WO2008021001A1 - Procédé de préparation d'un polymère renforcé par du caoutchouc de monomères cycliques - Google Patents

Procédé de préparation d'un polymère renforcé par du caoutchouc de monomères cycliques Download PDF

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WO2008021001A1
WO2008021001A1 PCT/US2007/017162 US2007017162W WO2008021001A1 WO 2008021001 A1 WO2008021001 A1 WO 2008021001A1 US 2007017162 W US2007017162 W US 2007017162W WO 2008021001 A1 WO2008021001 A1 WO 2008021001A1
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Prior art keywords
rubber
functionalized
monomer
functional group
polymer
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PCT/US2007/017162
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English (en)
Inventor
Robert P. Dion
Ravi B. Shankar
David R. Wilson
Michael T. Malanga
Martin C. Beebe
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Dow Global Technologies, Inc.
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Publication of WO2008021001A1 publication Critical patent/WO2008021001A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to rubber-reinforced polymers derived from cyclic monomers.
  • Macrocyclic oligomers have been developed which form polymeric compositions with desirable properties such as strength, toughness, high gloss and solvent resistance.
  • preferred macrocyclic oligomers are macrocyclic polyester oligomers such as those disclosed in U.S. Patent 5,498,651, incorporated herein by reference.
  • Such macrocyclic polyester oligomers are excellent starting materials for producing polymer composites because they exhibit low melt viscosities, which facilitate good impregnation and wet-out in composite applications. Furthermore, such macrocyclic oligomers are easy to process using conventional processing techniques.
  • the rubber particles tend to be incompatible with the polymerized macrocyclic oligomer, leading to difficulties in forming the dispersion and poor interfacial adhesion between the polymer and rubber phases. This poor adhesion leads to a loss of physical properties. Compounding often leads to a degradation of the polymerized macrocyclic oligomer and possibly the rubber. As a result, it would be desirable to provide another method for preparing a polymerized macrocyclic oligomer that has good impact properties. It would be further desirable to provide a method by which one can readily form a dispersion of rubber particles in a polymerized macrocyclic oligomer.
  • this invention is a process for preparing a rubber-modified polymer of a cyclic monomer, comprising a) forming a solution of a functionalized rubber and a cyclic monomer that polymerizes in a ring-opening polymerization reaction and b) polymerizing the cyclic monomer in the presence of the functionalized rubber to form a dispersion of the rubber particles in the polymerized monomer.
  • This invention is also a graft dispersion of a synthetic rubber in a polymer of a cyclic monomer that polymerizes in a ring-opening polymerization reaction, wherein the dispersion contains from about 1 to about 33% of the synthetic rubber, based on the combined weight of the rubber and the polymer, and the rubber is dispersed within the polymer in the form of particles having a volume average particle size of less than 10 microns.
  • This invention is also a process for grafting a rubber to an organic polymer, comprising
  • the invention also includes a process for forming a rubber-modified organic polymer, comprising
  • the invention still further includes a functionalized adduct which is the reaction product of (1) an organic polymer that contains at least one allylic hydrogen atom with (2) a triazolinedione compound that is substituted on the nitrogen atom at the 4-position with a substituent that contains at least one functional group, wherein the functionalized adduct also contains said at least one functional group.
  • the organic polymer is a rubber.
  • the functional groups permit the adduct to engage in a variety of chemical reactions, such as grafting, block polymerization, the introduction of various types of side chains or specialized functional groups, crosslinking reactions and the like.
  • the invention is also an organic polymer having at least one pendant group represented by the structure
  • R represents an unsubstituted (except for the X group) or inertly substituted aromatic, aliphatic or alicyclic organic group and X represents a reactive functional group.
  • Reactive in this context means that the functional group will react with a coreactive functional group on an organic polymer to form a covalent bond to the organic polymer.
  • Inertly substituted means that the group contains no substituent that is reactive with the reactive functional group X or the triazolinedione group.
  • the pendant group can serve as a functional group through which the polymer can engage in a wide variety of chemical reactions.
  • a rubber-modified polymer of a cyclic monomer is formed from a solution of the cyclic monomer and the rubber.
  • the rubber may be dissolved in the cyclic monomer, but more typically both the rubber and monomer will be dissolved in a suitable solvent.
  • the cyclic monomer is polymerized in the presence of the rubber and the solvent (if present) to form a rubber-modified polymer.
  • the rubber becomes dispersed as a plurality of small particles within a continuous matrix of the polymerized monomer.
  • the rubber becomes grafted to the polymerized cyclic monomer.
  • the cyclic monomer is a cyclic polymerizable material that polymerizes in a ring-opening polymerization reaction.
  • cyclic monomers examples include cyclic lactones, cyclic esters, cyclic amides and the like, which conveniently contain a 4-7 member ring containing one or more ester or amide linkages. Such cyclic monomers may be substituted or unsubstituted. Suitable substituent groups include halogen, alkyl, aryl, alkoxyl, cyano, ether, sulfide or tertiary amine groups. Substituent groups preferably are not reactive with an ester or amide group.
  • cyclic monomers examples include glycolide, dioxanone, l,4-dioxane-2,3-dione, ⁇ -caprolactone, tetramethyl glycolide, ⁇ -butyrolactone, lactide, ⁇ -butyrolactone and pivalolactone.
  • Preferred cyclic monomers include macrocyelic oligomers, which contain two or more ester linkages in a ring structure that includes at least 8 atoms bonded together to form the ring.
  • the macrocyelic oligomer includes two or more structural repeat units that are connected through the ester linkages.
  • the structural repeat units may be the same or different.
  • the number of repeat units in the macrocyelic oligomer suitably ranges from about 2 to about 8.
  • the macrocyelic oligomer will include a mixture of molecules having varying numbers of repeat units.
  • a preferred class of macrocyelic oligomers is represented by the structure
  • A is a divalent alkyl, divalent cycloalkyl or divalent mono- or polyoxyalkylene group
  • B is a divalent aromatic or divalent alicyclic group
  • y is a number from 2 to 8.
  • suitable macrocyelic oligomers corresponding to structure II include oligomers of 1,4-butylene terephthalate, 1,3-propylene terephthalate, 1,4- cyclohexenedimethylene terephthalate, ethylene terephthalate, and 1,2-ethylene- 2,6-naphthalenedicarboxylate, and copolyester oligomers comprising two or more of these.
