CN104448429A - Method for preparing composite material for automotive air spring rubber airbag - Google Patents

Method for preparing composite material for automotive air spring rubber airbag Download PDF

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Publication number
CN104448429A
CN104448429A CN201410679412.2A CN201410679412A CN104448429A CN 104448429 A CN104448429 A CN 104448429A CN 201410679412 A CN201410679412 A CN 201410679412A CN 104448429 A CN104448429 A CN 104448429A
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rubber
parts
air spring
matrix material
mixing
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CN104448429B (en
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商好峰
李广全
宋立伟
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SHANDONG ZHENGKAI MACHINERY TECHNOLOGY Co Ltd
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SHANDONG ZHENGKAI MACHINERY TECHNOLOGY Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a method for preparing a composite material for an automotive air spring rubber airbag. The method comprises the following steps: firstly, adding butadiene rubber, polyurethane rubber, chloroprene rubber, polyvinyl chloride, calcium carbonate, zinc oxide and boron nitride into a mixing stirrer for uniformly mixing, then adding the mixture into a reflux unit, adding cyclohexane, carrying out heating reflux, filtering to obtain a solid mixture, drying the solid mixture by using hot nitrogen, transferring the solid mixture into a reaction kettle, adding stearic acid, polydimethylsiloxane, graphene, silicon dioxide, sodium allylsulfonate, diphenylamine and hydroxypropyl cellulose, heating in an inert gas atmosphere to react to obtain an intermediate, adding an accelerator CZ1-3, an accelerator DM 3 and dimethyl diallyl ammonium chloride, uniformly mixing and transferring the mixture into a rubber mixing machine for rubber mixing, and finally, putting rubber material after rubber mixing into a vulcanizing machine for vulcanizing and then discharging. The composite material for the automotive air spring rubber airbag, provided by the invention, has excellent mechanical properties, ozone aging resistance and heat aging resistance.

Description

A kind of preparation method of automobile air spring-rubber air bag matrix material
Technical field
The invention belongs to automotive suspension field of new, be specifically related to a kind of preparation method of automobile air spring-rubber air bag matrix material.
Background technology
Pneumatic cushioning is a kind of curved capsule of being fitted by rubber, netting twine, is commonly called as pneumatic tyre, ripple pneumatic tyre, air bag, bellows etc.Capsule both ends need be connected with two block plates, form a delivery air chamber.Rubber and netting twine itself do not provide the bearing capacity to load, but have been come by the pressurized air be filled with in capsule.Its bent capsule number is generally 1 ~ 3 bent capsule, but also can be designed and manufactured into more than 4 songs or 5 songs as required, can also two pneumatic cushionings superpositions be used under certain condition.The key part of pneumatic cushioning is rubber-bag, and it is made up of outer glue-line, cord body and hose lining.Outer layer glue is protective layer, for the contact of the extraneous factors such as isolated ozone, oxygen and cord body, prevents carcass stock compound aging.Cord body is the pressure bearing layer of rubber spring, inside has multilayer nylon cord fabrics as framework material.Hose lining is air retaining wall.At present the natural rubber that adopts as the elastomeric material of rubber-bag more, but due to the resistance to ozone of natural rubber, heatproof air aging performance poor, easily there is crack performance in product, finally cause product early failure in life-time service process.In order to improve the aging resistance of rubber-bag, there is company to adopt chloroprene rubber to produce rubber-bag, but having bonded poor due to chloroprene rubber and nylon cord, use needs cannot have been met; Also there is the over-all properties that research employing chloroprene rubber combines with natural rubber for improving rubber-bag simultaneously, but the degree improved is little, still can not meet current automotive industry develops rapidly for the more and more higher requirement of corresponding automobile air elastomeric material performance requriements, therefore need to carry out further to research and develop a kind of mechanical property and the excellent air elastomeric material of ageing resistance, make it be applied to automobile air rubber materials better.
Summary of the invention
The object of the invention is to the preparation method that a kind of automobile air spring-rubber air bag matrix material is provided to overcome above the deficiencies in the prior art, making matrix material have excellent mechanical property and resistance to ozone ageing and resistant to heat aging performance.
