CA2023353A1 - Polyurethane for flexible fuel containers - Google Patents
Polyurethane for flexible fuel containersInfo
- Publication number
- CA2023353A1 CA2023353A1 CA002023353A CA2023353A CA2023353A1 CA 2023353 A1 CA2023353 A1 CA 2023353A1 CA 002023353 A CA002023353 A CA 002023353A CA 2023353 A CA2023353 A CA 2023353A CA 2023353 A1 CA2023353 A1 CA 2023353A1
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- thermoplastic polyurethane
- glycol
- molecular weight
- tensile strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2390/00—Containers
Abstract
ABSTRACT
A polyurethane reinforced fabric molded flex-ible fuel tank comprises a high molecular weight ther-moplastic polyurethane polymer binder melt applied to reinforcing fabric and molded into a flexible fuel tank or container for storage of gasoline or jet fuels. The polyurethane polymer has an average molecular weight from about 60,000 to about 500,000 and particularly exhibits excellent fuel resistance.
The high molecular weight thermoplastic poly-urethane comprises the polymeric reaction product of an ethylene ether oligomer glycol intermediate co-reacted with a non-hindered diisocyanate and an extender glycol to produce the polyurethane polymer. The ethylene ether oligomer glycol intermediate is selected from (a) a diethylene glycol-aliphatic linear polyester or (b) a polyethylene glycol. The oligomer glycol intermediate has an average molecular weight from about 500 to about 5,000.
A polyurethane reinforced fabric molded flex-ible fuel tank comprises a high molecular weight ther-moplastic polyurethane polymer binder melt applied to reinforcing fabric and molded into a flexible fuel tank or container for storage of gasoline or jet fuels. The polyurethane polymer has an average molecular weight from about 60,000 to about 500,000 and particularly exhibits excellent fuel resistance.
The high molecular weight thermoplastic poly-urethane comprises the polymeric reaction product of an ethylene ether oligomer glycol intermediate co-reacted with a non-hindered diisocyanate and an extender glycol to produce the polyurethane polymer. The ethylene ether oligomer glycol intermediate is selected from (a) a diethylene glycol-aliphatic linear polyester or (b) a polyethylene glycol. The oligomer glycol intermediate has an average molecular weight from about 500 to about 5,000.
Description
~ 1890072 POLYURETHANE FOR FLEXIBLE FUEL CONTAINERS
FIELD OF THE INVENTION
cj The present invention pertains to polyurethane elastomers and more particularly to high molecular weight, thermoplastic polyurethanes used in the molding of fabric reinforced, portable flexible fuel containers utilized, for example, by the military for the storage of gasoline or jet fuels.
BACKG~OUND
Flexible fuel tanks utilized for the storage of gasoline or jet fuel require exte~ded fuel resistance and hydrolytic stability along with toughness, resiliency, and sufficient flexibility to maintain strength and integrity in weather extremes while in constant contact with aliphatic hydrocarbon fuels. Rigid structure fuel tanks can be constructed of fiberglass or nylon fabrics saturated with thermosetting polymers which ordinarily provide good rigid structural properties along with the desired fuel resistance. However, crosslinked polymers do not provide the necessary flexibility and resiliency required in the construction of flexible fuel tanXs.
Although, generally, thermoplastic polymers and par-ticular thermoplastic polyurethanes can provide flexibil-ity, they invariably do not exhibit adequate structural strengths and flexibility and lack long term resistance to hydrocarbon liquid fuels as well as necessary hydro-lytic stability. The physical properties and specifica-tions of polymers, polymeric composites, and flexible fuel tanks constructed therefrom are set forth in MIL
T52983B (17 September 1984) and the test for fuel resis-tance is set forth in ASTM D471-79 and particularly for 2 ~
resistance to fuels B and D. Fuel tanks generally have been suggested based on polyurethane polymers. In U.S.
Patent No. 4,487,913, for instance, complex thermosetting polyurethane polymers are crosslinked in the construction of aircraft fuel tanks typically comprising rigid struc-tures. Similarly, U.S. Patent No. 4,565,729 discloses a multilayer rigid laminate for rigid structural fuel tanks used on aircraft based on thermosetting amine crosslinked polyurethane polymers. Polyurethane coated fabrics used in unrelated flexible fabric constructions are disclosed in U.S. Patent No. 4,689,385 (face masks) and U.S. Patent No. 2,657,151 (raincoats). Unreinforced thermoplastic polyurethane elastomers for general use are disclosed in U.S. Patent No. 4,169,196, U.S. Patent No. 3,528,948 and U.S. Patent No. 3,706,710 based on polyester polyols reacted with diisocyanates and extended with low molecu-lar weight diols. In addition to not being combined with fabrics for either rigid or flexible reinforced products, the polymers disclosed in these patents are merely gener-al purpose polyurethane elastomers which do not necessar-ily exhibit high resistance to aliphatic hydrocarbon fuels or hydrolytic resistance or other structural and utility characteristics necessary for the construction of flexible fuel tanks. Other polyurethane polymers includ-ing polyester based polyurethanes are disclosed in thefollowing patents: U.S. Patent No. 2,871,218 disclosing extruded plastic sheets resistant to hydrocarbon solvents but soluble in polar solvents; U.S. Patent No. 4,400,498 pertaining to heat and solvent res~stant crosslinked polyurQthanes particularly adapted to disperse ~illers and pigments and useful for adhesives; U.S. Patent No.
4,191,818 directed to heat rasistent, crosslinked cry-stalline polyurethanes used in ela~tomeric cast moldings;
U.S. Patent No. 3,214,411 suggesting polyester poly-urethane polymers adapted to be heat crosslinked in high heat injection molding processes; and U.S. Patent No.
FIELD OF THE INVENTION
cj The present invention pertains to polyurethane elastomers and more particularly to high molecular weight, thermoplastic polyurethanes used in the molding of fabric reinforced, portable flexible fuel containers utilized, for example, by the military for the storage of gasoline or jet fuels.
BACKG~OUND
Flexible fuel tanks utilized for the storage of gasoline or jet fuel require exte~ded fuel resistance and hydrolytic stability along with toughness, resiliency, and sufficient flexibility to maintain strength and integrity in weather extremes while in constant contact with aliphatic hydrocarbon fuels. Rigid structure fuel tanks can be constructed of fiberglass or nylon fabrics saturated with thermosetting polymers which ordinarily provide good rigid structural properties along with the desired fuel resistance. However, crosslinked polymers do not provide the necessary flexibility and resiliency required in the construction of flexible fuel tanXs.
