CA1160394A - Polyester urethane and container made therefrom - Google Patents

Abstract

Abstract A polyester urethane fuel cell having at least one layer of a reaction product of an organic polyisocyanate and a mixed polyester and a curative. In the preferred embodiment the fuel cell has a barrier layer composed of a polyester urethane formed from reacting bis(4-cyclohexyl isocyanate) with 10 to 90 mol percent of polyhexamethylene ortho phthalate and 90 to 10 mol percent of a polycaprolactane and curative. The mixed polyesters are either a blend or co-condensation product of a monomeric polyol of less than 5 carbon atoms with an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.

Description

Polyester Urethane and Container Made Therefrom Tec nical F_eld This invention relates to a polyester urethane covered fabric container for fuel and to the method of making said container. More particularly this invention relates to a novel polyester urethane.

Prior Art Polyure-thane fuel cells or container have been made and used almost exclusively on light aircraft. As aircraft has become more advanced and sophisticated so have the demands for better performance of the ~uel cells. These demands are particularly noteworthy as polyether urethanes have low strength relative to the polyester urethanes. In turn the polyester urethanes have a -tendency to hydrolyze in the presence of moisture. To illustrate this problem polyurethane covered fabrics with a suitable barrier layer have been used in aircraft fuel cells for a number of years~ Unfortunately the polyurethane made from a prepolymer of polytetramethylene adipate and organic polyisocyanate, avaiIable under the trademark designation Hylene WS~M and cured with 4,4'-methylene dianiline showed a large loss of its tensile ; strength af-ter seven days in a steam chamber.

Disclosure of the Invention A new polyurethane was developed that possesses these improvemen-ts without sacrificing other properties necessary as fuel cell building material. These properties incIude (l) fuel resistance because the urethane is in contact with fuel; ~2) low temperature flexibility because of extreme weather conditions and high alti-tudes reached by aircraft; and (33 resistance to swelling in anti-icing ~luids, like ethylene glycol monomethyl ether (methyl cellusolve) or diethylene glycol monobutyl ether (butyl carbitol), which are added to fuel to prevent the moisture in it from freezing.
I have discovered that a special polyester urethane can he made by using either an aliphatic or an ali.cyclic polyisocyanate to react with either a blend of a polyester ~ and a polyester B or a copolymer of these and curing them with a diamine curative.
This polyurethane comprises the reaction product of an aliphatic or alicyclic polyisocyanate with a mixed polyester selected from the class consisting of ~1) a copolyester having the structure obtained by condensation of a polyol of less than 900 molecular weight with an aliphatic dicarboxylic acid preferably containing at least 6 carbon atoms and an aromatic dicarboxylic acid and (2) a blend of an aliphatic polyester and an aromatic polyester and cured with a curative containing at least two groups selected from the class of amine and hydroxyl.
The dicarboxylic acid preferred is alphalic and contains from 6 to 9 carbon atoms or can be composed of a mixture of isophthalic and azelaic acid.
The polyester may contain 1 to 10 mol percent of trifunctionality. Also these polyurethanes can be used to make a polyester urethane fuel cell having at least one layer of an elastomer composed of reaction product of an aliphatic or an alicyclic polyisocyanate with mixed polyesters having structures obtained by condensation of a monomeric polyol of less 400 molecular weight with a blend of 10 to 90 mol pecent of an aromatic dicarboxylic acid and 90 to 10 mol percent of an aliphatic dicarboxylic acid of 6 to 9 carbon atoms to give at:least 3 mol percent free NCO and then curing with a curative containing hydroxyl or amino groups.
These polyesters can be used to make fuel cells.
.~ These polyester fuel cells have at least one layer of an elastomer composed of reaction product of an aliphatic or an alicyclic polyisocyanate with mixed polyesters having structures obtained by condensation of a monomeric polyol of less 400 molecular weight with ~h~

~ 16039~
-2a-a blend of 10 to 90 mol percent of an aromatic dicarboxylic acid and 90 to 10 mol percent of an aliphatic dicarboxylic acid of 6 to 9 carbon atoms to give at least 3 mol percent free NCO and then curing with a curative contalning hydroxyl or amino groups.
The preferred fuel cell of this invention has a fuel barrier layer composed of a polyester urethanè
obtained by reacting methylene bis(4-cyclohexyliso-cyanate~ with 10 to 90 mol percent of polyhexamethylene ortho phthalate and 90 to 10 mol percent of polycaprolactone to form a prepolymer and curing the prepolymer with a diamine. The preferred diamine for making the fuel cell is meta-phenylene diamine.

