder.
  • One-stage rubber mixing add raw rubber, 1/2 filler, active agent, and processing aids to the internal mixer at a temperature of 110°C and a time of 10 minutes, and then discharge the mixed rubber;
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 80°C, the pressure is controlled at 18MPa; the injection curing temperature is 190°C, and the curing time is 42min; after the vulcanization, the injection vulcanizing machine will The bladder is ejected from the mold cavity, and a high-strength tire curing bladder is prepared.
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 80°C, the pressure is controlled at 18MPa; the injection curing temperature is 200°C, and the curing time is 40min; after the vulcanization, the injection vulcanizing machine will The bladder is ejected from the mold cavity, and a high-strength tire curing bladder is prepared.
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 75°C, the pressure is controlled at 17MPa; the injection curing temperature is 190°C, and the curing time is 38min; after the vulcanization, the injection vulcanizing machine will The bladder is ejected from the mold cavity, and a high-strength tire curing bladder is prepared.
  • One-stage rubber mixing add raw rubber, 1/2 filler, active agent, and processing aids to the internal mixer at a temperature of 95°C and a time of 6 minutes, and then discharge the mixed rubber;
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine, the temperature of the screw is controlled at 70°C, the pressure is controlled at 16MPa; the injection curing temperature is 180°C, and the curing time is 35min; after the vulcanization, the injection vulcanizing machine will The bladder is ejected from the mold cavity, and a high-strength tire curing bladder is prepared.
  • Injection vulcanization Put the film obtained in S24 into an injection vulcanizing machine.
  • the temperature of the screw is controlled at 70°C and the pressure is controlled at 16MPa; the injection vulcanization temperature is 180°C and the vulcanization time is 30min; after vulcanization, the injection vulcanizing machine will
  • the bladder is ejected from the mold cavity, and a high-strength tire curing bladder is prepared.
  • the hardness of the film used to prepare the tire curing bladder is 58-65A
  • the tensile strength is 12-15MPa
  • the tear strength is 28-33kN/m
  • the elongation at break is 600-700%
  • the tensile strength is 300%.
  • the stress is 8-10MPa
  • the permanent deformation is 20-30%.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)

Abstract

La présente invention concerne le domaine technique de la production et du traitement de vessies de vulcanisation de pneu et concerne un procédé de fabrication d'une vessie de vulcanisation de pneu à haute résistance. Dans les matières premières de la vessie de vulcanisation de pneu, du caoutchouc brut comprend du caoutchouc butyle et du caoutchouc butyle bromé ; une charge comprend du noir de carbone à résistance structurale élevée à l'usure, du noir de carbone d'acétylène, du graphite et de l'oxyde d'aluminium ; un agent actif correspond à des particules de mélange maître d'oxyde de zinc ; un auxiliaire de traitement comprend de l'acide stéarique et de la paraffine ; un agent de vulcanisation comprend une résine vulcanisée et du soufre. Le degré d'insaturation du caoutchouc butyle est de 0,5 à 2 % et le caoutchouc butyle bromé contient de 1,5 à 2,5 % de brome. Le procédé de préparation comprend : tout d'abord l'exécution d'un mélange de caoutchouc en trois étapes pour traiter une feuille de caoutchouc, puis l'injection et la vulcanisation pour obtenir la vessie de vulcanisation de pneu. Par comparaison avec l'état de la technique, la présente invention présente les avantages suivants : le caoutchouc butyle et le caoutchouc butyle bromé sont utilisés en tant que caoutchouc brut et une extrudeuse de caoutchouc est utilisée en tant que dispositif de mélange de caoutchouc en trois étapes, de sorte qu'un temps de mélange à haute température soit raccourci, la stabilité du caoutchouc butyle bromé soit maintenue, le but d'un mélange uniforme soit obtenu, et le temps de vulcanisation puisse être raccourci, la résistance étant améliorée.
PCT/CN2019/126523 2019-12-16 2019-12-19 Procédé de fabrication d'une vessie de vulcanisation de pneu à haute résistance Ceased WO2021120085A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911293041.3 2019-12-16
CN201911293041.3A CN110698776A (zh) 2019-12-16 2019-12-16 一种高强度轮胎硫化胶囊的制备方法

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Cited By (7)

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CN114734567A (zh) * 2022-03-03 2022-07-12 江阴市昌雄金属科技有限公司 一种轮胎气门嘴用高强度橡胶密封垫片的加工工艺
CN115707751A (zh) * 2021-08-18 2023-02-21 黄冈聚奥铭新材料有限公司 一种环保隔音减震材料
CN116120647A (zh) * 2022-12-26 2023-05-16 宣城博源橡塑有限公司 一种脱硫废轮胎胶粉直接生产混炼胶及其生产工艺
CN116199979A (zh) * 2023-01-10 2023-06-02 苏州硕宏高分子材料有限公司 一种预分散橡胶促进剂及其制备的橡胶
CN118006051A (zh) * 2024-04-08 2024-05-10 寿光福麦斯轮胎有限公司 一种轮胎气密层用橡胶组合物及其制备方法
CN120209467A (zh) * 2025-04-15 2025-06-27 浙江百朗士新材料有限公司 一种耐低温溴化丁基橡胶材料及其制备方法
CN121182081A (zh) * 2025-11-24 2025-12-23 摩肯(厦门)实业有限公司 一种丁基橡胶及其制备方法

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CN111423740A (zh) * 2020-03-30 2020-07-17 安徽佳通乘用子午线轮胎有限公司 一种硫化胶囊用橡胶组合物及其制备方法
CN113429689A (zh) * 2021-06-29 2021-09-24 三角轮胎股份有限公司 超高导热轮胎硫化胶囊橡胶组合物及其生产胶囊的工艺
CN113563671A (zh) * 2021-07-23 2021-10-29 威海市润通橡胶有限公司 一种轮胎硫化胶囊及其制备方法

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