Although, generally, thermoplastic polymers and par-ticular thermoplastic polyurethanes can provide flexibil-ity, they invariably do not exhibit adequate structural strengths and flexibility and lack long term resistance to hydrocarbon liquid fuels as well as necessary hydro-lytic stability. The physical properties and specifica-tions of polymers, polymeric composites, and flexible fuel tanks constructed therefrom are set forth in MIL
T52983B (17 September 1984) and the test for fuel resis-tance is set forth in ASTM D471-79 and particularly for 2 ~
resistance to fuels B and D. Fuel tanks generally have been suggested based on polyurethane polymers. In U.S.
Patent No. 4,487,913, for instance, complex thermosetting polyurethane polymers are crosslinked in the construction of aircraft fuel tanks typically comprising rigid struc-tures. Similarly, U.S. Patent No. 4,565,729 discloses a multilayer rigid laminate for rigid structural fuel tanks used on aircraft based on thermosetting amine crosslinked polyurethane polymers. Polyurethane coated fabrics used in unrelated flexible fabric constructions are disclosed in U.S. Patent No. 4,689,385 (face masks) and U.S. Patent No. 2,657,151 (raincoats). Unreinforced thermoplastic polyurethane elastomers for general use are disclosed in U.S. Patent No. 4,169,196, U.S. Patent No. 3,528,948 and U.S. Patent No. 3,706,710 based on polyester polyols reacted with diisocyanates and extended with low molecu-lar weight diols. In addition to not being combined with fabrics for either rigid or flexible reinforced products, the polymers disclosed in these patents are merely gener-al purpose polyurethane elastomers which do not necessar-ily exhibit high resistance to aliphatic hydrocarbon fuels or hydrolytic resistance or other structural and utility characteristics necessary for the construction of flexible fuel tanks. Other polyurethane polymers includ-ing polyester based polyurethanes are disclosed in thefollowing patents: U.S. Patent No. 2,871,218 disclosing extruded plastic sheets resistant to hydrocarbon solvents but soluble in polar solvents; U.S. Patent No. 4,400,498 pertaining to heat and solvent res~stant crosslinked polyurQthanes particularly adapted to disperse ~illers and pigments and useful for adhesives; U.S. Patent No.
4,191,818 directed to heat rasistent, crosslinked cry-stalline polyurethanes used in ela~tomeric cast moldings;
U.S. Patent No. 3,214,411 suggesting polyester poly-urethane polymers adapted to be heat crosslinked in high heat injection molding processes; and U.S. Patent No.
3,012,992 disclosing load bearing, crosslinked poly-urethane castings and plastics. U.~. Patent No.
4,439,552 discloses cellular polyurethane foams, whereas U.S. Patent No. 4,762,884 discloses radiation activated crosslinked polyurethanes.
The physical, chemical and structural require-ments for flexible fuel tanks are set forth in MIL-T-52983B (17 September 1984) including prolonged flexi-bility and durability, resiliency and toughness, es-pecially prolonged hydrocarbon fuel resistance and hydro-lytic stability, high tensile strength before and after immersion in water or fuel, and certain stress-strain requirements such as tensile strength, percent elonga-tion, and percent modulus. However, various polyurethane polymers ordinarily considered to exhibit excellent physical properties have been found inadequate. Poly-urethane polymers based on polycaprolactone polyol, polytetramethylene ether glycol, and poly(tetramethylene adipate) glycol, are unsatisfactory and in particular lack satisfactory resistance to aliphatic hydrocarbon fuels. Polycaprolactone polyurethanes and polyether polytetramethylene ether glycol polyurethanes, for ex-ample, exhibited adequate hydrolytic stability but lacked sufficient resistance to liquid hydrocarbon fuels.
.
SUM~ARY OF THE INVENTION
It now has been found that a flexible, resil-ient fuel tank exhibiting excellent fuel resistance exceeding the requirements of ASTM D471-79 can be con-structed from a high molecular weight, thermoplastic polyurethane polymeric binder combined with a fibrous mat reinforce~ent and molded into a flexible fuel container construction. The polyurethane polymer has an average 2~2~3~ c3 ~, molecular weight from about 60,000 to about ~00,000 and comprises a hydroxyl terminated ethylene ether oligomer glycol intermediate having an average molecular weight from about 500 to 5,000 reacted with a non-hindered diisocyanate and an extender glycol to produce a high molecular weight thermoplastic polyurethane. The ethyl-ene ether oligomer glycol intermsdiate is selected from (a) an hydroxyl terminated, diethylene glycol aliphatic linear polyester and (b) a polyethylene glycol. The polyurethane thermoplastic can be combined, e.g. melt applied, with a fibrous mat or similar reinforcement and molded under heat into a flexible fuel container having excellent fuel resistance and hydrolytic stability.
-- These and other advantages of the present invention will become more apparent by referring to the detailed description of the invention and the illustrative ex-amples.
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic polyurethane polymer of the present invention, useful as an elastomeric melt or binder in a fabric reinforced flexible fuel tank, com-prises the reaction of a hydroxyl terminated ethylene ether oligomer intermediate with a non-hindered diiso-cyanate and an extender glycol, where the oligomer can be a diethylene glycol-aliphatic polyester, or a polyethylene glycol.
Referring first to the polyester intermediate, a hydroxyl terminated, saturated polyester polymer is synthesized by reacting excess equivalents of diethylene glycol with considerably lesser equivalents of an alipha-tic, preferably an alkyl, dicarboxylic acid having four to ten carbon atoms where the most preferred is adipic acid. Other useful dicarboxylic acids include succinic, glutaric, pimelic, suberic, azelaic and sebacic acids.
The most preferred polyester intermediate is polydi-ethylene glycol adipate. In accordance with this aspect of the present invention, excess moles of diethylene glycol are reacted with lesser moles of dicarboxylic acid at levels from about 5 mole percent to about 50 mole per-cent excess of glycol to provide a hydroxyl terminated polyester oliqomer chain having an average molecular weight between about 500 to 5000 and preferably between about 700 and 2500. The short chain polyester oligomer contains repeating diethylene ether structures and com-prises on an equivalent basis from about 1.05 to 1.5 equivalents of diethylene glycol co-reacted with one equivalent of dicarboxylic acid to produce the low mole-cular weight polyester oligomer intermediate. The high excess equivalents of diethylene glycol controls the molecular weight of the polyester oligomer preferably below 2500 and further assures a hydroxyl terminated linear polyester oligomer. The polyester oligomers synthesized by reacting the diethylene glycol with lesser equivalents of dicarboxylic acid at temperatures of from about 300F to 450F in the absence or in the presence of an esterification catalyst such as stannous chloride for time sufficient to reduce the Acid No. to about zero.
