CN101293874B - Polyalcohol-filling material coupling additive agent - Google Patents
Polyalcohol-filling material coupling additive agent Download PDFInfo
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- CN101293874B CN101293874B CN 200710097690 CN200710097690A CN101293874B CN 101293874 B CN101293874 B CN 101293874B CN 200710097690 CN200710097690 CN 200710097690 CN 200710097690 A CN200710097690 A CN 200710097690A CN 101293874 B CN101293874 B CN 101293874B
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- 0 *C1(*)C(*)(*)N=C(*)*1 Chemical compound *C1(*)C(*)(*)N=C(*)*1 0.000 description 3
- JSEHNJFUJCVGHW-UHFFFAOYSA-N CSc1ccccc1C1=NCCO1 Chemical compound CSc1ccccc1C1=NCCO1 JSEHNJFUJCVGHW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides polymer-filler coupling compounds with formula of B-A-Sx-N. In these compounds, B is an azacyclo part containing oxygen or sulphur or a tin alkyl part; Sx is a polysulfide, wherein x is an integer from 2 to approximately 10; A is a coupling atom or group for forming a bridge bond between B and Sx; and N is a blocking group. Sx can be disulfides. N can be conventional blocking groups or other groups such as -A-B. The invention also provides a method for modifying polymers containing unsaturated C-C bonds and promoting filler dispersion by using the polymer-filler coupling compounds. The invention further provides a vulcanized rubber composition containing the polymer-filler coupling compounds and a method for preparing the vulcanized rubber composition using the polymer-filler coupling compounds.
Description
Technical field
The composition that is used for coupling polymer and filler, and the polymer composition that comprises these coupling compositions.
Background technology
The dust dispersion quality of filler in polymeric composition namely is scattered in to uniform filling the degree in whole compositions, can affect the character of operation of the full thing of aggregation group.Can be subject to filler property of dust dispersion quality impact in polymeric composition is to lag behind.Difference between the energy of the recovery when for example, elastomeric hysteresis refers to apply the energy that makes elastomerics distortion and elastomerics and returns to its initial indeformable state.A kind of reinforced filling of known elasticity body molecule and introducing or the impact of the interaction between several filler lag behind.
The elastomeric hysteresis of compounding and other physical properties can be by guaranteeing that filler is well dispersed in whole polymkeric substance and improves.When showing that the good elasticity formulation that lags behind is used for goods such as band, tire etc., when standing mechanical stress during use, these goods show the resilience of increase and the character of the heat generation (heat build-up) that reduces.For example, in pneumatic tyre, the rolling resistance and the heat generation that reduce between the lagged value of reduction and usage period are relevant.This in pneumatic tyre the reduction of rolling resistance and heat generation can bring lower fuel consumption for the vehicle that uses this tire.
Summary of the invention
Polyalcohol-filling material coupling compound described herein has formula B-A-S
x-N.In these compounds, B is the nitrogen heterocyclic part that contains aerobic or sulphur, perhaps tin alkyl part; S
xBe polysulfide, wherein x is 2 to approximately 10; A is for forming B and S
xBetween connection atom or the group of bridged bond; With N be capping group.S
xCan be disulphide.N can for traditional capping group or other group such as-A-B.
Use the method for polyalcohol-filling material coupling compound also in this description.Polymer-modified method comprises that the polymkeric substance that will contain unsaturated C-C in its molecular structure contacts with the polyalcohol-filling material coupling compound.The method that promotes filler to disperse in polymeric composition comprises to be made by polyalcohol-filling material coupling compound modified polymkeric substance and the filler reaction with the B surface group partly that is bonded to compound.Polyalcohol-filling material coupling compound, polymkeric substance and filler also can be simultaneously but not are mixed in turn, to promote the dispersion of filler in polymeric composition.
But the method that contains the vulcanizate compositions of polyalcohol-filling material coupling compound and use this polyalcohol-filling material coupling compound to make vulcanizate compositions is also described herein.But vulcanizate compositions be included in the elastomerics that contains unsaturated C-C in its molecular structure, hysteresis reduction amount the polyalcohol-filling material coupling compound, have filler and the vulcanizing agent of the surface group of the B part that is bonded to the polyalcohol-filling material coupling compound.But the method for making vulcanized elastomer composition comprises and is mixed together just described vulcanizate compositions and sulfuration said composition.
Embodiment
Can how make and use desired example of the present invention as those of ordinary skills, this specification sheets proposes following example: have formula B-A-S
xBut the compound of-N, comprise the polymer composition of these compounds, in polymeric composition, use these compounds method, contain the vulcanizate compositions of this polyalcohol-filling material coupling compound, and use this polyalcohol-filling material coupling compound to make the method for vulcanizate compositions.Provide this to describe with the requirement of satisfied realization and best mode and do not apply the not in the claims restriction of narration.
Has formula B-A-S
xThe compound of-N is for promoting that the dispersion of filler in polymeric composition is useful, and this polymeric composition is included in the polymkeric substance that has unsaturated C-C in its molecular structure.Has formula B-A-S at these
xIn the compound of-N, B is the nitrogen heterocyclic part that contains aerobic or sulphur, perhaps allyltin part; Sx is polysulfide, and wherein x is 2 to approximately 10; A is connected atom or group for what form bridged bond between B and the Sx; With N be capping group.
