CN102532613A - Rubber composition - Google Patents
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Abstract
The invention provides a rubber composition. According to the invention, low-cost alkadiene rubbers are adopted, such as natural rubber (NR) and isoprene rubber (IR); a single alkadiene rubber component can be used, and a combination of two or more than two alkadiene rubber components can also be used; an anti-aging agent used in the rubber composition meets the requirements of European Union REACH environmental protection law, and the rubber composition contains high-content anti-aging active components; an accelerating agent used in the rubber composition can generate fewer nitrocompounds, and the processing property and mechanical property of the rubber composition are equivalent to those of the rubber composition in which a common anti-aging agent and a common accelerating agent are used. The invention simultaneously provides a pneumatic tyre using the rubber composition as a material. Specifically, the invention relates to a rubber composition which comprises a rubber component containing diene rubbers, an environment-friendly anti-aging agent and an environment-friendly accelerating agent; and the invention further relates to a pneumatic tyre using the rubber composition as a material.
Description
Technical field
The present invention relates to a kind of rubber combination, it uses inexpensive polyisoprene rubber to substitute tree elastomer, and its used anti-aging agent meets the requirement of the REACH of European Union environmental regulation, and the anti-aging effective component content is high, and its used promotor produces less nitroso compound.The present invention also relates to the pneumatic tyre that is combined as raw material with this simultaneously.
Background technology
According to IISRP, 2008 world's polyisoprene rubber (IR) throughput be 61.1 ten thousand t/a.The IR trade mark mainly contains: Muscovite SKI-3 (titanium is IR) series and SKI-5 (neodymium is IR) series, and SKI-3 series comprises SKI-3, SKI-3S, SKI-5 series comprises SKI-5, SKI-5PM; The Nipol2200 series of Nippon Zeon Co., Ltd., and the Natsyn of U.S. Goodyear company series.In state-owned many enterprises and scientific research institutions research and develop rare-earth isoprene rubber of new generation, mainly contain Jilin Petrochemical company, institute, Qingdao Icos Corp., Maoming Lu Hua company should be changed in Chinese Academy of Sciences Changchun, and Yanshan Petrochemical research institute.
Expect 2010, Chinese NR production is 750,000 t, and still less than 1/3 of Chinese demand, Chinese natural gum output zone is less, needs a large amount of imports, and the natural gum price volalility is bigger.Simultaneously; External import is also high to the polyisoprene rubber price of China: in August, 2010; Russia's titanium is that polyisoprene rubber SKI-3 quotation is about about 23500-25500 unit/ton; The SKI-5PM info quote is at 28000-28500 unit/ton, and the Rui Weng IR2200 of the company quotation of area, Jiangsu and Zhejiang Provinces is about 29000 yuan/ton.The extensive oil refining apparatus of China will provide a large amount of inexpensive isoprene monomers, can produce a large amount of polyisoprene rubbers, and the price that polyisoprene rubber is lower becomes one of its advantage of competing with tree elastomer and import polyisoprene rubber.According to measuring and calculating, Chinese IP stock number was 370,000 t in 2009, can produce the IR of 350,000 t at least, just can reduce the NR import volume of 350,000 t.
The Application Areas of polyisoprene rubber is mainly medical products, food and tree elastomer suitable application area, like tire and engineering goods etc.Wherein, polyisoprene rubber partly replaces tree elastomer to be used for tyre stock, is one of direction of polyisoprene rubber extensive application, becomes the focus of research.If IR replaces NR with 20% ratio, Recipe need not adjustment and just can use smoothly, only will consume NR250 ten thousand t in 2010 in tyre industry, and then the IR consumption just can reach 500,000 t, can reduce the NR import volume of 500,000 t.Russia's application percentage of IR in tire production is 50% at present, and China is if can reach this ratio, and then the demand of IR is bigger.
In addition, the REACH environmental protection system of European Union has also produced no small influence to Chinese rubber and tyre industry.
The REACH system; Middle translated name " registering, assess, authorize restrictive system " about chemical; Be the long-range consideration of European Union based on protection human health and environmental safety; Also for improving European Union's chemical industry competitive power, pursue social sustainable development simultaneously, be about to a unified chemical monitoring management system of setting up.
The REACH rules are mainly managed registration, assessment, permission and the restriction etc. of products such as the weaving in 30,000 number of chemical article and downstream thereof, light industry, pharmacy.It is with replacing European Union's existing 40 multinomial instruction and rules about chemical, and involvement aspect is quite wide.In the rules to enterprise have the greatest impact be the registration, for the novel substance more than 1 ton, new legislation came into force back 60 days, manufacturer, importor will be accomplished registration.
The REACH rules of European Union are shown great attention in the global in front maximum tbt of export enterprise as current lying across always.From 28, the October of judgement to 2008 that tire is had a mind to release; 15 kinds high concern materials (SVHC:Substance of Very HighConcern) inventory is formally effective; Rules renewal each time is though brought the rising of reply cost, the increase of workload; But technical innovation, the progress of quality have also been brought simultaneously.The REACH rules are come China, originate in tyre industry exactly.
Chinese tire output reached 3.5 hundred million in 2008, and wherein 40% products export had become the first in the world tire production and big export country at that time.But " two anti-" case that came one after another in 2009, " special guarantor " case have but been shrouded one haze for the prospect of Chinese tire export enterprise, and more the crisis of reality has approached Chinese tire enterprise simultaneously.
