CN110218460A - A kind of preparation method of tire curing bladder - Google Patents
A kind of preparation method of tire curing bladder Download PDFInfo
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- CN110218460A CN110218460A CN201910462397.9A CN201910462397A CN110218460A CN 110218460 A CN110218460 A CN 110218460A CN 201910462397 A CN201910462397 A CN 201910462397A CN 110218460 A CN110218460 A CN 110218460A
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- China
- Prior art keywords
- parts
- tire curing
- rosin
- temperature
- curing bladder
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- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 56
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 54
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 239000002775 capsule Substances 0.000 claims abstract description 20
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 18
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000012188 paraffin wax Substances 0.000 claims abstract description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 38
- 238000004073 vulcanization Methods 0.000 claims description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 22
- 150000001993 dienes Chemical class 0.000 claims description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 230000032050 esterification Effects 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000004359 castor oil Substances 0.000 claims description 8
- 235000019438 castor oil Nutrition 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 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 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 19
- 235000011187 glycerol Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000003487 anti-permeability effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000013020 embryo development Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000001993 wax 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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to tire curing bladder preparation technical fields, and in particular to a kind of preparation method of tire curing bladder.The present invention disperses butyl rubber powder in paraffin oil, addition neoprene obtains rubber powder oil emulsion, rosin is reacted to obtain modified rosin with maleic anhydride, aluminium hydroxide is placed in potassium hydroxide solution and is dissolved by heating, incorporation white carbon black obtains zeolite gel, by chlorinated paraffin, ammonium persulfate, modified rosin, the mixings such as stearic acid are at low temperature resistant tire curing bladder, butyl rubber powder is swollen in paraffin oil in the present invention, lead to the intermolecular reaction force attenuation of paraffin oil, improve the heat oxygen aging resistance stability of butyl rubber, zeolite granular is conducive to increase the interior friction for solidifying rear tyre curing bag, improve the elasticity under its condition of high temperature, after chlorinated paraffin is in the paraffin oil for being added to melting, be conducive to miscible with paraffin oil, the viscoelastic property of capsule is changed significantly, deform flexibility and recovery, it has broad application prospects.
Description
Technical field
The invention belongs to tire curing bladder preparation technical fields, and in particular to a kind of preparation side of tire curing bladder
Method.
Background technique
With the continuous development of World Auto Industry and the rapid growth of global highway, the type of automobile is increasingly
More, travel speed is getting faster, higher and higher to the quality requirements of tire, thus is also more next to the quality requirements of tire-mold
It is more smart.
Tyre vulcanization is that the tyre cover base of forming is put into sulfide model, vulcanizes under certain temperature, pressure, makes
Tire reaches the physical property of optimum cure degree and requirement.Tyre vulcanization can significantly improve the performance of tire, especially machine
Tool performance.
Tire curing bladder is the important tool of tyre vulcanization, is mainly used for for curing medium being isolated with tire base inner surface
It opens, while transmitting heat and pressure on tire base inner surface.Tire curing bladder will be subjected to the operating condition of some harshnesses, including
High temperature, significantly flexion, co-vulcanization and vulcanizing agent are migrated from unvulcanized tire base.The service life of curing bag is to tire
Factory's production efficiency has a significant impact, its effect of tire curing bladder is internal mainly in tire vulcanization process to fill compressed gas, fills
Nitrogen fills superheated water etc., makes its extension, props up tire sealant embryogenesis internal pressure vulcanized tyre.Therefore tire curing bladder need to have
Preferable heat transmitting and high pressure stability；In heating sulfidation, capsule is needed to have certain deformation characteristics, thus needed
Have certain deformation flexibility and good recovery；Due to that cannot be contacted with water in tire vulcanization process, capsule
Must have the function of preventing overheat water penetration, otherwise tire will generate slot, rounded bead toe and starved, occur delamination when serious
, there is waster so as to cause the tire of vulcanization in equal Appearance quality defects；Capsule needs are used for multiple times, it is therefore desirable to have certain
Durability and high-strength characteristic, need to have many characteristics in view of tyre capsule, therefore, the preparation process of tyre capsule needs
Pay attention to.
