CN101522778A - Particle-matrix composition coated with mixture comprising polysulfide polymer - Google Patents

Particle-matrix composition coated with mixture comprising polysulfide polymer Download PDF

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CN101522778A
CN101522778A CNA2007800373062A CN200780037306A CN101522778A CN 101522778 A CN101522778 A CN 101522778A CN A2007800373062 A CNA2007800373062 A CN A2007800373062A CN 200780037306 A CN200780037306 A CN 200780037306A CN 101522778 A CN101522778 A CN 101522778A
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composition
particle
group
sulphur
carbon atom
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S·C·J·皮埃克
R·N·达塔
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Teijin Aramid BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention pertains to a composition comprising a particle and a matrix, wherein the particle is at least partially coated with a compound or a mixture of compounds comprising at least one of a) a polysulfide polymer and a curing system; and b) a cured polysulfide polymer obtained from a polysulfide polymer having at least two epoxy end groups. Most preferred polysulfide polymers are: formula (I), (II), (III) and formula (IV) wherein n is independently 1-200 and R' is formula (V) wherein m is 0 to 10, R3 is independently H or CH3, and the end indicated with the double asterisk is bonded to the epoxide group. The invention further relates to particle-elastomers comprising said composition, and skim products, tires, tire treads, and belts comprising these particle-elastomers.

Description

Particle-matrix composition with the mixture coating that contains polysulfide polymer
The present invention relates to a kind of composition that comprises particle and matrix, wherein particle to small part is applied by the mixture of formulation, and relates to a kind of particle-elastic composition.The invention further relates to the clear product of the glue that comprises described particle-elastic composition, tire, tyre surface and belt (belt).
In tire and belt industry, except other performances, also need better mechanical property, long-pending thermal characteristics and hysteretic properties.For a long time with regard to the known mechanical property that can improve rubber by the cross-linking density that uses a large amount of sulphur to increase vulcanized rubber as linking agent.Use a large amount of sulphur to bring and produce big calorimetric shortcoming, can significantly reduce the thermotolerance and the warping strength cracking of the finished product thus by it.In order to eliminate above-mentioned shortcoming, proposed in sulphur-vulcanization system to add the chopped strand handled, by the pellet of its manufacturing or the pellet of handling, particularly by polysulphide, Bunte salt and sulphuring treatment.These pellets contain wax in addition to improve processing.
In JP 66008866, disclose and used the adhesion promotor of sulfuration benzothiazole as tynex.But, this method can not provide have low crack expansibility, low modulus loss and hang down tire and the belt of tg δ.In JP 56129280, JP 60072928, JP 60072929 and JP 60072972, polysulfide polymer is applied as the part of binding system, thereby fiber such as polyester and Kevlar are bonded in rubber.These methods none can provide have low crack expansibility, low modulus loss and hang down tire and the belt of tg δ.
In WO 2006/087161, use polysulphide, sulphur and Bunte salt to handle fiber, and it is sneaked in the rubber.The document has been described with sulphur and has been used the polysulphide monomer, and this composition is as the curing system of Bunte salt.The present invention relates to polysulfide polymer rather than Bunte salt.
At US 3,673, in 150, use Thiokol A impregnated glass fiber, described Thiokol A is the polymkeric substance that obtains from sodium tetrasulfide and ethylene dichloride, molecular formula is (CH 2CH 2S 4) n, and it does not contain epoxide group.If regard Thiokol A as according to polysulfide polymer of the present invention, then US 3,673,150 composition lacks curing system.If regard Thiokol A as solidifying agent, then it is to utilize two or more a plurality of sulphur atom to come the solidifying agent of cross-linked polyolefin chain, but it can not solidify Thiokol A itself.Therefore Thiokol A is not the curing system of polysulfide polymer, and depends on the definition of Thiokol A, it or polysulfide polymer or curing system, but can not be the two simultaneously.
The pellet of waxing itself is known in the art.For example, for example wax coating aromatic poly pellet of use polymeric component is disclosed in EP 0 889 072.Yet the polysulfide polymer that does not use the content of wax applies these pellets.
At US 6,068, disclose a kind of pellet in 922, but it comprises Kevlar and extruded polymer, for example polyethylene, polypropylene or polymeric amide.These fibers can be coated with typical tackiness agent (RF, Resins, epoxy, siloxanes), do not apply but mention polysulfide polymer.
The invention provides and a kind ofly use the novel treated particle of a class such as chopped strand, staple fibre, slurry or powder to solve the scheme of the problems referred to above on by sulfur vulcanization at rubber, and a kind of particle and pellet thereof be provided, it has solved the hysteresis quality in the long-standing reduction rubber combination and the problem of heat generation.
For this reason, the present invention relates to a kind of composition that comprises particle and matrix, wherein particle is applied by the mixture of formulation or formulation to small part, and this formulation comprises in the following component at least a:
A) polysulfide polymer and curing system; With
B) from having the solidified polysulfide polymer that at least two epoxy-terminated polysulfide polymers obtain.
