CN106928564B - Chlorosulfonated polyethylene rubber composition - Google Patents
Chlorosulfonated polyethylene rubber composition Download PDFInfo
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- CN106928564B CN106928564B CN201710158956.8A CN201710158956A CN106928564B CN 106928564 B CN106928564 B CN 106928564B CN 201710158956 A CN201710158956 A CN 201710158956A CN 106928564 B CN106928564 B CN 106928564B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
- C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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Abstract
The invention provides a chlorosulfonated polyethylene rubber composition, which belongs to the field of rubber materials, has excellent scorch resistance, has scorch time (ts5) of more than 30min at 120 ℃, and excellent physical properties, effectively ensures the safety in the processing process and meets the requirements of product performance. The chlorosulfonated polyethylene rubber composition further comprises the following components in parts by weight based on 100 parts of chlorosulfonated polyethylene rubber: 5-15 parts of magnesium oxide, 1-3 parts of microcrystalline wax, 2-4 parts of lubricant, 0.5-1 part of anti-aging agent, 5-20 parts of carbon black, 20-40 parts of silicon powder, 30-60 parts of light calcium carbonate, 20-30 parts of plasticizer, 1.5-2.5 parts of vulcanizing agent and 1-2 parts of accelerator.
Description
Technical Field
The invention relates to the field of rubber materials, in particular to a chlorosulfonated polyethylene rubber material, and particularly relates to a chlorosulfonated polyethylene rubber composition with excellent scorch resistance.
Background
In recent years, with the rapid development of the automobile industry, the requirements of automobile rubber hoses on rubber materials are higher and higher, and the CSM (chlorosulfonated polyethylene rubber) material is widely applied to automobile power steering rubber hoses, fuel rubber hoses and crankcase ventilation rubber hoses due to the good comprehensive balance performance of heat resistance, weather aging resistance and oil resistance.
However, due to the existence of sulfonyl chloride groups in the molecular structure of chlorosulfonated polyethylene rubber, the chlorosulfonated polyethylene rubber has flexible selection of a vulcanization system, and the high reactivity of the sulfonyl chloride groups causes the traditional CSM rubber material to be easily scorched in the processing process, thereby causing the waste of materials and labor in the production process. Therefore, the study of the improvement of the scorch resistance of CSM compounds is very important.
Disclosure of Invention
The invention aims to provide a chlorosulfonated polyethylene rubber composition, the main material of which is chlorosulfonated polyethylene rubber, and the obtained rubber composition has excellent scorch resistance and high safety performance in the production process through the optimization of a filling system and a vulcanization system.
The invention provides a chlorosulfonated polyethylene rubber composition, which further comprises the following components in parts by weight based on 100 parts of chlorosulfonated polyethylene rubber: 5-15 parts of magnesium oxide, 1-3 parts of microcrystalline wax, 2-4 parts of lubricant, 0.5-1 part of anti-aging agent, 5-20 parts of carbon black, 20-40 parts of silicon powder, 30-60 parts of light calcium carbonate, 20-30 parts of plasticizer, 1.5-2.5 parts of vulcanizing agent and 1-2 parts of accelerator.
According to a preferable technical scheme, the chlorosulfonated polyethylene rubber is chlorosulfonated polyethylene rubber with the chlorine content of 33-37%.
As a preferable technical scheme, the magnesium oxide is high-activity magnesium oxide, and the iodine absorption value is 120-180.
Preferably, the plasticizer is an ester softener, including but not limited to dioctyl phthalate, dioctyl sebacate and trioctyl trimellitate, and more preferably, the plasticizer is trioctyl trimellitate.
As a preferred technical scheme, the vulcanizing agent is dipentamethylenethiuram tetrasulfide.
As a preferable technical scheme, the accelerant is N, N' -m-phenylene bismaleimide.
Alternatively, the lubricant is lubricant WS 180.
As an optional technical scheme, the silicon powder is silicon powder 750.
As an alternative, the carbon black is a fast extrusion carbon black.
The invention also provides application of the chlorosulfonated polyethylene rubber composition in preparing automobile rubber hoses.