The use temperature of tire curing bladder is generally 180~200 DEG C, and the medium of contact is mainly superheated water, overheat steaming
Vapour, compressed air or nitrogen, and the extension ratio of tire curing bladder is very big, and high temperature resistant, which does not reach requirement, can directly result in sulphur
The service life for changing capsule is lost.The generally existing mechanical performance of the tire curing bladder of the prior art is insufficient, after repeated use
The defect of intensity rapid drawdown additionally needs to improve the requirement such as resistance to extension, heat resistant, easy mold release, there is the service life of capsule
The raising of one matter.
Therefore, the quality and service life for how improving tire curing bladder are current one of research tendencies.
Summary of the invention
Present invention mainly solves the technical issues of, deformed under high fever vulcanization environment for current tire curing bladder flexibly
Property and not ideal enough, bad to the anti-permeability of the thermal medium defect of recovery, provide a kind of tire curing bladder
Preparation method.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
The specific preparation step of tire curing bladder are as follows:
(1) N- dimethyl polyacrylamide, castor oil, zeolite gel, rubber powder oil emulsion, modified rosin, hard by chlorinated paraffin, N
Resin acid sequentially adds and carries out mixing in mixer, and control mixing time is 10~12min, and smelting temperature is 135~145 DEG C, obtains
To masterbatch；
(2) masterbatch is put into open mill, is kneaded 4~5min, to film cooled to room temperature, the film of extrusion is packed into
In the screw rod of injector, film enters in die cavity after screw extruding, and injection vulcanization, control vulcanization temperature are carried out under screw pressure
Degree is 190~195 DEG C, and vulcanization time is 50~60min, after vulcanization, capsule is ejected die cavity with injection press, is taken turns
Tire curing bag；
The specific preparation step of modified rosin are as follows:
(1) paraffin oil is placed in stirred tank, is heated to 90~100 DEG C, with the revolving speed insulated and stirred of 200~300r/min
20~30min, then butyl rubber powder is added into stirred tank, continue to be dispersed with stirring 40~50min, be then poured into oil bath pan,
Neoprene is added into oil bath pan, is heated to 200~220 DEG C, after keeping the temperature 10~15min, with 500~600r/min's
Revolving speed stirs at low speed 30~35min, then obtains rubber powder oil emulsion with the revolving speed high speed shearing emulsification of 4000~4200r/min；
(2) 60~65g rosin is added in the four-hole boiling flask that condenser pipe, blender, dropping funel are housed, under nitrogen protection,
150~160 DEG C are heated to, blender is started, is stirred with the revolving speed of 400~550r/min, after rosin all fusing, then
Be added 35~40g rosin, while stirring with dropping funel with the drop rate of 3~4mL/min to four-hole boiling flask be added dropwise 30~
35mL maleic anhydride after being added dropwise, is warming up to 200~220 DEG C, and 1~2h of insulation reaction obtains diene product；
(3) 40~45mL glycerol is added in Xiang Shangshu diene product, to above-mentioned four-hole boiling flask heat temperature raising, insulation reaction 7~
8h is naturally cooling to room temperature, and discharging obtains esterification products, esterification products are filtered by vacuum, and extracts small molecule product out, is changed
Property rosin；
The specific preparation step of zeolite gel are as follows:
20~30g aluminium hydroxide is put into the three-necked flask for the potassium hydroxide solution for being 40% equipped with 70~80mL mass fraction,
Heat temperature raising, insulation reaction, then it is cooled to room temperature, 30~40g white carbon black is added to three-necked flask, with 300~400r/min's
1~2h is mixed in revolving speed, obtains zeolite gel.
In the specific preparation step (1) of tire curing bladder masterbatch raw material according to parts by weight, including chlorinated paraffin 10
~15 parts, N, 4~5 parts of N- dimethyl polyacrylamide, 0.8~1.0 part of castor oil, 20~30 parts of zeolite gel, rubber powder emulsification
Oily 40~50 parts, 10~12 parts of modified rosin, 8~10 parts of stearic acid.
Temperature is 70~80 DEG C when being kneaded in open mill in the specific preparation step (2) of tire curing bladder, controls glue
The slice speed of item is 5m/min.
The temperature of control screw rod is 60~65 DEG C, spiral shell when injection vulcanization in the specific preparation step (2) of tire curing bladder
Rod pressure is 17~20MPa.
