CN104774353A - Butadiene rubber composition - Google Patents
Butadiene rubber composition Download PDFInfo
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- CN104774353A CN104774353A CN201510134672.6A CN201510134672A CN104774353A CN 104774353 A CN104774353 A CN 104774353A CN 201510134672 A CN201510134672 A CN 201510134672A CN 104774353 A CN104774353 A CN 104774353A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a butadiene rubber composition. The composition comprises, by weight, 100 parts of butadiene rubber, 56-64 parts of carbon black, 1-4 parts of stearic acid, 2-7 parts of zinc oxide, 1.1-4.2 parts of a promoter, 1-4 parts of sulfur, 3-7 parts of rubber oil and 0.1-5 parts of an antioxidant KY-616. The KY-616 is added to the butadiene rubber composition, so the composition has good thermo-oxidative aging resistance; with the increase of the amount of the KY-616, the mechanical performances and the thermo-oxidative aging resistance of vulcanized rubber are improved, and the oxidation induction time increases first and then tends to stability; and the suitable amount of the KY-616 in BR (butadiene rubber) is 1phr. The butadiene rubber composition has the advantages of substantially improved processing property, enhanced scorch resistance, prolonged vulcanization time, reduced vulcanization speed, improved mechanical performances, and improved thermo-oxidative aging resistance.
Description
Technical field
The present invention relates to technical field of rubber preparation, particularly a kind of cis-1,4-polybutadiene rubber composition.
Background technology
Macromolecular material is in storage, processing, use procedure, and be easily subject to the effect of heat, oxygen, ozone, mechanical force etc., its Structure and Properties is changed, loses use value gradually, this phenomenon is called the aging of macromolecular material.And in rubber, owing to its molecular chain containing a large amount of double bonds, thermo-oxidative ageing problem is more outstanding.In order to suppress or delay the generation of oxidizing reaction, usually in rubber, add oxidation inhibitor.Primary antioxidant the most frequently used at present has Hinered phenols and arylamine class, and wherein hindered phenol has the advantage such as nondiscoloration, nontoxic pollution-free, widespread use in macromolecular material.
In general, oxidation inhibitor, except should having good antioxidant property, also should possess good thermostability, resistance to migration and resistant to extraction.But the oxidation inhibitor that at present great majority use is small-molecule substance, there is the shortcomings such as volatile, not resistance to migration and extracting of being heated, be unfavorable for its existence steady in a long-term in the polymer, be thus difficult to meet the anti-aging requirement that material grows with each passing day.In recent years, in order to overcome traditional lower molecular weight oxidation inhibitor not shortcoming such as resistant to extraction, Chinese scholars has carried out large quantity research to the preparation of macromole oxidation inhibitor and the application in macromolecular material thereof, and macromole oxidation inhibitor has become an important directions of oxidation inhibitor development.Cis-1,4-polybutadiene rubber (BR) is the second largest in the world general synthetical glue being only second to styrene-butadiene rubber(SBR) (SBR) at present, about the research of the oxidation inhibitor of cis-1,4-polybutadiene rubber is less.
Chinese invention patent 201310711836.8 (publication date on April 23rd, 2014) discloses a kind of Novel butadiene rubber, comprise: divinyl, polyisoprene, extending oil, carbon black powder and additive, described divinyl accounts for 43% in Novel butadiene rubber, described polyisoprene accounts for 9% in Novel butadiene rubber, described extending oil accounts for 26% in Novel butadiene rubber, described carbon black powder accounts for 6% in Novel butadiene rubber, described additive accounts for 16% in Novel butadiene rubber, described additive comprises catalyzer, terminator and antiaging agent.The Novel butadiene rubber that this invention discloses, have employed multiple high quality raw material, the Novel butadiene rubber obtained improves wet-sliding resistant performance and processing characteristics, and tearing toughness is high, and tackiness is good, has wide range of applications; But the correlation technique content of the oxidation inhibitor about cis-1,4-polybutadiene rubber is not recorded in this invention.