More preferably, said composition comprises the linearity with formula A-B-C or the polysulfide polymer compound of branching, and wherein B is the structure division that comprises the repeating unit of 1-200 following formula independently:
-[X-R 2-X-R 1-S x]-
Wherein
X is CH independently 2, S or O;
X is 2,3 or 4;
R 1And R 2Be independently selected from and replace or the arylidene of alkylidene group, replacement or the unsubstituted 6-10 of a having carbon atom of the unsubstituted 1-10 of a having carbon atom, have the alkylene oxide group of 1-5 carbon atom and have the alkyleneoxyalkylene group of 2-10 carbon atom; Wherein substituting group is the structure division that comprises the repeating unit of 1-200 following formula independently:
D-[X-R 2-X-R 1-S x]-E
Wherein X, R 1, R 2Has previous given implication with x;
Perhaps X, R 1And R 2Be key independently, condition is X-R 2-X-R 1Structure division contains at least two atoms;
A and C are independently selected from hydrogen and contain group at least a in halogen, epoxy group(ing), hydroxyl, isocyanate group, silyl and the vinyl; With
D and one of E have the implication identical with A for key and another.
This compound can have the molecular structure of substantially linear, but also can have the linear structure of part branching.In following formula, if R 1And/or R 2The alkylidene group with 1-10 carbon atom of implication for replacing, or the arylidene with 6-10 carbon atom of replacement, substituting group is to comprise 1-200 formula D-[X-R independently 2-X-R 1S xThe structure division of the repeating unit of]-E, and the radicals R in described repeating unit 1And R 2Be independently selected from alkylidene group, arylidene, have the alkylene oxide group of 1-5 carbon atom and have the alkyleneoxyalkylene group of 2-10 carbon atom with 6-10 carbon atom with 1-10 carbon atom.
X is preferably selected from S and O.The alkylidene group that can give an example is methylene radical, ethylidene, propylidene, isopropylidene, butylidene (class), isobutylidene, inferior neo-pentyl, hexylidene etc.The arylene group that can give an example is phenylene, benzylidene or methyl benzylidene etc., and X-R 2-X-R 1-part can be the alkyleneoxyalkylene group group, and as methylene oxygen methylene, inferior ethoxyl ethylidene, inferior methoxyl group inferior ethoxyl, inferior ethoxyl inferior ethoxyl and inferior propoxy-propylidene etc., wherein oxygen can be substituted by sulphur.For example concrete example can be expressed from the next:
-CH 2OCH 2OCH 2-；-C 2H 4OCH 2OC 2H 4-；-C 2H 4OC 2H 4OC 2H 4-；
-C 3H 6OCH 2OC 3H 6-；-C 2H 4OC 2H 4OC 2H 4OC 2H 4-；-CH 2SCH 2SCH 2-；
-C 2H 4SCH 2SC 2H 4-；-C 2H 4SCH 2SC 2H 4-；-C 2H 4OC 2H 4SC 2H 4OC 2H 4-。
Most preferred divalent organic group X-R 2-X-R 1-be the group that is expressed from the next :-C 2H 4OCH 2OC 2H 4-.
Above-mentioned divalent organic group can be by comprising 1-200 following formula independently the substituent branched of repeating unit:
D-[X-R 2-X-R 1-S x]-E，
Wherein X, R 1, R 2Has previous given implication with x.
The example of reactive terminal group A and C (and/or D and E) includes but not limited to glycidyl ether, vinyl triethoxyl silicomethane and (3-glycidyl oxygen base propyl group) trimethoxy silicomethane of Epicholorohydrin, dihydroxyphenyl propane.Most preferably group A and C are the reaction product of the glycidyl ether of H, glycidyl and polysulfide polymer (wherein A or C are H) and reactive compounds dihydroxyphenyl propane or F.Slight branching and nonbranched polysulfide polymer with 5-38 repeating unit can be with trade(brand)name Thioplast on market TMG,
Figure A200780037306D00091
Thioplast TMEPS and
Figure A200780037306D00092
ELP has bought.
Wherein most preferred polysulfide polymer is the polymkeric substance of commercially available following structure:
Figure A200780037306D00093
(formula I)
Figure A200780037306D00094
(formula II)
Figure A200780037306D00095
(formula III)
With
Figure A200780037306D00096
(formula IV)
Wherein n for 1-200 and R ' is independently
Figure A200780037306D00101
Wherein m is 0-10, R 3Be H or CH independently 3, and be incorporated into epoxide group with the end that double asterisk is represented.
For similar compounds, many different curing systems have been described, the 39-45 page or leaf in the Journal of Applied Polymer Science of the 4th phase of volume nineteen fifty-nine the 2nd and at Topics in Sulfur Chemistry for example, the 3rd volume is in the 26th page.Curing system includes but not limited to the combination of plumbous oxide (IV), oxidation Mn (IV), pf resin of low molecular weight, vulcabond and polyisocyanates, diepoxide and polyepoxide, dicumyl peroxide, cumene hydroperoxide, calcium peroxide, zinc peroxide, sodium perborate, sodium periodate, iodine, peroxy-disulfuric acid tetrabutylammonium, paraquinonedioxime and sulphur and polysulphide.Preferred curing system is the combination of the polysulphide (C) of sulphur and following formula:
Figure A200780037306D00102
N=2-6 wherein;
R is independently selected from hydrogen, halogen, nitro, hydroxyl, C 1-C 12Alkyl, C 1-C 12Alkoxyl group and C 7-C 12Aralkyl.