The present invention is realized by following technique means:
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with cis-1,4-polybutadiene rubber 30-40 part of parts by weight, urethanes 20-30 part, chloroprene rubber, 20-30 part, polyvinyl chloride 10-20 part, calcium carbonate 2-6 part, zinc oxide 1-4 part and boron nitride 0.8-2 part join in mixing and blending machine, are uniformly mixed, and obtain mixture one;
Step 2, joins in reflux by mixture one, adds 80-100 part hexanaphthene, is uniformly mixed, reflux hexanaphthene, and backflow 30-40 minute, filters to obtain solid mixture;
Step 3, solid mixture step 2 obtained uses hot nitrogen to dry up, and is transferred in reactor, then adds the stearic acid 3-6 part with parts by weight, polydimethylsiloxane 2-5 part, Graphene 3-8 part, silica 1-4 parts, sodium allylsulfonate 1-3 part, pentanoic 1-3 part and hydroxypropylcellulose 2-6 part, under the atmosphere of protection of inert gas, be heated to 50-60 DEG C, stirring reaction 120-150 minute, obtains intermediate;
Step 4, in the intermediate that step 3 obtains, add the accelerant CZ 1-3 part with parts by weight, altax 1-2 part and dimethyl diallyl ammonium chloride 0.8-2 part, proceed to after mixing in rubber mixing machine, glue furnacing temperature 90-100 DEG C, refining glue time 20-30 minute;
Step 5, refines the sizing material after glue and puts into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material by step 4.
The preparation method of described automobile air spring-rubber air bag matrix material, the condition be uniformly mixed in step one can be stirring velocity 200-220 rev/min, churning time 40-50 minute.
The preparation method of described automobile air spring-rubber air bag matrix material, the temperature of hot nitrogen described in step 3 can be 70-80 DEG C.
The preparation method of described automobile air spring-rubber air bag matrix material, rare gas element described in step 3 can be nitrogen or argon gas.
The preparation method of described automobile air spring-rubber air bag matrix material, in step 3, the stirring velocity of stirring reaction can be 80-100 rev/min.
The preparation method of described automobile air spring-rubber air bag matrix material, the condition of sulfuration in step 5 can for carry out sulfuration at twice, primary vulcanization temperature is 180-190 DEG C, curing time 10-20 minute, then 220-240 DEG C is warming up to, carry out second time sulfuration, second time curing time is 7-10 minute.
Automobile air spring-rubber air bag matrix material provided by the invention has good over-all properties, and wherein tensile strength reaches more than 36.5MPa, and elongation at break reaches more than 752%, and notched Izod impact strength reaches 88kJ/m 2above, flex crack reaches more than 3,200,000 times, ozone-resistant aging property reaches more than 200h flawless, heat aging property tests 80 DEG C, 200h back draft change rate of strength reaches within 2.6%, elongation at break velocity of variation reaches within 4.5%, has excellent mechanical property and ageing-resistant performance.
The present invention is by good component proportion and preparation process, obtain the automobile air spring-rubber air bag matrix material with excellent mechanical property, resistance to ozone ageing and heat aging property, can be good at, in automobile air spring, carrying out the needs of satisfied current development.
Embodiment
In following examples, if without specified otherwise, all numbers are all expressed as weight part.
Embodiment 1
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 30 parts of parts by weight, urethanes 20 parts, chloroprene rubber, 20 parts, polyvinyl chloride 10 parts, 2 parts, calcium carbonate, 1 part, zinc oxide and boron nitride 0.8 part join in mixing and blending machine, are uniformly mixed, obtain mixture one;
Step 2, joins in reflux by mixture one, adds 80 parts of hexanaphthenes, is uniformly mixed, reflux hexanaphthene, refluxes 30 minutes, filters to obtain solid mixture;
Step 3, solid mixture use temperature step 2 obtained is that the hot nitrogen of 70 DEG C dries up, and is then transferred in reactor, then the stearic acid 3 parts with parts by weight is added, polydimethylsiloxane 2 parts, Graphene 3 parts, silica 1 part, sodium allylsulfonate 1 part, pentanoic 1 part and hydroxypropylcellulose 2 parts, be heated to 50 DEG C, stirring reaction 120 minutes under the atmosphere of nitrogen protection, stirring velocity is 80 revs/min, obtains intermediate;
Step 4, adds the accelerant CZ 1 part with parts by weight in the intermediate that step 3 obtains, and altax 1 part and dimethyl diallyl ammonium chloride 0.8 part, proceed to after mixing in rubber mixing machine, glue furnacing temperature 90 DEG C, the 20 minutes glue time of refining;
Step 5, step 4 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 180 DEG C, and curing time 10 minutes, is then warming up to 220 DEG C, carry out second time sulfuration, second time curing time is 7 minutes.
