CN1296027A - Method and making reinforced elastomer, elastomer compound material and tyre having same - Google Patents
Method and making reinforced elastomer, elastomer compound material and tyre having same Download PDFInfo
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- CN1296027A CN1296027A CN 99123553 CN99123553A CN1296027A CN 1296027 A CN1296027 A CN 1296027A CN 99123553 CN99123553 CN 99123553 CN 99123553 A CN99123553 A CN 99123553A CN 1296027 A CN1296027 A CN 1296027A
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Abstract
The present invention relates to a method capable of forming filler reinforced material in elastomer body interior on site to prepare the said elastomer containing filler reinforced material to obtain the elastomer/filler composite, and the tyre using the said reinforced elastomer as component. Said invention includes rubber composite of at least two elastomers, in which one of the described elastomers is the composite preformed from elastomer and site-formed filler reinforced material. Said invention also discloses a tyre using the said rubber composite as component, in particular it relates to a tread of the said tyre.
Description
This specification sheets and same date in DN1998-208, DN1998-209 that United States Patent and Trademark Office submits and three parts of specification sheetss of DN1998-210 in addition two parts relevant.
The present invention relates in elastomer body the on-the-spot filler-reinforced material that forms, prepare the method for producing elastomers that comprises this reinforcement filler dispersion, the elastomerics of gained/filler complex body and comprise the tire of this reinforced resilent body composition.
The invention still further relates at least two kinds of elastomeric rubber combinations, one of wherein said elastomerics is the pre-formation complex body of elastomerics and the on-the-spot filler-reinforced material that forms.The invention still further relates to a kind of tire that contains this rubber combination as its composition.Relate in particular to a kind of tire with this composition tyre surface.
Elastomerics is used granular reinforcement filler always, as carbon black, strengthens with precipitated silica sometimes.
Rubber and filler carried out routine under shear conditions when mixing, strengthen filler sometimes, especially silicon-dioxide is difficult to form enough uniform dispersion in rubber combination.
But strengthen filler particles sometimes and form in rubber combination enough that dispersion is desirable just uniformly.
On the one hand, existing so far people proposes, base catalysis sol-gel by tetraethoxysilane (TEOS) transforms the on-the-spot silicon-dioxide that forms, with form silicon-dioxide polysiloxane polymer (as, poly-(dimethyl siloxane) or (PDMS)) dispersion in the elastomerics.For example, referring to " Precipitation of Silica-Titania Mixed-Oxide FillersInto Poly (dimethylsiloxane) Networks (precipitation of silica-titania mixed oxide filler in poly-(dimethyl siloxane) reticulated structure) " of J.Wen and J.Mark; Rubber Chem andTech (rubber chemistry and technology), (1994), 67 volumes, № 5, (806-819 page or leaf).
Propose a kind of method for preparing rubber product, that is, TEOS has been mixed with the solution of unvulcanized rubber in organic solvent, then it has been carried out the sol-gel condensation reaction, obtained a kind of finely powdered silica.For example, referring to Japanese Patent Application Publication 93/02152.
In addition, proposed a kind of composition of making by sol-gel method that comprises basic rubber and spherical silicon dioxide, its median size is that 10-30 micron and specific surface area are the 400-700 meters squared per gram.It is said that this composition can be used for the flap of tire.For example, referring to Japanese Patent Application Publication 6145429.
In addition, proposed a kind of tread rubber composition of making by the sol-gel conversion method, it consists of basic rubber and preparing spherical SiO 2.For example, referring to Japanese Patent Application Publication 6116440 and relevant Japanese Patent Application Publication 2561569.
Have again, be reported that in advance in the grafting two (3-triethoxysilylpropyltetrasulfide) tetrasulfides form in the organic solution of styrene/butadiene rubbers of triethoxysilyl, with TEOS by the on-the-spot silicon-dioxide that forms of solgel reaction.(people such as Hashim in rubber chemistry and technology, 71 volumes, " two (3-triethoxysilylpropyltetrasulfide) tetrasulfide is to the influence of the silicon-dioxide strengthening material of styrene butadiene rubbers " in the 289-299 page or leaf).
In specification sheets of the present invention, used term " phr " typically refers to " umber of corresponding each material in per 100 parts by weight of rubber or the elastomerics ".
In specification sheets of the present invention, except as otherwise noted, term " rubber " and " elastomerics " (if you are using) are used interchangeably.Term " rubber combination ", " compounding rubber " and " rubber compounding material " (if you are using) are used interchangeably, be meant " with various compositions and material fusion or blended rubber ", these terms are that the those of skill in the art in rubber mix or rubber compounding field are known.
According to the present invention, proposed a kind ofly on-the-spotly in elastomer body to form filler dispersion and make the method for elastomerics/filler complex body, comprising:
A) with filler precursor, condensation reaction promotor and be selected from elastomer body (A) and the elastomer body of elastomer body (B) in medium (1), it is the organic solvent solution of described elastomer body, or (2), mix in the aqueous latex of described elastomer body, but preferably in organic solvent solution, to cause the condensation reaction of described filler precursor, for elastomer body (A), with optional for elastomer body (B), add organosilane subsequently and react, finish described condensation reaction then with described filler/filler precursor; Reclaim the elastomerics/filler complex body of gained then; Or
B) in rubber internal mixer, with filler precursor, condensation reaction promotor be selected from elastomer body (A) and the elastomer body of elastomer body (B) is mixed, to cause the condensation reaction of described filler precursor, for elastomer body (A), and it is optional for elastomer body (B), in rubber internal mixer, add organosilane subsequently and react, finish described condensation reaction then with described filler/filler precursor; Reclaim the elastomerics/filler complex body of gained then; Or
C) elastomer body that will be selected from elastomer body (A) and elastomer body (B) is immersed in the liquid filler precursor, described filler precursor is infiltrated up in the described elastomer body, so that this elastomer body swelling, condensation reaction promotor is applied on the described swelling elastomer body to cause the condensation reaction of described filler precursor, for elastomer body (A), and it is optional for elastomer body (B), add organosilane subsequently and react, finish described condensation reaction then with described filler/filler precursor; Reclaim the elastomerics/filler complex body of gained then; Wherein said elastomer body (A) is selected from least a in the multipolymer of the homopolymer of conjugated diolefine, multipolymer, conjugated diolefine and the vinyl aromatic compounds of conjugated diolefine (preferably from vinylbenzene and alpha-methyl styrene, more preferably vinylbenzene); Wherein said elastomer body (B) is selected from least a based on the diene elastomer that the metal alkoxides functionalized end groups is arranged, and for example, it has logical formula I:
(I) elastomerics-X-(OR)
n
Wherein X is selected from silicon, titanium, aluminium and boron, preferred silicon, R is selected from the alkyl with 1-4 carbon atom, preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-, more preferably ethyl, and n is 3 (for silicon and titaniums) and 2 (for aluminium and boron), and wherein said elastomerics is selected from least a in the multipolymer of the homopolymer of conjugated diolefine, multipolymer, conjugated diolefine and the vinyl aromatic compounds of conjugated diolefine (preferably from vinylbenzene and alpha-methyl styrene, more preferably vinylbenzene);
And wherein said filler precursor is to be selected from least a among structural formula (II A), (the II B) and (II C):
(ⅡA)???(OR)
x(R’)
y
(ⅡB)???(RO)
x(R’)
yM-O-M’(R’)
z(RO)
w
(ⅡC)???(RO)
x(R’)
yM-(CH
2)
r-M’(R’)
z(RO)
w
Wherein M and M ' are identical or different, are selected from silicon, titanium, zirconium, aluminium and boron, preferred silicon, wherein R and R ' are selected from the alkyl with 1-4 carbon atom respectively, preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-, wherein preferred ethyl of R and R ' preferable methyl, and wherein the summation of x+y and w+z integer is respectively 3 or 4, depend on the valency of corresponding M or M ' and decide, therefore when its corresponding M or M ' are boron or aluminium, are 3, otherwise are 4, and wherein r is 1-15, preferred 1-6;
Wherein said organosilane is to be selected from least a in structure formula III, (IV) and (V), that is:
The organosilane of structure formula III:
(Ⅲ)????Z-R
1-S
m-R
1-Z
Wherein m is the number of 2-about 8, and the mean value of m is (a) about 2-about 2.6 or (b) about 3.5-about 4.5;
Wherein Z is by following structural formula, and preferred (Z3) represents:
R wherein
2Identical or different, be selected from alkyl and phenyl separately, preferable methyl and ethyl with 1-4 carbon atom; R
3Be identical or different alkoxyl group, the alkyl of wherein said alkoxyl group is selected from the alkyl with 1-4 carbon atom respectively, be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-, preferred ethyl, therefore (Z) preferred (Z3) is the triethoxysilicane groups; And R
1For being selected from the replacement that has 1-18 carbon atom altogether or substituted alkyl and have the replacement of 6-12 carbon atom altogether or the group of unsubstituting aromatic yl, wherein R not
1Be preferably selected from ethyl, propyl group and butyl;
The alkylalkoxy silane of structure formula IV:
(Ⅳ)????(OR
4)
3-Si-R
5
R wherein
4Be identical or different alkyl, be selected from methyl, ethyl, n-propyl and sec.-propyl with 1-3 carbon atom; And R
5Be selected from and have 1-18 carbon atom, the alkyl of preferred 8-18 carbon atom and have the aryl or the alkyl substituting aromatic base of 6-12 carbon atom, wherein R5 preferred alkyl; With
The functional organosilane of structural formula (V):
(Ⅴ)????(OR
6)
3-Si-(CH
2)
y-Y
R wherein
6Be to have 1-3, the identical or different alkyl of preferred 1-2 carbon atom, be selected from methyl, ethyl, n-propyl and sec.-propyl, preferred ethyl, y is 1-12, or the integer of 2-4, and Y is selected from primary amino, sulfydryl, epoxide, thiocyano, vinyl, methacrylic acid group, urea groups, isocyanato and quadrol group;
Further, provide a kind of rubber combination according to described method preparation according to the present invention.
In addition according to the present invention, a kind of goods of at least a component of forming by described rubber combination are provided.
Further according to the present invention, described goods are selected from industrial belt and hose.
In addition according to the present invention, provide a kind of tire of at least a component of forming by described rubber combination.
Further according to the present invention, provide a kind of tire of the tyre surface of forming by described rubber combination.
Be appreciated that importantly elastomerics/filler complex body is to form like this, at first, in based on the elastomer body of diene, cause the condensation reaction of filler precursor, before finishing reaction, organosilane and the on-the-spot filler that forms are reacted then.
In the method, for the on-the-spot filler dispersion that forms in the main body elastomerics,, adopted like solgel reaction with regard to the start-up portion of condensation reaction.
