CA1107893A - Elastomeric compositions and seals - Google Patents
Elastomeric compositions and sealsInfo
- Publication number
- CA1107893A CA1107893A CA293,362A CA293362A CA1107893A CA 1107893 A CA1107893 A CA 1107893A CA 293362 A CA293362 A CA 293362A CA 1107893 A CA1107893 A CA 1107893A
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- Canada
- Prior art keywords
- equivalent weight
- parts
- dihydroxy
- butene
- elastomeric
- Prior art date
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/6775—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE This invention relates to improved elastomeric polyurethane compositions and seals which show increased resistance to the degrading effects of contact with fluids containing phosphate esters relative to conventional poly-urethane elastomers. The elastomeric composition includes the reaction product of ?,3'-dimethyl-4,4'-diphenyl diiso-cyanate; one or more polycaprolactone polyols; and a chain extender which includes a linear aliphatic compound defining a chain of carbon atoms which includes at least one unsatur-ated carbon-carbon bond and which is terminated at each end with a hydroxyl group. An example of a preferred chain extender is 1,4-dihydroxy-2,3-dibromo-2-butene.
Description
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
.
This invention pertains, in general, to improved poly-urethane elastomer compositions which are used in contact with phosphate-ester-based hydraulic fluids.
DESCRIPTION OF THE PRIOR ART
. .
The term "polyurethane elastomers" is generally applied to elastomeric or rubberlike polymers which contain significant numbers of urethane groups, which have the characteristic structure O
N - C - O -, whether the urethane group repeats regularly throughout the macromolecule or not. Such elastomers are ordinarily prepared by the reaction of a polyisocyanate compound with compounds hav-ing two or more "active hydrogens". Such active-hydrogen com-pounds include polyhydroxy compounds, generally termed polyols, and compounds containing amino groups or carboxyl groups. The active hydrogen compound can contain functional groups in addi-tion to groups which supply replaceable hydrogens. Thus hydroxyl-terminated polyethers and polyesters have been used to react with polyisocyanates to prepare polyurethanes, as have poly-caprolactone polyols, which contain both ester and ether groups in addition to hydroxyl groups. A detailed discussion of prior-art polyurethane compositions may be found in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed., (Interscience, 1970), Vol. 21, pp. 56-106.
Generally in commercial practices a "prepolymer" tech-nique is utilized to prepare polyurethane elastomers, in which a diisocyanate is reacted with a polyol, usually a hydroxyl-terminated polyester or polyether, to form an isocyanate-terminated prepolymer. The polyols used in forming the poly-.~, , ~
/~,1 ~
1 78~3 urethane elastomers generally have molecular weights in therange of about 1,000 to about 3,000. The diisocyanates em-ployed are ordinarily aromatic compounds, because their bulky molecular structure contributes rigidity and tensile strength to the polymer. Two aromatic diisocyanates commonly used in the preparation of polyurethane elastomers are 4,4'-diphenyl-methane diisocyanate, designated MDI, and 3,3'-dimethyl-4,4'-diphenyl diisocyanate, designated TODI. A partial listing of other aromatic diisocyanates particularly useful in the pre-paration of polyurethane elastomers is set forth in Table 16,page 77 of Kirk-Othmer, cited above. During the prepolymer formation step the molecular weight of the material is in-creased to the range of 25,000 to 50,000.
This prepolymer is then further reacted with a second active-hydrogen compound, ordinarily of lower molecular weight than the polyol used to prepare the prepolymer. This second step is referred to as a "chain extension" reaction, and the second active-hydrogen reactant is termed a "chain extender".
Gylcol (1,2 ethanediol); 1,4 butanediol; diamines; and tri-hydroxy compounds have been used as chain extenders. The chainextension reaction causes the segments of prepolymer to join together to produce a very high molecular weight linear material.
Chain extension normally does not provide any cross-linking.
However, if a trihydroxy compound such as trimethyolpropane is used for chain extension, branching of the polymer will occur.
The above steps are usually carried out at elevated temp-eratures in the vicinity of about 100C and may or may not be catalyzed.
Up to this point the polyurethane polymer exists mainly as a very high molecular weight polymeric material. In order to provide the final physical properties associated with a 11~7~3 thermoset elastomeric material, the polymer must be cross-linked. This is accomplished by joining the long polymer chains together through the reaction of free (unreacted) diisocyanate groups on one macromolecule with urethane and/or substituted urea groups on another macromolecule to form allophanate and/or biuret cross-links respectively.
In addition to the prepolymer method discussed above for preparing polyurethane elastomers, a "one-shot" technique is also sometimes used. l'he one-shot method involves mixing active-hydrogen compounds of different molecular weights and reactingthe resultant mixture with a polyisocyanate.
Within the polyurethane elastomer family, it is possible to obtain a wide range of values for the physical and chemical properties of the elastomer by appropriate selection of the specific raw materials, their formulation, or their relative amount within the formulation, as is well known in the art.
Conventional polyurethane elastomers have advantages not possessed by other elastomeric materials; namely: 1) excellent abrasion resistance; 2) higher tear strength; 3) high tensile modulus; 4) high tensile strength at break; 5) outstand-ing toughness; 6) excellent resistance to oxygen and ozone;
and 7) excellent resistance to mineral oil.
Because of their overall good abrasion resistance, high coeffecient of friction, low noise level, and particularly their excellent resistance to mineral oils, polyurethane elastomers have found wide use as gaskets, wiper rings, valve seats, and other such seals in hydraulic systems which employ mineral-oil hydraulic fluids.
Seals for hydraulic systems made of conventional poly-urethane elastomers, however, suffer a serious limitation whichhas become increasingly important in recent years. Because of the fire hazard which attends the use of mineral-oil hydraulic ;3 fluids, users and manufacturers of hydraulic systems often employ phosphate-ester hydraulic fluids in place of mineral oils.
