CN107337814B - A kind of high-damping rubber material and preparation method thereof - Google Patents
A kind of high-damping rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high-damping rubber materials, it is mainly prepared by following mass parts raw material: 100 parts of rubber, 1-4 parts of sulphur, 3-8 parts of anti-aging agent, 3-10 parts of zinc oxide, 1-5 parts of stearic acid, 20-75 parts of polar filler, 5-20 parts of plasticizer, 1-3 parts of accelerant CZ, it is anti-to revert 0.2-2 parts of agent, hindered phenol and/or 10-50 parts of hindered amine；Rubber is the combination of polar rubber or polar rubber and non-polar rubber；When rubber is the combination of polar rubber and non-polar rubber, the quality of polar rubber is not less than 20 parts；Polar filler is lignin fibre and/or white carbon black.Preparation method of the invention: carrying out high-temperature mixing for all raw materials in addition to sulphur and promotor, cooling, obtains masterbatch；Sulphur is added in masterbatch and promotor is kneaded, stands, vulcanization obtains high-damping rubber material.The thermal stability of high-damping rubber material of the invention is had excellent performance, and is confirmed to be precipitated without small molecule by hot oxygen accelerated ageing, can be met long-time requirement.
Description
Technical field
The invention belongs to field of rubber materials more particularly to a kind of with good performance steady in the long-term use process
Qualitative high-damping rubber and preparation method thereof.
Background technique
With the development of modern science and technology and the continuous improvement of human living standard, people are to work and life environment
Comfort propose higher requirement, thus how effectively to administer all kinds of vibrations and the pollution of noise, it has also become scientist
One of important topic of care.Rubber has good damping due to its distinctive viscous-elastic behaviour, extensive at present
The damping noise reduction for being applied to the fields such as rail traffic, building, machinery.
Rubber plastic blend is a kind of common method for improving damping, as disclosed a kind of high resistant in CN201410128421 patent
Buddhist nun's rubber support and preparation method thereof, but this method generally requires and is individually mixed plastic pellet with plasticizer, increases rubber
The use of the equipment such as the moulding process of glue material and kneader.It is de- that CN201610882263 discloses a kind of automobile hindered phenol illiteracy
The fillers such as montmorillonite, cork fibrous are utilized to design resistance in native nitrile rubber composite damping material and preparation method thereof, the patent
Damping material, but it is related to the use of a variety of organic solvents such as dimethylbenzene, hydroxide sodium hypophosphite, the process is more complicated.
In addition, rubber during long-time service, is heated, the effect of oxygen, rubber molecular chain is easy aging fracture, performance
It can have greatly changed.For high-damping rubber, performance change is not only by the effect of thermo-oxidative ageing, while high-damping rubber
A large amount of operation oil and small organic molecule are often dosed in glue to be obstructed substance, is easy to be precipitated after thermo-oxidative ageing, and the performance oxygen that is heated is old
It is bigger compared with ordinary rubber material to change influence.
And be to improve this technical problem, it substantially improves, improves in terms of the synthesis of macromolecular chain hindered phenol at present
Hindered phenol is easy the problem of being precipitated in high-damping rubber, and it is single to solve damping stability performance, can not improve comprehensively.And
High-damping rubber not only can be occurred molecular chain rupture by the effect of hot oxygen, also suffer from simultaneously during long-time service
The problem of hindered phenol, operation oil are precipitated, this technical problem needs to carry out synthesis improvement.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Plant the high-damping rubber and preparation method thereof of stability with good performance in the long-term use process.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of high-damping rubber material is mainly prepared from the following materials by mass parts:
100 parts of rubber,
1-4 parts of sulphur,
3-8 parts of anti-aging agent,
3-10 parts of zinc oxide,
1-5 parts of stearic acid,
20-75 parts of polar filler,
5-20 parts of plasticizer,
1-3 parts of accelerant CZ,
It is anti-to revert 0.2-2 parts of agent,
Hindered phenol and/or 10-50 parts of hindered amine；
The rubber is polar rubber, or the combination for polar rubber and non-polar rubber；When the rubber is polarity
When the combination of rubber and non-polar rubber, the quality of polar rubber is not less than 20 parts；By rubber polar groups with it is organic small
Molecular hybrid improves the damping capacity of rubber material, while reducing small molecule by the constraint of weak bond effect and being precipitated.
