WO2002085981A1 - Cycloolefin polymer blends with diene polymer - Google Patents
Cycloolefin polymer blends with diene polymer Download PDFInfo
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- WO2002085981A1 WO2002085981A1 PCT/US2002/013044 US0213044W WO02085981A1 WO 2002085981 A1 WO2002085981 A1 WO 2002085981A1 US 0213044 W US0213044 W US 0213044W WO 02085981 A1 WO02085981 A1 WO 02085981A1
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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
- 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
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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
- 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
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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
- 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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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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
- 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 more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- 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
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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
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
Definitions
- This invention relates to polymer blends and more particularly to cyclic olefm containing polymers or bridged polycyclic hydrocarbon containing polymers blended with polybutadienes.
- the medical materials be environmentally compatible as a great deal of medical products are disposed of in landfills and through incineration. Further benefits are realized by using a material which is thermoplastically recyclable.
- PVC may generate objectionable amounts of hydrogen chloride (or hydrochloric acid when contacted with water) upon incineration, causing corrosion of the incinerator.
- the components of the infusion delivery set be free from or have a minimal content of low molecular weight additives such as plasticizers, stabilizers and the like.
- these components can be extracted into the therapeutic solutions that come into contact with the material.
- the additives may react with the therapeutic agents or otherwise render the solution ineffective. This is especially troublesome in bio-tech drug formulations where the concentration of the drug is measured in parts per million (ppm), rather than in weight or volume percentages. Even minuscule losses of the bio-tech drug can render the formulation unusable. Because bio-tech formulations can cost several thousand dollars per dose, it is imperative that the dosage not be changed.
- PNC Polyvinyl chloride
- Polyolef ⁇ ns typically are compatible with medical applications because they have minimal extractability to the fluids and contents which they contact. Most polyolefms are environmentally sound as they do not generate harmful degradants upon incineration, and in most cases are capable of being thermoplastically recycled. Many polyolefms are cost effective materials that may provide an economic alternative to PVC. However, there are many hurdles to overcome to replace all the favorable attributes of PVC with a polyolefin. For example, because of the inert nature of polyolefms, due in part to the non- polar nature of the polymer, difficulties have been encountered in bonding the polyolefin materials to rigid housings positioned along the infusion pathway of an infusion set. Typically, medical containers such as I. V.
- bags are connected to apatient through a series of connected tubing that have in fluid communication drip chambers, Y-type injection sites, venous catheters and the like between the bag and the patient.
- Many of these components include rigid housings manufactured from polycarbonates, acrylics, ABS, copolyesters and the like.
- the housings have sleeves in which the tubing is inserted in a telescoping fashion to attach the tube to the housing. Therefore, it is necessary for the medical tubing to be connected to the rigid housing to form a fluid tight seal with the housings.
- PVC tubing is typically secured within such housings using solvent bonding techniques.
- Solvent bonding requires exposing the end of the tubing to be inserted into the housing to a solvent such as cyclohexanone or methyl ethyl ketone. The solvent effectively softens or dissolves the PVC so when the tubing is inserted into the housing, a bond is formed.
- Solvent bonding techniques are ineffective on certain polyolefms including polyethylene and polypropylene. Problems have also been encountered in using adhesive bonding techniques.
- European Patent Application No. 0 556 034 discloses a medical instrument of a material containing a resin of a cyclic olefin compound or a bridged polycyclic hydrocarbon compound.
- the EP '034 Application discloses making devices such as syringes, injection needles, drip chambers, blood bags and tubing from these resins. hile the EP '034 Patent application discloses a non-PVC material for fabricating medical products it does not disclose a method for bonding a rigid housing of a cyclic olefin to a flexible tubing of a cyclic olefin or other polyolefms.
- Cycloolefin blends are also well known for providing rigid, injection molded parts.
- U.S. PatentNo. 5,359,001 discloses a multiple component polymer blend having a first component of a cycloolefin, a second component of a polyolefin and a third component of a cycloolefin block copolymer to compatibilize the cycloolefin and polyolefin.