Phosphate esters,however, attack conventional polyurethane elastomeric materials, causing them to swell and lose strength.
A conventional polyurethane-elastomer seal in contact with a phosphate-ester hydraulic fluid will weaken and have a substan-tially shortened useful life compared to the same seal in con-tact with a mineral-oil hydraulic fluid. In high-pressure hydraulic systems employing phosphate-ester hydraulic fluids, there is a significant risk that a seal made of a conventional polyurethane elastomer will fail catastrophically.
Other elastomeric materials, such as certain highly fluoronated polymers, are available which can withstand attack by fluids containing phosphate esters, but generally these mat-erials are significantly more expensive than conventional poly-urethane elastomers and, moreover, have a lower abrasion resist-ance.
I have invented an elastomeric polyurethane composition which is highly resistant to fluids containing phosphate esters, yet retains without significant impairment the advantages of conventional polyurethane elastomers. This composition is particularly adapted for use in fabricating elastomeric seals which avoid the problems associated with conventional polyure-thane elastomeric seals in contact with phosphate-ester hydraulic fluids.
SUMMARY OF THE INVENTION
-This invention relates to an improved elastomeric poly-urethane composition which is resistant to fluids containing phosphate esters, such as phosphate-ester hydraulic fluids. The composition includes the reaction product of 3,3'-dimethyl-4,4'-diphenyl diisocyanate (TODI), one or more polycaprolactone polyols, and a chain extender which includes a linear aliphatic compound ! -4-11~78~3 defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsatur-ated carbon-carbon bond.
A preferred chain extender of the present invention, particularly for applications in which the elastomeric poly-urethane composition will not contact mineral oils, is 1,4-dihydroxy-2,3-dibromo-2-butene. A second chain extender, preferred for applicat:ions in which resistance to both mineral oils and phosphate esters is required, is a mixture of 1,4-butanediol and 1,4-dihydroxy-2,3-dibromo-2-butene. For example, a mixture of about 12 percent by weight 1,4-butanediol and about 88 percent by weight 1,4-dihydroxy-2,3-dibromo-2-butene used as a chain extender in the present invention lead to an elastomeric polyurethane composition with excellent re-sistance to both mineral-oil and phosphate-ester hydraulic fluids.
The present invention further relates to an elastomeric seal which is resistant to fluids containing phosphate esters.
The seal is made of an elastomeric polyurethane composition of the present invention. Seals of the present invention may be incorporated to advantage in hydraulic machines to seal reser-voirs, lines, and other containers of hydraulic fluids contain-ing phosphate esters.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Elastomeric polyurethane compositions of the present invention can be synthesized by substantially the same techniques as conventional polyurethane elastomers. The two-step prepolymer method is ordinarily preferred for preparing the composition, al-though it is contemplated that for some applications it may be advantageous to premix the polycaprolactone polyol with the chain extender before reacting the mixture with the diisocyanate in a one-shot process. Other sequences of reaction steps may also be X
i~7~3 used to prepare the composition.
One ingredient used to synthesize elastomeric poly-urethane compositions of the present invention is 3,3'-di-methyl-4,4'-diphenyl diisocyanate (TODI), which is commercially available.
Polycaprolactone polyols are generally made by reacting an~ -caprolactone with an initiator such as diethylene glycol (2,2'-oxydiethanol). Polycaprolactone polyols of various mole-cular weight distributions are commercially available. Pre-ferred polycaprolactone polyols for the present invention havemolecular weights in the range of from 1,000 to 3,000.
Preferred chain extenders for the present invention include one or more of the following compounds: 1,4-dihydroxy-
FIELD OF THE INVENTION
.
This invention pertains, in general, to improved poly-urethane elastomer compositions which are used in contact with phosphate-ester-based hydraulic fluids.
DESCRIPTION OF THE PRIOR ART
. .
The term "polyurethane elastomers" is generally applied to elastomeric or rubberlike polymers which contain significant numbers of urethane groups, which have the characteristic structure O
N - C - O -, whether the urethane group repeats regularly throughout the macromolecule or not. Such elastomers are ordinarily prepared by the reaction of a polyisocyanate compound with compounds hav-ing two or more "active hydrogens". Such active-hydrogen com-pounds include polyhydroxy compounds, generally termed polyols, and compounds containing amino groups or carboxyl groups. The active hydrogen compound can contain functional groups in addi-tion to groups which supply replaceable hydrogens. Thus hydroxyl-terminated polyethers and polyesters have been used to react with polyisocyanates to prepare polyurethanes, as have poly-caprolactone polyols, which contain both ester and ether groups in addition to hydroxyl groups. A detailed discussion of prior-art polyurethane compositions may be found in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd ed., (Interscience, 1970), Vol. 21, pp. 56-106.
Generally in commercial practices a "prepolymer" tech-nique is utilized to prepare polyurethane elastomers, in which a diisocyanate is reacted with a polyol, usually a hydroxyl-terminated polyester or polyether, to form an isocyanate-terminated prepolymer. The polyols used in forming the poly-.~, , ~
/~,1 ~
1 78~3 urethane elastomers generally have molecular weights in therange of about 1,000 to about 3,000. The diisocyanates em-ployed are ordinarily aromatic compounds, because their bulky molecular structure contributes rigidity and tensile strength to the polymer. Two aromatic diisocyanates commonly used in the preparation of polyurethane elastomers are 4,4'-diphenyl-methane diisocyanate, designated MDI, and 3,3'-dimethyl-4,4'-diphenyl diisocyanate, designated TODI. A partial listing of other aromatic diisocyanates particularly useful in the pre-paration of polyurethane elastomers is set forth in Table 16,page 77 of Kirk-Othmer, cited above. During the prepolymer formation step the molecular weight of the material is in-creased to the range of 25,000 to 50,000.
This prepolymer is then further reacted with a second active-hydrogen compound, ordinarily of lower molecular weight than the polyol used to prepare the prepolymer. This second step is referred to as a "chain extension" reaction, and the second active-hydrogen reactant is termed a "chain extender".