Compared with the existing CSM rubber compound, the CSM rubber compound provided by the invention optimizes a filling system and a vulcanization system of the CSM rubber composition, and the developed CSM rubber compound has excellent scorch resistance. The conventional CSM rubber has the scorching time (ts5) at 120 ℃ of 5-15 min, and the scorching phenomenon is very easy to occur in the extrusion processing process.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a chlorosulfonated polyethylene rubber composition, which further comprises the following components in parts by weight based on 100 parts of chlorosulfonated polyethylene rubber: 5-15 parts of magnesium oxide, 1-3 parts of microcrystalline wax, 2-4 parts of lubricant, 0.5-1 part of anti-aging agent, 5-20 parts of carbon black, 20-40 parts of silicon powder, 30-60 parts of light calcium carbonate, 20-30 parts of plasticizer, 1.5-2.5 parts of vulcanizing agent and 1-2 parts of accelerator.
In a preferred embodiment of the invention, the chlorosulfonated polyethylene rubber is chlorosulfonated polyethylene rubber CSM40 with the chlorine content of 33-37%. The manufacturers include but are not limited to the lucky star cloud chemical, the Jiangxi Rainbow chemical or Nippon Cao Kabushiki Kaisha. Specifically, the chlorine content of the chlorosulfonated polyethylene rubber may be 33%, 34%, 35%, 36%, 37%, the chlorine content in the CSM rubber selected from the above chlorine contents has a significant influence on the performance thereof, the CSM40 selected from the above chlorine contents may have excellent ozone resistance, weather resistance, heat resistance, flame retardancy, water resistance, chemical resistance, oil resistance, abrasion resistance, and the like, and the chlorine content of the CSM rubber may be combined with a filler system and a vulcanization system to significantly improve the scorch resistance of the rubber composition.
In a preferred embodiment of the present invention, the magnesium oxide is high-activity magnesium oxide with an iodine absorption value of 120-180, and specifically, the activity of the magnesium oxide may be 120, 130, 140, 150, 160, 170, 180. The high-activity magnesium oxide with iodine absorption value can be matched with CSM rubber material to be vulcanized to promote a vulcanization system. Most preferably, the magnesium oxide activity 150, particularly MgO-150, available from Japan synergy, is used, and the effect is best in the process of compounding with CSM sizing.
In a preferred embodiment of the present invention, the plasticizer is an ester softener, including but not limited to dioctyl phthalate DOP, dioctyl sebacate DOS, trioctyl trimellitate TOTM, and more preferably, the plasticizer is trioctyl trimellitate TOTM. The ester plasticizer has better effect on rubber used at low temperature, and in the specific embodiment of the invention, the effect of adding TOTM is more beneficial to improving the performance of the composition than DOP and DOS.
In a preferred embodiment of the invention, the vulcanizing agent is the vulcanizing agent TRA, i.e. dipentamethylenethiuram tetrasulfide, the main function of which is to cause the formation of a crosslinked network between the molecular chains of the CSM by reaction with the reactive groups.
In a preferred embodiment of the invention, the accelerator is preferably HVA-2, i.e. N, N' -m-phenylene bismaleimide, which has the main function of increasing the degree of crosslinking in the vulcanization reaction and at the same time of extending the scorch time of the compound. Compared with the existing scorch-resistant auxiliary agent, the HVA-2 selected by the invention can be optimally matched with chlorosulfonated polyethylene rubber and other components, so that the optimal scorch-resistant effect is achieved.
In an alternative embodiment of the present invention, lubricant WS180 is selected as the lubricant, silica powder 750 is selected as the silica powder, and carbon black is rapidly extruded. Wherein, the lubricant WS180 is a German STRUKTOL product, and can obviously improve the roll sticking property of CSM rubber material in the processing process; the silicon powder 750 is a Fuyang Ripu chemical product and can improve the processing performance of rubber materials as an inorganic filler.
The embodiment of the invention also provides application of the chlorosulfonated polyethylene rubber composition in preparing automobile rubber hoses. By utilizing the excellent scorch resistance of the chlorosulfonated polyethylene rubber composition, the safety in the whole production process is high, no potential safety hazard exists in production and reproduction, and meanwhile, the prepared automobile rubber tube can meet the use requirement in a high-temperature environment of 130 ℃.