In tyre industry, use the robber materials and the rubber ingredients (carbon black, anti-aging agent, promotor, filling wet goods) that meet the REACH of European Union rules to produce high-grade tire, be the only way of enterprise developing foreign market.
Patent US5556907A discloses a kind of rubber combination; The tire tread glue formulation little for rolling resistance, that wear resistance is good; This prescription contains the isoprene-butadiene-polystyrene ternary integrated rubber (the Tg scope is at-90 ℃ to 20 ℃) that accounts for rubber matrix 30-100% mass parts, accounts for other one or more elastomer materials (newborn poly-conjugated-diolefin-styrenerubber of 0-50phr or the polybutadiene rubber of 0-30phr) of rubber matrix 0-70% mass parts; (the BET specific surface area is at 150-250m with the WHITE CARBON BLACK of 20-90phr
2Between/the g), and with the proportional carbon black of the consumption of WHITE CARBON BLACK, as weighting agent.But its used anti-aging agent is common anti-aging agent, rather than the environment-friendly type anti-aging agent.
Substitute in the research of natural gum at polyisoprene rubber, it is documented, with synthetic polyisoprene equivalent replacement tree elastomer, suitably adjust vulcanization system in the agricultural tyre tread glue formula; Russia polyisoprene rubber SKI-3 all replaces tree elastomer, with cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR) and usefulness, all obtains good result, but adopts the Russian polyisoprene rubber of import more, and price is higher.
The present invention aims to provide a kind of rubber combination; It adopts inexpensive polyisoprene rubber partly to substitute tree elastomer; And use meets the anti-aging agent of the REACH of European Union environmental regulation requirement; And the vulcanization accelerator that produces less nitroso compound, and the processing characteristics of rubber combination, vulcanization characteristics and mechanical mechanics property and relatively prescription is quite.The present invention relates to the pneumatic tyre that uses this rubber combination simultaneously.
Summary of the invention
The present invention relates to a kind of rubber combination, its characteristic has the following aspects:
1. a rubber combination is characterized in that, said rubber combination contains the dience rubber component; The instance of dience rubber component is preferably tree elastomer (NR), polyisoprene rubber (IR), various polybutadiene rubber (BR); Said dience rubber component can use separately also can two kinds and two or more combination use; Rubber components with 100 weight parts is a benchmark, contains 70-100 weight %, preferred 75-100 weight %, preferred 75-95 weight %; Preferred 80-100 weight %, preferred 80-95 weight %, preferred 85-100 weight %, the tree elastomer of preferred 85-95 weight %; And 0-30 weight %, preferred 0-25 weight %, preferred 5-25 weight %, preferred 0-20 weight %; Preferred 5-20 weight %, preferred 0-15 weight %, the polyisoprene rubber of preferred 5-15 weight %.
2. the rubber combination of embodiment 1, wherein polyisoprene rubber has two kinds: 1 and 2; 1 polyisoprene rubber weight-average molecular weight M
wBe 1,300,000-2,500,000, molecular weight distributing index M
w/ M
nBe 2.2-5.6, cis-1, the 4-structural content is 96-98%, fugitive constituent＜0.6wt%, ash content＜0.5wt%, mooney viscosity (ML1+4min, 100 ℃) is 70 ± 5, proportion is 0.90-0.92g/cm
32
#Polyisoprene rubber peak molecular weight M
pBe 1,410,000-1,510,000, number-average molecular weight M
nBe 270,000-470,000; 1, the 4-structural content is 95-98%, wherein, cis-1, the 4-structural content is 95-97%; Gel content is 0.14-2%, and second-order transition temperature Tg is-57 to-59 ℃, and mooney viscosity (ML1+4min, 100 ℃) is 66-84.
3. like each described compsn of previous embodiments, wherein 1
#The polymerization method of polyisoprene rubber is that isoprene monomer carries out solution polymerization under the rare earth catalyst effect; Wherein said isoprene monomer is a polymerization-grade; Said rare earth catalyst can be inert hydrocarbon solvent for neodymium series catalysts and wherein said solvent;
The polymerization method of the rare-earth isoprene rubber that the present invention uses, wherein the isoprene monomer concentration in the polyreaction material is 10-20wt%, is preferably 13-17wt%, is benchmark with the gross weight of whole polyreaction material.
The polymerization method of the rare-earth isoprene rubber that the present invention uses, the 'inertia' in wherein said " inert hydrocarbon solvent " is with negative interference reaction process not and/or be not principle with reactive component and reaction.Particularly, the instance of said inert hydrocarbon solvent can be selected from pentane, iso-pentane, hexane, hexanaphthene, methylcyclohexane, heptane, octane, benzene,toluene,xylene and isopropyl benzene.
The polymerization method of the rare-earth isoprene rubber that uses in the present invention; The consumption of wherein said neodymium series catalysts should suitably be selected based on the principle of industrial economy; Can not be too small or excessive, because the too small reaction process that possibly be unfavorable for carries out fast, excessively then not only can increase process cost; Also possibly make ash oontent increase in the resulting polymer product, be unfavorable for the subsequent disposal or the application of said product.
