CN101418109A - High temperature and high damping resistant rubber composite using polynorbornene rubber as main body - Google Patents
High temperature and high damping resistant rubber composite using polynorbornene rubber as main body Download PDFInfo
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- CN101418109A CN101418109A CNA2007100473378A CN200710047337A CN101418109A CN 101418109 A CN101418109 A CN 101418109A CN A2007100473378 A CNA2007100473378 A CN A2007100473378A CN 200710047337 A CN200710047337 A CN 200710047337A CN 101418109 A CN101418109 A CN 101418109A
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Abstract
The invention relates to a high-temperature resistant and high-damping rubber composition using polynorbornene rubber as a main body, which is characterized in that the composition bases on blending of the polynorbornene rubber and silicon rubber, uses blend of ethylene propylene diene rubber and ethylene-methyl acrylate copolymer as a compatibilizer for blending the polynorbornene rubber and the silicon rubber, simultaneously uses 2, 5-dimethyl-2, 5 (tertbutylperoxy) hexane as a vulcanizing agent and a vinyl triethoxy silicane as coupling agents. The rubber materials are mixed in an internal mixer at a temperature of 130 DEG C.
Description
Technical field
The present invention relates to the rubber item industry in the chemical industry field, specifically, relate to the rubber combination that resistant to elevated temperatures rubber item that a kind of manufacturing has the vibration and noise reducing function is used.
Background technology
The people of contemporary society generally pursue comfortable quiet life, so to having vibration and noise reducing materials with function and goods thereof special demand is arranged.Especially when automobile becomes one of requisite vehicles of people, to riding comfort, drive safety, the enforcement high speed of automobile and take luxury and all proposed more and more higher requirement.For solving a large amount of pollution problem, safety problem and the noise problem of bringing of using of automobile, relevant scientific and technological engineering technical personnel do a lot of work, and one of them important topic is to take the vibration and noise reducing measure to high-temperature exhaust pipe.Rubber is a kind of material with high inner friction performance, can be converted into heat energy to the mechanical energy that causes vibrations and noise effectively, thereby be damping vibration attenuation material the most frequently used in the engineering design, and elastomeric material is easy to process, can by extrude, working method such as mold pressing, injection, make different shape, satisfy different working conditionss.
Poly-norbornene rubber is succeeded in developing by French CdF Chimie company at first, and it is to be obtained by ethene and cyclopentadiene copolymerization by the Diels-Alder catalyzer.Have following molecular structure:
General name code name is PNR.The maximum feature of this rubber is very soft, can make durometer level and forgive the elastomer material of rubber sponge to various solid rubbers, in view of its high damping damping and amortization, can make shockproof, as to alleviate noise component at aspects such as automobile, railway, navigation, building, sports goodss, be expected to develop the shock insulation material that adapts to entire spectrum and (be illustrated in clean brook chief editor's " robber materials handbook, Chemical Industry Press, 1996, P308-310).But the ozone-resistant aging property of poly-norbornene rubber is not good, and resistance to elevated temperatures is also not ideal enough.When list is made the damping goods with this rubber, if will with some mechanical equipment coordination, often requirement simultaneously can have certain heatproof and endurance quality, and therefore, the anti-ozone ageing and the high thermal resistance that improve the poly-norbornene rubber goods have suitable realistic meaning.
Summary of the invention
What the purpose of this invention is to provide that a kind of resistance to elevated temperatures that can both prepare easily in ordinary rubber source mill obtains obviously to improve is main body high-temperature resistant rubber composition (this composition is referred to as sizing material in ordinary rubber source mill) with the poly-norbornene rubber, and this composition can be processed into the high temperature and high damping resistant rubber item with specified shape and function behind suitable means molding sulfuration.
The present invention realizes like this, described composition is based on poly-norbornene rubber, it is characterized in that, said composition is based on the fusion blend of poly-norbornene rubber and silicon rubber, is the expanding material of poly-norbornene rubber and silicon rubber fusion blend with the blend of terpolymer EP rubber and ethylene-methyl acrylate copolymer.
