CN100415824C - High-damping oil-resistant rubber composition - Google Patents
High-damping oil-resistant rubber composition Download PDFInfo
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- CN100415824C CN100415824C CNB2004100931461A CN200410093146A CN100415824C CN 100415824 C CN100415824 C CN 100415824C CN B2004100931461 A CNB2004100931461 A CN B2004100931461A CN 200410093146 A CN200410093146 A CN 200410093146A CN 100415824 C CN100415824 C CN 100415824C
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Abstract
The present invention relates to a high-damping oil-resistant rubber composition which takes polynorbornene rubber as a main body. The present invention is characterized in that the composition is prepared by taking mix and common blend of the polynorbornene rubber and nitrile rubber as foundation, taking dicumyl peroxide as a common crosslink agent, and taking tri-allyl isocyanurate as an assistant crosslink agent. The nitrile rubber contains 23 to 30% of acrylonitrile. The weight ratioof polynorbornene rubber and butadiene acrylonitrile rubber is (85 to 75): (15 to 25) by weight, an 80 to 20 is preferred.
Description
Technical field
The present invention relates to a kind of rubber combination that is used to make damping damping rubber goods, specifically, relate to a kind of itself to have the high-damping oil-resistant rubber composition that high damping properties is the poly-norbornene rubber of feature.
Background technology
Along with improving constantly of human living standard, people are also more and more higher to environment requirement of living in, and science and technology development impels the power of machinery equipment to increase, faster rotational speed, it is outstanding that vibration that causes therefrom and sound nuisance more and more show, promptly influence the work-ing life of machinery equipment except meeting, cause outside the early stage damage of equipment, also can be to people's work efficient, the physically and mentally healthy harmful effect that produces tackles this class vibration and noise effective means and is and uses efficiently that damping material absorbs, intercepts, shields and shake or the relay of noise.Rubber is a kind of material with high inner friction performance, can be effectively be converted into heat energy to the mechanical energy of vibrations and noise, and elastomeric material is easy to process, can by extrude, various working methods such as mold pressing, injection, make different shape, satisfy different working conditionss.Therefore, rubber is one of most popular damping material in the engineering.
Poly-norbornene rubber is succeeded in developing by French CDF Chimie company at first, and it is to be obtained by ethene and cyclopentadiene ring-opening copolymerization by the Diels-Alder catalyzer.Have following molecular structure, ASTM name code name is PNR.
The maximum feature of this rubber is very soft, can make the elastomer material that durometer level comprises rubber sponge and 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 disadvantage of poly-norbornene rubber is, it is as natural rubber, do not possess enough oil-proofnesss (referring to Dr.-lng.W.Goht, " Elastomere Dicht-und Konstruktionswerkstoffe ", P38), when it is used for the damping damping, during especially for some mechanical means, often require it can have certain oil resistance, therefore, the oil resistant class dielectric behavior of raising poly-norbornene rubber has suitable realistic meaning.
Summary of the invention
The purpose of this invention is to provide a kind of oil resistant class dielectric behavior that can both prepare easily and obtain the obviously high-damping oil-resistant rubber composition based on poly-norbornene rubber of improvement, the range of application of poly-norbornene rubber is further widened in ordinary rubber source mill.
The present invention realizes like this, it is a kind of high-damping oil-resistant rubber composition based on poly-norbornene rubber, it is characterized in that, said composition is based on the fusion blend of poly-norbornene rubber and paracril, with the dicumyl peroxide is co-crosslinker, is additional crosslinker with the triallyl isocyanurate.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, paracril is that people know universal oil resisting rubber, so the present invention just is conceived to improve with paracril the oil resistance of poly-norbornene rubber, chemical structure in view of poly-norbornene rubber, solubility parameter, there are certain difference in aspects such as inter-vulcanizability and paracril, therefore in order to realize both effective blend, the present inventor is to the acrylonitrile content of paracril, and the doping level of paracril and vulcanization system have been done meticulous screening.
As everyone knows, the oil resistance of paracril so increase acrylonitrile content, helps improving oil resistance along with the increase of acrylonitrile content improves; But along with the increase of acrylonitrile content, the polarity of paracril also can increase, so the consistency variation of itself and nonpolar poly-norbornene rubber is unfavorable for realizing both effective blend, causes physical and mechanical properties to descend.A large amount of evidences in order to realize effective blend of poly-norbornene rubber and paracril, improve the oil resistance of poly-norbornene rubber, and the acrylonitrile content of paracril is preferably 23～30%.Acrylonitrile content is low excessively, is improving DeGrain aspect the oil resistance.At this moment, the fusion blending ratio of poly-norbornene rubber and paracril is preferably by weight: 85～75/15～25, preferred 80/20.The mixing proportion of paracril is excessive, can undermine poly-norbornene rubber inherent damping damping capacity, otherwise the mixing proportion deficiency of paracril can cause oil resistance to reduce.