Embodiment 2
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 32 parts of parts by weight, urethanes 23 parts, chloroprene rubber, 21 parts, polyvinyl chloride 13 parts, 3 parts, calcium carbonate, 2 parts, zinc oxide and boron nitride 1 part join in mixing and blending machine, be uniformly mixed, the condition of being uniformly mixed is stirring velocity 205 revs/min, and churning time 42 minutes, obtains mixture one;
Step 2, joins in reflux by mixture one, adds 85 parts of hexanaphthenes, is uniformly mixed, reflux hexanaphthene, refluxes 33 minutes, filters to obtain solid mixture;
Step 3, solid mixture use temperature step 2 obtained is that the hot nitrogen of 73 DEG C dries up, and is then transferred in reactor, then the stearic acid 4 parts with parts by weight is added, polydimethylsiloxane 3 parts, Graphene 5 parts, silica 1 part, sodium allylsulfonate 2 parts, pentanoic 1 part and hydroxypropylcellulose 2 parts, be heated to 55 DEG C, stirring reaction 128 minutes under the atmosphere of argon shield, stirring velocity is 85 revs/min, obtains intermediate;
Step 4, adds the accelerant CZ 1 part with parts by weight in the intermediate that step 3 obtains, and altax 1 part and dimethyl diallyl ammonium chloride 1.3 parts, proceed to after mixing in rubber mixing machine, glue furnacing temperature 92 DEG C, the 24 minutes glue time of refining;
Step 5, step 4 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 185 DEG C, and curing time 13 minutes, is then warming up to 226 DEG C, carry out second time sulfuration, second time curing time is 8 minutes.
Embodiment 3
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 37 parts of parts by weight, urethanes 26 parts, chloroprene rubber, 28 parts, polyvinyl chloride 15 parts, 5 parts, calcium carbonate, 2 parts, zinc oxide and boron nitride 1.5 parts join in mixing and blending machine, be uniformly mixed, the condition of being uniformly mixed is stirring velocity 210 revs/min, and churning time 46 minutes, obtains mixture one;
Step 2, joins in reflux by mixture one, adds 92 parts of hexanaphthenes, is uniformly mixed, reflux hexanaphthene, refluxes 35 minutes, filters to obtain solid mixture;
Step 3, solid mixture use temperature step 2 obtained is that the hot nitrogen of 76 DEG C dries up, and is then transferred in reactor, then the stearic acid 5 parts with parts by weight is added, polydimethylsiloxane 4 parts, Graphene 6 parts, silicon-dioxide 3 parts, sodium allylsulfonate 3 parts, pentanoic 2 parts and hydroxypropylcellulose 5 parts, be heated to 58 DEG C, stirring reaction 140 minutes under the atmosphere of nitrogen protection, stirring velocity is 95 revs/min, obtains intermediate;
Step 4, adds the accelerant CZ 2 parts with parts by weight in the intermediate that step 3 obtains, and altax 2 parts and dimethyl diallyl ammonium chloride 1.6 parts, proceed to after mixing in rubber mixing machine, glue furnacing temperature 95 DEG C, the 28 minutes glue time of refining;
Step 5, step 4 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 190 DEG C, and curing time 16 minutes, is then warming up to 232 DEG C, carry out second time sulfuration, second time curing time is 9 minutes.
Embodiment 4
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 40 parts of parts by weight, urethanes 30 parts, chloroprene rubber, 30 parts, polyvinyl chloride 20 parts, 6 parts, calcium carbonate, 4 parts, zinc oxide and boron nitride 2 parts join in mixing and blending machine, be uniformly mixed, the condition of being uniformly mixed is stirring velocity 220 revs/min, and churning time 50 minutes, obtains mixture one;
Step 2, joins in reflux by mixture one, adds 100 parts of hexanaphthenes, is uniformly mixed, reflux hexanaphthene, refluxes 40 minutes, filters to obtain solid mixture;
Step 3, solid mixture use temperature step 2 obtained is that the hot nitrogen of 80 DEG C dries up, and is then transferred in reactor, then the stearic acid 6 parts with parts by weight is added, polydimethylsiloxane 5 parts, Graphene 8 parts, silicon-dioxide 4 parts, sodium allylsulfonate 3 parts, pentanoic 3 parts and hydroxypropylcellulose 6 parts, be heated to 60 DEG C, stirring reaction 150 minutes under the atmosphere of nitrogen protection, stirring velocity is 100 revs/min, obtains intermediate;
Step 4, adds the accelerant CZ 3 parts with parts by weight in the intermediate that step 3 obtains, and altax 2 parts and dimethyl diallyl ammonium chloride 2 parts, proceed to after mixing in rubber mixing machine, glue furnacing temperature 100 DEG C, the 30 minutes glue time of refining;
Step 5, step 4 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 190 DEG C, and curing time 20 minutes, is then warming up to 240 DEG C, carry out second time sulfuration, second time curing time is 10 minutes.