  • the macrocyclic oligomer is preferably one having a melting temperature of below about 200 0 C and preferably in the range of about 150-190°C.
  • a particularly preferred cyclic oligomer is an oligomer of 1,4-butylene terephthalate.
  • macrocyclic oligomers are suitably prepared by reacting a diol with a diacid, diacid chloride or diester, or by depolymerization of a linear polyester.
  • the method of preparing the cyclic oligomer is generaUy not critical to this invention.
  • the rubber is any elastomeric material that is soluble in the cyclic monomer or a mixture of the cyclic monomer and solvent, at the relative proportions that are present in the starting solution. It is preferred that the rubber is soluble to the extent of at least 15% by weight, preferably at least 20% by weight and more preferably at least 25% by weight in a 50/50 by weight solution of the cyclic monomer and solvent.
  • styrene- butadiene rubbers examples include styrene- butadiene rubbers, polybutadiene rubbers, EPDM (ethylene propylene diene monomer) rubbers, butadiene-nitrile rubbers, polyisoprene rubbers, acrylate- butadiene rubbers, polychloroprene rubbers, acrylate-isoprene rubbers, ethylene- vinyl acetate rubbers, poly(propylene oxide) rubbers, poly(propylene sulfide) rubbers, and thermoplastic polyurethane rubbers.
  • Preferred rubbers have functional groups which allow them to become grafted to the polymer of the cyclic monomer. A preferred grafting mechanism is described more fully below.
  • the functional groups may include unconjugated carbon-carbon double or triple bonds, or various types of other groups that can react with a coreactive functional group on the polymerized cyclic monomer, or with a separate grafting agent.
  • the rubber is preferably one that is soluble at a temperature of 200 0 C or below, especially 180 0 C or below, in some non-reactive solvent (i.e., one that does not react with the rubber) and/or a cyclic monomer as described below. Solubility facilitates blending with a cyclic monomer or polymer thereof and the formation of finely dispersed rubber particles. It is favored by the lack of significant cross-linking and moderate molecular weights. Molecular weight of the rubber is not considered to be critical to the invention.
  • Rubbers having number average molecular weights in the range of 5,000 to 1,000,000 or more are suitable.
  • a preferred class of rubbers includes those containing one or more allylic hydrogen atoms. Rubbers of this type include homopolymers and copolymers of conjugated dienes such as butadiene, isoprene (2- or 3-methyl-l,3-butadiene), cyclopentadiene, chloroprene (2- or 3-methyl-l,3-butadiene) and the like. Copolymers may be random or block (including diblock, triblock or other multiblock) copolymers.
  • Rubbers of particular interest include polybutadiene rubber, polyisoprene rubber, polychloroprene rubber, random copolymers of a conjugated diene with acrylonitrile or methacrylonitrile (especially acrylonitrile-butadiene copolymers), block and polyblock copolymers of one or more conjugated dienes with one or more vinyl aromatic monomers, particularly styrene/butadiene, styrene/isoprene, styrene/butadiene/styrene, or styrene/isoprene/styrene block polymers; random polymers of one or more conjugated dienes with one or more vinyl aromatic monomers; random or block copolymers of one or more conjugated or non- conjugated dienes with one or more olefins, in particular the so-called EPDM rubbers, which are copolymers of ethylene, propylene and a diene monomer (usually norbornad
  • the cyclic monomer is preferably polymerized in the presence of the rubber and a solvent.
  • the solvent is any solvent which dissolves the cyclic monomer and the rubber at some temperature below the boiling temperature of the solvent.
  • the solvent preferably has a boiling temperature at or above the desired polymerization temperature, although it is possible to use a somewhat lower-boiling solvent if the polymerization is conducted at superatmospheric pressures.
  • the solvent preferably is one having a boiling temperature of about 100 to about 300 0 C, especially from about 100 to about 200 0 C.
  • the solvent should not be reactive with the cyclic monomer or the rubber, any grafting agent that may be present, or any optional comonomer, chain extender, polymer, impact modifier or rubber that may be present.
  • Suitable solvents include • halogenated, especially chlorinated, hydrocarbons such as ortho-dichlorobenzene, aromatic and/or alkyl- substituted aromatic hydrocarbons, high boiling ethers, ketones and esters.
  • the solution of the cyclic monomer and rubber in the solvent can be made in various ways. In one variation, the cyclic monomer is dissolved into the solvent, and the rubber is then dissolved into the resulting cyclic monomer solution. In another variation, the rubber, solvent and cyclic monomer are all combined together and heated to a temperature sufficient to dissolve the cyclic monomer and rubber. In yet another variation, separate solutions of the rubber and cyclic monomer are formed and then blended. The cyclic monomer solution can be added to the rubber solution as a liquid.
  • the cyclic monomer solution is a solid at the temperature of mixing, it can be dispersed as a particulate solid into the rubber solution, and the resulting mixture heated if necessary to dissolve the cyclic monomer.
  • any material can be added to another continuously, intermittently or incrementally.
  • the raw materials are preferably dried before forming the solution.
  • solvent is provided to dissolve both the cyclic monomer and rubber (any soluble optional components as described more fully below) to form a solution that is liquid at the polymerization temperature.
  • the amount of solvent can be varied significantly to provide a desirable concentration of the cyclic monomers and rubber (and optional soluble materials) in the solution.
  • a suitable concentration of solvent is from about 20 to 95% of the combined weight of the solvent, cyclic monomers, rubber and any optional soluble materials that may be present.
  • a more suitable concentration thereof is from 30 to 80% by weight.
  • An especially suitable concentration is about from 40 to 75% by weight. It is possible to practice the invention by forming a somewhat dilute blend of rubber and cyclic monomer in the solvent, and then let the blend down into more cyclic monomer prior to or during the polymerization step.
  • a suitable amount of rubber is up to about 33% of the combined weight of rubber and the cyclic monomer. If copolymerizable materials and or additional polymers are present in the solution, a suitable amount of rubber is up to 33% of the combined weight of rubber, cyclic monomer, copolymerizable materials and additional polymers. It is generally useful to provide at least 1% by weight of the rubber, on the same basis. Preferred ranges are from 2 to 30%, from 5 to 30%, from 10 to 30% and from 10 to 25% by weight of the rubber, on the same basis as just described.