Each raw material of rubber powder oil emulsion in the specific preparation step of modified rosin (1), according to parts by weight, including paraffin 20~30
Part, 5~10 parts of butyl rubber powder, 15~20 parts of neoprene.
Rosin be added and maleic anhydride mass ratio are 3.0~3.5 in the specific preparation step of modified rosin (2).
Temperature is 270~280 DEG C when insulation reaction in the specific preparation step of modified rosin (3), and control is taken out when vacuum filtration
Vacuum degree is 100~200Pa in vacuum instrument.
Insulation reaction temperature is 100~110 DEG C in the specific preparation step of zeolite gel, needs to keep the temperature instead before being cooled to room temperature
Aluminium hydroxide should be made all to dissolve.
The beneficial effects of the present invention are:
(1) present invention disperses butyl rubber powder in paraffin oil at a certain temperature, is subsequently placed into oil bath pan, adds neoprene
Rubber, by stirring at low speed mixing, high speed shearing emulsification obtain rubber powder oil emulsion, rosin and maleic anhydride are placed in heating condition
Lower reaction obtains diene product, then by diene product and glycerine esterification, extracts small molecule product out, obtain modified rosin, will
Aluminium hydroxide is placed in potassium hydroxide solution and dissolves by heating, and white carbon black is mixed after cooling, obtains zeolite gel by mixing,
By chlorinated paraffin, N, N- dimethyl polyacrylamide, ammonium persulfate, the mixed gel of zeolite, rubber powder oil emulsion, modified rosin,
The mixings such as stearic acid are at masterbatch, then mill is made film and carries out injection vulcanization and obtains low temperature resistant tire curing bladder, the present invention
Middle butyl rubber powder is to be dispersed in paraffin oil with small particles form, and diene component makes butyl rubber in paraffin oil in butyl rubber
Middle swelling, butyl rubber just will form special reticulated structure, and the intermolecular spacing of paraffin oil increases, and cause paraffin oil intermolecular
Reaction force attenuation, it makes the intersolubility between the rosin by diene and esterification modification and butyl rubber molecules as cosolvent
Increase, improve the content of the conjugated double bond of butyl rubber, heat oxygen aging resistance stability improves, and is easier to chlorinated paraffin hair
Raw halogenation, improves the anti-permeability to thermal medium；
(2) zeolite granular is conducive to increase the interior friction for solidifying rear tyre curing bag in zeolite gel in the present invention, increases wheel
The creep rate of tire curing bag improves the elasticity under its condition of high temperature, successively reacts with maleic anhydride and ethyl alcohol with rosin
To modified rosin, since there are two electrophilic carbonyl, maleic anhydride and rosin can be on the double key carbon of maleic anhydride
Reaction is gone on smoothly under conditions of heating, does not need any catalyst, and obtained maleic rosin increases the degree of functionality of molecule, horse
Carry out rosin and glycerine reaction generates modified rosin resin, reaction belongs to polyesterification reaction, can reduce Malaysia pine by polyesterification
Fragrant acid value, improves its softening point, and improve its stability, after chlorinated paraffin is in the paraffin oil for being added to melting, due to chlorine
Fossil waxes fusing point is lower, is conducive to miscible with paraffin oil, its surface energy can be reduced when chlorinated paraffin switchs to amorphous state by crystalline state
To the saturation component in Adsorption Paraffin oil, and swelling action occurs under these saturation component effects, by adsorbing and being swollen
Effect forms the aggregated structure of paraffin oil and is converted from colloidal sol type to gel-type structure, to change the viscous of capsule significantly
Elastic energy, deforms flexibility and recovery, has broad application prospects.
