CN101568583B - Rubber composition for belt, and rubber belt - Google Patents
Rubber composition for belt, and rubber belt Download PDFInfo
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- CN101568583B CN101568583B CN2008800011579A CN200880001157A CN101568583B CN 101568583 B CN101568583 B CN 101568583B CN 2008800011579 A CN2008800011579 A CN 2008800011579A CN 200880001157 A CN200880001157 A CN 200880001157A CN 101568583 B CN101568583 B CN 101568583B
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Abstract
Disclosed is a rubber composition for a belt, which is suitable for an industrial rubber belt having less energy loss and excellent durability including flex crack growth resistance. Specifically disclosed is a rubber composition for a belt, which comprises: 90 to 5 mass% of a vinyl-cis-polybutadiene rubber (A) comprising 1 to 30 mass% of a specific syndiotactic-1,2-polybutadiene crystal fiber (b)and 99 to 70 mass% of a cis-polybutadiene rubber (a), wherein the syndiotactic-1,2-polybutadiene crystal fiber (b) has an average fiber length of 200 nm or less and an average fiber aspect ratio of 10 or less, contains crystal fibers having fiber length of 200 nm or less at a density of 90 fibers or more per 25 [mu]m<2>, and has a melting point of 170 DEG C or higher; 10 to 95 mass% of a diene rubber (B) which is different from the component (A); and a rubber reinforcing agent (C) in an amount of 20 to 70 parts by mass relative to 100 parts by mass of the total amount of the rubber components(A) and (B), wherein the rubber reinforcing agent (C) comprises at least carbon black and silica, and the content of silica in the rubber reinforcing agent (C) is 70 mass% or less.
Description
Technical field
The present invention relates to be applicable in light weight, energy waste is lower, such as wearing qualities such as anti-flexing be full of cracks growth and low-heat-generations excellent and while the belt of the industrial rubber band that physical properties averages out on processibility, essential property, weather resistance and energy saving with rubber combination and string rubber.
Background technology
Generally speaking, the industrial rubber band roughly is divided into the transmission belt and the travelling belt that transmits article of transferring power.Available robber materials comprises tree elastomer, polybutadiene rubber, SBR styrene butadiene rubbers, propylene diene rubber, X 050, chlorosulfonated polyethylene rubber, paracril and hydrogenated nitrile-butadiene rubber.
The rubber combination that in string rubber, uses need have bigger tensile strength, suitable hardness, snappiness, elasticity, good flexibility and bigger shock-resistance, and also need realize energy-conservation and lightweight.In order to satisfy these needs, use inorganic strengthening agent or staple fibre have been proposed to strengthen.Utilizing staple fibre to carry out instance of enhanced is disclosed in the patent documentation 1 as rubber composition for conveyor belt.Said rubber combination comprises tree elastomer and contains rule-1 between crystallinity, the divinyl rubber of 2-polybutadiene (being also referred to as the vinyl cis-polybutadiene rubber).Said tree elastomer and said divinyl rubber are cooperated to keep such as basic physical properties such as high tensile and wear resistance and to be reduced in the energy expenditure when being used for travelling belt.
Patent documentation 1:JP 2004-346220A
Summary of the invention
Invent problem to be solved
The increase that also causes dynamic heat build up that increases such as the amount of inorganic strengthening agents such as carbon black of the tensile strength in the time of can adding strong hardness, tensile stress, fracture, wear resistance etc.It also causes the problem of the proportion increase of title complex, because this is inappropriate for lightweight.On the other hand, the rubber combination described in the patent documentation, 1, the ultra-fine dispersion of 2-polyhutadiene staple fibre crystal in divinyl rubber or matrix components is not enough.Therefore, problem is on processibility, tensile stress, tensile strength and anti-flexing be full of cracks growth, to bring into play enough effects always.
For solve as above problem, the invention provides be applicable in light weight, energy waste is lower, the belt of and the rerum natura favorable industrial string rubber that processibility, essential property, weather resistance and energy saving on average out excellent such as wearing qualities such as anti-flexing be full of cracks growth and low-heat-generations is with rubber combination and string rubber.
The means of dealing with problems
For realizing as above target, thus research and found that then certain vinyl cis-polybutadiene rubber can make the use level of silicon-dioxide in said rubber stiffener become below the 70 quality % with cooperating as the carbon black of rubber stiffener and silicon-dioxide enthusiastically such as the inventor.This situation makes it possible to provide energy waste less and such as excellent industrial rubber bands of wearing quality such as anti-flexing be full of cracks growths.In other words; The invention provides belt and use rubber combination; Said compsn comprises: (A) the vinyl cis-polybutadiene rubber of 90 quality %～5 quality %; This rubber comprises specific the rule 1 of (b) 1 quality %～30 quality %; 2-polyhutadiene crystal fibre and (a) cis-polybutadiene rubber of 99 quality %～70 quality %, said crystal fibre has crystal fibre average fiber length, the average aspect ratio 10 below that is equal to or less than 200nm, and staple length is the per 25 μ m of number of the following crystal fibre of 200nm
2Be equal to or greater than 90, and have the fusing point more than 170 ℃; (B) polydiene except that (A) of 10 quality %～95 quality %; (C) with respect to the rubber constituent (A)+(B) of 100 mass parts and the rubber stiffener of 20 mass parts～70 mass parts that cooperate; Wherein, Said rubber stiffener (C) contains carbon black and silicon-dioxide at least, and the use level of the said silicon-dioxide in the wherein said rubber stiffener is below the 70 quality %.String rubber of the present invention comprises as the said belt of rubber substrate uses rubber combination.
The invention effect
The present invention can provide the belt of the rerum natura favorable industrial string rubber that is applicable to that energy waste is low, excellent such as wearing qualities such as anti-flexing be full of cracks growths and on processibility, essential property, weather resistance and energy saving, average out with rubber combination and string rubber.
Description of drawings
[Fig. 1] be sample A-1 and (b) 5000 times of electron photomicrographs of sample A-2 (a), all by image analysis software (from the Win ROOF of three paddy business societies) binaryzation.