This paper thinks, what obviously be different from prior art is the reaction of specifying organosilane and the on-the-spot condensation product (all in elastomer body) that forms, to form gained filler dispersive elastomerics strengthening material in vulcanized elastomer not.
In the method, but condensation reaction products subsequently generating structure formula II material (as, the condensation reaction of TEOS) with the product of the organosilane co-reactant of structure formula III, (IV) or (V), on-the-spot formation filler dispersion in elastomer body, and can further itself react with the main body elastomerics.
Another place that obviously is different from prior art is the filler interior on-the-spot formation of metal alkoxides functionalized elastomeric phosphor bodies endways of regulation, described elastomer body have the part that is used for coupling elastomerics and on-the-spot synthetic polarity filler (as, trialkoxysilyl or tri-alkoxy titanyl part), therefore can reduce adding the demand of additional difunctionality coupling agent subsequently, as: the organosilane polysulfide, help the synthetic filling that the scene forms is bonded on the elastomerics.Therefore, in some cases, if necessary, only need this additional difunctionality coupling agent of minimum quantity to get final product.
Also can subsequently various reinforcement fillers be mixed with the reinforcement filler complex body that this elastomerics/scene forms.
For example, this additional filler can be carbon black, precipitated silica and other filler that comprises hydroxyl in its surface, and as the precipitated silica and the modified carbon black of adulterated al, they have aluminium hydroxide and/or silicon hydroxide on the surface separately at it.
The silico-aluminate that the example of the precipitated silica of this adulterated al forms as the co-precipitation by silicate and aluminate.The example of modified carbon black as by with organosilane pyroprocessing carbon black or by with organosilane with oil smoke the carbon black that makes its outside surface have silicon hydroxide altogether in high temperature.
According to the present invention, providing a kind of is the elastomer blended composition that basic elastomerics is formed by at least two kinds of diene, wherein a kind of elastomerics is preformed elastomerics/filler dispersion, it is the complex body of elastomerics and the on-the-spot filler dispersion that forms of the present invention, in the elastomerics is 100phr, it is made up of following compositions: (A) at least a diene of the about 90phr of about 10-is the elastomerics on basis, be selected from isoprene and 1, the homopolymer of 3-divinyl and multipolymer, and at least a diene (is selected from isoprene and 1, the 3-divinyl) (is selected from least a in vinylbenzene and the alpha-methyl styrene with vinyl aromatic compounds, optimization styrene) multipolymer, (B) at least a described preformed elastomerics/filler complex body of the about 10phr of about 90-, (C) at least a additional hardening filler, but condition is the described on-the-spot total amount that forms filler and described additional hardening filler is the about 120phr of about 30-, and wherein said additional hardening filler can be selected from, precipitated silica for example, silico-aluminate, carbon black, has hydroxyl in its surface, as: at least a in the modified carbon black of hydroxyl and/or silicon hydroxide group and (D) optionally add have can with as described in the filler reaction group and can with as described in the coupling agent of another group of elastomerics reaction.
Further according to the present invention, a kind of goods of at least a component of forming by described blend rubber composition are provided.
According to the present invention, provide a kind of goods that are selected from industrial belt and hose in addition, it contains at least a component of being made up of described blend rubber composition.
Further according to the present invention, provide a kind of tire of at least a component of forming by described blend rubber composition.
In addition according to the present invention, provide a kind of tire of the tyre surface of forming by described blend rubber composition.
The typical example of the described filler precursor of structural formula (II A) such as tetraethoxy orthosilicic acid, ethanolato-titanium, positive propoxy titanium, tri sec-butoxy aluminum, tert.-butoxy zirconium, n-butoxy zirconium, four n-propoxyzirconium, oxyethyl group boron, triethoxy silicic acid methyl esters and diethoxy silicic acid dimethyl ester.
The typical example of the described filler precursor of structural formula (II B) is as two sec-butoxy alumina ethyl triethoxy silicane alkane and six oxyethyl group sily oxide.
The typical example of the described filler precursor of structural formula (II C) such as two (triethoxysilyl) methane and two (triethoxysilyl) ethane.
The typical example of the described filler precursor of structure formula III as:
(A) in its many sulphur bridges, comprise 2-4, the organosilane disulphide of average 2-2.6 sulphur atom and
(B) in its many sulphur bridges, comprise 2-8, the organosilane polysulfide of average 3.5-4.5 sulphur atom;
Wherein the alkyl of the alkoxyl group of disulphide and polysulfide part is selected from methyl, ethyl and propyl group, and the alkyl of preferably ethyl, and silyl part is selected from ethyl, propyl group, especially n-propyl and butyl, preferably n-propyl.
Should be appreciated that the sulphur bridge activity of organosilane disulphide (A) and organosilane polysulfide (B) has a great difference.Especially, the sulphur atom of organosilane disulphide (A) mainly is a disulphide, and mutual key is more a lot of by force than the epithio atom of organosilane polysulfide (B).Therefore, organosilane polysulfide (B) a kind of sulfur donor of at high temperature in rubber combination, can saying so, the sulphur atom of organosilane disulphide (A) then can not be thought sulfur donor in this article.This phenomenon can produce substantial effect to the preparation of sulfur curable rubber combination.
When two (3-alkoxysilylalkyl) polysulfide, as two (3-(ethoxymethyl) silylation propyl group) when disulphide can be preferred organosilane disulphide (A), the typical example of this organosilane disulphide (A) is 2,2 '-two (trimethoxysilylethylgroup group) disulphide; 3,3 '-two (trimethoxy-silylpropyl) disulphide; 3,3 '-two (triethoxysilylpropyltetrasulfide) disulphide; 2,2 '-two (triethoxysilyl ethyl) disulphide; 2,2 '-two (tripropoxy-sil(ic)ane base ethyl) disulphide; 2,2 '-two (three sec-butoxy silyl ethyls) disulphide; 3,3 '-two (three tert.-butoxy ethyls) disulphide; 3,3 '-two (triethoxysilyl ethyl tolylene) disulphide; 3,3 '-two (trimethoxysilylethylgroup group tolylene) disulphide; 3,3 '-two (three isopropoxide propyls) disulphide; 3,3 '-two (three octyloxy propyl group) disulphide; 2,2 '-two (2 '-ethyl hexyl oxy silyl ethyl) disulphide; 2,2 '-two (dimethoxy (ethoxymethyl) silylation ethyl) disulphide; 3,3 '-two (methoxy ethoxy propoxy-silyl propyl group) disulphide; 3,3 '-two (methoxyl group dimetylsilyl propyl group) disulphide; 3,3 '-two (cyclohexyloxy dimetylsilyl propyl group) disulphide; 4,4 '-two (trimethoxysilyl butyl) disulphide; 3,3 '-two (trimethoxysilyl-3-methyl-propyl) disulphide; 3,3 '-two (tripropoxy-sil(ic)ane base-3-methyl-propyl) disulphide; 3,3 '-two (dimethoxy-methyl silyl-3-ethyl propyl) disulphide; 3,3 '-two (trimethoxysilyl-2-methyl-propyl) disulphide; 3,3 '-two (Dimethoxyphenyl silyl-2-methyl-propyl) disulphide; 3,3 '-two (trimethoxysilyl cyclohexyl) disulphide; 12,12 '-two (trimethoxysilyl dodecyl) disulphide; 12,12 '-two (triethoxysilyl dodecyl) disulphide; 18,18 '-two (trimethoxysilyl octadecyl) disulphide; 18,18 '-two (methoxyl group dimetylsilyl octadecyl) disulphide; 2,2 '-two (trimethoxysilyl-2-methylethyl) disulphide; 2,2 '-two (triethoxysilyl-2-methylethyl) disulphide; 2,2 '-two (tripropoxy-sil(ic)ane base-2-methylethyl) disulphide; With 2,2 '-two (three octyloxies silyl-2-methylethyl) disulphide.
These organosilane disulphide are preferably: 3,3 '-two (trimethoxy-silylpropyl) disulphide; 3,3 '-two (triethoxysilylpropyltetrasulfide) disulphide; 3,3 '-two (methoxyl group dimetylsilyl propyl group) disulphide; With 3,3 '-two (cyclohexyloxy dimetylsilyl propyl group) disulphide.
When two (3-alkoxysilylalkyl) polysulfide, in the time of can being preferred organosilane polysulfide (B) as two (3-triethoxysilylpropyltetrasulfide) tetrasulfides or trisulphide, the typical example of this organosilane polysulfide (B) is two (3-trimethoxy-silylpropyl) trisulphides; Two (3-trimethoxy-silylpropyl) tetrasulfide; Two (3-triethoxysilylpropyltetrasulfide) trisulphide; Two (3-triethoxysilylpropyltetrasulfide) tetrasulfide; Two (3-triethoxysilyl ethyl tolylene) trisulphide; With two (3-triethoxysilyl ethyl tolylene) tetrasulfide.
For the alkylalkoxy silane of structure formula IV, described aryl or substituted aryl can be, for example benzyl, phenyl, tolyl, methyl tolyl and Alpha-Methyl tolyl.
The effect of alkylalkoxy silane, for example be for the specific modality of designing on-the-spot synthetic filling and with the adhesivity of elastomer body matrix.
The typical example of alkylalkoxy silane is for example (but being not limited to), propyl-triethoxysilicane, Union carbide A-162, hexadecyl triethoxyl silane and octadecyltriethoxy silane.
The amino butyl triethoxyl silane of the typical example of the primary amino functional organosilane of structural formula (V) such as 3-aminopropyltriethoxywerene werene, 2-amino-ethyl triethoxyl silane and 4-.The typical example of Mercaptofunctional organosilane such as 3-sulfydryl propyl-triethoxysilicane, 2-mercaptoethyl triethoxyl silane and 4-sulfydryl butyl triethoxyl silane.The typical example of epoxide functional organosilane is as (3-glycidoxypropyl) triethoxyl silane.The typical example of thiocyano functional organosilane such as 3-thiocyano propyl triethoxy silicane.The typical example of vinyl functional organosilane such as vinyltriethoxysilane.The typical example of urea/ureido functional organosilane such as urea groups propyl-triethoxysilicane.The typical example of isocyanato functional organosilane such as 3-isocyanato propyl-triethoxysilicane.The typical example of quadrol is N (3-triethoxysilyl) propyl group quadrol.
The effect of the functional organosilane of structural formula (V) for example is in order to help filler to be adhered on the elastomer body matrix.
In fact, elastomerics (A) can consider to be selected from based on the elastomerics of diene and the elastomeric component of elastomerics (B), isoprene and 1 for example, the homopolymer of 3-divinylic monomer and multipolymer, be selected from isoprene and 1, the multipolymer of at least a monomer in the 3-divinyl and aromatic vinyl compound (being selected from vinylbenzene and alpha-methyl styrene, optimization styrene), and composition thereof.