The polymer blending technology is the technology that is usually used in the elastomeric material modification at present, can realize learning from other's strong points to offset one's weaknesses of two or more materials, and silicon rubber (MQ) is that people know high-temperature resistant rubber, and its life-time service temperature can be up to 200～250 ℃.But well-known, what silicon rubber was that a class has following structure is the macromolecular elastomer of main chain with the siloxanes:
In the said structure formula, what only have the x part is dimethyl silicone rubber; The methyl vinyl silicone rubber that is that comprises x and z part; What add the y part is phenyl siloxane rubber.But, no matter be any silicon rubber, the skeleton of its molecular chain all is a siloxanes, structurally is very different with the poly-norbornene rubber that with carbon-carbochain is molecular backbone chain, so be difficult to reach compatible fully on thermodynamics.For the fusion blend of this family macromolecule material, must be able to form not homogeneous heterogeneous system of microcosmic, just can reach ideal blend effect.For this reason, the present invention to the expanding material that is applicable to silicon rubber and poly-norbornene rubber fusion blend, vulcanization system, can do meticulous screening by the compounding process that reinforced filling is promoted two kinds of interactional coupling agents of rubber and fusion blend.
Modern studies have shown that to macromolecular material fusion blend, in two kinds of less compatible macromolecular materials, mix these two kinds of macromolecular materials are all had to a certain degree the third polymkeric substance of consistency, can promote the blend effect of these two kinds of macromolecular materials, people are referred to as expanding material to this class material.Through a large amount of screening studies, the present inventor finds, the blend of terpolymer EP rubber and ethylene-methyl acrylate copolymer particularly after they are the mutual blend of 1:1 by weight, can be used as effective expanding material of poly-norbornene rubber and silicon rubber fusion blend.
Just as above-mentioned, the objective of the invention is to improve the heat-resisting and ozone resistance of poly-norbornene rubber by fusion silicon rubber, evidence, the strength and extension property of the cross-linked rubber that obtains after poly-norbornene rubber and the silicon rubber fusion blend descends with the increase of silicon rubber content, but the conservation rate of aging back strength and extension property improves with the increase of silicon rubber content.The present invention considers the over-all properties of high temperature and high damping resistant rubber combination, sets poly-norbornene rubber and silicon rubber fusion blending ratio, is preferably by weight: 75-65/25-35.
Expanding material as these two kinds of rubber fusion blend, be the consumption of weight meter 1:1 blend in composition of the present invention of terpolymer EP rubber and ethylene-methyl acrylate copolymer, add and be 100 weight parts together in poly-norbornene rubber and silicon rubber, be preferably 10～15 weight parts.
During two or more blend rubber, the performance of final product depends on that to a great extent can they realize synchronic curing, and this has great relation with the curing system of selecting for use.According to the present invention, adopt 2,5-dimethyl-2,5 (t-butyl peroxy) hexane [abbreviates it as " two-2; 5 in the industry " ] as the vulcanizing agent of the present composition, this at first is because with 2, and 5-dimethyl-2,5 (t-butyl peroxy) hexane is during as vulcanizing agent, the cross-linked speed of two kinds of rubber is close, help realizing that both sulfurized are synchronous, general being easy to get of this in addition organo-peroxide, easy to utilize.The material that makes has tensile strength height, high temperature resistant, advantage such as compression set is little.At this moment add in poly-norbornene rubber and silicon rubber and be 100 weight parts together, consumption is preferably 1.2～2.0 weight parts.
The present composition is when mixing, particularly when high-temperature mixing, ethylene-propylene-diene monomer gumminess as one of expanding material component obviously descends, so can promote the compatible role of itself and silicon rubber during high-temperature mixing, in addition, the application of coupling agent may further improve compatibilization effect by the interaction of reinforced fillings such as itself and white carbon black and then the interaction that can increase silicon rubber and terpolymer EP rubber.Described here coupling agent is vinyltriacetoxy silane (trade name A-151), and the consumption in this composition adds and is 100 weight parts together in poly-norbornene rubber and silicon rubber, is preferably 2.5～3.5 weight parts.
