CN104927110A - Flame retardant rubber composition and application thereof - Google Patents
Flame retardant rubber composition and application thereof Download PDFInfo
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- CN104927110A CN104927110A CN201510305333.XA CN201510305333A CN104927110A CN 104927110 A CN104927110 A CN 104927110A CN 201510305333 A CN201510305333 A CN 201510305333A CN 104927110 A CN104927110 A CN 104927110A
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- flame retardant
- rubber composition
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- retardant rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a flame retardant rubber composition and application thereof. The flame retardant rubber composition does not contain decabromodiphenyl ether, is superior in flame retardancy, and is prepared from natural rubber, 2,2',3,3',4,4',5,5',6,6'-decabromobibenzyl, antimonous oxide, red phosphorus and an assistant. Through the synergistic effect of 2,2',3,3',4,4',5,5',6,6'-decabromobibenzyl, antimonous oxide and red phosphorus, the flame retardancy of a tire sizing material in a formula is greatly improved, so that the prepared rubber does not burn easily and self-extinguishes in case of open fire; the invention further provides the application of the flame retardant rubber composition in the field of tire preparation.
Description
Technical field
The present invention relates to field of rubber preparation, particularly relate to a kind of flame retardant rubber composition and application thereof.
Background technology
The development of automotive industry has benefited from the substantial advance of each assembly self-technique.Tire is as the important component part of automobile, and its Status of development directly affects the progress of automotive industry.
Tire is everlasting under complicated and exacting terms and is used, and it subjects various distortion, load, power and high/low temperature effect in motion, therefore must have higher load-carrying properties, hauling ability, shock-absorbing capacity.
The half that the world consumes rubber mass is used for tire production, and visible tire consumes the ability of rubber.And rubber has inflammable feature, in the complicated environment for use of tire, the flame retardant properties of rubber seems especially important.
Aerated rubber tyre, is generally all made up of rubber and framework material, but rubber is one extremely incendive material in atmosphere, for long-term at high temperature, the vehicle of operation in the environment of burning things which may cause a fire disaster, is easy to tyre catching fire phenomenon occurs, leaves larger hidden danger to safety of life and property.Traditional terms of settlement all can use efficient flame-retarding agent decabromodiphynly oxide as tire formulation fire retardant in formula, but because European Union thinks that decabromodiphynly oxide is harmful, thus forbid using decabromodiphynly oxide in tire, and then tyre industry is progressively prohibited in tire formulation use decabromodiphynly oxide.
Summary of the invention
Embodiments provide one not containing decabromodiphynly oxide, and the flame retardant rubber composition of superior flame retardant property and application thereof.
Do not use decabromodiphynly oxide in flame retardant rubber composition of the present invention, the sizing material made with the present composition, when near burning things which may cause a fire disaster, has nonflammable and has the function of meeting naked light and certainly putting out.
The present invention is by the synergy of TDE, antimonous oxide and red phosphorus, cross use TDE as main flame retardant, and using antimonous oxide and red phosphorus to work in coordination with TDE implements fire-retardant, significantly promote the flame retardant properties of tire sizing compound formula.
In view of this, the invention provides a kind of flame retardant rubber composition and application thereof, can comprise:
Natural rubber, cis-1,4-polybutadiene rubber, TDE, antimonous oxide, red phosphorus and auxiliary agent.
Preferably, by weight, described natural rubber, cis-1,4-polybutadiene rubber, TDE, antimonous oxide and red phosphorus obtain total amount: auxiliary agent is 103 ~ 181:50 ~ 83.
Preferably, described auxiliary agent comprises:
One or more in strengthening agent, anti-aging agent, lubricant, softening agent, vulcanizing agent and vulcanization accelerator.
Preferably, described strengthening agent is:
One or both in carbon black or white carbon black.
Preferably, described anti-aging agent comprises:
One or both in zinc oxide or quinoline anti-aging agent.
Preferably, described auxiliary agent comprises:
Carbon black, zinc oxide, stearic acid, Ursol D anti-aging agent, quinoline anti-aging agent, paraffin, sulfenamide type accelerators and sulphur.