Gylcol (1,2 ethanediol); 1,4 butanediol; diamines; and tri-hydroxy compounds have been used as chain extenders. The chainextension reaction causes the segments of prepolymer to join together to produce a very high molecular weight linear material.
Chain extension normally does not provide any cross-linking.
However, if a trihydroxy compound such as trimethyolpropane is used for chain extension, branching of the polymer will occur.
The above steps are usually carried out at elevated temp-eratures in the vicinity of about 100C and may or may not be catalyzed.
Up to this point the polyurethane polymer exists mainly as a very high molecular weight polymeric material. In order to provide the final physical properties associated with a 11~7~3 thermoset elastomeric material, the polymer must be cross-linked. This is accomplished by joining the long polymer chains together through the reaction of free (unreacted) diisocyanate groups on one macromolecule with urethane and/or substituted urea groups on another macromolecule to form allophanate and/or biuret cross-links respectively.
In addition to the prepolymer method discussed above for preparing polyurethane elastomers, a "one-shot" technique is also sometimes used. l'he one-shot method involves mixing active-hydrogen compounds of different molecular weights and reactingthe resultant mixture with a polyisocyanate.
Within the polyurethane elastomer family, it is possible to obtain a wide range of values for the physical and chemical properties of the elastomer by appropriate selection of the specific raw materials, their formulation, or their relative amount within the formulation, as is well known in the art.
Conventional polyurethane elastomers have advantages not possessed by other elastomeric materials; namely: 1) excellent abrasion resistance; 2) higher tear strength; 3) high tensile modulus; 4) high tensile strength at break; 5) outstand-ing toughness; 6) excellent resistance to oxygen and ozone;
and 7) excellent resistance to mineral oil.
Because of their overall good abrasion resistance, high coeffecient of friction, low noise level, and particularly their excellent resistance to mineral oils, polyurethane elastomers have found wide use as gaskets, wiper rings, valve seats, and other such seals in hydraulic systems which employ mineral-oil hydraulic fluids.
Seals for hydraulic systems made of conventional poly-urethane elastomers, however, suffer a serious limitation whichhas become increasingly important in recent years. Because of the fire hazard which attends the use of mineral-oil hydraulic ;3 fluids, users and manufacturers of hydraulic systems often employ phosphate-ester hydraulic fluids in place of mineral oils.
Phosphate esters,however, attack conventional polyurethane elastomeric materials, causing them to swell and lose strength.
A conventional polyurethane-elastomer seal in contact with a phosphate-ester hydraulic fluid will weaken and have a substan-tially shortened useful life compared to the same seal in con-tact with a mineral-oil hydraulic fluid. In high-pressure hydraulic systems employing phosphate-ester hydraulic fluids, there is a significant risk that a seal made of a conventional polyurethane elastomer will fail catastrophically.
Other elastomeric materials, such as certain highly fluoronated polymers, are available which can withstand attack by fluids containing phosphate esters, but generally these mat-erials are significantly more expensive than conventional poly-urethane elastomers and, moreover, have a lower abrasion resist-ance.
I have invented an elastomeric polyurethane composition which is highly resistant to fluids containing phosphate esters, yet retains without significant impairment the advantages of conventional polyurethane elastomers. This composition is particularly adapted for use in fabricating elastomeric seals which avoid the problems associated with conventional polyure-thane elastomeric seals in contact with phosphate-ester hydraulic fluids.
SUMMARY OF THE INVENTION
-This invention relates to an improved elastomeric poly-urethane composition which is resistant to fluids containing phosphate esters, such as phosphate-ester hydraulic fluids. The composition includes the reaction product of 3,3'-dimethyl-4,4'-diphenyl diisocyanate (TODI), one or more polycaprolactone polyols, and a chain extender which includes a linear aliphatic compound ! -4-11~78~3 defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsatur-ated carbon-carbon bond.
A preferred chain extender of the present invention, particularly for applications in which the elastomeric poly-urethane composition will not contact mineral oils, is 1,4-dihydroxy-2,3-dibromo-2-butene. A second chain extender, preferred for applicat:ions in which resistance to both mineral oils and phosphate esters is required, is a mixture of 1,4-butanediol and 1,4-dihydroxy-2,3-dibromo-2-butene. For example, a mixture of about 12 percent by weight 1,4-butanediol and about 88 percent by weight 1,4-dihydroxy-2,3-dibromo-2-butene used as a chain extender in the present invention lead to an elastomeric polyurethane composition with excellent re-sistance to both mineral-oil and phosphate-ester hydraulic fluids.
The present invention further relates to an elastomeric seal which is resistant to fluids containing phosphate esters.
The seal is made of an elastomeric polyurethane composition of the present invention. Seals of the present invention may be incorporated to advantage in hydraulic machines to seal reser-voirs, lines, and other containers of hydraulic fluids contain-ing phosphate esters.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Elastomeric polyurethane compositions of the present invention can be synthesized by substantially the same techniques as conventional polyurethane elastomers. The two-step prepolymer method is ordinarily preferred for preparing the composition, al-though it is contemplated that for some applications it may be advantageous to premix the polycaprolactone polyol with the chain extender before reacting the mixture with the diisocyanate in a one-shot process. Other sequences of reaction steps may also be X
i~7~3 used to prepare the composition.
One ingredient used to synthesize elastomeric poly-urethane compositions of the present invention is 3,3'-di-methyl-4,4'-diphenyl diisocyanate (TODI), which is commercially available.
Polycaprolactone polyols are generally made by reacting an~ -caprolactone with an initiator such as diethylene glycol (2,2'-oxydiethanol). Polycaprolactone polyols of various mole-cular weight distributions are commercially available. Pre-ferred polycaprolactone polyols for the present invention havemolecular weights in the range of from 1,000 to 3,000.