  • a rubber-modified polymer is formed by subjecting the solution of cyclic monomer and rubber to conditions sufficient to polymerize the cyclic monomer.
  • Methods of polymerizing cyclic oligomers are well known. Examples of methods for polymerizing cyclic monomers are described in U. S. Patent Nos. 6,369,157 and 6,420,048 WO 03/080705, and U. S. Published Application 2004/0011992, among many others. Any of these conventional polymerization methods is suitable for use with this invention. In general, the polymerization reaction is conducted at an elevated temperature in the presence of a polymerization catalyst as described below.
  • the polymerization is conducted at a temperature at which the solution is a liquid.
  • the temperature should be sufficient to provide a commercially reasonable polymerization rate and high conversion of the oligomer to polymer.
  • temperature should be sufficient for any grafting reaction between the rubber and the cyclic monomer (or its polymer) to occur.
  • the particular temperature at which those conditions are achieved will of course depend on the particular solvent, particular cyclic monomer and the relative proportions of each that are present, as well as the nature of any grafting reaction.
  • Suitable polymerization temperatures are typically from about 100°C to about 300 0 C, with a temperature range of from about 100 0 C to about 220 0 C being preferable, a temperature range of from 100 to 185°C being more preferable and temperature ranges of from 150 to 185°C or from 165 to 185°C being especially preferred.
  • the ability to polymerize at the relatively low preferred and especially preferred temperature ranges provides an economical polymerization rate while reducing the formation of degradation products.
  • the polymerization is continued for a time sufficient to polymerize the cyclic oligomer to a desired molecular weight and conversion.
  • a period of about 2 minutes or greater, more preferably about 10 minutes or greater and most preferably about 15 minutes or greater is generally sufficient.
  • a period of no longer than about 60 minutes, such as about 40 minutes or less and more preferably about 25 minutes or less, is generally sufficient to complete the polymerization process.
  • the polymerized cyclic monomer typically will crystallize and precipitate from the solution, unless the polymerization temperature is above the crystallization temperature of the polymer.
  • the polymerizate often contains entrapped solvent and is typically a solid material at room temperature.
  • Solvent removal is conveniently done using conventional methods of decanting, drying, distillation, vacuum distillation, filtration, extraction or combinations of these. Extraction methods are of particular interest. Extraction methods can be performed on the solidified or molten dispersion by contacting it with an extractant in which the solvent is miscible.
  • the extractant is generally a volatile hydrocarbon
  • the polymer is suitable for use in various melt-processing procedures to make molded or shaped articles.
  • the dissolved rubber particles will phase separate from the solution as the polymerization proceeds to form fine rubber particles dispersed within a continuous polymer matrix.
  • co-continuous rubber and polymer phases may be formed.
  • the preferred form of the product will contain dispersed rubber particles in a continuous polymer matrix.
  • the catalyst can be added during the polymerization or just prior to heating to polymerization temperatures.
  • the catalyst may instead be incorporated into the rubber/cyclic monomer solution as it is prepared, by blending it into the solvent and/or cyclic monomer (or an optional component).
  • Tin- or titanate-based polymerization catalysts are of particular interest. Examples of such catalysts are described in U.S. Patent 5,498,651 and U.S. Patent 5,547,984, the disclosures of which are incorporated herein by reference. One catalyst may be used, or two or more catalysts may be used together or sequentially.
  • Illustrative examples of classes of tin compounds that may be used in the invention include monoalkyltin hydroxide oxides, monoalkyltinchloride dihydroxides, dialkyltin oxides, bistrialkyltin oxides, monoalkyltin trisalkoxides, dialkyltin dialkoxides, trialkyltin alkoxides, tin compounds having the formula (III) and tin compounds having the formula (IV)
  • organotin compounds that may be used in this invention include l.l. ⁇ . ⁇ -tetra-n-butyl-l. ⁇ -distanna ⁇ -lO-tetraoxacyelodecane, n-butyltinchloride dihydroxide, di-n-butyltin oxide, di-n-octyltin oxide, n-butyltin tri-n-butoxide, di-n- butyltin di-n-butoxide, 2,2-di-n-butyl-2-stanna-l,3-dioxacycloheptane, and tributyltin eth oxide.
  • tin catalysts described in U.S. Patent No. 6,420,047 may be used in the polymerization reaction.
  • Illustrative examples include tetraalkyl titanates e.g., tetra(2-ethylhexyl) titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate.
  • Other illustrative examples include those described in WO 06/009803.
  • Suitable polymerization catalysts can be represented as where n is 2 or 3, each R 7 is independently an inertly substituted hydrocarbyl group, Q is an anionic ligand, and Z is a group having a tin, zinc, aluminum or titanium atom bonded directed to the adjacent oxygen atom.
  • Suitable Z groups include — SnR 7 nQ(3-n>, where R 7 , Q and n are as described before; — ZnQ, where Q is as described before, — Ti(QJs, where Q is as described before, and — A1R 7 P (Q)(2 P ), where R 7 is as described before and p is zero, 1 or 2.
  • Preferred Q groups include — OR 7 groups, where R 7 is as described above.
  • R 7 and/or OR 7 groups may be divalent radicals that form ring structures including one or more of the tin or other metal atoms in the catalyst.
  • Preferred Z groups are — SnR 7 n Q(3-n), — Ti(O R 7 )3 and — A1R 7 P (OR 7 )(2. P ).
  • n is preferably 1 or 2.
  • Examples of particular polymerization catalysts of this type include l,3-dichloro-l, l,3,3-tetrabutyldistannoxane, l.S-dibromo-l.l.S.S- tetrabutyldistannoxane; l,3-difLuoro-l,l,3,3-tetrabutyldistannoxane; 1,3-diacetyl- 1,1,3,3-tetrabutyldistannoxane; l-chloro-3-methoxy-l,l,3,3-tetrabutyldistannoxane; l,3-methoxy-l,l,3,3-tetrabutyldistannoxane; 1,3-ethoxy- 1, 1,3,3- tetrabutyldistannoxane; l,3-(l,2-glycolate)-l, 1,3,3-tetrabutyldistannox
  • Enough catalyst is provided to provide a desirable polymerization rate and to obtain the desired conversion of oligomers to polymer, but it is usually desirable to avoid using excessive amounts of a catalyst.