Chinese invention patent 201410516405.0 (publication date on February 4th, 2015) discloses a kind of cis-1,4-polybutadiene rubber, comprise following moiety: cis-polybutadiene mixture 30-50 part, hexanaphthene 5-9 part, cobalt oxide 1-3 part, zinc oxide 2-5 part, sulphur 3-7 part, stearic acid 1-3 part, nickel naphthenate 1-5 part, triisobutyl aluminium 5-9 part, boron trifluoride diethyl etherate 2-4 part, heptane 2-6 part, hydrogen gasoline 3-8 part, accelerator NS 15-19 part, HAF10-13 part, the oily 11-15 part of ASTM type 103, aluminum oxide clinker 2-8 part, chlorxylone 2-5 part.Described cis-polybutadiene mixture is formed by cis 1，4-polybutadiene and cis 1,3-mixed with polybutadiene.Described cis 1，4-polybutadiene and cis 1,3-polyhutadiene account for mixture total weight amount than being 2:5.The cis-1,4-polybutadiene rubber that this invention provides contains cis-polybutadiene mixture, can effectively reduce tear strength, improves wet-sliding resistant performance and tackiness, possesses lower heat generation.Equally, the correlation technique content of the oxidation inhibitor about cis-1,4-polybutadiene rubber is not recorded in this invention.
Oxidation inhibitor KY-616 (or claiming Wingstay L, Lowinox CPL, Vanox L etc.) is a kind of Condenced Phenols kind antioxidant, and its chemical structural formula as shown in Figure 1.This oxidation inhibitor molecular weight is comparatively large, better with polymer compatibility, and having the features such as heat-resisting, resistance to extraction, is a kind of novel macromolecule oxidation inhibitor developed in recent years, and its applied research in macromolecular material receives the concern of investigator.Li Zhihong have studied the thermo oxidative aging performance of oxidation inhibitor KY-616 in natural rubber, finds that it shows good stabilization effect in natural rubber, and its water-fast extracting performance is better than amine antioxidants-MB.Luo Jing have studied oxidation inhibitor KY-616 and applies in condom manufacture, finds in the condom goods prepared at natural rubber latex, and the ageing resistance of oxidation inhibitor KY-616 is better than antioxidant 264 and oxidation inhibitor methene 4426-S.But the applied research of oxidation inhibitor KY-616 in BR then rarely seen report.The application have studied the impact of oxidation inhibitor KY-616 on cis-1,4-polybutadiene rubber (BR) vulcanization characteristics, mechanical property and heatproof air aging performance, to evaluate the antioxidant effect of KY-616 in butadiene type rubber, and determine the Optimum of oxidation inhibitor KY-616, for the performance promoting cis-1,4-polybutadiene rubber (BR) provides technical support.
Summary of the invention
Provide hereinafter about brief overview of the present invention, to provide about the basic comprehension in some of the present invention.Should be appreciated that this general introduction is not summarize about exhaustive of the present invention.It is not that intention determines key of the present invention or integral part, and nor is it intended to limit the scope of the present invention.Its object is only provide some concept in simplified form, in this, as the preorder in greater detail discussed after a while.
The object of the invention is to overcome the deficiencies in the prior art, a kind of cis-1,4-polybutadiene rubber composition is provided.
The present invention is realized by following technical scheme, and the present invention relates to a kind of cis-1,4-polybutadiene rubber composition, described composition is made up of each component of following parts by weight,
Cis-1,4-polybutadiene rubber 100,
Carbon black 56-64,
Stearic acid 1-4,
Zinc oxide 2-7,
Promotor 1.1-4.2,
Sulphur 1-4,
Rubber oil 3-7,
Oxidation inhibitor KY-6160.1-5.
Compared with prior art, the present invention has following beneficial effect: cis-1,4-polybutadiene rubber composition of the present invention with the addition of KY-616, and oxidation inhibitor KY-616 achieves good thermo oxidative aging effect; Along with the increase of KY-616 consumption, the mechanical property of cross-linked rubber and heatproof air aging performance improve, and oxidation induction time first increases the value that tends towards stability afterwards; The Optimum of KY-616 in BR is 1phr, and cis-1,4-polybutadiene rubber composition processing characteristics of the present invention significantly promotes, and anti-incipient scorch ability strengthens, and curing time extends, and vulcanization rate reduces, and mechanical property of vulcanized rubber and thermo oxidative aging performance promote.