Preferred chain extenders for the present invention include one or more of the following compounds: 1,4-dihydroxy-
2-butene; 1,4-dihydroxy-2-butyne; and 1,4-dihydroxy-2,3-dibromo-2-butene. Any of these compounds can be used alone or mixed with a conventional chain extender. Significantly, each of these three preferred chain extenders is a hydroxyl-terminated linear aliphatic compound which includes a double bond or a triple bond between two carbon atoms in the chain. The ratio of the effective equivalent weight of such hydroxyl-terminated, unsaturated compound or mixture of such compounds to the equiv-alent weight of the diisocyanate TODI preferably lies in the range of from about 0.3 to about 0.9.
As will be recognized by those skilled in this art, the elastomeric polyurethane composition of the present invention can include stabilizers, plasticizers, pigments, fillers, ex-tenders, and the like in addition to the reaction product of the ingredients set forth above.
The elastomeric polyurethane compositions can be cast and formed by conventional methods. Thus elastomeric seals of the present invention such as gaskets, wiper rings, and valve seats are preferably manufactured by the same techniques as are 7~3~3 used to fabricate seals from conventional polyurethane elasto-mers.
EXAMPLES
Two samples of elastomeric polyurethane compositions were prepared: a control sample of a conventional polyurethane elastomer, designated A, and a test sample of a elastomeric polyurethane composition of the present invention, designated B.
Table I lists the ingredients and proportions (in parts by weight) used.
Table I
Ingredient Proportion (parts by weight) Sample ASample B
"Niax Diol D-560" 100 100 1,4-butanediol 10.26 --1,4-dihydroxy-2,3-dibromo-2-butene -- 27.8 "Niax Diol D-560" is the trade name of a polycaprolactone poly-ol having a mean molecular weight of about 2000 sold by Union Carbide Corporation. TODI designates 3,3'-dimethyl-4,4'-di-phenyl diisocyanate.
Sample B, the test sample, was prepared according to the following procedure. The polycaprolactone polyol was dehydrated by melting and heating it with stirring under a vacuum of about 10-20 Torr. After dehydration, the polycaprolactone polyol was heated to 148C, the diisocyanate TODI was added, and the re-sultant mixture was stirred for 15 minutes under a vacuum to form a prepolymer. The temperature of the prepolymer was then adjusted to 120C and the chain extender 1,4-dihydroxy-2,3-dibromo-2-butene was stirred in. Standard test specimens were formed by casting this mixture in a steel mold heated to 125C.
After the specimens solidified, they were cured for 48 hours in an oven maintained at 100C.
Test specimens of the control sample A were prepared by the same procedure, except that the chain extender 1,4-butane-diol was substituted for 1,4-dihydroxy-2,3-dibromo-2-butene.
To compare the physical properties of these two samples, a series of standard tests were run which are commonly used in the polyurethane industry to characterize polyurethane elasto-mers. The results of the tests are set forth in Table II below.
Table II
Test Units or Results Symbol Sample A Sample B
Hardness (Shore A) points 93/40 96/45 Tensile Strength psi 4322 2075 Elongation percent 463 381 Elongation Set percent 22 80 25% Modulus psi 1103 1283 50~ Modulus psi 1225 1351 100% Modulus psi 1402 1496 200% Modulus psi 1802 1736 300% Modulus psi 2418 1938 Tear Strength (C, Nicked) PLI 389 338 Tear Strength (Die C) PLI 693 525 Resilience percent 31 35 The tensile, elongation, and modulus measurements were carried out on a ring specimen 52.6mm OD x 44.6mm ID x 3.2mm thick.
The samples were tested using an x head speed of 20 in./min.
Tear measurements were made according to the procedures of ASTM
test D-624.
To compare the compatibility of the two samples to phosphate esters, specimens of each were submerged for 168 hours at about 70C in a typical phosphate-ester hydraulic fluid, "Pydraul 50-E" sold by Monsanto Company. Table III lists the changes in three significant physical properties after sub-mergence in the phosphate ester hydraulic fluid.
Table III
Test Units or Results Symbol Sample A Sample B
Increase in Volume percent +16 +8.4 10Decrease in Hardness (Shore A) points -4 -2 Loss in Tear Strength (Die C) percent -30 0 The compatibility tests were performed using Die C tear speci-mens as described in ASTM test D-624 and the procedure specif-ied in ASTM test D-471.
As demonstrated by Table III above, the control sample A
exhibited a greater degree of swelling, more reduction of hard-ness, and a greater loss of tear strength then test Sample B
after extended exposure to a phosphate ester hydraulic fluid. t In fact, the sample of elastomeric polyurethane composition of the present invention exhibited no loss of tear strength after contact with the fluid. Thus the elastomeric polyurethane com-position of Sample B is proven to be more resistant to phosphate-ester hydraulic fluids than the conventional polyurethane elastomer of Sample A.
Five batches of polyurethane elastomer were prepared according to the procedure set forth in Example 1, except that the relative proportions of 1,4-butanediol and 1,4-dihydroxy-2,3-dibromo-2-butene in the chain extender were varied between 0 and 100 mole percent in 25 mole percent increments. The reaction ingredients and proportions in parts by weight are set forth in Table IV below.
7~3 Table IV
Ingredient Proportion (parts by weight) Sample _ D _ _ G
"Niax Diol D-560" 100 100 100 100 100 1,4-butanediol 10.2 7.6 5.05 2.5 0 1,4-dihydroxy-2,3-dibromo-2-butene 0 6.9 13.8 20.8 27.6 "Staboxol I" 0 0 0 0 "Staboxol I" is an additive for polyurethane sold by Farben-fabriken Bayer A. G. and identified as a carbodumide.
The physical characteristics of these five samples are set forth in Table V below. The test procedures were the same as those set forth in Example 1. Sample C, whose chain extender is pure 1,4-butanediol, was the control sample.