Preferably, with parts by weight, described composition comprises:
Preferably, described TDE is main flame retardant, by weight, and described TDE: the total amount of antimonous oxide and red phosphorus is 3:1.2 ~ 1.7, for stoping rubber combustion.
The present invention also provides foregoing flame retardant rubber combination preparing the application in tire.
As can be seen from the above technical solutions, the embodiment of the present invention has the following advantages:
The present invention, by the synergy of TDE, antimonous oxide and red phosphorus, under the prerequisite not using decabromodiphynly oxide, significantly promotes the flame retardant properties of tire sizing compound formula.
The present invention, on fire-retardant basis, with the addition of auxiliary agent cis-1,4-polybutadiene rubber, high wear-resistant carbon black, zinc oxide, stearic acid, Ursol D anti-aging agent, quinoline anti-aging agent, paraffin, sulfenamide type accelerators and sulphur, while improving flame retardant rubber properties, because auxiliary agent is nonflammable, the interpolation of auxiliary agent reduces the degree of natural rubber, and flame retardant properties improves further.
Each proportioning raw materials is optimized for by the present invention, be by weight: natural rubber 40-60, cis-1,4-polybutadiene rubber 40-60, high wear-resistant carbon black 40-60, zinc oxide 3-6, stearic acid 2-4, Ursol D anti-aging agent 1-3, quinoline anti-aging agent 1-3, paraffin 1-3, sulfenamide type accelerators 1-2, sulphur 1-2, TDE 15-35, antimonous oxide 5-20, red phosphorus 3-6, the optimization of component proportion makes rubber flame-retarded effect strengthen, when not using decabromodiphynly oxide, use TDE is main flame retardant, by the different types of efficient flame-retarding agent of proportioning, play the effect of cooperative flame retardant, reach from fire from the function put out.
Meanwhile, the embodiment of the present invention additionally provides the application of flame retardant rubber composition in tire preparation field, and prepared tire, flame retardant properties significantly improves.
Embodiment
Embodiments provide a kind of flame retardant rubber composition and application thereof, for the preparation of the rubber with flame retardant properties, and then prepare the tire with flame retardant properties.
Material therefor of the present invention is common commercially available material, and performance is as follows, and brand does not limit:
Natural rubber: 20# standard rubber, ash content <1.0%; Impurity <0.16%; Volatile matter <0.8%; For the basic rubber of the present composition;
Cis-1,4-polybutadiene rubber: high-cis cis-1,4-polybutadiene rubber, ash content <0.2%; Volatile matter <0.8%; For the basic rubber of the present composition;
Carbon black: particulate state; 105 DEG C of weight loss on heating <1.5%; 325 screen residue <0.05%; As rubber reinforcing filler, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Zinc oxide: Powdered; Zinc oxide content >99.5%; 325 screen residue <0.15%; Acetic acid insolubles <0.008%; As rubber vulcanization activator, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Stearic acid: particulate state; Iodine number <8gI
2/ 100g; Congelation point 57.0 ± 5.0 DEG C; Acid number 200.0 ± 12.0mgKOH/g; As rubber vulcanization activator, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
TDE: Powdered; Bromine content >81%; Particle diameter <3um; Free bromine content <20ppm; As fire retardant, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Antimonous oxide: Powdered; Particle diameter 0.3 ~ 0.9um; Impurity <0.5%; As fire retardant, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Red phosphorus: particulate state; Red phosphorus content >98.5%; Yellow phosphorus content <0.005%; Free acid <0.5%; Particle diameter 60 ~ 80 order; Moisture <0.25%; As fire retardant, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Amines antioxidants: particulate state; Ctystallizing point >45 DEG C; Weight loss on heating <0.5%; For sizing material provides ageing-resistant performance, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Quinoline anti-aging agent: particulate state; Softening temperature 90.0 ± 5.0 DEG C; Weight loss on heating <0.5%; For sizing material provides ageing-resistant performance, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Paraffin: particulate state; Congelation point 63 ~ 67 DEG C; Refractive index (80 DEG C) 1.4300 ~ 1.4400; For sizing material provides ageing-resistant performance, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Sulphur: Powdered; Total sulfur >98%; 200 mesh sieve screenings <0.5%; 80 DEG C, 3 hours weight loss on heating <0.5%; As rubber vulcanization linking agent, and act synergistically with other auxiliary agents of the present invention, concrete effect does not limit herein;
Sulfenamide type accelerators: Powdered; First fusing point >104 DEG C; 70 DEG C, 3 hours weight loss on heating <0.5%, as rubber vulcanization promotor, and act synergistically with other auxiliary agents of the present invention, and concrete effect does not limit herein; .