When being used for this specification sheets, the nitrogen heterocyclic that term contains aerobic or sulphur partly means to comprise the structure that is embodied in formula I, II and III:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4, R
5, R
6And R
7Each be the C of hydrogen, side chain or straight chain independently
1-C
20The C of alkyl, side chain or straight chain
3-C
20The C of cycloalkyl, side chain or straight chain
6-C
20The C of aryl, side chain or straight chain
7-C
20Alkaryl, or A, wherein A is for forming B and S
xBetween connection atom or the group of bridged bond.To doing the R group, each R group can be identical, such as hydrogen; Each R group can be different, such as two or more different groups; Or some R groups can be identical and other R group is different, such as R
1Can be A, R
2Can be hydrogen, other R group can be identical or different alkyl.
The allyltin part can comprise formula-CH=CHCH
2Sn (R
8)
3, R wherein
8C for side chain or straight chain
1-C
20The C of alkyl, side chain or straight chain
3-C
20The C of cycloalkyl, side chain or straight chain
6-C
20The C of aryl, side chain or straight chain
7-C
20Alkaryl or its mixture.Allyltin-CH partly is bonded to B-A-S
xThe A group of-N compound is to form (allyltin part)-A-S
x-N.
Connect atom or group A and can be the C of side chain or straight chain
1-C
20The C of alkylene moiety, side chain or straight chain
3-C
20The C of cycloalkylidene part, side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part.In addition, A can comprise [A '-(Z-A ")
k], wherein A ' and A " are the C of side chain or straight chain
1-C
20The C of alkylene moiety, side chain or straight chain
3-C
20The C of cycloalkylidene part, side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; Z is oxygen, sulphur or C=O; And k is 1 to approximately 4.For example, A can comprise and B and/or S
xWith adjacent, or the phenyl of para-linkage.As another example, A can comprise (CH
2)
m, wherein m is 1 to approximately 10.
S
xGroup is polysulfide.This polysulfide can have two or more sulphur atoms.For example, polysulfide can have 2 to about 10 sulphur atoms, and namely x is 2 to approximately 10.Usually, the sulphur atom of existence is more, for the N group, and capping group, easier of the dereaction B-A-S that dissociates
Y-1-S-molecule.The N group can have the sulphur atom that still associates when separating, and namely leavings group can be-S-S
Z-1-N.Subscript y and z represent with separately from the number of the sulphur atom of the molecular association of separating, wherein x=y+z.
The N group can or comprise that for traditional capping group for example aforesaid B-A-group (is B-A-S
x-A-B) other group.The other example of capping group comprises those groups of the sulphur part that becomes known for the end-blocking sulfydryl.For the capping group of these types, sulfydryl hydrogen is by not affecting the sulfydryl organic moiety (namely at B-A-S
xIn the situation of-N molecule, B part) reactive another group substitutes.Suitable sulfydryl capping group can include, but are not limited to be disclosed in US 6,127,468; 6,204,339; 6,528,673; 6,635,700; 6,649,684 and 6,683, those of 135, for described sulfydryl capping group, its disclosure is incorporated herein with for referencial use.Can be with the deblocking agent at B-A-S
xAdd during the manufacturing processed after-N and filler reaction have occured, so that B-A-S
xThe sulphur atom of-N molecule and rubber bonding.Can need therein any mix stages of deblocking to add as one-component any time of deblocking agent during the compounding process.Sulfurating stage through the compounding of being everlasting needs deblocking, and the final mix stages that is added in of deblocking agent adds.The deblocking agent can be contained in the sulfur vulcanization bag (package), and plays vulcanization accelerator, particularly when making up with zinc salt.The example of deblocking agent is well-known for those skilled in the art.
B-A-S
xA non-limiting example of-N compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide (2OPD), shown in formula IV:
Particularly, 2OPD is B-A-S
x-A-B type molecule, wherein x is 2, namely N be-A-B and this A are identical in the every side of molecule with the B group.If B-A-S
1-be leavings group, two same molecules are formed by the structure shown in the formula V so:
At B-A-S
xIn-A-B type the molecule, the A part can be identical, as in the 2OPD molecule, and perhaps can be different.Similarly, at B-A-S
xIn-A-B type the molecule, the B part can be identical, as in the 2OPD molecule, and perhaps can be different.B-A-S
xThe other non-limiting example of-N compound is two-[2-(2-thiazolyl)-phenyl]-disulphide (2TPD), shown in formula VI:
Can use the general chemistry synthetic method with production exemplary compounds and other B-A-S
x-N compound and do not carry out excessive experiment.Exemplary method for the production of 2OPD is disclosed in the following examples A.Yet, recognize and use other known chemical synthesis process of other parent material and intermediate also can use to produce these and other B-A-S
x-N compound.
Polymkeric substance used herein contains carbon-to-carbon unsaturated bond and comprises thermoplastic polymer and thermosetting polymer in its molecular structure.This unsaturated link(age) can be along the main polymer chain existence and/or with existence such as side group such as ethylenic groups (ethylenic group).The suitable elastomerics that contains carbon-to-carbon unsaturated bond in its molecular structure comprises natural and synthetic rubber, as passing through the polymeric aliphatic conjugated diolefine, particularly each molecule contains those of 4 to 8 carbon atoms, those that produce such as but not limited to divinyl, isoprene, pentadiene etc., the perhaps multipolymer of these diene and ter-polymers.Elastomeric main polymer chain used herein can contain quite a large amount of unsaturated link(age)s.For example, the C-C at least about 5% can be unsaturated link(age) in main polymer chain.