  • the mole ratio of transesterification catalyst to cyclic monomer can range from about 0.01 mole percent or greater, more preferably from about 0.1 mole percent or greater and more preferably 0.2 mole percent or greater.
  • the mole ratio of transesterification catalyst to cyclic monomer is from about 10 mole percent or less, more preferably 2 mole percent or less, even more preferably about 1 mole percent by weight or less and most preferably 0.6 mole percent or less.
  • Various additional materials may be incorporated into the polymerization solution or combined with the polymerization solution prior to or during its polymerization.
  • the polymerization may be conducted in the presence of various chain extenders, polymers, crosslinkers, impact modifiers, fillers, and/or rubbers to produce various modified polymers. These materials may be incorporated into the polymerization solution prior to or during the polymerization step. It is preferred that these materials be soluble or miscible in the polymerization solution.
  • a suitable polyfunctional chain extending compound is one having two or more functional groups which will react with functional groups on the polymerized cyclic monomer (and/or another polymer in the blend).
  • suitable functional groups are epoxy, isocyanate, ester, hydroxyl, carboxylic acid, carboxylic acid anhydride or carboxylic acid halide groups. More preferably, the functional groups are isocyanate or epoxy, with epoxy functional groups being most preferred.
  • Preferred epoxy-containing chain extenders are aliphatic or aromatic glycidyl ethers.
  • Preferable isocyanate-containing chain extenders include both aromatic and aliphatic diisocyanates.
  • the chain extender has about 2 to about 4, more preferably about 2 to about 3 and most preferably about 2 such functional groups per molecule, on average.
  • the chain extender material suitably has an equivalent weight per functional group of 500 or less.
  • a suitable amount of chain extender provides, for example, at least 0.25 mole of functional groups per mole of reactive groups in the polymerized cyclic monomer.
  • the polymerization solution may also include or be blended with one or more polymeric materials which will form a polymer blend with the polymerized cyclic monomer during the polymerization reaction.
  • polymeric materials include, for example, polyesters such as poly( ⁇ -caprolactam), polybutylene terephthalate, polyethylene adipate, polyethylene terephthalate and the like, polyamides, polycarbonates, polyurethanes, polyether polyols, polyester polyols, and amine-functional polyethers and/or polyesters.
  • Polyolefins such as polymers and interpolymers of ethylene, propylene, a butylene isomer and/or other polymerizable alkenes
  • functional groups that react with functional groups on the polymerized cyclic monomer, rubber, grafting agent (if present) and/or a chain extending agent
  • Other polymeric materials that are compatible with the cyclic monomer and/or the polymerized cyclic monomer or contain functional groups that permit them to be coupled to the polymerized cyclic monomer are also useful. Certain of these polymers may engage in transesterification reactions with the cyclic monomer or its polymer during the polymerization process to form block copolymers.
  • Polymeric materials having reactive functional groups may be coupled to the polymerized cyclic monomer or rubber with chain extenders as described above.
  • Suitable functionalized polymeric materials contain about 1 or more, more preferably about 2 to about 3 and most preferably about 2 such functional groups per molecule, on average, and have an equivalent weight per functional group of greater than 500. Their molecular weights are suitably up to about 100,000, such as up to about 20,000 or up to about 10,000.
  • the polymeric material has a glass transition temperature significantly lower (such at least 10 0 C lower or at-least 30 0 C lower) than the glass transition temperature of the polymerized cyclic monomer alone. The lower glass transition temperature polymeric materials tend to improve the ductility and impact resistance of the resulting product.
  • An especially suitable polyfunctional polymer is a polyether polyol or polyester polyol.
  • the polymerization may be conducted in the presence of filler particles.
  • the filler particles may be in principle any particulate filler, but the advantages of the invention are especially seen when the filler is in the form of submicron-sized particles, or is a layered material that can be partially or fully exfoliated into sub- micron-sized particles.
  • Particles having a smallest dimension of about 0.6 nanometers or greater and preferably about 1 nanometer or greater, up to about 1 micron or less, such as up to about 50 nanometers, up to about 20 nanometers and especially to about 10 nanometers or less are of particular interest.
  • Particle sizes in this invention refer to volume average particle sizes of the dispersed filler particles, measured using an appropriate analytical method such as transmission electron spectroscopy, not simply to the as-received filler, which may be in the form of aggregates, or may have a layered structure, which is often subdivided into smaller materials during the process of making the composite.
  • the filler particles have an aspect ratio of about 10 or greater, more preferably about 100 or greater and most preferably about 500 or greater.
  • “Aspect ratio” as used herein means the length of the largest dimension of a platelet or fiber divided by the smallest dimension, which is preferably the platelet or fiber thickness.
  • Filler particles include, but are not limited to glass (including powders, microspheres and fibers); carbons and graphites including powders, platelets, fibers, and nanotubes; silicates including talc, feldspar, wollastonite and clays; hydroxides including alumina trihydrate and magnesium hydroxide; metals including powders, flakes and fibers; ceramics including powders, platelets, whiskers and fibers; in addition to inorganic oxides, carbonates, sulfates, aluminates, aluminosilicates, stearates and borates.
  • the filler particles may function as a colorant such as pigment, or dye, and/or may function as a catalyst, stabilizer or flame retardant.
  • Filler particles can also include organic materials such as synthetic or natural polymer powders or fibers, cellulosic powders or fibers including wood, starch and cotton; as well as vegetable matter. Such fillers are used for replacing the more expensive polymer, for reinforcement and strengthening, for impact modification, for coloring, for improving the flammability resistance, for improving optical, electrical or magnetic properties, for mold release and/or various other improvements in cost, processability or performance. Fillers of particular interest are highly expanded graphites and exfoliated clays.
  • the expanded graphite suitably has a BET (Brunauer, Emmett and Teller) surface area of at least 15 m 2 /g. Preferably, the BET surface area is at least 30 m 2 /g.
  • BET Brunauer, Emmett and Teller
  • the BET surface area is at least 100 m 2 /g.
  • An even more preferred expanded graphite has a BET surface area of at least 200 m 2 /g.
  • a still more preferred expanded graphite has a BET surface area of at least 500 m 2 /g.
  • the upper limit on the BET surface area is in principal up to about 2700 m 2 /g, which is the theoretical surface area of fully expanded graphite.
  • expanded graphite having a surface area up to about 1500 m 2 /g or even up to about 1000 m 2 /g works well in this invention.