- the '001 Patent discloses such blends for impact modifying the highly rigid and brittle cycloolefms.
- the ' 001 Patent does not disclose a method for solvent bonding these blends.
- United States Patent No. 5,863,986 discloses polymer alloy blends of a cycloolefin copolymers with one or more core-shell particles and one or more block copolymers. Again, these polymer blends are tough on impact and have high flexural strength and elongation at break. The '986 patent does not disclose a method for solvent bonding the polymer alloy blends.
- the present invention provides a polymer composition having: a first component selected from homopolymers and copolymers of cyclic olefin containing polymers and bridged polycyclic hydrocarbon containing polymers, the first component being present in an amount from about 1-99% by weight of the composition; and a second component is selected from homopolymers and copolymers of a diene having from 4 to 12 carbons, the second component being present in an amount from about 99% to about 1% by weight of the composition.
- FIG. 1 shows a diagrammatic view of an infusion delivery set
- FIG.2 shows a diagrammatic view of a syringe barrel having end closures solvent bonded thereto
- FIG. 3 shows a perspective view of a Y-type injection site DETAILED DESCRIPTION OF THE INVENTION
- FIG. 1 shows an infusion delivery set 10 having an IV. container 12 and port tube 14 connected to a tubing 16 which provides at its distal end a venous catheter 18 for establishing fluid-flow access to a vascular system of a patient. Positioned at intermediate portions of the infusion pathway is a drip chamber 20 and a Y-type inj ection site 22.
- a drip chamber 20 Positioned at intermediate portions of the infusion pathway is a drip chamber 20 and a Y-type inj ection site 22.
- FIG. 2 shows a syringe barrel 24 having end closures 26 solvent bonded on opposite ends of the syringe barrel. Of course the end closure 26 can be on one or both ends of the syringe barrel 24.
- the present invention provides polymers and copolymers containing monomers of cyclic olefins (which sometimes shall be referred to as cyclic olefin containing polymers) and blends thereof as well as homopolymers and copolymers containing monomers of bridged polycyclic hydrocarbons (which sometimes shall be referred to as bridged polycyclic hydrocarbon containing polymers) and blends thereof to fabricate both the flexible, rigid and semi-rigid components of the delivery set 10 and further provides solvent bonding and cement bonding techniques for attaching together olefin components to fabricate medical device assemblies and subassemblies contained in an infusion set or other medical devices well known in the medcial arts.
- polyolefin used herein is meant to include homopolymers and copolymers of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonenene, and decene.
- Suitable copolymers of ethylene include: (a) ethylene copolymerized with monomers selected from the group of ⁇ -olefms having 3-10 carbons, lower alkyl and lower alkene substituted carboxylic acids and ester and anhydride derivatives thereof, (b) ethylene propylene rubbers, (c) EPDM, and (d) ionomers.
- the carboxylic acids have from 3-10 carbons.
- Such carboxylic acids therefore include acetic acid, acrylic acid and butyric acid.
- the term "lower alkene” and “lower alkyl” is meant to include a carbon chain having from 3-18 carbons more preferably 3-10 and most preferably 3-8 carbons.
- a subset of this group of comonomers includes, as a representative but non-limiting example, vinyl acetates, vinyl acrylates, methyl acrylates, methyl methacrylates, acrylic acids, methacrylic acids, ethyl acrylates, and ethyl acrylic acids.
- these homopolymers, copolymers and polymer blends will have a glass transition temperature of greater than 50 °C, more preferably from about 70 °C to about 180°C, a density greater than 0.910 g/cc and more preferably from 0.910g/cc to about 1.3 g/cc and most preferably from 0.980 g/cc to about 1.3 g/cc and have from at least about 20 mole % of a cyclic aliphatic or a bridged polycyclic in the backbone of the polymer more preferably from about 30-65 mole % and most preferably from about 30- 60 mole %.
- suitable cyclic olefin monomers are monocyclic compounds having from 5 to about 10 carbons in the ring.
- the cyclic olefins can be selected from the group consisting of substituted and unsubstituted cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene.