Particularly, in the polymerization method of preparation rare-earth isoprene rubber of the present invention, be benchmark wherein in every mole of isoprene monomer, the consumption of said neodymium series catalysts is generally 1 * 10
-5～4 * 10
-4MolNd is preferably 1.5 * 10
-5～2.5 * 10
-4MolNd.
Said neodymium series catalysts is a patented claim formerly, can be the one Chinese patent application of 200910244026.X referring to application number specifically, and this patented claim is introduced through reference in its entirety at this.
More specifically, mainly to comprise conjugated diene, carboxylic acid neodymium compound, general formula be AlR to said neodymium series catalysts
3Aluminum alkyls or general formula be AlHR
2Alkyl aluminium hydride or the two mixture (wherein R is C
1-C
6The straight or branched alkyl) and halogen contained compound, be benchmark wherein in every moles of carboxylic acids neodymium compound, the content of said conjugated diene is about 20-100 mole; Be preferably about 25-80 mole; More preferably about 30-70 mole, the content of said aluminum alkyls or alkyl aluminium hydride or the two mixture is about 5-30 mole, is preferably about 6-25 mole; With the content of said halogen contained compound be about 2-10 mole, be preferably about 2-4 mole.
In said neodymium series catalysts, the specific examples of said conjugated diene includes but not limited to C
4-C
6Conjugated diene monomer, like divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene and their mixture are preferably divinyl or isoprene, most preferably are isoprene.
In said neodymium series catalysts, said carboxylic acid neodymium compound can be C
1-C
20The carboxylic acid neodymium is preferably C
6-C
10The carboxylic acid neodymium, they can be neodymium naphthenate or branched alkyl carboxylic acid's neodymium, specific examples includes but not limited to neodymium naphthenate, neodymium octoate, isocaprylic acid neodymium, n-nonanoic acid neodymium, neodecanoic acid neodymium and capric acid neodymium.
In said neodymium series catalysts; The specific examples of said aluminum alkyls includes but not limited to trimethylaluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three amyl group aluminium and three hexyl aluminium; Be preferably tri-butyl aluminum and triisobutyl aluminium, more preferably triisobutyl aluminium; The specific examples of said alkyl aluminium hydride includes but not limited to diethyl aluminium hydride, hydrogenation dibutyl aluminium and diisobutylaluminium hydride, is preferably hydrogenation dibutyl aluminium and diisobutylaluminium hydride, more preferably diisobutylaluminium hydride.
In said neodymium series catalysts, said halogen contained compound can be for having general formula AlR
2The aikyl aluminum halide of X or have general formula Al
2R
3X
3Sesquialkyl aluminium, wherein R can be ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, X can be bromine or chlorine; Said halogen contained compound also can be halogen-containing organic cpds, and specific examples includes but not limited to benzyl chloride, bromotoluene, tertiary butyl chloride, methyl chloride silane and silicon tetrachloride; Be preferably aluminium diethyl monochloride, sesquialter aluminium triethyl and a chloro-di-isobutyl aluminum with said halogen contained compound; And
2
#The preparation method of polyisoprene rubber is following: isoprene monomer carries out solution polymerization under catalyst action, and wherein said isoprene monomer is a polymerization-grade, and said catalyzer can be inert hydrocarbon solvent for Titanium series catalyst and wherein said solvent.
Particularly, the preparation method of polyisoprene rubber is following: under nitrogen protection, in the 5L reactor drum, add the 1490g hexane, 350g isoprene IP adds TiCl
4The hexane solution of/triisobutyl aluminium/phenyl ether catalyzer, catalyst levels are 1.0 * 10
-3Mol Ti/mol IP, monomer concentration are 19wt%; 20 ℃ down reaction to obtain the polymer weight percentage composition in 2 hours be 17% the polymers soln that contains active catalyst, it is suitable-1 that above-mentioned glue obtains through aftertreatment, the dried glue of 4-TR 301.
4. like each described rubber combination of previous embodiments, it is characterized in that, is benchmark with the rubber components of 100 weight parts; Contain the 1.0-3.0 weight part, preferred 1.2-2.5 weight part, preferred 1.5-2.5 weight part; Preferred 1.8-2.5 weight part, the anti-aging agent of preferred 1.8-2.2 weight part.
5. like each described rubber combination of previous embodiments; Wherein have 3 kinds of anti-aging agent, said 3 kinds of anti-aging agent are respectively: N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA), N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent 4020), 2; 2; 4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD), anti-aging agent meets the requirement of the REACH of European Union environmental regulation.
6. like each described rubber combination of previous embodiments, wherein said anti-aging agent meets following 3 requirements:
1) restriction of European Union's control objectionable impurities instruction (ROHS):
6 kinds of objectionable impuritiess comprise: plumbous Pb, mercury Hg, sexavalent chrome Cr
6+, polybromodiphenyl ether PBDE, PBBs PBB (above 5 kinds of substances content are lower than 1000ppm), cadmium Cd (content is lower than 100ppm).
