Alloy blends of polyurethane and rubber

a technology of polyurethane and blend, applied in the field of rubber formulation, can solve the problems of deficient gas barrier performance, deficient air retention or elastic properties, bladders or “cores” made of natural rubber, etc., and achieve the effect of improving barrier properties

Inactive Publication Date: 2005-12-01
SANDUSKY DONALD ALLAN +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0015] An aspect of the present invention provides barrier articles with novel formulations for use in hollow or inflatable articles, such as tennis balls, basketballs, volleyballs, soccer balls, inner tubes, and tires having substantially improved barrier properties.

Problems solved by technology

These cured rubber components are fabricated with conventional rubber milling and molding methods and form products that are sufficient in some properties but are typically deficient in either air retention or elastic properties.
Bladders, or “cores,” made from natural rubber can suffer from deficient gas barrier performance, undesirably high rubber aging, and undesirable rubber hysteresis attributes.
Natural rubber is known to age harden over time and suffers from high hysteresis in that the rubber does not readily recover its pre-stretched elastic properties.
Moreover, because of the deficient gas barrier performance of natural rubber, the pressure gradient between the pressurized inside and ambient outside, causes air to gradually diffuse from balls made from natural rubber.
Loss of air ultimately renders these balls unsuitable for play.
As a result of undesirable rubber aging and poor rubber hysteresis properties, the bounce and feel of these balls tends to decay substantially within the normal use timeframe.
However, they are significantly deficient in resilience which negatively affects their bounce, control, and feel.
Deficiencies in resilience exacerbates vulnerability of articles such as innertubes to puncture damage.
However, because of pressure differential between inside the core and outside, the air gradually diffuses to the outside, causing “softening” of the ball which results in loss of good bounce and playability.
However, once a tennis ball is removed from its pressurized can, air pressure loss starts and softening of the ball resumes and play consistency continues to deteriorate.
On the other hand, in the premium performance soccer balls, natural latex rubber bladders are employed for superior foot-speed and control, but at a significant air retention penalty.
The poor air retention of natural rubber soccer balls becomes an even bigger problem on a long hot summer day.
However, these airless tennis balls do not have the same “feel” and bounce as the pressurized balls, consequently pressureless balls have not been adopted by tennis professionals.
Another difficult approach is to employ a flexible barrier spray-coated inside the bladder or core halves.
However, each of these is expensive and cumbersome to employ.
In the case of sulfur hexafluoride, internal pressure actually increases with time due to pneumatic pumping of air molecules from the outside the ball into the inside of the ball driven by the partial pressure gradient and limited by the relatively slow permeability of the sulfur hexafluoride.
Moreover, these tennis balls, which are made of a molded spherical shell of elastomeric material, such as natural rubber or artificial rubber suffer from the same softening due to air leakage in between the pumping events.

Method used

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  • Alloy blends of polyurethane and rubber
  • Alloy blends of polyurethane and rubber

Examples

Experimental program
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examples

[0059] Exemplary embodiments of the present invention used PTMEG-based polyurethanes, Adiprene® CM (ACM) and Millathane® E-34 (ME34), and a polyester-based polyurethane, Millathane® M76 (MM76) (Adiprene and Millethane are trademarks of TSE Industries, Inc.). These polyurethanes are combined with rubbers to make the inventive barrier articles. Typically, the natural rubber and MPU are blended in e.g. a Banbury mixer along with additives and curatives until thoroughly mixed to achieve the desired consistency as described above. The natural rubbers employed are isoprene materials typically used in conventional sports balls. The natural rubber formulations are Standard Malaysian Rubber formulations, grade GP (SMR GP). SMR GP is processed from mixed latex and rubber sheets. Formula information for SMR GP sub-grades GP1, GP2, and GP4 are listed below in tables 1, 2 and 3.

