Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • 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
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/22—Thermoplastic resins
• • 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
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• • 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
  • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31692—Next to addition polymer from unsaturated monomers
  • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
  • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

• thermoplastic vulcanizates TPV
• TPE thermoplastic elastomers
• the industrial hose and belting markets generally require a peel strength of at least 8 to 12 pli for candidate matrix materials for fiber reinforced hoses and belting.
• Preferred functional groups are carboxylic acid groups and/or anhydride from a di or poly carboxylic acid .
• the polyolefin can be derived from polymerizing monoolefins or from polymerizing diolefins and then hydrogenating them to obtain similar microstructures to polyolefins. These polyolefins from diolefins can be block copolymers with other monomers such as strye ⁇ e.
• the functionalized polyolefin and the polyolefin with the low flexural modulus and low crystallinity are the only required components of a hot-melt composition with excellent adhesion to polar polymers and textile fibers.
• a crosslinked rubber is present so that the rubbery properties of a thermoplastic vulcanizate are present.
• both a conventional high modulus polyolefin and rubber are present.
• the high modulus polyolefin can increase the stiffness and/or increase the softening temperature of the composition for uses requiring stiffness or having a higher use temperature requiring a higher softening temperature for the TPV.
• Hydrosilylation crosslinking is a particularly advantageous type of crosslinking for the rubber phase as it has minimal side reactions with the functionalized polyolefin allowing the functionalized polyolefin to be blended with the other components before crosslinking the rubber phase.
• the first polyolefin, with low flexural modulus (tangent) can generally be any polyolefin with low polyolefin crystallinity and a flexural modulus desirably from about 5,000 to about 20,000 psi (34.5 - 1 38 MPa), more desirably from about 7,500 to about 1 7,500 psi (51 .7 - 1 21 MPa) and preferably from about 9,000 to about 1 6,000 psi (62 to 1 1 0.4 MPa) .
• the flexural modulus is measured by ASTM D 790A test method at 23 °C.
• the first polyolefin can be a homopolymer with low crystallinity due to random or regular variations in tacticity, a copolymer that has low crystallinity due to the comonomer(s) and/or random or regular variations in tacticity (including blockly homo and copolymers) , and polymers prepared by blending or grafting together oligomers or polymers.
• atactic and isotactic polypropylene PP
• in-situ blends long isotactic PP sequence metallocene catalyszed ethylene-propylene copolymers (EP's)
• elastic PPs with stereoblocks of atactic PP and isotactic PP which can be metallocene catalyzed
• isotactic PPs with metallocene catalyzed asymmetrical stereoerrors isotactic PP and atactic
• a generally amorphous polyolefin a polyolefin having less than 1 0 weight percent crystallinity and preferably less than 3 weight percent crystallinity
• This generally amorphous polyolefin is different than EPDM rubber in that it desirably has at least 7b mole percent and more desirably at least 80, 85 , or 90 mole percent repeating units from a single olefin monomer, preferably propylene.
• amorphous polyolefin When used in lieu of a low crystallinity polyolefin it should be used in an amount from about 5 to about 75 parts by weight, more desirably from about 7.5 to about 37 or 43 parts by weight per 1 00 parts total weight of semi-crystalline polyolefins in the thermoplastic phase.
• polyolefins with less than 1 0 weight percent crystallinity will be considered as amorphous.
• the functionalized polyolefin When used in a thermoplastic vulcanizate (TPV) it is desirably used in an amount from about 1 0 or 1 5 to about 200 parts by weight, more desirably from about 1 5 or 20 to about 1 00 or 200 and preferably from about 40 to about 80 parts by weight per i 00 parts by weight of rubbers in the TPV. it is also desirabie that the functionalized polyolefin be present in an amount from about 1 0 to about 60 parts by weight and more desirably from about 1 2.5 to about 50 parts by weight per 100 total parts of polyolefin in the thermoplastic phase.