Reference examples 1
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 37 parts of parts by weight, urethanes 26 parts, chloroprene rubber, 28 parts, polyvinyl chloride 15 parts, 5 parts, calcium carbonate, 2 parts, zinc oxide and boron nitride 1.5 parts join in mixing and blending machine, be uniformly mixed, the condition of being uniformly mixed is stirring velocity 210 revs/min, and churning time 46 minutes, obtains mixture one;
Step 2, joins in reflux by mixture one, adds 92 parts of hexanaphthenes, is uniformly mixed, reflux hexanaphthene, refluxes 35 minutes, filters to obtain solid mixture;
Step 3, solid mixture use temperature step 2 obtained is that the hot nitrogen of 76 DEG C dries up, then be transferred in reactor, then add the polydimethylsiloxane 4 parts with parts by weight, Graphene 6 parts, silicon-dioxide 3 parts, sodium allylsulfonate 3 parts and pentanoic 2 parts, be heated to 58 DEG C, stirring reaction 140 minutes under the atmosphere of nitrogen protection, stirring velocity is 95 revs/min, obtains intermediate;
Step 4, adds the accelerant CZ 2 parts with parts by weight in the intermediate that step 3 obtains, and altax 2 parts and dimethyl diallyl ammonium chloride 1.6 parts, proceed to after mixing in rubber mixing machine, glue furnacing temperature 95 DEG C, the 28 minutes glue time of refining;
Step 5, step 4 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 190 DEG C, and curing time 16 minutes, is then warming up to 232 DEG C, carry out second time sulfuration, second time curing time is 9 minutes.
Reference examples 2
A preparation method for automobile air spring-rubber air bag matrix material, comprises the following steps:
Step one, by with the cis-1,4-polybutadiene rubber 37 parts of parts by weight, urethanes 26 parts, chloroprene rubber, 28 parts, polyvinyl chloride 15 parts, 5 parts, calcium carbonate, 2 parts, zinc oxide and boron nitride 1.5 parts join in mixing and blending machine, be uniformly mixed, the condition of being uniformly mixed is stirring velocity 210 revs/min, and churning time 46 minutes, obtains mixture one;
Step 2, then mixture one is transferred in reactor, then adds the stearic acid 5 parts with parts by weight, polydimethylsiloxane 4 parts, Graphene 6 parts, silicon-dioxide 3 parts, sodium allylsulfonate 3 parts, pentanoic 2 parts and hydroxypropylcellulose 5 parts, 58 DEG C are heated under the atmosphere of nitrogen protection, stirring reaction 140 minutes, stirring velocity is 95 revs/min, obtains intermediate;
Step 3, adds the accelerant CZ 2 parts with parts by weight in the intermediate that step 2 obtains, and altax 2 parts and dimethyl diallyl ammonium chloride 1.6 parts, proceed to after mixing in rubber mixing machine, glue furnacing temperature 95 DEG C, the 28 minutes glue time of refining;
Step 4, step 3 is refined the sizing material after glue and put into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material, wherein the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 190 DEG C, and curing time 16 minutes, is then warming up to 232 DEG C, carry out second time sulfuration, second time curing time is 9 minutes.
Performance test is carried out to the matrix material that above embodiment and reference examples prepare, specific as follows:
As can be seen from above test-results, automobile air spring-rubber air bag matrix material provided by the invention has good over-all properties, wherein tensile strength reaches more than 36.5MPa, and elongation at break reaches more than 752%, and notched Izod impact strength reaches 88kJ/m 2above, flex crack reaches more than 3,200,000 times, ozone-resistant aging property reaches more than 200h flawless, heat aging property tests 80 DEG C, 200h back draft change rate of strength reaches within 2.6%, elongation at break velocity of variation reaches within 4.5%, has excellent mechanical property and ageing-resistant performance.In above embodiment, the composite property that embodiment 3 prepares is more outstanding, therefore can as most preferred embodiment.
Reference examples 1 and reference examples 2 are the further proving tests carried out on the basis of above embodiment 3, wherein do not add stearic acid and hydroxypropylcellulose in step 3 in reference examples 1, other processes are identical with embodiment 3, result causes the performance of flex crack and resistance to ozone ageing to decrease drastically, heat aging property also has certain decline simultaneously, illustrate that adding of these two kinds of components can be played enhancing ozone-resistant aging property to matrix material provided by the invention and improve flex crack number of times, to a certain degree also can improve resistant to heat aging performance simultaneously.In preparation process, the hexanaphthene reflux course of step 2 in embodiment 3 is not carried out in reference examples 2, and directly carry out the mixing of each component, result causes the properties of matrix material all to decrease drastically, therefore can illustrate that the process of the hexanaphthene backflow of step 2 in preparation process can the internal structure of reinforced composite, improve the over-all properties of matrix material.