  • BET surface area measurements can be performed using a Micromeritics TRISTAR 3000 device. Samples are out-gassed at 250 0 C and 0.1 Torr for 12 hours prior to measurements, and surface areas are determined from the region between P/Po of 0 and 0.2. An average of eight data points is used to determine the BET value.
  • Another suitable expanded graphite is one that has been expanded to a volume of at least 100 cc/g. Volumes of at least 200 cc/g are preferred and volumes of at least 300 cc/g are even more preferred.
  • the expanded graphite preferably lacks an intense crystalline peak in its WAXS spectrum at a d-spacing of about 3.363 ⁇ 0.2 (about 26.5 degrees 2 ⁇ ).
  • WAXS is conveniently performed for purposes of this invention using a Rigaku MiniFlex diffractometer with a Cu Ka radiation source, initial, final and step angles being 5, 30 and 0.02 degrees, respectively.
  • a preferred expanded graphite has a volume of at least 200 cc/g, a BET surface area of at least 30 m 2 /g and a WAXS diffraction peak at 3.363 ⁇ 0.2 d- spacing that is no greater than 10% in intensity of the signal produced by the unexpended graphite.
  • a more preferred expanded graphite has a volume of at least 300 cc/g, a BET surface area of at least 100 m 2 /g and no detectable WAXS diffraction peak at 3.363 ⁇ 0.2 d-spacing.
  • An even more preferred expanded graphite has a volume of at least 300 cc/g, a BET surface area of at least 500 m 2 /g and no detectable WAXS diffraction peak at 3.363 + 0.2 d-spacing.
  • Various methods of for-ming expanded graphite particles are known. Among those methods are those described in U. S. Patent Nos. 3,404,061, 4,895,713, 5,176,863, 6,406,612 and 6,416,683, U. S. Published Patent Applications 2003- 0116753, 2004-0000735, 2004-0033189 and 2004-0034151.
  • a temperature in the range of 600 0 C to 1100 0 C is generally preferred.
  • the graphite particles are preferably heated very rapidly to the expansion temperature. Heating can be performed in various manners, such as by placing the particles into a heated oven or by applying microwave energy to the particles.
  • the expanding agent typically includes a mineral acid such as sulfuric acid or nitric acid. Combinations of these may be used. Certain organic acids may be used as expansion aids, as described, for example, in U. S. Patent No. 6,416,815. Organic reducing agents, in particular aliphatic alcohols, can also be used, also as described in U. S. Patent No. 6,416,815.
  • the graphite may contain a small quantity of ash.
  • An oxidant such as potassium chlorate, potassium permanganate and/or hydrochloric acid may also be used.
  • a graphite that is intercalated with these expanding agents may contain as much as 50% oxygen by weight (of the graphite less intercalating materials).
  • a typical amount of oxygen in the intercalated sample is about 20-40% by weight.
  • the expanded graphite more typically contains from about 10 to about 25% by weight oxygen.
  • the starting graphite material preferably has an average particle size of at least 50, more preferably at least 75 microns, and preferably up to about 1000 microns, more preferably up to 500 microns. Smaller particles tend to expand less due to the loss of expansion agent at their edges. Larger particles are more difficult to intercalate fully with the expansion agent.
  • Expandable graphite flakes and/or powders are commercially available and can be used as starting materials. Examples of such expandable graphite products are available commercially under the tradenames GrafTech® 160-50N (from GRAFTech Inc., Advanced Energy Technologies Division, Parma, OH) and HP-50 (from HP Material Solutions, Northridge, CA). These can be expanded by heating to the aforementioned temperature ranges.
  • the GRAFTech 160-50N product is intercalated with nitric and sulfuric acids, and is believed to further contain an organic acid and alkanol reducing agent. The intercalated materials are believed to constitute 20-30% by weight of the expandable graphite product.
  • An expanded graphite of particular interest is made by intercalating a native graphite or an expandable graphite flake as just described with a mixture of sulfuric and nitric acids, optionally further with potassium chlorate and hydrochloric acid.
  • An expandable graphite which is particularly suitable for this purpose is the Graphtec® 160-50 material.
  • An intercalation process as described by Staudenmaier in Ber. Dtsch. Chem. Ges. 1898, 31 p. 1484 is suitable and preferred.
  • the intercalated material is dried and expanded as described before.
  • the expanded graphite produced by this process typically assumes a vermiform (worm-like) appearance, with a longest particle size generally in the range of about 0.1 to about 10 millimeters.
  • the expanded graphite particles are often referred to as "worms". These expanded graphite particles can be used directly without further treatment to reduce particle size.
  • Clays that are useful in this invention are minerals or synthetic materials having a layered structure, in which the individual layers can be separated to form platelets with thickness in the range of 5-100 angstroms.
  • Suitable clays include kaolinite, halloysite, serpentine, montmorillonite, beidellite, nontronite, hectorite, stevensite, saponite, illite, kenyaite, magadiite, muscovite, sauconite, vermiculite, volkonskoite, pyrophylite, mica, chlorite or smectite.
  • the clay comprises a natural or synthetic clay of the kaolinite, mica, vermiculite, hormite, illite or montmorillonite groups.
  • Preferred kaolinite group clays include kaolinite, halloysite, dickite, nacrite and the like.
  • Preferred montmorillonites include montmorillonite, nontronite, beidellite, hectorite, saponite, bentonite and the like.
  • Preferred minerals of the illite group include hydromicas, phengite, brammalite, glauconite, celadonite and the like.
  • the preferred layered minerals include those often referred to as 2:1 layered silicate minerals like muscovite, vermiculite, beidelite, saponite, bentonite, hectorite and montmorillonite, wherein montmorillonite is most preferred.
  • Preferred minerals of the hormite group include sepiolite and attapulgite, where the layered structure is interrupted in one dimension resulting in fibrous or lath-like particle morphology.
  • admixtures prepared therefrom may also be employed as well as accessory minerals including, for instance, quartz, biotite, limonite, hydrous micas, feldspar and the like.
  • the layered minerals described above may be synthetically produced by a variety of processes, and are known as synthetic hectorites, saponites, montmorillonites, micas as well as their fluorinated analogs.