For band glycidyl functional group's polysulfide polymer, can select any epoxy curing systems known in the art.The example of solidifying agent includes but not limited to polyvalent alcohol such as polyvinyl alcohol and polyether glycol, multi-anhydride, polycarboxylic acid, polyisocyanates and primary amine.In some cases, need other catalyzer to be cured.In addition, the polysulfide polymer itself that has at least two glycidyls can solidify, and does not need to add curing system.Term has at least two epoxy-terminated " solidified " polysulfide polymers and is meant that having at least two epoxy-terminated polysulfide polymer molecules is connected in other by its glycidyl to small part and has at least two epoxy-terminated polysulfide polymer molecules.
In preferred embodiments, the present invention relates to have the composition that comprises particle and matrix of enhanced rubber performance in elastomerics.Matrix can be wax or polymkeric substance.Said composition contains the matrix of 85wt% at the most, preferred wax based on the weight of composition.The example of suitable wax is for having senior alkyl chain such as C 22-C 38The Microcrystalline Wax of alkyl chain, paraffin or long alkyl chain fatty acid wax are as C 12-C 40Alkanoic acid.Except wax, but matrix also can be selected from extruded polymer.Useful especially for example is polyethylene, polypropylene or polymeric amide, but or the mixture of these extruded polymers and wax.But extruded polymer can be modification or unmodified polymkeric substance and multipolymer.
The composition that comprises coated particle can be the form of particle itself, perhaps can be compressed into pellet by traditional method.Perhaps, particle can be contained in the matrix and be configured as pellet, for example by particle-matrix composition is cut into pellet.
Pellet can be protected and contain according to any particle of the present invention.Preferred particle is selected from aromatic poly, polyester, polymeric amide, Mierocrystalline cellulose, glass and carbon.Particle can be any form, as chopped strand, staple fibre, slurry, fibril, fine strip body, bead, powder etc.Preferred aramid fiber (it comprises chopped strand, staple fibre and slurry) and powder, more particularly poly-(poly P phenylene diamine terephthalamide) particle or (poly P phenylene diamine terephthalamide/paraphenylene terephthalamide 3,4 '-oxygen diphenylene diamines) multipolymer (co-poly-(and paraphenylene/3,4 '-oxydiphenylene terephthalamide) particle.Most preferably chopped strand, staple fibre and powder.Powder and bead have additional advantage, and promptly they need not the spinning step and can directly be obtained by polymkeric substance.
Term " pellet " except pellet, comprises the term of synonym or tight association, as sheet, piece, ingot, granule etc.Pellet can be made by any particle, comprise chopped fibres (shot cut fiber), chopped strand (chopped fiber), staple fibre, slurry, fibril, fine strip body, bead and powder, but by with these particles and wax and/or extruded polymer matrix and to apply chemical mixed.
For example, pellet can be according to the method preparation of describing among the WO 0058064.Perhaps, can directly use chopped strand or powder etc., wax, polysulfide polymer and non-essential polysulphide curing system to prepare pellet.But with particle and wax and/or extruding polymerization matrix and optional solidifying agent and other chemical intense mixing, and optionally heating to the melting temperature of wax or extruded polymer or more than.Mixture forms grain or sheet under the temperature of the fusing point that is lower than wax or extruded polymer then.Based on the weight of composition, the consumption of wax (but and/or extruded polymer) can be 85wt% at the most.Perhaps, pellet also can be made by the mixture of particle and matrix, adds polysulfide polymer and curing system then; Thereby and/or interpolation solidified polysulfide polymer applies the particle that is contained in the pellet to small part.
To the processing of its composition based on above-mentioned polysulfide polymer and polysulfide sulfur chemicals, preferred Thiokol LP, 2-sulfydryl-benzothiazole disulphide, described chemical further contain sulphur or sulphur donor.Composition of the present invention also can contain as the wax of carrier to be processed to improve.The example of suitable wax is for having senior alkyl chain such as C 22-C 38The Microcrystalline Wax of alkyl chain, paraffin or long alkyl chain fatty acid wax are as C 12-C 40Alkanoic acid.After processing, said composition can directly be used or can be ground into suitable size, thereby is used for rubber compound suitably.After processing, fiber can be cut to suitable length to be used for rubber stock, maybe can be by above-mentioned chemical treatments chopped strand, can and comprise that maybe the above-mentioned chemical of wax mixes with chopped strand, optionally heating also forms the form of easy metering feed (well dosable).
Perhaps, can handle the particle that comprises fiber and powder based on the glycidyl functional polysulfide polymer that wherein no longer needs solidifying agent, or by its pellet that makes.
Based on the weight of composition, suitable coated weight is 0.5-50wt%, preferred 1-30wt%, more preferably 2-15wt%.
The processing of composition can be used polysulfide polymer, 2-mercaptobenzothiazole disulphide (MBTS) and sulphur, and for example the solution in the toluene or described chemical carry out in the dispersion in the toluene for example at suitable solvent.Can use other benzothiazole derivants to replace 2-mercaptobenzothiazole disulphide.
Can use polysulfide polymer, 2-mercaptobenzothiazole disulphide (MBTS) and sulphur suitable solvent for example the solution in the toluene or described chemical in toluene for example dispersion or use the pellet of the method preparation that the mixture of described chemical in suitable matrix such as stearic acid describe in handling according to WO 0058064.Based on the weight of composition, the consumption of matrix can be 85wt% at the most.