The polar filler is lignin fibre and/or white carbon black.It selects lignin, white carbon black as polar filler, increases
Add the active force between hindered amine or hindered phenol and filler, avoids the precipitation of small organic molecule object.
Above-mentioned high-damping rubber material, it is preferred that hindered phenol is used in combination with hindered amine, and weak bond can be improved by synergistic effect
Formation, thus improve rubber material damping capacity and reduce small molecule be precipitated.
Above-mentioned high-damping rubber material, it is preferred that its raw material further include:
5-75 parts of lamella filler and the coupling agent for accounting for lamella packing quality content 0.5%-20%；
The lamella filler is one or more of mica, kaolin and montmorillonite；The coupling agent be KH-550 and
One or more of Si-69.When rubber is blended with lamella filler, rubber molecular chain is inserted between lamella filler, is formed
On the one hand special intercalation configuration can play barrier action to the migration of the small molecules such as operation oil, hindered amine, hindered phenol, separately
One side lamella filler can form blocking effect to extraneous heat, oxygen, ozone, avoid the aging of rubber material, fill out simultaneously
Coupling agent is added, has increased by active force between small organic molecule, filler and rubber molecular chain；The lamella filler blocking effect shows
It is intended to as shown in Figure 1.
Above-mentioned high-damping rubber material, it is preferred that the polar rubber is NBR rubber (nitrile rubber), CIIR rubber
One or more of (chlorinated scoline), BIIR rubber (brombutyl).
Above-mentioned high-damping rubber material, it is preferred that the hindered phenol has alkyl group, and the carbon atom number in alkyl group is
15 or more, and there are two or more cyclic structures.The hindered phenol with long chain alkyl group class formation is selected, on the one hand
The resistance to precipitation of impeding material with chain alkyl is had excellent performance, and on the other hand the hindered phenol with chain alkyl increases and rubber
Compatibility between matrix can be avoided hindered phenol precipitation.
Above-mentioned high-damping rubber material, it is preferred that the hindered phenol be hindered phenol KHY-1330, hindered phenol 1076, by
Hinder one of phenol 1010, hindered phenol 1098, hindered phenol AO-60, hindered phenol AO-80, hindered phenol 3114, hindered phenol 3115 or several
Kind.
Above-mentioned high-damping rubber material, it is preferred that the hindered amine is hindered amine 770 and/or hindered amine GW-3346.
Above-mentioned high-damping rubber material, it is preferred that anti-recovery agent selection PK900, WK901, HS258,
One or more of WY918, ZXK900, compensating action is played in the fracture of strand when vulcanizing to long-time, to meet big
Vulcanization needs type rubber product for a long time.
Above-mentioned high-damping rubber material, it is preferred that the anti-aging agent includes 1-3 parts of anti-aging agent RDs and 2-5 parts of anti-aging agents
4010NA。
Above-mentioned high-damping rubber material, it is preferred that the plasticizer is DOP (dioctyl phthalate) or aromatic hydrocarbons
Oil.
The inventive concept total as one, the present invention also provides a kind of preparation method of above-mentioned high-damping rubber material, packets
Include following steps:
(1) high-temperature mixing will be carried out in all raw materials investment mixer in addition to sulphur and promotor, it is cooling, obtain mother
Refining glue；
(2) masterbatch is put on opening rubber mixing machine, is homogeneously added into sulphur and promotor is kneaded, it is quiet
It sets, is finally vulcanized, obtain the high-damping rubber material.