2) show great attention to material for 15 kinds:
4,4 '-two amido ditanes, phthalic acid tolyl butyl ester (BBP), phthalic acid two (2-ethylhexyl) ester (DEHP), phthalic acid dibutyl ester (DBP), anthracene, hexabromocyclododecane (HBCDD), sodium dichromate 99 two hydrates, xylol musk (MX), short chain clorafin (SCCP), white arsenic, lead hydrogen arsenate, cobalt dichloride, bis oxide tributyl tin, arsenous ethide hydrochlorate, arsenic powder.The concentration of above material in anti-aging agent all≤0.1% (weight ratio W/W).
3) polycyclic aromatic hydrocarbons (PAHs):
Benzo (a) pyrene content should be lower than 10
-6(massfraction, down with), simultaneously, below 8 kinds of poly-ring aromatic compounds total contents should be lower than 10
-5, be respectively benzanthrene (BaA), benzo (b) fluoranthene (BbFA), benzo (k) fluoranthene (BkFA), benzo (J) fluoranthene (BjFA), acenaphthene (CHR), benzo (a) pyrene (BaP), dibenzo (a, h) anthracene (DBahA) and benzo (e) pyrene (BeP).
7. like each described rubber combination of previous embodiments, wherein said anti-aging agent RD meets following requirement: the staple of anti-aging agent RD is 2,2; 4-trimethylammonium-1,2-dihyaroquinoline polymer is in anti-aging agent RD; Have only dimer, tripolymer, the tetramer that the anti-aging effect is arranged; And dimeric anti-aging effect is best, and used environment-friendly type anti-aging agent RD-E dimer content reaches 49-52%, and two, three, tetramer total content reaches 70-72%.
8. like each described rubber combination of previous embodiments, it is characterized in that, is benchmark with the rubber components of 100 weight parts, contains the 0.5-1 weight part, preferred 0.6-1 weight part, preferred 0.6-0.9 weight part, the vulcanization accelerator of preferred 0.7-0.9 weight part.
9. like each described rubber combination of previous embodiments, it is characterized in that said vulcanization accelerator is the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, said promotor produces less nitroso compound.
10. like each described rubber combination of previous embodiments, it is characterized in that, is benchmark with the rubber components of 100 weight parts; Contain the 45-55 weight part; Preferred 45-50 weight part, preferred 50-55 weight part, preferred 47-53 weight part; The carbon black of preferred 49-54 weight part, the sooty kind can preferred industrial reference black 7
#, high abrasion furnace black(HAF) N330, medium super abrasion furnace black N220.
11., it is characterized in that, be benchmark with the rubber components of 100 weight parts like each described rubber combination of previous embodiments; Contain the 1.5-2.5 weight part, preferred 1.5-2.0 weight part, preferred 1.8-2.3 weight part; Preferred 1.7-2.2 weight part, the sulphur of preferred 2.0-2.5 weight part.
12. like each described rubber combination of previous embodiments; It is characterized in that, be benchmark with the rubber components of 100 weight parts, contains the 3.0-4.0 weight part; Preferred 3.0-3.5 weight part; Preferred 3.2-3.7 weight part, preferred 3.4-3.9 weight part, the zinc oxide of preferred 3.5-4.0 weight part.
13. like each described rubber combination of previous embodiments; It is characterized in that, be benchmark with the rubber components of 100 weight parts, contains the 2.0-3.0 weight part; Preferred 2.0-2.5 weight part; Preferred 2.2-2.7 weight part, preferred 2.4-2.9 weight part, the Triple Pressed Stearic Acid of preferred 2.5-3.0 weight part.
Make the pneumatic tyre of material 14. use each described rubber combination of previous embodiments.
Embodiment
Rubber combination described in the invention comprises dience rubber component and environment-friendly type anti-aging agent, promotor.
The instance of dience rubber component has tree elastomer (NR), polyisoprene rubber (IR), various polybutadiene rubber (BR).Said dience rubber component can be used separately also can two kinds and two or more combination use.Preferred use tree elastomer, and synthetic high-cis polyisoprene rubber.The consumption of rubber does, is benchmark with the rubber components of 100 weight parts, contains the tree elastomer of 70-100 weight %, and the polyisoprene rubber of 0-30 weight %.
For tree elastomer, its mooney viscosity is 65-75.
For polyisoprene rubber, two trades mark are arranged: 1
#Polyisoprene rubber weight-average molecular weight Mw is 1,300,000-2,500,000, and molecular weight distributing index Mw/Mn is 2.2-5.6, cis-1; 4-structural content 96-98%, fugitive constituent＜0.6wt%, ash content＜0.5wt%; Mooney viscosity (ML1+4min, 100 ℃) is 70 ± 5, and proportion is 0.90-0.92g/cm
32
#Polyisoprene rubber peak molecular weight M
pBe 1,410,000-1,510,000, number-average molecular weight M
nBe 270,000-470,000; 1, the 4-structural content is 95-98%, wherein, cis-1, the 4-structural content is 95-97%; Gel content is 0.14-2%, and second-order transition temperature Tg is-57 to-59 ℃, and mooney viscosity (ML1+4min, 100 ℃) is 66-84.
1 of the present invention's use
#Polyisoprene rubber; Its polymerization method is that isoprene monomer carries out solution polymerization under the rare earth catalyst effect, and wherein said isoprene monomer is a polymerization-grade, can be purchased acquisition; Said rare earth catalyst can be inert hydrocarbon solvent for neodymium series catalysts and wherein said solvent.