The preparation of the present composition should be adopted high-temperature mixing technology, promptly except that vulcanizing agent, the main ingredient of said composition, it is mixed to comprise that poly-norbornene rubber, silicon rubber, expanding material, coupling agent, weighting agent, dispersion agent all drop in 130 ℃ of hot Banburies fusion.After the discharging, at normal temperatures, with opening rubber mixing machine admixture vulcanizing agent.
High temperature and high damping resistant composition based on poly-norbornene rubber of the present invention compared with prior art, has tangible progress, at first, it has improved the high temperature resistant grade of poly-norbornene rubber, thereby has widened the use range of poly-norbornene rubber, secondly, the expanding material that the present invention selects for use, vulcanizing agent and coupling agent, all be the general auxiliary agent that is easy to get on the general Chemical market, thereby the source is unquestionable, easy to utilize.Once made the steam discharge pipe damping rubber components of passenger car with the present composition, its effect of vibration and noise reduction at this type high temp position is obvious, detects and the entrucking tyre mileage test through user's laboratory, and reflection is good.
Embodiment
Intend below the present invention being described in further detail, but the present invention is in no way limited to these embodiment by embodiment and comparative example.
Embodiment 1～3 and comparative example 1～12
The composition of embodiment 1～3 and comparative example 1～12 (sizing material) prescription is all listed in table 1, and each matching component consumption is all in weight part, and wherein, PNR is a poly-norbornene rubber, and QM is silicon rubber (this example all adopts methyl vinyl silicone rubber); Expanding material is 1:1 (weight meter) blend of terpolymer EP rubber and ethylene-methyl acrylate copolymer; Coupling agent is vinyltriacetoxy silane (A-151); Superoxide is 2,5-dimethyl-2, and 5-(t-butyl peroxy) hexane [two-2,5], the DCP in the comparative example 11 is a dicumyl peroxide; The AF-52 that dispersion agent is produced for TUV chemical company.All sizing materials are all used 130 ℃ of mixer mixings except that comparative example 12, and add vulcanizing agent (superoxide) with mill at normal temperatures again.Comparative example 12 adopts Banbury mixer normal temperature calendering process.Comparative example 1 and 2 is that the blending ratio of two kinds of rubber does not meet the present invention; Comparative example 3～5th, the coupling agent consumption does not meet the present invention; Comparative example 6～8th, the expanding material consumption does not meet the present invention; Comparative example 9～11st, superoxide are used and are not met the present invention; Comparative example 12 is that the sizing material preparation method does not meet the present invention.
More than each routine test result also as shown in table 1, these performance numbers all record according to corresponding national standards.By table 1 as seen, adopt the present invention program, can obtain preferable over-all properties.
Claims (6)
1, a kind of high temperature and high damping resistant rubber combination based on poly-norbornene rubber, it is characterized in that, said composition is based on the fusion blend of poly-norbornene rubber and silicon rubber, is the expanding material of poly-norbornene rubber and silicon rubber fusion blend with the blend of terpolymer EP rubber and ethylene-methyl acrylate copolymer.
2, the high temperature and high damping resistant rubber combination based on poly-norbornene rubber according to claim 1 is characterized in that, poly-norbornene rubber and silicon rubber fusion blending ratio are: 75～65/25～35 by weight.
3, the high temperature and high damping resistant rubber combination based on poly-norbornene rubber according to claim 1, it is characterized in that, described as the terpolymer EP rubber of expanding material and the blend of ethene-methyl acrylate copolymer, both blending ratios, be 1:1 by weight, the consumption of this blend in described composition adds and is 100 weight parts together in poly-norbornene rubber and silicon rubber, is 10～15 weight parts.