Above-mentioned preparation method, it is preferred that in the step (1), the temperature of high-temperature mixing is 110-130 DEG C；
In the step (2), time of standing be for 24 hours more than, the temperature of vulcanization is 140-160 DEG C, and the time of vulcanization is
15-30min。
Compared with the prior art, the advantages of the present invention are as follows:
(1) thermal stability of high-damping rubber material of the invention is had excellent performance, and is confirmed by hot oxygen accelerated ageing without small
Molecule is precipitated, and can meet long-time requirement.
(2) high-damping rubber material of the invention can satisfy the large-scale rubber such as one meter of size or more high-damp rubber support
Vulcanization needs product for a long time, and curability conservation rate is more excellent.
(3) high-damping rubber material equivalent damping ratio of the invention is greater than 25%, and energy consumption effect protrudes.
(4) preparation process of high-damping rubber material of the invention is special without increasing compared with the preparation of traditional rubber material
Process, preparation process are simple.
Detailed description of the invention
Fig. 1 is lamella filler isolation effectiveness principle schematic diagram in the present invention.
Fig. 2 is the testing machine structure schematic diagram of present invention test damping capacity.
Fig. 3 is the example master drawing that service-test machine of the present invention to form hysteresis loop by loading to sample.
Marginal data:
1, locking nut；2, connecting plate；3, fixture；4, pin shaft one；5, lower fixture；6, pin shaft two；7, the gap that disappears plate；8, disappear gap
Ring.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to specific embodiment.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The evaluation of damping capacity shears sample using two panels in following embodiments and comparative example, as shown in Fig. 2: passing through
Connecting plate 2 is connect by locking nut 1 with rubber loading tester and upper fixture, is connected test sample and fixture 3 by pin shaft 1
It connects；The sample other end is fixed by lower fixture 5 and pin shaft 26, to guarantee that sample is steady in load, using 7 He of gap plate that disappears
The gap that disappears ring 8 is fixed.Load deflection is set as the 100% of sample rubber thickness, loading frequency 2Hz.Equivalent damping ratio Heq
The energy W absorbed in hysteresis loop is loaded according to the above methoddWith elastic deformation can the ratio between W, as shown in Fig. 3, calculation formula are as follows:
Long-time curability passes through reversion percentage (Rt) characterization, the smaller sulfuration resistant for indicating sizing material of reversion percentage value
Performance of reverting is better, i.e., more suitable long-time vulcanization needs, and calculation formula is as follows:
Wherein, MHFor sizing material peak torque, MLFor sizing material minimum torque, MtReach torsion in t hours after peak torque for sizing material
Square value, institute's measured data is R under the conditions of 150 DEG C in the present invention3It reverts rate.
Comparative example:
The high-damping rubber material of this comparative example, is mainly prepared from the following materials:
Nitrile rubber (butyronitrile content > 38%) 30kg,
Natural rubber 70kg,
Sulphur 2kg,
Anti-aging agent RD 2kg,
Antioxidant 4010NA 3.5kg,
Zinc oxide 5kg,
Stearic acid 2kg,
Carbon black N110 55kg,
DOP 10kg、
Accelerant CZ 1.5kg,
AO-60 30kg。
The preparation method of the high-damping rubber material of the present embodiment, comprising the following steps:
(1) mixer is cooling, by above-mentioned raw materials in all raw materials investment mixer in addition to sulphur and promotor into
Row mixing, using 120 DEG C of high-temperature mixings, the slice on opening rubber mixing machine is cooling, obtains masterbatch；
(2) on the masterbatch investment opening rubber mixing machine obtained step (1), be homogeneously added into sulphur, accelerant CZ into
Row is kneaded, and is then allowed to stand and is parked more than for 24 hours, then vulcanizes 20min at 150 DEG C to get high-damping rubber material is arrived.
