CN105315511A - Natural rubber and butadiene rubber blend and preparation method therefor and application thereof - Google Patents
Natural rubber and butadiene rubber blend and preparation method therefor and application thereof Download PDFInfo
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- CN105315511A CN105315511A CN201410372872.0A CN201410372872A CN105315511A CN 105315511 A CN105315511 A CN 105315511A CN 201410372872 A CN201410372872 A CN 201410372872A CN 105315511 A CN105315511 A CN 105315511A
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Abstract
The invention discloses a natural rubber and butadiene rubber blend and a preparation method therefor and an application thereof. The blend comprises the following components in parts by weight: 70-85 parts of natural rubber, 15-30 parts of butadiene rubber, 1.0-2.5 parts of a sulfur carrier auxiliary agent, 5-100 parts of carbon black and/or white carbon black and 10-15 parts of other accessory ingredients. The preparation method comprises the steps of: mixing natural rubber with butadiene rubber; then successively adding the carbon black and/or white carbon black, the other accessory ingredients and the sulfur carrier auxiliary agent; mixing the components to obtain a rubber compound; and then vulcanizing the rubber compound to obtain the blend. The natural rubber and butadiene rubber blend disclosed by the invention has extremely excellent low-temperature crystallization resistance, a vulcanized rubber product of the blend has a quite small low-temperature rigidity rate of change, and the blend is simple and convenient in preparation process and low in cost, and can be widely used in the field of damping rubber products.
Description
Technical field
The present invention relates to blend rubber Material Field, be specifically related to a kind of low temperature resistant natural rubber and cis-polybutadiene Blends and its preparation method and application.
Background technology
Natural rubber not only has good mixed refining process performance, also has higher compound physical mechanical property, is widely used in manufacturing in sebific duct, adhesive tape, damping products.Although the second-order transition temperature of natural rubber is-72 DEG C, but because natural rubber is a kind of crystal type rubber, it often just loses elasticity under the low temperature more much higher than second-order transition temperature, shows the phenomenon that hardness, Young's modulus and rubber product rigidity increase.In order to improve the resistance to low temperature of natural rubber, usually adopt following methods from the viewpoint of elastomeric material: (1) also improves the low-temperature performance of natural rubber by other glue kinds; (2) certain plasticizers is added.But these methods have following deficiency: although the temperature limit of brittleness of blend compounds material reduces, significantly cannot reduce the increase of natural rubber Young's modulus at low temperatures, also just cannot solve the Natural Rubber Products problem that stiffness variation rate is excessive at low temperatures.Add softening agent and can reduce its second-order transition temperature, but, very little to the low temperature crystallization performance impact of natural rubber, fundamentally cannot improve the low temperature resistant crystal property of natural rubber, thus the resistance to low temperature of natural rubber cannot be significantly improved.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of and have splendid low temperature resistant crystal property, natural rubber and cis-polybutadiene Blends and its preparation method and application that its vulcanized rubber products has very little low temperature toughness velocity of variation.
For solving the problems of the technologies described above, the technical solution used in the present invention is a kind of natural rubber and cis-polybutadiene Blends, described blend comprises the component of following mass parts: natural rubber 70 parts ~ 85 parts, cis-1,4-polybutadiene rubber (i.e. cis-polybutadiene rubber) 15 parts ~ 30 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described blend comprises the component of following mass parts: natural rubber 80 parts ~ 85 parts, cis-1,4-polybutadiene rubber 15 parts ~ 20 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described natural rubber comprises one or more in pearl glue, smoke sheet rubber, air dried sheet(ADS) glue, crepe rubber, natural rubber with constant viscosity.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described cis-1,4-polybutadiene rubber comprises and contains intermingle with cis-rich polybutadiene rubber, contains intermingle with low cis polybutadiene rubber or contain intermingle with superelevation cis-polybutadiene rubber.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described sulfur-donor auxiliary agent is phosphorodithioate.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described carbon black comprises N100 series, N200 series, N300 is serial, N400 is serial, N500 is serial, N600 is serial, N700 is serial, N800 is serial, N900 is serial, one or more in Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, described white carbon black comprises precipitated silica and/or thermal silica.
In above-mentioned natural rubber and cis-polybutadiene Blends, preferably, other Synergist S-421 95 described comprises one or more in promotor, vulcanizing agent, promoting agent, anti-aging agent, tenderizer and silane coupling agent.In the present invention, other Synergist S-421 95 can select the conventional variety that coordinates with natural rubber and consumption as required.