This elastomerics, especially the typical example of elastomerics (A) is a cis 1,4-polyisoprene, cis 1,4-polyhutadiene, isoprene/butadiene multipolymer, styrene/butadiene copolymers (comprising the multipolymer of emulsion polymerization preparation and the multipolymer of organic solvent polyreaction preparation), styrene/isoprene multipolymer, 3,4-polyisoprene, trans 1, styrene/isoprene/butadiene tri-component multipolymer, have about 90% vinyl of about 35-high vinyl polybutadiene, and composition thereof.
The typical example that is used for the elastomeric component of elastomerics (B) is the cis 1 of organic solvent polyreaction preparation, 4-polyisoprene, cis 1,4-polyhutadiene, isoprene/butadiene multipolymer, styrene/butadiene copolymers, styrene/isoprene multipolymer, 3,4-polyisoprene, trans 1, styrene/isoprene/butadiene tri-component multipolymer, and composition thereof.
Reality can be used as tin coupling or the end capped elastomerics of tin based on the elastomerics (A) of diene in the present invention.The elastomerics based on diene of this modification can for example prepare like this, promptly in organic solution, to be selected from one or more diene monomers and (be selected from 1,3-divinyl and isoprene) or the monomer and 1 of styrene monomer, 3-divinyl and/or isoprene carry out polymerization or copolymerization together, before stopping polyreaction, come the polymkeric substance of this work of modification with tin then.
This tin coupling or end capped elastomerics are passable, it for example is cis 1,4-polyisoprene, cis 1, styrene/butadiene copolymers, styrene/isoprene/butadiene tri-component multipolymer, isoprene/butadiene multipolymer and styrene/isoprene multipolymer.
Usually, this elastomeric key character is, major portion in the elastomerics, preferably at least about 50%, the Sn key of more general about 60-85% is keyed on the diene units of multipolymer, it can be called " Sn-diene base key " in this article, as the divinyl base key under the divinyl terminated polymer situation.
Elastomer modification can be undertaken by the mode of routine as tin coupling or tin end-blocking, and this is that those skilled in the art are known.
For example, copolymer elastomer can be in organic solution, makes by with alkyl lithium catalyst vinylbenzene and 1,3-butadiene and/or isoprene being carried out copolymerization.Also can use promotor or catalyzer conditioning agent.This polymerisation process is that those skilled in the art are known.After forming copolymer elastomer, and catalyzer active while of tool still, promptly when thinking that still this multipolymer is a kind of further polymeric active copolymer, the reaction by reactive polymer and tin compound stops this polyreaction.Can use various tin compounds, usually preferred tin tetrachloride.Therefore, consider that the valency of tin is 4, it has been generally acknowledged that modified copolymer corresponding molecular weight occurs and jumps or increase when coupling, this modified copolymer is called coupling elastomerics starlike or that be shaped sometimes simultaneously.On the other hand, if use trialkyl tin compound, have only a halogen atom to use so, so this modified copolymer is a kind of end capped multipolymer.This method for preparing coupling and end-capped copolymer (making by the organolithium catalyzer) is that those skilled in the art are known.Should be appreciated that this modified copolymer can be the mixture of coupling and end-capped copolymer.
The example of tin modification or link coupled phenylethylene/butadiene can be referring to for example United States Patent (USP) 5064910.
Tin coupling polymer or copolymer elastomer be organo-tin compound also, carry out the tin coupling as tri-chlorination tin alkyl, Dutch loquid base tin and monochlor(in)ate trialkyltin, generate the variant of tin coupled copolymers, wherein the monochlor(in)ate trialkyltin generates the tin end-capped copolymer simply.
Therefore, tin coupling elastomerics can be a kind of like this product, promptly in organic solvent solution, and organolithium catalyst based in the presence of, the product that at least a conjugated diolefine is reacted or vinylbenzene and at least a conjugated diolefine one are reacted; Wherein said diene is selected from 1,3-butadiene and isoprene, then with reactive polymer and structural formula: R
7 4-vSnX
nAt least a compound react, wherein n is the integer (comprising 4) of 1-4, X is the halogen that is selected from chlorine, iodine and bromine, preferred chlorine; R
7For being selected from the alkyl of methyl, ethyl, propyl group and butyl.
Another aspect of the present invention, as mentioned above, can make it to hold with organoalkoxysilane unit etc. based on the elastomerics of diene functionalized, shown in the structure formula I.This terminal group functional can for example carry out like this, promptly when the elastomerics that forms based on diene, and use chlorine triethoxyl silane or 3 in organic solvent solution, 3 '-two (triethoxy propyl group) disulphide makes monomeric anionic polymerisation all standing.
For elastomeric this terminal group functional, elastomerics is preferably made by the organic solvent polyreaction, and be selected from styrene/butadiene copolymers, isoprene/butadiene multipolymer, cis 1,4-polyhutadiene, cis 1, the high vinyl polybutadiene of 4-polyisoprene, styrene/isoprene multipolymer, the about 35-of contents of ethylene about 90% and styrene/isoprene/butadiene tri-component copolymer elastomer at least a.
For the carbon black strengthening material that has silicon hydroxide in its surface, this modified carbon black can be at high temperature, by coming the intensive treatment carbon black with organosilane or by it is smoked to handle and prepares with organosilane and innage temperature.
Reality in the present invention, as mentioned above, the on-the-spot filler-reinforced material that forms can form in the elastomer body in being included in organic solvent solution or in the latex, preferably forms in organic solvent solution.
For example, elastomerics can provide in organic solvent solution by following steps: (A) elastomerics is dissolved in appropriate organic solvent, in toluene, hexane, hexanaphthene or THF (tetrahydrofuran (THF)), or (B) provide elastomerics as adhesive paste or polymkeric substance, promptly from the solution of the organic solvent solution polyreaction of proper monomer, to be provided at the elastomerics in the solution.Obtaining elastomeric this organic solvent solution polyreaction by monomer is that those skilled in the art are known.
This elastomerics can be by in hydrated soap solution, suitable monomers is aggregated into elastomer based latex and provides with latex.This method for preparing latex is that those skilled in the art are known.
In addition, reality in the present invention, on-the-spot form strengthen filler also can be at rubber banburying device, as Banbury type mixing tank or in forcing machine,, promote the described condensation reaction of filler precursor then and form by elastomerics and filler precursor are carried out blend.Rubber and polymkeric substance Banbury mixer are known.
Therefore, Banbury mixer for example can be at least a intermittent type Banbury mixer (as a Banbury type internal rubber mixer), if wherein suitable each component is added in one or more continuous banburying steps in proper order, and after mixing/reaction reaches required degree, from mixing tank, take out.
Also can use the successive reaction hybrid technology.For example, can use and extrude mixing machine continuously.Extrude normally twin screw extruder of mixing machine, wherein screw rod can corotation revolving die formula or the despining pattern be rotated and its bossing interlock mutually of axle separately.The L/D of screw rod profile (length over diameter) ratio is preferably 5-70, and this is somewhat dependent upon required mixing effectiveness and the degree of scatter of composition in elastomer blend.It is that those skilled in the art are known that this reactivity of various elastomericss and each composition is extruded hybrid system.For example referring to United States Patent (USP) 5711904.For example, can consider that forcing machine is a kind of twin screw extruder, wherein at first extruded in the mixing machine addings of elastomer body, filler precursor and condensation reaction promotor, after the total reaction time that adds elastomerics and the about 50-70% of precursor and on the corresponding interval length of forcing machine, the organosilane of choosing wantonly is added in the reaction mixture in the forcing machine subsequently.
In order to prepare elastomerics/filler complex body in the liquid filler precursor, therefore elastomerics swelling in the presence of Liquid precursor is also absorbed by elastomer body is immersed in.Therefore, Liquid precursor can be impregnated in the elastomer body simply.Usually, the amount of Liquid precursor can be regulated, so that a small amount of (if any) Liquid precursor keeps not being absorbed.In addition, simply the swelling elastomerics is taken out from the container of its steeping liq precursor, perhaps Liquid precursor is discharged from this container simply.Under any circumstance, condensation reaction promotor is applied (normally directly) to the swelling elastomerics, usually put on its outside surface, and be dispersed in the swelling elastomerics by the precursor that absorbs, can promote the condensation reaction of the intravital filler precursor of elastic body active like this, and on-the-spot the generation or the formation filler dispersion.Before condensation reaction is finished, optional organosilane is added in the swelling elastomerics.It is contemplated that, elastomer body is cut into individual chip, these fragments are immersed in the suitable vessel that contains the liquid filler precursor and mix; Swelling elastomerics with gained takes out from remaining liquid filler precursor then.Then, condensation reaction promotor can be applied on the swelling elastomer body fragment.Before condensation reaction is finished, optional organosilane is added in the swelling elastomerics.
In the present invention's practice, can use various acidity or alkaline condensation reaction promotor, it is generally acknowledged that this is that those skilled in the art are known.For example, the typical example of basic-type accelerator is ammonia, ammonium hydroxide, N-butylamine, tert-butylamine, tetrahydrofuran (THF) (THF), Sodium Fluoride, range protein line style polyamine, as penten, diaminopropanes, diethylenetriamine, Triethylenetetramine (TETA) and PAH, as poly-(allyl amine hydrogenchloride), poly-(L-Methionin hydrobromide), poly-(L-arginine hydrochloride) and poly-(L-Histidine hydrochloride).For example, the typical example of acidic-type accelerator is phosphoric acid, acetate, hydrofluoric acid and sulfuric acid.
Also can use metal-salt and metal oxide promotor or inhibitor as silane condensation reaction (that is: Lewis acid or alkali reaction).The example of metal-salt is zinc sulfate, Tai-Ace S 150, Zinic stearas and aluminum stearate.The example of metal oxide is zinc oxide and aluminum oxide.
Also can use the silicon rubber condensation reaction to solidify used typical catalyst.Its example is two (2 ethyl hexanoic acid) tin and two (neodecanoic acid) tin.
The selection of condensation reaction promotor depends in fact to a certain extent whether elastomerics is in organic solvent solution or a kind of latex, and this is that those skilled in the art determine easily.
Therefore, condensation reaction usable acid or alkali promotor are controlled, and this is somewhat dependent upon filler and forms required kinetics and required on-the-spot filling-material structure.
For example, although individual condition can change, but acid or alkali condensation reaction promotor or any other condensation reaction promotor all can be sequentially added into, can at first promote the hydrolysis (acidic-type accelerator) of organoalkoxysilane like this, then, second promotes silane condensation reaction (basic-type accelerator) with the real on-the-spot filler that forms.