Characteristics with rubber of unsaturated carbon chains are well-known in the art, shown in the ANSI/ASTM standard D1418-79A that unsaturated chain rubber wherein refers to R rubber.R class rubber comprises natural rubber and at least part of by the derivative various synthetic rubber of diolefine.The below enumerates for the non exhaustive property that can be used for the R class rubber of the present composition: Acrylester Butadiene Rubber; Divinyl rubber; The chloro-butyl rubber; Chloroprene rubber; Synthetic isoprene; Paracril; Acrylonitrile chloroprene rubber; Nitrile-synthetic polyisoprene (nitrile-isoprene rubber); Natural rubber; Styrene-butadiene rubber(SBR); Vinylbenzene-neoprene and styrene isoprene rubber.Rubber with carbon-to-carbon unsaturated bond used herein also can be different from R rubber, such as but not limited to by the ethylene-propylene diene monomers derivative and generally have its carbon bond approximately 3% to the about 8% EPDM rubber as unsaturated C-C.
The further example that can be used for the synthetic polymer of composition disclosed herein includes but not limited to homopolymerization product and homologue and derivative such as dimethyl butadiene, dimethylbutadiene and the pentadiene of divinyl, and the multipolymer that is formed by divinyl or its homologue or derivative and other unsaturated organic compound.Wherein the latter is alkene, for example is called again ethene, propylene or the iso-butylene of the polyisobutene of isoprene-isobutylene rubber with formation with isoprene copolymer; Can with the vinyl compound of diene monomers such as divinyl and isoprene copolymer; Vinylformic acid, vinyl cyanide, methacrylonitrile, methacrylic acid and alpha-methyl styrene, (ortho-, meta-or p-) vinyl toluene and vinylbenzene, with the latter compound of polymerizing butadiene with formation styrene-butadiene rubber(SBR), and vinyl ester and various unsaturated aldehyde, ketone and ether, such as propenal and ethyl vinyl ether etc.
Usually, the elastomeric example with the composition use comprises the homopolymer of conjugate diene monomer and multipolymer and the terpolymer of conjugate diene monomer and mono vinyl aromatic monomer and triolefin.More specifically, the elastomeric example that uses with composition comprises natural rubber, synthetic polyisoprenes, polyhutadiene, polystyrene, styrene-butadiene copolymer, isoprene-butadiene multipolymer, isoprene-styrol copolymer, styrene-isoprene-butadiene terpolymer, paracril, vinyl cyanide, divinyl and cinnamic terpolymer, and composition thereof.
B-A-S
x-N compound and in its molecular structure, contain chemical reaction explanation in approach 1 between the polymkeric substance of unsaturated C-C.In approach 1, polymkeric substance (P) be expressed as have can with " n " mole B-A-S
x" n " individual repeating unit of-N reaction.From the viewpoint of reality, recognize not all in the polymerizable molecular structure available reactive site will react, thereby " n " means to represent the mean number of reactive site.For convenient, the polymer-modified P-(S that is expressed as that will in approach 1, produce
y-A-B)
nAs discussed above, symbol " y " is illustrated in-S
zThe leave away number of sulfur atoms of rear and this molecular association of-N group, x=z+y in the base.
Approach 2-9 represents other reaction, i.e. P-(S
y-A-B)
nThe B of compound partly is bonded to the reactive group of filling surface.The reaction product from the approach 1 that comprises polymkeric substance is used in the discussion here.Yet the reaction of B part is independent of B-A-S
xThe reaction of-N compound and polymkeric substance and occuring.That is, for B-A-S
x-N compound there is no need to be bonded to polymkeric substance so that the reaction of B part-filler occurs.The reaction of B part-filler can be at B-A-S
xBefore-N compound is coupled to polymkeric substance, occur simultaneously or afterwards.
As illustrated in approach 2-9, the B part can comprise and contain and the oxygen of carbon black (CB) surface group reaction or the nitrogen heterocyclic part of sulphur, so that P-(S
y-A-B)
nWith mixing so that carbon black directly is bonded to the B part of compound of carbon black.Thereby filler is combined along the molecular structure of polymkeric substance with the reaction of polymkeric substance by B.
The such reaction of approach 10 expressions, in this reaction, P-(S
y-A-B)
nB part can comprise and the allyltin that is present in the surperficial o-quinone structural response on the carbon black so that P-(S
y-A-B)
nWith mixing so that carbon black directly is bonded to P-(S of carbon black filler
y-A-B)
nThe B part of compound, and carbon black filler is combined along the molecular structure of polymkeric substance with the reaction of polymkeric substance by B.
Approach 1:
Approach 2:
Approach 3:
Approach 4:
Approach 5:
Approach 6:
Approach 7:
Approach 8
Approach 9:
Approach 10:
In each reaction illustrated by approach 2-10, if a plurality of reactive group is present on filler particles or the aggregate, surpass a B-A-S
x-N molecule can be bonded to carbon black filler particle or aggregate.Have in addition and B-A-S
xOther filler of the surface group of the B partial reaction of-N can mix with carbon black and be combined along the molecular structure of polymkeric substance with the reaction of polymkeric substance by B.For example, mineral filler such as but not limited to talcum, kaolin, clay, metal oxide, aluminium hydrate, mica etc., has such reactive surfaces group, and these fillers can use with the form of the mixture that contains carbon black.
As illustrated in above approach 1, polymer-modified can be by will in its molecular structure, containing unsaturated C-C polymkeric substance and aforesaidly have a formula B-A-S
xThe compound of-N contacts to produce, and is polymer-modified to form.B-A-S
xThe scope of the amount of-N compound can for from approximately 0.1 to about 30 % by weight, calculate based on the weight of the polymkeric substance that will be modified.In addition, B-A-S
xThe scope of the amount of-N compound can for polymkeric substance from approximately 0.5 to about 10 % by weight.In addition, B-A-S
xThe scope of the amount of-N compound can for polymkeric substance approximately 1 to about 8 % by weight.Modified-reaction can solution or under condition of no solvent (solid state reaction) carry out.Can be with B-A-S
x-N compound refines by any conventional art such as roller or adds in the rubber in Banbury.