- Suitable substituents include lower alkyl, acrylate derivatives and the like.
- suitable bridged polycyclic hydrocarbon monomers have two or more rings and more preferably contain at least 7 carbons.
- the rings can be substituted or unsubstituted.
- Suitable substitutes include lower alkyl, aryl, aralkyl, vinyl, allyloxy, (meth) acryloxy and the like.
- the bridged polycyclic hydrocarbons are selected from the group consisting of those disclosed in the above incorporated patents and patent applications.
- Suitable bridged polycyclic hydrocarbon containing polymers are sold by Ticona under the tradename TOP AS, by Nippon Zeon under the tradename ZEONEX and ZEONOR, by Daikyo Gomu Seiko under the tradeanme CZ resin, and by Mitsui Petrochemical Company under the tradename APEL.
- Suitable comonomers include ⁇ -olefins having from 3-10 carbons, aromatic hydrocarbons, other cyclic olef ⁇ ns and bridged polycyclic hydrocarbons.
- pendant groups are for compatibilizing the cyclic olefin containing polymers and the bridged polycyclic hydrocarbon containing polymers with more polar polymers including amine, amide, imide, ester, carboxylic acid and other polar functional groups.
- Suitable pendant groups include aromatic hydrocarbons, carbon dioxide, monoethylenically unsaturated hydrocarbons, acrylonitriles, vinyl ethers, vinyl esters, vinylamides, vinyl ketones, vinyl halides, epoxides, cyclic esters and cyclic ethers.
- the monethylencially unsaturated hydrocarbons include alkyl acrylates, and aryl acrylates.
- the cyclic ester includes maleic anhydride.
- Suitable two-component blends of the present invention include as a first component the homopolymers and copolymers of the cyclic olefin containing polymers and the bridged polycyclic hydrocarbon containing polymers (collectively hereinafter sometimes referred to as "COCs") described above in Section I.
- the COCs should be present in an amount from about 1-99% by weight of the blend, more preferably from about 30-99%, and most preferably from about 35-99 weight percent or any combination or subcombination of ranges therein.
- the first components has a glass transition temperature of from about 70°C to about 130°C and more preferably from about 70-110°C.
- the blends further include a second component in an amount by weight of the blend of from about 99-1 %, more preferably from about 70-1% and most preferably from about 65-1%.
- the second component is selected from the group consisting of homopolymers and copolymers of ethylene, propylene, butene, hexene, octene, nonene, decene and styrene.
- the second component preferably has a density of from about 0.870- 0.960 g/cc and more preferably from about 0.910-0.960 g/cc and more preferably from about 0.930-0.960 g/cc.
- the second component is selected from the group consisting of homopolymers and copolymers of dienes having from 4 to 12 carbons and more preferably from 4 to 8 carbons and most preferably 4 carbons.
- the dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, etc.
- the polymer of interest is a syndiotactic 1,2-polybutadiene and even more preferably a low crystallinity, syndiotactic 1 ,2 polybutadiene.
- Suitable resins include those sold by JSR (Japan Synthetic Rubber) under the grade designations: JSRRB 810, JSRRB 820, and JSR RB 830.
- the polybutadiene is present in an amount by weight of the blend from about 99% to about 1%.
- the second component will be present in an amount by weight from about 99% to about 51%.
- the second component will be present in an amount from about 50% to about 1%.
- Suitable three-component blends include as a third component a COC selected from those COCs described in Part I above and different from the first component.
- the second COC will have a glass transition temperature of higher than about 120 °C when the first COC has a glass transition temperature lower than about 120°C.
- the third component is present from about 10-90% by weight of the blend and the first and second components should be present in a ratio of from about 2: 1 to about 1 :2 respectively of the first component to the second component.
- Medical devices such as those shown in FIG. 1 may be fabricated from the COCs set forth above.
- the present invention provides for fabricating, rigid, semi-rigid and flexible devices from the COCs.
- rigid herein is parts having a modulus of elasticity of at least 150,000 psi when measured in accordance with ASTM D790.