During two or more blend rubbers, the performance of final product depends on that to a great extent can they realize covulcanization, and the realization of covulcanization has great relation with the curing system of selecting for use again.According to the present invention, adopt the co-crosslinker of dicumyl peroxide (DCP) as these two kinds of rubber, this at first is because with dicumyl peroxide during as linking agent, the cross-linked speed of two kinds of rubber is close, help realizing covulcanization, general being easy to get of this in addition organo-peroxide, easy to utilize.Make excellent property such as ageing-resistant, the compression set of material.If use the general Sulfur-promotor curing system of rubber industry, because the solubleness of this class curing system in poly-norbornene rubber and paracril is big-difference very again, be difficult to realize that two kinds of sulfurations behind the blend rubber are synchronous, so that the physical and mechanical properties of final product is undesirable.
Test shows, as the suitable consumption of the dicumyl peroxide of co-crosslinker is: adding and be 100 weight parts together in poly-norbornene rubber and paracril, is 2～3 weight parts.In order further to improve cross-linking efficiency, improve the physical and mechanical properties of products therefrom, the present invention selects for use triallyl isocyanurate (TAIC) as the co-crosslinking auxiliary agent.Its suitable consumption is: poly-norbornene rubber and paracril add and are 100 weight part meters together, are 1～2 weight part.
High-damping oil-resistant rubber composition based on poly-norbornene rubber of the present invention compared with prior art, has tangible progress, at first, it has changed the insufficient shortcoming of poly-norbornene rubber oil resistance, make it to be applied to and the contacted occasion of mineral oils, thereby widened the Application Areas of poly-norbornene rubber; Secondly, the present invention select for use dicumyl peroxide as the co-crosslinker of blended rubber, select for use triallyl isocyanurate as the co-crosslinking auxiliary agent, these two kinds of materials all are common agents commonly used in the ordinary rubber factory, thereby the source is easy to get, and are easy to utilize.Once made the damping damping rubber spare of using in certain Chinese-foreign cooperation engineering with the present composition, test performance meets the requirements comprehensively through foreign side, and access authentication passes through.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention never is confined to these embodiment.The performance test results described in the embodiment, the numerical value that all refers to adopt the method for corresponding national standards regulation to record.
The fusion blend preparation of rubber master batch
For ease of showing effect of the present invention, at first prepare poly-norbornene rubber and paracril rubber master batch respectively by prescription shown in the table 1, used poly-norbornene rubber is NS * 15AB that Nippon Zeon Co., Ltd. produces, and this rubber master batch called rubber master batch A, used paracril is respectively butyronitrile-18, butyronitrile-26 and butyronitrile-40, and names successively and be rubber master batch B, rubber master batch C and rubber master batch D.
Table 1
| The component title | Consumption (weight part) |
| Rubber (poly-norbornene rubber or paracril) | 100 |
| High wear-resistant carbon black N330 | 50 |
| Dispersion agent | 1.5 |
| Microcrystalline wax | 2 |
| Anti-aging agent 4020 | 2 |
| Coupling agent | 1.7 |
| Co-crosslinking auxiliary agent TAIC | 1.5 |
Each component of table 1 is mixed in Banbury mixer, and dump temperature is controlled to be 120～130 ℃.
Embodiment 1～3 and comparative example 1～9
Press rubber master batch A, B, C, the D rubber master batch of the listed component preparation of table 1, according to shown in table 2 and the table 3 by different way after the fusion blend, sneak into different curing systems and consumption, make test with 160 ℃ * 8min sulfuration and use standard test piece, the test result that obtains is concluded as table 2 and table 3.
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Fusion blending ratio (w/w) | Rubber master batch A/ rubber master batch C=80/20 | Rubber master batch A/ rubber master batch C=85/15 | Rubber master batch A/ rubber master batch C=75/25 | Rubber master batch A/ rubber master batch C=80/20[annotates 1] | Rubber master batch A/ rubber master batch C=70/30 | Rubber master batch A/ rubber master batch C=90/10 | Rubber master batch A/ rubber master batch C=100/0 |
| Curing system | DCP 2.7 weight parts | DCP 2.5 weight parts | DCP 3.0 weight parts | DCP 2.7 weight parts | DCP 2.7 weight parts | DCP 2.7 weight parts | DCP 2.7 weight parts |
| Tensile strength, MPa | 16.77 | 16.2 | 16.9 | 14 | 13.8 | 16.3 | 17.92 |
| Tensile yield, % | 523 | 527 | 520 | 500 | 400 | 511 | 565 |
| Hardness (Shao Er A) | 71 | 69 | 72 | 63 | 69 | 73 | 75 |
| ASTM No.1 oil (100 ℃ * 70h), Λ % | +13.5 | +13.7 | +12 | +20 | +8 | +26.5 | +119 |
| ASTM No.1 oil (100 ℃ * 70h), Λ % | +46 | +45 | +43 | +60 | +38 | +67 | +128.5 |
| Oil fuel (room temperature * 168h), Λ % | +55 | +53 | +56 | +90 | +40 | +78 | +103 |
Annotate 1: in this embodiment, all do not add in rubber master batch A and the rubber master batch C with co-crosslinking auxiliary agent TAIC.