As a total technical conceive, the present invention also provides the preparation method of a kind of above-mentioned natural rubber and cis-polybutadiene Blends, comprises the following steps:
(1) added by natural rubber in general rubber preparing device, plasticate 20min ~ 30min at the temperature of 20 DEG C ~ 50 DEG C, then adds cis-1,4-polybutadiene rubber and mix;
(2) successively add carbon black and/or white carbon black, other Synergist S-421 95, sulfur-donor auxiliary agent in the mixture obtained to step (1), then conveniently refine the mixing 20min ~ 30min of glue method, melting temperature is 60 DEG C ~ 80 DEG C, obtains rubber unvulcanizate;
(3) by the rubber unvulcanizate age overnight that step (2) obtains, then conveniently rubber vulcanization process at 100 DEG C ~ 200 DEG C by rubber unvulcanizate sulfuration 30min ~ 60min, obtain natural rubber and cis-polybutadiene Blends.
As total technical conceive, the natural rubber that the present invention also provides a kind of above-mentioned natural rubber and cis-polybutadiene Blends or above-mentioned preparation method to obtain and the application of cis-polybutadiene Blends in vibration isolation rubber arts.Wherein, this blend is mainly used in the damping products fields such as track traffic, automobile, aircraft, steamer, bridge pad, instrument and aerospace.
Compared with prior art, the invention has the advantages that:
The present invention adopts natural rubber and the cis-1,4-polybutadiene rubber of specific blending ratio, employ a kind of special sulfur-donor auxiliary agent to prepare and have splendid low temperature resistant crystal property, its vulcanized rubber products has natural rubber and the cis-polybutadiene Blends of very little low temperature toughness velocity of variation simultaneously.One aspect of the present invention improves the kindliness of sizing material by introducing cis-1,4-polybutadiene rubber molecular chain, on the other hand, the special cross-link bond formed by sulfur-donor auxiliary agent stops natural rubber and cis-1,4-polybutadiene rubber crystallization at low temperatures, thus increased substantially the resistance to low temperature of sizing material, finally significantly reduce the low temperature toughness velocity of variation of rubber shock-absorbing product, meet the use properties requirement of product at extremely frigid zones.
Sulfur-donor auxiliary agent (phosphorodithioate) of the present invention is not containing nitrosamine, overcure-reversion and the physically aged performance of sizing material can be improved, solubleness in sizing material is higher, and favorable dispersity, participate in can generating close to the polysulfidic bond of 50% and the single, double sulfide linkage of 50% in the sulfidation of sizing material, because it generates this special crosslinking bond type in Vulcanization Process of Rubber, thus effectively can stop the crystallization at low temperatures of natural rubber and cis-1,4-polybutadiene rubber, significantly improve the resistance to low temperature of natural rubber.And in the prior art, the performance that this sulfur-donor auxiliary agent can destroy rubber low temperature crystallization has never seen report.
Preparation method's operating procedure of the present invention is simple, with low cost, first natural rubber is mixed with cis-1,4-polybutadiene rubber by using general rubber preparing device, then successively carbon black and/or white carbon black, other Synergist S-421 95, sulfur-donor auxiliary agent is added, prepare the natural rubber and cis-polybutadiene Blends with excellent low temperature resistant crystal property, significantly reduce rubber product stiffness variation rate at low temperatures simultaneously, the damping products fields such as track traffic, automobile, aircraft, steamer, bridge pad, instrument and aerospace can be widely used in.
Embodiment
Below in conjunction with concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Embodiment
A kind of natural rubber of the present invention and cis-polybutadiene Blends, comprise the component of following mass parts: natural rubber 70 parts ~ 85 parts, cis-1,4-polybutadiene rubber 15 parts ~ 30 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
Preferably, this blend comprises the component of following mass parts: natural rubber 80 parts ~ 85 parts, cis-1,4-polybutadiene rubber 15 parts ~ 20 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
In the present embodiment, natural rubber comprise in pearl glue, smoke sheet rubber, air dried sheet(ADS) glue, crepe rubber, natural rubber with constant viscosity one or more.
In the present embodiment, cis-1,4-polybutadiene rubber comprises and contains intermingle with cis-rich polybutadiene rubber, contains intermingle with low cis polybutadiene rubber or contain intermingle with superelevation cis-polybutadiene rubber.