Can directly use aforesaid powder or chopped strand, wax and polysulfide polymer (A), 2-mercaptobenzothiazole disulphide (MBTS) and sulphur to prepare pellet.Preferred wax is a stearic acid.Based on the weight of composition, the consumption of wax can be 85wt% at the most.
Preferred coating comprises 10-98wt%, the more preferably polysulfide polymer of 50-95wt%, and 0.1-20wt%, the more preferably curing system of 0.5-10wt% and optional 0.01-10wt%, the more preferably sulphur of 0.2-2.5wt% is based on coating wt.The amount of sulphur is the amount of the sulphur that uses itself, or the sulfur content that produces during use sulphur donor.In composition, preferred stearic amount is 85wt% at the most, is preferably 45wt%-67wt%.
The implication of term " coating " is known for the technician and can be found in any relevant textbook.Therefore the particle that applies is the particle that contains coating material layer (coating) in its surface.Apply if particle is a part, then only the part of particle is covered by described layer.In principle, with particle coating and to make pellet or particle is made that pellet applies then be as broad as long.Application composition will permeate pellet fully and apply wherein each particle.Coating material or part coating material equally can be between the fibers of particle, or even between long filament and microfilament, permeate, thereby impregnated particles.Can heat-treat the composition that comprises polysulfide polymer with glycidyl end group.Preferably through 1-60 minute temperature heating combination at 80 ℃-200 ℃.More preferably through 5-25 minute temperature heating combination at 120 ℃-170 ℃.
On the other hand, the present invention relates to a kind of rubber combination, it is rubber, sulphur and optional sulphur donor and according to the vulcanization reaction product of composition of the present invention.Composition of the present invention is as modulus enhancement dose, intensity improving agent and weaken hysteresis.The sulfuration process that carries out in the presence of said composition is also disclosed simultaneously, and the application of these compositions in the sulphur-vulcanization reaction of rubber.
In addition, the present invention relates to the sulfuration process that in the presence of described composition, carries out and the application of these compositions in the sulphur-vulcanization reaction of rubber.In addition, the present invention also comprises the rubber product that contains at least some following rubber, and described rubber vulcanizes in the presence of described composition, preferably uses sulfur vulcanization.Similar with other but do not use the sulphur-vulcanization system of any described composition to compare, the invention provides excellent hysteresis behavior, and improved several rubber performances, and all the other performances are not had remarkable detrimentally affect.
The present invention is applicable to all natural rubbers and synthetic rubber.The example of this class rubber includes but not limited to natural rubber, styrene-butadiene rubber(SBR), divinyl rubber, synthetic polyisoprene, paracril, chloroprene rubber, isoprene isobutene rubber, bromination isoprene isobutene rubber, chlorination isoprene isobutene rubber, ethylene-propylene-diene trimer, with the combination of two or more above-mentioned rubber, and the combination of one or more these rubber and other rubber and/or thermoplastics.
Sulphur, optional and sulphur donor provide sulfur content required in the sulfuration process together.The example of operable sulphur comprises various types of sulphur in the sulfuration process, as powder sulphur, precipitated sulfur and insoluble sulphur.The example of sulphur donor is including, but not limited to tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, six sulfuration two (pentamethylene) thiurams, four sulfuration two (pentamethylene) thiurams, dithio morpholine and composition thereof.
The sulphur donor can replace or use together with sulphur.This paper term " sulphur " also should comprise the mixture of sulphur and sulphur donor.In addition, when the amount of with regard to the sulphur donor, mentioning the sulphur that uses in the sulfuration process, mean the sulphur donor amount of specifying sulfur content required of being equivalent to that provides.
More particularly, the present invention relates to a kind of sulphur-vulcanizate compositions, it comprises the vulcanization reaction product of following material: (a) at least a natural or synthetic rubber of 100 weight parts; (b) sulphur of 0.1-25 weight part or sulphur and/or sulphur donor are to provide the sulphur that is equivalent to the 0.1-25 weight part; (c) composition of the present invention of 0.1-20 weight part preferably comprises powder, chopped strand, staple fibre or by its pellet that makes.
Particle of the present invention is based on natural polymer and synthetic polymer.The example of this base polymer including, but not limited to aromatic poly as to aromatic poly, polymeric amide, polyester, Mierocrystalline cellulose such as artificial silk, glass and carbon, and two or more combination of these yarns.
Most preferably particle is poly-(poly P phenylene diamine terephthalamide) fiber, and it can trade(brand)name
Figure A200780037306D0014180700QIETU
Bought from the market, perhaps (poly P phenylene diamine terephthalamide/paraphenylene terephthalamide 3,4 '-oxygen diphenylene diamines) multipolymer, it can trade(brand)name Bought from the market.
