(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`
`
`(43) International Publication Date
`21 May 2004 (21.05.2004)
`
`(10) International Publication Number
`
`WO 2004/041898 A1
`
`(51) International Patent Classification7:
`C08] 5/18
`
`C08G 18/48,
`
`(21) International Application Number:
`PCT/USZOO3/03 1980
`
`(22) International Filing Date:
`
`8 October 2003 (08.10.2003)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`10/283,528
`
`30 October 2002 (30.10.2002)
`
`US
`
`(71) Applicant: NOVEON IP HOLDINGS CORP. [US/US];
`9911 Brecksville Road, Cleveland, Ohio 44141—3247 (US).
`
`(81) Designated States (national): AE, AG, AL, AM, AT, AU,
`AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU,
`CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI, GB, GD, GE,
`GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR,
`KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK,
`MN, MW, MX, MZ, NI, NO, NZ, OM, PG, PH, PL, PT,
`RO, RU, SC, SD, SE, SG, SK, SL, SY, TJ, TM, TN, TR,
`TT, TZ, UA, UG, UZ, VC, VN, YU, ZA, ZM, ZW.
`
`(84) Designated States (regional): ARIPO patent (GH, GM,
`KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW),
`Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European patent (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
`ES, FI, FR, GB, GR, HU, IE, IT, LU, MC, NL, PT, RO,
`SE, SI, SK, TR), OAPI patent (BF, BJ, CF, CG, CI, CM,
`GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Declaration under Rule 4.17:
`
`as to applicant ’s entitlement to apply for and be granted a
`patent (Rule 4.17(ii))for all designations
`
`ONDER, Kemal;
`(72) Inventor:
`Brecksville, OH 44141 (US).
`
`8476 Timber Trail,
`
`Published:
`
`with international search report
`
`(74) Agents: POWELL, Joe, A. et al.; Noveon, Inc., Legal De—
`partment, 9911 Brecksville Road, Cleveland, OH 44141—
`3247 (US).
`
`For two—letter codes and other abbreviations, refer to the ”Guid—
`ance Notes on Codes and Abbreviations ” appearing at the begin—
`ning of each regular issue of the PCT Gazette.
`
`(54) Title: MONOLITHIC THERMOPLASTIC ETHER POLYURETHANE HAVING HIGH WATER VAPOR TRANSMISSION
`
`
`
`2004/041898A1||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||l
`
`(57) Abstract: A thermoplastic polyurethane comprising a tetrahydrofuran based polyether diol intermediate chain extended with
`selective types of diols has good water vapor transmission but is resistant to liquid water through put, has good dimensional stability,
`o good softness and elasticity, good tensile set and is non blocking. The thermoplastic polyurethane can be made by either a one shot
`process as in an extruder or by a prepolymer route and can be formed into a monolithic sheet or film for such uses as a roofing
`W
`membrane, house wrapping, tubing, fiber, wound dressing, and the like.
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-1-
`
`‘ MONOLITHIC THERMOPLASTIC ETHER POLYURETHANE HAVING HIGH
`
`WATER VAPOR TRANSMISSION
`
`FIELD OF INVENTION
`
`5
`
`The
`
`present
`
`invention
`
`relates
`
`to
`
`a
`
`polyether
`
`thermoplastic
`
`polyurethane extrudable at high speeds into sheets or films having good
`
`water vapor transmission but is resistant to liquid water penetration. The
`
`thermoplastic polyurethane displays a unique combination of properties such
`
`as softness, elasticity, crystallinity, and good dimensional stability.
`
`10
`
`BACKGROUND OF THE INVENTION
`
`Heretofore, various polymers having micropores formed therein have
`
`been used as moisture vapor transmitting membranes. Such polymers are
`
`alleged as being resistant to liquid water throughput but permit water vapor
`
`15
`
`to pass therethrough. These micropore structures are generally not suitable
`
`for wraps because they tend to leak liquid water.
`
`European patent application 708,212 A1 relates to an underlayment,
`
`particularly for inclined, heat—insulated roofs with a nonwoven fabric layer
`
`that is permeable to water vapor, but resistant to liquid water; and to a
`
`20
`
`reinforcing layer that is arranged on and bonded to the fabric layer and is
`
`also permeable to water vapor, but impermeable to liquid water.
`
`SUMMARY OF THE INVENTION
`
`The thermoplastic polyurethane of the present invention is preferably
`
`25
`
`derived from a
`
`tetrahydrofuran polyether
`
`intermediate reacted with a
`
`diisocyanate and low amounts of selective chain extenders to form a non—
`
`perforated, solid, crystalline sheet or film.