In the present embodiment, sulfur-donor auxiliary agent is phosphorodithioate.
In the present embodiment, carbon black comprises N100 series, N200 series, N300 is serial, N400 is serial, N500 is serial, N600 is serial, N700 is serial, N800 is serial, N900 is serial, one or more in Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black.
In the present embodiment, white carbon black comprises precipitated silica and/or thermal silica.
In the present embodiment, other Synergist S-421 95 comprise in promotor, vulcanizing agent, promoting agent, anti-aging agent, tenderizer and silane coupling agent one or more.
The natural rubber of above-mentioned the present embodiment and a preparation method for cis-polybutadiene Blends, comprise the following steps:
(1) added by natural rubber in general rubber preparing device, plasticate 20min ~ 30min at the temperature of 20 DEG C ~ 50 DEG C, then adds cis-1,4-polybutadiene rubber and mix;
(2) successively add carbon black and/or white carbon black, other Synergist S-421 95, sulfur-donor auxiliary agent in the mixture obtained to step (1), then conveniently refine the mixing 20min ~ 30min of glue method, melting temperature is 60 DEG C ~ 80 DEG C, obtains rubber unvulcanizate;
(3) by the rubber unvulcanizate age overnight that step (2) obtains, then conveniently rubber vulcanization process at 100 DEG C ~ 200 DEG C by rubber unvulcanizate sulfuration 30min ~ 60min, obtain natural rubber and cis-polybutadiene Blends.
Natural rubber prepared by above-mentioned the present embodiment and cis-polybutadiene Blends can be used for vibration isolation rubber arts.
Embodiment 1
A kind of natural rubber of the present invention and cis-polybutadiene Blends, specifically comprise component (being mass parts) as shown in table 1.As a comparison, table 1 additionally provides the rubber compounding of comparative example 1 and comparative example 2.Material in table 1 all can obtain buying on the market, and in table 1, the unit of each material is mass fraction.
The rubber compounding table of table 1 embodiment 1 and comparative example 1,2
The natural rubber of above-mentioned the present embodiment and a preparation method for cis-polybutadiene Blends, comprise the following steps:
(1) prepare burden according to the formula of embodiment in table 11, first add in general rubber preparing device by natural rubber (No. 3 smoke sheet rubbers), plasticate 20min at 50 DEG C, in rubber preparing device, then adds cis-1,4-polybutadiene rubber BR9000 mix;
(2) successively carbon black N550, precipitated silica, zinc oxide, stearic acid, amines antioxidants 4020, quinoline type antioxidant RD, Microcrystalline Wax, silane coupling agent Si-69, Sulfur and phosphorodithioate SDT is added in mixture step (1) obtained, then conveniently the mixing 20min of glue method is refined, melting temperature is 80 DEG C, obtains rubber unvulcanizate;
(3) by the rubber unvulcanizate age overnight that step (2) obtains, then conveniently rubber vulcanization process at 150 DEG C by rubber unvulcanizate sulfuration 30min, complete the preparation process of natural rubber and cis-polybutadiene Blends (i.e. cross-linked rubber).This natural rubber and cis-polybutadiene Blends can be used for vibration isolation rubber arts.
The physical and mechanical properties of the natural rubber that above-mentioned the present embodiment is obtained and cis-polybutadiene Blends (cross-linked rubber) lists in table 2.As seen from the table, natural rubber and cis-1,4-polybutadiene rubber blended after, the traditional performance change of cross-linked rubber is little, and the cold-resistant coefficient of compression in 30 minutes significantly improves, illustrate that the low temperature crystallization of sizing material significantly reduces, finally considerably reduce the low temperature toughness velocity of variation of product, meet the use properties requirement of product at extremely frigid zones.