2
#The preparation method of polyisoprene rubber is following: isoprene monomer carries out solution polymerization under catalyst action, and wherein said isoprene monomer is a polymerization-grade, and said catalyzer can be inert hydrocarbon solvent for Titanium series catalyst and wherein said solvent.
Anti-aging agent is two kinds of p phenylenediamine type antioxidant: 4010NA and 4020, a kind of quinoline type antioxidant: RD.
The staple of anti-aging agent RD is 2,2,4-trimethylammonium-1; 2-dihyaroquinoline polymer; In anti-aging agent RD, have only dimer, tripolymer, the tetramer that the anti-aging effect is arranged, and dimeric anti-aging effect is best; The used environment-friendly type anti-aging agent dimer content of this patent reaches 49-52%, and two, three, tetramer total content reaches 70-72%.
2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (arborescens) Polymerizcd 2,2,4-trimethyl-1,2-dihydroquinoline (Resin)
Structural formula:
Trade name: anti-aging agent RD
Antioxidant 4010NA has another name called anti-aging agent IPPD, and its staple is N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
N-sec.-propyl-N '-diphenyl-para-phenylene diamine N-Isopropyl-N '-phenyl-p-phenylene dianime structural formula:
Trade name: antioxidant 4010NA, anti-aging agent IPPD
Anti-aging agent 4020 has another name called antioxidant D MBPPD, and its staple is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine.
N-(1 N-(1,3-Dimethyl butyl)-N '-phenyl-p-phenylene diamine
Structural formula:
Trade name; Antioxidant D MBPPD, anti-aging agent 4020
The consumption of anti-aging agent does, is benchmark with the rubber components of 100 weight parts, preferably adds the 1-3 weight part, preferred 1.2-2.5 weight part, preferred 1.5-2.5 weight part, preferred 1.8-2.5 weight part, preferred 1.8-2.2 weight part.Relevant harmful substance contents in its anti-aging agent meets following standard:
1) 6 kinds of objectionable impuritiess:
Plumbous Pb, mercury Hg, sexavalent chrome Cr
6+, polybromodiphenyl ether PBDE, PBBs PBB (above 5 kinds of substances content are lower than 1000ppm), cadmium Cd (content is lower than 100ppm).
2) show great attention to material for 15 kinds:
4,4 '-two amido ditanes, phthalic acid tolyl butyl ester (BBP), phthalic acid two (2-ethylhexyl) ester (DEHP), phthalic acid dibutyl ester (DBP), anthracene, hexabromocyclododecane (HBCDD), sodium dichromate 99 two hydrates, xylol musk (MX), short chain clorafin (SCCP), white arsenic, lead hydrogen arsenate, cobalt dichloride, bis oxide tributyl tin, arsenous ethide hydrochlorate, arsenic powder.The concentration of above material in anti-aging agent all≤0.1% (weight ratio W/W).
3) polycyclic aromatic hydrocarbons (PAHs):
Benzo (a) pyrene content should be lower than 10
-6(massfraction, down with), simultaneously, below 8 kinds of poly-ring aromatic compounds total contents should be lower than 10
-5, be respectively benzanthrene (BaA), benzo (b) fluoranthene (BbFA), benzo (k) fluoranthene (BkFA), benzo (J) fluoranthene (BjFA), acenaphthene (CHR), benzo (a) pyrene (BaP), dibenzo (a, h) anthracene (DBahA) and benzo (e) pyrene (BeP).
Used vulcanization accelerator is TBBS, in the course of processing, produces less carcinogenic substance---nitroso compound.The consumption of promotor does, is benchmark with the rubber components of 100 weight parts, preferably adds the 0.5-1 weight part, preferred 0.6-1 weight part, preferred 0.6-0.9 weight part, preferred 0.7-0.9 weight part.
Promotor is TBBS, has another name called accelerator NS, and its staple is the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide.
The N-tertiary butyl-2-[4-morpholinodithio base sulphenamide N-tert-Butyl-2-benzothiazolesulphenamide structural formula,
Trade name: accelerator NS
Promotor is that the staple of CZ is N-cyclohexyl-2-[4-morpholinodithio base sulphenamide.
N-cyclohexyl-2-[4-morpholinodithio base sulphenamide N-Cyclohexyl-2-benzothiazole sulphenamide structural formula,
Trade name: accelerant CZ
Also contain carbon black in the rubber combination of the present invention.Carbon black can adopt industrial reference black 7
#, high abrasion furnace black(HAF) N330, medium super abrasion furnace black N220, preferred medium super abrasion furnace black N220.The sooty consumption is a benchmark with the rubber components of 100 weight parts, preferably adds the 45-55 weight part.
The preferred sulphur of vulcanizing agent in the rubber combination of the present invention, its add-on is a benchmark with the rubber components of 100 weight parts, preferably adds the 1.5-2.5 weight part.
Also contain zinc oxide and Triple Pressed Stearic Acid in the rubber combination of the present invention, its add-on is a benchmark with the rubber components of 100 weight parts, and zinc oxide preferably adds the 3-4 weight part, and Triple Pressed Stearic Acid preferably adds the 2-3 weight part.