Accompanying drawing explanation
Below with reference to the accompanying drawings illustrate embodiments of the invention, above and other objects, features and advantages of the present invention can be understood more easily.Parts in accompanying drawing are just in order to illustrate principle of the present invention.In the accompanying drawings, same or similar technical characteristic or parts will adopt same or similar Reference numeral to represent.
Fig. 1 is the chemical structural formula of oxidation inhibitor KY-616;
Fig. 2 is the infrared spectra of oxidation inhibitor KY-616;
Fig. 3 is the vulcanization curve figure of the BR rubber unvulcanizate adding different amounts oxidation inhibitor KY-616;
Fig. 4 is that oxidation inhibitor KY-616 consumption and digestion time are on the impact of BR cross-linked rubber tensile strength;
Fig. 5 is that oxidation inhibitor KY-616 consumption and digestion time are on the impact of BR cross-linked rubber elongation at break.
Embodiment
With reference to the accompanying drawings embodiments of the invention are described.The element described in an accompanying drawing of the present invention or a kind of embodiment and feature can combine with the element shown in one or more other accompanying drawing or embodiment and feature.It should be noted that for purposes of clarity, accompanying drawing and eliminate expression and the description of unrelated to the invention, parts known to persons of ordinary skill in the art and process in illustrating.
Embodiment 1
The cis-1,4-polybutadiene rubber composition that the present invention relates to, is made up of each component of following parts by weight, cis-1,4-polybutadiene rubber 100, carbon black 56-64, stearic acid 1-4, zinc oxide 2-7, promotor 1.1-4.2, sulphur 1-4, rubber oil 3-7, oxidation inhibitor KY-6160.1-5.
Preferably, described promotor is accelerant CZ or altax, or is the mixing of accelerant CZ and altax.Preferably, described promotor is the mixing of accelerant CZ and altax, wherein accelerant CZ 1-3, altax 0.1-1.2.
Preferably, described composition is made up of each component of following parts by weight: cis-1,4-polybutadiene rubber 100, carbon black 60, stearic acid 2, zinc oxide 5, accelerant CZ 1.5, altax 0.5, sulphur 2, rubber oil 6, oxidation inhibitor KY-6160.8-4.
Preferably, described composition is made up of each component of following parts by weight: cis-1,4-polybutadiene rubber 100, carbon black 60, stearic acid 2, zinc oxide 5, accelerant CZ 1.5, altax 0.5, sulphur 2, rubber oil 6, oxidation inhibitor KY-6161.
Preferably, described rubber oil is environment-friendly rubber oil.
The cis-1,4-polybutadiene rubber composition component related in the present embodiment is as follows: BR100, carbon black 60, stearic acid 2, zinc oxide 5, accelerant CZ 1.5, altax 0.5, sulphur 2, environment-friendly rubber oil 6, oxidation inhibitor KY-6161.
One, experimentation:
1.1 starting material
Cis-1,4-polybutadiene rubber (BR): BR9000, Beijing Yanshan Petrochemical rubber and plastic chemical industry limited liability company;
P-methyl phenol-dicyclopentadiene-isobutyl resin (oxidation inhibitor KY-616): Jiangsu Feiya Chemistry Industry Co., Ltd;
High wear-resistant carbon black (HAF): N330, Shanghai Cabot Chemical Co., Ltd.;
Environment-friendly rubber oil: pitch limited-liability company of CNOOC;
Zinc oxide (ZnO), stearic acid (SA), Sulfur (S), N-cyclohexyl-2-[4-morpholinodithio sulphenamide (accelerant CZ) and 2,2'-dithio-bis-benzothiazole (altax): Science and Technology Ltd. is contained in Jinchang, Guangzhou.
1.2 basic recipe
BR100, carbon black 60, stearic acid 2, zinc oxide 5, accelerant CZ 1.5, altax 0.5, sulphur 2, environment-friendly rubber oil 6, oxidation inhibitor KY-6161.