[Fig. 2] shows the figure of the relation of the mould port expansion in embodiment 1～4 and the comparative example 2～4, anti-flexing be full of cracks growth and Δ H, and wherein the use level of rubber stiffener equals 40 mass parts.
Embodiment
Generally speaking, contained vinyl cis-polybutadiene rubber (A) configuration is as follows in rubber combination at belt of the present invention.That is, it comprise (b) 1 quality %～30 quality % have fusing point more than 170 ℃ between rule-1,2-polyhutadiene (hereinafter is called " 1, the 2-polyhutadiene ") crystal fibre and (a) cis-polybutadiene rubber of 99 quality %～70 quality %.
For above-mentioned 1,2-polyhutadiene crystal fibre (b), the average fiber length of crystal fibre is equal to or less than 200nm, is preferably below the 150nm.Average aspect ratio is below 10, to be preferably below 4.Staple length is the per 25 μ m of crystal fibre number below the 200nm
2Be equal to or greater than 90, preferred per 25 μ m
2Be more than 100.Fusing point is more than 170 ℃, is preferably 190 ℃～220 ℃.
Preferably, belt of the present invention comprises the unsaturated polymer substance (c) that each repeating unit has at least one unsaturated double-bond with the contained vinyl cis-polybutadiene rubber (A) of rubber combination.Preferably, said unsaturated polymer substance (c) is attracted to 1, in the 2-polyhutadiene crystal fibre (b) and be dispersed in matrix components or the cis-polybutadiene rubber (a).The boiling n-hexane insolubles of said vinyl cis-polybutadiene rubber (A) is 1,2-polyhutadiene crystal fibre (b) and part or all of unsaturated polymer substance (c).Be adsorbed onto 1, the ratio (percentage of grafting) of the unsaturated polymer substance (c) on the 2-polyhutadiene crystal fibre (b) can be calculated through infrared absorption spectrum analysis.Be adsorbed onto 1, the ratio (percentage of grafting) of the unsaturated polymer substance (c) on the 2-polyhutadiene crystal fibre (b) is 5 quality %～200 quality %, is preferably 10 quality %～120 quality %, is preferably 20 quality %～90 quality % especially.Drop into and have following preferred effect in this scope: rule-1 between having improved, the dispersiveness of 2-polyhutadiene crystal fibre (b), and the reduction of the various physical propertiess that prevented in said vinyl cis-polybutadiene rubber, possibly to cause.Said boiling n-hexane insolubles is that 2g vinyl cis-polybutadiene rubber (A) boils the residue that extracts through the Soxhlet method after 4 hours in the 200mL normal hexane, and its numerical value is represented with quality %.
The staple of cis-polybutadiene rubber (a) comprises high-cis-1 self and with at least a as in the polyhutadiene of primary structure of high-cis-1,4 structure.What expect is that said cis-polybutadiene rubber has following character.Be that cis-1,4 constituent is generally more than the 90mol%, be preferably more than the 95mol%.Mooney viscosity (ML
1+4, 100 ℃: hereinafter is called " ML ") and be 10～130, be preferably 15～80.Toluene solution viscosity (hereinafter is called " T-cp ") is 10cp～200cp, is preferably 10cp～150cp.What expect is not contain gel component basically.
Said vinyl cis-polybutadiene rubber contains 1; 2-polyhutadiene crystal fibre (b) and cis-polybutadiene rubber (a); Ratio is the cis-polybutadiene rubber (a) of 99 quality %～70 quality %: 1 of 1 quality %～30 quality %, 2-polyhutadiene crystal fibre (b).Be higher than above-mentionedly 1, the ratio of 2-polyhutadiene crystal fibre (b) causes bigger by 1 easily in cis-polybutadiene rubber (a), 2-polyhutadiene crystal fibre (b) the staple fibre crystallization, make dispersed variation.Be lower than above-mentioned 1, the ratio of 2-polyhutadiene crystal fibre (b) reduced utilize this 1, the reinforced effects of 2-polyhutadiene crystal fibre (b).In the case, be difficult to performance such as the distinctive excellent properties of processibility, tensile stress, tensile strength and anti-flexing be full of cracks growth etc., this is undesirable.Unsaturated polymer substance (c) is 0.1 quality %～30 quality % with the ratio of vinyl cis-polybutadiene rubber (A), is preferably 1 quality %～20 quality %.Drop on and have following preferred effect in this scope: improved 1, the dispersiveness of 2-polyhutadiene crystal fibre (b), and the reduction of the various physical propertiess that prevented in said vinyl cis-polybutadiene rubber, possibly to cause.
Above-mentioned vinyl cis-polybutadiene rubber can suitably be produced through following production technique.
In the production of vinyl cis-polybutadiene rubber (A), generally use varsol to carry out the polymerization of 1,3-butadiene.It is below 9.0 that said varsol preferably comprises SP (hereinafter is called " SP value "), more preferably the varsol below 8.5.7.2), Skellysolve A (SP value: 7.0), octane (SP value: 7.5), hexanaphthene (SP value: 8.1) and normal butane (SP value: 6.6) instance with varsol of the SP value below 9.0 comprises fat hydrocarbon or alicyclic hydrocarbon type, like normal hexane (SP value:.Wherein, can preferably use hexanaphthene.
The SP value of solvent is known in rubber industry brief guide (rubber industry association, Japan, the 4th edition, 721 pages, on January 20th, 1994) etc.
The SP value has improved 1 less than the use of 9.0 solvent, the dispersiveness of the short crystal fibre of 2-polyhutadiene in matrix components or cis-polybutadiene rubber.As a result, gained vinyl cis-polybutadiene rubber can show the excellent properties such as processibility, tensile stress, tensile strength and anti-flexing be full of cracks growth etc.