For example, polymer-modified any time that can be after polymerization is for example by with B-A-S
x-N compound joins from the caking agent that polymerization obtains, by this compound being sprayed on the dry polymer sulfuration rubber powder or obtaining by compound being joined add in the polymeric composition that has polymkeric substance before the filler.
Thereby the method that promotes filler to disperse in polymeric composition can comprise the following step: (a) by with polymkeric substance with have formula B-A-S
xThe compound reaction of-N, modification has this polymkeric substance of unsaturated C-C in its molecular structure, polymer-modified to form, and (b) with polymer-modified filler reaction with comprising the B surface group partly that can be bonded to this compound.
In another example, the method that promotes filler to disperse in polymeric composition can comprise the step that is mixed together following material: (i) have the polymkeric substance of unsaturated C-C in its molecular structure, (ii) have formula B-A-S
xThe compound of-N; (iii) comprise the filler of the surface group of the B part that can be bonded to this compound.
Vulcanizable elastor composition according to the present invention comprises: the elastomerics that contains unsaturated C-C in its molecular structure; Hysteresis reduction amount have a formula B-A-S
xThe compound of-N, for example elastomeric approximately 0.1 to about 30 % by weight; The filler that comprises the surface group of the B part that can be bonded to this compound; And vulcanizing agent.Vulcanizing agent means to be generally used for the sulfuration bag (package) that contains sulphur and promotor in sulphur-compositions of vulcanize rubbers.Filler is carbon black or carbon black and the mixture of other filler with the surface group that can be combined with the B of compound part.In an example, with B-A-S
x-N compound joins in the master batch that contains elastomerics and filler.In another example, as mentioned above, B-A-S
x-N compound can with the elastomerics pre-reaction to form modified elastomer.In a further example, B-A-S
x-N compound can by refining again stage or final mix stages with its adding with elastomerics and filler reaction.
Thereby the method for making vulcanized elastomer composition can comprise the following step: (a) be mixed together following material: (i) contain the elastomerics of unsaturated C-C in its molecular structure, (ii) have formula B-A-S
xThe compound of-N (iii) comprises the filler of the surface group of the B part that can be bonded to compound, and (iv) vulcanizing agent; And (b) sulfuration said composition.
The method of making vulcanized elastomer composition can comprise the following step: (a) be mixed together following material: (i) elastomerics by in its molecular structure, having unsaturated C-C with have formula B-A-S
xThe modified elastomer that the compound of-N reacts to prepare (ii) comprises the filler of the surface group of the B part that can be bonded to compound, and (iii) vulcanizing agent; And (b) sulfuration said composition.
React after the two all occurs at S-polymkeric substance and B-filler, resulting Vulcanizable elastor composition comprises following material: (a) (i) has the elastomerics of unsaturated C-C in its molecular structure, (ii) has formula B-A-S
xThe compound of-N, and (iii) comprise the reaction product of filler of the surface group of the B part that is bonded to this compound; And (b) vulcanizing agent.
Can be in the tread mix mixing material, utilize multipolymer or the terpolymer of conjugated diolefin polymer or conjugate diene monomer and mono vinyl aromatic monomer with 100 parts of rubber, or their the tread rubber blend that comprises natural rubber, synthetic rubber and its blend that can use with any tradition.Such rubber is that those skilled in the art are well-known, and it includes, but are not limited to paracril, silicon rubber, fluoroelastomer, ethylene, propylene acids rubber, vinyl-vinyl acetate copolymer, epichloro hydrin rubber, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, hydrogenated nitrile-butadiene rubber, tetrafluoroethylene-propylene rubber etc.When Vulcanizable elastor composition of the present invention and traditional blend rubber, amount can approximately 10 % by weight to 20 % by weight that comprise total rubber than changing widely under the lower bound.Minimum will mainly depend on required physical properties.
Vulcanizable elastor composition can with the mixture compounding of reinforced filling such as carbon black or carbon black and other filler.Can use any type of carbon black.Carbon black can exist from about 0phr to the about amount of 100phr with scope.In addition, carbon black can be with approximately 5 to approximately 80phr compounding, in addition, can use from approximately 20 to the about amount of 70phr.Carbon black can comprise that the carbon black of common available commercial production is any.For example, can also use and have surface-area and be at least about 20m
2/ g is to as high as 200m
2The carbon black of/g in addition, has surface-area and is at least about 35m
2/ g is to as high as 200m
2The carbon black of/g.Surface area values is those that measure by the ASTM test D-1765 that uses cetyl trimethylammonium bromide (CTAB) technology.
In the available carbon black, furnace black, channel black and dim are arranged.More specifically, the example of carbon black comprise that super wear-resisting stove (SAF) is black, high abrasion stove (HAF) black, extrude soon black, the thin stove (FF) of stove (FEF) black, in super wear-resisting stove (ISAF) black, partly strengthen that stove (SRF) is black, MPC medium processing channel black, hard processing channel black and conductive channel black.Operable other carbon black comprises acetylene black.The typical carbon black that uses comprises N110, N121, N220, N231, N242, N293, N299, N326, N330, N332, N339, N343, N347, N351, N358, N375, N472, N539, N472, N539, N550, N660, N683, N754 and N765.Also can use oxygenated black.Carbon black can be by any suitable conventional art oxidation, as passing through ozone, dichromate or oxidizing acid oxidation.For example, can use and utilize nitrogenous oxidizing acid or the carbon black of ozone oxidation.The appropriate means example of producing oxygenated black is disclosed in US3,914,148; In 4,075,140 and 4,075,157, it is incorporated herein with for referencial use.Depend on the specific end use of compound, can select suitable carbon black.When preparation product of the present invention, can use the mixture of two or more above-mentioned carbon blacks.Used carbon black can be with granular form or the flocculation agent material of granulation not in preparation filled vulcanizate of the present invention.Can use the carbon black of not granulation to help to reach even mixing.