1.3 instrument and equipment
Banbury mixer (LN-1, profit takes machinery (Dongguan) Industrial Co., Ltd.),
Rubber mixing mill (XK-168, profit takes machinery (Dongguan) Industrial Co., Ltd.),
Vulcanizing press (KSHR 100, ShenZhen,GuangDong Ke Sheng Machinery Co., Ltd.),
Tension testing machine (UT-2080, U-Can Dynatex Inc.),
Without rotor vulkameter (UR-2010SD-A, U-Can Dynatex Inc.),
DSC (Q20, TA instrument company of the U.S.),
Climatic chamber (GT-717, Gotech Testing Machines (Dongguan) Co., Ltd.),
Fourier transform infrared spectrometer (Tensor 27, German Bruker).
The preparation of 1.4 cis-1,4-polybutadiene rubber cross-linked rubbers
Plasticate cis-1,4-polybutadiene rubber in Banbury mixer 2min, then adds carbon black, zinc oxide, stearic acid, the mixing 8min of rubber oil, wherein shuts down cleaning scrap stock every 2min, mixing evenly after, binder removal is for subsequent use.Then according to formula, oxidation inhibitor, promotor, sulphur are conventionally joined in sizing material obtained above on a mill until, after slice, obtains rubber unvulcanizate.Rubber unvulcanizate is sulfuration on compression molding glue after room temperature parks 24h, and curing temperature is 160 DEG C, and curing time is the sulfurizing time (T measured without rotor vulkameter
90).
1.5 testing and characterization
Infrared spectra is tested by KBr pressed disc method, and test specification is 4000-400cm
-1, resolving power is 4cm
-1, scanning times is 16 times.Vulcanization characteristics test measures according to GB/T16584-1996, and temperature is 160 DEG C.Tensile property measures according to GB/T528-2009, and rate of extension is 500mm/min.Heat aging property is pressed GB/T3512-2001 and is measured, aging condition 100 DEG C × (24,48,72,96,120) h.Oxidation induction time utilizes DSC to carry out according to GB/T19466.6-2009, first, sample is at 60 DEG C, 5min is kept under the nitrogen flow rate of 50mL/min, 170 DEG C are risen to afterwards with the heat-up rate of 20 ° of C/min, keep after 5min, change the oxygen atmosphere that flow is 50mL/min into, from logical oxygen to the time occurred required for oxidation heat liberation peak be oxidation induction time (OIT).
Two, implementation result;
2.1FT-IR analyze
The infrared spectra of oxidation inhibitor KY-616 as shown in Figure 2.In fig. 2,3611cm
-1for the stretching vibration absorption peak of phenolic hydroxyl group, 3485cm
-1for part phenolic hydroxyl group creates the stretching vibration absorption peak after association.2950cm
-1and 2870cm
-1be respectively asymmetric stretching vibration and the symmetrical stretching vibration absorption peak of methyl.1465cm
-1and 1447cm
-1be respectively the flexural vibration absorption peak of methylene radical and methyl, because methyl absorption peak is comparatively strong, absorption peak location comparison is close, thus both absorption peaks be there occurs partly overlap.1395cm
-1and 1361cm
-1for the flexural vibration absorption peak of the tertiary butyl, 1170cm
-1for the C-O stretching vibration absorption peak of phenolic hydroxyl group, 858cm
-1with 766cm
-1for the out-of-plane deformation vibration absorption peak of phenyl ring.
2.2 oxidation inhibitor KY-616 are on the impact of BR rubber unvulcanizate vulcanization characteristics
The vulcanization characteristics curve of interpolation different amounts oxidation inhibitor KY-616 rubber unvulcanizate and curing parameter are respectively as shown in Figure 3 and Table 1.Can find out, along with the increase of oxidation inhibitor KY-616 consumption, on the one hand, the minimum torque of rubber unvulcanizate in sulfidation all becomes downward trend with maximum torque, show that oxidation inhibitor KY-616 has certain softening power to rubber unvulcanizate, the processing characteristics of rubber unvulcanizate can be improved
[8]; On the other hand, time of scorch and sulfurizing time slowly increase, and vulcanization rate declines, and shows that oxidation inhibitor KY-616 can prevent incipient scorch, delay the sulfuration of rubber, and its reason may be because oxidation inhibitor captures the free radical that rubber produces in sulfidation.