Specific embodiment
According to parts by weight, 20~30 parts of paraffin oils are placed in stirred tank, are heated to 90~100 DEG C, with 200~
Revolving speed 20~30min of insulated and stirred of 300r/min, then 5~10 parts of butyl rubber powder are added into stirred tank, continue stirring point
40~50min is dissipated, is then poured into oil bath pan, 15~20 parts of neoprenes are added into oil bath pan, it is heated to 200~
220 DEG C, after keeping the temperature 10~15min, 30~35min is stirred at low speed with the revolving speed of 500~600r/min, then with 4000~4200r/
The revolving speed high speed shearing emulsification of min obtains rubber powder oil emulsion；60~65g rosin is added equipped with condenser pipe, blender, dropping liquid leakage
In the four-hole boiling flask of bucket, under nitrogen protection, 150~160 DEG C is heated to, starts blender, with 400~550r/min's
Revolving speed stirring adds 35~40g rosin after rosin all fusing, while stirring with dropping funel with 3~4mL/min's
30~35mL maleic anhydride is added dropwise to four-hole boiling flask in drop rate, after being added dropwise, is warming up to 200~220 DEG C, insulation reaction 1
~2h obtains diene product；40~45mL glycerol is added into above-mentioned diene product, to above-mentioned four-hole boiling flask heat temperature raising
To 270~280 DEG C, 7~8h of insulation reaction is naturally cooling to room temperature, and discharging obtains esterification products, esterification products vacuum is taken out
Filter, control vacuum degree are 100~200Pa, extract small molecule product out, obtain modified rosin；20~30g aluminium hydroxide is put into dress
Have in the three-necked flask that 70~80mL mass fraction is 40% potassium hydroxide solution, is heated to 100~110 DEG C, heat preservation is anti-
It should all be dissolved up to aluminium hydroxide, after being cooled to room temperature, 30~40g white carbon black be added to three-necked flask, with 300~400r/
1~2h is mixed in the revolving speed of min, obtains zeolite gel；According to parts by weight, by 10~15 parts of chlorinated paraffins, 4~5 parts of N,
N- dimethyl polyacrylamide, 0.8~1.0 part of castor oil, 20~30 parts of zeolite gels, 40~50 parts of rubber powder oil emulsions, 10~
12 parts of modified rosins, 8~10 parts of stearic acid, which sequentially add, carries out mixing in mixer, control mixing time is 10~12min, close
Refining temperature is 135~145 DEG C, obtains masterbatch；Masterbatch is put into open mill, is mixed under the conditions of 70~80 DEG C of temperature
Refining, the slice speed for controlling adhesive tape is 5m/min, is kneaded 4~5min, and to film cooled to room temperature, the film of extrusion is filled
Enter in the screw rod of injector, film enters in die cavity after screw extruding, and the temperature for controlling screw rod is 60~65 DEG C, screw pressure
For 17~20MPa, injection vulcanization is carried out under the screw pressure, control curing temperature is 190~195 DEG C, vulcanization time 50
Capsule after vulcanization, is ejected die cavity with injection press, obtains tire curing bladder by~60min.
Example 1
The preparation of rubber powder oil emulsion:
According to parts by weight, 20 parts of paraffin oils are placed in stirred tank, are heated to 90 DEG C, kept the temperature with the revolving speed of 200r/min
20min is stirred, then 5 parts of butyl rubber powder are added into stirred tank, continues to be dispersed with stirring 40min, be then poured into oil bath pan, to
15 parts of neoprenes are added in oil bath pan, are heated to 200 DEG C, after keeping the temperature 10min, are stirred at low speed with the revolving speed of 500r/min
30min, then rubber powder oil emulsion is obtained with the revolving speed high speed shearing emulsification of 4000r/min.
The preparation of diene product:
60g rosin is added in the four-hole boiling flask that condenser pipe, blender, dropping funel are housed, under nitrogen protection, heat temperature raising
To 150 DEG C, start blender, stirred with the revolving speed of 400r/min, after rosin all fusing, adds 35g rosin, side stirring
While 30mL maleic anhydride is added dropwise to four-hole boiling flask with the drop rate of 3mL/min with dropping funel, after being added dropwise, it is warming up to
200 DEG C, insulation reaction 1h obtains diene product.
The preparation of modified rosin:
40mL glycerol is added into above-mentioned diene product, 270 DEG C, insulation reaction 7h are heated to above-mentioned four-hole boiling flask,
It is naturally cooling to room temperature, is discharged, is obtained esterification products, esterification products are filtered by vacuum, control vacuum degree is 100Pa, is extracted out small
Molecular product obtains modified rosin.
The preparation of zeolite gel:
20g aluminium hydroxide is put into the three-necked flask for the potassium hydroxide solution for being 40% equipped with 70mL mass fraction, heat temperature raising
To 100 DEG C, after being cooled to room temperature, 30g white carbon black is added to three-necked flask until aluminium hydroxide all dissolutions in insulation reaction, with
1h is mixed in the revolving speed of 300r/min, obtains zeolite gel.