In order to make those skilled in the art understand technical scheme of the present invention better, below by specific embodiment, the present invention is described in further detail.
Embodiment 1
Be by weight: natural rubber 40kg, cis-1,4-polybutadiene rubber 60kg, carbon black 50kg, zinc oxide 3kg, stearic acid 2kg, Ursol D anti-aging agent 1kg, quinoline anti-aging agent 1kg, paraffin 1kg, sulfenamide type accelerators 1kg, sulphur 1kg, TDE 30kg, antimonous oxide 10kg, red phosphorus 3kg.
Adopted by above-mentioned composition material 3 sections of calendering process to process, 3 sections mixing all carries out in F370 type Banbury mixer, and rotor speed is 10-60r/min; 3 sections of mixing rear mill slices; Order of addition(of ingredients): add natural rubber 40kg in one section, cis-1,4-polybutadiene rubber 60kg, carbon black 50kg, zinc oxide 3kg, stearic acid 2kg, Ursol D anti-aging agent 1kg, quinoline anti-aging agent 1kg, paraffin 1kg, TDE 30kg, antimonous oxide 10kg, red phosphorus 3kg, dump temperature 165 DEG C; Two sections are refined process again for rubber unvulcanizate; Three sections add sulphur 1kg and sulfenamide type accelerators 1kg, and dump temperature is 102 DEG C.After parking 4 hours, sizing material carries out sidewall component extrusion, then it is shaping to park 8 hours laggard road wheel tyre blanks, is finally sulfided into final tire to fetus.
The present invention is by different fire retardant proportionings synergy, and make rubber have higher flame retardant properties, performance test is in table 1.
Embodiment 2
Be by weight: natural rubber 45kg, cis-1,4-polybutadiene rubber 55kg, high wear-resistant carbon black 55kg, zinc oxide 5kg, stearic acid 4kg, Ursol D anti-aging agent 3kg, quinoline anti-aging agent 2kg, paraffin 3kg, TDE 25kg, antimonous oxide 8kg, red phosphorus 5kg.
Adopted by above-mentioned composition material 3 sections of calendering process to process, 3 sections mixing all carries out in F370 type Banbury mixer, and rotor speed is 10-60r/min; 3 sections of mixing rear mill slices; Order of addition(of ingredients): add natural rubber 40kg in one section, cis-1,4-polybutadiene rubber 60kg, carbon black 50kg, zinc oxide 3kg, stearic acid 2kg, Ursol D anti-aging agent 1kg, quinoline anti-aging agent 1kg, paraffin 1kg, TDE 30kg, antimonous oxide 10kg, red phosphorus 3kg, dump temperature 165 DEG C; Two sections are refined process again for rubber unvulcanizate; Three sections add sulphur 2kg and sulfenamide type accelerators 2kg, and dump temperature is 102 DEG C.After parking 4 hours, sizing material carries out sidewall component extrusion, then it is shaping to park 8 hours laggard road wheel tyre blanks, is finally sulfided into final tire to fetus.
The present invention is by different fire retardant proportionings synergy, and make rubber have flame retardant properties, performance test is in table 1.
Table 1 Mechanics Performance Testing
From data, the embodiment of the present invention 1 and 2 prepares rubber, and carry out processing with 3 sections of calendering process and prepare tire, through hardness, pull apart, tensile strength, resilience, tear strength, subdue breach and oxygen index seven performance tests for 300,000 times, tire prepared by the present composition, hardness, pull apart, tensile strength, resilience, tear strength with subdue breach data 300,000 times and all meet the relevant national standard of tire.