  • Synthetic clays can be prepared via a number of methods which include the hydrolysis and hydration of silicates, gas solid reactions between talc and alkali fluorosilicates, high temperature melts of oxides and fluorides, hydrothermal reactions of fluorides and hydroxides, shale weathering as well as the action of acid clays, humus and inorganic acids on primary silicates.
  • the clay is preferably modified with an organic -onium compound, such as described in U. S. Patent No.
  • the -onium compound is a salt comprising a negatively-charged counter-ion and a positively- charged nitrogen, phosphorus or sulfur atom.
  • Particularly useful -onium compounds have at least one ligand with a five or greater carbon atom chain.
  • the -onium compound has at least one ligand with a five or greater carbon atom chain and at least one (and preferably two or more) other ligand containing a functional group having an active hydrogen atom that is capable of reacting with the cyclic monomer during the polymerization reaction.
  • the anion counterion in the -onium compound can be any anion which forms a salt with an - onium compound and which can be exchanged with an anionic species on the clay particle.
  • various kinds of optional materials may be incorporated into the polymerization process. Examples of such materials include reinforcing agents (such as glass, carbon or other fibers), flame retardants, colorants, antioxidants, preservatives, mold release agents, lubricants, UV stabilizers, and the like.
  • the rubber-modified polymer resulting from the polymerization may be further processed to increase its molecular weight.
  • Two approaches to accomplishing this are solid state polymerization and chain extension.
  • Solid state polymerization is achieved by post-curing the composite by exposing it to an elevated temperature. This may be done during melt-processing operations or in a subsequent step.
  • a suitable post-curing temperature is from about 170 0 C, about 180 0 C, or about 195°C, up to about 220 0 C, about 210 0 C or about 205 0 C, but below the melting temperature of the polymer phase.
  • the solid state polymerization is preferably performed in a non-oxidizing environment such as under a nitrogen or argon atmosphere and is preferably performed under vacuum and/or flowing inert gas to remove volatile components.
  • Post-curing time times of from 1 to 12 hours, such as from 2 to 10 hours or from 2 to 4 hours are generally suitable.
  • the polymerized cyclic monomer is advanced to a weight average molecular weight of about 60,000 or greater, more preferably about 80,000 or greater and most preferably about 100,000 or greater. It is usually not necessary to use additional catalyst to obtain solid state advancement.
  • Chain extension is performed by contacting the polymerized cyclic monomer with a polyfunctional chain extending agent.
  • the polyfunctional chain extending agent contains two or more functional groups that react with functional groups on the polymerized cyclic monomer, to couple polymer chains and thus increase molecular weight. Suitable such polyfunctional chain extending agents are described more fully below. No additional catalyst is usually required and elevated temperatures as described hereinbefore are used for the chain extension reaction.
  • the product of this process contains polymerized cyclic monomer and a rubber phase.
  • the rubber is in most cases incompatible with the polymerized cyclic monomer and will tend to form a discrete phase. As discussed before, it is most preferred that the rubber phase be distributed in the form of dispersed, finely divided particles within a continuous phase of the polymerized cyclic monomer.
  • the rubber particles preferably have a longest dimension in the range of 0.1 to 10 microns, especially from 0.1 to 2 microns.
  • the reactive and coreactive functional groups are selected together so that they will react with each other under the conditions of the polymerization reaction to form a covalent bond between the rubber and polymerized cyclic monomer (or the cyclic monomer itself, followed by polymerization of the oligomer).
  • polymers of cyclic monomers typically contain terminal carboxyl, carboxylic acid ester, hydroxyl, amine or carboxylic acid amide groups
  • the reactive functional group on the rubber is preferably one that will react with such groups to form a covalent bond. Examples of such groups include isocyanate, carboxyl, carboxylic acid ester, hydroxyl, primary or secondary amino and like groups.
  • grafting agents can be used to help form the desired grafting. These grafting agents generally contain at least two different functional groups, one of which is reactive with the rubber but not the polymerized cyclic monomer and the other of which is reactive with the polymerized cyclic monomer (or the cyclic monomer itself) but not the rubber.
  • the grafting agent may be pre- reacted with the rubber or a portion of the cyclic monomer, in effect introducing functional groups to the rubber or cyclic monomer, as the case may be. It is possible in some cases simply to introduce the grafting agent into the polymerization solution.
  • a preferred approach to using, a grafting agent is to form an adduct of the rubber with the agent. Such an adduct suitably contains from about 1 to about 20, preferably from about 1 to about 10 and more preferably from about 1 to about 8 of the added functional groups per molecule.
  • a preferred type of grafting agent is a functionalized triazolinedione compound.
  • Such a triazolinedione grafting agent is represented by the structure:
  • the reactive functional group X will be selected in conjunction with the organic polymer or the cyclic monomer, and in particular in conjunction with coreactive functional groups that are present on the organic polymer or cyclic monomer.
  • the reactive group X is preferably selected such that it is not highly reactive with carbon-carbon unsaturation (such as carbon-carbon double bonds or carbon-carbon triple bonds) or allylic hydrogens.
  • “Aliylic” hydrogens are, for purposes of this invention, hydrogen atoms attached to a carbon atom which is adjacent to a conjugated or non-conjugated, carbon-carbon double or triple bond. Allylic hydrogens are illustrated generally by reference to structures (VTI)
  • Suitable reactive groups X include, for example: a) carboxylic acid, carboxylic , acid anhydride, carboxylic acid amide, carboxylic acid halide, carboxylic acid ester, carbamate, urea, carbonate, sulfonic acid halide, or sulfonic acid groups, which can react with hydroxyl, ester, amide, isocyanate, primary or secondary amino or epoxide coreactive functional groups on the organic polymer; and b) epoxide groups, which can react with primary amino, secondary amino or isocyanate coreactive functional groups on the organic polymer.
  • the carbazate ester can be represented by the structure R'-O-C(O)-NH-NH2, where R' is hydrocarbyl, preferably lower alkyl, such as Ci-4 alkyl, and particularly methyl or ethyl.
  • This reaction forms R'-O-C(O)-NH-NH-C(O)-NH-R-X as illustrated by Reaction Scheme 1.
  • the 3,5-dioxo-[l,2,4] triazolidine compound then can be reacted with chlorine or other oxidant to extract the hydrogens bonded to the nitrogen atoms at the 1 and 2 positions and form a double bond between those nitrogen atoms.
  • a 3,5-dioxo- [l,2,4]triazolinedione compound is formed in this manner.