`
`In addition to high water vapor
`
`transmission
`
`but
`
`good
`
`resistance
`
`to
`
`liquid water
`
`throughput,
`
`the
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-2-
`
`polyurethane has several favorable properties such as high speed extrusion,
`
`low Shore A hardness (softness), good elasticity (T9 of minus ~30°C or less),
`
`suitable crystallinity for rapid extrusion and non-blocking, good dimensional
`
`stability in water at 24 hours, and the like.
`
`DETAILED DESCRIPTION OF THE DRAWINGS
`
`FIG.
`
`1
`
`is a graph showing the moisture vapor transmission of the
`
`composition of Example 1;
`
`10
`
`1;
`
`FIG. 2 is a graph showing DCS scans of the composition of Example
`
`FIG. 3 is a graph showing the moisture vapor transmission of the
`
`composition of Example 3;
`
`FIG. 4 is a graph showing DCS scans of the composition of Example
`
`15
`
`4;
`
`FIG. 5 is a graph showing the moisture vapor transmission of the
`
`composition of Example 4; and
`
`FIG. 6 is a graph showing DCS scans of the composition of Example
`
`20
`
`25
`
`30
`
`DETAILED DESCRIPTION
`
`The thermoplastic polyurethanes having a unique combination of
`
`properties contain a polyether
`
`intermediate derived from tetrahydrofuran
`
`monomers so that
`
`tetramethylene oxide repeat units are present
`
`in the
`
`intermediate which also has terminal hydroxyl groups. Optionally, selective
`
`types of other alkylene oxide monomers can be utilized in addition to the
`
`tetrahydrofuran monomers to form ether copolymers such as propylene oxide
`
`or a mixture of propylene oxide with ethylene oxide since other types of
`
`monomers generally yield poor dimensional stability. The ether intermediate
`
`generally has a number average molecular weight of from about 500 to
`
`

`

`WO 2004/041898
`
`PCT/US2003/031980
`
`-3-
`
`about 4,000, desirably from about 1,000 to about 2,500, and preferably
`
`from about 1,500 to about 2,200 as determined by hydroxyl end groups.
`
`The amount of the one or more optional comonomers is generally from about
`
`15 to about 75 and desirably from about 20 to about 30 parts by weight per
`
`100 total parts by weight of the tetrahydrofuran monomers. The amount of
`
`the ethylene oxide monomers, when utilized, is generally from about 15% to
`
`about 50% and desirably from about 20% to about 30% based upon the
`
`total weight of the propylene oxide and ethylene oxide monomers.
`
`The polyether intermediate is one of three main ingredients forming
`
`the thermoplastic urethanes of the present invention and the amount thereof
`
`is generally from about 60% to about 80%, desirably from about 65% to
`
`about 75%, and preferably from about 67% to about 73% by weight based
`
`upon the total weight of the polyether intermediate, a polyisocyanate, and a
`
`chain extender. The amount of polyisocyanate is generally from about 20%
`
`to about 30% and desirably from about 22% to about 28% by weight, and
`
`the amount of the chain extender is from 1% to about 10% and desirably
`
`from about 2% to about 8% by weight, based upon the total weight of the
`
`polyether intermediate, the polyisocyanate, and the chain extender.
`
`The polyisocyanates of
`
`the present
`
`invention generally have the
`
`formula RlNCO)n where n is generally from 2 to 4 with 2 being highly
`
`preferred inasmuch as
`
`the
`
`composition is
`
`a
`
`thermoplastic.
`
`Thus,
`
`polyisocyanates having a functionality of 3 or 4 are utilized in very small
`
`amounts, for example less than 5% and desirably less than 2% by weight
`
`based upon the total weight of all polyisocyanates, inasmuch as they cause
`
`crosslinking.
`
`R
`
`can be
`
`aromatic,
`
`cycloaliphatic,
`
`and
`
`aliphatic,
`
`or
`
`combinations thereof generally having a total of from 2 to about 20 carbon
`
`atoms.
`
`Examples of suitable aromatic diisocyanates
`
`include diphenyl
`
`methane-4, 4’~diisocyanate (MDI), H12 MDl, m-xylylene diisocyanate (XDl),
`
`m-tetramethyl xylylene diisocyanate (TlVlXDl), phenylene—1,4—diisocyanate
`
`(PPDI),
`
`1,5—naphthalene diisocyanate
`
`(NDI),
`
`and diphenylmethane-3,3’-
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-4-
`
`dimethoxy—4,4’-diisocyanate
`
`(TODI).