Vulcanizable elastic composition can also contain extra processing additives and traditional rubber accelerator, comprise for example extra filler, softening agent, antioxidant, promoting agent, scorch retarder, promotor, pigment, vulcanizing agent, processing additives such as oil and resin, comprise tackifying resin, pigment, lipid acid, zinc oxide, wax, antioxidant, antiozonidate and peptizer.As known to the those skilled in the art, depend on the desired use of the vulcanizable and material (rubber) that sulphur has vulcanized of sulphur, select above-mentioned additive and generally use with traditional amount Application standard rubber mix equipment and operation.Such elastic composition shows the hysteresis that reduces when using traditional vulcanization of rubber condition sulfuration, it means to have the increase resilience when standing mechanical stress, the product of the rolling resistance of reduction and the heat generation that reduces.Prediction comprises the product of tire, transmission belt etc.Certainly, the rolling resistance of reduction is useful character for meridian line style and oblique cord fabric type pneumatic tyre, thereby can use Vulcanizable elastor composition of the present invention to be formed for the tread mix of such tire.Can be according to being disclosed in US5,866,171,5,876,527,5,931,211 and 5,971,046 structure is made pneumatic tyre, and it openly is incorporated herein with for referencial use.Can also use said composition to form other elastic tyre parts such as base portion glue, sidewall rubber, carcass squeegee (body plyskims), gum filler etc.
Thereby, but example comprises the vulcanized rubber of above-mentioned vulcanizate compositions, with the tire of at least one parts that comprises the Containing Sulfur elastic composition, filler, the vulcanizing agent of the mixture that this vulcanized elastomer composition is included in the elastomerics that has unsaturated C-C in its molecular structure, comprise carbon black or carbon black and other filler and have formula B-A-S
xThe reaction product of the compound of-N.For example, tyre element can be tire tread.
If use, the typical amount of tackifier resins comprises approximately 0.5 to about 10phr, usually approximately 1 to about 5phr.The typical amount of compounding auxiliary agent comprises approximately 1 to 50phr.Such compounding auxiliary agent can comprise, for example aromatics, cycloalkanes and/or the paraffinic treated oil.
The representative of anti degradant that can be in rubber combination comprises the amine of monohydric phenol, bis-phenol, thiobisphenol, polyphenol, hydroquinone derivatives, phosphoric acid ester, phosphoric acid ester blend, monothioester, naphthylamines, bis-phenol amine (diphenol amines) and other Diaromatic amine derivatives, Ursol D, quinoline and blend.Anti degradant is usually with the approximately extremely approximately amount of 10phr use of 0.1phr of scope.In addition, anti degradant can use in the scope of about 0.5phr to 6phr.For example, the amount of typical antioxidant comprises approximately 0.1 to about 5phr.Representational antioxidant can be for example diphenyl-para-phenylene diamine and other antioxidant, as is disclosed in Vanderbilt Rubber Handbook (1978), those of 344 to 366 pages.The amount of typical antiozonidate can comprise approximately 0.1phr to about 5phr.
If use, the typical amount of lipid acid that can comprise the mixture of stearic acid, palmitinic acid, linolic acid or one or more lipid acid can comprise approximately 0.5 to about 3phr.The amount of typical wax comprises approximately 1 to about 2phr.Usually use Microcrystalline Wax.If use, the typical amount of peptizer comprises approximately 0.1 to about 1phr.For example, typical peptizer can be pentachlorophenol and dibenzamidodiphenyl disulfide.For example, can use pentachlorophenol with the amount of about 0.1phr to 0.4phr.In addition, pentachlorophenol can be from approximately using in 0.2 to 0.3phr the scope.
The representative that can be used for the treated oil of rubber combination of the present invention comprises aliphatic series-cycloalkanes aromatic resin, polyoxyethylene glycol, petroleum oil, ester plasticizer, vulcanized vegetable oil, Stockholm tar, resol, petroleum resin, polyester and resin.These treated oils can use take scope as about 0 to about 50phr conventional amounts.In addition, this process oil can approximately use in 5 to 25phr the scope.
Those skilled in the art easily understand, rubber combination should by in the rubber compounding field usually known method come compounding, but as the additive material of various sulfide polymers and various common uses such as vulcanizing agent, activator, scorch retarder, promotor etc. are mixed.
The reinforced rubber mixing material can be in a conventional manner vulcanizes with known vulcanizing agent such as sulphur and promotor.Do not affect curing time according to polymer modification of the present invention and filler combination, thereby the rubber compounding material can vulcanize the time of conventional amounts.When using vulcanizing agent, the amount of employed this reagent is 0.1 to 5 weight part, based on 100 parts by weight of rubber materials.In addition, the amount of employed vulcanizing agent can be 0.1 to 3 weight part, based on 100 parts by weight of rubber materials, and, in addition, can use from about 0.1phr to the about scope of 2phr.Vulcanizing agent can be used alone or in combination.For purpose of the present invention, sulfuration or crosslinked polymkeric substance will refer to vulcanized rubber.For general disclosed suitable vulcanizing agent, can be with reference to Kirk-Othmer,
Encyclopedia of ChemicalTechnology, 3rd ed., Wiley Interscience, N.Y.1982, Vol.20, pp.365-468, especially " Vulcanization Agents and AuxiliaryMaterials, " pp.390-402.