The preparation of masterbatch:
According to parts by weight, by 10 parts of chlorinated paraffins, 4 parts of N, N- dimethyl polyacrylamide, 0.8 part of castor oil, 20 parts of zeolites
Gel, 40 parts of rubber powder oil emulsions, 10 parts of modified rosins, 8 parts of stearic acid, which sequentially add, carries out mixing in mixer, when controlling mixing
Between be 10min, smelting temperature be 135 DEG C, obtain masterbatch.
The preparation of tire curing bladder:
Masterbatch is put into open mill, is kneaded under the conditions of 70 DEG C of temperature, the slice speed for controlling adhesive tape is 5m/min,
It is kneaded 4min, to film cooled to room temperature, the film of extrusion is packed into the screw rod of injector, film is after screw extruding
Into in die cavity, the temperature for controlling screw rod is 60 DEG C, screw pressure 17MPa, and injection vulcanization is carried out under the screw pressure, is controlled
Curing temperature processed is 190 DEG C, vulcanization time 50min, after vulcanization, capsule is ejected die cavity with injection press, is taken turns
Tire curing bag.
Example 2
The preparation of rubber powder oil emulsion:
According to parts by weight, 25 parts of paraffin oils are placed in stirred tank, are heated to 95 DEG C, kept the temperature with the revolving speed of 250r/min
25min is stirred, then 7 parts of butyl rubber powder are added into stirred tank, continues to be dispersed with stirring 45min, be then poured into oil bath pan, to
17 parts of neoprenes are added in oil bath pan, are heated to 210 DEG C, after keeping the temperature 13min, are stirred at low speed with the revolving speed of 550r/min
33min, then rubber powder oil emulsion is obtained with the revolving speed high speed shearing emulsification of 4100r/min.
The preparation of diene product:
63g rosin is added in the four-hole boiling flask that condenser pipe, blender, dropping funel are housed, under nitrogen protection, heat temperature raising
To 155 DEG C, start blender, stirred with the revolving speed of 480r/min, after rosin all fusing, adds 38g rosin, side stirring
While 33mL maleic anhydride is added dropwise to four-hole boiling flask with the drop rate of 3mL/min with dropping funel, after being added dropwise, it is warming up to
210 DEG C, insulation reaction 1h obtains diene product.
The preparation of modified rosin:
43mL glycerol is added into above-mentioned diene product, 275 DEG C, insulation reaction 7h are heated to above-mentioned four-hole boiling flask,
It is naturally cooling to room temperature, is discharged, is obtained esterification products, esterification products are filtered by vacuum, control vacuum degree is 150Pa, is extracted out small
Molecular product obtains modified rosin.
The preparation of zeolite gel:
25g aluminium hydroxide is put into the three-necked flask for the potassium hydroxide solution for being 40% equipped with 75mL mass fraction, heat temperature raising
To 105 DEG C, after being cooled to room temperature, 35g white carbon black is added to three-necked flask until aluminium hydroxide all dissolutions in insulation reaction, with
1h is mixed in the revolving speed of 350r/min, obtains zeolite gel.
The preparation of masterbatch:
According to parts by weight, by 13 parts of chlorinated paraffins, 4 parts of N, N- dimethyl polyacrylamide, 0.9 part of castor oil, 25 parts of zeolites
Gel, 45 parts of rubber powder oil emulsions, 11 parts of modified rosins, 9 parts of stearic acid, which sequentially add, carries out mixing in mixer, when controlling mixing
Between be 11min, smelting temperature be 140 DEG C, obtain masterbatch.
The preparation of tire curing bladder:
Masterbatch is put into open mill, is kneaded under the conditions of 75 DEG C of temperature, the slice speed for controlling adhesive tape is 5m/min,
It is kneaded 4min, to film cooled to room temperature, the film of extrusion is packed into the screw rod of injector, film is after screw extruding
Into in die cavity, the temperature for controlling screw rod is 63 DEG C, screw pressure 18MPa, and injection vulcanization is carried out under the screw pressure, is controlled
Curing temperature processed is 193 DEG C, vulcanization time 55min, after vulcanization, capsule is ejected die cavity with injection press, is taken turns
Tire curing bag.