`
`Examples
`
`of
`
`suitable
`
`aliphatic
`
`diisocyanates
`
`include
`
`isophorone
`
`diisocyanate
`
`(IPDI),
`
`1,4—cyclohexyl
`
`diisocyanate (CHDI), hexamethylene diisocyanate (HDI), 1,6—diisocyanato—
`
`2,2,4,4—tetramethyl hexane (TMDI), 1,10-decane diisocyanate, and trans—
`
`dicyclohexylmethane diisocyanate (HMDI). A highly preferred diisocyanate is
`
`MDl containing less than about 3% by weight of ortho—para (2,4) isomer.
`
`Generally any conventional catalyst can be utilized to react
`
`the
`
`diisocyanate with the polyether intermediate or the chain extender and the
`
`same is well known to the art and to the literature. Examples of suitable
`
`catalysts include the various alkyl ethers or alkyl thiol ethers of bismuth or
`
`tin wherein the alkyl portion has from 1
`
`to about 20 carbon atoms with
`
`specific examples including bismuth octoate, bismuth laurate, and the like.
`
`Preferred catalysts include the various tin catalysts such as stannous
`
`octoate, dibutyltin dioctoate, dibutyltin dilaurate, and the like. The amount
`
`of such catalyst is generally small such as from about 20 to about 200 parts
`
`per million based upon the total weight of
`monomers.
`
`the polyurethane forming
`
`In addition to the selective types of polyether intermediates utilized, it
`
`is an important aspect of the present invention to use selective types of
`
`chain extenders in order to achieve the unique combination of physical
`
`properties of
`
`the thermoplastic polyurethanes of
`
`the present
`
`invention.
`
`While butane diol is preferred, ethylene glycol, hexane diol, dipropylene diol,
`
`ethoxylated hydroquionone and 1,4-cyclohexylydiene
`
`diol
`
`can also be
`
`utilized. Low amounts of the chain extender are utilized in order to keep the
`
`number of hard segments of the polyurethane low and thus to produce a
`
`soft, elastic, resilient, but high moisture vapor transmissible polyurethane.
`
`Thermoplastic polyurethanes of the present invention are preferably
`
`made via a "one shot" process wherein all
`
`the components are added
`
`together simultaneously or substantially simultaneously to a heated extruder
`
`and reacted to form the polyurethane.
`
`The equivalent
`
`ratio of
`
`the
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2004/041898
`
`PCT/US2003/031980
`
`-5-
`
`diisocyanate to the total equivalents of the hydroxyl terminated polyether
`
`intermediate and the diol chain extender is generally from about 0.95 to
`
`about 1.10, desirably from about 0.98 to about 1.05, and preferably from
`
`about 0.99 to about 1.03. The equivalent ratio of the hydroxyl terminated
`
`polyether to the hydroxyl terminated chain extender is generally from 0.5 to
`
`about 1.5 and preferably from about 0.70 to about
`
`1.
`
`Reaction
`
`temperatures utilizing urethane catalyst are generally from about 175°C to
`
`about 245°C and preferably from about 180°C to about 220°C. The number
`
`average molecular weight of the thermoplastic polyurethane is generally from
`
`about 10,000 to about 150,000 and desirabEy from about 50,000 to about
`
`100,000 as measured by GPC relative to polystyrene standards.
`
`The thermoplastic polyurethanes can also be prepared utilizing a
`
`prepolymer process.
`
`In the prepolymer
`
`route,
`
`the hydroxyl
`
`terminated
`
`tetramethylene oxide based polyether intermediate is reacted with generally
`
`an equivalent excess of one or more polyisocyanates to form a prepolymer
`
`solution having free or unreacted polyisocyanate therein.
`
`Reaction is
`
`generally carried out at temperatures of from about 80°C to about 220°C
`
`and preferably from about 150°C to about 200°C in the presence of a
`suitable urethane catalyst. Subsequently, a selective type of chain extender
`
`as noted above is added in an equivalent amount generally equal
`
`to the
`
`isocyanate end groups as well as to any free or unreacted diisocyanate
`
`compounds. The overall equivalent ratio of the total diisocyanate to the total
`
`equivalent of the hydroxyl terminated polyether and the chain extender is
`
`thus from about 0.95 to about 1.10, desirably from about 0.98 to about
`
`1.05 and preferably from about 0.99 to about 1.03. The equivalent ratio of
`
`the hydroxyl terminated polyether to the chain extender is generally from
`
`about 0.5 to about 1.5 and desirably from about 0.7 to about 1. The chain
`
`extension reaction temperature is generally from about 180°C to about
`
`250°C with from about 200°C to about 240°C being preferred. Typically the
`
`1O
`
`15
`
`20
`
`25
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`~6-
`
`prepolymer route can be carried out
`
`in any conventional device with an
`
`extruder being preferred. Thus, the polyether intermediate is reacted with an
`
`equivalent excess of a diisocyanate in a first portion of the extruder to form
`
`a prepolymer solution and subsequently the chain extender is added at a
`
`downstream portion and reacted with the prepolymer solution.