In the production of vinyl cis-polybutadiene rubber (A), 1,3-butadiene is mixed with said varsol, regulate the water concentration in the gained solution then.With respect to stating organo-aluminium compound behind the every 1mol that in solution, is used as cis-1,4 polymerizing catalyst, water-content is preferably 0.1mol～1.0mol, is preferably 0.2mol～1.0mol especially.In this scope, can obtain enough catalyst activities, and can obtain suitable cis-1,4 structural content and molecular weight.In addition, can be suppressed at gel in the polymerization generation and thereby prevent that gel from adhering on aggregation container.Therefore, the successive polymerization time can preferably be prolonged.But the application of known method is regulated water concentration.Through porous filter material to its add with dispersive method (JP 4-85304A) also be effective.
In through the above-mentioned solution of regulating the water concentration acquisition, added as cis 1 organo-aluminium compound of one of 4-polymerizing catalyst.Said organo-aluminium compound comprises by general formula AlR
nX
3-nThe preferred available compound of expression.Its suitable specific examples comprises monochlor(in)ate diethyl aluminum, monobromination diethyl aluminum, monochlor(in)ate diisobutyl aluminum, monochlor(in)ate dicyclohexyl aluminium, monochlor(in)ate phenylbenzene aluminium and sesquialter diethylaluminum chloride.With respect to the total amount of the 1,3-butadiene of every 1mol, the consumption of said organo-aluminium compound preferably is no less than 0.1mmol, more preferably 0.5mmol～50mmol.
Then, in being added with the mixing solutions of machine aluminium compound, add solubility cobalt cpd as cis-1,4 polymerizing catalyst so that 1,3-butadiene carries out cis-1,4 polymerization.Said solubility cobalt cpd dissolves in or is dispersed in used varsol or the liquid 1,3-butadiene.Suitable instance comprises: the beta-diketon complex compound of cobalt, like acetylacetone cobalt (II) and acetylacetone cobalt (III); The beta-ketoester complex compound of cobalt is like the methyl aceto acetate complex compound; Organic carboxyl acid cobalt salt with 6 above carbon atoms is like cobalt octoate, cobalt naphthenate and cobaltous benzoate; With the halogenation cobalt complex, like NSC 51149 pyridine complex and NSC 51149 ethanol complex.With respect to the 1,3-butadiene of every 1mol, the consumption of said solubility cobalt cpd preferably is no less than 0.001mmol, more preferably is no less than 0.005mmol.The mol ratio (Al/Co) of said chlorination organoaluminum and said solubility cobalt cpd preferably is no less than 10, more preferably is no less than 50.Other available materials except that said solubility cobalt cpd comprises the organic carboxylate of nickel, organic complex salt, organolithium compound, the organic carboxylate of neodymium and the organic complex salt of neodymium of nickel.
Cis-1,4 polymerization temperature is contemplated to be scope for greater than 0 ℃～100 ℃, is preferably 10 ℃～100 ℃, more preferably 20 ℃～100 ℃.Polymerization time (mean residence time) preferably 10 minutes～2 hours.Preferably, carry out cis-1,4 polymerization so that the polymer concentration after cis 1,4 polymerization becomes 5 quality %～26 quality %.Aggregation container can comprise single container or plural connection container.Carry out polymerization so that solution obtains stirring and mixing in aggregation container (polymerization reactor).Be used for the polymeric aggregation container and can comprise the aggregation container that the whisking appliance that is used for high soltion viscosity is installed, for example, the device described in the JP 40-2645B.
In the production of said vinyl cis-polybutadiene rubber, in cis-1,4 polymerization, can use the known molecular weight regulator, for example, the non-conjugated diene class is like cyclooctadiene, propadiene and methyl-prop diene (1); With the alhpa olefin class, like ethene, propylene and butene-1.In addition, can use known gelling suppressor factor to be suppressed at the generation of gel in the middle of the polymerization.The content of cis-1,4 structure in polymerisate is more than the 80mol%, to be preferably more than the 90mol%.Mooney viscosity is 10～130, is preferably 15～80.The controlled polymerization product is to be substantially free of gel component.
In the cis that is as above obtained-1,4 polymerization reaction mixture,, added at least by general formula AlR as rule-1,2 polymerizations (hereinafter being called " 1,2 polymerization ") catalyzer
3The organo-aluminium compound and the dithiocarbonic anhydride of expression in case of necessity, add above-mentioned solvable cobalt cpd, so that 1,3-butadiene carries out 1,2 polymerization, thereby in the presence of these additives, produce said vinyl cis-polybutadiene.In this case, can 1,3-butadiene be added in the above-mentioned polymerization reaction mixture.Select as another kind, unreacted 1,3-butadiene is reacted with it and need not add.By general formula AlR
3The suitable instance of the organo-aluminium compound of expression comprises trimethylaluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and triphenyl aluminum.With respect to the 1,3-butadiene of every 1mol, said organo-aluminium compound is preferably more than the 0.1mmol, particularly more than 0.5mmol～50mmol.Dithiocarbonic anhydride is restriction especially not, but expectation is moisture-free.The concentration of dithiocarbonic anhydride is for being no more than 20mmol/L, being preferably 0.01mmol/L～10mmol/L especially.The surrogate of dithiocarbonic anhydride can comprise known thiocarbanil and xanthation compound.
1,2 polymeric temperature is-5 ℃～100 ℃, is preferably-5 ℃～70 ℃, more preferably 0 ℃～50 ℃.In 1,2 polymeric polymerization system, with respect to the cis-1 of per 100 mass parts; 4 polymerization reaction mixtures, can add 1 mass parts～50 mass parts, be preferably 1 mass parts～1,3-butadiene of 20 mass parts to be to be increased in 1; In 2 polymerizations 1, the productive rate of 2-polyhutadiene.Polymerization time (mean residence time) is 10 minutes～2 hours.Preferably, carry out 1,2 polymerization so that the polymer concentration after 1,2 polymerization becomes 9 quality %～29 quality %.Aggregation container can comprise single container or plural connection container.Carry out said polymerization so that solution obtains stirring and mixing in aggregation container (polymerization reactor).Owing to uprise and make polymkeric substance to adhere to easily in 1,2 polymerization medium viscosity, thereby the aggregation container that is used in 1,2 polymerization can comprise the aggregation container that the whisking appliance that is used for high soltion viscosity is installed, for example, and the device described in the JP 40-2645B.