Based on 100 parts rubber, be generally the 0.1-25 weight part with the amount of the sulphur of rubber compounding, more preferably the 0.2-8 weight part.With the amount of the sulphur donor of rubber compounding amount, the amount of the sulphur of equivalent in the time of promptly can providing and use sulphur itself for sulphur that a great deal of can be provided.Based on 100 parts rubber, with the amount of the composition of rubber compounding be the 0.1-25 weight part, more preferably 0.2-10.0 weight part, most preferably 0.5-5 weight part.These compositions can be used as Preblend and use, and perhaps add simultaneously or separately, and they also can add with other rubber compounding compositions.In most of the cases, also wish in the rubber compounding thing, to add vulcanization accelerator.Usually can use known vulcanization accelerator.Preferred vulcanization accelerator comprises: mercaptobenzothiazole, 2,2 '-mercaptobenzothiazole disulphide; Sulfinyl amine promotor comprises N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine, the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine, N, N-dicyclohexyl-2-[4-morpholinodithio sulfinyl amine and 2-(morpholinothio) benzothiazole; Thiophosphoric acid derivative promotor, thiurams, dithiocarbamate, vulkacit D, di-o-tolyl guanidine, two sulphur formamyl sulfinylamines, xanthogenate/ester class, triazines promotor and composition thereof.
If use vulcanization accelerator, then consumption is the 0.1-8 weight part, based on the rubber combination of 100 weight parts.More preferably, vulcanization accelerator accounts for the 0.3-4.0 weight part, based on the rubber of 100 weight parts.Other traditional rubber accelerators also can use according to their usual amounts.For example, can comprise toughener such as carbon black, silica, clay, chalk and other mineral fillers in the rubber combination, and the mixture of filler.Also can use other additives such as treated oil, tackifier, wax, antioxidant, antiozonidate, pigment, resin, softening agent, processing aid, ointment, compounding agent and such as the activator of stearic acid and zinc oxide according to traditional known quantity.The more full rubber accelerator that can use with the present invention is referring to W.Hofmann, " Rubber Technology Handbook ", the 4th chapter, RubberChemicals and Additives, the 217-353 page or leaf, Hanser Publishers, Munich 1989.
In addition, also can in rubber combination, use scorch retarder such as Tetra hydro Phthalic anhydride, PMA, mellitic acid three acid anhydrides, 4-methylphthalic acid acid anhydride, trimellitic acid 1,2-anhydride, 4-chloro-phthalic anhydride, N-cyclohexyl-sulfo-phthalic imidine, Whitfield's ointment, phenylformic acid, maleic anhydride and N nitrosodiphenyl amine according to traditional known quantity.At last, in application-specific, also can use cable wire adhesion promotor (steel-cord adhesion promoter) as cobalt salt and dithio vitriol according to traditional known quantity.
This technology under 110-220 ℃ temperature through carrying out in 24 hours at the most.More preferably this technology through 8 hours at the most, is carried out in the presence of 0.1-20 weight part composition under 120-190 ℃ of temperature, more particularly uses the composition that comprises chopped strand, staple fibre or pellet.Even more preferably use the 0.2-5 parts of by weight of coated chopped strand, coating staple fibre or by its fiber pellet that makes.All above-mentioned additives about rubber combination also can use in sulfuration process of the present invention.
In the embodiment of preferred sulfuration process, sulfuration through 8 hours at the most, and is carried out in the presence of at least a vulcanization accelerator of 0.1-8 weight part under 120-190 ℃ of temperature, based on the rubber of 100 weight parts.
The present invention also comprises manufacture, and as the clear product of glue, tire, tyre surface, tire cushion or belt, these goods are included in the present composition and have sulfurized sulphur-vulcanized rubber down.
The present invention is described further by the following example, but it should not be construed as the formation any limitation of the invention.
Experimental technique
In the following example, except as otherwise noted, the compounding of rubber, sulfuration and test are carried out according to standard method: with basic formulation at Farrel Bridge TMMix (under 50 ℃, preheating spinner velocity 77rpm, mixing time 6 minutes, full cooling) in 1.6 liters of Banbury Banbury mixeies of BR.
At Schwabenthan Polymix TMIn formulation, add sulfuration composition (friction 1:1.22,70 ℃ of temperature, 3 minutes) in the 150L two roller mills.Use Monsanto according to ISO 6502/1999 TMRheometer MDR 2000E (0.5 ° of arc) measures curing performance.Deducting minimal torque (ML) as the Delta S of degree of crosslinking definition by peak torque (MH) obtains.
By at Fontyne TMCompression molding vulcanizes sheet material and specimen in the TP-400 compressor.
Use Zwick TM1445 tester for elongation carry out Elongation test (the ISO-2 dumbbell is according to ASTMD412-87 test tensile property, according to ASTM D 624-86 test tear strength).
Use the Zwick abrasion meter, with volumetric wear (DIN 53516) the test wear resistance of per 40 meters mobile routes.
Use Goodrich TMFlexometer (load 1MPa, stroke 0.445cm, frequency 30Hz, 100 ℃ of starting temperatures, 120 minutes working times or up to explosion; ASTM D 623-78) tests long-pending heat and compression set behind the dynamic load.
Use Eplexor TMDynamic mechanical analysis instrument (prestrain 10%, frequency 15Hz, ASTM D2231) carries out dynamic mechanical analysis, for example out-of-phase modulus and tangent δ (table 5).