Table V
Units or Test Symbol Results Sample _ _ E
Hardness (Shore A) points 89 87 89 93 95 Tensile Strength psi3137 3216 49833870 3621 Elongation percent 367319 368 353402 Elongation Setpercent 13 6 9 15 43 25% Modulus psi 829748 814 9771261 50% Modulus psi 937814 917 10671305 100% Modulus psi 1142986 1140 12891439 200% Modulus psi 150714941679 17781800 300% Modulus psi 219628032798 28342475 Tear Strength (C, Nicked)PLI 324185 203 277374 Tear Strength (Die C) PLI 568462 519 548617 Resilience percent 30 35 36 37 30 Spec. Gravity -- 1.17 1.19 1.22 1.24 1.26 . ~
~7~3 The compatibility of these samples with the phosphate-ester hydraulic fluid "Pydraul 50-E" was tested by immersing specimens formed from the samples in the fluid for 168 hours at 70C.
The changes induced by this treatment are set forth in Table VI.
Table VI
-Units or Test _ymbol Result Sample _ _ E F G
Increase in Volume percent +21 +21 +21 +17 +11 10Decrease in Hardness (Shore A) points -4 -3 -4 -3 -2 Loss of Tear Strength (Die C) percent -35 -31-25 -27 -14 As can be seen from Table VI above, any 1,4-dihydroxy-2,3-dibromo-2-butene in the chain extender is beneficial, and substantial resistance to deterioration caused by contact with phosphate-ester containing fluid is obtained when the two-component chain extender of this example contains greater than 25 mole percent 1,4-dihydroxy-2,3-dibromo-2-butene.
EX~MPLE 3 The following elastomeric polyurethane composition, Sample H, was prepared generally according to the procedure set forth in Example 1:
"Niax Diol D-560" 100 parts by weight (28 parts by equivalent weight) TODI 48 parts by weight (100 parts by equivalent weight) 1,4-dihydroxy-2,3- 20.59 parts by weight dibromo-2-butene (47 parts by equivalent weight) 1,4-butanediol 2.69 parts by weight (17 parts by equivalent weight) "Staboxol I" 1 part by weight.
Specimens of this composition were immersed for 168 hours in four different hydraulic fluids, two mineral-oil based and two phosphate-ester based. The temperatures at which the hydraulic fluids were maintained during the exposure of the specimens to the fluids and the changes in volume, hardness, and ~78~3 tear strength induced by the exposure are set forth in Table VII.
Table VII
Temperature Increase Decrease Loss in Hydraulic in Volume in Hardness Tear Strength Fluid (C) (percent) (points) (percent) "Pydraul 5OE" 70 32 -3 -4 "Pydraul 5OE" 100 35 -4 0 "Monsanto 230" 70 26 -2 0 "Monsanto 230" 100 28 -3 0 ASTM Oil #170 0 +1 0 ASTM Oil #1100 7 -1 0 ASTM Oil #370 6 +1 0 ASTM Oil #3100 0 0 0 "Monsanto 230" is the trade name of a phosphate-ester hydraulic fluid sold by Monsanto Company. ASTM Oils #1 and 3 are standard mineral oils. The test procedures were the same as were carried out in connection with Tables III and VI above.
Table VII demonstrates that the elastomeric polyurethane composition of Sample H is resistent to both mineral-oil hydraul-ic fluids and phosphate-ester hydraulic fluids. Note that the hardness of the composition actually increases upon exposure to the mineral oils at 70C.
Similar tests were carried out on the following elasto-meric polyurethane composition, Sample I:
"Niax Diol D-560" 100 parts by weight (28 parts by equivalent weight) TODI 48 parts by weight (100 parts by equivalent weight) 1,4-dihydroxy-2,3- 25.87 parts by weight dibromo-2-butene (58 parts by equivalent weight).
This composition exhibited superior resistance to phosphate esters compared to Sample H, but significantly lower resistance to mineral oils.
!~
11~7~3~3 Four batches of elastomeric polyurethane composition were prepared generally according to the procedure of Example 1, except that 1,4-dihydroxy-2-butene and 1,4-dihydroxy-2-butyne were used as chain extenders in addition to the two chain extenders of Example 1. The reaction ingredients and proportions in parts by weight are set forth in Table VIII
below. Equimolar amounts of chain extender were employed in the four samples.
Table VIII
Ingredient Proportion (parts by weight) Sample J K L M
"Niax Diol D-560" 100 100 100100 1,4-butanediol 10.00 -- -- --1,4-dihydroxy-2-butene -- 9.69 -- --1,4-dihydroxy-2-butyne -- -- 9.47 --1,4-dihydroxy-2,3-dibromo-2-butene -- -- -- 25.87 Physical characteristics of these samples are set forth in Table IX below. The test procedures were the same as those set forth in Example 1. Sample J was a control sample.
Table IX
Units or Test Symbol Results Sample J K _ M
Hardness (Shore A)points 93 91 87 95 Tensile Strength psi 3137 3026 2842 3549 Elongation percent 367 421 333 431 Elongation Set percent 13 12 10 55 300% Modulus psi2196 1928 2460 2545 Tear Strength (Die C) PLI 568 463 440 717 !
11~78~3 The compatibility of these four samples with the phosphate-ester hydraulic fluid "Pydraul 50-E" was tested by immersing specimens formed from the samples in the fluid for 168 hours at three different temperatures. The changes induced by this treatment are set forth in Table X.
Table X
.
Units or Tempera-Test Symbol ture (C) Results _ Sample _ K L M_ Increase in Volumepercent 20 9 4 3 4 Decrease in Hardnesspoints 20 -2 -1 -1 0 (Shore A) 100 -9 ~5 ~3 ~4 Loss of Tear Strengthpercent 20 -11 0 -4 -6 (Die C) As may be seen in Table X, Samples K, L, and M all exhibit substantially improved resistance to attack by phosphate-ester hydraulic fluids compared to the control Sample J.