The properties of rubber of table 2 embodiment and comparative example and elastic side bearing product performance test result
| Performance test results | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Hardness, Shore A | 55 | 58 | 56 |
| 300% stretches surely, MPa | 8.4 | 10.1 | 9.5 |
| Tensile yield, % | 496 | 465 | 473 |
| Tensile strength, MPa | 18.8 | 22.3 | 19.8 |
| Compression set (70 DEG C × 24h), % | 11 | 12 | 12 |
| Temperature limit of brittleness (many SAMPLE METHOD), DEG C | -61 | -52 | -61 |
| The cold-resistant coefficient of compression in 30 minutes | 0.52 | 0.36 | 0.30 |
| Product low temperature Static stiffness velocity of variation, % | 7.9％ | 84％ | 110％ |
* note: the cold-resistant coefficient of compression in 30 minutes is non-GB test method, testing method is carried out according to the measuring method of the cold-resistant coefficient of GB6034-85 vulcanized rubber compression substantially, the place wherein changed is, in 6.5 testing sequences in GB6034-85, instrument compression set is put into low-temperature bottle together with by the sample compressed, 30.0 ± 0.1min is changed into by freezing 5.0 ± 0.1min, unclamp handwheel and remove compression load in 10S, make sample recover 3 ± 0.1min in low-temperature bottle, read from dial gauge and recover high h2 and record.It is exactly to measure sizing material crystallization trend at low temperatures that this method extends freezing time, and the numerical value of display is larger, and under showing low temperature, rebound resilience is better, and under the low temperature of sizing material, crystallization is also less.
From embodiment and the comparative example of the invention described above, low temperature resistant natural rubber of the present invention and cis-polybutadiene Blends not only have lower rubber temperature limit of brittleness, the low temperature toughness velocity of variation of its vulcanized rubber products significantly reduces simultaneously, and there is excellent physical and mechanical properties, there is using value comparatively widely in rubber industry.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.All technical schemes belonged under thinking of the present invention all belong to protection scope of the present invention.It is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a natural rubber and cis-polybutadiene Blends, it is characterized in that, described blend comprises the component of following mass parts: natural rubber 70 parts ~ 85 parts, cis-1,4-polybutadiene rubber 15 parts ~ 30 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
2. natural rubber according to claim 1 and cis-polybutadiene Blends, it is characterized in that, described blend comprises the component of following mass parts: natural rubber 80 parts ~ 85 parts, cis-1,4-polybutadiene rubber 15 parts ~ 20 parts, sulfur-donor auxiliary agent 1.0 parts ~ 2.5 parts, carbon black and/or white carbon black 5 parts ~ 100 parts, other Synergist S-421 95 10 parts ~ 15 parts.
3. natural rubber according to claim 1 and cis-polybutadiene Blends, is characterized in that, described natural rubber comprise in pearl glue, smoke sheet rubber, air dried sheet(ADS) glue, crepe rubber, natural rubber with constant viscosity one or more.
4. natural rubber according to claim 1 and cis-polybutadiene Blends, is characterized in that, described cis-1,4-polybutadiene rubber comprises and contains intermingle with cis-rich polybutadiene rubber, contains intermingle with low cis polybutadiene rubber or contain intermingle with superelevation cis-polybutadiene rubber.
5. natural rubber according to claim 1 and cis-polybutadiene Blends, is characterized in that, described sulfur-donor auxiliary agent is phosphorodithioate.
6. the natural rubber according to any one of Claims 1 to 5 and cis-polybutadiene Blends, it is characterized in that, described carbon black comprises N100 series, N200 series, N300 is serial, N400 is serial, N500 is serial, N600 is serial, N700 is serial, N800 is serial, N900 is serial, one or more in Sweet natural gas semi-reinforcing hydrocarbon black, Sweet natural gas thermally oxidized black and mixed gas carbon black.
7. the natural rubber according to any one of Claims 1 to 5 and cis-polybutadiene Blends, is characterized in that, described white carbon black comprises precipitated silica and/or thermal silica.
8. the natural rubber according to any one of Claims 1 to 5 and cis-polybutadiene Blends, is characterized in that, other Synergist S-421 95 described comprise in promotor, vulcanizing agent, promoting agent, anti-aging agent, tenderizer and silane coupling agent one or more.
9. the natural rubber according to any one of claim 1 ~ 8 and a preparation method for cis-polybutadiene Blends, comprise the following steps:
(1) added by natural rubber in general rubber preparing device, plasticate 20min ~ 30min at the temperature of 20 DEG C ~ 50 DEG C, then adds cis-1,4-polybutadiene rubber and mix;
(2) successively add carbon black and/or white carbon black, other Synergist S-421 95, sulfur-donor auxiliary agent in the mixture obtained to step (1), then conveniently refine the mixing 20min ~ 30min of glue method, melting temperature is 60 DEG C ~ 80 DEG C, obtains rubber unvulcanizate;
(3) by the rubber unvulcanizate age overnight that step (2) obtains, then conveniently rubber vulcanization process at 100 DEG C ~ 200 DEG C by rubber unvulcanizate sulfuration 30min ~ 60min, obtain natural rubber and cis-polybutadiene Blends.