It is to reduce by elastomerics-filler complex body to form the best evenly required mixing energy of filler dispersion that use comprises the on-the-spot elastomeric special benefits of aforementioned pre-formation that forms filler, promptly in elastomerics, disperse more equably, and less the flocking together of single filler particles forms bigger aggregate.This is an ideal, because it can improve the processing characteristics of elastic composition when elastomerics mixed with other rubber compounding composition simultaneously, and the various performances of gained rubber combination and various tire use properties.These improved foundations are, for example reduce the hysteresis phenomenon of rubber combination and improve the wear resistance of rubber combination, this obviously is that the on-the-spot filler that produces forms the more result of homogeneous dispersion, and can improve filler and the interactional effectiveness of elastomer body, this is particularly evident to the tire tread rubber combination.
It is contemplated that the rubber combined body of pre-formation of the present invention can make the reinforcement filler, especially hydrophilic filler particle (as: silicon-dioxide, silico-aluminate and titanium dioxide) more effectively is distributed in the rubber combination fully.
It is contemplated that the present invention helps to use better required filler, the on-the-spot particulate that forms of restriction partly reassociates, can make it better, more be evenly dispersed in the elastomer body like this and the rubber combination of gained in.
Among the present invention, it is contemplated that, as on-the-spot synthetic filler, strengthen the buildup effect that the preformed whole complex of filler can reduce filler particles based on the elastomerics of diene, thereby promote hydrophilic filler (as: silicon-dioxide) more to be evenly dispersed in the rubber combination.
In one aspect of the invention, the rubber combination of preformed elastomer composite body and added resilience body preferably forms by following steps: (a) at least two continuous mixing steps, under situation without any solidifying agent, the compounding composition of this complex body and routine is carried out extremely about 160-180 ℃ top temperature of hot mechanically mixing (ⅰ), when reaching described top temperature, in the about 5-10 of described high-temperature ℃, continue about 1-10 minute, or (ⅱ) to about 155-165 ℃ top temperature, when reaching described top temperature, in the about 5-10 of described temperature ℃, continue about 4-20 minute, (b) final hot mechanically mixing step was wherein mixed sulfur curable agent and curing catalyst about 1-4 minute to the about 90-120 of temperature ℃ with described mixture then; But between aforementioned mixing step, rubber stock is cooled to about below 40 ℃.
Because depend on spinner velocity, packing factor and the rubber combination of mixing tank itself to a certain extent, the time that reaches top temperature can be about 2-5 minute.Term " packing factor " it is believed that it is that those skilled in the art are known, and it is the volume part of the shared Banbury mixer of rubber combination itself.Other parameter is equal to, and the rubber combination with high oil content needs the long period to reach top temperature usually.
In fact, rubber internal mixer is preferred for single mixing step.
In described mixing step, term " solidifying agent " typically refers to vulcanization of rubber solidifying agent, this means sulphur and the vulcanization accelerator that accompanies thereof, though be not preferred, can use peroxide firming agent.
The carbon black that can be used for typical reinforcing rubber of the present invention, comprise the various carbon blacks that are used to prepare the carbon black complex body, the carbon black of the about 30-180 of iodine sorption value (ASTM tests D1510) for example is sometimes even up to about 20-150 centimetre of about 250 gram/kilograms and DBP (dibutyl phthalate) adsorptive value (ASTM tests D2414)
3The carbon black of/100 grams.This sooty typical example and corresponding ASTM methods of test can referring to, The Vanderbilt Rubber Handbook for example, 1990 editions (416-418 page or leaf).
The final physical performance of this rubber combination depends on used carbon black complex body, used coupling agent and rubber combination itself to a certain extent.
Also a kind of sulfur curable composition of rubber combination itself by uncured elastic composition sulfuration is obtained.Sulfur curable carries out by conventional methods, promptly solidifies one suitable period under high-temperature and high-pressure conditions.
The solidifying agent that is used for the sulfur curable rubber combination is to be usually used in the elastomeric various solidifying agent of sulfur curable, generally includes sulphur and one or more suitable curing catalysts, also has scorch retarder sometimes.These solidifying agent and the application in the sulfur curable elastic composition thereof are that those skilled in the art are known.
The method for continuously mixing that is used to prepare the sulfur curable rubber combination also is that those skilled in the art are known, wherein at first elastomerics is mixed in one or more steps of so-called " unproductive mixing step " with each relevant composition, be the last mixing step that adds solidifying agent subsequently, so-called " productivity mixing step ".
In the present invention, additional elastomerics based on diene can with aforementioned elastic composition, carry out blend as the homopolymer of conjugated diolefine and the multipolymer of multipolymer and conjugated diolefine and vinyl aromatic compounds.These diene can, for example be selected from isoprene and 1,3-butadiene, and these vinyl aromatic compounds can be selected from vinylbenzene and alpha-methyl styrene.This elastomerics or rubber, for example be selected from cis 1,4-polyisoprene rubber (natural and/or synthetic rubber, preferred natural rubber), 3, the 4-polyisoprene rubber, styrene/butadiene copolymers rubber, the isoprene/butadiene copolymer rubber, the styrene/isoprene copolymer rubber, the styrene/isoprene/butadiene tri-component copolymer rubber, cis 1, the 4-polybutadiene rubber, trans 1,4-polybutadiene rubber (70-95% is trans), low vinyl polybutadiene rubber (10-30% vinyl), vinyl 1, the high vinyl polybutadiene rubber of the about 35-of 2-content about 90%, butadiene/acrylonitrile copolymer with the emulsion polymerization preparation.
Be interpreted as, additional silicon-dioxide, especially precipitated silica and/or carbon black also can carry out blend with the described complex body of preformed reinforced resilent body and added resilience body.
In the present invention, if you are using, term " precipitated silica " also comprises the precipitation silico-aluminate of precipitated silica form.These precipitated silicas for example by soluble silicate, obtain as the acidifying of water glass (do not comprise silica gel).
These silicon-dioxide are characterised in that the BET surface-area that for example uses nitrogen to record is preferred about 40-600, more general about 50-300 meters squared per gram (m
2/ g).The BET method of meter area is described in Brunauer, Emmett and Teller:Journal of American ChemicalSociety (JACS) (1938), 309 pages.Also can be with reference to DIN Method 66131.
Usually, the feature of silicon-dioxide is that also its DBP (dibutyl phthalate) adsorptive value is about 100-400, is more generally about 150-300 milliliter/100 grams.
Can consider various commercially available precipitated silicas are used for the present invention, as (at this only as an example, being not limited to this) with the silicon-dioxide of Hi-Sil trade mark (product by name 210,243 etc.) available from PPGIndustries; With the silicon-dioxide of name of an article Zeosil 1165MP available from Rhone-poulenc; And with name of an article VN2 and VN3, BV3380GR etc. available from Degussa Ag with the silicon-dioxide of Zeopol 8745 available from Huber.
Can use various coupling agents, wherein many is that those skilled in the art are known.For example, can use two (trialkoxysilyl alkyl) polysulfides, it comprises about 8 sulphur atoms of 2-, on average about 2-5 sulphur atom in its many sulphur bridges.For example, many sulphur bridges can comprise average about 2-3 or 3.5-5 sulphur atom.Alkyl can be selected from, for example methyl, ethyl and propyl group.Therefore, representational coupling agent can be for example two (triethoxysilylpropyltetrasulfide) polysulfides, comprises 2-8 in its many sulphur bridges, on average about 2-5 sulphur atom.
Should be appreciated that coupling agent (if liquid form) can be used in combination with the carbon black carrier, promptly before joining rubber combination, carry out premix with carbon black, and this sooty content amounts of carbon black in the building rubber compound composition formula normally.
Those skilled in the art are understood that easily, rubber combination can carry out compounding by the common known the whole bag of tricks in rubber compounding field, but as with various sulphur curable component rubber and various additive commonly used, as auxiliary curing agent (as sulphur, activator, scorch retarder and accelerator), processing aid (as oil, comprise various resins, silicon-dioxide and the softening agent of tackifying resin), filler, pigment, lipid acid, zinc oxide, wax, antioxidant and antiozonant, peptizing agent and strengthening material (as, carbon black).Those skilled in the art know, can vulcanize and the purposes of vulcanizing material (rubber) is selected above-mentioned additive according to sulphur, use with convention amount usually.
When the preparation rubber combination, the tackifying resin of typical amount (if you are using) is about 0.5-10phr, about usually 1-5phr.The typical amount of processing aid is about 1-5phr.These processing aids can comprise, for example aromatics, cycloparaffin series and/or alkane family treated oil.The typical amount of antioxidant is about 1-50phr.Representative antioxidants can be, for example phenylbenzene-right-phenylenediamine and other antioxidant, and The Vanderbilt Rubber Handbook for example, (1978 editions) (344-346 page or leaf) is disclosed.The typical amount of antiozonant is about 1-5phr.
The typical amount of lipid acid (if you are using) is about 0.5-5phr, and it comprises the mixture of stearic acid, palmitinic acid, linolic acid and one or more lipid acid.
Usually, stearic acid uses with not pure state relatively, in the rubber compounding practice so-called " stearic acid ", and therefore also appellation like this in specification sheets of the present invention and practice.
The typical amount of zinc oxide is about 1-5phr.The typical amount of wax is about 1-5phr.Usually use Microcrystalline Wax.The typical amount of peptizing agent (if you are using) is about 0.1-1phr.Peptizing agent can be, for example reptazin and dibenzoyl ADP based bisulfide.
Sulfuration is to carry out in the presence of the sulphur stiffening agent.The example of suitable sulphur stiffening agent comprises elementary sulfur (free sulphur) or supplies sulfur vulcanization agent, for example curing amine, polymerization polysulfide or sulphur olefin addition product.Vulcanizing agent preferred elements sulphur.Those skilled in the art know that the consumption of sulphur stiffening agent is about 0.5-4phr, even in some cases up to about 8phr, wherein preferably about 1-2.5, about sometimes 1-2.
The performance that accelerator is used to control sulfuration required time and/or temperature and improves vulcanized rubber.In one embodiment, can use single accelerator system, promptly main accelerator.Usually total consumption of preferred main accelerator is about 0.5-4, preferably about 0.8-2phr.In another embodiment, can use main accelerator and the mixture that helps accelerator, the consumption that wherein helps accelerator is about 0.05-3phr, can improve the performance of vulcanized rubber like this by activation.The mixture of these accelerators is estimated and can be produced synergistic effect to final performance, therefore is better than to a certain extent and is used alone accelerator production.In addition, can use its effect accelerator of being postponed, in that it is inoperative but can be cured satisfactorily under the normal process temperature under common curing temperature.Also can use the sulfuration scorch retarder.Can be used for suitable accelerator of the present invention is amine, disulphide, guanidine, thiocarbamide, thiazole, thiuram, sulfinyl amine, dithiocarbamate and xanthate.The preferred sulfinyl amine of main accelerator.If use and help accelerator, help the preferred guanidine of accelerator, dithiocarbamate or thiuram compound so.