It is not intended to limit the present invention to the specific embodiments described above. For example, the composition of the present invention can be made in a one-shot process, and the polymerization reactions can be catalyzed with conventional catalysts such as tertiary amines or metallic catalysts. It is recognized that these and other changes may be made in the compositions and processes specifically described herein without departing from the scope and teachings of the instant invention, and it is intended to encompass all other embodiments, alternatives and modifications consistent with the present invention.
As will be recognized by those skilled in this art, the elastomeric polyurethane composition of the present invention can include stabilizers, plasticizers, pigments, fillers, ex-tenders, and the like in addition to the reaction product of the ingredients set forth above.
The elastomeric polyurethane compositions can be cast and formed by conventional methods. Thus elastomeric seals of the present invention such as gaskets, wiper rings, and valve seats are preferably manufactured by the same techniques as are 7~3~3 used to fabricate seals from conventional polyurethane elasto-mers.
EXAMPLES
Two samples of elastomeric polyurethane compositions were prepared: a control sample of a conventional polyurethane elastomer, designated A, and a test sample of a elastomeric polyurethane composition of the present invention, designated B.
Table I lists the ingredients and proportions (in parts by weight) used.
Table I
Ingredient Proportion (parts by weight) Sample ASample B
"Niax Diol D-560" 100 100 1,4-butanediol 10.26 --1,4-dihydroxy-2,3-dibromo-2-butene -- 27.8 "Niax Diol D-560" is the trade name of a polycaprolactone poly-ol having a mean molecular weight of about 2000 sold by Union Carbide Corporation. TODI designates 3,3'-dimethyl-4,4'-di-phenyl diisocyanate.
Sample B, the test sample, was prepared according to the following procedure. The polycaprolactone polyol was dehydrated by melting and heating it with stirring under a vacuum of about 10-20 Torr. After dehydration, the polycaprolactone polyol was heated to 148C, the diisocyanate TODI was added, and the re-sultant mixture was stirred for 15 minutes under a vacuum to form a prepolymer. The temperature of the prepolymer was then adjusted to 120C and the chain extender 1,4-dihydroxy-2,3-dibromo-2-butene was stirred in. Standard test specimens were formed by casting this mixture in a steel mold heated to 125C.
After the specimens solidified, they were cured for 48 hours in an oven maintained at 100C.
Test specimens of the control sample A were prepared by the same procedure, except that the chain extender 1,4-butane-diol was substituted for 1,4-dihydroxy-2,3-dibromo-2-butene.
To compare the physical properties of these two samples, a series of standard tests were run which are commonly used in the polyurethane industry to characterize polyurethane elasto-mers. The results of the tests are set forth in Table II below.
Table II
Test Units or Results Symbol Sample A Sample B
Hardness (Shore A) points 93/40 96/45 Tensile Strength psi 4322 2075 Elongation percent 463 381 Elongation Set percent 22 80 25% Modulus psi 1103 1283 50~ Modulus psi 1225 1351 100% Modulus psi 1402 1496 200% Modulus psi 1802 1736 300% Modulus psi 2418 1938 Tear Strength (C, Nicked) PLI 389 338 Tear Strength (Die C) PLI 693 525 Resilience percent 31 35 The tensile, elongation, and modulus measurements were carried out on a ring specimen 52.6mm OD x 44.6mm ID x 3.2mm thick.
The samples were tested using an x head speed of 20 in./min.
Tear measurements were made according to the procedures of ASTM
test D-624.
To compare the compatibility of the two samples to phosphate esters, specimens of each were submerged for 168 hours at about 70C in a typical phosphate-ester hydraulic fluid, "Pydraul 50-E" sold by Monsanto Company. Table III lists the changes in three significant physical properties after sub-mergence in the phosphate ester hydraulic fluid.
Table III
Test Units or Results Symbol Sample A Sample B
Increase in Volume percent +16 +8.4 10Decrease in Hardness (Shore A) points -4 -2 Loss in Tear Strength (Die C) percent -30 0 The compatibility tests were performed using Die C tear speci-mens as described in ASTM test D-624 and the procedure specif-ied in ASTM test D-471.
As demonstrated by Table III above, the control sample A
exhibited a greater degree of swelling, more reduction of hard-ness, and a greater loss of tear strength then test Sample B
after extended exposure to a phosphate ester hydraulic fluid. t In fact, the sample of elastomeric polyurethane composition of the present invention exhibited no loss of tear strength after contact with the fluid. Thus the elastomeric polyurethane com-position of Sample B is proven to be more resistant to phosphate-ester hydraulic fluids than the conventional polyurethane elastomer of Sample A.
Five batches of polyurethane elastomer were prepared according to the procedure set forth in Example 1, except that the relative proportions of 1,4-butanediol and 1,4-dihydroxy-2,3-dibromo-2-butene in the chain extender were varied between 0 and 100 mole percent in 25 mole percent increments. The reaction ingredients and proportions in parts by weight are set forth in Table IV below.
7~3 Table IV
Ingredient Proportion (parts by weight) Sample _ D _ _ G
"Niax Diol D-560" 100 100 100 100 100 1,4-butanediol 10.2 7.6 5.05 2.5 0 1,4-dihydroxy-2,3-dibromo-2-butene 0 6.9 13.8 20.8 27.6 "Staboxol I" 0 0 0 0 "Staboxol I" is an additive for polyurethane sold by Farben-fabriken Bayer A. G. and identified as a carbodumide.
The physical characteristics of these five samples are set forth in Table V below. The test procedures were the same as those set forth in Example 1. Sample C, whose chain extender is pure 1,4-butanediol, was the control sample.