4, the high temperature and high damping resistant rubber combination based on poly-norbornene rubber according to claim 1, it is characterized in that, in described composition, adopt 2,5-dimethyl-2,5 (t-butyl peroxy) hexane is a vulcanizing agent, its consumption adds in poly-norbornene rubber and silicon rubber and is 100 weight parts together, is 1.2～2.0 weight parts.
5, the high temperature and high damping resistant rubber combination based on poly-norbornene rubber according to claim 1, it is characterized in that, in described composition, adopt the vinyltriacetoxy silane conduct in order to promote poly-norbornene rubber and the interactional coupling agent of silicon rubber, its consumption adds in poly-norbornene rubber and silicon rubber and is 100 weight parts together, is 2.5～3.5 weight parts.
6, the compounding process of the described high temperature and high damping resistant rubber combination based on poly-norbornene rubber of a kind of claim 1, it is characterized in that, except that vulcanizing agent, the main ingredient of said composition, it is mixed to comprise that poly-norbornene rubber, silicon rubber, expanding material, coupling agent, weighting agent, dispersion agent all drop in 130 ℃ of hot Banburies fusion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100473378A CN101418109A (en) | 2007-10-23 | 2007-10-23 | High temperature and high damping resistant rubber composite using polynorbornene rubber as main body |
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| CNA2007100473378A CN101418109A (en) | 2007-10-23 | 2007-10-23 | High temperature and high damping resistant rubber composite using polynorbornene rubber as main body |
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| CN101418109A true CN101418109A (en) | 2009-04-29 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694500A (en) * | 2013-11-15 | 2014-04-02 | 西安汉华橡胶科技有限公司 | Polynorbornene-containing damping rubber production method |
| CN103724908A (en) * | 2013-12-31 | 2014-04-16 | 长城汽车股份有限公司 | Low-hardness high-damping rubber composition and preparation method thereof |
| AT516679A1 (en) * | 2015-01-08 | 2016-07-15 | Karall Gerhard | Rubber compound composition |
| CN106939129A (en) * | 2017-03-27 | 2017-07-11 | 芜湖锐华暖通科技有限公司 | A kind of sound insulation material for drainage pipe and preparation method thereof |
| CN107353451A (en) * | 2017-06-05 | 2017-11-17 | 薛念念 | A kind of automotive suspension bushing high damping cushion rubber material and preparation method thereof |
| CN115651324A (en) * | 2022-10-28 | 2023-01-31 | 北京建筑大学 | Wide-temperature-range high-damping composite rubber material and preparation method thereof |
-
2007
- 2007-10-23 CN CNA2007100473378A patent/CN101418109A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694500A (en) * | 2013-11-15 | 2014-04-02 | 西安汉华橡胶科技有限公司 | Polynorbornene-containing damping rubber production method |
| CN103694500B (en) * | 2013-11-15 | 2015-11-25 | 西安汉华橡胶科技有限公司 | A kind of production method of the damping rubber containing poly-bornylene |
| CN103724908A (en) * | 2013-12-31 | 2014-04-16 | 长城汽车股份有限公司 | Low-hardness high-damping rubber composition and preparation method thereof |
| CN103724908B (en) * | 2013-12-31 | 2016-06-29 | 长城汽车股份有限公司 | Soft highly damping rubber composition and preparation method thereof |
| AT516679A1 (en) * | 2015-01-08 | 2016-07-15 | Karall Gerhard | Rubber compound composition |
| CN106939129A (en) * | 2017-03-27 | 2017-07-11 | 芜湖锐华暖通科技有限公司 | A kind of sound insulation material for drainage pipe and preparation method thereof |
| CN107353451A (en) * | 2017-06-05 | 2017-11-17 | 薛念念 | A kind of automotive suspension bushing high damping cushion rubber material and preparation method thereof |
| CN115651324A (en) * | 2022-10-28 | 2023-01-31 | 北京建筑大学 | Wide-temperature-range high-damping composite rubber material and preparation method thereof |
| CN115651324B (en) * | 2022-10-28 | 2024-06-04 | 北京建筑大学 | Wide-temperature-range high-damping composite rubber material and preparation method thereof |
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