Embodiment 1
According to WO 0058064 preparation aramid staple fiber pellet, and it contains the Twaron of 80wt% and the polyamide resin of 20w%.In such a way these pellets are handled:
Thioplast TMEPS 25 and Thioplast TMEPS 70 can buy from Akzo NobelThioplast on market.Thioplast TMEPS25 is the blend of the polysulfide polymer of formula I and IV, and wherein R ' is-CH 2-And n is less than 7, and its viscosity is that the 2-3Pas and the degree of branching are 2mol%.Thioplast TMEPS 70 is the polysulfide polymers with slight branching of following formula, wherein R ' epoxy group(ing) for the diglycidyl ether by making dihydroxyphenyl propane or F with have identical structural formula but the group that obtains by the displaced polysulfide polymer precursors reaction of H of R ' wherein, wherein n is less than 7, and its viscosity under 20 ℃ is that the 5-10Pas and the degree of branching are 0.57.With Thioplast TMEPS is dissolved in the toluene in the presence of a small amount of isohexadecane, obtains Thioplast TMEPS is that 66wt% and isohexadecane are the toluene solution of 2.6wt%.The tensio-active agent Elfapur of preparation 2.3wt% TMThe aqueous solution of LM 75 S.Under violent stirring with Thioplast TMSolution adds in the described aqueous solution, obtains stable dispersion with after-applied ultraturrax (high-shear), and it comprises the Thioplast of about 8wt% TMEPS.About 25g was flooded about 5 minutes in the above-mentioned dispersion of 110mL the aromatic poly pellet, leach treated pellet and dry afterwards.After drying, with pellet 150 ℃ of following thermal treatments 15 minutes.
The Kevlar pellet composition is summarised in the table 1.
Table 1 Kevlar composition and processing
Particle: matrix: polysulfide polymer (wt%:wt%:wt%) Handle Remarks Project
Twaron:PA:EPS?25＝71.4:17.9:10.7 Do not have Relatively T1
Twaron:PA:EPS?70＝69.0:17.2:13.8 Do not have Relatively T2
Twaron:PA:EPS25＝73.1:18.3:8.6 15’，150℃ The present invention T3
Twaron:PA:EPS?70＝75.5:18.9:5.6 15’，150℃ The present invention T4
The PA=polyamide resin; EPS 25=Thioplast EPS 25; EPS 70=Thioplast EPS 70.
The promotor of using is N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS).
The detailed description of prescription is listed in the table 2.
Table 2 comprises the rubber compounding of Kevlar composition
Figure A200780037306D0018180906QIETU
NR is a natural rubber; BR is a polyhutadiene; 6PPD is N-1, and 3-dimethylbutyl-N '-phenyl-Ursol D, TMQ are polymeric 2,2, and 4-trimethylammonium-1,2-dihydroquinoline antioxidant, CBS are N-cyclohexyl benzo thiazole sulfinyl amine.
Vulcanized rubber listed in the table 2 is tested according to the ASTM/ISO standard.A and B are control experiment (rubber is only arranged), and C and D are comparative experiments (uncured), and 1 and 2 is according to experiment of the present invention.The result is shown in table 3-6.
100 ℃ of following mixtures of table 3 are to the influence (mooney viscosity) of processing characteristics.
Experiment → A B C D 1 2
ML(1+4)MU 54 55 57 55 59 59
The data of the ML in the table 3 (1+4) value show that fiber composition according to the present invention shows low viscosity.
150 ℃ of following mixtures of table 4 are to the influence of delta moment of torsion
Experiment → A B C D 1 2
Delta?S，Nm 1.75 1.79 1.83 1.78 1.82 1.80
The data of the delta S value in the table 4 show according to composition of the present invention (mixture 1 and 2) not influence of degree of crosslinking.
Table 5 fiber composition improves the evaluation of mechanical property
Experiment → A B C D 1 2
Modulus, 300%, MPa 13.1 14.8 14.8 14.5 15.6 15.4
Tear strength, kN/m 135 120 130 130 145 145
From table 5 data presented, can know and find out that the present composition (mixture 1 and 2) that contains polysulfide polymer has better modulus and tear strength.
Table 6 improves the evaluation of dynamic properties
Experiment → A B C D 1 2
Temperature rises, ℃ 32 37 28 28 26 26
The explosion time, min 25 18 29 35 42 45
Out-of-phase modulus, MPa 1.2 1.33 1.21 1.25 1.05 1.09
Tangent δ 0.158 0.167 0.159 0.156 0.136 0.138
It may be noted that the composition (mixture 1 and 2) that contains polysulfide polymer shows the dynamic properties of improvement.
Embodiment 2
According to WO 0058064 preparation aramid staple fiber pellet, and it contains the Twaron of 80wt% and the polyvinyl resin of 20wt%.In such a way pellet is handled:
Figure A200780037306D0019181038QIETU
LP 32 can be from Toray Fine Chemicals Co. on market, and Ltd. has bought.
Figure A200780037306D0019181034QIETU
LP 32 is polysulfide polymer blends of slight branching of the polysulphide of formula I and III, and n average out to 24, and its viscosity is that the 45Pas and the degree of branching are 0.5 mole of %.
Will
Figure A200780037306D0019181028QIETU
LP 32 is dissolved in the toluene, obtains 66wt%'s
Figure A200780037306D0019181017QIETU
LP 32 solution.The tensio-active agent Elfapur of preparation 1.7wt% TMThe aqueous solution of LM 75 S.Will under violent stirring
Figure A200780037306D0019181023QIETU
LP 32 solution add in the described aqueous solution, obtain stable dispersion with after-applied ultraturrax (high-shear), and it contains about 10wt%'s
Figure A200780037306D0019181012QIETU
LP 32.