It is generally acknowledged, oxygen index is more than or equal to the material of 27%, and meeting naked light can from breath.
Elastomeric material oxygen index prepared by the embodiment of the present invention 1,2 is respectively 27.2% and 27.5%, and far above 19.6% of conventional tyre, superior flame retardant property, meets naked light from putting out.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. a flame retardant rubber composition, is characterized in that, comprises natural rubber, cis-1,4-polybutadiene rubber, TDE, antimonous oxide, red phosphorus and auxiliary agent.
2. flame retardant rubber composition according to claim 1, is characterized in that, by weight, described natural rubber, cis-1,4-polybutadiene rubber, TDE, antimonous oxide and red phosphorus obtain total amount: auxiliary agent is 103 ~ 181:50 ~ 83.
3. flame retardant rubber composition according to claim 1, is characterized in that, described auxiliary agent comprises:
One or more in strengthening agent, anti-aging agent, lubricant, softening agent, vulcanizing agent and vulcanization accelerator.
4. flame retardant rubber composition according to claim 3, is characterized in that, described strengthening agent is:
One or both in carbon black and white carbon black.
5. flame retardant rubber composition according to claim 3, is characterized in that, described anti-aging agent comprises:
One or both in amines antioxidants and quinoline anti-aging agent.
6. flame retardant rubber composition according to claim 3, is characterized in that, described auxiliary agent comprises:
Carbon black, zinc oxide, stearic acid, Ursol D anti-aging agent, quinoline anti-aging agent, paraffin, sulfenamide type accelerators and sulphur.
7. flame retardant rubber composition according to claim 6, is characterized in that, with parts by weight, described composition comprises:
8. flame retardant rubber composition according to claim 1, is characterized in that, described TDE is main flame retardant, by weight, and described TDE: the total amount of antimonous oxide and red phosphorus is 3:1.2 ~ 1.7, for stoping rubber combustion.
9. the flame retardant rubber composition according to any one of claim 1-8 is preparing the application in tire.
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| CN201510305333.XA CN104927110B (en) | 2015-06-04 | 2015-06-04 | A kind of flame retardant rubber composition and its application |
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| CN201510305333.XA CN104927110B (en) | 2015-06-04 | 2015-06-04 | A kind of flame retardant rubber composition and its application |
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| CN104927110A true CN104927110A (en) | 2015-09-23 |
| CN104927110B CN104927110B (en) | 2017-07-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254940A (en) * | 2015-11-16 | 2016-01-20 | 济南泰星精细化工有限公司 | Rubber composition for tire |
| WO2018058284A1 (en) * | 2016-09-27 | 2018-04-05 | 崔楠 | Flame-retardant macromolecule cable material |
| CN114230871A (en) * | 2021-12-23 | 2022-03-25 | 三角轮胎股份有限公司 | Heat-resistant flame-retardant bead rubber composition and tire thereof |
| WO2024142541A1 (en) * | 2022-12-26 | 2024-07-04 | 横浜ゴム株式会社 | Rubber composition for conveyor belt, and conveyor belt |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254940A (en) * | 2015-11-16 | 2016-01-20 | 济南泰星精细化工有限公司 | Rubber composition for tire |
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| CN114230871A (en) * | 2021-12-23 | 2022-03-25 | 三角轮胎股份有限公司 | Heat-resistant flame-retardant bead rubber composition and tire thereof |
| WO2024142541A1 (en) * | 2022-12-26 | 2024-07-04 | 横浜ゴム株式会社 | Rubber composition for conveyor belt, and conveyor belt |
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| Publication number | Publication date |
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| CN104927110B (en) | 2017-07-21 |
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Address after: Mellerud Conghua Ao town Guangzhou city Guangdong province 510940 No. 3 Applicant after: Wanli tire Limited by Share Ltd Address before: Mellerud Conghua Ao town Guangzhou city Guangdong province 511400 No. 3 Applicant before: Guangzhou Fengli Rubber Tire Co., Ltd. |
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