In order to more clearly describe the chlorosulfonated polyethylene rubber composition provided in the examples of the present invention in detail, the following description will be given with reference to specific examples.
Example 1
The rubber composition for the automobile rubber tube comprises the following components in parts by weight:
| serial number | Components | Amount per part |
| 1 | CSM40 | 100 |
| 2 | MgO-180 | 10 |
| 3 | Microcrystalline wax | 2 |
| 4 | Lubricant WS180 | 3 |
| 5 | Antiager NBC | 1 |
| 6 | Fast extrusion of carbon black | 10 |
| 7 | Silicon powder 750 | 30 |
| 8 | Light calcium carbonate | 40 |
| 9 | Plasticizer TOTM | 25 |
| 10 | Vulcanizing agent TRA | 2.5 |
| 11 | Accelerator HVA-2 | 1 |
The performance tests are as follows:
example 2
The rubber composition for the automobile rubber tube comprises the following components in parts by weight:
| serial number | Components | Amount per part |
| 1 | CSM40 | 100 |
| 2 | MgO-150 | 10 |
| 3 | Microcrystalline wax | 2 |
| 4 | Lubricant WS180 | 3 |
| 5 | Antiager NBC | 0.5 |
| 6 | Fast extrusion of carbon black | 10 |
| 7 | Silicon powder 750 | 20 |
| 8 | Light calcium carbonate | 50 |
| 9 | Plasticizer TOTM | 25 |
| 10 | Vulcanizing agent TRA | 1.5 |
| 11 | Accelerator HVA-2 | 2 |
The performance tests are as follows:
example 3
The rubber composition for the automobile rubber tube comprises the following components in parts by weight:
| serial number | Components | Amount per part |
| 1 | CSM40 | 100 |
| 2 | MgO-120 | 15 |
| 3 | Microcrystalline wax | 3 |
| 4 | Lubricant WS180 | 2 |
| 5 | Antiager NBC | 1 |
| 6 | Fast extrusion of carbon black | 20 |
| 7 | Silicon powder 750 | 20 |
| 8 | Light calcium carbonate | 60 |
| 9 | Plasticizer TOTM | 30 |
| 10 | Vulcanizing agent TRA | 2.0 |
| 11 | Accelerator HVA-2 | 1.5 |
The performance tests are as follows:
example 4
The rubber composition for the automobile rubber tube comprises the following components in parts by weight:
the performance tests are as follows:
comparative example 1:
an example of a traditional mating CSM formulation is as follows:
| serial number | Components | Amount per part |
| 1 | CSM40 | 100 |
| 2 | Ordinary MgO | 5 |
| 3 | Common protective wax | 2 |
| 4 | Lubricant agent | 3 |
| 5 | Antiager NBC | 1 |
| 6 | Fast extrusion of carbon black | 50 |
| 7 | Light calcium carbonate | 50 |
| 8 | Plasticizer | 40 |
| 9 | Vulcanizing agent TRA | 2 |
| 10 | Pentaerythritol | 3 |
| 11 | Scorch retarder DM | 0.5 |
The performance tests are as follows:
comparative example 2:
the use of scorch retarder DM in conventional vulcanization systems instead of HVA-2 according to the invention is exemplified by the following:
| serial number | Components | Amount per part |
| 1 | CSM40 | 100 |
| 2 | MgO-150 | 10 |
| 3 | Microcrystalline wax | 2 |
| 4 | Lubricant WS180 | 3 |
| 5 | Antiager NBC | 0.5 |
| 6 | Fast extrusion of carbon black | 10 |
| 7 | Silicon powder 750 | 20 |
| 8 | Light calcium carbonate | 50 |
| 9 | Plasticizer TOTM | 25 |
| 10 | Vulcanizing agent TRA | 1.5 |
| 11 | Scorch retarder DM | 2 |
The performance tests are as follows:
as can be seen from the examples 1-4 and the comparative example 1, the chlorosulfonated polyethylene rubber composition of the present invention, through optimization with a filling system and a vulcanization system, has significantly excellent scorch resistance and significant effects compared with the existing conventional CSM rubber compound, and significantly improves the production safety of the rubber compound.