Zinc oxide and stearic acid are generally used for vulcanized elastomer.Zinc oxide is usually take scope as using from about traditional amount of 0.5 to about 5phr.Stearic acid is usually take scope as using from about traditional amount of 1 to about 4phr.
In the presence of the sulfur vulcanization agent, vulcanize.The example of suitable sulfur vulcanization agent comprises " rubber special-purpose " (rubbermaker ' s) solubility sulphur; Sulphur gives vulcanizing agent (sulfurdonating vulcanizing agents) such as curing amine, the many sulphur of polymerization or sulphur olefin adducts; With insoluble polymerised sulphur.The sulfur vulcanization agent can be the mixture of solubility and insoluble polymerised sulphur.The sulfur vulcanization agent can be used take scope as about 0.1 to about 10phr amount.In addition, the sulfur vulcanization agent can be take scope as using from about 1.5 to about 5phr amount, and in addition, the sulfur vulcanization agent can be in about 1.5 to about 3.5phr scope.
Promotor being used for controlled required time of sulfuration and/or the character of temperature and raising vulcanized rubber.Be used for vulcanization accelerator of the present invention without particular limitation of.The representative of traditional promotor comprises amine, guanidine, thiocarbamide, mercaptan, thiuram, sulphenamide, dithiocarbamate(s) and xanthan acids.Extra example comprises thiazoles vulcanization accelerator such as 2-mercaptobenzothiazole, benzothiazyl disulfide, N cyclohexyl 2 benzothiazole sulfenamide (CBS), uncle N--2-[4-morpholinodithio sulphenamide (TBBS) etc.; With guanidine vulcanization accelerator such as vulkacit D (DPG) etc.Used vulcanization accelerator can be approximately 0.1 to about 10phr.In addition, vulcanization accelerator can be take scope as from approximately 0.1 to about 5phr or approximately 0.2 adding to the about amount of 3phr.
Vulcanizable elastor composition of the present invention can be by obtaining with the physical properties of the gained mixing material that reaches expectation with mixing these components under time enough and sufficiently high temperature such as mixing facilities such as mill, Banbury mixer etc.The mixing of vulcanizable elastic composition can be by finishing in the rubber mix field known method of those of skill in the art.For example can be with these compositions mixing more than two stages, by " master batch " stage at least (comprising mixing of elastomerics and at least a portion carbon black and/or silicon-dioxide and other composition); " terminal stage " consists of, and generally vulcanizing agent added in " terminal stage ".Also may exist wherein in the situation that do not add the mix stages that composition refines this mixture again.Can add the B-A-Sx-N compound in any stage of hybrid technique.
Mixing temperature can from a stage to another phase change.Yet, with regard to purpose of the present invention, B-A-S
x-N compound, elastomerics and filler can approximately 60 ℃ to approximately mixing under 200 ℃ the mixing temperature.In addition, elastomerics and filler can be at approximately 90 ℃ to approximately 190 ℃, and other approximately 120 ℃ to approximately mixing under 180 ℃ the mixing temperature.In an example, part filler and/or B-A-S
x-N compound can join in the elastomerics in masterbatch stage, and residuum is in again refining stage adding.
Embodiment
The B-A-S of the following examples illustrated example
x-N compound and the preparation that contains the elastic composition of this compound.These embodiment also are not intended to limit, because can use other method of this compound of preparation and rubber combination and different rubber compounding compositions under the scope of the claim that does not break away from the following stated.
Embodiment A
Synthesizing of two-[2-(2-oxane base)-phenyl]-disulphide (2OPD)
20g 2,2 ' in 28.6mL thionyl chloride (390mmol)-dithio-two-(phenylformic acid) mixture (65mmol) was refluxed 12 hours, then filter.Use rotatory evaporator dry filtrate, collect 15.0g 2,2 '-dithio-two-(Benzoyl chloride) powder (44mmol).The productive rate of this reaction is 68%.
Then with 2,2 '-dithio-two-(Benzoyl chloride) sneak in the 300mL chloroform.In this mixture, under agitation drip the solution that is included in the 10.7g 2-monoethanolamine (175mmol) in the 200mL chloroform that remains under 0 ℃.After finishing adding, the gained mixture 25 ℃ of lower stirrings 2 hours, is formed precipitation during this period.Then, will precipitate and collect after filtration and use the 200mL water washing.Then, will precipitate drying, produce light brown powder.Collect 13.5g 2,2 '-dithio-two-[N-(hydroxyethyl)-benzamide] and (34mmol), provide 77% productive rate.
Then, 15mL thionyl chloride (204mmol) under agitation is added dropwise to 2,2 '-dithio-two-[N-(hydroxyethyl)-benzamide] powder in.This mixture is poured in the 150mL ether, formed white precipitate.Then with sedimentation and filtration and be dissolved in the water.The precipitation that then will dissolve is with cold 20% sodium hydroxide neutralization and use chloroform extraction.With the dry hexane recrystallization of also using of chloroform extract.Collect 7g pair-[2-(2-oxazolinyl)-phenyl]-disulphide (20mmol), 59% productive rate is provided.Should synthetic overall yield be 15%.
Embodiment B
In order to determine 2OPD for the impact of rubber hysteresis property, preparation contains four kinds of rubber compounding compositions of solution S BR, carbon black and other typical compounding composition.As shown in table 1, preparation reference composition (C1), two kinds contain the composition (E1 and E2) of 2OPD and contain the known commercially available additive that in natural rubber, reduce to lag behind (
1162, can obtain from Sumitomo Chemical Company) comparative composition (C2).