The hydroxyl terminated polyester oligomer intexmediate is further reacted with considerably excess equivalents of non-hindered diisocyanate along with extender glycol in a so-called one-shot or simultaneous coreaction of oligomer, diisocyanate, and extender glycol to produce the very high molecular weight linear polyure-thane having an average molecular weight broadly from about 60,000 to 500,000, preferably from about 80,000 to 180,000, and mo~t preferably ~rom about 100,000 to 180,000. The very high molecular weight linear polyure-thane based on the polyester oligomer in accordance with s~ 3 `1 ` ;
this aspect of the invention is unique in that an extra-ordinary high molecular weight polyurethane polymer is produced from a low molecular weight polyester oligomer prepolymer.
In accordance with a further aspect of this invention an ethylene ether oligomer glycol intermediate comprising a polyethylene glycol can be co-reacted with non-hindered diisocyanate and extender glycol to produce the high molecular weight polyurethane polymer. Useful polyethylene glycols are linear polymers of the general formula H-(OCH2CH2)-nOH where n is the number of repeat-ing ethylene ether units and n is at least 11 and between 11 and about 115. On a molecular weight basis, the useful range of polyethylene glycols have an average molecular weight from about 500 to 5000 and preferably from about 700 to 2500. Commercially available poly-ethylene glycols useful in this invention are typically designated as polyethylene glycol 600, polyethylene glycol 1500, and polyethylene glycol 4000.
In accordance with this invention, high molecu-lar weight thermoplastic polyurethanes are produced by reacting together preferably in a one-shot prscess the ethylene ether oligomer glycol intermediate, an aromatic or aliphatic non-hindered diisocyanate, and an extender glycol. On a mole basis, the amount of extender glycol for each mole of oligomer glycol intermediate is from about 0.1 to about 3.0 moles, desirably from about 0.2 to about 2.1 moles, and preferably from about 0.5 to about 1.5 moles. On a mole basis, the high molecular weight polyurethane polymer comprises ~rom about 0.97 to about 1.02 moles, and preferably about 1.0 moles of non-hin-dered diisocyanate for every 1.0 total moles of both the extender glycol and the oligomer glycol (i.e. extender glycol + oligomer glycol = 1.0).
Useful non-hindered diisocyanates comprise aromatic non-hindered diisocyanates and include, for example, 1,4-diisocyanatobenzene (PPDI), 4,4'-methylene-bis (phenyl isocyanate) MDI), 1,5-naphthalene diiso-cyanate (NDI), m-xylene diisocyanate (XDI), as well as non-hindered, cyclic aliphatic diisocyanates such as 1,4-cyclohexyl diisocyanate (CHDI), and H12 MDI. The most preferred diisocyanate is MDI. Suitable extender glycols (i.e. chain extenders) are aliphatic short chain glycols having two to six carbon atoms and containing only primary alcohol groups. Preferred glycols include diethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, and 1,6-hexane diol with the most preferred glycol being 1,4-butane diol.
In accordance with the present invention, the hydroxyl terminated ethylene ether oligomer intermediate, the non-hindered diisocyanate, and the aliphatic extender glycol are co-reacted simultaneo-lsly in a one-shot poly-merization process at a temperature above about 100C and usually about 120C, whereupon the reaction is exothermic and the reaction temperature is increased to about 200C
to 250C.
The resulting high molecular weight, ther-moplastic polyurethane of this invention is particularly useful as a polymeric binder melt applied to reinforcing fabric which can be molded under heat and pressure into a flexible fuel tank for storage of gasoline or jet fuels.
The polyurethane particularly exhibits excellent resis-tance to fuels B and D measured according to ASTM D471-79. In particular, the polyurethane of this inventionexhibits an original tensile strength of at least 3,000, desirably at least 4,000 and preferably at least 5,000 psi and advantageously exhibits a tensile strength after 14 days immersion in fuel B of at least 80 percent, desirably at least 85 percent, and preferably at least 95 percent of the original tensile strength.
Fuel B is defined as in ASTM D471-79 as 30 percent toluene and 70 percent isoctane by volume.
Fuel D is defined as in ASTM D471-79 as 60 percent isoctane and 40 percent toluene by volume.
The polyurethane further exhibits excellent resistance to styrene as well as excellent hydrolytic stability. Resistance to styrene was tested by immersing polyurethane test films of about 250 microns thickness for one day, 3 days, and seven days respectively. At the end of each test period, stress-strain properties, volume swell and weight gain were determined.
The merits of the present invention will be better understood by referring to the following illustra-tive examples.
~ J~3~,~
_g_ Example 1 Pol~ester:
Poly(diethylene adipate) glycol is commercially available as Formrez 11-112 from Witco and Inolex 1100-110 and had the following characteristics:
Backbone molecular weight 1103 Hydroxyl number lOl Acid No. 0.1 Percent water content 0.024 The resulting polyester was blended with 1,4-butane diol and MDI on a weight basis as follows:
Polyurethane;
0.2S moles (275 grams) of poly(diethylene adipate) glycol with a molecular weight of llO0 was blended at 60C with 0.515 moles (46.36 grams) of 1,4-butanediol chain extender. This blend or physical mix-ture was then reacted with 0.765 moles (191.25 grams) of methylene bis diphenyl diisocyanate (MDI) by a standard random melt polymerization procedure. This procedure involved heating the poly(diethylene adipate) glycol/1,4-butane diol blend and MDI separately to about 100C and then mixing the ingredients. The reaction is exothermic and raises the temperature to about 200 to 250C in about 1 to 5 minutes, during which time polymerization takes place as evidenced by an increase in viscosity. Stabili-zers such a~ W absorbers and antioxidants and lubricants (i.e. processing aids) can be added as desired during the polymerization step or added to the monomers prior to the raaction. The polyurethane had a melt index (190C/8700 grams) of 3.5 grams/lO minutes.
Polyurethane Test:
Samples were prepared for fuel immersion test-ing in fuels B and D immersion testing with the results indicated hereafter in Tables IA and IB.
T~LE lA
Fuel B resistance according to ASTM D471-79.
a) Immediate melt index (190C/8700 gms. load) = 35 gms/
10 min.
b) Original proerties Tensile strength = 5000 psi % Elongation = 570 300% Modulus = 1900 psi c~ Fuel B immersion 70 hours ~ 23C
Tensile strength = 4500 psi ~ Elongation = 600 300% Modulus = 1700 psi % Volume change = 8.43 - % Weight change = 5.89 d) Fuel B immersicn two weeks ~ 23C
Tensile strength = 4300 psi % Elongation = 600 300% Modulus = 1700 psi % Volume change = 7.33 % Weight change = 4.69 3 i-3; ~
TABL~_IB
Fuel D resistance according to ASTM D471-79.
a) Immediate melt index (190C/8700 gms. load) = 35 gms/10 min.
b) Oriqinal ~ro~erties Tensile Strength = 5000 psi % Elongation = 570 300% Modulus = 1900 psi c) Fuel D immersion 70 hou~s Q 23C
Tensile strength = 3750 psi % Elongation = 600 300% Modulus = 1550 psi % Volume change = 11.24 % Weight change = 7.09 d) Fuel D immersion two weeks ~ 23C
Tensile strength = 3600 psi % Elongation = 570 300% Modulus = 1500 psi % Volume change = 9.55 % Weight change = 6.85 Exam~le 2 0.2 moles (290 grams) of polyethylene glycol ~Dow E-1450) with a molecular weight of 1450 was blended at 60C with 0.844 moles (75.96 grams) of 1,4-butanediol chain extender. This blend or physical mixture was then reacted with 1.044 moles (26 grams) of methylene bis di-phenyl diisocyanate (MDI) by a standard high temperature random melt polymerization procedure. The polymerization procedure was as described in Example 1. Test data including phy~ical properties and ~uel resistance are set forth in Tables IIA, IIB, and IIC.