Except carbon black and coupling agent, the existence of above composition and relative quantity can not be thought theme of the present invention, because the present invention more relates generally to the preparation and the application of the aforementioned pre-formation elastomer composite body with whole silicon-dioxide dispersiveness.
Each composition mixes at least two steps usually, that is, at least one unproductive step is a productivity mixing step subsequently.Usually final solidifying agent is mixed in the final step that generally is called " productivity " mixing step, wherein common under certain temperature of the mixing temperature that is lower than previous unproductive mixing step, or mix under the outlet temperature.Rubber, carbon black and coupling agent (if use) are mixed in one or more unproductive mixing steps.Term " unproductive " and " productivity " mixing step are that rubber mix field those of skill in the art are known.
In at least one unproductive (NP) mixing step, various materials are carried out hot mechanically mixing, and allow mixing temperature reach for example certain temperature between 140-190 ℃.
Rubber combination of the present invention can be used for various uses.For example, it can be used for various tire formulations.These tires can be constructed by known the whole bag of tricks, moulding, molding and curing, and this is conspicuous to this field those of skill in the art.
By reference following examples, the present invention may be better understood, and except as otherwise noted, umber wherein and percentage ratio are all by weight.
The embodiment I
In the present embodiment, pre-elastomerics/filler the complex body that forms is preparation like this: the butadiene/styrene copolymers elastomerics is dissolved in the hydrocarbon solvent, in this solution, add the liquid filler precursor then, and in elastomer body, come on-the-spot synthetic filling dispersion by condensation reaction.
Should be appreciated that, present embodiment is represented to a certain extent by co polystyrene in organic solvent and 1,3-divinyl and the elastomerics adhesive paste that obtains because in fact, more preferably utilize the elastomerics adhesive paste usually rather than elastomerics are dissolved in the organic solvent again.
An experimental section for present embodiment before finishing condensation reaction, adds organosilane in the mixture.
By this method, the on-the-spot filler that forms of gained be a kind of in the main body elastomerics whole dispersive form.
The sample of elastomerics/filler complex body is designated as sample A (in the present embodiment as contrast), B and C in this example.
For present embodiment, the elastomerics that is used for sample A and B be lithium catalyst based in the presence of, by co polystyrene in organic solvent solution and 1,3-butadiene, reclaim elastomerics then and obtain.This elastomerics can be called " S-SBR " in this embodiment, and its combined styrene content is about 18%.
For present embodiment, the elastomerics that is used for sample C is similar to the elastomerics that is used for sample A and B, just make 1 with two (triethoxysilylpropyltetrasulfide) disulphide (in its many sulphur bridges, on average comprising about 2.2 sulphur atoms), 3-divinyl and cinnamic copolyreaction all standing, generate the end capped styrene/butadiene copolymers elastomerics of the single sulfane of triethoxysilylpropyltetrasulfide, its combined styrene content is about 18%.This elastomerics can be called " ST-SBR " in the present embodiment
This experiment is carried out in the hexane solvent by at first S-SBR or ST-SBR according to circumstances being dissolved in.To add as the liquid tetraethoxysilane (TEOS) of filler precursor in the elastomer solution then, wherein TEOS and elastomeric weight ratio are about 1/2, add entry (weight ratio of water and TEOS is about 2/1) and 1 then, 3-diaminopropanes condensation reaction promotor (promotor being comprises about 2% weight of the whole mixture of water).
Condensation reaction is when stirring this mixture, about room temperature, or carry out under about 25 ℃.
For sample B and C, before the condensation reaction of TEOS, two (3-triethoxysilylpropyltetrasulfide) disulphide (on average comprising about 2.2 sulphur atoms in its many sulphur bridges) are added in the reaction system.When stirring this mixture, allow be reflected at and carried out under about 25 ℃ about 1 hour.
Gained sample A, B and C reclaim about 3 hours of about 80 ℃ of following dryings by in draft furnace.
The content of the silica filler dispersion that the scene of elastomerics/filler complex body forms can be determined by thermogravimetric analysis.The on-the-spot silica dioxide granule that forms can be a globular basically, and its diameter is about 5-300 nanometer, and dentrite turgidity is to a certain degree arranged, and this can measure by transmission type microscope.
Sample A (contrast), B and C are summarized in following table 1:
| Table 1 | |||
| Material | A (contrast) | Sample B | Sample C |
| 1) elastomerics | S-SBR | S-SBR | ST-SBR |
| 2) filler precursor | TEOS | TEOS | TEOS |
| 3) add disulphide | No | Be | Be |
| 4) the on-the-spot silica filler (% weight) that forms | 18 | 20 | 25 |
Although the physicals of rubber combination, normally measure as modulus and elongation at the sulfur curable rubber combination, but also measure these values of not vulcanizing sample A, B and C, especially because it seems, the interior on-the-spot formation filler dispersion of elastomer body can form the elastomerics/filler complex body that these performances to be determined is had sufficient size stability, shown in following table 1A:
| Table 1A | |||
| Performance | Sample A | Sample B | Sample C |
| 1) modulus (300%), MPa | 1.1 | 1.5 | 2.3 |
| 2) elongation (%) | 700 | 620 | 575 |
Importantly be appreciated that, modulus and elongation values that sample A is measured show, on-the-spot synthetic filling reality can produce strengthening effect or effect in elastomer body, because if there is not on-the-spot synthetic filling, those skilled in the art can expect that this elastomeric modulus value is much smaller, and elongation values is much bigger.
In table 1A, sample B has higher modulus and lower elongation performance to show, elastomer body can be strengthened more by forming elastomerics/filler complex body, described elastomerics/filler complex body is by using TEOS filler precursor, and before condensation reaction finishes, add organosilane disulphide subsequently and form, rather than use TEOS separately as sample A.
In table 1A, sample C has higher modulus and lower elongation performance also to show, compare with more conventional elastomer body (in sample A) with independent use TEOS, and with use TEOS and add organosilane disulphide and more conventional elastomer body (in sample B) is compared, by using metal alkoxides end functionalized elastomeric body and TEOS filler precursor, and before condensation reaction finishes, add organosilane disulphide subsequently and form elastomerics/filler complex body, meeting even enhancing more.
For sample B and C, shown higher strengthening effect thinks also that in this article being particularly conducive to preparation forms elastomerics/filler complex body in advance, can be mixed with out the elastic composition that is used to make various products with other elastomerics and optional additional hardening filler subsequently, for example comprise tire components.
The embodiment II
In the embodiment that this illustrative is considered meticulously, elastomerics/filler complex body is preparation like this: with butadiene/styrene copolymers elastomerics and liquid filler precursor, be that tetraethoxysilane or TEOS do and mix, in elastomer body, come on-the-spot synthetic filling dispersion then by condensation reaction.
For present embodiment, elastomerics and liquid filler precursor are done in biaxial extruder and are mixed, and make the filler precursor carry out condensation reaction.
Like this, can prepare elastomerics/filler complex body, wherein on-the-spot formation filler can be a whole dispersive form in the main body elastomerics.
The sample of elastomerics/filler complex body is designated as sample D (being used as contrast in the present embodiment), E and F in this example.
The elastomerics that is used for sample D (contrast) and E be lithium catalyst based in the presence of, by co polystyrene in organic solvent solution and 1,3-butadiene, reclaim elastomerics then and obtain.This elastomerics can be called " S-SBR " in this embodiment, and its combined styrene amount is about 18%.
The elastomerics that is used for sample F is similar to the elastomerics that is used for sample D and E, just make 1 with two (triethoxysilylpropyltetrasulfide) disulphide (in its many sulphur bridges, on average comprising about 2.2 sulphur atoms), 3-divinyl and cinnamic copolyreaction all standing, generate the end capped styrene/butadiene copolymers elastomerics of the single sulfane of triethoxysilylpropyltetrasulfide, its combined styrene amount is about 18%.This elastomerics can be called " ST-SBR " in this embodiment
For the present embodiment, elastomerics/filler complex body is preparation like this, at first, S-SBR or ST-SBR are according to circumstances added in the forcing machine, then TEOS (TEOS is about 1/2 with elastomeric weight ratio) is added in the elastomerics with penten condensation reaction promotor (promotor is about 3.5% weight of whole mixture).
Biaxial extruder is in about 170 ℃ of operations down, and the overall stop mixing time of each composition in forcing machine is about 10 minutes.Unproductive mixed rubber composition (comprising elastomerics) is added in the extruder barrel, on certain position that is equivalent to the overall residence time about 25%, filler precursor and condensation reaction promotor are added in the forcing machine then.
For sample E and F, before the condensation reaction of TEOS is finished, on certain position that is equivalent to the overall residence time about 50%, in the organosilane adding forcing machine with two (triethoxysilylpropyltetrasulfide) disulphide (in its many sulphur bridges, on average comprising about 2.2 sulphur atoms) forms.
The on-the-spot silica dioxide granule that forms can be a globular basically, and its diameter is about 5-300 nanometer, and certain dentrite turgidity is arranged, and this can measure by transmission type microscope.
Following table 2 gathers, and has provided the content of the scene formation silica filler of sample D (contrast), E and F:
The embodiment III
| Table 2 | |||
| Material | D (contrast) | Sample E | Sample F |
| 1) elastomerics | S-SBR | S-SBR | ST-SBR |
| 2) filler precursor | TEOS | TEOS | TEOS |
| 3) add disulphide | No | Be | Be |
| 4) the on-the-spot silica filler (% weight) that forms | 16 | 20 | 28 |
In the present embodiment, elastomerics/filler complex body is preparation like this: with butadiene/styrene copolymers elastomerics and liquid filler precursor, be that tetraethoxysilane or TEOS do and mix, in elastomer body, come on-the-spot synthetic filling dispersion then by condensation reaction.
For present embodiment, elastomerics and liquid filler precursor are done in Banbury type rubber internal mixer and are mixed.
Like this, can prepare elastomerics/filler complex body, the wherein on-the-spot filler that forms can be a whole dispersive form in the main body elastomerics.
The sample of elastomerics/filler complex body is designated as sample G (being used as contrast in the present embodiment), H and I in this example.
The elastomerics that is used for sample G (contrast) and H be lithium catalyst based in the presence of, by co polystyrene in organic solvent solution and 1,3-butadiene, reclaim elastomerics then and obtain.This elastomerics can be called " S-SBR " in this embodiment, and its combined styrene amount is about 18%.