Description of the Invention Sprayable polyurethane can be formulated from these polyurethanes which have excellent hydrolysis resistance and are suitable for the manufacture of fuel storage cells or tanks. The new urethanes aIso show excellent low temperature flexibility and resistance to fuel and anti-icing fluids. To achieve all of thesP
properties preferably a urethane prepolymer~is made by reacting an aliphatic diisocyanate methylene bis(4-cyclohexylisocyanate) (Hylene WST~I~ and a polyester derived from the reaction of a glycol with a mixture of an aromatic and an aliphatic dicarboxylic acid. The prepolymer is then cured with a diamine curative to form a film.
The excellent hydrolysis resistance of the urethane film of thLs invention is shown by the tensile strength retention after 120~ days of exposure ~o a lO0 percent relative humidity environment at 70C. or after 12 to 14 days in a~steam chamber at 100C. A~ tenslle retention of at least 50 percent in either test is ; 35 considered superior to the prior art urethanes. Two tests are performed to show the fuel resistance of the film. The film is soaked for 72 hours at 57C. in a 'E~' -2b-hydrocarbon solution oE isooctane/toluene at 70/30 by volume designated herein as Larmol. A tensile retention of at least 40 percent after the test is required. The second test measures the volume change or swelling of the film after three days of soaking in the same hydrocarbon fluid (modified ASTM 2-471-59T).
A volume change value of 22 percent or less is considered satisfactory.
Another sample was soaked in a 75125 mixture of water and ethylene glycol monomethyl ether or diethylene glycol monobutyl ether. The film is considered to have excellent anti-icing fluid resistance if it retains 60 percent or more of its original tensile after 72 hours of soaking in the fluid.

''~3 1 :1 8~3~4 The low temperature flexibility of the film was shown by a modified Masland Bend Test, The test is run by dropping a weight of 3.09 kilograms from a height of 27.94 centimeters on a 1.27 x 3.62 cen-timeter strip in the form of a loop.
The test was repeated at various temperatures. The film passed the tes-t at or below -94 C, without breaking into two pieces after the weight drop.

The following representative examples illustrate -the invention wherein parts and percentages are by weight unless otherwise designated.

A 2000 molecular weight polyes-ter made by condensa-tion of 1,6-he~ane diol with a 1:1 mol ratio o~ a mixture o:~
isophthalic and azelaic acids was degassed and used -to make a prepolymer. This polyester was reac-ted with methylene bis(4-cyclohexylisocyanate) according to the formulations in Table I to give -the urethane prepolymers. The prepolymers were dissolved in the specified solvent or mixture of solvents to form a diluted prepolymer. The dilu-te prepolymers were then mi~ed with diamine curati~e solutions and additives as shown in the formuiations in Tables II and III. The resultant solutions were used to spray on polyethylene slabs to give tack-free films in about fi~e minu-tes to about an hour. Most of -the solvents in -the film evaporated after standing overnight ( ~ 18 hours) a-t ambient temperatures.
The films were postcured in a 65 -to 71 C. oven for 18 hours before they were tested. Table II gives the physical properties of the films. These films passed the Masland Bend Test at ~95 C. and had ~olume change in Larmol solvent test of 18 to 22 percent.

Polyhexamethylene 50/50 isophthalate/azelate polyol of 1000 molecular weight was reacted with Hylene WS at an isocyanate to hydroxyl ratio of 1.65 to form a prepolymer.
The prepolymer was dilu-ted to 64 percent solids using toluene (see Table IV). This dilute prepolymer was blended with di-lu-te prepolymer ~ in Table I and films were prepared by spray-ing according to -the formulations in Table V. The excellent 1 .1 6039~

physical properties are listed in the same table.

__ A variation of the prepolymers in Example 1 can be made by the introduction of some tri~unctionality into the 5 polymer backbone, Trimethylolpropane is used at 1.0 pbw per lQ~ pbw polyhexamethylene 50/50 isophthalate/azelate polyol.
The mixture of polymeric polyol and monomeric triol was reacted with Hylene WSTM to make a prepolymer (see Table VI).
The prepolymer is diluted to 50 percent solids using a 50:50 mixture of toluene and methylethyl ketone and is mixed with different curative solutions to prepare films by spraying. The ~ormulations and the excellent resistance of the films to steam aging at 100 C. is shown in Table VII. Other physical properties are also included in the table.