Table 1 compounding prescription
aphr
bSolution S BR35% vinylbenzene, 19% vinyl, 20phr aromatic oil;
cN399
dN-(1,3-dimethylbutyl)-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine (antioxidant)
e4mmol
f8mmol
g8mmol
hVulkacit D (DPG)
iUncle N--2-[4-morpholinodithio sulphenamide (TBBS)
In order to measure the character of composition in the table 1, carry out a plurality of tests, comprise mooney viscosity; Tensile property and the strain that comprises tan delta (tan δ), out-of-phase modulus (G ') and Payne effect (△ G ').Test-results is shown in table 2.The measurement of mooney viscosity (measurement before taking off fire) is carried out with ectotrochanter under 130 ℃, when rotor has rotated 4 minutes with the form record of moment of torsion.Before rotor starting, with sample 130 ℃ of lower preheatings 1 minute.Use the standard program described in the ASTM-D412 to measure the tensile property of vulcanized rubber room temperature and 100 ℃ are lower.The tension test sample is the ring with diameter 1.3mm and thickness 1.9mm.The measurement length of 25.4mm is used for calculating tensile property.Whether reduce in order to measure hysteresis, under 50 ℃ and 15Hz, use the ARES-A rheometer to measure at the tan δ under 5% strain and G ' and the △ G ' under 0.1 to 20% strain.Tan δ and G ' also can measure (value of 25 ℃, 50 ℃ and 75 ℃ is shown in table 2) during thermograde (temperature ramp) under 2% constant strain and the 15Hz.
Table 2: the comparison of composition character
Tan δ is the measuring of ratio of the modulus lost of composition and storage modulus, has found at the numerical value of 50 ℃ of lower tan δ lowlyer, and the hysteresis of composition is lower.As finding out by the value that is shown in table 2, compare with the C2 composition with C1, show the Mooney viscosity value that reduces, approximate ring tension values (under room temperature and 100 ℃) and the hysteresis (hanging down tan δ) that reduces with the rubber of 2OPD compounding.The mooney viscosity that increases represents the processibility that can improve.Represent that to the approximate ring tension values of the rubber of 2OPD compounding composition has similar physical strength.The rolling resistance that improves in the tire tread by these composition manufacturings at tan δ value representation lower under 50 ℃ with the rubber of 2OPD compounding.
In a word, with exemplary B-A-S
x-N compound 2OPD joins the hysteresis that brings reduction in the rubber combination, and it is illustrated in and uses B-A-S
xThe rolling resistance that improves in the tire tread of-N compound manufacturing.
This written explanation uses embodiment with open the present invention, comprises best mode, also makes those skilled in the art can carry out and use the present invention.The patentable scope of the present invention is limited by claims, and can comprise other embodiment that those skilled in the art expect.If they have not different from the word language of claims key elements, if perhaps they comprise and the not obvious different key elements that are equal to of the word language of claims, other embodiment like this, it can obtain before the applying date or after the applying date in the application, means in the scope of claims.
Claims (36)
1. one kind has formula B-A-S
xThe compound of-N, wherein:
B is the nitrogen heterocyclic part that contains aerobic or sulphur;
S
xBe polysulfide, wherein x is 2 to 10;
A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With
N is-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl.
2. one kind has formula B-A-S
xThe compound of-N, wherein,
B is the nitrogen heterocyclic part that contains aerobic or sulphur;
S
xBe polysulfide, wherein x is 2 to 10;
A be [A '-(Z-A ")
k], wherein A ' and A " are the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; Z is oxygen, sulphur or C=O; And k is 1 to 4;
N is-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl.
3. compound according to claim 1, wherein, S
xBe disulphide.
4. compound according to claim 1, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
5. one kind comprises for promoting filler to have a formula B-A-S what composition disperseed
xThe composition of the compound of-N, said composition are included in the polymkeric substance that contains unsaturated C-C in its molecular structure and have the filler of the surface group that reacts with B, and wherein this filler is the mixture of carbon black or carbon black and mineral filler; B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl.
6. one kind comprises for promoting filler to have a formula B-A-S what composition disperseed
xThe composition of the compound of-N, said composition are included in the polymkeric substance that contains unsaturated C-C in its molecular structure and have the filler of the surface group that reacts with B, and wherein this filler is the mixture of carbon black or carbon black and mineral filler; B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A be [A '-(Z-A ")
k], wherein A ' and A " are the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; Z is oxygen, sulphur or C=O; And k is 1 to 4; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl.
7. composition according to claim 5, wherein, S
xBe disulphide.
8. composition according to claim 5, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
9. composition according to claim 5, wherein, this mineral filler is talcum, kaolin, clay, metal oxide, aluminium hydrate, mica or its mixture.
10. polymer-modified preparation method, it comprises the polymkeric substance that will contain unsaturated C-C in its molecular structure and has formula B-A-S
xThe compound of-N contacts to form polymer-modified, and wherein, B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl.
11. method according to claim 10, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
12. one kind by method claimed in claim 10 produce polymer-modified.
13. a method that promotes that filler disperses in polymeric composition, it comprises the following step:
(a) with polymer modification, it comprises and will contain the polymkeric substance of unsaturated C-C and have formula B-A-S in its molecular structure
xThe compound of-N contacts to form polymer-modified, and wherein B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl; With
(b) the filler reaction of this polymer-modified surface group with comprising the B part that is bonded to this compound, wherein this filler is the mixture of carbon black or carbon black and mineral filler.
14. method according to claim 13 wherein, has formula B-A-S
xThe amount of the compound of-N is elastomeric 0.1 % by weight to 30 % by weight.