• TPV thermoplastic vulcanizate
• VNB 5-vinyl-2-norbornene
• EPDM for hydrosilylation crosslinking
• Another preferred rubber for hydrosilylation crosslinking is a copolymer or terpolymer of isobutylene and divinyl aromatic compounds. These polymers are described in U.S. Patent Nos. 4, 91 6, 1 80 and 2,671 ,774, hereby incorporated by reference. These polymers desirably comprise from about 94 to about 99 or 99.5 weight percent repeating units from isobutylene, from about 0 or 0.5 to about 3 or 5 weight percent repeating units from a conjugated diene and from about 0.5 to about 3 or 5 weight percent repeating units from a divinyl aromatic monomer having the formula
• X is an aromatic (aryl) or an alkyl substituted aromatic moiety, and each R may be the same or different and is selected from hydrogen or a C1-5 alkyl.
• Divinyl benzene is a preferred example of the above divinyl aromatic monomer.
• T represents the group
• any hydrosilylation catalyst or cataiyst precursor capable of generating a catalyst in situ, which will catalyze the hydrosilylation reaction with the carbon-carbon bonds of the rubber, can be used .
• Such catalysts have included transition metals of Group VII I such as palladium, rhodium, platinum and the like, including compiexes of tnese metals.
• Chioropiatinic acid has been disclosed as a useful catalyst in U.S. Patent No. 4,803,244 and European Application No. 651 ,009, which further disclose that the catalyst may be used at concentrations of 5 to 1 0,000 parts per million parts by weight rubber and 1 00 to 200,000 parts per million parts by weight rubber, respectively.
• Concentrations of catalyst in the range of about 0.01 to about 20, 40 or 50 parts per million parts by weight of rubber, expressed as platinum metal, in combination with a diene-containing rubber having carbon-carbon multiple bonds which are predominately sterically unhindered, are effective in rapidly and completely curing the rubber in the process of dynamically vulcanizing blends of thermoplastic resin and rubber Catalyst concentrations of about 0. 1 to about 4 or 40 parts per million by weight expressed as platinum metal, and based on the weight of rubber, are particularly preferred.
• Fillers and extenders include conventional inorganics such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black and the like.
• the rubber processing oils generally are paraffinic, naphthenic or aromatic oils derived from petroleum fractions. The type will be that ordinarily used in conjunction with the specific rubber or rubbers present in the composition, and the quantity of processing oil based on the total rubber content of the thermoplastic elastomer may range from zero or 50 to several hundred parts by weight per hundred parts by weight of rubber.
• the oils and other additives contain no or very low concentrations of compounds that interfere with the activity of the catalyst. These include phosphines, amines, sulfides or other compounds that may be classified as Lewis bases.
• the rubber component of the thermoplastic elastomer is generally present as small, i.e. micron-size particles within a continuous thermoplastic resin matrix, although a co-continuous morphology or a phase inversion is also possible depending upon the amount of rubber relative to plastic and the degree of cure of the rubber.
• the rubber is desirably at least partially crosslinked, and preferably is completely or fully crosslinked. It is preferred that the rubber be crosslinked by the process of dynamic vulcanization.
• dynamic vulcanization means a vulcanization or curing process for a rubber blended with a thermoplastic resin, wherein the rubber is vulcanized under conditions of shear at a temperature at which the mixture will flow.
• a dynamic vulcanizate as described above when using peroxide, sulfur, and the phenolic curatives.
• Peroxide curatives may cause some chain scission of polyolefins.
• the functionalized polyolefin is generally, but not necessarily, added after curing the rubber phase, to avoid any chemical interaction between the curative and the functional groups of the functionalized polyolefin.
• the addition of the functionalized polyolefin can occur in the same equipment or separate equipment from the preparation of the thermoplastic vulcanizate.
• the polyolefin with the low crystallinity and low flexural modulus can be added in any stage of the processing, e.g. before or after curing the rubber phase.