Instead of diluting the prepolymer of Example 1 -the prepolymer was used as a hot melt to prepare a casting without the use o~ any organic solvent. The prepolymer was 20 heated and degassed at the same time. When the tempera-ture reached 100 C. the vacuum was broken and the molten curative and additive were added according to Table IX.
The mixture was -thoroughly stirred and then poured into molds to make test samples like .122 to .152 centimeter thick tensile sheet and a 1.77 centimeter thick block or a molded part like a nipple fitting for an aircraft fuel cell.
Castings were made from prepolymers using 1,4-cyclohexane bis(methylisocyanate) (CBMI) and methylene bis(4-cyclo-hexylisocyanate) containing about 70 percent of the trans, trans isomer (70 percent trans, trans H12MDI). mese formulations and the physical properties are listed in Tables VIII and IX.

An aircraft fuel cell or tank was made by spray coa-ting a waxed cardboard form with the polyurethane reaction mix-ture of Example 1 to give a film 0.5 to 3 mils thick.
Then this film was spray coated with a barrier material to build up a barrier coating of about 1 to 5 mils, and preferably 1.5 to 3 mils.

~ 394 Then over the barrier coat additional spray coats of the polyurethane reaction mixture of Example 1 were applied to give a finished fuel cell having the necessary filling and emptying openings. Optionally various fabric or reinforcing 5 materials are included between spray coats in accordance with the customary fuel cell construction techniques.
The barrier material used to spray build the barrier layer was a reaction mixture composed of 100 parts o prepolymer formed by reacting 95~4 parts of Hylene WS~M with 10 100 parts of a mixture of 50/50 polyhexamethylene ortho-phthalate of 570 molecular weight and polycaprolactone of 520 molecular weight and 8.71 parts of meta-phenylene diamine in sufficien-t solvent, such as methylethyl ketone or toluene, to give a 50 to 65 percent solid dispersions.
The cured fuel cell was removed from the cardboard form in normal manner. This cell passed tests required -to be accepted as a commercial fuel cell. It is indeed amazing to see the cell pass -the fuel diffusion and hydrolysis test when the barrier per se and the coating materials per se do 20 not pass this diffusion too. Also, the cell has excellent hydrolysis resistance. Thus it is evident this combination of materials has a synergist effect.
Although the specification has described the polyesters as a mixture of two or more polyesters or as co-esterified ones it is desirable in the claims for simplici-ty to refer to these two types of polyesters as mixed polyester without regard to whether -they are co-condensation products or physical mixtures of two or more condensation products.
Also, this -term "mixed polyester" hereto~ore has related to ma-terial having structure obtained by condensation of a monomeric polyol of less 400 molecular weight with a dicarboxylic acid or anhydride5 preferably of 6 to 9 carbon atoms. I-t should be appreciated that a small amount of trifunctionality, preferably about 1 -to 10 mol percen-t, can be useful and desirable. Generally the mixed polyesters useful in this invention have molecular weights of about 500 to ~000 with the preferred range being about 1000 to 3000 molecular weight.
Generally the mixed polyesters are reacted with excess 3 9 '~

organic polyisocyana-te with about 3 to 10 mol percent excess being preferred in forming the reac-tion product.
Normally the reaction product is cured with a curative in amounts of abou-t 85 to 100 percent of the excess isocyanate~
Useful curatives are the monorneric polyols of 2 to 3 hydroxyls of less 400 molecular weight and the amine of the diamine type selected from aliphatic, cycloaliphatic aromatic classes. Representative examples of the monomeric polyols are ethylene glycol, butane glycol, diethanol carbamate and diethylene glycol.
TABLE I
bL.CL~:13D~L9S=~ A B C D E
Polyhexamethylene Isophthalate/~zelate ~ 1/1, MW 1800 100 15 Polyhexamethylene Isophthalate/Azelate 1/1, MW 2100 100 100 100 100 Hylene WSTM 29.1 22. L~5 23.7026.20 27.44 Equivalent NCO/
Equivalent OH 2.00 1.80 1.90 2.10 2.20 20 % NCO of 64% Prepolymer in toluene 2.35 % NCO of 50% Prepolymer in toluene/MEK ~ 1/1 1. 27 1.42 1.73 1.89 `~ TABLE II

2 Cure Formulation 1 (Parts) Dilute Prepolymer A in toluene, 64% solids110.00 Methyl ethyl ketone (MEK) 30.00 ~ Masterbatch a* 20.00 -~ Stabaxol P, a polycarbodiimide 0,70 30 30% meta-phenylenediamine (MP~) in MEK 9.85 * Masterbatch a composition of leveling agen-t 2.50 Epo~ lOOlT~in MEK 10~00 Methyl ethyl ketone 87.50 A~ter 90 days in 100% RHAfter 35 =a~L~5~Co3e~L~ E~Chamber ~ 70 C. 128 Days ; 100% Modulus, Kg/cm2 :56 47 51 300% Modulus, Kg/cm2 . 130 130 150 Ultimate Tensile,Kg/cm2 220 260 260 Ultimate Elongation ~o 400 410 390 ~, 116V39~