Preferably; Through the cis-1 of as above carrying out; The 4 polymerizations production of the said vinyl cis-polybutadiene rubber of 1,2 polymeric then are included in and add each repeating unit in the production process of said vinyl cis-polybutadiene rubber and have the step of the unsaturated polymer substance (c) of a unsaturated double-bond at least.If said unsaturated polymer substance after the production of said vinyl cis-polybutadiene rubber, for example adds when cooperating, it can not bring into play effect of the present invention.The random time till 1,2 polymerization before cis-1,4 polymerization preferably; Further preferably before cis-1,4 polymerization and/or afterwards, more preferably 1; During 2 polymerizations,, said unsaturated polymer substance gets in the said polymerization reaction mixture thereby being added said production system.
Preferably, at least a in the crystallinity polyhutadiene, liquid polybutadiene and their verivate that are selected from TR 301, fusing point and are lower than 170 ℃ of unsaturated polymer substance (c).
The instance of TR 301 comprises common synthetic polyisoprenes (as containing the cis 1 of the above cis-structure of 90mol%, the 4-TR 301), liquid polyisoprene, using trans-polyisoprene and other TR 301 through modifying.
The preferred embodiment that said fusing point is lower than 170 ℃ crystallinity polyhutadiene comprises that fusing point is 0 ℃～150 ℃ a crystallinity polyhutadiene, like lower melting point 1, and 2-polyhutadiene and trans polybutadiene.
The instance of said liquid polybutadiene comprises the ultra-low molecular polyhutadiene below the intrinsicviscosity [η]=1.Intrinsicviscosity [η] is the numerical value of deriving from following expression formula.In the case, supply to 0.1g sample rubber and 100mL toluene in the triangular flask and 30 ℃ of dissolvings fully.10mL said solution be added to Cannon-Fenske dynamic viscosity meter the lowering time (T) to measure said solution that place the Water Tank with Temp.-controlled that remain on 30 ℃ in thereafter.
η sp=T/T
0-1 (T
0: the lowering time when having only toluene)
ηsp/c＝[η]+k’[η]
2c
(η sp: specific viscosity, k ': Huggins constant (0.37), c: sample concentration (g/mL))
The instance of said verivate comprises polyhutadiene and the hydrogenate of their verivate of the carboxyl modified of isoprene-isobutylene copolymers, isoprene-styrol copolymer, SIS, liquid ring oxidation polyhutadiene, liquid.
In above-mentioned unsaturated polymer substance, preferred use be isoprene, SIS and fusing point be 70 ℃～110 ℃ 1, the 2-polyhutadiene.Said unsaturated polymer substance can use separately or use with two or more mixtures.
As stated; If added unsaturated polymer substance (c); Then unsaturated polymer substance (c) the effect on the consistency greatly improved in gained vinyl cis-polybutadiene rubber (A) fusing point be higher than 170 ℃ 1, the dispersiveness of 2-polyhutadiene in matrix components or cis-polybutadiene rubber.As a result, said vinyl cis-polybutadiene rubber has the rerum natura such as the excellence of processibility, tensile stress, tensile strength and anti-flexing be full of cracks growth etc.
With respect to vinyl cis-polybutadiene rubber (A), the addition of said unsaturated polymer substance is preferably 0.1 quality %～30 quality %, more preferably 1 quality %～20 quality %.Regardless of the time of adding, after interpolation, preferably stirred more preferably 10 minutes～30 minutes 10 minutes～3 hours.
In the production of said vinyl cis-polybutadiene rubber, can add at least a in organic cpds with one or more oxygen keys and the macromolecular compound.Preferably, these compounds can comprise such as the compound that contains ether, epoxy group(ing), carboxyl, ester group, hydroxyl or carbonyl.Particular compound can comprise acid anhydrides, Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol, aliphatic ether, aromatic oxide; Aliphatic carboxylic acid, aromatic carboxylic acid, unsaturated carboxylic acid, aliphatic carboxylic acid esters,, aromatic carboxylic acid esters, esters of unsaturated carboxylic acids, resol, nylon resin, urethane, polyoxyethylene glycol, epoxidized polybutadiene, polyester, epoxidation vinyl benzene-polybutadiene copolymer and polyarylether.
In polymerization system, add and have the organic cpds of one or more oxygen keys and at least a cis-polybutadiene and 1 that has changed as the matrix components of said vinyl cis-polybutadiene rubber in the macromolecular compound, the interface avidity between the 2-polybutadiene.This has caused said 1, the influence of the improvement of the above-mentioned physical properties of the decentralized and said vinyl cis-polybutadiene rubber of fiber crystalline list of 2-polybutadiene.
After polyreaction reaches certain rate of polymerization, can add known inhibitor according to usual way.The instance of said inhibitor can comprise 4 of the DBPC 2,6 ditertiary butyl p cresol (BHT) of phenol, Phosphorus Wytox 312 (TNP), sulphur class, 6-two (octyl group thiomethyl) ortho-cresol and dilauryl-3,3 '-thiodipropionic acid ester (TPL).These can use separately or use with two or more combinations.With respect to the said vinyl cis-polybutadiene rubber of 100 mass parts, said inhibitor adds with 0.001 mass parts～5 mass parts.Then, add polymerization terminator to stop said polyreaction.The method that is used for this comprises that polymerization reaction mixture is supplied to polymerization after polyreaction stop container; And a large amount of polar solvents are provided in said polymerization reaction mixture, and for example, such as alcohols such as methyl alcohol and ethanol, or water.Another method comprises that importing is such as mineral acids such as hydrochloric acid and sulfuric acid, such as organic acid or hydrogen chloride gas such as acetate and phenylformic acid in polymeric solution.These methods are known.Then, according to usual way, separated and collected, washing and dry gained vinyl cis-polybutadiene rubber are to obtain target vinyl cis-polybutadiene rubber.