`
`Any
`
`conventional extruder can be utilized, with extruders equipped with barrier
`
`screws having a length to diameter ratio of at least 20 and preferably at
`
`least 25.
`
`Useful additives can be utilized in suitable amounts and include
`
`opacifying pigments, colorants, mineral
`
`fillers, stabilizers,
`
`lubricants, UV
`
`absorbers, processing aids, and other additives as desired. Useful opacifying
`
`pigments include titanium dioxide, zinc oxide, and titanate yellow, while
`
`useful tinting pigments include carbon black, yellow oxides, brown oxides,
`
`raw and burnt sienna or umber, chromium oxide green, cadmium pigments,
`
`chromium pigments, and other mixed metal oxide and organic pigments.
`
`Useful fillers include diatomaceous earth (superfloss) clay, silica, talc, mica,
`
`wallostonite, barium sulfate, and calcium carbonate.
`
`If desired, useful
`
`stabilizers
`
`such as
`
`antioxidants
`
`can be used and
`
`include phenolic
`
`antioxidants, while useful photostabilizers include organic phosphates, and
`
`organotin thiolates (mercaptides). Useful lubricants include metal stearates,
`
`paraffin
`
`oils
`
`and
`
`amide waxes. Useful UV absorbers
`
`include
`
`2—(2'-
`
`hydroxyphenol)benzotriazoles and 2—hydroxybenzophenones.
`
`Plasticizer additives can also be utilized advantageously to reduce
`
`hardness without affecting properties.
`
`The thermoplastic ether polyurethanes of the present invention made
`
`utilizing selective monomers as set forth hereinabove have unexpectedly
`
`been found to yield a unique combination of properties which render the
`
`polyurethane suitable for numerous end uses set forth herein below. The
`
`thermoplastic polyurethane has a high crystalinity such as from about 3 J/g
`
`to about 10 J/g and desirably from about 4 J/g to about 8 J/g as measured
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-7-
`
`by a differential scanning colorimeter. Such crystallinity permits extrusion of
`
`films and sheets at high speeds such as at
`
`least 25 meters per minute,
`
`desirably from about 30 to about 60 meters per minute and preferably from
`
`about 40 to about 50 meters per minute on a 120 millimeter extruder fitted
`
`with a 120 centimeter slit die set at a gap of 4 mils. Such extrusion rates
`
`are faster than conventional polyurethanes of similar hardness and lower
`
`crystallinity. The conventional, prior art products with lower crystallinity
`
`contain high level of lubricants and antiblocking agents which reduce the
`
`moisture vapor transmission rates.
`
`Crystallinity also imparts good non-
`
`blocking properties so the sheets or films can be rolled upon itself without
`
`sticking. Yet,
`
`the thermoplastic ether polyurethane is generally soft and
`
`elastic.
`
`The ASTM D-2240 Shore A hardness is generally about 80 or less,
`
`desirably from about 68 to about 78, and preferably from about 70 to about
`
`75. The polyurethanes of the present invention are very elastic due in part
`
`to the low Tg thereof which is generally less than about minus 30°C,
`
`desirably less than about minus 40°C, and preferably from about minus 40°C
`
`to about minus 75°C as measured by differential scanning calorimeter,
`
`10°C/min temperature program. The resilience or elasticity is somewhat
`
`similar to rubber in that the polymer can be elongated generally from about
`
`50% to about 300% or 500% and desirably from about 100% to about
`
`200% with ready retraction to its original length.
`
`Another desirable attribute of the thermoplastic polyurethanes of the
`
`present
`
`invention is that they have excellent dimensional stability of less
`
`,
`
`than 10%, desirably less than 5% and preferably less than about 3% or
`
`about 1.5% weight gain after being immersed in water for 24 hours, ASTM
`
`D-471~98.
`
`A notable property of the thermoplastic polyurethane is its excellent
`
`water vapor transmission as measured by a Mocon Permatran-W model
`
`1O
`
`15
`
`20
`
`25
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`~8-
`
`instrument at a thickness of 1
`
`to 4 mils, (25 to 100 microns) at 38°C and
`
`100% relative humidity which is at least 1,500, desirably from about 1,500
`
`to about 2,500, and preferably from about 1,700 to about 2,000 grams per
`
`square meter per 24 hours at atmospheric pressure.