Example 3
The preparation of rubber powder oil emulsion:
According to parts by weight, 30 parts of paraffin oils are placed in stirred tank, are heated to 100 DEG C, protected with the revolving speed of 300r/min
Temperature stirring 30min, then 10 parts of butyl rubber powder are added into stirred tank, continue to be dispersed with stirring 50min, is then poured into oil bath pan
In, 20 parts of neoprenes are added into oil bath pan, are heated to 220 DEG C, it is low with the revolving speed of 600r/min after keeping the temperature 15min
Speed stirring 35min, then rubber powder oil emulsion is obtained with the revolving speed high speed shearing emulsification of 4200r/min.
The preparation of diene product:
65g rosin is added in the four-hole boiling flask that condenser pipe, blender, dropping funel are housed, under nitrogen protection, heat temperature raising
To 160 DEG C, start blender, stirred with the revolving speed of 550r/min, after rosin all fusing, adds 40g rosin, side stirring
While 35mL maleic anhydride is added dropwise to four-hole boiling flask with the drop rate of 4mL/min with dropping funel, after being added dropwise, it is warming up to
220 DEG C, insulation reaction 2h obtains diene product.
The preparation of modified rosin:
45mL glycerol is added into above-mentioned diene product, 280 DEG C, insulation reaction 8h are heated to above-mentioned four-hole boiling flask,
It is naturally cooling to room temperature, is discharged, is obtained esterification products, esterification products are filtered by vacuum, control vacuum degree is 200Pa, is extracted out small
Molecular product obtains modified rosin.
The preparation of zeolite gel:
30g aluminium hydroxide is put into the three-necked flask for the potassium hydroxide solution for being 40% equipped with 80mL mass fraction, heat temperature raising
To 110 DEG C, after being cooled to room temperature, 40g white carbon black is added to three-necked flask until aluminium hydroxide all dissolutions in insulation reaction, with
2h is mixed in the revolving speed of 400r/min, obtains zeolite gel.
The preparation of masterbatch:
According to parts by weight, by 15 parts of chlorinated paraffins, 5 parts of N, N- dimethyl polyacrylamide, 1.0 parts of castor oil, 30 parts of zeolites
Gel, 50 parts of rubber powder oil emulsions, 12 parts of modified rosins, 10 parts of stearic acid, which sequentially add, carries out mixing in mixer, control mixing
Time is 12min, and smelting temperature is 145 DEG C, obtains masterbatch.
The preparation of tire curing bladder:
Masterbatch is put into open mill, is kneaded under the conditions of 80 DEG C of temperature, the slice speed for controlling adhesive tape is 5m/min,
It is kneaded 5min, to film cooled to room temperature, the film of extrusion is packed into the screw rod of injector, film is after screw extruding
Into in die cavity, the temperature for controlling screw rod is 65 DEG C, screw pressure 20MPa, and injection vulcanization is carried out under the screw pressure, is controlled
Curing temperature processed is 195 DEG C, vulcanization time 60min, after vulcanization, capsule is ejected die cavity with injection press, is taken turns
Tire curing bag.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that rubber powder oil emulsion is not added.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that modified rosin is not added.
Comparative example 3: the tire curing bladder of Nanjing company production.By tire curing bladder produced by the present invention and
Tire curing bladder in comparative example is detected, and testing result is as shown in table 1:
Tensile strength test
Using the regulation in standard GB/T528-2009 physical mechanical property test method, carried out at room temperature on electronic tensile machine
Test, tensile speed 500mm/min.
Tear strength properties test
Using the regulation in standard GB/T529-2008 physical mechanical property test method, carried out at room temperature on electronic tensile machine
Test, tensile speed 500mm/min.
Service life test
Tire curing bladder in tire curing bladder produced by the present invention and comparative example is carried out to the tire of 195/65R15 size
It forms (conditions of vulcanization: 185 DEG C, 8min), checks the access times until capsule perforation.Index is bigger, indicates the longevity of capsule
It orders longer.
1 performance measurement result of table
According to data in table 1 it is found that tire curing bladder produced by the present invention, has mechanical strength height, permanent set low, resistance to
The features such as high-temperature behavior is good, anti-permeability is strong, and production cost is low, simple process, long service life, no pollution to the environment,
It is easy to use, there is wide prospect of the application.