Table 1 adds the curing parameter of the BR rubber unvulcanizate of different amounts oxidation inhibitor KY-616
2.3 oxidation inhibitor KY-616 are on the impact of BR cross-linked rubber oxidation induction time
By the oxidation induction time (OIT) of DSC curve test cross-linked rubber, be evaluate oxidation inhibitor to one of the simplest method of polymers against oxidative effect.As can be seen from Table 2, compared with the BR cross-linked rubber not adding any oxidation inhibitor, the OIT value of adding the BR of oxidation inhibitor KY-616 obviously increases, and describes oxidation inhibitor KY-616 and has good antioxidant effect to BR.When oxidation inhibitor KY-616 consumption is increased to 1 and 2phr from 0, OIT value increases comparatively obvious, is increased to 96.7min and 107.4min respectively from 45min, and along with oxidation inhibitor KY-616 consumption continuation increase, small size decline has appearred in the OIT value of BR cross-linked rubber on the contrary.Therefore, the Optimum of oxidation inhibitor KY-616 in cis-1,4-polybutadiene rubber is about 1-2phr.
Table 2KY-616 consumption is on the impact of the oxidation induction time of BR cross-linked rubber
| Consumption (phr) | Oxidation induction time (OIT)/(min) |
| 0 | 45 |
| 0.5 | 66 |
| 1 | 96.7 |
| 2 | 107.4 |
| 3 | 103.4 |
| 4 | 101.2 |
2.4 oxidation inhibitor KY-616 are on the impact of BR mechanical property of vulcanized rubber and thermo oxidative aging performance
The tensile strength of the cis-1,4-polybutadiene rubber cross-linked rubber of interpolation different amounts oxidation inhibitor KY-616 and the relation of elongation at break and digestion time are respectively as shown in Figure 4 and Figure 5.As can be seen from the figure, when not having aging, along with the increase of oxidation inhibitor KY-616 consumption, tensile strength, the elongation at break of cross-linked rubber raise.This illustrates that oxidation inhibitor KY-616 is conducive to improving the mechanical property of BR cross-linked rubber.Its reason may be BR in the process of mixing and sulfidization molding, and oxidation inhibitor KY-616 effectively inhibits the generation that BR is aging, and oxidation inhibitor KY-616 consumption is more, and probability aging in cross-linked rubber preparation process is less.
As can be seen from Fig. 4 and Fig. 5, along with the increase of digestion time, cross-linked rubber tensile strength and elongation at break decline, and the cross-linked rubber fall of wherein not adding oxidation inhibitor is maximum, and lowering speed is the fastest.And the cross-linked rubber fall that with the addition of oxidation inhibitor is less, speed is slower.This also illustrates KY-616, to suppressing the thermo-oxidative ageing of BR cross-linked rubber, there is good effect.In addition as can be seen from Fig. 4 and Fig. 5 also, after identical time aging to cross-linked rubber, along with the increase of KY-616 consumption, the tensile strength of cross-linked rubber and elongation at break correspondingly become large, namely thermo oxidative aging effect improves, but when KY-616 consumption is more than 1phr, then its increase rate is little.Therefore, when oxidation inhibitor KY-616 consumption is greater than 1phr, cross-linked rubber can reach good thermo oxidative aging effect.But consider cost factor, the Optimum of KY-616 is 1phr.
Embodiment 2
The cis-1,4-polybutadiene rubber composition component related in the present embodiment is as follows: BR100, carbon black 56, stearic acid 1, zinc oxide 2, accelerant CZ 1, altax 0.1, sulphur 1, environment-friendly rubber oil 3, oxidation inhibitor KY-6160.1.Preparation method is with reference to embodiment 1.
Implementation result: cis-1,4-polybutadiene rubber composition processing characteristics prepared by the present embodiment significantly promotes, anti-incipient scorch ability strengthens, and curing time extends, and vulcanization rate reduces, and mechanical property of vulcanized rubber and thermo oxidative aging performance promote.
Embodiment 3
The cis-1,4-polybutadiene rubber composition component related in the present embodiment is as follows: BR100, carbon black 64, stearic acid 4, zinc oxide 7, accelerant CZ 3, altax 1.2, sulphur 4, environment-friendly rubber oil 7, oxidation inhibitor KY-6165.Preparation method is with reference to embodiment 1.