• the functionalized polyolefin can be added before the crosslinking (curing) step eliminating the extra addition step after crosslinking.
• the polar polymer can be any polymer mo. e polar than polyolefins.
• the polar polymer can be a molded or shaped article onto which a thermoplastic coating is applied or it may be in the form of sheets or fibers.
• the polar polymer and the fiber or sheet reinforcement may be any high tensile modulus material (e.g. above 1 30,000 psi, more desirably above 1 80,000 psi) that can desirably be formed into fibers or sheets. Examples include polyesters, polyamides, glass fibers, natural fibers such as cellulosic, etc.
• the fibers can be woven, bundled, yarns, non-woven, etc.
• Tables II - VI were prepared by melt blending the added components to a preformed thermoplastic vulcanizate described in Table I.
• Table VII was a simple hot melt adhesive formed by melting a polyolefin and a functionalized polyolefin.
• the compositions in Tables VIII and IX were prepared by adding the functionalized polyolefin before crosslinking with a catalyzed hydrosilylation crosslinking agent.
• Table I is a formulation for a generic thermoplastic vulcanizate.
• the thermoplastic vulcanizate is conventionally prepared as described in U.S. Patent No. 4, 1 30,535.
• thermoplastic vulcanizate prepared according to the recipe of Table I .
• the examples were prepared by compression molding the blend of the functionalized polyolefin and the thermoplastic vulcanizate to a nylon 6,6 and polyester fiber blend substrate at 425° F for 5 minutes of a 1 5 minute cycle time.
• Fusabond ® PMD-353D gives greater increases in adhesion than the other three functionalized polyolefins, especially when the object is to achieve adhesion above 1 0 or 1 2 pli (pounds per linear inch) .
• Fusabond ® PMD-353D is a maleic anhydride functionalized polypropylene random copolymer which is advertised as being 1 .5 % by weight grafted maleic anhydride by its manufacturer Dupont Canada, Inc.
• the next best functionalized polyolefin was Polybond ® 3000, a 1 .0 to 1 .5 % maleic anhydride modified isotactic polypropylene which was used at the 65.2 or 81 .5 parts by weight level to achieve 1 2 pli adhesion.
• the other functionalized polyolefins were less effective.
• melt flow (measured in g/1 0 min) and the Peel Strength of the various polypropylenes blends are included in Table VII below as it was initially postulated that higher melt flow polyethylenes would better adhere to textile fibers due to increased flow and better wetting.
• the polymer blends from Rexflex ® W1 01 from Huntsman and Adflex ® KS357P from Montell gave dramatically superior adhesion to Nylon 6/6 woven fabric than the other polypropylene blends.
• the samples were prepared by compression molding at 425 °F for 5 min. as part of a 1 5 min cycle. Surprisingly, there was no correlation between melt flow and adhesion.
• the two superior polypropylenes were differentiated from the others based upon low crystallinity and lower flexural modulus.
• the crystallinity of Rexflex ® W1 01 was 1 2-1 8 and the crystallinity of Adflex ® KS357P was 1 5-20 wt.% .
• the flexural modulus (tangent) of Rexflex ® W1 01 was 8,000-1 5000 psi and the flexural modulus (tangent) of Adflex ® KS357P was 1 0,000-1 7,000 psi.
• thermoplastic vulcanizate compositions of this disclosure are useful as matrix materials for a variety of fiber and/or metal reinforced materials such as hoses, tubing, fiber reinforced sheeting or membranes, belting, wire reinforced articles, metal rubber composites, etc.
• the blends of low flexural modulus polyolefin and functionalized polyolefin are useful as thermoplastics with excellent adhesion to molded articles, textile fibers, and/or metal or as adhesives, either alone or used to bond a thermoplastic vulcanizate to a high modulus fiber or sheet. While in accordance with the Patent Statutes, the best mode and preferred embodiment have been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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