In the production process of said vinyl cis-polybutadiene rubber, the mother liquor of polymerization reaction mixture contains remaining unreacted 1,3-butadiene, varsol and dithiocarbonic anhydride after gained vinyl cis-polybutadiene rubber is obtained in separation.Usually through distillation said 1,3-butadiene is separated from said mother liquor with varsol.In addition, having used the technology of absorption/separation dithiocarbonic anhydride or the technology of separation dithiocarbonic anhydride dirt settling removes dithiocarbonic anhydride and collects 1,3-butadiene and the varsol that is substantially free of dithiocarbonic anhydride with separation.In addition; Use distillation and come from the mother liquor of polymerization reaction mixture, to collect three kinds of compositions; And can use the technology of said absorption/separating technology or said separation dithiocarbonic anhydride dirt settling to remove dithiocarbonic anhydride from distillment, to separate; Thereby collect the 1,3-butadiene and the varsol that are substantially free of dithiocarbonic anhydride.Dithiocarbonic anhydride of so collecting and varsol can be reused with the new 1,3-butadiene combination that replenishes.
In the production of above-mentioned vinyl cis-polybutadiene rubber (A); Obtained vinyl cis-polybutadiene (e) solution through aforesaid method; Said solution contains the 10 quality %～60 quality % that are in the cis-polybutadiene matrix; Be preferably 1 of 20 quality %～50 quality %, 2-polyhutadiene crystal fibre (b).In this solution, can be that the above cis-polybutadiene (f) of 80mol% carries out the solution mixing to generate vinyl cis-polybutadiene rubber (A) with varsol and cis-1,4 structural content.
5 quality % toluene solution viscosity of said cis-polybutadiene are 30cp～250cp, are preferably 50cp～200cp, and 100cp～200cp more preferably.
Can similarly obtain to treat solution blended cis-polybutadiene (f) with cis-1,4 step of polymerization of carrying out 1,3-butadiene through adding above-mentioned cis-1,4 polymerizing catalyst.
Cis-1,4 structural content of gained cis-polybutadiene (f) is more than the 80mol%, to be preferably more than the 90mol%, and more preferably more than the 95mol%.It also has 10～130, is preferably 15～80 mooney viscosity especially, and is substantially free of gel component.It also has 10cp～250cp, is preferably the 5 quality % toluene solution viscosity (Tcp) of 30cp～200cp.
Mix in the vinyl cis-polybutadiene rubber (A) that obtains at solution through vinyl cis-polybutadiene (e) and cis-polybutadiene (f), (e) and ratio (f) be preferably (e): (f)=1: 1～9.
Production technique according to said vinyl cis-polybutadiene rubber (A); Contained vinyl cis-polybutadiene rubber can long-time continuous production in rubber combination at belt of the present invention, and under higher catalyst efficiency, have the operability of good catalyst component and have industrial advantage.Particularly, it can be under having the situation of industrial advantage with the high conversion continuous production polymeric solution can not be attached in the aggregation container inwall and paddle with other a little less than on the mixing part.
The fusing point that the vinyl cis-polybutadiene rubber (A) that obtains through aforesaid method comprises (b) 1 quality %～30 quality % usually is 1 more than 170 ℃, 2-polyhutadiene crystal fibre and (a) cis-polybutadiene rubber of 99 quality %～70 quality %.Cis-polybutadiene rubber (a) contains the cis-1 more than the 80mol% in microstructure, 4-structure and remaining anti-form-1,4-structure and 1,2-structure (vinyl).Fusing point is 1 more than 170 ℃; 2-polyhutadiene crystal fibre (b) is such crystal fibre: it has 170 ℃～220 ℃ fusing point; The average fiber length of crystal fibre is equal to or less than 200nm, and average aspect ratio is below 10, and staple length is the per 25 μ m of crystal fibre number below the 200nm
2Be equal to or greater than 90.The ML of cis-polybutadiene rubber (a) is preferably 10～130, and more preferably 15～80.
The expectation be, belt of the present invention with rubber combination in contained vinyl cis-polybutadiene rubber (A) have following properties.
(i) said 1,2-polyhutadiene crystal fibre (b) has the reducing viscosity (molecular weight index) in 0.5～4 the scope, η sp/c.
(ii) said cis-polybutadiene (a) has cis-1,4 structural content more than the 90mol% in microstructure.
The toluene solution viscosity and the relation between the mooney viscosity of (iii) said cis-polybutadiene (a) are T-cp/ML >=1.
(iv) said cis-polybutadiene (a) has 1.0～5.0 the interior intrinsicviscosity [η] of scope.
The vinyl cis-polybutadiene rubber that so generates can show excellent physical properties, such as processibility, tensile stress, tensile strength and anti-flexing be full of cracks growth.For this reason; Preferably be dispersed in 1 in the said vinyl cis-polybutadiene rubber; 2-polyhutadiene crystal fibre partly is dispersed in the matrix of said cis-polybutadiene rubber as tiny crystallization with monodisperse status; And with have the bigger by 1 of reunion, the coexistence of 2-polyhutadiene crystal fibre.Remove fusing point and be said 1 more than 170 ℃, beyond the 2-polyhutadiene crystal fibre, preferably above-mentioned unsaturated polymer substance also is dispersed in the matrix of said cis-polybutadiene rubber.Preferably; Said unsaturated polymer substance has higher with 1 in the matrix of said cis-polybutadiene rubber; The avidity of 2-polyhutadiene crystal fibre, and be dispersed in physical adsorption and chemically adsorbed state said 1, near the 2-polyhutadiene crystal fibre.If as stated, fusing point is 1 more than 170 ℃, and 2-polyhutadiene crystal fibre and said unsaturated polymer substance coexistence also are dispersed in the matrix of said cis-polybutadiene rubber, and it is excellent that then above-mentioned rerum natura becomes, and this is preferred.
Polydiene except that (A) (B) cooperates with the vinyl cis-polybutadiene rubber of as above being produced (A) of 90 mass parts～5 mass parts with 10 mass parts～95 mass parts.Preferably, polydiene (B) is at least a in tree elastomer and the TR 301.