- semi-rigid is parts having a modulus of elasticity of greater than 20,000 psi but less than 150,000 psi when measured in accordance with ASTM D790.
- flexible is articles having a modulus of elasticity of less than about 20,000 psi when measured in accordance with ASTM D790.
- suitable polymers also include other polyolefms such as ethylene vinyl acetate copolymers having a vinyl acetate content of from about 5% to about 32%, ethylene methacrylate copolymers, ethylene and ⁇ -olef ⁇ n copolymers having a density of less than 0.910 g/cc, flexible polypropylenes such as Huntsman's REFLEX and Montell's ADFLEX and stereo block homopolymers of polypropylene disclosed in U.S. PatentNo. 5,594,080.
- Suitable polymers also include polymer blends and films such as those disclosed in U.S. Patent No. 5,849,843 and U.S. PatentNo. 5,998,019.
- FIG. 3 shows a Y-type injection site.
- the injection site 30 has a rigid housing 32 containing a septum 34 at one end 36 of two legs of the Y.
- the septum 34 is held in place by swaged ends 40 of the rigid housing.
- the process of swaging is more fully set forth in U.S. Patent No. 5,658,260 (See FIGS. 20-28 and accompanying text) which is incorporated in its entirety herein by reference and made a part hereof.
- the present invention provides a method for assembling components of an infusion set into medical assemblies using solvent bonding techniques.
- Solvent bonding techniques can be used to join together any combination of rigid, semi-rigid and flexible parts including joining two rigid components, a rigid component to a semi-rigid component, a rigid component to a flexible component, a semi-rigid component to a flexible component, a semi-rigid component to another semi-rigid component, and certain flexible components to one another.
- the method of solvent bonding includes the steps of: (1) providing a first article of apolymer composition described above in Sections I andll such as those having af ⁇ rst component of cyclic olefin containing polymer or a bridged polycyclic hydrocarbon containing polymer, the first component being present in an amount from about 30% to about 100%) by weight of the composition; (2) providing a second article of a material selected from the group comprising low crystallinity polymers; (3) applying a solvent to one of the first article or the second article to define an interface area; and (4) bonding the first article to the second article along the interface area.
- Suitable low crystallinity polymers to fabricate the second article include COCs, COC blends having minimally 30% COC by weight, polymethyl pentene, polyolefins having a modulus of elasticity of less than 10,000 psi when measured in accordance with ASTM D790, and styrene containing polymers without modulus limitations.
- Suitable solvents are those having a solubility parameter of less than about 20
- (MPa)'" more preferably less than about 19 (MPa) 1/2 and most preferably less than about 18 (MPa) 1/2 and include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, mixtures of aliphatic hydrocarbons, mixtures of aromatic hydrocarbons and mixtures of aromatic and aliphatic hydrocarbons.
- Suitable aliphatic hydrocarbons include substituted and unsubstituted hexane, heptane, cyclohexane, cycloheptane, decalin, and the like.
- Suitable aromatic hydrocarbons include substituted and unsubstituted aromatic hydrocarbon solvents such as xylene, tetralin, toluene, and cumene.
- Suitable hydrocarbon substituents include aliphatic substituents having from 1-12 carbons and include propyl, ethyl, butyl, hexyl, tertiary butyl, isobutyl and combinations of the same. What is meant by the terms "aliphatic hydrocarbon" and
- Suitable solvents will also have a molecular weight less than about 200 g/mole, more preferably less than about 180 g/mole and most preferably less than about 140 g/mole.
- the first article can be rigid, semi-rigid and flexible medical product selected from the group consisting of Y-sites, filter housings, drip chambers, heparin locks, injection sites, catheters, spikes, syringe barrels, closures, tubings, oxygenators, pump casettes, valves, burretes, and any medical article or component.
- the second article can be rigid, semi-rigid and flexible polymeric material selected from the group comprising polyolefins, styrene containing polymers, cyclic olefin containing polymers and bridged polycyclic hydrocarbon containing polymers.
- the second article can be of the same device set forth for the first article.