About 25g is comprised 80wt%
Figure A200780037306D0019181006QIETU
With 20wt% is poly the aromatic poly pellet was approximately being flooded about 5 minutes in the 150mL dispersion, leaching pellet and the drying handled afterwards.
Sulphur and 2-mercaptobenzothiazole disulphide are dissolved in the toluene, obtain containing the solution of 0.4wt% sulphur and 0.8wt% 2-mercaptobenzothiazole disulphide.Will
Figure A200780037306D0019181000QIETU
LP 32 is dissolved in the toluene and adds the toluene solution that contains sulphur and 2-mercaptobenzothiazole disulphide, obtains containing 8wt%
Figure A200780037306D0019180954QIETU
The solution of LP 32,0.4wt% 2-mercaptobenzothiazole disulphide and 0.2wt% sulphur.
Second crowd of about 25g comprised 80wt%
Figure A200780037306D0019180947QIETU
With 20wt% is poly the aromatic poly pellet was approximately being flooded about 5 minutes in the above-mentioned solution of 100mL, leaching pellet and the drying handled afterwards.
Third and fourth crowd of about 25g comprised 80wt%
Figure A200780037306D00201
With 20wt% poly to the aromatic poly pellet respectively with contain
Figure A200780037306D00202
The fusion stearic acid of LP 32 and containing
Figure A200780037306D00203
The fusion stearic acid of LP 32,2-mercaptobenzothiazole disulphide and sulphur mixes.Remove the excessive slightly stearic acid that solidifies subsequently with granulate cooling, and by screening, described stearic acid may contain on a small quantity
Figure A200780037306D00204
32,2-mercaptobenzothiazole disulphide and sulphur.
The Kevlar composition is summarised in the table 7.
Table 7 fiber pellet composition
Component Form (wt%:wt%:wt%) Remarks Project
Twaron:PE:LP?32:Elfa 67.8:17.0:13.6:1.6 Relatively T5
Twaron:PE:SA:LP32 30.2:7.6:57.8:4.4 Relatively T6
Twaron:PE:LP32:MBTS:S 71.5:17.9:9.9:0.5:0.2 The present invention T7
Twaron:PE:SA:LP32:MBTS:S 30.6:7.7:56.9:4.5:0.2:0.1 The present invention T8
The PE=polyethylene;
Figure A200780037306D00205
LP 32; Elfa=Elfapur TMLM 75 S; MBTS=2-mercaptobenzothiazole disulphide; The SA=stearic acid
The promotor of using is N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS).
The detailed description of prescription is listed in the table 8.
Table 8 comprises the rubber compounding of aromatic poly pellet
Figure A200780037306D00211
NR is a natural rubber; BR is a polyhutadiene; 6PPD is N-1, and 3-dimethylbutyl-N '-phenyl-Ursol D, TMQ are polymeric 2,2,4-trimethylammonium-1,2-dihydroquinoline antioxidant.
Vulcanized rubber listed in the table 8 is tested according to the ASTM/ISO standard.E and F are control experiment (rubber is only arranged), and G and H are comparative experiments (no curing systems), and 3 and 4 is according to experiment of the present invention.The result is shown in table 9-12.
100 ℃ of following mixtures of table 9 are to the influence (mooney viscosity) of processing characteristics.
Experiment → E F G H 3 4
ML(1+4)MU 53 55 53 53 54 51
The data of the ML in the table 9 (1+4) value show that fiber composition according to the present invention shows low viscosity.
150 ℃ of following mixtures of table 10 are to the influence of delta moment of torsion
Experiment → E F G H 3 4
Delta?S，Nm 1.72 1.75 1.76 1.79 1.97 1.92
Delta torque value data in the table 10 show according to fiber composition of the present invention (wherein, polysulfide polymer and curing system all exist, mixture 3 and 4) and show the strongest reinforced effects.
The fiber that table 11 was handled improves the evaluation of mechanical property
Experiment → E F G H 3 4
Modulus, 300%, MPa 13.2 14.8 13.9 14.7 15.5 15.5
Hardness (IRHD) 71 71 73 72 75 75
From table 11 data presented, can know and find out that the fiber composition of the present invention (mixture 3 and 4) that contains polysulfide polymer and solidifying agent has better modulus and hardness.
Table 12 improves the evaluation of dynamic properties
Experiment → E F G H 3 4
Temperature rises, ℃ 24 26 24 24 19 20
Out-of-phase modulus, MPa 1.12 1.07 1.11 0.96 0.89 0.87
Tangent δ 0.157 0.148 0.146 0.136 0.120 0.122
It may be noted that the fiber composition (mixture 3 and 4) that contains polysulfide polymer and curing system simultaneously shows the dynamic properties of improvement.

Claims (21)

1, a kind of composition that comprises particle and matrix, wherein particle is applied by the mixture of formulation or formulation to small part, and this formulation comprises at least a in the following component:
A) polysulfide polymer and curing system; With
B) from having the solidified polysulfide polymer that at least two epoxy-terminated polysulfide polymers obtain.
2, the composition of claim 1, wherein particle is fiber, fine strip body, fibril, powder or bead.