The high-damping rubber material that this comparative example is obtained is tested according to GB/T528 test method, and tensile strength is
19.8MPa, elongation at break 420%, DMTA measure rubber material maximum loss factor 1.1；Anti-recovery rate R3It is 35%,
It is 21% that equivalent damping ratio, which is calculated, by design scheme in damping capacity.The high-damping rubber material of preparation is placed in 70 DEG C of drums
There are a large amount of precipitates in aging 168h in wind baking oven, the rubbery sample surface after aging, and tensile strength change rate is 12%, fracture
Elongation change rate 18%, rubber material equivalent damping ratio change rate 30% after aging；Rubber material room temperature obtained is parked
360 days, there is precipitate, tensile strength change rate 18%, elongation at break change rate 21%, equivalent damping ratio change in specimen surface
Rate 35%.
Embodiment 1:
A kind of high-damping rubber material of the invention, is mainly prepared from the following materials:
Nitrile rubber (butyronitrile content > 38%) 30kg,
Natural rubber 70kg,
Sulphur 2kg,
Anti-aging agent RD 2kg,
Antioxidant 4010NA 3.5kg,
Zinc oxide 5kg,
Stearic acid 2kg,
Lignocellulosic 20kg,
Carbon black N110 55kg,
DOP 10kg、
Accelerant CZ 1.5kg,
AO-60 30kg、
The anti-agent PK900 1kg that reverts.
The preparation method of the high-damping rubber material of the present embodiment, comprising the following steps:
(1) mixer is cooling, by above-mentioned raw materials in all raw materials investment mixer in addition to sulphur and promotor into
Row mixing, using 120 DEG C of high-temperature mixings, the slice on opening rubber mixing machine is cooling, obtains masterbatch；
(2) on the masterbatch investment opening rubber mixing machine obtained step (1), be homogeneously added into sulphur, accelerant CZ into
Row is kneaded, and is then allowed to stand and is parked more than for 24 hours, then vulcanizes 20min at 150 DEG C to get high-damping rubber material is arrived.
The high-damping rubber material that the present embodiment is obtained is tested according to GB/T528 test method, and tensile strength is
21.9MPa, elongation at break 456%, DMTA measure rubber material maximum loss factor 1.6；Anti-recovery rate R3It is 20%,
It is 23% that equivalent damping ratio, which is calculated, by design scheme in damping capacity；The high-damping rubber material of preparation is placed in 70 DEG C of drums
Aging 168h in wind baking oven, the rubbery sample surface after aging is without precipitate, and tensile strength change rate is 10%, elongation at break
Change rate 16%, rubber material equivalent damping ratio change rate 25% after aging；Rubber material room temperature obtained is parked 360 days,
Specimen surface becomes without precipitate, tensile strength change rate 15%, elongation at break change rate 17%, rubber material equivalent damping ratio
Rate 15%.
Embodiment 2:
A kind of high-damping rubber material of the invention, is mainly prepared from the following materials:
The preparation method of the high-damping rubber material of the present embodiment, comprising the following steps:
(1) mixer is cooling, by above-mentioned raw materials in all raw materials investment mixer in addition to sulphur and promotor into
Row mixing, using 120 DEG C of high-temperature mixings, the slice on opening rubber mixing machine is cooling, obtains masterbatch；
(2) on the masterbatch investment opening rubber mixing machine obtained step (1), be homogeneously added into sulphur, accelerant CZ into
Row is kneaded, and is then allowed to stand and is parked more than for 24 hours, then vulcanizes 20min at 150 DEG C to get high-damping rubber material is arrived.
The high-damping rubber material that the present embodiment is obtained is tested according to GB/T528 test method, and tensile strength is
23.2MPa, elongation at break 431%, DMTA measure rubber material maximum loss factor 1.8；Anti-recovery rate R3For
19%, it is 23.5% that equivalent damping ratio, which is calculated, by design scheme in damping capacity.High-damping rubber material will be prepared to be placed in
Aging 168h in 70 DEG C of convection ovens, rubbery sample surface after aging is without precipitate, aging post-tensioning change rate of strength 7%,
Elongation at break change rate 14%, rubber material equivalent damping ratio change rate 15% after aging；By rubber material room temperature obtained
It parks 360 days, specimen surface is without precipitate, tensile strength change rate 8%, elongation at break change rate 15%, rubber material etc.