Table V
Units or Test Symbol Results Sample _ _ E
Hardness (Shore A) points 89 87 89 93 95 Tensile Strength psi3137 3216 49833870 3621 Elongation percent 367319 368 353402 Elongation Setpercent 13 6 9 15 43 25% Modulus psi 829748 814 9771261 50% Modulus psi 937814 917 10671305 100% Modulus psi 1142986 1140 12891439 200% Modulus psi 150714941679 17781800 300% Modulus psi 219628032798 28342475 Tear Strength (C, Nicked)PLI 324185 203 277374 Tear Strength (Die C) PLI 568462 519 548617 Resilience percent 30 35 36 37 30 Spec. Gravity -- 1.17 1.19 1.22 1.24 1.26 . ~
~7~3 The compatibility of these samples with the phosphate-ester hydraulic fluid "Pydraul 50-E" was tested by immersing specimens formed from the samples in the fluid for 168 hours at 70C.
The changes induced by this treatment are set forth in Table VI.
Table VI
-Units or Test _ymbol Result Sample _ _ E F G
Increase in Volume percent +21 +21 +21 +17 +11 10Decrease in Hardness (Shore A) points -4 -3 -4 -3 -2 Loss of Tear Strength (Die C) percent -35 -31-25 -27 -14 As can be seen from Table VI above, any 1,4-dihydroxy-2,3-dibromo-2-butene in the chain extender is beneficial, and substantial resistance to deterioration caused by contact with phosphate-ester containing fluid is obtained when the two-component chain extender of this example contains greater than 25 mole percent 1,4-dihydroxy-2,3-dibromo-2-butene.
EX~MPLE 3 The following elastomeric polyurethane composition, Sample H, was prepared generally according to the procedure set forth in Example 1:
"Niax Diol D-560" 100 parts by weight (28 parts by equivalent weight) TODI 48 parts by weight (100 parts by equivalent weight) 1,4-dihydroxy-2,3- 20.59 parts by weight dibromo-2-butene (47 parts by equivalent weight) 1,4-butanediol 2.69 parts by weight (17 parts by equivalent weight) "Staboxol I" 1 part by weight.
Specimens of this composition were immersed for 168 hours in four different hydraulic fluids, two mineral-oil based and two phosphate-ester based. The temperatures at which the hydraulic fluids were maintained during the exposure of the specimens to the fluids and the changes in volume, hardness, and ~78~3 tear strength induced by the exposure are set forth in Table VII.
Table VII
Temperature Increase Decrease Loss in Hydraulic in Volume in Hardness Tear Strength Fluid (C) (percent) (points) (percent) "Pydraul 5OE" 70 32 -3 -4 "Pydraul 5OE" 100 35 -4 0 "Monsanto 230" 70 26 -2 0 "Monsanto 230" 100 28 -3 0 ASTM Oil #170 0 +1 0 ASTM Oil #1100 7 -1 0 ASTM Oil #370 6 +1 0 ASTM Oil #3100 0 0 0 "Monsanto 230" is the trade name of a phosphate-ester hydraulic fluid sold by Monsanto Company. ASTM Oils #1 and 3 are standard mineral oils. The test procedures were the same as were carried out in connection with Tables III and VI above.
Table VII demonstrates that the elastomeric polyurethane composition of Sample H is resistent to both mineral-oil hydraul-ic fluids and phosphate-ester hydraulic fluids. Note that the hardness of the composition actually increases upon exposure to the mineral oils at 70C.
Similar tests were carried out on the following elasto-meric polyurethane composition, Sample I:
"Niax Diol D-560" 100 parts by weight (28 parts by equivalent weight) TODI 48 parts by weight (100 parts by equivalent weight) 1,4-dihydroxy-2,3- 25.87 parts by weight dibromo-2-butene (58 parts by equivalent weight).
This composition exhibited superior resistance to phosphate esters compared to Sample H, but significantly lower resistance to mineral oils.
!~
11~7~3~3 Four batches of elastomeric polyurethane composition were prepared generally according to the procedure of Example 1, except that 1,4-dihydroxy-2-butene and 1,4-dihydroxy-2-butyne were used as chain extenders in addition to the two chain extenders of Example 1. The reaction ingredients and proportions in parts by weight are set forth in Table VIII
below. Equimolar amounts of chain extender were employed in the four samples.
Table VIII
Ingredient Proportion (parts by weight) Sample J K L M
"Niax Diol D-560" 100 100 100100 1,4-butanediol 10.00 -- -- --1,4-dihydroxy-2-butene -- 9.69 -- --1,4-dihydroxy-2-butyne -- -- 9.47 --1,4-dihydroxy-2,3-dibromo-2-butene -- -- -- 25.87 Physical characteristics of these samples are set forth in Table IX below. The test procedures were the same as those set forth in Example 1. Sample J was a control sample.
Table IX
Units or Test Symbol Results Sample J K _ M
Hardness (Shore A)points 93 91 87 95 Tensile Strength psi 3137 3026 2842 3549 Elongation percent 367 421 333 431 Elongation Set percent 13 12 10 55 300% Modulus psi2196 1928 2460 2545 Tear Strength (Die C) PLI 568 463 440 717 !
11~78~3 The compatibility of these four samples with the phosphate-ester hydraulic fluid "Pydraul 50-E" was tested by immersing specimens formed from the samples in the fluid for 168 hours at three different temperatures. The changes induced by this treatment are set forth in Table X.
Table X
.
Units or Tempera-Test Symbol ture (C) Results _ Sample _ K L M_ Increase in Volumepercent 20 9 4 3 4 Decrease in Hardnesspoints 20 -2 -1 -1 0 (Shore A) 100 -9 ~5 ~3 ~4 Loss of Tear Strengthpercent 20 -11 0 -4 -6 (Die C) As may be seen in Table X, Samples K, L, and M all exhibit substantially improved resistance to attack by phosphate-ester hydraulic fluids compared to the control Sample J.
It is not intended to limit the present invention to the specific embodiments described above. For example, the composition of the present invention can be made in a one-shot process, and the polymerization reactions can be catalyzed with conventional catalysts such as tertiary amines or metallic catalysts. It is recognized that these and other changes may be made in the compositions and processes specifically described herein without departing from the scope and teachings of the instant invention, and it is intended to encompass all other embodiments, alternatives and modifications consistent with the present invention.