15. method according to claim 13, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
16. method according to claim 13, wherein, this mineral filler is talcum, kaolin, clay, metal oxide, aluminium hydrate, mica or its mixture.
17. a method that promotes that filler disperses in polymeric composition, it comprises and is mixed together following material: the polymkeric substance that (i) has unsaturated C-C in its molecular structure; (ii) has formula B-A-S
xThe compound of-N, wherein B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the group that partly forms for formula II of the described nitrogen heterocyclic that contains aerobic or sulphur:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl;
(iii) have the filler of the surface group of the B part that is bonded to this compound, wherein this filler is the mixture of carbon black or carbon black and mineral filler.
18. method according to claim 17 wherein, has formula B-A-S
xThe amount of the compound of-N is elastomeric 0.1 % by weight to 30 % by weight.
19. method according to claim 17, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
20. method according to claim 17, wherein, this mineral filler is talcum, kaolin, clay, metal oxide, aluminium hydrate, mica or its mixture.
21. but a vulcanizate compositions, it comprises:
(a) in its molecular structure, contain the elastomerics of unsaturated C-C;
(b) hysteresis reduction amount has a formula B-A-S
xThe compound of-N, wherein B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl;
(c) comprise the filler of the surface group of the B part that is bonded to this compound, wherein this filler is the mixture of carbon black or carbon black and mineral filler; With
(d) vulcanizing agent.
22. composition according to claim 21 wherein, has formula B-A-S
xThe hysteresis reduction amount of the compound of-N is elastomeric 0.1 % by weight to 30 % by weight.
23. composition according to claim 21, wherein, this elastomerics is the homopolymer of conjugate diene monomer or multipolymer or the terpolymer of conjugate diene monomer and mono vinyl aromatic monomer or triolefin.
24. composition according to claim 21, wherein, this elastomerics is the terpolymer of natural rubber, synthetic polyisoprenes, polyhutadiene, polystyrene, styrene-butadiene copolymer, isoprene-butadiene multipolymer, isoprene-styrol copolymer, styrene-isoprene-butadiene terpolymer, paracril, acrylonitrile-butadiene-styrene (ABS), with and the combination.
25. composition according to claim 21, wherein, this compound is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
26. composition according to claim 21, wherein, this mineral filler is talcum, kaolin, clay, metal oxide, aluminium hydrate, mica or its mixture.
27. composition according to claim 21, wherein, this vulcanizing agent is sulphur.
28. a tire, it comprises and contains at least one parts that right requires 21 described compositions.
29. tire according to claim 28, wherein, these parts are tire tread.
30. a method of making vulcanized elastomer composition, it comprises:
(a) be mixed together following material: the elastomerics that (i) in its molecular structure, contains unsaturated C-C; (ii) has formula B-A-S
xThe compound of-N, wherein B is the nitrogen heterocyclic part that contains aerobic or sulphur; S
xBe polysulfide, wherein x is 2 to 10; A is for forming B and S
xBetween the linking group of bridged bond, it is the C of side chain or straight chain
6-C
20The C of arylidene part or side chain or straight chain
7-C
20The alkyl arylene part; With N be-A-B;
Wherein, the described nitrogen heterocyclic that contains aerobic or sulphur partly is formula II:
Wherein X is oxygen or sulphur; R
1, R
2, R
3, R
4And R
5Each be the C of hydrogen, side chain or straight chain independently
1-C
20Alkyl;
(iii) comprise the filler of the surface group of the B part that is bonded to this compound, wherein this filler is the mixture of carbon black or carbon black and mineral filler; (iv) vulcanizing agent; And
(b) sulfuration said composition.
31. method according to claim 30 wherein, has formula B-A-S
xThe compound of-N is elastomeric 0.1 % by weight to 30 % by weight.
32. method according to claim 30, wherein, this elastomerics is the homopolymer of conjugate diene monomer or multipolymer or the terpolymer of conjugate diene monomer and mono vinyl aromatic monomer or triolefin.
33. method according to claim 30, wherein, this elastomerics is terpolymer, the paracril of natural rubber, synthetic polyisoprenes, polyhutadiene, polystyrene, styrene-butadiene copolymer, isoprene-butadiene multipolymer, isoprene-styrol copolymer, styrene-isoprene-divinyl, the terpolymer of acrylonitrile-butadiene-styrene (ABS), with and combination.
34. method according to claim 30, wherein, this has formula B-A-S
xThe compound of-N is two-[2-(2-oxazolinyl)-phenyl]-disulphide.
35. method according to claim 30, wherein, this mineral filler is talcum, kaolin, clay, metal oxide, aluminium hydrate, mica or its mixture.
36. method according to claim 30, wherein, this vulcanizing agent is sulphur.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091449A (en) * | 1990-08-02 | 1992-02-25 | The Goodyear Tire & Rubber Company | Alpha-(2,4-dihydroxy)phenyl N-phenyl nitrone and its use in the modification of diene containing polymers |
| US5821290A (en) * | 1995-10-04 | 1998-10-13 | Compagnie Generale des Etablissements Micheline--Michelin & Cie | Silylated rubber diene polymer containing organosilane |
-
2007
- 2007-04-28 CN CN 200710097690 patent/CN101293874B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091449A (en) * | 1990-08-02 | 1992-02-25 | The Goodyear Tire & Rubber Company | Alpha-(2,4-dihydroxy)phenyl N-phenyl nitrone and its use in the modification of diene containing polymers |
| US5821290A (en) * | 1995-10-04 | 1998-10-13 | Compagnie Generale des Etablissements Micheline--Michelin & Cie | Silylated rubber diene polymer containing organosilane |
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