Be engaged in belt of the present invention and can comprise carbon black and silicon-dioxide at least with the rubber stiffener in the rubber combination (C), and other various WHITE CARBON BLACKs, treated carbonates and ultra granular Magnesium Silicate q-agent.Preferred especially carbon black comprises that like particle diameter be below the 90nm and Witcizer 300 (DBP) oil number is the above carbon black of 70mL/100g, for example FEF, FF, GPF, SAF, ISAF, SRF and HAF.
Belt of the present invention with rubber combination in; The rubber combination of forming by vinyl cis-polybutadiene rubber (A) and polydiene (B) with respect to 100 mass parts; The use level of rubber stiffener (C) is 20 mass parts～70 mass parts, is preferably 30 mass parts～60 mass parts.The use level of silicon-dioxide in said rubber stiffener is preferably below the 70 quality %, 5 quality %～65 quality % more preferably, and be preferably 10 quality %～63 quality % especially.The increase of the use level of silicon-dioxide can reduce energy waste.Yet the silica volume that surpasses 70 quality % makes the durability deterioration such as anti-flexing be full of cracks growth etc.
Belt of the present invention with rubber combination in, energy waste can have the index Δ H by 1 expression of following expression formula.In other words, if Δ H is littler, then can confirm energy waste still less.Δ H is preferably below 0.1, more preferably below 0.08.
[expression formula 1]
ΔH＝(SG×tanδ)/M25
(wherein, SG refers to the proportion (g/cm at 23 ℃
3); Tan δ is to be that 10Hz, dynamic deformation are 2% o'clock loss factor at 60 ℃, frequency; And M25 is the tensile stress (MPa) when 25% elongation).
Belt of the present invention can obtain through using Bunbury mixing machine, mill (open roll mill), kneading mixing machine or twin screw kneader to mix/mediate mentioned component with rubber combination.
In the time of if desired, can belt of the present invention be mixed together/mediate with rubber combination and the Synergist S-421 95 that is usually used in rubber industry such as vulcanizing agent, vulcanization accelerator, inhibitor, filler, treated oil, zinc white and Triple Pressed Stearic Acid etc.
The available instance of said vulcanizing agent comprises known vulcanizing agent, for example, and sulphur, organo-peroxide, resin cure agent, such as MOXs such as Natural manganese dioxide.
The available instance of said vulcanization accelerator comprises known vulcanization accelerator, for example, and aldehyde, ammonia, amine, guanidine, thiocarbamide, thiazole, thiuram, MGD and xanthogenate.
The instance of said inhibitor can be amine-ketone, imidazoles, amine, phenols, sulphur class and Phosphorus inhibitor.
The instance of said filler comprises: mineral filler, like lime carbonate, magnesium basic carbonate, clay, yellow lead oxide and zeyssatite; And organic filler, like regenerated rubber and Powdered rubber.
The available instance of said treated oil can be the fragrant same clan, cycloalkane and paraffinic treated oil.
Embodiment
With illustrated embodiment and comparative example the present invention is specified.In embodiment and comparative example, measured physical properties and the title complex of gained rubber combination and the rerum natura of sulfide of the rubber of said vinyl cis-polybutadiene rubber as follows.According to be given as the index that calculates on 100 the basis at comparative example 1, assessed the rerum natura of title complex and sulfide.
The physical properties of rubber
Use mooney's viscosimeters (from the SMV-202 of Shimadzu Seisakusho Ltd.) with preheating in 1 minute with measured mooney viscosity (ML in 4 minutes based on JIS-K6300 at 100 ℃
1+4, 100 ℃) numerical value.
Intrinsicviscosity [η] is the numerical value of deriving from following expression formula.In the case, supply to 0.1g sample rubber and 100mL toluene in the triangular flask and 30 ℃ of dissolvings fully.10mL said solution be added to Cannon-Fenske dynamic viscosity meter the lowering time (T) to measure said solution that place the Water Tank with Temp.-controlled that remain on 30 ℃ in thereafter.
η sp=T/T
0-1 (T
0: the lowering time when having only toluene)
ηsp/c＝[η]+k’[η]
2c
(η sp: specific viscosity, k ': Huggins constant (0.37), c: sample concentration (g/mL))
Use Cannon-Fenske viscometer No.400 to measure toluene solution viscosity (T-cp) at 25 ℃.In the case, in 50mL toluene, use viscometer calibration standard solution (JIS-Z8809) then the 2.28g polymer dissolution as standardized solution.
Microstructure is measured through infrared absorption spectrum analysis.According to cis 740cm
-1, trans 967cm
-1, vinyl 910cm
-1The absorption intensity at place is than calculating said microstructure.
For η sp/c, measured reducing viscosity as 1 at 135 ℃ of o-dichlorobenzene solutions, the benchmark of 2-polyhutadiene crystal fibre molecular weight by 0.20g/dL.
For said 1, the fusing point and the content of 2-polyhutadiene crystal fibre use difference formula scanning calorimeter (from the DSC-50 of Shimadzu Seisakusho Ltd.) to obtain the endothermic curve under 10 ℃/minute temperature rise rate.Said fusing point is confirmed as peak temperature and said content is calculated by caloric receptivity.
Average fiber length, the staple length that has obtained crystal fibre as follows is the following crystal fibre number of 200nm and the average aspect ratio of crystal fibre.Said vinyl cis-polybutadiene rubber is vulcanized in the mixing solutions of sulfur monochloride and dithiocarbonic anhydride and uses ultra micro slicing machine (from Leica) from gained sulfide, to downcut ultrathin section(ing).Observe said section to take 5000 times of photos with transmission electron microscope (from the H-7100FA of Hitachi society).Use image analysis software (from the Win ROOF of three paddy business societies) with said photo at 25 μ m
2Carry out binaryzation in the scope to obtain staple length, length-to-diameter ratio and crystal fibre area.Then, through with crystal fibre on duty with area fraction with average fiber length and length-to-diameter ratio on average they are converted into the average fiber length of crystal fibre and the average aspect ratio of crystal fibre.The crystal fibre number is through calculating the said 1 of per 1 quality %, and the staple length in the 2-polyhutadiene crystal fibre content is that the crystal fibre number below the 200nm obtains.