`
`The upright cup
`
`moisture vapor transmission at a 1 mil thickness at 23°C and 50% relative
`
`humidity and atmospheric pressure is at least 200, desirably from about 250
`
`to about 450 and preferably from about 275 to about 350 grams per square
`
`meter per 24 hours, ASTM E—96.
`
`The mechanical properties of the thermoplastic polyurethane are good
`
`in that tensile strengths according to ASTM D—412/D-638 is generally at
`
`least about 20 or 30, and preferably from about 35 to about 60 MPa.
`
`Tensile set at 200% elongation according to ASTM D-412 is generally less
`
`than 15%, desirably less than 10%, and preferably less than about 8%.
`
`Inasmuch as the thermoplastic elastomer when sheeted or formed into
`
`film, cast or blown films, etc. is a solid, that is a monolithic barrier free of
`
`any perforations,
`
`it can be used in any application where high water vapor
`
`transmission is desired such as building wrap as for a house, a roofing
`
`membrane as in roofing material, as a wound dressing layer for application to
`
`a person or animal, for waterproof textiles, and the like. Other applications
`
`include tubing for pneumatics or peristaltic pumps, elastic fibers as for
`
`Spandex ®
`
`applications, gaskets, hose jacketing, and the like. Molded
`
`articles can also be made such as shoe straps, overmolding over
`
`rigid
`
`plastics and metals for soft touch handles and covers. Further, laminates of
`
`the thermoplastic ether polyurethane elastomers of the present invention can
`
`be made wherein the backing layer can be woven or non—woven polyester,
`
`polypropylene, paper, polyvinyl chloride, nylon, and the like.
`
`Since the various article,
`
`layers, sheets, films, etc, formed from the
`
`polyurethanes of the invetnion are solid, they are substantially free of pin
`
`holes, perforations and the like.
`
`In, other words, they contain a perforated
`
`area of less than 1%,
`
`less than 0.5%, 0.01%, or 0.005%. To test the
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-9-
`
`presence of pin holes membranes were attached to frames set at 45° angle
`
`and soaked with shower heads placed above the frames to simulate rain for
`
`at least a few hours. The presence of pin holes show up as wet circles on
`
`the reverse side of membranes. They are counted per unit area of (m2)
`
`membrane and membranes showing pinholes (measured as leak spots) in
`
`number above 0.001/m2 are not used.
`
`The present invention will be better understood by reference to the
`
`following examples which serve to illustrate, but not to limit the invention.
`
`10
`
`15
`
`EXAMPLES
`
`Example 1 (One Shot)
`
`Polyether polyol PTMEG of molecular weight 2000 Daltons is charged
`
`into a heated (90°C) and agitated tank blended with based on 100 points by
`
`weight of the final polymer weight, with 0.3% by weight antioxidant and
`
`0.3% by weight uv stabilizer. A second preheated tank was charged with
`
`the chain extender, 1,4-butanedio,l and kept at 50°C. A third preheated
`
`20
`
`agitated tank contained 4,4’-methylenebisphenylisocyanate (MDI).
`
`The
`
`ingredients of three tanks were metered accurately into throat of a 40mm
`
`co—rotating twin-screw extruder reactor made by Werner & Pfleiderer Corp.,
`
`Ramsay, NJ.
`
`The extruder had 11 barrel sections which were heated
`
`between 190°C to 205°C. The end of the extruder was coupled to an
`
`25
`
`under—water pelletizer after a six hole die equipped with screen packs. The
`
`following formulation was run continuously by metering 25.07 pts of MDI,
`
`5.82 pts of 1,-4-butanediol and 68.5 pts of polyol
`
`(PTMEG). Extruder
`
`throughput was adjusted to 150 lbs/hr while from a separate sm‘all tank
`
`50ppm (based on polymer) of stannous octoate catalyst was injected into
`
`30
`
`polyol stream. The product was underwater pelletized and collected in a
`
`heated silo at 105°C to dry the product for three hours.
`
`The product
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-10-
`
`produced in this way was extruded into 2 mils thick void free films with a
`
`single screw extruder fitted with a flat film die. Extruder speed can be
`
`varied from 30 to 70 without causing any tackiness and very little rise in
`
`melt temperature. The properties of the film was measured and listed in
`
`Table 1 and the moisture vapor transmission and the DCS scans are set forth
`
`respectively in FIGS. 1 and 2.