The elastomerics that is used for sample I is similar to the elastomerics that is used for sample G and H, just make 1 with two (triethoxysilylpropyltetrasulfide) disulphide (in its many sulphur bridges, on average comprising about 2.2 sulphur atoms), 3-divinyl and cinnamic copolyreaction all standing, generate the end capped styrene/butadiene copolymers elastomerics of the single sulfane of triethoxysilylpropyltetrasulfide, its combined styrene amount is about 18%.This elastomerics can be called " ST-SBR " in this embodiment
For the present embodiment, elastomerics/filler complex body is preparation like this, at first, S-SBR or ST-SBR are according to circumstances added in the rubber internal mixer, then TEOS (TEOS is about 1/2 with elastomeric weight ratio) is added in the elastomerics with penten condensation reaction promotor (promotor is about 3.5% weight of whole mixture).
This mixture was mixed in rubber internal mixer about 8 minutes to about 170 ℃.
For sample H and I, before the condensation reaction of TEOS, after about 6 minutes of above 8 minutes mixing times for reference, organosilane that will two (3-triethoxysilylpropyltetrasulfide) disulphide (on average comprising about 2.2 sulphur atoms in its many sulphur bridges) forms adds in the Banbury type internal rubber mixer.
The on-the-spot silica dioxide granule that forms can be a globular basically, and its diameter is about 5-300 nanometer, and certain dentrite turgidity is arranged, and this can measure by transmission type microscope.
Sample G (contrast), H and I are summarized in following table 3:
| Table 3 | |||
| Material | G (contrast) | Sample H | Sample I |
| 1) elastomerics | ????S-SBR | ????S-SBR | ????ST-SBR |
| 2) filler precursor | ????TEOS | ????TEOS | ????TEOS |
| 3) add disulphide | No | Be | Be |
| 4) the on-the-spot silica filler (% weight) that forms | ?????16 | ?????20 | ?????28 |
Although the physicals of rubber combination, normally measure as modulus and elongation for the sulfur curable rubber combination, but also these values of not vulcanizing sample G, H and I are measured in decision, especially because, it seems that the intravital on-the-spot formation filler dispersion of elastic body active can form the elastomerics/filler complex body that these performances to be determined is had sufficient size stability, shown in following table 3A:
| Table 3A | |||
| Performance | Sample G | Sample H | Sample I |
| 1) modulus (300%), | ???1 | ???1.6 | ???2.2 |
| 2) elongation (%) | ???750 | ???610 | ???600 |
Importantly be appreciated that, modulus and elongation values that sample G is measured show, on-the-spot synthetic filling can actually produce strengthening effect or effect in elastomer body, because if there is not on-the-spot synthetic filling, those skilled in the art can expect that this elastomeric modulus value is much smaller, and elongation values is much bigger.
In table 3A, sample H higher modulus and lower elongation performance show, elastomer body can be used TEOS filler precursor, and adds organosilane disulphide subsequently before condensation reaction finishes and form elastomerics/filler complex body and strengthen more, rather than uses TEOS separately as sample G.
In table 3A, sample I higher modulus and lower elongation performance also show, compare with more conventional elastomer body (in sample G) with independent use TEOS, and with use TEOS and add organosilane disulphide and more conventional elastomer body (in sample H) is compared, elastomer body can be by using metal alkoxides end functionalized elastomeric body and TEOS filler precursor, and before condensation reaction finishes, add organosilane disulphide subsequently and elastomerics/filler complex body of forming, even strengthen more.
For sample H and I, given higher strengthening effect thinks also that in this example being particularly conducive to preparation forms elastomerics/filler complex body in advance, can be mixed with the elastic composition that is used to make various products with other elastomerics and optional additional hardening filler subsequently, for example comprise tire components.
The embodiment IV
In the embodiment of this illustrative meticulous consideration, elastomerics/filler complex body is preparation like this: the butadiene/styrene copolymers elastomerics is immersed in the liquid filler precursor, be among tetraethoxysilane or the TEOS, allow Liquid precursor be infiltrated up to elastomerics itself, in elastomer body, come on-the-spot synthetic filling dispersion then by condensation reaction.
Like this, the filler of scene formation is a whole dispersive form in the main body elastomerics.The sample of elastomerics/filler complex body is designated as sample J (in the present embodiment as contrast), K and L in this example.
The elastomerics that is used for sample J (contrast) and K be lithium catalyst based in the presence of, by co polystyrene in organic solvent solution and 1,3-butadiene, reclaim elastomerics then and obtain.This elastomerics can be called " S-SBR " in this embodiment, and its combined styrene amount is about 18%.
The elastomerics that is used for sample L is similar to the elastomerics that is used for sample J and K, just make 1 with two (triethoxysilylpropyltetrasulfide) disulphide (in its many sulphur bridges, on average comprising about 2.2 sulphur atoms), 3-divinyl and cinnamic copolyreaction quenching, generate the end capped styrene/butadiene copolymers elastomerics of the single sulfane of triethoxysilylpropyltetrasulfide, its combined styrene amount is about 18%.This elastomerics can be called " ST-SBR " in this embodiment
For the present embodiment, elastomerics/filler complex body is preparation like this, at first, under about 25 ℃, S-SBR or ST-SBR according to circumstances are immersed in the liquid filler precursor (TEOS) about 1 hour,, can form the swelling elastomerics like this so that TEOS soaks into or penetrates in the elastomerics.N-butylamine condensation reaction promotor is applied on the swelling elastomerics.The consumption of condensation reaction promotor is about 3% weight of elastomerics and TEOS in the swelling elastomerics.
For sample J and K, before the condensation reaction of TEOS, two (3-triethoxysilylpropyltetrasulfide) disulphide (on average comprising about 2.2 sulphur atoms in its many sulphur bridges) are applied on the swelling elastomerics that contains TEOS.
The on-the-spot silica dioxide granule that forms can be a globular basically, and its diameter is about 5-300 nanometer, and certain dentrite turgidity is arranged, and this can measure by transmission type microscope.
Following table 4 gathers, and has provided the dioxide-containing silica of sample J (contrast), K and L:
| Table 4 | |||
| Material | J (contrast) | Sample K | Sample L |
| 1) elastomerics | ????S-SBR | ????S-SBR | ????ST-SBR |
| 2) filler precursor | ????TEOS | ????TEOS | ????TEOS |
| 3) add disulphide | No | Be | Be |
| 4) the on-the-spot silica filler (% weight) that forms | ????16 | ????19 | ????24 |
The embodiment V
For present embodiment, can consider to use the pre-formation elastomerics/filler complex body of embodiment I, II, III and VI to prepare for illustrative elastic composition sample.
Prepared sample is designated as sample 1-16 in this example, and wherein sample 1,2,5,6,9,10,13 and 14 comes down to the comparative sample of present embodiment.
Comparative sample 1,5,9 and 13 prepares like this: with the mixing step of at least one preparation (unproductive), first mixing step, in rubber internal mixer, carry out blend with precipitated silica with as two (triethoxysilylpropyltetrasulfide) disulphide (on average comprising about 2.2 sulphur atoms in its many sulphur bridges) of coupling agent with rubber combination, described rubber combination is the composition of styrene/butadiene rubbers and other rubber compounding composition (eliminating free sulphur).In mixing step subsequently, free sulphur and accelerator are mixed with rubber combination.
Prepare comparative sample 2,6 and 10 as second comparative sample with similar approach, difference just adds the pre-formation elastomer composite body of embodiment I-IV in the nonproductive mixing step of aforementioned preparation property.
Prepare sample 3,4,7,8,11,12,15 and 16 as sample 1 with similar approach, difference is just in described preparation (unproductive) mixing step, to form elastomerics/filler complex body in advance, rather than the contrast of embodiment I-IV forms complex body in advance and rubber combination carries out blend.Therefore, can regulate the amount of precipitated silica according to the add-on of organosilane disulphide.
Specifically be, the rubber combination that comprises the material of mentioning among the table 1-4 carries out in BR Banbury mixing tank, adopt three independent reinforced (mixing) steps, promptly two ready-mixed steps and final blending step prepare, wherein the temperature of three general steps is respectively 170 ℃, 160 ℃ and 120 ℃, and the time was respectively about 8 minutes, 2 minutes and 2 minutes.After each mixing step, with rubber combination by the gross discharging in two roller mills, the short period of time ground and mixed, flat board or the sheet material with rubber takes out from grinding machine then, and is cooled to about 30 ℃ or lower.
The pre-amount that forms elastomerics/filler complex body, S-SBR, ST-SBR, precipitated silica and organosilane disulphide provides as " variable " in following table 5.
1) the pre-formation elastomerics/filler complex body that in embodiment I, II, III and IV, prepares respectively.
2) the styrene/butadiene copolymers rubber of solution polymerization preparation derives from GoodyearTire ﹠amp; Rubber Company comprises-70 ℃ approximately of about 18% vinylbenzene and Tg.
3) cis 1 elastomerics derives from Goodyear Tire ﹠amp with trade(brand)name BUDENE_ 1207; Rubber Company.
4) oil.
5) lipid acid mainly is stearic acid.
6) Zeosil 1165 MP derive from Rhone Poulenc.
7) as 50/50 blend with the complex body of X266S trade(brand)name available from Degussa GmbH, or Si266 (trade(brand)name of Degussa) and sooty complex body.Si266 is two (3-triethoxysilylpropyltetrasulfide) disulphide (I), thinks on average to comprise about 2.2 sulphur atoms in its many sulphur bridges.Therefore, complex body comprises 50% organosilane disulphide.
8) derive from Kali Chemie Company of Germany with the S8 elementary sulfur.
9) phenylenediamine type.
10) available from the complex body X50S of Degussa GmbH, it is the Si69 (trade(brand)name of Degussa GmbH, or be called two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (II), on average comprise about 3.8 sulphur atoms in its many sulphur bridges) and sooty 50/50 blend, so think that the organosilane tetrasulfide is 50% of a complex body, be 50% activity therefore.
Sample molding in suitable mould is also solidified or vulcanized about 16 minutes to about 160 ℃.For sample 1-4, following table 6 has gathered the adding variable of various materials.
For sample 5-8, following table 7 has gathered the adding variable of various materials.
For sample 9-12, following table 8 has gathered the adding variable of various materials.
For sample 13-16, following table 9 has gathered the adding variable of various materials.