The physical properties of title complex
Use mooney's viscosimeters (from the SMV-202 of Shimadzu Seisakusho Ltd.) with preheating in 1 minute with measured mooney viscosity (ML in 4 minutes based on JIS-K6300 at 100 ℃
1+4, 100 ℃) numerical value.The more for a short time viscosity that shows of numerical value is low more good more with flowability.
For mould port expansion (Die swell), use processing characteristics test machine (from the MPT of Monsanto Co.) at 100 ℃ and 100sec
-1Shearing rate under measured the benchmark that likens to of the area of section of said title complex when extruding and the area of section of nib (wherein L/D=1.5mm/1.5mm) into the dimensional stability of said title complex.Numerical value is more for a short time to show that to extrude processibility good more.
The physical properties of sulfide
Measuring method according to the JIS-K6253 regulation has been measured hardness.
Measured 100% tensile stress based on JIS-K6251.Numerical value shows that more greatly tensile stress is high more.
Tensile strength when having measured fracture based on JIS-K6251.Numerical value shows that more greatly tensile strength is high more.
Measured tear strength based on JIS-K6252.Numerical value shows that more greatly tear stress is high more.
For anti-flexing be full of cracks growth, use DeMattia flexing test machine (making institute) from last island based on JIS-K6260 measured with sample holder with the be full of cracks length after the move distance flexing of 20mm 100,000 times.Numerical value is more for a short time to show that anti-flexing be full of cracks growth is good more.
Energy saving
For M25 (MPa), measured (measuring 23 ℃ of temperature) tensile stress when 25% extends based on the said method of JIS-K6251.
60 ℃, 10Hz and 2% distortion down use RPA2000 (from Alpha TechnologiesInc.) measured loss factor (tan δ).The more for a short time energy waste that shows of numerical value is fewer good more with situation.
Measured proportion (SG) based on the said method of JIS-K6268.
Derive Δ H according to above-mentioned expression formula 1 by above-mentioned observed value.
By deriving Δ H (index) with following expression formula 1 with SG (index), tan δ (index) and M25 (index) definition that will the relative value of the situation of measurement numerical value (SG, tan δ, M25) as 100 of resulting composition is represented in comparative example 1.
[expression formula 1]
Δ H (index)=(SG (index) * tan δ (index))/M25 (index)
Make example 1 (vinyl cis-polybutadiene rubber: the manufacturing of sample A-1)
Be ready to the stainless steel reactor that is equipped with whisking appliance crossed with nitrogen replacement, to wherein supplying with 3.5L polymeric solution (divinyl: 30 quality %, hexanaphthene: 70 quality %) with 5L internal volume.In addition, add 5.3mmol water, 10.5mmol diethylaluminum chloride, 1.8mmol dithiocarbonic anhydride, 32mmol cyclooctadiene and 0.03mmol cobalt octoate, then stir 30 minutes to carry out cis-1,4 polymerization (a-1) at 50 ℃.Supply with TR 301 (IR) (ML=87, cis-1,4 structure=98mol%), then stirred 1 hour of 10 quality % (with respect to gained vinyl cis-polybutadiene rubber) again at 50 ℃ to gained polymerisate solution.After this, add 560mL divinyl, 4.5mmol water, 13.4mmol chlorination triethyl aluminum and 0.07mmol cobalt octoate, then stir 30 minutes to carry out 1,2 polymerization (b-1) at 50 ℃.To wherein adding as 4 of inhibitor the methanol solution of 6-two (octyl group thiomethyl) ortho-cresol, polymerization termination then.After this, unreacted divinyl and 2-butylene are removed in evaporation, then 105 ℃ of vacuum-dryings 60 minutes to obtain vinyl cis-polybutadiene rubber (A-1).Vinyl cis-polybutadiene rubber (A-1) has the boiling n-hexane insolubles, and said boiling n-hexane insolubles is 1,2-polyhutadiene crystal fibre (b) and part or all of unsaturated polymer substance.Can calculate through infrared absorption spectrum analysis and to be adsorbed onto 1, the ratio of the said unsaturated polymer substance on the 2-polyhutadiene (percentage of grafting).Said boiling n-hexane insolubles is that 2g vinyl cis-polybutadiene rubber (A-1) is boiled the residue that extracts through the Soxhlet method after 4 hours in the 200mL normal hexane; Its numerical value with quality % represent (it be except that the system that is added with unsaturated polymer substance 1, the content of 2-polyhutadiene crystal fibre).Infrared absorption spectrum analysis by the boiling n-hexane insolubles in gained vinyl cis-polybutadiene rubber (A-1) is calculated, and is adsorbed onto 1, and the ratio of the TR 301 on the 2-polyhutadiene (percentage of grafting) is 67 quality %.
Make example 2 (vinyl cis-polybutadiene rubbers: the manufacturing of sample A-2)
Except said varsol is become benzene and do not add the TR 301 (unsaturated polymer substance) from hexanaphthene, similarly produced vinyl cis-polybutadiene rubber (A-2) through the method for manufacture of sample A-1.
The physical properties of sample A-1 and sample A-2 is as shown in table 1.
[table 1]
*1: staple length is the crystal fibre number below the 200nm
Then, supply with tree elastomer, carbon black and silicon-dioxide shown in the cooperation table in the table 2 to above-mentioned sample A-1 again, and vulcanize promotor and the Synergist S-421 95 the sulphur removing shown in the table 4.Use the Bunbury mixing machine to mix/mediate said mixture 4 minutes, use mill then so that said vulcanization accelerator and sulphur are cooperated to obtain the title complex of embodiment 1～8.In addition, similar with embodiment 1～8, above-mentioned sample A-1 and A-2 are cooperated to obtain the title complex of comparative example 1～6 by use level as shown in table 3.Measured embodiment 1～8 and comparative example 1～6 title complex physical properties and be presented in table 2 and the table 3.