Implementation result: cis-1,4-polybutadiene rubber composition processing characteristics prepared by the present embodiment significantly promotes, anti-incipient scorch ability strengthens, and curing time extends, and vulcanization rate reduces, and mechanical property of vulcanized rubber and thermo oxidative aging performance promote.
As fully visible, cis-1,4-polybutadiene rubber composition of the present invention with the addition of KY-616, and oxidation inhibitor KY-616 achieves good thermo oxidative aging effect; Along with the increase of KY-616 consumption, the mechanical property of cross-linked rubber and heatproof air aging performance improve, and oxidation induction time first increases the value that tends towards stability afterwards; The Optimum of KY-616 in BR is 1phr, and cis-1,4-polybutadiene rubber composition processing characteristics of the present invention significantly promotes, and anti-incipient scorch ability strengthens, and curing time extends, and vulcanization rate reduces, and mechanical property of vulcanized rubber and thermo oxidative aging performance promote.
Meanwhile, the present invention also studies the preparation method of cis-1,4-polybutadiene rubber composition, and the preparation method of cis-1,4-polybutadiene rubber composition is made up of following steps:
Step one, gets cis-1,4-polybutadiene rubber, puts into Banbury mixer and plasticates; Step 2, adds carbon black, zinc oxide, stearic acid, rubber oil afterwards, mixing, obtains blend glue stuff; Step 3, gets oxidation inhibitor, promotor and sulphur, adds in blend glue stuff, obtains rubber unvulcanizate; Step 4, leaves standstill afterwards, sulfuration, obtains described cis-1,4-polybutadiene rubber composition.
Preferably, in step one, described in time of plasticating be 1-3min.Further preferably, in step one, described in time of plasticating be 2min.
Preferably, in step 2, the described mixing time is 5-9min.Further preferably, in step 2, the described mixing time is 8min.
Preferably, in step 4, described leaving standstill is specially room temperature and parks 20-30 hour.Further preferably, in step 4, described leaving standstill is specially room temperature and parks 24 hours.
Preferably, in step 4, the temperature of described sulfuration is 150-165 DEG C.Further preferably, in step 4, the temperature of described sulfuration is 160 DEG C.Preferably, in step 4, the time of described sulfuration is the sulfurizing time measured without rotor vulkameter.
Meanwhile, the invention still further relates to the application of KY-616 as the composition modified additive of cis-1,4-polybutadiene rubber.
Preferably, described application is specially, in cis-1,4-polybutadiene rubber composition, add KY-616, and then promotes the processing characteristics of cis-1,4-polybutadiene rubber composition.
Preferably, described application is specially, in cis-1,4-polybutadiene rubber composition, add KY-616, and then lifting prevents incipient scorch ability.
Preferably, described application is specially, in cis-1,4-polybutadiene rubber composition, add KY-616, and then extends curing time and reduce vulcanization rate.
Preferably, described application is specially, in cis-1,4-polybutadiene rubber composition, add KY-616, and then promotes thermo oxidative aging.
In sum, the present invention proposes a kind of cis-1,4-polybutadiene rubber composition of excellent performance, simultaneity factor have studied the preparation method of described cis-1,4-polybutadiene rubber composition, it is also proposed the whole new set of applications of KY-616 simultaneously, find that KY-616 can be applied to cis-1,4-polybutadiene rubber composition, play modification and promote the beyond thought technique effect of rubber performance.Cis-1,4-polybutadiene rubber composition processing characteristics of the present invention significantly promotes, and anti-incipient scorch ability strengthens, and curing time extends, and vulcanization rate reduces.Oxidation inhibitor KY-616 has good thermo oxidative aging effect in BR.Along with the increase of KY-616 consumption, the mechanical property of cross-linked rubber and heatproof air aging performance improve, and oxidation induction time first increases the value that tends towards stability afterwards.The Optimum of KY-616 in BR is 1phr.