~5~
Days in Steam Chamber @ 100 C.
After 90 daysA~ter 100% Modulus, Kg/cm 300% Modulus, Kg/cm2 176 176 140 Ult Tensile, Kg/cm2 . 240 240 176 Ult Elong. % 360 360 Tensile Retention after 72 hours in Larmol ~ 57 C~ % 44 Tensi~eReten-tion after 72 hours in Aqueous Antiicing Fluid ~ 57 C. ~o 77 TABLE III
Cure Formula-tion 2 3 4 5 Dil Prepolymer, B, g 150 Dil Prepolymer C, g 150 15 Dil Prepolymer D, g 150 Dil Prepolymer E, g 150 Masterbatch b*, g ~0 30 30 30 30% MPD/MEK, g 7.27 8.139.90 10.8 Hydrolysis Resis-tance 20 Test Res_lts Original: 100% Modulus, Kg/cm2 24 32 48 51 300% Modulus, Kg!cm2 10 91 150 170 Ult Tensile, Kg/cm2 260 240 260 300 Ult Elong, % 410 420 380 360 25 After 120 days over H20 ~, 7oo C 100% Modulus, Kg/cm' 31 39 300% Modulus, Kg/cm2 84 100 70 C. Ult TensileJ Kg/cm2 160 170 Ult Elong, % 440 380 30 Tensile Retention after 72 hrs in ~armol ~ 57 C. % 46 51 48 51 Tensile Re-tention after 72 hrs in A~ueous Antiicing Fluid ~ 57 C. % 62 76 60 64 "Masland" Bend Test -95 -95 -95 35 Volume Change in Larmol, %22 21 21 20 * Masterbatch b Composition: Modaflow 1.25 pbw 80% Epon 1001/MEK 6.25 pbw MEK 92 50 pbw

3 9 '1 TABLE IV
~ 5~ 1u ~_~5~ F
Polyhexame-thylene Isophthalate/
Azela-te ~ 1/1, MW 1000 100.0 pbw 5 Hylene WS 43.2 pbw Equiv NCO/Equiv OH 1.62 % NCO of 64% prepolymer in Toluene 2.31 TABLE V
~= Y~ u~ 6 7 8 __2__10 10 Dilute Prepolymer A, g 80.0 80.0 80.080.0 80.0 Dilute Prepolymer F, g 80.0 80.0 800080.0 80.0 30% MPD/MEX, g 14.2 14.2 14.2 14.214.2 80% Epon 1001/MEK, g 5.0 7.0 Masterbatch c * -- -- 8.0 12.016.0 -Hyd~ sis Resistance_Test Results Original 100% Modulus, Kg/cm2 57 65 62 60 58 300% Modulus, Kg/cm2 176 220 180 200 176 : Ult Tensile, Kg/cm2 270 320 270 290 240 Ult Elong, % 380 360 370 370 350 After 128 days over H20 ~ 70 C.
.
100% Modulus, Kg/cm2 43 46 48 47 49 300% Modulus, Kg/cm2 110 130 140 150 170 Ult Tensile, Kg/cm2 200 240 220 200 260 Ult Elong, % 400 400 380 360 368 Tensile Retention af-ter 72 h~urs in Larmol ~ 57 C., % 54 Tensile Retention after 72 hours in Aqueous ~ntiicing Fluid ~ 57 C.,% 92 "Masland~ Bend Test _95 _95 3 Volume Change in Larmol 9 % 17 17 16 16 Mas-terbatch c Composition: Santowhite 1.00 pbw 80% Epon 1001/MEK 6.oo pbw p-Methoxyphenol 1.00 pbw MEK 3.43 pbw ;