Claims (8)
1. a kind of preparation method of tire curing bladder, it is characterised in that specific preparation step are as follows:
(1) N- dimethyl polyacrylamide, castor oil, zeolite gel, rubber powder oil emulsion, modified rosin, hard by chlorinated paraffin, N
Resin acid sequentially adds and carries out mixing in mixer, and control mixing time is 10~12min, and smelting temperature is 135~145 DEG C, obtains
To masterbatch；
(2) masterbatch is put into open mill, is kneaded 4~5min, to film cooled to room temperature, the film of extrusion is packed into
In the screw rod of injector, film enters in die cavity after screw extruding, and injection vulcanization, control vulcanization temperature are carried out under screw pressure
Degree is 190~195 DEG C, and vulcanization time is 50~60min, after vulcanization, capsule is ejected die cavity with injection press, is taken turns
Tire curing bag；
The specific preparation step of the modified rosin are as follows:
(1) paraffin oil is placed in stirred tank, is heated to 90~100 DEG C, with the revolving speed insulated and stirred of 200~300r/min
20~30min, then butyl rubber powder is added into stirred tank, continue to be dispersed with stirring 40~50min, be then poured into oil bath pan,
Neoprene is added into oil bath pan, is heated to 200~220 DEG C, after keeping the temperature 10~15min, with 500~600r/min's
Revolving speed stirs at low speed 30~35min, then obtains rubber powder oil emulsion with the revolving speed high speed shearing emulsification of 4000~4200r/min；
(2) 60~65g rosin is added in the four-hole boiling flask that condenser pipe, blender, dropping funel are housed, under nitrogen protection,
150~160 DEG C are heated to, blender is started, is stirred with the revolving speed of 400~550r/min, after rosin all fusing, then
Be added 35~40g rosin, while stirring with dropping funel with the drop rate of 3~4mL/min to four-hole boiling flask be added dropwise 30~
35mL maleic anhydride after being added dropwise, is warming up to 200~220 DEG C, and 1~2h of insulation reaction obtains diene product；
(3) 40~45mL glycerol is added in Xiang Shangshu diene product, to above-mentioned four-hole boiling flask heat temperature raising, insulation reaction 7~
8h is naturally cooling to room temperature, and discharging obtains esterification products, esterification products are filtered by vacuum, and extracts small molecule product out, is changed
Property rosin；
The specific preparation step of the zeolite gel are as follows:
20~30g aluminium hydroxide is put into the three-necked flask for the potassium hydroxide solution for being 40% equipped with 70~80mL mass fraction,
Heat temperature raising, insulation reaction, then it is cooled to room temperature, 30~40g white carbon black is added to three-necked flask, with 300~400r/min's
1~2h is mixed in revolving speed, obtains zeolite gel.
2. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the tyre vulcanization
In the specific preparation step (1) of capsule masterbatch raw material according to parts by weight, including 10~15 parts of chlorinated paraffin, N, N- dimethyl
4~5 parts of polyacrylamide, 0.8~1.0 part of castor oil, 20~30 parts of zeolite gel, 40~50 parts of rubber powder oil emulsion, modified pine
It is 10~12 parts, 8~10 parts of stearic acid fragrant.
3. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the tyre vulcanization
Temperature is 70~80 DEG C when being kneaded in open mill in the specific preparation step (2) of capsule, and the slice speed for controlling adhesive tape is 5m/
min。
4. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the tyre vulcanization
In the specific preparation step (2) of capsule when injection vulcanization the temperature of control screw rod be 60~65 DEG C, screw pressure be 17~
20MPa。
5. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the modified rosin
Each raw material of rubber powder oil emulsion in specific preparation step (1), according to parts by weight, including 20~30 parts of paraffin, butyl rubber powder 5~
10 parts, 15~20 parts of neoprene.
6. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the modified rosin
Rosin be added and maleic anhydride mass ratio are 3.0~3.5 in specific preparation step (2).
7. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the modified rosin
Temperature is 270~280 DEG C when insulation reaction in specific preparation step (3), and control vacuumizes vacuum degree in instrument when vacuum filtration
For 100~200Pa.
8. a kind of preparation method of tire curing bladder according to claim 1, it is characterised in that: the zeolite gel
Insulation reaction temperature is 100~110 DEG C in specific preparation step, needs insulation reaction to keep aluminium hydroxide whole before being cooled to room temperature
Dissolution.
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Application publication date: 20190910 |