- the method comprises the steps of: (1) providing a first article of a polymer composition comprising: (a) a first component obtained by polymerizing a norbornene monomer and an ethylene monomer, the norbornene monomer being present in an amount of at least about 20 mole percent of the copolymer, the first component being present in an amount from about 30% to about
- composition 100% by weight of the composition; and (b) a second component of a first ethylene and ⁇ -olefin copolymer, the second component being in an amount from about 70%) to about 0% by weight of the composition; (2) providing a second article of low crystallinity polymers; (3) applying a solvent to one of the first article or the second article to define an interface area; and (4) bonding the first article to the second article along the interface area.
- the method comprises the steps of: (1) providing a first article of a polymer composition comprising: (a) a first component obtained by polymerizing a norbornene monomer and an ethylene monomer, the norbornene monomer being present in an amount of at least about 20 mole percent of the copolymer, the first component being present in an amount from about 1% to about 99% (or from about 99%) to about 51%) or from about 50% to about 1%) by weight of the composition; and (b) a second component of a homopolymer or copolymer of a diene having from 4 to 12 carbons (more preferably one of the polybutadiene polymers discussed in detail above), the second component being present in an amount from about
- the third component can be selected from the group comprising polyethylene copolymers having a density less than 0.880 g/cc, polymethyl pentene, polypropylene having a modulus of less than 10,000 psi and more preferably less than 4,000 psi, and certain styrene containing copolymers and interpolymers. Typically these flexible type polypropylenes are atactic. Certain polypropylene copolymers with ethylene are also suitable.
- Suitable styrene containing polymers include Dow's interpolymer of styrene sold under the tradename INDEX.
- Other suitable styrene containing polymers include SBS, SIS and hydrogenated derivatives thereof such as SEBS and SEPS.
- Suitable polyolefins for the first and second articles can be selected from the group comprising homopolymers and copolymers of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonenene, and decene.
- Suitable copolymers of ethylene include: (a) ethylene copolymerized with monomers selected from the group of ⁇ -olefins having 3-10 carbons, lower alkyl and lower alkene substituted carboxylic acids and ester and anhydride derivatives thereof, (b) ethylene-propylene rubbers, (c) EPDM, and (d) ionomers.
- the carboxylic acids have from 3-10 carbons.
- Such carboxylic acids therefore include acetic acid, acrylic acid and butyric acid.
- the term "lower alkene” and “lower alkyl” is meant to include a carbon chain having from 3-18 carbons more preferably 3-10 and most preferably 3-8 carbons.
- this group of comonomers includes, as a representative but non-limiting example, vinyl acetates, vinyl acrylates, methacrylates, methyl methacrylates, acrylic acids, methyl acrylic acids, ethyl acrylates, and ethyl acyrlic acids.
- the first component of the cement composition can also be a copolymer of the cyclic olefins or the bridged polycyclic hydrocarbons set forth above in Section I.
- Suitable comonomers of the COCs can be selected from the group comprising ⁇ -olef ⁇ ns having from 2-10 carbons, aromatic hydrocarbons, cyclic hydrocarbons, and bridged polcyclic hydrocarbons.
- the first component is a copolymer of a norbornene monomer and an ethylene monomer and more preferably the norbornene monomer is present in at least about 20 mole percent of the copolymer and even more preferably the norbornene is present from about 30 to about 60 mole percent.
- the cement composition can also have an additional optional component selected from the group of polyethylene copolymers having a density less than about 0.880 g/cc, polymethyl pentene, polypropylene having a modulus of less than about 10,000 psi and more preferably less than about 4,000 psi, and certain styrene containing copolymers and interpolymers. Typically these flexible type polypropylenes are atactic. Certain polypropylene copolymers with ethylene are also suitable. Suitable styrene and ethylene containing polymers include Dow's interpolymer of styrene sold under the tradename
- Example I Test methods for resin properties: Tensile Modulus: ASTM D638. Flexural Modulus: ASTM D790. Glass Transition Temperature: DSC. Light Transmittance: ASTM D1003.
- Topas resins are produced by Ticona, a member of the Hoechst Group.