3 9 ~
g TABLE VI
G
Polyhexamethylene Isophthalate/Azelate ~ 1/1, MW 2150 100.0 pbw 5 ~rime-thylolpropane 1.0 pbw Hylene WSTM 30.23 pbw Equiv NC0/Equiv Total OH 2.00 % NC0 of 50% Prepolymer in MEK/Toluene 1.87 TABLE VII
Cure Formulation 11 12 13 14 ~ 16 50% Prepolymer G in 1:1 MEK: TolueIle, g 150.0 150.0 150.0 150.0 150.0 150.0 Masterbatch b (see -table III), g 30.0 30.030~030.0 30.0 30.0 20% 1,3-bis (aminomethyl) cyclohexane/MEK g 21.3 - 20% Isophorone-diamine in 3:1 MIBK:MEK, g 25.5 20 30% meta-Phenylene-diamine/MEK, g 10.7 10.7 10.7 20% bis(4-amino-cyclohexyl) methane/
MEK, g 31.5 10% Stabaxol 5 P/Toluene, g 7.5 10% Staboxol M/MEK, g 7.5 Hydrol~is Resi tance Test Results.
Original:
100% Mod~l~us,Kg/cm2 52 6258 45 60 58 3 300% Modulus,Kg/cm2 170 220190 150 220 190 Ul-t Tensil~ Kg/cm2 250 280250 176 225 240 Ult Elong, % 360 330 3~O 330 305 330 100% Modulus~Kg/cm2 51 65L~8 84 47 56 300% Modulus,Kg/cm2 170 220130 260 130 190 Ult Ten~ile,Kg/cm2 220 240134 260 140 210 Ult Elong, % 330 310 310 300 31Q 310 "Masland" ~ nd Test, F
-70 ~70 -70 -100 -100 -70 TABLE VIII
H _ I
Polyhexamethylene Isophthalate/Azelate @ 1/1, MW 2140 100.O pbw lOO.O pbw ~70% trans, trans-H12MDI -- 24.5 pbw CBMI 18.2 pbw --Equiv NCO/Equiv OH 2.00 2.00 /0 NCO of Prepolymer 3,33 3.oo .
TABLE TX
Cure Formulation ~ 18 l9_ 20 21 Prepolymer A, 100% solids, pbw 100 100 Prepolymer H, 100% solids, pbw 100 15 Prepolymer I, 100% solids, pbw 100 lOO
Epon 828? pbw L~ O 4. 4~ 4~0 L~.o 50/50 Caytur 7/
polyhexamethylene Isophthalate/Azelate 2 (MW 2140~ pbW 12.0 10.0 50/50 MPD/Polyhexa-methylene/Isophthalate/
: Azelate (MW 2140) pbw 8.61 ~ 7.96 7.17 __ Amine Level O g3 O. 93 0.93 0.93 o .93 Original:
100% Modulus,Kgfcm2 49 48 19 42 35 300% Modulus,Kg/cm2 156 170 46 77 91 Ult Tensile,Kg/cm2 370 380 310 340 260 Ult Elong,~% 400 390 510 510 440 Crescent Tear,Kg/cm57.251.8 35.7 58.9 46.4 Shore A Hardness 82 77 60 84 65 While certain representative embodiments and details have been shown for the purpose of illustrating the invention it will be apparent to those skilled in this art -that various changes and modifications may be made therein without departing from the spirit or scope of the inven-tion.

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polyurethane comprising the reaction product of an aliphatic or alicyclic polyisocyanate with a mixed polyester selected from the class consisting of (1) a copolyester having the structure obtained by condensation of a polyol of less than 900 molecular weight with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and (2) a blend of an aliphatic polyester and an aromatic polyester and cured with a curative containing at least two groups selected from the class of amine and hydroxyl.

2. The polyurethane of Claim 1 where the polyol condensed with the dicarboxylic acid contains at least 6 carbon atoms.

3. The polyurethane of Claim 2 wherein the aliphatic dicarboxylic acid contains from 6 to 9 carbon atoms.

4. The polyurethane of Claim 2 wherein the dicarboxylic acids are composed of a mixture of isophthalic and azelaic.

5. The polyurethane of Claim 1 wherein the polyester contains 1 to 10 mol percent of trifunctionality.

6. A polyester urethane fuel cell having at least one layer of an elastomer composed of reaction product of an aliphatic or an alicyclic polyisocyanate with mixed polyesters having structures obtained by condensation of a monomeric polyol of lass 400 molecular weight with a blend of 10 to 90 mol percent of an aromatic dicarboxylic acid and 90 to 10 mol percent of an aliphatic dicarboxylic acid of 6 to 9 carbon atoms to give at least 3 mol percent free NCO and then curing with a curative containing hydroxyl or amino groups.

7. The fuel cell of Claim 6 having a fuel barrier layer composed of a polyester urethane obtained by reacting methylene bis(4-cyclohexylisocyanate) with 10 to 90 mol percent of polyhexamethylene ortho phthalate and 90 to 10 mol percent of polycaprolactone to form a prepolymer and curing the prepolymer with a diamine.

8. The fuel cell of Claim 6 wherein the diamine is meta-phenylene diamine.