Comparative example 5 is to change the DCP curing system among the embodiment 1 into the sulfur vulcanization system, mixes N cyclohexyl 2 benzothiazole sulfenamide 1.5 weight parts, tetramethyl-thiuram disulfide 0.7 weight part, zinc oxide 5 weight parts, Sulfur 1.5 weight parts, vulkacit D that is:
Table 3
0.7 weight part.Comparative example 6 and 7 is that the DCP consumption among the embodiment 1 is changed into 1.5 and 3.5 weight parts respectively.Comparative example 8 and 9 is respectively and changes the rubber master batch A/ rubber master batch C=80/20 among the embodiment 1 into rubber master batch A/ rubber master batch B=80/20 and rubber master batch A/ rubber master batch D=80/20, and all the other are all identical with embodiment 1, and test-results and embodiment's 1 is more as shown in table 3.As seen, adopt the present invention can obtain best overall equilbrium at aspects such as anti-various mineral oil media and physical and mechanical propertiess.
Claims (3)
1. high-damping oil-resistant rubber composition based on poly-norbornene rubber, it is characterized in that, said composition is co-crosslinker based on the fusion blend of poly-norbornene rubber and paracril with the dicumyl peroxide, is additional crosslinker with the triallyl isocyanurate; The acrylonitrile content of described paracril is 23～30%; The fusion blending ratio of poly-norbornene rubber and paracril is: 85～75/15～25 by weight.
2. high-damping oil-resistant rubber composition according to claim 1 is characterized in that, the consumption of described co-crosslinker dicumyl peroxide adds and is 100 weight parts together in poly-norbornene rubber and paracril, is 2～3 weight parts.
3. high-damping oil-resistant rubber composition according to claim 1 is characterized in that, the consumption of described crosslinking coagent triallyl isocyanurate adds and is 100 weight parts together in poly-norbornene rubber and paracril, is 1～2 weight part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100931461A CN100415824C (en) | 2004-12-17 | 2004-12-17 | High-damping oil-resistant rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100931461A CN100415824C (en) | 2004-12-17 | 2004-12-17 | High-damping oil-resistant rubber composition |
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| CN1789326A CN1789326A (en) | 2006-06-21 |
| CN100415824C true CN100415824C (en) | 2008-09-03 |
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| CNB2004100931461A Expired - Fee Related CN100415824C (en) | 2004-12-17 | 2004-12-17 | High-damping oil-resistant rubber composition |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040823A (en) * | 2009-10-23 | 2011-05-04 | 上海华向橡胶制品有限公司 | Damping rubber |
| CN102140207B (en) * | 2011-04-07 | 2012-12-26 | 上海交通大学 | Rubber base damping material and preparation method thereof |
| CN103045171B (en) * | 2013-01-21 | 2015-01-28 | 广东富华重工制造有限公司 | Dust inhibitor of friction material and application 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 |
| CN104130539B (en) * | 2014-08-11 | 2016-08-17 | 上海经纬峰实业有限公司 | A kind of fire-retardant highly damping rubber composition based on poly-norbornene rubber |
| 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 |
| CN112592461B (en) * | 2020-12-14 | 2022-02-11 | 北京化工大学 | Modified hydrogenated nitrile rubber material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000064481A (en) * | 1998-08-19 | 2000-02-29 | Hayakawa Rubber Co Ltd | Soundproof board, soundproof floor material, and soundproof floor structure |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000064481A (en) * | 1998-08-19 | 2000-02-29 | Hayakawa Rubber Co Ltd | Soundproof board, soundproof floor material, and soundproof floor structure |
Non-Patent Citations (4)
| Title |
|---|
| 辊筒贴面用的特种橡胶. 毕莲英.世界橡胶工业，第27卷第2期. 2000 |
| 辊筒贴面用的特种橡胶. 毕莲英.世界橡胶工业，第27卷第2期. 2000 * |
| 降冰片烯及其衍生物之利用. 崔昌亿，谭乃迪等.吉林化工学院学报，第13卷第1期. 1996 |
| 降冰片烯及其衍生物之利用. 崔昌亿，谭乃迪等.吉林化工学院学报，第13卷第1期. 1996 * |
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