  • the reactive functional group X may be present on the starting isocyanate compound, or may be introduced during or after any of the foregoing process steps, as appropriate.
  • the reaction of the isocyanate with the carbazate ester is conveniently performed in a solvent such as toluene at a temperature of about 40 to about 140 0 C. No catalyst is generally needed and yields approximating 100% are readily obtained in many cases.
  • Ring closure of this reaction product to give the triazolidinedione intermediate is conveniently performed in the presence of a strong base, such as excess alkali metal alkoxide.
  • a solvent may be used in the ring closure reaction.
  • the strong base is an alkali metal alkoxide
  • a suitable solvent is the corresponding alcohol, particularly methanol, ethanol, propanol and butanol.
  • Suitable alkali metals include sodium, potassium and lithium.
  • Preferred alkali metal alkoxides include sodium ethoxide, sodium methoxide and potassium butoxide. Yields approximating 100% are readily obtained in many cases.
  • Treatment of the triazolidinedione intermediate with chlorine is conveniently performed by bubbling chlorine through the triazolidinedione compound in an appropriate solvent such as methylene chloride or chloroform. This reaction can be performed at room temperature or a slightly elevated temperature if desired.
  • the triazolinedione compound has a characteristic red, purple-red or pink color.
  • Carboxylic acid-derived ⁇ functional groups X such as carboxylic acid, carboxylic acid anhydride, carboxylic acid amide, carboxylic acid ester, carbamate, urea, or carbonate, or sulfonic acid functional groups X, can be introduced into the triazolinedione compound through the use of a carboxylic acid ester-substituted isocyanate compound as a starting material.
  • the carboxylic acid ester functional group is conveniently converted to an acid group by reaction with an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or the like. This reaction is conveniently performed on the triazolidinedione intermediate, before reaction with chlorine to form the triazolinedione compound. Modification of the ester group to form other carboxylic acid-derived functional groups X can be done using a variety of reaction schemes.
  • the triazolinedione grafting agent can be used to form a functionalized adduct with a rubber that has at least one allylic hydrogen atom. Examples of suitable such rubbers have been described before. This rubber should not contain any substituents that will react with the functional group X on the triazolinedione grafting agent under the conditions of the adduct-forming reaction.
  • the reaction of the rubber with the triazolinedione grafting agent is conveniently performed in a melt or solution of the rubber. It is preferred to dissolve the rubber in a suitable solvent in order to conduct the reaction. Hydrocarbon and chlorinated hydrocarbon solvents are suitable for this purpose. Toluene is a particularly suitable solvent. The proportions of starting materials are selected to introduce the desired quantity of functional groups onto the rubber molecules.
  • the reaction proceeds at a reasonable rate at room temperature. Therefore, it is not necessary to conduct the reaction at elevated temperatures, although that can be done if desired. It is also possible to cool the reaction mixture to below room temperature if desired in order to control the rate of the reaction or for other purposes.
  • the adduct may be isolated from the solvent (if a solvent is used).
  • An antioxidant such as BHT may be added to the adduct in order to confer greater oxidative stability.
  • reaction of a carbon -carbon double or triple bond and an allylic hydrogen with the triazolinedione grafting agent introduces one or more groups represented by the structure
  • reaction Scheme 3 the reaction of a specific ester-functional triazolinedione grafting agent with a styrene-butadiene rubber can be represented schematically by Reaction Scheme 3:
  • reaction Scheme 3 The presence of the -C(O)OCHs groups permits the adduct to react with coreactive functional groups on an organic polymer to graft the rubber to the polymer.
  • the adduct suitably contains from about 1 to about 20, preferably from about 1 to' about 10 and more preferably from about 1 to about 8 of the triazolidinedione functional groups per molecule.
  • the groups X are reactive with carboxyl, carboxylic acid ester, amine or hydroxy groups terminal groups that will normally form on the polymerized cyclic monomer as it is polymerized.
  • Preferred X groups are therefore carboxylic acid, carboxylic acid ester, carboxylic acid anhydride, carboxylic acid amide, carbamate, urea, carbonate or sulfonic acid groups.
  • An especially preferred X group is a carboxylic acid, carboxylic acid amide or carboxylic acid ester group.
  • the grafting reaction can be represented schematically by Reaction Scheme 4.
  • the rubber is a butadiene-styrene copolymer
  • the grafting agent (after reaction with the butadiene-styrene copolymer) is a triazolidinedione substituted at the 4-position with a p-benzoic acid group or methyl ester thereof
  • the cyclic monomer is a 1,4- butylene terephthalate (CBT) oligomer.
  • the reaction occurs between a CBT oligomer molecule and the rubber adduct, and would be followed by polymerization of more CBT oligomer molecules onto the growing polymer chain.
  • this grafting reaction may occur either before or after the oligomer molecule has become polymerized.
  • the order of the grafting and polymerization reactions is not generally considered to be critical to the invention. Both grafting mechanisms are considered to be within the scope of the invention.
  • the triazolinedione grafting agent is generally useful in a variety of grafting applications, such as making alloys or blends of otherwise incompatible polymers and grafting rubbers to various types of polymers (other than polymerized cyclic monomers as described above).
  • at least one of the starting materials i.e., either a polymer or the rubber
  • the other polymer contains a coreactive functional group that reacts with the functional group on the grafting agent, again analogously to that described before.
  • an adduct of the rubber and the triazolinedione grafting agent is formed, as described above, and is present during the polymerization of a monomer that contains a coreactive functional group.
  • the polymerization is most preferably a ring-opening transesterification polymerization reaction or a condensation polymerization reaction. If the rubber is soluble in the monomer, it is not necessary to include a solvent. If the rubber is insoluble in the monomer, it is preferred to conduct the polymerization in the presence of a solvent, for reasons that have been described before. Solution polymerization processes help to form finely dispersed rubber particles in the polymerized product.
  • Monomers that can be polymerized in ring-opening polymerizations include those described before
  • Monomers that can be polymerized in condensation polymerizations include diesters such as dialkyl phthalates, dialkyl terephthalates (especially dimethyl terephthalate), diethyl adipate, or dimethyl succinate in combination with diols such as ethylene glycol, propylene glycol, 1,4-butane-diol and 1,6-hexanediol.
  • the functionalized adduct of the invention is capable of being crosslinked via reaction of the functional group X with an agent that contains two or more coreactive functional groups as described before.