TABLE 1GP1 Formula barrier article formulationGP1GP1FormulaFormulaIngredientDescriptionType(lb)(%)SMR GPNaturalRubber...

examples 1-12

[0062] MPU / rubber alloys were formed by mixing either Adiprene® CM (ACM), Millathane® E-34 (ME34), or Millathane® M76 (MM76) with a natural rubber component (SMR-GP) in proportions indicated in the tables below. The barrier articles further include about 50 wt % clay and other additives. For example, the description of Example 1, table 5, is for 50 / 50 ACM / SMR-GP a GP2 barrier article. The barrier article of Example 1 therefore contains 50 parts ACM and 50 parts SMR-GP based on weight and in addition includes the proportionate amount of fillers and additives of GP2 (table 2). Stated differently, Example 1 has the identical formulation as GP2 (table 2) except the amount of SMR-GP has been halved from 77.2 lbs to 38.6 lbs and replaced with 38.6 lbs of ACM.

[0063] As noted above in Tables 2 and 3, GP2 and GP4 barrier article formulations likewise included about 50 wt % clay and other additives. The results of permeability testing are presented in the table below. Example barrier article...

examples 13-24

[0066] Barrier articles with alloys of MPU and GP1, and including about 50 wt % clay and other additives, gave improved permeability relative to barrier article controls GP2 and GP4 and showed a strong correlation of temperature and permeability. The materials were prepared as in Examples 1-12, but tested as sheet examples. Example E, a sheet example, was made from GP1.

TABLE 6Oxygen290FNominalTrans.Est. OxygenMillSampleRelativePressureRatePermeabilityTimeThicknessHumidityTemp.Gradient(21% O2)(cm3 cm / cm2 ·ExampleUnitsminmils%deg. C.mm Hgcc / m2 days · Pa) 10−13 13.20 / 80103435257601065.1ACM / SMR-GPGP1 barrierarticle14.40 / 6010323525760773.5ACM / SMR-GPGP1 barrierarticle15.60 / 4010433525760402.5ACM / SMR-GPGP1 barrierarticle16.80 / 2015343525760351.7ACM / SMR-GPGP1 barrierarticle17.80 / 2015273525760512.0ACM / SMR-GPGP1 barrierarticle20.80 / 2015273525760923.5ME34 / SMR-GPGP1 barrierarticle21.20 / 80103335257601155.5ME34 / SMR-GPGP1 barrierarticle22.40 / 6010343525760874.2ME34 / SMR-GPGP1 barrierarticle23.60 / 401...

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Abstract

The present invention relates to a rubber formulation suitable for making barrier articles, such as inflatable sports balls or bicycle tubes, that resist the passage of gases, such as air, particularly as applicable to tennis balls, and more particularly to the rubber formulation which contains substantially amorphous, millable polyurethane alloyed with natural and/or synthetic rubbers.

Description

CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims benefit of the priority of Provisional Application No. 60 / 455,674 filed Mar. 18, 2003 and U.S. application Ser. No. 10 / 802,137 filed Mar. 17, 2004, now abandoned.FIELD OF THE INVENTION [0002] The present invention relates to a rubber formulation suitable for making barrier articles, such as inflatable sports balls or bicycle tubes that resist the passage of gases, such as air, particularly as applicable to tennis balls and more particularly to the rubber formulation which contains substantially amorphous, millable polyurethane alloyed with natural and / or synthetic rubbers. BACKGROUND OF THE INVENTION [0003] In rubber barrier articles for producing pressurized sports articles, such as hollow core tennis balls or bladders for soccer balls, volleyballs, basketballs or bicycle innertubes, vulcanizable natural or synthetic butyl rubbers and combinations thereof are commonly employed. These cured rubber components are f...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): A63B39/00A63B41/02B60C1/00B60C5/02C08K3/34C08L7/00C08L21/00C08L75/04
CPCA63B39/00A63B41/02B60C1/0008B60C5/02C08K3/346C08L7/00C08L75/04C08L21/00C08L2666/14C08L2666/08
Inventor SANDUSKY, DONALD ALLANMCINNIS, EDWIN L.
Owner SANDUSKY DONALD ALLAN
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