Claims (10)
1. An elastomeric polyurethane composition resistant to fluids containing phosphate esters; comprising the reac-tion product of:
(a) 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) a polyhydroxy compound selected from the group consisting of polycaprolactone polyols; and (c) a chain extender including an amount which is effective to provide resistance to phosphate esters of a lin-ear aliphatic compound defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsaturated carbon-carbon bond.
(a) 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) a polyhydroxy compound selected from the group consisting of polycaprolactone polyols; and (c) a chain extender including an amount which is effective to provide resistance to phosphate esters of a lin-ear aliphatic compound defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsaturated carbon-carbon bond.
2. The elastomeric polyurethane composition accord-ing to claim 1 in which the ratio of the effective equivalent weight of the linear aliphatic compound included in the chain extender to the equivalent weight of 3,3'-dimethyl-4,4'-di-phenyl diisocyanate lies in the range of from about 0.3 to about 0.9.
3. The elastomeric polyurethane composition accord-ing to claim 1 in which the linear aliphatic compound included in the chain extender is selected from the group consisting of 1,4-dihydroxy-2-butene; 1,4-dihydroxy-2-butyne; and 1,4-di-hydroxy-2,3-dibromo-2-butene.
4. The elastomeric polyurethane composition accord-ing to claim 3 in which the chain extender is a mixture of 1,4-butanediol and 1,4-dihydroxy-2,3-dibromo-2-butene.
5. The elastomeric polyurethane composition accord-ing to claim 3 in which the chain extender is 1,4-dihydroxy-2,3-dibromo-2-butene.
6. An elastomeric polyurethane composition resistant to fluids containing phosphate esters; comprising the reac-tion product of:
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol; and (c) about 58 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene.
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol; and (c) about 58 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene.
7. An elastomeric polyurethane composition resistant to fluids containing phosphate esters; comprising the reac-tion product of:
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol;
(c) about 47 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene; and (d) about 17 parts by equivalent weight of 1,4-butanediol.
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol;
(c) about 47 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene; and (d) about 17 parts by equivalent weight of 1,4-butanediol.
8. In a hydraulic machine comprising: a fluid con-tainer, a hydraulic fluid containing a phosphate ester, and elastomeric means for sealing the container; the improvement consisting of elastomeric means for sealing the container made of a polyurethane composition resistant to hydraulic fluids containing a phosphate ester, the polyurethane composition comprising the reaction product of:
(a) 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) a polyhydroxy compound selected from the group consisting of polycaprolactone polyols; and (c) a chain extender including an amount which is effective to provide resistance to phosphate esters of a lin-ear aliphatic compound defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsaturated carbon-carbon bond.
(a) 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) a polyhydroxy compound selected from the group consisting of polycaprolactone polyols; and (c) a chain extender including an amount which is effective to provide resistance to phosphate esters of a lin-ear aliphatic compound defining a chain of carbon atoms, each end of the chain being attached to a hydroxyl group, and the chain having an unsaturated carbon-carbon bond.
9. An elastomeric seal resistant to fluids contain-ing phosphate esters, the seal being composed of an elasto-meric polyurethane composition comprising the reaction product of:
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol; and (c) about 58 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene.
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol; and (c) about 58 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene.
10. An elastomeric seal resistant to fluids contain-ing phosphate esters, the seal being composed of an elasto-meric polyurethane composition comprising the reaction product of:
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol;
(c) about 47 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene; and (d) about 17 parts by equivalent weight of 1,4-butanediol.
(a) about 100 parts by equivalent weight of 3,3'-dimethyl-4,4'-diphenyl diisocyanate;
(b) about 28 parts by equivalent weight of a poly-caprolactone polyol;
(c) about 47 parts by equivalent weight of 1,4-dihydroxy-2,3-dibromo-2-butene; and (d) about 17 parts by equivalent weight of 1,4-butanediol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75709577A | 1977-01-05 | 1977-01-05 | |
| US757,095 | 1977-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107893A true CA1107893A (en) | 1981-08-25 |
Family
ID=25046325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,362A Expired CA1107893A (en) | 1977-01-05 | 1977-12-19 | Elastomeric compositions and seals |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS5466998A (en) |
| CA (1) | CA1107893A (en) |
| DE (1) | DE2800301C2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930574A (en) * | 1982-08-14 | 1984-02-18 | Konishiroku Photo Ind Co Ltd | Cleaning blade for electrophotographic copying machine |
| JPS6177538A (en) * | 1984-09-26 | 1986-04-21 | Toyota Motor Corp | Sheet adjusting apparatus for car |
| JPH0732919A (en) * | 1993-07-20 | 1995-02-03 | Mitsuba Electric Mfg Co Ltd | Driving device of power seat for vehicle |
| DE19537608A1 (en) | 1995-10-09 | 1997-04-10 | Rhone Poulenc Fibres Et Polyme | Polyurethane elastomers, process for their preparation and their use |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3651021A (en) * | 1968-05-03 | 1972-03-21 | Union Carbide Corp | Ethylenically unsaturated polylactone-based polyurethane elastomer and vulcanizates therefrom |
-
1977
- 1977-12-19 CA CA293,362A patent/CA1107893A/en not_active Expired
- 1977-12-29 JP JP15850277A patent/JPS5466998A/en active Pending
-
1978
- 1978-01-04 DE DE19782800301 patent/DE2800301C2/en not_active Expired
-
1980
- 1980-12-27 JP JP18933880A patent/JPS5736176A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5736176A (en) | 1982-02-26 |
| DE2800301A1 (en) | 1978-07-13 |
| JPS5466998A (en) | 1979-05-29 |
| DE2800301C2 (en) | 1982-09-16 |
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