Imitate variation of damping ratio rate 7%.
Embodiment 3:
A kind of high-damping rubber material of the invention, is mainly prepared from the following materials:
The preparation method of the high-damping rubber material of the present embodiment, comprising the following steps:
(1) mixer is cooling, by above-mentioned raw materials in all raw materials investment mixer in addition to sulphur and promotor into
Row mixing, using 120 DEG C of high-temperature mixings, the slice on opening rubber mixing machine is cooling, obtains masterbatch；
(2) on the masterbatch investment opening rubber mixing machine obtained step (1), be homogeneously added into sulphur, accelerant CZ into
Row is kneaded, and is then allowed to stand and is parked more than for 24 hours, then vulcanizes 20min at 150 DEG C to get high-damping rubber material is arrived.
The high-damping rubber material that the present embodiment is obtained breaks according to GB/T528 test method, tensile strength 22.3MPa
Elongation 443% is split, rubber material maximum loss factor 1.8 is measured；Anti-recovery rate R3It is 10%, damping capacity is by design
It is 33% that equivalent damping ratio, which is calculated, in scheme.The high-damping rubber material of preparation is placed in aging in 70 DEG C of convection ovens
168h, the rubbery sample surface after aging is without precipitate, aging post-tensioning change rate of strength 8%, elongation at break change rate
12%, equivalent damping ratio change rate 20%；Rubber material room temperature obtained is parked 360 days, specimen surface is stretched without precipitate
Change rate of strength 9%, elongation at break change rate 13%, rubber material equivalent damping ratio change rate 8%.
Embodiment 4:
A kind of high-damping rubber material of the invention, is mainly prepared from the following materials:
The preparation method of the high-damping rubber material of the present embodiment, comprising the following steps:
(1) mixer is cooling, by above-mentioned raw materials in all raw materials investment mixer in addition to sulphur and promotor into
Row mixing, using 120 DEG C of high-temperature mixings, the slice on opening rubber mixing machine is cooling, obtains masterbatch；
(2) on the masterbatch investment opening rubber mixing machine obtained step (1), be homogeneously added into sulphur, accelerant CZ into
Row is kneaded, and is then allowed to stand and is parked more than for 24 hours, then vulcanizes 20min at 150 DEG C to get high-damping rubber material is arrived.
The high-damping rubber material that the present embodiment is obtained breaks according to GB/T528 test method, tensile strength 24.2MPa
Elongation 615% is split, DMTA measures rubber material maximum loss factor 1.7；Anti-recovery rate R3It is 15%, damping capacity is pressed
It is 35% that equivalent damping ratio, which is calculated, in design scheme.The rubber material of preparation is placed in 70 DEG C of convection oven aging 168h,
Rubbery sample surface after aging is without precipitate, aging post-tensioning change rate of strength 3%, elongation at break change rate 11%, rubber
Glue material equivalent damping ratio change rate 5%；Rubber material room temperature obtained is parked 360 days, specimen surface is without precipitate, aging
Post-tensioning change rate of strength 4%, elongation at break change rate 12%, rubber material equivalent damping ratio change rate 3%.
Through the foregoing embodiment with the Comparison of experiment results of comparative example it can be found that the present invention can solve the analysis of small molecule
It goes wrong, effect is ideal when acting synergistically especially by hindered phenol with hindered amine and applying simultaneously with interlayer blocking effect.