In sum, automobile air spring-rubber air bag matrix material provided by the invention has excellent mechanical property and resistance to ozone ageing and heat aging property, can be good at being applied in automobile air spring, carrys out the needs of satisfied current development.

Claims (6)

1. a preparation method for automobile air spring-rubber air bag matrix material, is characterized in that, comprise the following steps:
Step one, by with cis-1,4-polybutadiene rubber 30-40 part of parts by weight, urethanes 20-30 part, chloroprene rubber, 20-30 part, polyvinyl chloride 10-20 part, calcium carbonate 2-6 part, zinc oxide 1-4 part and boron nitride 0.8-2 part join in mixing and blending machine, are uniformly mixed, and obtain mixture one;
Step 2, joins in reflux by mixture one, adds 80-100 part hexanaphthene, is uniformly mixed, reflux hexanaphthene, and backflow 30-40 minute, filters to obtain solid mixture;
Step 3, solid mixture step 2 obtained uses hot nitrogen to dry up, and is transferred in reactor, then adds the stearic acid 3-6 part with parts by weight, polydimethylsiloxane 2-5 part, Graphene 3-8 part, silica 1-4 parts, sodium allylsulfonate 1-3 part, pentanoic 1-3 part and hydroxypropylcellulose 2-6 part, under the atmosphere of protection of inert gas, be heated to 50-60 DEG C, stirring reaction 120-150 minute, obtains intermediate;
Step 4, in the intermediate that step 3 obtains, add the accelerant CZ 1-3 part with parts by weight, altax 1-2 part and dimethyl diallyl ammonium chloride 0.8-2 part, proceed to after mixing in rubber mixing machine, glue furnacing temperature 90-100 DEG C, refining glue time 20-30 minute;
Step 5, refines the sizing material after glue and puts into discharging after vulcanizer sulfuration, obtain automobile air spring-rubber air bag matrix material by step 4.
2. the preparation method of automobile air spring-rubber air bag matrix material according to claim 1, it is characterized in that, the condition be uniformly mixed in step one is stirring velocity 200-220 rev/min, churning time 40-50 minute.
3. the preparation method of automobile air spring-rubber air bag matrix material according to claim 1, is characterized in that, the temperature of hot nitrogen described in step 3 is 70-80 DEG C.
4. the preparation method of automobile air spring-rubber air bag matrix material according to claim 1, it is characterized in that, rare gas element described in step 3 is nitrogen or argon gas.
5. the preparation method of automobile air spring-rubber air bag matrix material according to claim 1, it is characterized in that, in step 3, the stirring velocity of stirring reaction is 80-100 rev/min.
6. the preparation method of automobile air spring-rubber air bag matrix material according to claim 1, it is characterized in that, in step 5, the condition of sulfuration is for carry out sulfuration at twice, primary vulcanization temperature is 180-190 DEG C, curing time 10-20 minute, then be warming up to 220-240 DEG C, carry out second time sulfuration, second time curing time is 7-10 minute.
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Publication number Priority date Publication date Assignee Title
CN108431112A (en) * 2015-09-14 2018-08-21 Mcpp创新有限责任公司 Flexibility molding crust
US10640071B2 (en) 2015-09-14 2020-05-05 Mcpp Innovation Llc Flexible molded skin
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CN105522882B (en) * 2016-01-26 2018-01-05 山东正凯机械科技有限公司 A kind of air suspension system for circulating gas operated
CN105837916A (en) * 2016-06-17 2016-08-10 国网山东省电力公司东阿县供电公司 High-strength corrosion resistance distribution box used for electric power
CN109971155A (en) * 2019-03-12 2019-07-05 河南大林橡胶通信器材有限公司 Ventilation round type clutch rubber pneumatic bag and preparation method thereof
CN110746563A (en) * 2019-10-24 2020-02-04 江苏理工学院 PEG ball-milling intercalation h-BN modified polyurethane heat-conducting composite material and preparation method thereof
CN110746563B (en) * 2019-10-24 2021-06-29 江苏理工学院 PEG ball-milling intercalation h-BN modified polyurethane heat-conducting composite material and preparation method thereof

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