  • the invention provides a new mechanism for curing an organic polymer or a rubber, by (1) reacting an organic polymer or rubber having at least one allylic hydrogen with a triazolinedione grafting agent and if necessary introducing at least one functional group X onto the resulting adduct and (2) reacting the functional groups X with at least one compound having two or more coreactive functional groups to crosslink the polymer or rubber.
  • a compound having two or more triazolinedione groups is used as a crosslinking or chain extension agent, or is used to couple two or more different organic polymers or rubbers.
  • a poly (triazolinedione) compound can be formed from the functionalized triazolinedione compound described above, by reacting it with another compound that has two or more coreactive functional groups.
  • the triazolinedione groups can react with allylic hydrogens in the manner described before to perform a variety of coupling, cross-linking or grafting functions.
  • the resulting ester is slurried in methylene chloride and chlorine gas is bubbled through the slurry. The slurry turns pink immediately upon introducing the chlorine gas. Once all of the starting ester is consumed, the resulting mixture of 4-(3,5-dioxo-3,5-dihydro-[l,2,4]triazol-4-yl) benzoic acid methyl ester in solvent is concentrated under reduced pressure.
  • a solution of a random copolymer of 21 wt.% styrene and 79 wt.% butadiene is prepared by dissolving 200 grams of the rubber in 2 liters of toluene.
  • the red coloration of the triazolinedione compound disappears rapidly upon addition, indicating that it has reacted with the rubber.
  • the reaction mixture is stirred for about 30 minutes once the addition is complete, and 2 g of BHT are then added, followed by more stirring.
  • the solution is then poured into methanol to precipitate the rubber adduct.
  • the recovered polymer is air dried overnight in the dark, cut into small pieces, washed with methanol and again air-dried in the dark under nitrogen. The air-dried adduct is then dried under vacuum at 45°C overnight to yield -200 g of adduct.
  • a rubber adduct is prepared in the manner described in Example 2, using 200 grams of the rubber and 0.306 gram (1.31 mmol) of the 4-(3,5-dioxo-3,5-dihydro- [l,2,4]triazol-4-yl) benzoic acid methyl ester (from Example 1).
  • the weight average molecular weight of the soluble fraction is determined to be about 51,000.
  • the rubber is dispersed in the product in the form of very finely divided particles.
  • Example 5 is prepared in the same manner, using the adduct of Example 2 instead of the adduct of Example 3.
  • the yield of polymer is about 84%; the weight average molecular weight of the soluble fraction is about 57,000.
  • the rubber particles are somewhat smaller than those of Example 4.
  • a rubber-modified polymer of cyclic butylene terephthalate is polymerized in the same manner as Example 4, except that unfunctionalized rubber is used instead of the adduct of Examples 2 or 3.
  • the resulting product has very large particles. Yield of polymer is 84-89% and the weight average molecular weight is about 107,000-119,000.

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Abstract

L'invention concerne un procédé de préparation d'un polymère renforcé par du caoutchouc de monomères cycliques. Conformément à l'invention, des monomères cycliques sont polymérisés en présence d'un caoutchouc fonctionnalisé. Un polymère modifié par du caoutchouc de monomère cyclique est formé. Le caoutchouc fonctionnalisé réagit avec des groupes fonctionnels coréactifs sur le monomère cyclique polymérisé pour former des liaisons covalentes entre le polymère et le caoutchouc.
PCT/US2007/017162 2006-08-10 2007-08-01 Procédé de préparation d'un polymère renforcé par du caoutchouc de monomères cycliques WO2008021001A1 (fr)

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Cited By (1)

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CN112442145A (zh) * 2019-08-29 2021-03-05 中国石油天然气股份有限公司 一种双官能团共轭二烯烃橡胶的制备方法

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US4104325A (en) * 1972-09-19 1978-08-01 Showa Denko K.K. Resin composition comprising cyano-substituted norborene polymers blended with graft copolymers
JPS59196324A (ja) * 1983-04-21 1984-11-07 Mitsui Petrochem Ind Ltd ポリオレフイン共重合ポリエステルの製法
EP0374576A2 (fr) * 1988-12-06 1990-06-27 Nippon Zeon Co., Ltd. Polymérisation du produit de réaction du dicyclopentadiène et d'un élastomère
EP0387662A2 (fr) * 1989-03-06 1990-09-19 Nippon Zeon Co., Ltd. Masse de mise en oeuvre de polynorbornène et article façonné
EP0532337A2 (fr) * 1991-09-12 1993-03-17 Mitsui Petrochemical Industries, Ltd. Composition de résine cyclooléfinique
WO2005067562A2 (fr) * 2004-01-08 2005-07-28 Teknor Apex Company Compositions de polymere renforce
WO2006028541A1 (fr) * 2004-06-18 2006-03-16 Dow Global Technologies, Inc. Melanges maitres a base d'oligomeres macrocycliques polymerisables contenant des charges dispersees

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Publication number Priority date Publication date Assignee Title
US4104325A (en) * 1972-09-19 1978-08-01 Showa Denko K.K. Resin composition comprising cyano-substituted norborene polymers blended with graft copolymers
JPS59196324A (ja) * 1983-04-21 1984-11-07 Mitsui Petrochem Ind Ltd ポリオレフイン共重合ポリエステルの製法
EP0374576A2 (fr) * 1988-12-06 1990-06-27 Nippon Zeon Co., Ltd. Polymérisation du produit de réaction du dicyclopentadiène et d'un élastomère
EP0387662A2 (fr) * 1989-03-06 1990-09-19 Nippon Zeon Co., Ltd. Masse de mise en oeuvre de polynorbornène et article façonné
EP0532337A2 (fr) * 1991-09-12 1993-03-17 Mitsui Petrochemical Industries, Ltd. Composition de résine cyclooléfinique
WO2005067562A2 (fr) * 2004-01-08 2005-07-28 Teknor Apex Company Compositions de polymere renforce
WO2006028541A1 (fr) * 2004-06-18 2006-03-16 Dow Global Technologies, Inc. Melanges maitres a base d'oligomeres macrocycliques polymerisables contenant des charges dispersees

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442145A (zh) * 2019-08-29 2021-03-05 中国石油天然气股份有限公司 一种双官能团共轭二烯烃橡胶的制备方法

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