- CZ Resin is marketed by the Diakyo Gomu Seiko and The West Company.
- Zeonex resin is produced by Nippon Zeon Co., Ltd.
- solubility parameters reported below are the Hansen Solubility Parameters at 25 degree C, as listed in the Polymer Handbook, 3 rd Ed., Chapter VII, Pages 540-544 unless otherwise specified.
- Example III Test articles and solvent bonding test results:
- Topas 8007/Engage 8003 30/70 semi-rigid weak COC Blend Composition Blend Material Strength of Solvent Bonding ' :D
- the solvent used is cyclohexane.
- the ULDPE specimen was made from Dow Chemicals Engage 8003 resin and was extruded into a tube.
- the EVA specimen was made from DuPont Elvax CM576 resin which had 28% VA content, and was extruded into a tube.
- the COC specimen was made from Topas 8007 resin and was injection molded into y-site with the bonding site in a tube geometry. IV Examples of using different solvents to bond COC containing devices:
- the COC cements were prepared by dissolving the COC into a solvent at room temperature. Elevated temperature such as 50°C can be used to enhance the speed of the preparation of the cement solution.
- a coc resin Topas 8007 1 % t solvent: Cyclohexane 99%wt
- H coc resin Topas 5013 20 %wt solvent: Cyclohexane 80%>wt
- Tubings made of ULDPE (Engage 8003) or EVA (Elvax CM 576) were extruded and cut into segments. Cement was applied between bonding interfaces of the tubing segments identified in the following table. The bonding was done by applying small amount of the cement at the bonding interface. Bond strength was measured by a hand pull test conducted one day after bonding.
- Engage 8003 to Engage 8003 A good Engage 8003 to Engage 8003 B good Engage 8003 to Engage 8003 C weak Engage 8003 to Engage 8003 D good Engage 8003 to Engage 8003 E good Engage 8003 to Engage 8003 F good Elvax CM 576 to Elvax CM 576 A weak Elvax CM 576 to Elvax CM 576 B good Elvax CM 576 to Elvax CM 576 C good Elvax CM 576 to Elvax CM 576 D good Elvax CM 576 to Elvax CM 576 E good Elvax CM 576 to Elvax CM 576 F good Elvax CM 576 to Elvax CM 576 G good Elvax CM 576 to Elvax CM 576 H good
- Blends of the components set forth in the following table were prepared with a Brabender mixer at 250°C at 50 rpm for 4 minutes.
- Films were prepared by compression molding at 450°F to a thickness about 0.4 mm.
- the Haze property is useful for the end user to see through the medical device for the purpose of examining the liquid level, particulates, contamination, or the presence of drugs.
- Lower haze gives clearer view and higher haze gives a fuzzy view.
- Low haze is frequently a desirable property for medical devices such as solution containers, drug delivery devices, IN. and blood sets, dialysis devices, and syringes.
- the haze and total light transmittance of the film were measured using a ColorQuest instrument with both sides of the film wetted with isopropyl alcohol to remove the effect of surface roughness.
- Example VII A Blends of COC with styrenic copolymers and polypropylene.
- the polymer blends that have lower haze, i.e. better clarity, are Topas 8007 blended with ethylene copolymers that have hexene comonomer polymerized with metallocene catalyst.
- the blends with the lowest haze are from the blends with polyethylene with hexene comonomer, polymerized with a metallocene catalyst and with a density of higher than 0.900 and more preferably higher than 0.93 (e.g. Marlex D350).
- Blends of Topas 8007 (Tg ⁇ 80 deg C) and polyethylene with different comonomers are also useful as polyethylene.
- Blends of Topas 6015 (Tg - 160 deg C) and polyethylene with different comonomers are also useful as polyethylene.
- Blends of Topas 6017 (Tg ⁇ 180 deg C), Topas 8007 (Tg ⁇ 80 deg C) and polyethylene with different comonomers.