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-11-
`
`Table 1
`
`Film Properties of Polymer of Example 1:
`
`Typical Properties
`
`Test Method
`
`Typical Values
`
`PHYSICAL
`
`Specific Gravity
`Shore Hardness (after 5 sec)
`
`MECHANICAL
`
`Tensile Strength
`Stress @
`100% Elongation
`300% Elongation
`Ultimate Elongation
`Tensile Set @ 200%
`Elongation
`Tear Strength
`Split Tear Resistance
`THERMAL
`
`Glass Transition Temperature
`Pellets
`Film (1.2 mil)
`Melt Temperature
`Pellets
`Film (1.2 mil)
`
`Crystallization Temperature
`Pellets
`Film (1.2 mil)
`Kofler Melt Point
`
`OTHER RELEVANT DATA
`Moisture Vapor Transmission
`
`Mocon (38°C/100% RH)
`
`Upright Cup (23‘C/50% RH)
`
`SI
`Units
`
`1.13
`72A
`
`English
`Units
`
`1.13
`72A
`
`ASTM D-792
`ASTM D-2240
`
`ASTM D—412/D-638
`ASTM D—412/D-638
`
`ASTM D—412/D-638
`ASTM D-412
`
`52.4 MPa
`
`7600 psi
`
`5.7 MPa
`10.2 MPa
`660%
`6%
`
`820 psi
`1480 psi
`660%
`6%
`
`ASTM D-624, Die C
`ASTM D—47O
`
`67.6 kN/m
`17.2 kN/m
`
`386 lb/in
`98 lb/in
`
`DSC
`
`Kofler
`
`67°C
`—69°C
`
`167°C
`170°C
`
`97°C
`90°C
`155°C
`
`89°F
`-92°F
`
`333°F
`338°F
`
`207°F
`194°F
`31 1°F
`
`ASTM D 6701
`
`ASTM E—96
`
`1880g/m2
`0 24h
`
`31Og/m2
`- 24h
`
`18809/m2
`0 24h
`
`31Og/m2
`0 24h
`
`Example 2 (One Shot)
`
`Polyether polyol PTMEG of molecular weight 2000 Daltons and
`
`dipropylene glycol
`
`(DPG) chain extender are
`
`charged into a heated (90°C)
`
`and agitated tank in at a ratio of 68.04:1.34 by weight and blended based
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-12_
`
`on the final polymer weight, with 0.3% by weight antioxidant and 0.3% by
`
`weight uv stabilizer. A second preheated tank was charged with the chain
`
`extender 1,4—butanediol and kept at 50°C. A third preheated agitated tank
`
`contained 4,4’—methylenebisphenylisocyanate (MDI).
`
`The ingredients of
`
`three tanks were metered accurately into throat of a 40mm co-rotating twin—
`
`screw extruder reactor made by Werner & Pfleiderer Corp., Ramsay, NJ.
`
`The extruder had 11 barrel sections which were heated between 190°C to
`
`205°C. The end of the extruder was coupled to an under—water pelletizer
`
`after a six hole die equipped with screen packs. The following formulation
`
`1O
`
`was run continuously by metering 25.07 pts of MDI, 4.94 pts of 1,-4-
`
`15
`
`20
`
`25
`
`butanediol and 69.4 pts of polyol (PTMEG)/(DPG) mixture from the first tank.
`
`PTMEG/DPS blend and BDO was combined and passed through a static
`
`mixer forming a single stream which was fed with the MDI stream into a
`
`heated
`
`pre-reactor which
`
`discharged
`
`the
`
`partially
`
`reacted mixture
`
`continuously into the extruder throat. Extruder throughput was adjusted to
`
`150 lbs/hr while from a separate small tank 50ppm (based on polymer) of
`
`stannous octoate catalyst was injected into polyol stream. The product was
`
`underwater pelletized and collected in a heated silo at 105°C to dry the
`
`product for three hours. Melt flow index (MFI) of the pelletized product was
`
`measured to be 15.6 at 200°C/3800gm. The product was extruded into 2
`
`mils thick void free films with a single screw extruder fitted with a flat film
`
`die. Extruder speed can be varied from 30 to 70 RPM without causing any
`
`tackiness and very little rise in melt temperature.
`
`Example 3 (One Shot)
`
`Polyether polyol PTMEG of molecular weight 1450 Daltons is charged into a
`
`heated (90°C) and agitated tank blended, based on the final polymer weight,
`
`with 0.3% by weight antioxidant and 0.3% by weight uv stabilizer. A
`
`second preheated tank was charged with the chain extender 1,4—butanediol
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-13-
`
`and kept at 50°C. A third preheated tank agitated tank contained 4,4’~
`
`methylene bisphenyl isocyanate (MDI). The ingredients of the three tanks
`
`were metered accurately into throat of a 40mm co-rotating twin-screw
`
`extruder reactor made by Werner & Pfleiderer Corp., Ramsay, NJ.