For the given rubber combination of table 6-9, recognize that importantly sample 1,5,9 and 14 has used no the present invention to form the precipitated silica strengthening material of elastomerics/filler complex body in advance.Therefore, with 12 parts of organosilane disulphide add in the elastomer blends with as added precipitated silica coupling agent (noted before as present embodiment, organosilane disulphide uses with 50/50 complex body of liquid disulphide and carbon black (as carrier), so the actual amount of organosilane disulphide is 6phr).
In addition, importantly recognize, for sample 2,6,10 and 14, wherein use the pre-elastomerics/filler complex body of making by TEOS filler precursor that forms, but in condensation reaction, do not add any organosilane to prepare pre-formation elastomerics/filler complex body, reduced the consumption of precipitated silica, but decent product 1,5,9 and 14 are such, in elastomer blends, added the additional organosilane disulphide of same amount.Like this, can think that this example provides a kind of homodisperse particle strengthening material is added more effective ways in the rubber combined body.
Also find out, for sample 3,7,11 and 15, wherein used the present invention who adds organosilane by TEOS filler precursor and in condensation reaction and make to form elastomerics/filler complex body in advance, reduce the add-on of precipitated silica, but in elastomer blends, added the additional organosilane disulphide of same amount.Like this, can think that this example provides another kind of homodisperse particle strengthening material is added more effective ways in the rubber combined body.
Also find out, for sample 4,8,12 and 16, wherein used by metal alkoxides terminal group functional elastomerics, TEOS filler precursor, and in condensation reaction, add organosilane and the present invention of making forms elastomerics/filler complex body in advance, reduced the amount that in elastomer blends, adds precipitated silica and additional organosilane disulphide simultaneously.In fact, reducing use organosilane disulphide mainly is to adapt to institute to add precipitated silica.Like this, can think that this paper provides another kind of homodisperse particle strengthening material is added more effective ways in the rubber combined body.
The meaning that these samples showed shows, the pre-formation elastomerics/filler complex body of the application of the invention preparation can obviously more effectively be introduced as homogeneous dispersion and make the rubber combination that contains this dispersion to strengthen filler and advance in the rubber combination.
The embodiment VI
Can make the tire that is of a size of 195/65R15, the rubber combination that uses sample 1-16 respectively is as its tyre surface.
Although provided some representational embodiment and detail with explanation the present invention, those skilled in the art obviously can carry out various changes and modifications under the situation that does not deviate from purport of the present invention and scope.
Claims (42)
1. the scene forms the method that filler dispersion prepares elastomerics/filler complex body in elastomer body, it is characterized in that: at the solution of the organic solvent of the described elastic body of medium (1), or in the aqueous latex of (2) described elastic body, with the filler precursor, condensation reaction promotor, with the elastomer body blending that is selected from elastomer body (A) and elastomer body (B), cause described condensation reaction of filling out the body precursor, and, for elastomer body (A), and it is optional for elastomer body (B), then before described condensation reaction is finished, add the organosilane material, and make itself and described filler/filler precursors reaction, then reclaim the elastomerics/filler complex body of gained; Wherein said elastomer body (A) be selected from conjugated diolefine homopolymer, conjugated diolefine multipolymer, conjugated diolefine and be selected from vinylbenzene and the multipolymer of the vinyl aromatic compounds of alpha-methyl styrene at least a; Wherein said elastomer body (B) be selected from least a based on the functionalized diene of end group metal alkoxides elastomerics, wherein said metal is selected from silicon, titanium, aluminium or boron, and wherein said elastomerics be selected from conjugated diolefine homopolymer, conjugated diolefine multipolymer, conjugated diolefine and be selected from vinylbenzene and the multipolymer of the vinyl aromatic compounds of alpha-methyl styrene at least a; Wherein said filler precursor is selected from least a material among structural formula (II A), (the II B) and (II C):
(ⅡA)???M(OR)
x(R’)
y
(ⅡB)???(RO)
x(R’)
yM-O-M’(R’)
z(RO)
w
(ⅡC)???(RO)
x(R’)
yM-(CH
2)
r-M’(R’)
z(RO)
w
Wherein M and M ' are identical or different, be selected from silicon, titanium, zirconium, boron and aluminium, wherein R and R ' are the alkyl that is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-separately respectively, and wherein x+y and w+z integer summation equal 4, unless when its M that links to each other or M ' were boron or aluminium, this add up to 3; And wherein r is 1-15;
Wherein said organosilane is at least a material that is selected from structure formula III, (IV) and (V), that is:
Organosilane polysulfide with structure formula III:
(Ⅲ)??????Z-R
1-S
m-R
1-Z
Wherein m is the number of 2-about 8, and the mean value of m is (a) about 2-about 2.6 or (b) about 3.5-about 4.5;
Wherein Z is represented by following structural formula:
R wherein
2Identical or different, be selected from alkyl and phenyl separately with 1-4 carbon atom; R
3Be identical or different alkoxyl group, the alkyl of wherein said alkoxyl group is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-; And R
1For being selected from the replacement that has 1-18 carbon atom altogether or substituted alkyl and have the replacement of 6-12 carbon atom altogether or the group of unsubstituting aromatic yl not;
The alkylalkoxy silane of structure formula IV:
(Ⅳ)????(OR
4)
3-Si-R
5
R wherein
4Be identical or different alkyl, be selected from methyl, ethyl, n-propyl and sec.-propyl; And R
5Be selected from alkyl and have the aryl or the alkyl substituting aromatic base of 6-12 carbon atom with 1-18 carbon atom; With
The functionalized organosilane of structural formula (V):
(Ⅴ)????(OR
6)
3-Si-(CH
2)
y-Y
R wherein
6Be identical or different alkyl, be selected from methyl, ethyl, n-propyl and sec.-propyl, y is the integer of 1-12, and Y is selected from primary amino, sulfydryl, epoxide, thiocyano, vinyl, methacrylic ester, urea groups, isocyanato and quadrol group.
2, according to the method for claim 1, it is characterized in that the solution of the described elastomeric organic solvent that described medium is made up of described elastomeric polymerization adhesive paste
According to the method for claim 1, it is characterized in that 3, described medium is described elastomeric elasticity latex.
4, according to each method of aforementioned claim, it is characterized in that described elastomerics is at least a elastomer body (A).
5, according to each method of claim 1-3, it is characterized in that described elastomerics is at least a elastomer body (B), and wherein elastomerics (B) has logical formula I:
(I) elastomerics-X-(OR)
n
Wherein X is selected from silicon, titanium, aluminium and boron, R is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-, and n is 3 (for for silicon and the titanium) and 2 (for aluminium and boron), and wherein said elastomerics is selected from least a in the multipolymer of the multipolymer of homopolymer, conjugated diolefine of conjugated diolefine and at least a conjugated diolefine and the vinyl aromatic compounds that is selected from vinylbenzene and alpha-methyl styrene.
6. according to the method for claim 5, it is characterized in that for elastomerics (B), X is a silicon, R is an ethyl, and n is 3, and for described elastomerics (B), described vinyl aromatic compounds is a vinylbenzene.
7. according to the method for claim 4, it is characterized in that, described elastomerics (A) is selected from 1, the homopolymer of 3-divinyl and isoprene and multipolymer, vinylbenzene and 1, at least a multipolymer, 1 in 3-divinyl and the isoprene, at least a tin coupled copolymers in the tin coupling polymer of 3-divinyl and isoprene and multipolymer, vinylbenzene and 1,3-butadiene and the isoprene, and composition thereof.
8. according to claim 5 and 6 each methods, it is characterized in that, described elastomerics (B) is selected from 1, the homopolymer of 3-divinyl and isoprene and multipolymer and 1,3-divinyl and/or isoprene and cinnamic multipolymer and composition thereof, and wherein said terminal group functional material is an organoalkoxysilane; The alkyl of wherein said organoalkoxysilane is selected from least a in ethyl, methyl, n-propyl and the sec.-propyl.
9. according to any one method of aforementioned claim, it is characterized in that described filler precursor is precursor (II A).
10. according to the method for claim 9, it is characterized in that for described filler precursor (II A), M and M ' are silicon, R is an ethyl, and R ' is that methyl and x+y summation are 4.
11. method according to claim 9, it is characterized in that described filler precursor is selected from least a in tetraethoxy ortho-silicate, ethanolato-titanium, positive propoxy titanium, tri sec-butoxy aluminum, tert.-butoxy zirconium, n-butoxy zirconium, four n-propoxyzirconium and oxyethyl group boron, triethoxy silicic acid methyl esters and the diethoxy silicic acid dimethyl ester.
12., it is characterized in that described filler precursor is precursor (II B) according to any one method among the aforementioned claim 1-8.
13. the method according to claim 12 is characterized in that, for described filler precursor (II B), M and M ' are silicon, and R is an ethyl, and R ' is a methyl, and x+y and w+z summation all are 4 separately.
14. the method according to claim 12 is characterized in that, described precursor (II B) is selected from least a in two sec-butoxy alumina ethyl triethoxy silicane alkane and the six oxyethyl group sily oxide.
15., it is characterized in that described filler precursor is precursor (II C) according to any one method among the aforementioned claim 1-8.
16. the method according to claim 15 is characterized in that, for described filler precursor (II C), M and M ' are silicon, and R is an ethyl, and R ' is a methyl, and x+y and w+z summation all are 4 separately.
17. the method according to claim 15 is characterized in that, described precursor (II C) is selected from least a of two sec-butoxy alumina ethyl triethoxy silicane alkane and six oxyethyl group sily oxide.
18., it is characterized in that described organosilane is a kind of organic polysulfide (III), and wherein Z is Z3, R according to any one method in the aforementioned claim
3Alkyl be selected from ethyl, n-propyl, sec.-propyl, normal-butyl and isobutyl-.
19. the method according to claim 18 is characterized in that, for described organosilane polysulfide (III), the mean value of m is about 2-about 2.6.
20. the method according to claim 18 is characterized in that, for described organosilane polysulfide (III), the about 3.5-of m average out to about 4.5.