3`~
TABLE IIA
Evaluation of Polyurethane of ExamPle 2 ASTM Test Procedure Tensile Strength (1) D-412. 3060 Elongation, % 560 100% Modulus, psi 1100 300% Modulus, psi 2030 Tensile Set, % 20 Graves Tear, ppi D-624 (Die C) 413 Trouser Tear, ppsi D-470 117 Shore Hardness, A/D D-2240 85/40 Vicat Softening, C D-1525 (B) gs Tg, C TP-113 -24 Specific Gravity D-792 1.22 Melt Index (190C/
8700 gms), gms/10 min. 29.5 (1) 30 mil extruded strip.
~2~
TABLE IIB
Evaluation of Hydrolytic Stability Melt Index (190C/8700 gm) gms/10 min. 40 oriainal Tensile Strength, psi 3470 Elongation, % 490 100% Modulus, psi 1450 300~ Modulus, psi 2600 Two We~ks Water @ 71C(1) Tensile Strength, psi 3750 (+8) Elongation, % 460 (-6) 100% Modulus, psil9oo (+31) -- 300% Modulus, psi3020 (+16) Four Weeks Water ~ 71C(1) Tensile Strength, psi3490 (+0. 6) Elongation, ~ 480 (-2) 100% Modulus, psi 1840 (+27) 300% Modulus, psi 2740 (+5) Six Weeks Water ~ 71C(1) Tensile Strength, psi3350 (-3) Elongation, % 410 (-16) 100% Modulus, psi 1900 (+31) 300% Modulus, psi 2800 (+8) ( ) = % Change ~1) A~ter immersion, prior to stress-strain testing, all samples were conditioned according to Method 6111 o~ FED-STD-601. All samples are dumbbells fro~ a 75 mil compression molded tensile sheet.
~ 3~J~
Evaluation o~ Produced Fuel "D" Resistance Sample Number 161-212-46B
Melt Index (190C/8700 gm) gms/10 min. 40 Oriainal propertie (1) Ten ile Strength, psi3870 Elongation, % 600 100% Modulus, psi 1280 300% Modulus, psi 2220 Immers~on Fuel D 70 hrs. @ 23C
Tensile Strength, psi3320 Elongation, % 500 100% Modulus, psi 1110 300% Modulus, psi 2220 ~ Volume Change 10.2 % Weight Change 7.1 Immexsion Fuel D 2 weeks @ 23C
Tensile Strength, psi3500 Elongation, % 440 100% Modulus, psi 1200 300% Modulus, psi 2420 % Volume Chan~s 9.9 % Weight Change 7.2 (1) 75 mil tensile sheets ~ '3 As apparent from the above data, good physical properties such as tensile strength, modulus, tear strength, and the like were obtained as well as good hydrolytic stability and fuel "D" resistance.
ExampLe 3 The poly(diethylene ether adipate) glycol of Example 2 was compared to two similarly prepared polyure-thanes except that the intermediate was replaced by (A~
poly(tetramethylene adipate) glycol or (B) polycaprolac-ton. Various physical data are set forth in Table III.
2~33~ ~
a~ o ~ O ~ r~ ~ -- ~ ~
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m~
~ o I o~
I` O O O ~ O O O ~` O O O ~i t`
g~ ~ o o o o ,~ O ,1 o ~ o ~1 ~ 2 ~1 ~ ~ ~ o ~1 U. o E~; ~ 8 0 0 C In 0 o o r~ ~
~ ~ I
~ ~`
1~ G ¦ ~`
E ~ I CD
~! ~ ' .~ ~
~; L ~ rl a ~ r, I ~ .,, d ~ ~
o g ~ ~ ~ g ~ ~ _ ~ J~3~
As apparent from Table III, the weight and volume change utilizing the polyester intermediate of the present invention, that is Example 2, was much lower that existing heratofore polyurethanes made utilizing the 5intermediates of A and B.
A polyurethane very similar to that of Example 1, made in a manner as set forth in Example 1, was tested 10for styrene resistance and compared to a similar conven-tional polyurethane made in a manner similar to Example 1 by reacting poly(tetramethylena adipate) glycol, 1,4-butane diol, and MDI.
Procedure 15Films of about 250 microns of each test sample were melt coated on release nylon. Test samples were immersed in styrene for 1 day, 3 days, and 7 days re-spectively. Stress-strain properties, volume swell, and weight gain were measured at the end of each timed immer-20sion. The results are shown in Table IV.
~ ~ ~ 3 ~
TABLE IV
Styrene EX. I TYPE
Resistance CONTRO~ POLYURETHANE
ld 3d 7d ld 3d 7d Vol. Swell % 59 62 68 15 15 13 Wt. Gain % 43 44 47 24 22 22 As apparent from Table IV, the volume swell and the weight gain of the polyurethane of the present inven-tion was dramatically lswer than that of a commercial polyurethane heretofore utilized in fuel resistant applications.
While in accordance with the Patent Statut-es, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
The physical, chemical and structural require-ments for flexible fuel tanks are set forth in MIL-T-52983B (17 September 1984) including prolonged flexi-bility and durability, resiliency and toughness, es-pecially prolonged hydrocarbon fuel resistance and hydro-lytic stability, high tensile strength before and after immersion in water or fuel, and certain stress-strain requirements such as tensile strength, percent elonga-tion, and percent modulus. However, various polyurethane polymers ordinarily considered to exhibit excellent physical properties have been found inadequate. Poly-urethane polymers based on polycaprolactone polyol, polytetramethylene ether glycol, and poly(tetramethylene adipate) glycol, are unsatisfactory and in particular lack satisfactory resistance to aliphatic hydrocarbon fuels. Polycaprolactone polyurethanes and polyether polytetramethylene ether glycol polyurethanes, for ex-ample, exhibited adequate hydrolytic stability but lacked sufficient resistance to liquid hydrocarbon fuels.
.