In the present invention, contriver, through great many of experiments, is surprised to find that methylphenol-dicyclopentadiene-isobutyl resin (KY-616) can produce unexpected technique effect preparing in cis-1,4-polybutadiene rubber composition.P-methyl phenol-dicyclopentadiene-isobutyl resin (KY-616) is a kind of novel macromolecule polyphenol antioxidant, has the features such as high reactivity, low volatility and excellent resistance to migration; In the present invention, applicant adopts infrared spectra (FT-IR) structure to KY-616 to characterize, and have studied the impact of its vulcanization characteristics on cis-1,4-polybutadiene rubber (BR), mechanical property and heatproof air aging performance.The present inventor finds that oxidation inhibitor KY-616 has the effect preventing incipient scorch He improve sizing material processing characteristics; Along with the increase of oxidation inhibitor KY-616 consumption, the mechanical property of BR cross-linked rubber and hot-air aging resistance improve, and oxidation induction time (OIT) first increases and is tending towards constant afterwards.The Optimum of KY-616 in BR is 1phr; The reasonable employment of oxidation inhibitor KY-616, serves beyond thought technique effect for the performance promoting cis-1,4-polybutadiene rubber composition.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (6)
1. a cis-1,4-polybutadiene rubber composition, is characterized in that, described composition is made up of each component of following parts by weight:
Cis-1,4-polybutadiene rubber 100,
Carbon black 56-64,
Stearic acid 1-4,
Zinc oxide 2-7,
Promotor 1.1-4.2,
Sulphur 1-4,
Rubber oil 3-7,
Oxidation inhibitor KY-616 0.1-5.
2. cis-1,4-polybutadiene rubber composition according to claim 1, is characterized in that, described promotor is accelerant CZ or altax, or is the mixing of accelerant CZ and altax.
3. cis-1,4-polybutadiene rubber composition according to claim 2, is characterized in that, described promotor is the mixing of accelerant CZ and altax, wherein accelerant CZ 1-3 part, altax 0.1-1.2 part.
4. cis-1,4-polybutadiene rubber composition according to claim 2, is characterized in that, described composition is made up of each component of following parts by weight:
Cis-1,4-polybutadiene rubber 100,
Carbon black 60,
Stearic acid 2,
Zinc oxide 5,
Accelerant CZ 1.5,
Altax 0.5,
Sulphur 2,
Rubber oil 6,
Oxidation inhibitor KY-616 0.8-4.
5. cis-1,4-polybutadiene rubber composition according to claim 2, is characterized in that, described composition is made up of each component of following parts by weight:
Cis-1,4-polybutadiene rubber 100,
Carbon black 60,
Stearic acid 2,
Zinc oxide 5,
Accelerant CZ 1.5,
Altax 0.5,
Sulphur 2,
Rubber oil 6,
Oxidation inhibitor KY-616 1.
6. cis-1,4-polybutadiene rubber composition according to claim 1, is characterized in that, described rubber oil is environment-friendly rubber oil.
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| CN201510134672.6A CN104774353A (en) | 2015-03-25 | 2015-03-25 | Butadiene rubber composition |
| PCT/CN2015/091547 WO2016150141A1 (en) | 2015-03-25 | 2015-10-09 | Butadiene rubber compound |
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| WO2016150141A1 (en) * | 2015-03-25 | 2016-09-29 | 江苏飞亚化学工业有限责任公司 | Butadiene rubber compound |
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| CN114426610A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for adjusting scorching time and normal vulcanization time of butadiene rubber |
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| CN104774353A (en) * | 2015-03-25 | 2015-07-15 | 江苏飞亚化学工业有限责任公司 | Butadiene rubber composition |
| CN104693519A (en) * | 2015-03-25 | 2015-06-10 | 江苏飞亚化学工业有限责任公司 | Preparation method for butadiene rubber composite |
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| JP4364540B2 (en) * | 2003-03-31 | 2009-11-18 | 日本エイアンドエル株式会社 | Vibration welding resin composition and lamp housing molded product for vehicle lamp |
| CN1896123A (en) * | 2005-07-12 | 2007-01-17 | 北京化工大学 | Improvement of rubber compression elasticity at low-temperature |
| CN101134825A (en) * | 2006-09-01 | 2008-03-05 | 上海保隆汽车科技股份有限公司 | Color-change resistant latch-locked valve cock rubber formula and method for making same |
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