Pneumatic tyre of the present invention can use the rubber combination of invention with the general method manufacturing, and tire is mainly heavy duty tire, and rubber combination is mainly used in the tread rubber of tire.Manufacturing processed is that rubber combination of the present invention elder generation before sulfuration that will be added with above-mentioned additive (if necessary) becomes the shape of a tire tread glue through extrusion process, then in tyre building machine, is molded into unvulcanized tire with general method.Then, in vulcanizer, press to pneumatic tyre for the sulfurized tire through heating and adding.
Embodiment
With instance the present invention is made a more detailed description below, but the present invention is not limited thereto.
1. raw material
Tree elastomer: SCR20
Polyisoprene rubber 1: mooney viscosity 65-75, China Petrochemical Industry Beijing Chemical Research Institute Yanshan Mountain branch is synthetic according to aforesaid method.
Polyisoprene rubber 2
#: mooney viscosity 66-84, China Petrochemical Industry Beijing Chemical Research Institute Yanshan Mountain branch is synthetic according to aforesaid method.
Carbon black: medium super abrasion furnace black N220
Anti-aging agent 1:4010NA, 4020, RD meet the REACH of European Union environmental regulation requirement (available from Jiangsu Sheng'Ao Chemical Technology Co., Ltd), represent 4010NA, 4020, the RD of environment-friendly type respectively with 4010NA-E, 4020-E, RD-E
Anti-aging agent 2:4010NA is not through the REACH of European Union environmental regulation authentication (available from Nan Hua company of China Petrochemical Industry)
Vulcanization accelerator TBBS, accelerant CZ, sulphur, zinc oxide, Triple Pressed Stearic Acid are commercially available.
2. process and testing method
According to the compsn shown in table 1, table 2 and the table 3; Every kind of raw material is through the mixing unvulcanized rubber compsn that obtains; Said rubber combination is handled through press vulcanization down at 145 or 150 ℃ and is obtained sulfide, and the performance of these rubber unvulcanizates and cross-linked rubber is measured as follows:
2.1 the processing characteristics of rubber unvulcanizate, vulcanization characteristics
The processing characteristics of sizing material characterizes with the mooney viscosity of rubber unvulcanizate, and mooney's viscosimeter (SMV-201 type, day island proper Tianjin company produces) test condition: ML (100 ℃, 1+4min)
Vulcanization characteristics test condition: no rotor vulkameter (Taiwan high Inland Steel produce): 1 ° of oscillation angle, frequency 1.7Hz, temperature 145 or 150 ℃ are with ts
1Characterize the scorch safety of sizing material, tc
90Characterize the sulfurizing time of sizing material.
2.2 the stretching tear resistance of cross-linked rubber
With the test of AG-20KNG type rubber puller system (day island proper Tianjin company produces), draw speed 500mm/min.
2.3 the wear resisting property of cross-linked rubber
Wear and tear with DIN and to represent, with rotating drum formula abrasion machine (the high Inland Steel in Taiwan produces) test.
2.4 the dynamic properties of cross-linked rubber
Adopt the U.S. DMA-2980 of TA company type viscoelastic spectrometer to measure frequency 2Hz, 5 ℃/min of temperature rise rate ,-120 ℃～100 ℃, sample size 40mm * 5mm * 1mm.With the wet-sliding resistant performance of tan δ (0 ℃) sign cross-linked rubber, tan δ (0 ℃) is big more, and expression cross-linked rubber wet-sliding resistant performance is better; With the rolling resistance of tan δ (60 ℃) sign cross-linked rubber, tan δ (60 ℃) is more little, and expression cross-linked rubber rolling resistance is more little.
2.5 the compression heat generation of cross-linked rubber
Temperature rise is subdued in the compression of adopting Y3000E type compression heat generation trier (the dark Electron equipment Co., Ltd of Beijing friend product) to measure cross-linked rubber.
1. polyisoprene rubber partly substitutes tree elastomer
Polyisoprene rubber partly substitutes the processing characteristics and the physical and mechanical properties of tree elastomer sizing material and sees table 1.
Can find out by table 1; Polyisoprene rubber substitutes tree elastomer with 20% and 30% proportional part; The processing characteristics of sizing material and mechanical mechanics property and use tree elastomer suitable fully; Wherein to be that polyisoprene rubber substitutes sizing material 300% stress at definite elongation of tree elastomer higher for titanium, and it is lower that compression deflects living heat, demonstrates better properties.
Table 1. polyisoprene rubber partly substitutes the result of tree elastomer
2. the use of environment-friendly type anti-aging agent
Table 2. environment-friendly type anti-aging agent replaces the rerum natura result of common anti-aging agent
Can find out by table 2; Antioxidant 4010NA-E, 4020-E, the common antioxidant 4010NA of RD-E equivalent substitution with environment-friendly type; And with the less accelerator TBBS equivalent substitution accelerant CZ of toxicity, the processing characteristics of sizing material and mechanical mechanics property and use common anti-aging agent fully and accelerant CZ suitable.Adopt some Example formulations, the time of scorch of its rubber unvulcanizate is longer, and the processing safety of rubber unvulcanizate improves, and the rolling resistance of cross-linked rubber is less, demonstrates better properties.