[table 2]
(I): cooperate prescription (mass parts)
(II): title complex (index)
(III): sulfide (index)
(IV): energy saving
(
*1): from the DiaBlack H of Mitsubishi Chemical society
(
*2): from the Nipsil AQ of Tosoh Silica
(
*3): from the Si69 of Degussa
(
*4): from the Nocceler NS of the emerging chemical society of imperial palace
(
*5): from the Nocceler D of the emerging chemical society of imperial palace
[table 3]
(I): cooperate prescription (mass parts)
(II): title complex (index)
(III): sulfide (index)
(IV): energy saving
(
*1): from the DiaBlack H of Mitsubishi Chemical society
(
*2): from the Nipsil AQ of Tosoh Silica
(
*3): from the Si69 of Degussa
(
*4): from the Nocceler NS of the emerging chemical society of imperial palace
(
*5): from the Nocceler D of the emerging chemical society of imperial palace
[table 4]
| Total Synergist S-421 95 | Use level (mass parts) |
| Treated oil ( *6) | 3 |
| Zinc oxide | 3 |
| Triple Pressed Stearic Acid | 2 |
| Inhibitor ( *7) | 2 |
(
*6): from 110 of Esso oil
(
*7): from the Antigen 6C of Sumitomo Chemical society
The title complex of embodiment 1～8 and comparative example 1～6 150 ℃ of press vulcanizations 30 minutes to obtain sulfide.Gained sulfide is carried out the measurement of physical properties, shown in table 2 and table 3.Fig. 2 has shown the relation of the mould port expansion in embodiment 1～4 and the comparative example 2～4, anti-flexing be full of cracks growth and Δ H, and wherein the use level of rubber stiffener equals 40 mass parts.
From the result of table 2 and table 3, can find; The title complex of embodiment 1～8 is compared the physical properties with improvement with sulfide with comparative example 1～6, as extrudes processibility, tensile stress, tensile strength, tear strength, the be full of cracks of anti-flexing growth, loss factor and Δ H.In addition, can find from Fig. 2 that the increase of silica volume has caused excellent Δ H value.Yet can find that the silica volume that surpasses 70 quality % in the toughener makes anti-flexing be full of cracks growth variation.
Claims (6)
1. a belt is used rubber combination, and said rubber combination comprises:
(A) the vinyl cis-polybutadiene rubber of 90 quality %～5 quality %; This rubber comprises specific the rule 1 of (b) 1 quality %～30 quality %; 2-polyhutadiene crystal fibre and (a) cis-polybutadiene rubber of 99 quality %～70 quality %; Said crystal fibre has crystal fibre average fiber length, the average aspect ratio below 10 that is equal to or less than 200nm, and staple length is the per 25 μ m of number of the crystal fibre below the 200nm
2Be equal to or greater than 90, and have the fusing point more than 170 ℃;
(B) polydiene except that (A) of 10 quality %～95 quality %; With
(C) with respect to the rubber constituent (A)+(B) of 100 mass parts and the rubber stiffener of 20 mass parts～70 mass parts that cooperate,
Wherein, said rubber stiffener (C) contains carbon black and silicon-dioxide at least, and the use level of the said silicon-dioxide in the wherein said rubber stiffener is below the 70 quality %.
2. belt as claimed in claim 1 is used rubber combination, and wherein, the Δ H that is represented by expression formula 1 is below 0.1:
[expression formula 1]
ΔH＝(SG×tanδ)/M25
Wherein, SG refers to the proportion at 23 ℃, and unit is g/cm
3Tan δ is to be that 10Hz, dynamic deformation are 2% o'clock loss factor at 60 ℃, frequency; And M25 is the tensile stress when 25% elongation, and unit is MPa.
3. according to claim 1 or claim 2 belt is used rubber combination, and wherein, said vinyl cis-polybutadiene rubber (A) has following properties (i)～(iv):
(i) said 1,2-polyhutadiene crystal fibre (b) has the molecular weight index η sp/c in 0.5～4 scope;
(ii) said cis-polybutadiene rubber (a) has the cis-structure content more than the 90mol% in microstructure;
The toluene solution viscosity and the relation between the mooney viscosity of (iii) said cis-polybutadiene rubber (a) are T-cp/ML >=1; With
(iv) said cis-polybutadiene rubber (a) has the intrinsicviscosity [η] in 1.0～5.0 scopes.
4. according to claim 1 or claim 2 belt is used rubber combination, and wherein, said polydiene (B) except that (A) comprises in tree elastomer and the TR 301 at least a.
5. belt as claimed in claim 3 is used rubber combination, and wherein, said polydiene (B) except that (A) comprises in tree elastomer and the TR 301 at least a.
6. string rubber, said string rubber comprises as each described belt in the claim 1～5 of rubber substrate uses rubber combination.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP047891/2007 | 2007-02-27 | ||
| JP2007047891 | 2007-02-27 | ||
| JP207124/2007 | 2007-08-08 | ||
| JP2007207124 | 2007-08-08 | ||
| PCT/JP2008/053314 WO2008105415A1 (en) | 2007-02-27 | 2008-02-26 | Rubber composition for belt, and rubber belt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101568583A CN101568583A (en) | 2009-10-28 |
| CN101568583B true CN101568583B (en) | 2012-01-11 |
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ID=41284144
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800011579A Expired - Fee Related CN101568583B (en) | 2007-02-27 | 2008-02-26 | Rubber composition for belt, and rubber belt |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101568583B (en) |
| ZA (1) | ZA200902612B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10011428B2 (en) | 2014-04-25 | 2018-07-03 | The Yokohama Rubber Co., Ltd. | Coating rubber composition for conveyer belts |
| CN104650430B (en) * | 2015-01-29 | 2017-04-05 | 浙江精深实业有限公司 | A kind of belt, belt preparation method and the belt drive unit for beveler |
-
2008
- 2008-02-26 CN CN2008800011579A patent/CN101568583B/en not_active Expired - Fee Related
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- 2009-04-16 ZA ZA200902612A patent/ZA200902612B/en unknown
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|---|---|
| CN101568583A (en) | 2009-10-28 |
| ZA200902612B (en) | 2009-12-30 |
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