10. the natural rubber that obtains of a natural rubber according to any one of claim 1 ~ 8 and cis-polybutadiene Blends or preparation method as claimed in claim 9 and the application of cis-polybutadiene Blends in vibration isolation rubber arts.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496659A (en) * | 2016-10-11 | 2017-03-15 | 常州市鼎升环保科技有限公司 | A kind of preparation method of Anti-impact shock-absorbing elastomeric material |
| CN107383468A (en) * | 2017-08-24 | 2017-11-24 | 芜湖凯奥尔环保科技有限公司 | A kind of cold-resistant compounded rubber and preparation method thereof |
| CN108384070A (en) * | 2018-01-31 | 2018-08-10 | 安徽中鼎密封件股份有限公司 | A kind of high temperature resistant low pressure is lower the natural rubber material of dynamic multiplying power |
| CN110511449A (en) * | 2019-09-16 | 2019-11-29 | 中交第一公路勘察设计研究院有限公司 | A kind of resistance to ultraviolet extremely cold area shock mount composite material and preparation method of resistance to ozone |
| CN110684242A (en) * | 2019-09-12 | 2020-01-14 | 十堰东森汽车密封件有限公司 | Natural rubber and butadiene rubber blending material with low damping coefficient and automatic wax precipitation and preparation method thereof |
| CN110724312A (en) * | 2019-09-05 | 2020-01-24 | 天长市宏福电子有限公司 | Anti-deformation damping material for pressure gauge and preparation method thereof |
| CN115521511A (en) * | 2022-09-16 | 2022-12-27 | 福沃克汽车技术（苏州）有限公司 | Rubber composition and preparation method and application thereof |
| CN115521511B (en) * | 2022-09-16 | 2024-05-10 | 福沃克汽车技术（苏州）有限公司 | Rubber composition and preparation method and application thereof |
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Cited By (11)
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| CN106496659A (en) * | 2016-10-11 | 2017-03-15 | 常州市鼎升环保科技有限公司 | A kind of preparation method of Anti-impact shock-absorbing elastomeric material |
| CN106496659B (en) * | 2016-10-11 | 2018-03-06 | 广东互典缓冲材料技术有限公司 | A kind of preparation method of Anti-impact shock-absorbing elastomeric material |
| CN107383468A (en) * | 2017-08-24 | 2017-11-24 | 芜湖凯奥尔环保科技有限公司 | A kind of cold-resistant compounded rubber and preparation method thereof |
| CN108384070A (en) * | 2018-01-31 | 2018-08-10 | 安徽中鼎密封件股份有限公司 | A kind of high temperature resistant low pressure is lower the natural rubber material of dynamic multiplying power |
| CN110724312A (en) * | 2019-09-05 | 2020-01-24 | 天长市宏福电子有限公司 | Anti-deformation damping material for pressure gauge and preparation method thereof |
| CN110684242A (en) * | 2019-09-12 | 2020-01-14 | 十堰东森汽车密封件有限公司 | Natural rubber and butadiene rubber blending material with low damping coefficient and automatic wax precipitation and preparation method thereof |
| CN110684242B (en) * | 2019-09-12 | 2022-01-14 | 十堰东森汽车密封件有限公司 | Natural rubber and butadiene rubber blending material with low damping coefficient and automatic wax precipitation and preparation method thereof |
| CN110511449A (en) * | 2019-09-16 | 2019-11-29 | 中交第一公路勘察设计研究院有限公司 | A kind of resistance to ultraviolet extremely cold area shock mount composite material and preparation method of resistance to ozone |
| CN110511449B (en) * | 2019-09-16 | 2021-09-07 | 中交第一公路勘察设计研究院有限公司 | Ozone-resistant ultraviolet-resistant extreme cold area damping support composite material and preparation method thereof |
| CN115521511A (en) * | 2022-09-16 | 2022-12-27 | 福沃克汽车技术（苏州）有限公司 | Rubber composition and preparation method and application thereof |
| CN115521511B (en) * | 2022-09-16 | 2024-05-10 | 福沃克汽车技术（苏州）有限公司 | Rubber composition and preparation method and application thereof |
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Application publication date: 20160210 |