21. the method according to claim 18 is characterized in that, described organosilane polysulfide (III) is selected from least a in the following compound:
2,2 '-two (trimethoxysilylethylgroup group) disulphide; 3,3 '-two (trimethoxy-silylpropyl) disulphide; 3,3 '-two (triethoxysilylpropyltetrasulfide) disulphide; 2,2 '-two (triethoxysilyl ethyl) disulphide; 2,2 '-two (tripropoxy-sil(ic)ane base ethyl) disulphide; 2,2 '-two (three sec-butoxy silyl ethyls) disulphide; 3,3 '-two (three tert.-butoxy ethyls) disulphide; 3,3 '-two (triethoxysilyl ethyl tolylene) disulphide; 3,3 '-two (trimethoxysilylethylgroup group tolylene) disulphide; 3,3 '-two (three isopropoxide propyls) disulphide; 3,3 '-two (three octyloxy propyl group) disulphide; 2,2 '-two (2 '-ethyl hexyl oxy silyl ethyl) disulphide; 2,2 '-two (dimethoxy (ethoxymethyl) silylation ethyl) disulphide; 3,3 '-two (methoxy ethoxy propoxy-silyl propyl group) disulphide; 3,3 '-two (methoxyl group dimetylsilyl propyl group) disulphide; 3,3 '-two (cyclohexyloxy dimetylsilyl propyl group) disulphide; 4,4 '-two (trimethoxysilyl butyl) disulphide; 3,3 '-two (trimethoxysilyl-3-methyl-propyl) disulphide; 3,3 '-two (tripropoxy-sil(ic)ane base-3-methyl-propyl) disulphide; 3,3 '-two (dimethoxy-methyl silyl-3-ethyl propyl) disulphide; 3,3 '-two (trimethoxysilyl-2-methyl-propyl) disulphide; 3,3 '-two (Dimethoxyphenyl silyl-2-methyl-propyl) disulphide; 3,3 '-two (trimethoxysilyl cyclohexyl) disulphide; 12,12 '-two (trimethoxysilyl dodecyl) disulphide; 12,12 '-two (triethoxysilyl dodecyl) disulphide; 18,18 '-two (trimethoxysilyl octadecyl) disulphide; 18,18 '-two (methoxyl group dimetylsilyl octadecyl) disulphide; 2,2 '-two (trimethoxysilyl-2-methylethyl) disulphide; 2,2 '-two (triethoxysilyl-2-methylethyl) disulphide; 2,2 '-two (tripropoxy-sil(ic)ane base-2-methylethyl) disulphide; With 2,2 '-two (three octyloxies silyl-2-methylethyl) disulphide.
22. the method according to claim 18 is characterized in that, described organosilane polysulfide material (III) is two (3-triethoxysilylpropyltetrasulfide) disulphide.
23. the method according to claim 18 is characterized in that, described organosilane polysulfide (III) is selected from least a in two (3-triethoxysilylpropyltetrasulfide) tetrasulfides and two (3-triethoxysilylpropyltetrasulfide) trisulphides.
24., it is characterized in that described organosilane is alkylalkoxy silane (IV) according to any one method of aforementioned claim.
25. according to each method of claim 1-17, it is characterized in that described organosilane is alkylalkoxy silane (IV), for described alkylalkoxy silane (IV), R
5For having the alkyl of 8-18 carbon atom.
26. the method according to claim 24 is characterized in that, described alkylalkoxy silane (IV) is selected from propyl-triethoxysilicane, Union carbide A-162, hexadecyl triethoxyl silane and the octadecyltriethoxy silane at least a.
27., it is characterized in that described organosilane is functionalized organosilane (V) according to any one method among the aforementioned claim 1-17.
28. the method according to claim 27 is characterized in that, for functionalized organosilane (V), R
6Be ethyl, and y is the integer of 2-4.
29. method according to claim 27, it is characterized in that described functionalized organosilane is selected from the 3-aminopropyltriethoxywerene werene, 2-amino-ethyl triethoxyl silane, the amino butyl triethoxyl silane of 4-, 3-sulfydryl propyl-triethoxysilicane, 2-mercaptoethyl triethoxyl silane, 4-sulfydryl butyl triethoxyl silane, (3-glycidoxypropyl) triethoxyl silane, the 3-thiocyano propyl triethoxy silicane, vinyltriethoxysilane, the urea groups propyl-triethoxysilicane, at least a in 3-isocyanato propyl-triethoxysilicane and N (3-triethoxysilyl) the propyl group quadrol.
30. according to any one method in the aforementioned claim, it is characterized in that, described elastomerics (A) is selected from least a in the following material: cis 1, the 4-polyisoprene, cis 1, the 4-polyhutadiene, the isoprene/butadiene multipolymer, styrene/butadiene copolymers (comprising the multipolymer of emulsion polymerization preparation and the multipolymer of organic solvent solution polyreaction preparation), the styrene/isoprene multipolymer, 3, the 4-polyisoprene, trans 1, the styrene/isoprene/butadiene tri-component multipolymer, the high vinyl polybutadiene that contains about 90% vinyl of the 35-that has an appointment
31. according to aforementioned claim 1,5,6,8 and 9-29 in any one method, it is characterized in that, the elastomeric component of elastomerics (B) is the elastomerics of organic solvent polyreaction preparation, be selected from cis 1, the 4-polyisoprene, cis 1, the 4-polyhutadiene, the isoprene/butadiene multipolymer, styrene/butadiene copolymers (comprising the multipolymer of emulsion polymerization preparation and the multipolymer of organic solvent solution polyreaction preparation), the styrene/isoprene multipolymer, 3, the 4-polyisoprene, trans 1, at least a with in the styrene/isoprene/butadiene tri-component multipolymer.
32. according to any one method among the aforementioned claim 1-29, it is characterized in that, described tin coupling elastomerics can be a kind of like this product, promptly, in organic solvent solution and organolithium catalyst based in the presence of, the product that at least a conjugated diolefine is reacted or vinylbenzene and at least a conjugated diolefine one are reacted; Wherein said diene is selected from 1,3-butadiene and isoprene, then with the polymkeric substance of living with have structural formula: R
7 4-vSnX
nAt least a compound react, wherein n is the integer (comprising 4) of 1-4, X is a chlorine; And R
7For being selected from the alkyl of methyl, ethyl, propyl group and butyl.
33. according to any one method in the aforementioned claim, it is characterized in that described filler precursor is at least a material that is selected from tetraethoxy ortho-silicate, ethanolato-titanium, positive propoxy titanium, tri sec-butoxy aluminum, tert.-butoxy zirconium, n-butoxy zirconium, four n-propoxyzirconium and oxyethyl group boron, triethoxy silicic acid methyl esters and diethoxy silicic acid dimethyl ester, two sec-butoxy alumina ethyl triethoxy silicane alkane and six oxyethyl group sily oxide, two (triethoxysilyl) methane and two (triethoxysilyl) ethane.
34. the method according to claim 33 is characterized in that, before finishing condensation reaction, at least a two (3-trialkoxysilyl alkyl) polysulfide and described filler/filler precursor is reacted.
35., it is characterized in that described condensation reaction promotor is selected from (a) basic-type accelerator, (b) acidic-type accelerator, (c) metal oxide and metal salt promoter and (d) organo-tin compound promotor according to any one method in the aforementioned claim.
36. according to any one method in the aforementioned claim, it is characterized in that described condensation reaction promotor is selected from ammonia, ammonium hydroxide, the N-butylamine, tert-butylamine, tetrahydrofuran (THF) (THF), Sodium Fluoride, penten, diaminopropanes, diethylenetriamine, Triethylenetetramine (TETA), poly-(allyl amine hydrochloride), poly-(L-Methionin hydrobromide), poly-(L-arginine hydrochloride), poly-(L-Histidine hydrochloride), phosphoric acid, acetate, hydrofluoric acid, sulfuric acid, zinc oxide, aluminum oxide, zinc sulfate, Tai-Ace S 150, Zinic stearas, aluminum stearate, at least a in two (2 ethyl hexanoic acid) tin and two (neodecanoic acid) tin.
37. elastomerics/filler complex body is characterized in that, it is to prepare according to the method for any one among the aforementioned claim 1-36.
38. elastic composition, it is characterized in that, elastomerics based on 100 weight parts, comprise: it is made up of following compositions: (A) at least a diene of the about 90phr of about 10-is the elastomerics on basis, (B) at least a elastomerics/filler complex body of the claim 37 of the about 10phr of about 90-, (C) at least a additional hardening filler, the wherein said on-the-spot total amount that forms filler and described additional hardening filler is the about 120phr of about 5-, and wherein said additional hardening filler is selected from precipitated silica, silico-aluminate as aluminate and silicate coprecipitate, carbon black, with by strengthening carbon black with the organosilane pyroprocessing or making its surface have at least a in the modified carbon black of hydroxyl by organosilane and innage temperature are smoked altogether, (D) add as required, have can with the group of described additional hardening filler reaction and can with the coupling agent of another group of described elastomerics reaction.
39. goods is characterized in that, it has at least a component of being made up of each elastic composition of claim 37-38.
40. a tire is characterized in that, it has at least a component of being made up of each elastic composition of claim 37-38.
41, a kind of tire is characterized in that, its tyre surface is made up of each elastic composition of claim 37-38.
42, a kind of tire, it is characterized in that forming by elastic composition, elastomerics based on 100 weight parts, described elastic composition is made up of following compositions: (A) at least a elastomerics based on diene of the about 90phr of about 10-, (B) at least a elastomerics/filler complex body of the claim 37-38 of the about 10phr of about 90-, (C) at least a additional hardening filler, the wherein said on-the-spot total amount that forms filler and described additional hardening filler is the about 120phr of about 5-, and wherein said additional hardening filler is selected from precipitated silica, silico-aluminate as aluminate and silicate coprecipitate, carbon black, with by strengthening carbon black with the organosilane pyroprocessing or making its surface have at least a in the modified carbon black of hydroxyl by organosilane and high temperature are smoked altogether, (D) add as required, have can with the group of described additional hardening filler reaction and can with the coupling agent of another group of described elastomerics reaction.
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| CN109563195A (en) * | 2016-07-22 | 2019-04-02 | 公共型股份公司希布尔控股 | For producing the method for branched modification rubber and the rubber composition and application thereof of the branched modification rubber comprising preparing by the method |
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1999
- 1999-11-11 CN CN 99123553 patent/CN1296027A/en active Pending
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| CN104558728A (en) * | 2015-01-15 | 2015-04-29 | 无为县华祥电缆材料有限公司 | High-strength chloride esterification polybutadiene rubber cable material |
| CN108136836A (en) * | 2015-11-13 | 2018-06-08 | 米其林集团总公司 | Composite material comprising metal parts and functional polymer's matrix |
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| CN109563195A (en) * | 2016-07-22 | 2019-04-02 | 公共型股份公司希布尔控股 | For producing the method for branched modification rubber and the rubber composition and application thereof of the branched modification rubber comprising preparing by the method |
| CN109563195B (en) * | 2016-07-22 | 2021-07-27 | 公共型股份公司希布尔控股 | Process for producing branched modified rubber, rubber composition comprising branched modified rubber prepared by the process, and use thereof |
| CN106609038A (en) * | 2016-11-28 | 2017-05-03 | 湖北航天化学技术研究所 | Silicone rubber coating layer deeply cured in closed environment |
| CN106609038B (en) * | 2016-11-28 | 2020-04-10 | 湖北航天化学技术研究所 | Silicone rubber coating layer deeply cured in closed environment |
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