Claims (8)
1. a kind of high-damping rubber material, which is characterized in that press mass parts, be mainly prepared from the following materials:
100 parts of rubber,
1-4 parts of sulphur,
3-8 parts of anti-aging agent,
3-10 parts of zinc oxide,
1-5 parts of stearic acid,
20-75 parts of polar filler,
5-20 parts of plasticizer,
1-3 parts of accelerant CZ,
It is anti-to revert 0.2-2 parts of agent,
Hindered phenol and/or 10-50 parts of hindered amine；The hindered phenol has alkyl group, the carbon atom number in alkyl group be 15 with
On, and there are two or more cyclic structures；
5-75 parts of lamella filler and the coupling agent for accounting for lamella packing quality content 0.5%-20%；
Wherein, the rubber is polar rubber, or the combination for polar rubber and non-polar rubber；When the rubber is polarity
When the combination of rubber and non-polar rubber, the quality of polar rubber is not less than 20 parts；The polar rubber is NBR rubber, CIIR
One or more of rubber, BIIR rubber；
The polar filler is lignin fibre.
2. high-damping rubber material as described in claim 1, which is characterized in that
The lamella filler is one or more of mica, kaolin and montmorillonite；The coupling agent is KH-550 and Si-69
One or more of.
3. high-damping rubber material as described in claim 1, which is characterized in that the anti-agent of reverting be PK900, WK901,
One or more of WY918, ZXK900 and DL-268.
4. high-damping rubber material as described in claim 1, which is characterized in that the hindered phenol be hindered phenol KHY-1330,
Hindered phenol 1076, hindered phenol 1010, hindered phenol 1098, hindered phenol AO-60, hindered phenol AO-80, hindered phenol 3114, hindered phenol
One or more of 3115；The hindered amine is one or more of hindered amine 770 and hindered amine GW-3346.
5. high-damping rubber material as described in claim 1, which is characterized in that the anti-aging agent includes 1-3 parts of anti-aging agent RDs
With 2-5 parts of antioxidant 4010NAs.
6. high-damping rubber material as described in claim 1, which is characterized in that the plasticizer is DOP or aromatic naphtha.
7. a kind of preparation method of high-damping rubber material as claimed in any one of claims 1 to 6, which is characterized in that including with
Lower step:
(1) high-temperature mixing will be carried out in all raw materials investment mixer in addition to sulphur and promotor, it is cooling, obtain masterbatching
Glue；
(2) masterbatch is put on opening rubber mixing machine, is homogeneously added into sulphur and promotor is kneaded, stood, most
After vulcanized, obtain the high-damping rubber material.
8. preparation method as claimed in claim 7, which is characterized in that in the step (1), the temperature of high-temperature mixing is 110-
130℃；
In the step (2), time of standing be for 24 hours more than, the temperature of vulcanization is 140-160 DEG C, and the time of vulcanization is 15-
30min。
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| CN111303580A (en) * | 2020-01-23 | 2020-06-19 | 上海锦湖日丽塑料有限公司 | High-damping low-noise ABS composition and preparation method thereof |
| CN111286130A (en) * | 2020-03-31 | 2020-06-16 | 苏州普茨迈精密航空设备有限公司 | Vehicle damping noise-reducing reinforcing damping fin and preparation process thereof |
| HRP20230784T1 (en) * | 2020-09-23 | 2023-10-27 | Suncoal Industries Gmbh | Rubber composition for an inner liner for pneumatic vehicle tyres |
| CN112029203A (en) * | 2020-09-24 | 2020-12-04 | 广东邦达实业有限公司 | High-damping rubber material with high vibration damping performance |
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| CN102050966B (en) * | 2009-11-06 | 2014-06-18 | 住友橡胶工业株式会社 | High-damping composition |
| US20130253143A1 (en) * | 2010-09-30 | 2013-09-26 | Kaneka Corporation | Composition containing branched polymer for damping material |
| JP5330460B2 (en) * | 2011-07-04 | 2013-10-30 | 住友ゴム工業株式会社 | High damping composition |
| CN103302930A (en) * | 2013-06-21 | 2013-09-18 | 四川大学 | Macromolecule-based flame-retarding and damping composite material and preparation method thereof |
| CN105295211A (en) * | 2015-11-20 | 2016-02-03 | 浙江世泰实业有限公司 | High-damping rubber composition and preparation method therefor |
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