SUM~ARY OF THE INVENTION
It now has been found that a flexible, resil-ient fuel tank exhibiting excellent fuel resistance exceeding the requirements of ASTM D471-79 can be con-structed from a high molecular weight, thermoplastic polyurethane polymeric binder combined with a fibrous mat reinforce~ent and molded into a flexible fuel container construction. The polyurethane polymer has an average 2~2~3~ c3 ~, molecular weight from about 60,000 to about ~00,000 and comprises a hydroxyl terminated ethylene ether oligomer glycol intermediate having an average molecular weight from about 500 to 5,000 reacted with a non-hindered diisocyanate and an extender glycol to produce a high molecular weight thermoplastic polyurethane. The ethyl-ene ether oligomer glycol intermsdiate is selected from (a) an hydroxyl terminated, diethylene glycol aliphatic linear polyester and (b) a polyethylene glycol. The polyurethane thermoplastic can be combined, e.g. melt applied, with a fibrous mat or similar reinforcement and molded under heat into a flexible fuel container having excellent fuel resistance and hydrolytic stability.
-- These and other advantages of the present invention will become more apparent by referring to the detailed description of the invention and the illustrative ex-amples.
DETAILED DESCRIPTION OF THE INVENTION
The thermoplastic polyurethane polymer of the present invention, useful as an elastomeric melt or binder in a fabric reinforced flexible fuel tank, com-prises the reaction of a hydroxyl terminated ethylene ether oligomer intermediate with a non-hindered diiso-cyanate and an extender glycol, where the oligomer can be a diethylene glycol-aliphatic polyester, or a polyethylene glycol.
Referring first to the polyester intermediate, a hydroxyl terminated, saturated polyester polymer is synthesized by reacting excess equivalents of diethylene glycol with considerably lesser equivalents of an alipha-tic, preferably an alkyl, dicarboxylic acid having four to ten carbon atoms where the most preferred is adipic acid. Other useful dicarboxylic acids include succinic, glutaric, pimelic, suberic, azelaic and sebacic acids.
The most preferred polyester intermediate is polydi-ethylene glycol adipate. In accordance with this aspect of the present invention, excess moles of diethylene glycol are reacted with lesser moles of dicarboxylic acid at levels from about 5 mole percent to about 50 mole per-cent excess of glycol to provide a hydroxyl terminated polyester oliqomer chain having an average molecular weight between about 500 to 5000 and preferably between about 700 and 2500. The short chain polyester oligomer contains repeating diethylene ether structures and com-prises on an equivalent basis from about 1.05 to 1.5 equivalents of diethylene glycol co-reacted with one equivalent of dicarboxylic acid to produce the low mole-cular weight polyester oligomer intermediate. The high excess equivalents of diethylene glycol controls the molecular weight of the polyester oligomer preferably below 2500 and further assures a hydroxyl terminated linear polyester oligomer. The polyester oligomers synthesized by reacting the diethylene glycol with lesser equivalents of dicarboxylic acid at temperatures of from about 300F to 450F in the absence or in the presence of an esterification catalyst such as stannous chloride for time sufficient to reduce the Acid No. to about zero.
The hydroxyl terminated polyester oligomer intexmediate is further reacted with considerably excess equivalents of non-hindered diisocyanate along with extender glycol in a so-called one-shot or simultaneous coreaction of oligomer, diisocyanate, and extender glycol to produce the very high molecular weight linear polyure-thane having an average molecular weight broadly from about 60,000 to 500,000, preferably from about 80,000 to 180,000, and mo~t preferably ~rom about 100,000 to 180,000. The very high molecular weight linear polyure-thane based on the polyester oligomer in accordance with s~ 3 `1 ` ;
this aspect of the invention is unique in that an extra-ordinary high molecular weight polyurethane polymer is produced from a low molecular weight polyester oligomer prepolymer.
In accordance with a further aspect of this invention an ethylene ether oligomer glycol intermediate comprising a polyethylene glycol can be co-reacted with non-hindered diisocyanate and extender glycol to produce the high molecular weight polyurethane polymer. Useful polyethylene glycols are linear polymers of the general formula H-(OCH2CH2)-nOH where n is the number of repeat-ing ethylene ether units and n is at least 11 and between 11 and about 115. On a molecular weight basis, the useful range of polyethylene glycols have an average molecular weight from about 500 to 5000 and preferably from about 700 to 2500. Commercially available poly-ethylene glycols useful in this invention are typically designated as polyethylene glycol 600, polyethylene glycol 1500, and polyethylene glycol 4000.
In accordance with this invention, high molecu-lar weight thermoplastic polyurethanes are produced by reacting together preferably in a one-shot prscess the ethylene ether oligomer glycol intermediate, an aromatic or aliphatic non-hindered diisocyanate, and an extender glycol. On a mole basis, the amount of extender glycol for each mole of oligomer glycol intermediate is from about 0.1 to about 3.0 moles, desirably from about 0.2 to about 2.1 moles, and preferably from about 0.5 to about 1.5 moles. On a mole basis, the high molecular weight polyurethane polymer comprises ~rom about 0.97 to about 1.02 moles, and preferably about 1.0 moles of non-hin-dered diisocyanate for every 1.0 total moles of both the extender glycol and the oligomer glycol (i.e. extender glycol + oligomer glycol = 1.0).
Useful non-hindered diisocyanates comprise aromatic non-hindered diisocyanates and include, for example, 1,4-diisocyanatobenzene (PPDI), 4,4'-methylene-bis (phenyl isocyanate) MDI), 1,5-naphthalene diiso-cyanate (NDI), m-xylene diisocyanate (XDI), as well as non-hindered, cyclic aliphatic diisocyanates such as 1,4-cyclohexyl diisocyanate (CHDI), and H12 MDI. The most preferred diisocyanate is MDI. Suitable extender glycols (i.e. chain extenders) are aliphatic short chain glycols having two to six carbon atoms and containing only primary alcohol groups. Preferred glycols include diethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, and 1,6-hexane diol with the most preferred glycol being 1,4-butane diol.
In accordance with the present invention, the hydroxyl terminated ethylene ether oligomer intermediate, the non-hindered diisocyanate, and the aliphatic extender glycol are co-reacted simultaneo-lsly in a one-shot poly-merization process at a temperature above about 100C and usually about 120C, whereupon the reaction is exothermic and the reaction temperature is increased to about 200C
to 250C.
The resulting high molecular weight, ther-moplastic polyurethane of this invention is particularly useful as a polymeric binder melt applied to reinforcing fabric which can be molded under heat and pressure into a flexible fuel tank for storage of gasoline or jet fuels.
The polyurethane particularly exhibits excellent resis-tance to fuels B and D measured according to ASTM D471-79. In particular, the polyurethane of this inventionexhibits an original tensile strength of at least 3,000, desirably at least 4,000 and preferably at least 5,000 psi and advantageously exhibits a tensile strength after 14 days immersion in fuel B of at least 80 percent, desirably at least 85 percent, and preferably at least 95 percent of the original tensile strength.