3, claim 1 or 2 composition, wherein polysulfide polymer is linearity or the hyperbranched compounds with formula A-B-C, wherein B is the structure division that comprises the repeating unit of 1-200 following formula independently:
-[X-R 2-X-R 1-S x]-
Wherein
X is CH independently 2, S or O;
X is 2,3 or 4;
R 1And R 2Be independently selected from and replace or the arylidene of alkylidene group, replacement or the unsubstituted 6-10 of a having carbon atom of the unsubstituted 1-10 of a having carbon atom, have the alkylene oxide group of 1-5 carbon atom and have the alkyleneoxyalkylene group of 2-10 carbon atom; Wherein substituting group is the structure division that comprises the repeating unit of 1-200 following formula independently:
D-[X-R 2-X-R 1-S x]-E
Wherein X, R 1, R 2Has previous given implication with x;
Perhaps X, R 1And R 2Be key independently, condition is X-R 2-X-R 1Structure division contains at least 2 atoms;
A and C are independently selected from hydrogen and contain group at least a in halogen, epoxy group(ing), hydroxyl, isocyanate group, silyl and the vinyl; With
D and one of E have the implication identical with A for key and another.
4, if the composition of claim 3 is R wherein 1And/or R 2The alkylidene group with 1-10 carbon atom of implication for replacing, or the arylidene with 6-10 carbon atom of replacement, wherein substituting group is to comprise 1-200 formula D-[X-R independently 2-X-R 1-S xThe structure division of]-E repeating unit, the radicals R in described repeating unit 1And R 2Be independently selected from alkylidene group, arylidene, have the alkylene oxide group of 1-5 carbon atom and have the alkyleneoxyalkylene group of 2-10 carbon atom with 6-10 carbon atom with 1-10 carbon atom.
5, claim 3 or 4 composition, wherein group A, C, D and/or the E of polysulfide polymer A-B-C are glycidyl or are diglycidyl ether or the diglycidyl ether of Bisphenol F or the group that their resin reaction obtains by making dihydroxyphenyl propane, condition is one of D and E for key and another are H, and A and C are H.
6, each composition of claim 1-5, wherein polysulfide polymer is at least a in the following polymkeric substance:
Figure A200780037306C00031
With
Wherein n for 1-200 and R ' is independently
Figure A200780037306C00041
Wherein m is 0-10, R 3Be H or CH independently 3, and be incorporated into epoxide group with the end that double asterisk is represented.
7, each composition of claim 1-6, its floating coat comprises polysulfide polymer and curing system, and wherein curing system is selected from the mixture of plumbous oxide (IV), manganese oxide (IV), pf resin of low molecular weight, vulcabond or polyisocyanates, diepoxide or polyepoxide, cumene hydroperoxide, dicumyl peroxide, calcium peroxide, zinc peroxide, sodium periodate, sodium perborate, peroxy-disulfuric acid tetrabutylammonium, paraquinonedioxime, iodine and sulphur and polysulphide.
8, the composition of claim 7, wherein curing system is the mixture of the polysulphide of sulphur and following formula,
N=2-6 wherein;
R is independently selected from hydrogen, halogen, nitro, hydroxyl, C 1-C 12Alkyl, C 1-C 12Alkoxyl group and C 7-C 12Aralkyl.
9, aforesaid right requires each composition, and its floating coat comprises the polysulfide polymer of 10-98wt% and the curing system of 0.1-20wt%, based on the weight of coating.
10, aforesaid right requires each composition, and its mesostroma is a wax.
11, the composition of claim 10, wherein wax is the saturated alkanoic acid with 12-40 carbon atom.
12, the composition of claim 11 comprises the aliphatic fatty acid wax of 85wt% at the most based on the weight of composition, or has C 22-C 38The synthetic Microcrystalline Wax of alkyl chain.
13, aforesaid right requires each composition, and wherein particle is selected from aromatic poly, polyester, polymeric amide, Mierocrystalline cellulose, glass and carbon.
14, aforesaid right requires each composition, and wherein particle is selected from chopped strand, staple fibre, slurry and powder.
15, aforesaid right requires each composition, and wherein particle is poly-(poly P phenylene diamine terephthalamide) fiber or (poly P phenylene diamine terephthalamide/paraphenylene terephthalamide 3,4 '-oxygen diphenylene diamines) copolymer fibre.
16, aforesaid right requires each composition, and wherein particle is for using the pretreated fiber of sizing material.
17, aforesaid right requires each composition, and wherein based on the weight of composition, coated weight is 0.5-50wt%, preferred 1-30wt%, more preferably 2-15wt%.
18, a kind of particle-elastic composition, it comprises:
(a) at least a natural or synthetic rubber of 100 weight parts;
(b) sulphur of 0.1-25 weight part and/or sulphur donor are to provide the sulphur that is equivalent to the 0.1-25 weight part; With
(c) each composition of the claim 1-17 of 0.1-20 weight part.
19, comprise the particle-elastic composition of claim 18 and the clear product of glue of the clear additive of glue.
20, the tire that comprises the clear product of glue of the composition of claim 18 and/or claim 19.
21, the tyre surface, buffer layer or the belt that comprise the clear product of glue of the particle-elastic composition of claim 18 and/or claim 19.
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US8541513B2 (en) * 2011-03-18 2013-09-24 Prc-Desoto International, Inc. Terminal-modified difunctional sulfur-containing polymers, compositions thereof and methods of use
US9663619B2 (en) 2012-08-01 2017-05-30 Toray Fine Chemicals Co., Ltd. Thiol group-containing polymer and curable composition thereof
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