3. the use of environment-friendly type promotor
The use of table 3 environment-friendly type promotor is to the influence of properties of rubber
Can find out by table 3; Use is than the vulcanization accelerator TBBS equivalent substitution accelerant CZ of environmental protection; And use the less non-environment-friendly type antioxidant 4010NA of quinoline environment-friendly type anti-aging agent RD-E equivalent substitution of toxicity; The processing characteristics of sizing material and mechanical mechanics property and use non-environment-friendly type promotor, anti-aging agent suitable, wherein the time of scorch ts of environment-friendly type prescription
1Longer, processing safety is better, and the compression of cross-linked rubber to deflect temperature rise lower, demonstrate better properties.
According to the present invention; A kind of rubber combination is provided; It adopts inexpensive polyisoprene rubber partly to substitute tree elastomer; And use the anti-aging agent meet the requirement of the REACH of European Union environmental regulation, and the vulcanization accelerator that produces less nitroso compound, and the processing characteristics of rubber combination, vulcanization characteristics and mechanical mechanics property are with relatively prescription is suitable.The invention still further relates to and use this rubber combination to make the pneumatic tyre of material.
Claims (14)
1. a rubber combination is characterized in that, said rubber combination contains the dience rubber component; The instance of dience rubber component is preferably tree elastomer (NR), polyisoprene rubber (IR), various polybutadiene rubber (BR); Said dience rubber component can use separately also can two kinds and two or more combination use; Rubber components with 100 weight parts is a benchmark, contains 70-100 weight %, preferred 75-100 weight %, preferred 75-95 weight %; Preferred 80-100 weight %, preferred 80-95 weight %, preferred 85-100 weight %, the tree elastomer of preferred 85-95 weight %; And 0-30 weight %, preferred 0-25 weight %, preferred 5-25 weight %, preferred 0-20 weight %; Preferred 5-20 weight %, preferred 0-15 weight %, the polyisoprene rubber of preferred 5-15 weight %.
2. the rubber combination of claim 1, wherein polyisoprene rubber weight-average molecular weight M
wBe 1,300,000-2,500,000, molecular weight distributing index M
w/ M
nBe 2.2-5.6, cis-1, the 4-structural content is 96-98%, fugitive constituent＜0.6wt%, ash content＜0.5wt%, mooney viscosity (ML1+4min, 100 ℃) is 70 ± 5, proportion is 0.90-0.92g/cm
3Perhaps
Polyisoprene rubber peak molecular weight M
pBe 1,410,000-1,510,000, number-average molecular weight M
nBe 270,000-470,000; 1, the 4-structural content is 95-98%, wherein, cis-1, the 4-structural content is 95-97%; Gel content is 0.14-2%, and second-order transition temperature Tg is-57 to-59 ℃, and mooney viscosity (ML1+4min, 100 ℃) is 66-84.
3. like each described compsn of aforementioned claim, wherein the polymerization method of polyisoprene rubber is following:
Isoprene monomer carries out solution polymerization under the rare earth catalyst effect, wherein said isoprene monomer is a polymerization-grade, and said rare earth catalyst can be inert hydrocarbon solvent for neodymium series catalysts and wherein said solvent; Perhaps
The preparation method of polyisoprene rubber is following: isoprene monomer carries out solution polymerization under catalyst action, and wherein said isoprene monomer is a polymerization-grade, and said catalyzer can be inert hydrocarbon solvent for Titanium series catalyst and wherein said solvent.
4. as each described rubber combination of aforementioned claim, it is characterized in that, is benchmark with the rubber components of 100 weight parts; Contain the 1.0-3.0 weight part, preferred 1.2-2.5 weight part, preferred 1.5-2.5 weight part; Preferred 1.8-2.5 weight part, the anti-aging agent of preferred 1.8-2.2 weight part.
5. like each described rubber combination of aforementioned claim; Wherein have 3 kinds of anti-aging agent, said 3 kinds of anti-aging agent are respectively: N-sec.-propyl-N '-diphenyl-para-phenylene diamine (antioxidant 4010NA), N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (anti-aging agent 4020), 2; 2; 4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD), anti-aging agent meets the requirement of the REACH of European Union environmental regulation.
6. like each described rubber combination of aforementioned claim, wherein said anti-aging agent meets following 3 requirements:
1) restriction of European Union's control objectionable impurities instruction (ROHS):
6 kinds of objectionable impuritiess comprise: plumbous Pb, mercury Hg, sexavalent chrome Cr
6+, polybromodiphenyl ether PBDE, PBBs PBB (above 5 kinds of substances content are lower than 1000ppm), cadmium Cd (content is lower than 100ppm).
2) show great attention to material for 15 kinds:
4,4 '-two amido ditanes, phthalic acid tolyl butyl ester (BBP), phthalic acid two (2-ethylhexyl) ester (DEHP), phthalic acid dibutyl ester (DBP), anthracene, hexabromocyclododecane (HBCDD), sodium dichromate 99 two hydrates, xylol musk (MX), short chain clorafin (SCCP), white arsenic, lead hydrogen arsenate, cobalt dichloride, bis oxide tributyl tin, arsenous ethide hydrochlorate, arsenic powder.The concentration of above material in anti-aging agent all≤0.1% (weight ratio W/W).