`
`The
`
`extruder had 11 barrel sections which were heated between 190°C to
`
`205°C. The end of the extruder was coupled to an under-water pelletizer
`
`after a six hole die equipped with screen packs. The following formulation
`
`was run continuously by metering 25.07 pts of MDl, 4.52 pts of
`
`1,—4—
`
`butanediol and 69.8 pts of polyol (PTMEG). PTMEG and BBQ was combined
`
`1O
`
`and passed through a static mixer forming a single stream which was fed
`
`with the MDl stream into a heated pre—reactor which discharged the partially
`
`reacted mixture continuously into the extruder throat. Extruder throughput
`
`was adjusted to 150 lbs/hr while from a separate small tank 50ppm (based
`
`on polymer) of stannous octoate catalyst was injected into the polyol
`
`15
`
`stream. The product was underwater pelletized and collected in a heated
`
`silo at 105°C to dry the product for three hours. Melt flow index (MFl) of the
`
`palletized product was measured to be 6.2 at 200°C/38009m. The product
`
`produced was extruded into 1
`
`to 4 mils thick void free films with a single
`
`screw extruder fitted with a flat film die. Extruder speed can be varied from
`
`20
`
`30 to 70 without causing any tackiness and very little rise in melt
`
`temperature. Moisture vapor transmission rates (MVT) are plotted in Figure 3
`
`and extrapolated to a value of 28009ms.m2/day measured with the Mocon
`
`Permatran—W Model instrument made by Mocon Company, Minneapolis, MN
`
`at 38°C and 100% relative humidity.
`
`25
`
`Example 4: (One Shot)
`
`Polyether polyol PTMEG of molecular weight 2000 Daltons is charged into a
`
`30
`
`heated (90°C) and agitated tank blended based on the final polymer weight,
`
`with 0.3% by weight antioxidant and 0.3% by weight uv stabilizer. A
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-14-
`
`second preheated tank was charged with the chain extender 1,4—butanediol
`
`and kept at 50°C.
`
`A third preheated agitated tank contained 4,4’-
`
`methylenebisphenylisocyanate (MDI). The ingredients of three tanks were
`
`metered accurately into throat of a 40mm co—rotating twin—screw extruder
`
`reactor made by Werner & Pfleiderer Corp., Ramsay, NJ. The extruder had
`
`11 barrel sections which were heated between 190°C to 205°C. The end of
`
`the extruder was coupled to an under—water pelletizer after a six hole die
`
`equipped with screen packs.
`
`The
`
`following
`
`formulation was
`
`run
`
`continuously by metering 25.07 pts of MDl, 4.52 pts of 1,—4—butanediol and
`
`69.8 pts of polyol
`
`(PTMEG). PTMEG and BBC was combined and passed
`
`through a static mixer forming a single stream which was fed with the MDl
`
`stream into a heated pre—reactor which discharged the partially reacted
`
`mixture continuously into the extruder throat. Extruder throughput was
`
`adjusted to 150 lbs/hr while from a separate small tank 50ppm (based on
`
`polymer) of stannous octoate catalyst was injected into polyol stream. 2%
`
`based on the polymer of diatomecous earth (superfloss) was also introduced
`
`into the extruder at barrel section 2 as a non blocking filler. The product was
`
`underwater pelletized and collected in a heated silo at 105°C to dry the
`
`product for three hours. Melt flow index (MFl) of the pelletized product was
`
`measured to be 6.2 at 200°C/38009m. The product produced was extruded
`
`into 1 to 4 mils thick void free films with a single screw extruder fitted with
`
`a flat film die. Extruder speed can be varied from 30 to 70 without causing
`
`any tackiness and very little rise in melt temperature. The properties of the
`
`film was measured and listed in Table 2 and the extrusion outputs are set
`
`1O
`
`15
`
`20
`
`25
`
`forth in Tables 3 and 4. DCS scans are set forth in FIG. 4 and moisture
`
`vapor transmission rates (MVT) is plotted in Figure 5 and extrapolates to a
`
`value of 3ZOOgms.m2/day measured with the Mocon Permatran—W Model
`
`instrument made by Mocon Company, Minneapolis, MN at 38°C and 100%
`
`relative humidity.