- the blend that has reduced haze contains Topas 8007 and a metallocene catalyst polymerized ethylene -hexene copolymer.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA03009793A MXPA03009793A (en) | 2001-04-25 | 2002-04-24 | Cycloolefin polymer blends with diene polymer. |
CA002445274A CA2445274A1 (en) | 2001-04-25 | 2002-04-24 | Cycloolefin polymer blends with diene polymer |
JP2002583505A JP2004524431A (en) | 2001-04-25 | 2002-04-24 | Cycloolefin polymer blend with diene polymer |
BR0209215-8A BR0209215A (en) | 2001-04-25 | 2002-04-24 | Polymeric composition |
EP02764341A EP1404759A1 (en) | 2001-04-25 | 2002-04-24 | Cycloolefin polymer blends with diene polymer |
KR10-2003-7013945A KR20030096333A (en) | 2001-04-25 | 2002-04-24 | Cycloolefin Polymer Blends with Diene Polymer |
NO20034762A NO20034762L (en) | 2001-04-25 | 2003-10-24 | Polymeric material comprising cycloolefin-containing polymer blended with diene polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/842,216 | 2001-04-25 | ||
US09/842,216 US6590033B2 (en) | 1999-09-09 | 2001-04-25 | Cycloolefin blends and method for solvent bonding polyolefins |
Publications (1)
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WO2002085981A1 true WO2002085981A1 (en) | 2002-10-31 |
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Family Applications (1)
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PCT/US2002/013044 WO2002085981A1 (en) | 2001-04-25 | 2002-04-24 | Cycloolefin polymer blends with diene polymer |
Country Status (9)
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US (1) | US6590033B2 (en) |
EP (1) | EP1404759A1 (en) |
JP (1) | JP2004524431A (en) |
KR (1) | KR20030096333A (en) |
BR (1) | BR0209215A (en) |
CA (1) | CA2445274A1 (en) |
MX (1) | MXPA03009793A (en) |
NO (1) | NO20034762L (en) |
WO (1) | WO2002085981A1 (en) |
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US8344070B2 (en) * | 2006-08-04 | 2013-01-01 | Exxonmobil Chemical Patents Inc. | Polymer compositions comprising cyclic olefin polymers, polyolefin modifiers, and fillers |
JP2008231411A (en) * | 2007-02-19 | 2008-10-02 | Kureha Corp | Resin composition for releasing sheet, releasing sheet, and method for producing flexible print circuit substrate or prepreg using the same |
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US8871864B2 (en) | 2010-09-09 | 2014-10-28 | Teknor Apex Company | Adhesive system, method of assembly of distinct components therewith |
US8871317B2 (en) | 2010-09-09 | 2014-10-28 | Teknor Apex Company | Curable adhesive system, method of assembly of distinct components therewith |
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- 2001-04-25 US US09/842,216 patent/US6590033B2/en not_active Expired - Fee Related
-
2002
- 2002-04-24 BR BR0209215-8A patent/BR0209215A/en not_active Application Discontinuation
- 2002-04-24 WO PCT/US2002/013044 patent/WO2002085981A1/en not_active Application Discontinuation
- 2002-04-24 CA CA002445274A patent/CA2445274A1/en not_active Abandoned
- 2002-04-24 EP EP02764341A patent/EP1404759A1/en not_active Withdrawn
- 2002-04-24 KR KR10-2003-7013945A patent/KR20030096333A/en not_active Application Discontinuation
- 2002-04-24 JP JP2002583505A patent/JP2004524431A/en not_active Withdrawn
- 2002-04-24 MX MXPA03009793A patent/MXPA03009793A/en unknown
-
2003
- 2003-10-24 NO NO20034762A patent/NO20034762L/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
US6590033B2 (en) | 2003-07-08 |
MXPA03009793A (en) | 2004-06-30 |
JP2004524431A (en) | 2004-08-12 |
EP1404759A1 (en) | 2004-04-07 |
NO20034762D0 (en) | 2003-10-24 |
BR0209215A (en) | 2005-02-09 |
NO20034762L (en) | 2003-12-05 |
CA2445274A1 (en) | 2002-10-31 |
KR20030096333A (en) | 2003-12-24 |
US20020055590A1 (en) | 2002-05-09 |
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