3) polycyclic aromatic hydrocarbons (PAHs):
Benzo (a) pyrene content should be lower than 10
-6(massfraction, down with), simultaneously, below 8 kinds of poly-ring aromatic compounds total contents should be lower than 10
-5, be respectively benzanthrene (BaA), benzo (b) fluoranthene (BbFA), benzo (k) fluoranthene (BkFA), benzo (J) fluoranthene (BjFA), acenaphthene (CHR), benzo (a) pyrene (BaP), dibenzo (a, h) anthracene (DBahA) and benzo (e) pyrene (BeP).
7. like each described rubber combination of aforementioned claim, wherein said anti-aging agent RD meets following requirement: the staple of anti-aging agent RD is 2,2; 4-trimethylammonium-1,2-dihyaroquinoline polymer is in anti-aging agent RD; Have only dimer, tripolymer, the tetramer that the anti-aging effect is arranged; And dimeric anti-aging effect is best, and used environment-friendly type anti-aging agent RD-E dimer content reaches 49-52%, and two, three, tetramer total content reaches 70-72%.
8. as each described rubber combination of aforementioned claim, it is characterized in that, is benchmark with the rubber components of 100 weight parts, contains the 0.5-1 weight part, preferred 0.6-1 weight part, preferred 0.6-0.9 weight part, the vulcanization accelerator of preferred 0.7-0.9 weight part.
9. like each described rubber combination of aforementioned claim, it is characterized in that said vulcanization accelerator is the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, said promotor produces less nitroso compound.
10. as each described rubber combination of aforementioned claim, it is characterized in that, is benchmark with the rubber components of 100 weight parts; Contain the 45-55 weight part; Preferred 45-50 weight part, preferred 50-55 weight part, preferred 47-53 weight part; The carbon black of preferred 49-54 weight part, the sooty kind can preferred industrial reference black 7
#, high abrasion furnace black(HAF) N330, medium super abrasion furnace black N220.
11. as each described rubber combination of aforementioned claim, it is characterized in that, be benchmark with the rubber components of 100 weight parts; Contain the 1.5-2.5 weight part, preferred 1.5-2.0 weight part, preferred 1.8-2.3 weight part; Preferred 1.7-2.2 weight part, the sulphur of preferred 2.0-2.5 weight part.
12. as each described rubber combination of aforementioned claim; It is characterized in that, be benchmark with the rubber components of 100 weight parts, contains the 3.0-4.0 weight part; Preferred 3.0-3.5 weight part; Preferred 3.2-3.7 weight part, preferred 3.4-3.9 weight part, the zinc oxide of preferred 3.5-4.0 weight part.
13. as each described rubber combination of aforementioned claim; It is characterized in that, be benchmark with the rubber components of 100 weight parts, contains the 2.0-3.0 weight part; Preferred 2.0-2.5 weight part; Preferred 2.2-2.7 weight part, preferred 2.4-2.9 weight part, the Triple Pressed Stearic Acid of preferred 2.5-3.0 weight part.
Make the pneumatic tyre of material 14. use each described rubber combination of aforementioned claim.
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| CN2010106228827A CN102532613A (en) | 2010-12-29 | 2010-12-29 | Rubber composition |
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| CN2010106228827A CN102532613A (en) | 2010-12-29 | 2010-12-29 | Rubber composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819761A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Novel isoprene rubber |
| CN110193890A (en) * | 2019-06-06 | 2019-09-03 | 益凯新材料有限公司 | A kind of wet process mixing continuous production technology of isoprene rubber |
| CN112694645A (en) * | 2020-12-30 | 2021-04-23 | 山东兴鸿源轮胎有限公司 | Tire sidewall rubber added with high-content TMQ (tetramethylbenzidine) and resistant to thermal oxidative aging and preparation method thereof |
| CN113512239A (en) * | 2021-04-30 | 2021-10-19 | 中国科学院长春应用化学研究所 | Rubber composition for tire side wall and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613493A (en) * | 2009-07-31 | 2009-12-30 | 北京市射线应用研究中心 | One meridian tyre belted layer parts and preparation technology |
| CN101743273A (en) * | 2007-06-08 | 2010-06-16 | 住友橡胶工业株式会社 | Rubber composition for side wall and pneumatic tire utilizing the same |
-
2010
- 2010-12-29 CN CN2010106228827A patent/CN102532613A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101743273A (en) * | 2007-06-08 | 2010-06-16 | 住友橡胶工业株式会社 | Rubber composition for side wall and pneumatic tire utilizing the same |
| CN101613493A (en) * | 2009-07-31 | 2009-12-30 | 北京市射线应用研究中心 | One meridian tyre belted layer parts and preparation technology |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819761A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Novel isoprene rubber |
| CN110193890A (en) * | 2019-06-06 | 2019-09-03 | 益凯新材料有限公司 | A kind of wet process mixing continuous production technology of isoprene rubber |
| CN110193890B (en) * | 2019-06-06 | 2020-05-19 | 益凯新材料有限公司 | Wet mixing continuous production method of isoprene rubber |
| CN112694645A (en) * | 2020-12-30 | 2021-04-23 | 山东兴鸿源轮胎有限公司 | Tire sidewall rubber added with high-content TMQ (tetramethylbenzidine) and resistant to thermal oxidative aging and preparation method thereof |
| CN113512239A (en) * | 2021-04-30 | 2021-10-19 | 中国科学院长春应用化学研究所 | Rubber composition for tire side wall and preparation method thereof |
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Application publication date: 20120704 |