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-15-
`
`Table 2
`
`Properties of Product of example 4
`
`Typical Properties
`
`Test Method
`
`Typical Values
`
`SI Unit
`
`English Units
`
`PHYSICAL
`
`Specific Gravity
`Shore Hardness (after 5 sec)
`
`MECHANICAL
`
`Tensile Strength
`Stress @
`100% Elongation
`300% Elongation
`Ultimate Elongation
`Tensile Set @ 200%
`Elongation
`Tear Strength
`Split Tear Resistance
`THERMAL
`
`Glass Transition Temperature
`Pellets
`Film (1.2 mil)
`Melt Temperature
`Pellets
`Film (1.2 mil)
`Crystallization Temperature
`Pellets
`Film (1.2 mil)
`Kofler Melt Point
`
`Compression Set
`Q 23 °C
`@ 70 00
`OTHER RELEVANT DATA
`
`Moisture Vapor Transmission
`
`ASTM D—792
`ASTM D-2240
`
`1.08
`72A
`
`1.08
`72A
`
`ASTM D-412/D-638
`ASTM D—412/D-638
`
`ASTM D—412/D-638
`ASTM D-412
`
`52.4 MP8
`
`7600 psi
`
`5.7 MPa
`10.2 MPa
`660%
`6%
`
`820 psi
`1480 psi
`660%
`6%
`
`ASTM D—624, Die C
`ASTM D-47O
`
`67.6 kN/m
`17.2 kN/m
`
`386 lb/in
`98 lb/in
`
`DSC
`
`Kofler
`
`-67°C
`-69°C
`
`167°C
`170°C
`
`97°C
`90°C
`155 °C
`
`—89°F
`-92°F
`
`333°F
`338°F
`
`207°F
`194°F
`311°F
`
`20%
`29%
`
`20%
`29%
`
`Moconi38°Cl100% RH)
`
`ASTM D 6701
`
`Upright Cup (23°C/50% RH)
`
`ASTM E—96
`
`18809/m2
`0 24h
`
`31 Og/m2
`' 24h
`
`1880g/m2
`0 24h
`
`31 Og/m2
`' 24h
`
`DIMENSIONAL STABILITY
`Immersion Results in Water
`Time 24 hrs
`
`ASTM D471-98
`
`Volume Change %
`Mass Change %
`
`0.96
`1 .03
`
`0.96
`1.03
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-16—
`
`Extrusion Output study on polymer of Example 4
`
`1 1/2" Akron Extruder 3:1 barrier screw Saxton Mixer, 12" wide die
`Temperature settings 355 °F 365 °F 375 °F, die 375 0F
`
`Table 3
`
`product
`
` Polymer of Example 4
`
`
`—---
`rpm
`psi
`amps
`°F
`(ave of 3)
`
`-———n
`-——_n
`
`--——-.I
`
`
`Table 4
`
`2 “A" Killion Extruder 24:1 barrier screw Saxton Mixer, 18" wide die
`Temperature settings 355 °F 365 "F 375 0F, die 375 0F
`
` rate
`(lb/h)
`
`speed
`
`pressure
`
`current melt T
`
`
`
`
`
`
`product
`
`rpm
`
`psi
`
`amps
`
`°F
`
`(ave of 3)
`
`
`
`
`
`Example 5 (Two Step)
`
`22.75 pts of MDI, 72.27 pts of PTMEG (2000 Daltons) and 0.004 pts
`
`of stannous octoate were blended and reacted by vigorous stirring in a 500
`
`ml steel beaker at 200°C for 2 minutes. 4.97 pts of 1,4—butanediol was
`
`then quickly added to this partially reacted prepolymer and stirring continued
`
`for additional 2 minutes. The polymer melt was poured to a teflon coated
`
`pan and cured for 2 hours at 105°C. The MFI
`
`index of this polymer was
`
`found to be 4.4 measured at 200°C under 3800 gm load. The weight
`
`average Mw GPC molecular weight was 229956 and number average Mn
`
`molecular weight was 66630 indicating high molecular weight product. The
`
`crystallinity was deter mined by DSC and shown in Figure 6 below.
`
`‘IO
`
`15
`
`20
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`_17_
`
`Integrated peaks at 8°C and 138°C indicate the material
`
`is sufficiently
`
`crystalline to be considered non—tacky for membrane extrusion purposes.
`
`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.
`
`

`

`WO 2004/041898
`
`PCT/U82003/031980
`
`-18—
`
`WHAT IS CLAIMED IS:
`
`1 .
`
`A thermoplastic polyurethane composition, comprising:
`
`the reaction product of a polyether intermediate having at
`
`least a
`
`tetramethylene oxide repeat unit, and optionally a repeat unit derived from
`
`propylene oxide or from propylene oxide and ethylene oxide; a diisocyanate;
`
`and a chain extender comprising ethylene glycol, butane diol, hexane diol,
`
`dipropylene diol, ethoxylated hydroquinone, or cyclohexylydiene diol, or
`
`combinations thereof;
`
`said composition having a water vapor transmission of at least 1,500
`
`grams per square meter per 24 hours at atmospheric pressure and 38°C, and
`
`100% relative humidity at a thickness of 1 to 4