Fuel B is defined as in ASTM D471-79 as 30 percent toluene and 70 percent isoctane by volume.
Fuel D is defined as in ASTM D471-79 as 60 percent isoctane and 40 percent toluene by volume.
The polyurethane further exhibits excellent resistance to styrene as well as excellent hydrolytic stability. Resistance to styrene was tested by immersing polyurethane test films of about 250 microns thickness for one day, 3 days, and seven days respectively. At the end of each test period, stress-strain properties, volume swell and weight gain were determined.
The merits of the present invention will be better understood by referring to the following illustra-tive examples.
~ J~3~,~
_g_ Example 1 Pol~ester:
Poly(diethylene adipate) glycol is commercially available as Formrez 11-112 from Witco and Inolex 1100-110 and had the following characteristics:
Backbone molecular weight 1103 Hydroxyl number lOl Acid No. 0.1 Percent water content 0.024 The resulting polyester was blended with 1,4-butane diol and MDI on a weight basis as follows:
Polyurethane;
0.2S moles (275 grams) of poly(diethylene adipate) glycol with a molecular weight of llO0 was blended at 60C with 0.515 moles (46.36 grams) of 1,4-butanediol chain extender. This blend or physical mix-ture was then reacted with 0.765 moles (191.25 grams) of methylene bis diphenyl diisocyanate (MDI) by a standard random melt polymerization procedure. This procedure involved heating the poly(diethylene adipate) glycol/1,4-butane diol blend and MDI separately to about 100C and then mixing the ingredients. The reaction is exothermic and raises the temperature to about 200 to 250C in about 1 to 5 minutes, during which time polymerization takes place as evidenced by an increase in viscosity. Stabili-zers such a~ W absorbers and antioxidants and lubricants (i.e. processing aids) can be added as desired during the polymerization step or added to the monomers prior to the raaction. The polyurethane had a melt index (190C/8700 grams) of 3.5 grams/lO minutes.
Polyurethane Test:
Samples were prepared for fuel immersion test-ing in fuels B and D immersion testing with the results indicated hereafter in Tables IA and IB.
T~LE lA
Fuel B resistance according to ASTM D471-79.
a) Immediate melt index (190C/8700 gms. load) = 35 gms/
10 min.
b) Original proerties Tensile strength = 5000 psi % Elongation = 570 300% Modulus = 1900 psi c~ Fuel B immersion 70 hours ~ 23C
Tensile strength = 4500 psi ~ Elongation = 600 300% Modulus = 1700 psi % Volume change = 8.43 - % Weight change = 5.89 d) Fuel B immersicn two weeks ~ 23C
Tensile strength = 4300 psi % Elongation = 600 300% Modulus = 1700 psi % Volume change = 7.33 % Weight change = 4.69 3 i-3; ~
TABL~_IB
Fuel D resistance according to ASTM D471-79.
a) Immediate melt index (190C/8700 gms. load) = 35 gms/10 min.
b) Oriqinal ~ro~erties Tensile Strength = 5000 psi % Elongation = 570 300% Modulus = 1900 psi c) Fuel D immersion 70 hou~s Q 23C
Tensile strength = 3750 psi % Elongation = 600 300% Modulus = 1550 psi % Volume change = 11.24 % Weight change = 7.09 d) Fuel D immersion two weeks ~ 23C
Tensile strength = 3600 psi % Elongation = 570 300% Modulus = 1500 psi % Volume change = 9.55 % Weight change = 6.85 Exam~le 2 0.2 moles (290 grams) of polyethylene glycol ~Dow E-1450) with a molecular weight of 1450 was blended at 60C with 0.844 moles (75.96 grams) of 1,4-butanediol chain extender. This blend or physical mixture was then reacted with 1.044 moles (26 grams) of methylene bis di-phenyl diisocyanate (MDI) by a standard high temperature random melt polymerization procedure. The polymerization procedure was as described in Example 1. Test data including phy~ical properties and ~uel resistance are set forth in Tables IIA, IIB, and IIC.
3`~
TABLE IIA
Evaluation of Polyurethane of ExamPle 2 ASTM Test Procedure Tensile Strength (1) D-412. 3060 Elongation, % 560 100% Modulus, psi 1100 300% Modulus, psi 2030 Tensile Set, % 20 Graves Tear, ppi D-624 (Die C) 413 Trouser Tear, ppsi D-470 117 Shore Hardness, A/D D-2240 85/40 Vicat Softening, C D-1525 (B) gs Tg, C TP-113 -24 Specific Gravity D-792 1.22 Melt Index (190C/
8700 gms), gms/10 min. 29.5 (1) 30 mil extruded strip.
~2~
TABLE IIB
Evaluation of Hydrolytic Stability Melt Index (190C/8700 gm) gms/10 min. 40 oriainal Tensile Strength, psi 3470 Elongation, % 490 100% Modulus, psi 1450 300~ Modulus, psi 2600 Two We~ks Water @ 71C(1) Tensile Strength, psi 3750 (+8) Elongation, % 460 (-6) 100% Modulus, psil9oo (+31) -- 300% Modulus, psi3020 (+16) Four Weeks Water ~ 71C(1) Tensile Strength, psi3490 (+0. 6) Elongation, ~ 480 (-2) 100% Modulus, psi 1840 (+27) 300% Modulus, psi 2740 (+5) Six Weeks Water ~ 71C(1) Tensile Strength, psi3350 (-3) Elongation, % 410 (-16) 100% Modulus, psi 1900 (+31) 300% Modulus, psi 2800 (+8) ( ) = % Change ~1) A~ter immersion, prior to stress-strain testing, all samples were conditioned according to Method 6111 o~ FED-STD-601. All samples are dumbbells fro~ a 75 mil compression molded tensile sheet.
~ 3~J~
Evaluation o~ Produced Fuel "D" Resistance Sample Number 161-212-46B
Melt Index (190C/8700 gm) gms/10 min. 40 Oriainal propertie (1) Ten ile Strength, psi3870 Elongation, % 600 100% Modulus, psi 1280 300% Modulus, psi 2220 Immers~on Fuel D 70 hrs. @ 23C
Tensile Strength, psi3320 Elongation, % 500 100% Modulus, psi 1110 300% Modulus, psi 2220 ~ Volume Change 10.2 % Weight Change 7.1 Immexsion Fuel D 2 weeks @ 23C
Tensile Strength, psi3500 Elongation, % 440 100% Modulus, psi 1200 300% Modulus, psi 2420 % Volume Chan~s 9.9 % Weight Change 7.2 (1) 75 mil tensile sheets ~ '3 As apparent from the above data, good physical properties such as tensile strength, modulus, tear strength, and the like were obtained as well as good hydrolytic stability and fuel "D" resistance.