In addition, the components of the rubber composition are matched with each other, the added accelerator is screened by creative labor by optimizing the synergistic action of the components, and the comparison of performance test data of the example 2 and the comparative example 2 shows that the effect of the addition of HVA-2 after screening of the components of the composition is also remarkable compared with the scorch resistance of the existing scorch retarder DM, so that the safety of production and reproduction of rubber compounds is ensured.
Claims (8)
1. The chlorosulfonated polyethylene rubber composition is characterized by further comprising the following components in parts by weight based on 100 parts of chlorosulfonated polyethylene rubber: 5-15 parts of magnesium oxide, 1-3 parts of microcrystalline wax, 2-4 parts of lubricant, 0.5-1 part of anti-aging agent, 5-20 parts of carbon black, 20-40 parts of silicon powder, 30-60 parts of light calcium carbonate, 20-30 parts of plasticizer, 1.5-2.5 parts of vulcanizing agent and 1-2 parts of accelerator; the magnesium oxide is high-activity magnesium oxide, and the iodine absorption value is 120-180; the vulcanizing agent is dipentamethylenethiuram tetrasulfide, and the accelerator is N, N' -m-phenylene bismaleimide.
2. The chlorosulfonated polyethylene rubber composition according to claim 1, wherein the chlorosulfonated polyethylene rubber is a chlorosulfonated polyethylene rubber having a chlorine content of 33 to 37%.
3. The chlorosulfonated polyethylene rubber composition of claim 1, wherein the plasticizer is an ester softener comprising, but not limited to, dioctyl phthalate, dioctyl sebacate, trioctyl trimellitate.
4. The chlorosulfonated polyethylene rubber composition of claim 3, wherein the plasticizer is trioctyl trimellitate.
5. The chlorosulfonated polyethylene rubber composition according to claim 1, wherein the lubricant is lubricant WS 180.
6. The chlorosulfonated polyethylene rubber composition according to claim 4, wherein the silicon powder is silicon powder 750.
7. The chlorosulfonated polyethylene rubber composition of claim 1, wherein the carbon black is a fast extruding carbon black.
8. Use of the chlorosulfonated polyethylene rubber composition of any one of claims 1 to 7 in the preparation of an automotive rubber hose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710158956.8A CN106928564B (en) | 2017-03-16 | 2017-03-16 | Chlorosulfonated polyethylene rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710158956.8A CN106928564B (en) | 2017-03-16 | 2017-03-16 | Chlorosulfonated polyethylene rubber composition |
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| CN106928564B true CN106928564B (en) | 2020-04-10 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344861A (en) * | 1989-08-16 | 1994-09-06 | Tosoh Corporation | Chlorosulfonated polyethylene polymer composition |
| CN101696305A (en) * | 2009-10-29 | 2010-04-21 | 天津鹏翎胶管股份有限公司 | Chlorosulfonated polyethylene lead-free recipe for power steering pipe |
| CN101735523A (en) * | 2009-12-11 | 2010-06-16 | 天津鹏翎胶管股份有限公司 | Chlorinated polyethylene rubber tube prescription resistant to power steering fluid |
-
2017
- 2017-03-16 CN CN201710158956.8A patent/CN106928564B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344861A (en) * | 1989-08-16 | 1994-09-06 | Tosoh Corporation | Chlorosulfonated polyethylene polymer composition |
| CN101696305A (en) * | 2009-10-29 | 2010-04-21 | 天津鹏翎胶管股份有限公司 | Chlorosulfonated polyethylene lead-free recipe for power steering pipe |
| CN101735523A (en) * | 2009-12-11 | 2010-06-16 | 天津鹏翎胶管股份有限公司 | Chlorinated polyethylene rubber tube prescription resistant to power steering fluid |
Non-Patent Citations (1)
| Title |
|---|
| N,N’-间苯撑马来酰亚胺硫化剂在CSM中的应用;杨永成;《合成橡胶工业》;19890829;第12卷(第4期);255-257 * |
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