ExampLe 3 The poly(diethylene ether adipate) glycol of Example 2 was compared to two similarly prepared polyure-thanes except that the intermediate was replaced by (A~
poly(tetramethylene adipate) glycol or (B) polycaprolac-ton. Various physical data are set forth in Table III.
2~33~ ~
a~ o ~ O ~ r~ ~ -- ~ ~
~ ~; o æ o 0 u~ _l u~ 0 U~ O
m~
~ o I o~
I` O O O ~ O O O ~` O O O ~i t`
g~ ~ o o o o ,~ O ,1 o ~ o ~1 ~ 2 ~1 ~ ~ ~ o ~1 U. o E~; ~ 8 0 0 C In 0 o o r~ ~
~ ~ I
~ ~`
1~ G ¦ ~`
E ~ I CD
~! ~ ' .~ ~
~; L ~ rl a ~ r, I ~ .,, d ~ ~
o g ~ ~ ~ g ~ ~ _ ~ J~3~
As apparent from Table III, the weight and volume change utilizing the polyester intermediate of the present invention, that is Example 2, was much lower that existing heratofore polyurethanes made utilizing the 5intermediates of A and B.
A polyurethane very similar to that of Example 1, made in a manner as set forth in Example 1, was tested 10for styrene resistance and compared to a similar conven-tional polyurethane made in a manner similar to Example 1 by reacting poly(tetramethylena adipate) glycol, 1,4-butane diol, and MDI.
Procedure 15Films of about 250 microns of each test sample were melt coated on release nylon. Test samples were immersed in styrene for 1 day, 3 days, and 7 days re-spectively. Stress-strain properties, volume swell, and weight gain were measured at the end of each timed immer-20sion. The results are shown in Table IV.
~ ~ ~ 3 ~
TABLE IV
Styrene EX. I TYPE
Resistance CONTRO~ POLYURETHANE
ld 3d 7d ld 3d 7d Vol. Swell % 59 62 68 15 15 13 Wt. Gain % 43 44 47 24 22 22 As apparent from Table IV, the volume swell and the weight gain of the polyurethane of the present inven-tion was dramatically lswer than that of a commercial polyurethane heretofore utilized in fuel resistant applications.
While in accordance with the Patent Statut-es, the best mode and preferred embodiment has been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.
Claims (19)
1. A high molecular weight, thermoplastic polyurethane characteristically resistant to aliphatic hydrocarbon fuels, said polyurethane adapted for use as an aliphatic hydrocarbon fuel barrier in the construction of flexible fuel containers, the polyurethane comprising:
a thermoplastic polyurethane having an aver-age molecular weight from about 60,000 to 500,000 com-prising a hydroxyl terminated ethylene ether oligomer intermediate having an average molecular weight from about 500 to 5,000 reacted with a non-hindered diisocya-nate and an extender glycol to produce said thermoplastic polyurethane, said oligomer intermediate being selected from (a) a hydroxyl terminated diethylene glycol-ali-phatic linear polyester, or (b) a polyethylene glycol;
wherein said hydroxyl terminated diethylene glycol-aliphatic linear polyester (a) is produced by esterifying a diethylene glycol with an aliphatic dicar-boxylic acid having from 4 to 10 carbon atoms to produce a linear saturated polyester oligomer;
wherein said polyethylene glycol (b) con-sists of repeating ethylene ether units n wherein n is from about 11 to about 115, wherein said non-hindered diisocyanate is an aromatic or cyclic aliphatic diisocyanate, wherein said extender glycol is a non-ether glycol having from 2 to 6 carbon atoms and containing only primary alcohol groups.
a thermoplastic polyurethane having an aver-age molecular weight from about 60,000 to 500,000 com-prising a hydroxyl terminated ethylene ether oligomer intermediate having an average molecular weight from about 500 to 5,000 reacted with a non-hindered diisocya-nate and an extender glycol to produce said thermoplastic polyurethane, said oligomer intermediate being selected from (a) a hydroxyl terminated diethylene glycol-ali-phatic linear polyester, or (b) a polyethylene glycol;
wherein said hydroxyl terminated diethylene glycol-aliphatic linear polyester (a) is produced by esterifying a diethylene glycol with an aliphatic dicar-boxylic acid having from 4 to 10 carbon atoms to produce a linear saturated polyester oligomer;
wherein said polyethylene glycol (b) con-sists of repeating ethylene ether units n wherein n is from about 11 to about 115, wherein said non-hindered diisocyanate is an aromatic or cyclic aliphatic diisocyanate, wherein said extender glycol is a non-ether glycol having from 2 to 6 carbon atoms and containing only primary alcohol groups.
2. A thermoplastic polyurethane according to Claim 1, wherein the original tensile strength thereof is at least 3,000 psi, and wherein the tensile strength after 14 days immersion in fuel B is at least 80 percent of the original tensile strength.
3. A thermoplastic polyurethane according to Claim 1, wherein said hydroxyl terminated polyester oligomer (a) contains on the average from 4 to 8 repeat-ing ester units and has an average molecular weight from about 700 to 2500.
4. A thermoplastic polyurethane according to Claim 3, wherein said dicarboxylic acid is adipic acid, and wherein from about 5 to about 50 percent excess moles of said diethylene glycol is utilized for each mole of said aliphatic dicarboxylic acid.
5. A thermoplastic polyurethane according to Claim 4, wherein the diisocyanate is 4,4'-methylenebis(phenyl isocyanate), and wherein said diiso-cyanate is simultaneously reacted with said extended glycol and said ethylene ether oligomer intermediate.
6. A thermoplastic polyurethane according to Claim 5, wherein the extender glycol is 1,4-butane diol, and wherein the amount of said extender glycol to said oligomer glycol intermediate is from about 0.1 to about 3.0 moles.
7. A thermoplastic polyurethane according to Claim 3, wherein the amount of said diisocyanate is from about 0.97 to 1.02 moles for every total one mole of said oligomer intermediate and said extender glycol, and wherein the molecular weight of said thermoplastic polyurethane is from about 80,000 to about 180,000.
8. A thermoplastic polyurethane according to Claim 6, wherein the amount of said diisocyanate if from about 0.97 to 1.02 moles for every total one mole of said oligomer intermediate and said extender glycol, and wherein the molecular weight of said thermoplastic polyurethane is from about 80,000 to about 180,000, and wherein the tensile strength of said thermoplastic poly-urethane after 14 days immersion in fuel B is at least 85 percent of the original tensile strength.
9. A thermoplastic polyurethane according to Claim 8, wherein said thermoplastic polyurethane has a molecular weight of from about 100,000 to about 180,000, and wherein the tensile strength of said thermoplastic polyurethane after 14 days immersion in fuel B is at least 85 percent of the original tensile strength.
10. A thermoplastic polyurethane according to Claim 2, wherein said tensile strength retention after 14 days immersion in fuel B is at least 90 percent of the original tensile strength.
11. A thermoplastic polyurethane according to Claim 2, wherein said polyurethane is melt applied to a reinforcing fabric to penetrate said reinforcing fabric and produce a polyurethane-fabric composite, and said composite is molded into a flexible fuel container.
12. A thermoplastic polyurethane according to Claim 5, wherein said polyurethane is melt applied to reinforcing fabric to penetrate said reinforcing fabric and produce a polyurethane-fabric composite, and said composite is molded into a flexible fuel container.
13. A thermoplastic polyurethane according to Claim 8, wherein said polyurethane is melt applied to reinforcing fabric to penetrate said reinforcing fabric and produce a polyurethane-fabric composite, and said composite is molded into a flexible fuel container.
14. In a process for fabricating a flexible fuel container for containing aliphatic hydrocarbon fuels, comprising the steps of providing the thermo-plastic polyurethane of Claim 2, melt applying said polyurethane to a reinforcing fabric to the extent of penetrating said reinforcing fabric to form a polyure-thane-fabric composite, and molding said composite into a flexible fuel container.
15. In a process for fabricating a flexible fuel container for containing aliphatic hydrocarbon fuels, comprising the steps of providing the thermo-plastic polyurethane of Claim 6, melt applying said polyurethane to a reinforcing fabric to the extent of penetrating said reinforcing fabric to form a polyure-thane-fabric composite, and molding said composite into a flexible fuel container.
16. A process for synthesizing the polyure-thane in Claim 2, wherein the thermoplastic polyurethane is produced from hydroxyl terminated polyester oligomer produced by esterifying excess equivalents of diethylene glycol with lesser equivalents of adipic acid.
17. A thermoplastic polyurethane according to Claim 1, wherein said polyurethane has excellent styrene resistance.
18. A thermoplastic polyurethane according to Claim 5, wherein said polyurethane has excellent styrene resistance.
19. A thermoplastic polyurethane according to Claim 9, wherein said polyurethane has excellent styrene resistance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/399,645 US5047495A (en) | 1989-08-28 | 1989-08-28 | Polyurethane for flexible fuel containers |
| US07/399,645 | 1989-08-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023353A1 true CA2023353A1 (en) | 1991-03-01 |
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ID=23580371
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023353A Abandoned CA2023353A1 (en) | 1989-08-28 | 1990-08-15 | Polyurethane for flexible fuel containers |
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| Country | Link |
|---|---|
| US (1) | US5047495A (en) |
| EP (1) | EP0415177A3 (en) |
| JP (1) | JPH03157416A (en) |
| KR (1) | KR910004691A (en) |
| CN (1) | CN1049853A (en) |
| BR (1) | BR9004108A (en) |
| CA (1) | CA2023353A1 (en) |
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| US3214411A (en) * | 1961-05-10 | 1965-10-26 | Mobay Chemical Corp | Polyester urethanes made with diphenylmethane diisocyanate which are processable by thermoplastic techniques |
| DE1301910B (en) * | 1963-06-25 | 1969-08-28 | Elastomer Ag | Process for the production of thermoplastically processable polyurethanes |
| GB1156784A (en) * | 1965-08-24 | 1969-07-02 | Ici Ltd | Treatment of Shaped Articles |
| US3539482A (en) * | 1967-09-20 | 1970-11-10 | Goodrich Co B F | Soluble poly(etherurethane)s |
| US3706710A (en) * | 1970-12-31 | 1972-12-19 | Hooker Chemical Corp | Process for preparing discoloration-resistant curable polyurethane coatings |
| US3901852A (en) * | 1974-07-29 | 1975-08-26 | Upjohn Co | Thermoplastic polyurethanes prepared from 4,4'-methylenebis (phenyl isocyanate) |
| US4191818A (en) * | 1975-10-25 | 1980-03-04 | Basf Wyandotte Corporation | Process for preparing heat-resistant polyurethane elastomers having no secondary softening range |
| US4169196A (en) * | 1977-10-14 | 1979-09-25 | The Upjohn Company | Process for improving thermoplastic polyurethanes |
| DE2918027C2 (en) * | 1979-05-04 | 1986-05-28 | Akzo Gmbh, 5600 Wuppertal | Ultrafiltration membranes made from linear polyurethanes |
| JPS57111311A (en) * | 1980-12-29 | 1982-07-10 | Nippon Polyurethan Kogyo Kk | Thermoplastic polyurethane resin |
| US4439552A (en) * | 1981-05-08 | 1984-03-27 | Gravi-Mechanics Co. | Method of preparing a urethane prepolymer and polymer |
| US4565729A (en) * | 1983-06-09 | 1986-01-21 | Goodyear Aerospace Corporation | Polyurethane laminate of contrasting layers and process therefor |
| US4487913A (en) * | 1984-03-12 | 1984-12-11 | Goodyear Aerospace Corporation | Fuel and hydrolysis resistant polyurethane |
| CA1232396A (en) * | 1986-01-08 | 1988-02-02 | Kenneth E. Macphee | Polyurethane-based elastomeric material |
| DE3613790A1 (en) * | 1986-04-24 | 1987-10-29 | Bayer Ag | METHOD FOR PRODUCING THERMOPLASTIC POLYURETHANES FOR RADIATION CROSSLINKING AND THEIR USE |
| US4877856A (en) * | 1987-08-31 | 1989-10-31 | The Bf Goodrich Company | Soft thermoplastic polyurethane for blown film application |
| US4871789A (en) * | 1988-04-18 | 1989-10-03 | The Dow Chemical Company | Reinforced polymer compositions having excellent distinctness of image |
-
1989
- 1989-08-28 US US07/399,645 patent/US5047495A/en not_active Expired - Lifetime
-
1990
- 1990-08-15 EP EP19900115609 patent/EP0415177A3/en not_active Withdrawn
- 1990-08-15 CA CA002023353A patent/CA2023353A1/en not_active Abandoned
- 1990-08-20 BR BR909004108A patent/BR9004108A/en unknown
- 1990-08-24 CN CN90107190A patent/CN1049853A/en active Pending
- 1990-08-27 JP JP2222657A patent/JPH03157416A/en active Pending
- 1990-08-28 KR KR1019900013258A patent/KR910004691A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0415177A2 (en) | 1991-03-06 |
| US5047495A (en) | 1991-09-10 |
| EP0415177A3 (en) | 1992-02-19 |
| JPH03157416A (en) | 1991-07-05 |
| KR910004691A (en) | 1991-03-29 |
| BR9004108A (en) | 1991-09-03 |
| CN1049853A (en) | 1991-03-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |