CA1115894A - Polyurethane composition and articles thereof - Google Patents
Polyurethane composition and articles thereofInfo
- Publication number
- CA1115894A CA1115894A CA287,732A CA287732A CA1115894A CA 1115894 A CA1115894 A CA 1115894A CA 287732 A CA287732 A CA 287732A CA 1115894 A CA1115894 A CA 1115894A
- Authority
- CA
- Canada
- Prior art keywords
- ester
- hydroxy
- diisocyanate
- castor oil
- glycol
- 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.)
- Expired
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
- B01D63/022—Encapsulating hollow fibres
- B01D63/023—Encapsulating materials
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
ABSTRACT
A cured polyurethane composition for hollow fiber separatory devices is provided wherein a polyurethane prepolymer is cross-linked or cured with an ester of a polyhydric alcohol which con-tains two or three hydroxyl groups, e.g., propylene glycol mono-ricinoleate, and an aliphatic acid of at least 12 carbon atoms and one or more epoxy and/or hydroxy groups per molecule.
A cured polyurethane composition for hollow fiber separatory devices is provided wherein a polyurethane prepolymer is cross-linked or cured with an ester of a polyhydric alcohol which con-tains two or three hydroxyl groups, e.g., propylene glycol mono-ricinoleate, and an aliphatic acid of at least 12 carbon atoms and one or more epoxy and/or hydroxy groups per molecule.
Description
1 ~I~L~ OF INvENrIoN
2 The present invention relates to polymeric compositions 8 designated as polyurethanes and, more particularly, relates to 4 such polyurethanes derived from a prepolymer of a multifunctional 6 agent such as castor oil and an organic diisocyanate which is 6 cured with a cross-linking agent comprising the ester of a poly-q hydric alcohol having two or three hydroxyl groups and an 8 aliphatic acid of at least 12 carbon atoms and one or more epoxy 9 and/or hydroxy groups per molecule.
BACKGROUND OF INVENTION
Polyurethane compositions obtained by reacting a suitable 12 prepolymer of an organic diisocyanate and a curing agent such as a polyalkylene glycol are generally well-known. Ordinarily, the 14 organic diisocyanate is reacted with a suitable polyfunctional 1~ compound that contains active hydrogen groups to provide a pre-16 polymer composition. The prepolymer is thereafter reacted with 17 a suitable curing or cross-linking agent to provide the poly-18 urethan:e composition. For instance, U.S. Patent No. 3,362,921 1~ discloses an elastomeric polyurethane derived from a prepolymer obtained by reacting castor oil and an organic diisocyanate such 21 as toluene diisocyanate. The resulting prepolymer is cross-22 linked by reaction with a suitable ester of a polyhydric alcohol 28 which contains at least four hydroxy groups, e.g., pentaerythritol 24 monorlcinoleate. U.S. Patent No. 3,362,921 discloses that it is essential to utilize a cross-linking or curing agent derived from 26 esters of polyhydric alcohols that contain at least four hydroxy 27 groups in order to obtain a cured polyurethane having desirable 28 elastomeric properties for potting applications.
THE INVENTION
According to the present invention, there is provided a 31 polyurethane composition obtained by reacting a diisocyanate pre-82 polymer ~-rith an ester of a polyhydric alcohol ~hich contains t~o 1~5894 or three hydroxy groups and an aliphatic acid of at least 12 carbon atoms and one or more epoxy and/or hydroxy groups per molecule.
Thus, one feature of the invention is a hollow fiber separatory device comprising a hollow fiber bundle consisting of a plurality of fine hollow fibers whose end portions are potted in a tube-sheet and whose open fiber ends terminate in a tube-sheet face, the resulting bundle being sealed within a casing to form a separatory cell having one or more fluid ports which allow for the passage of one fluid through the fibers and another around the fibers without mixing of the two fluids, said tube-sheet comprising a cured polyurethane composition consisting essentially of:
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol wih at least one mole per polyol hydroxy group of an organic diisocyanate, and B. A cross-linking agent comprising the ester of i. a polyhydric alcohol containing two or three hydroxy groups, and ii. an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule and blends of said ester and blown castor oil.
Another feature is a cured polyurethane comprising the reaction product of: (1~ the product of the reaction of (a) a polyester prepared from bifunctional ingredients including at least one dibasic carboxylic acid and at least one bifunction-al reactant in which the functional groups are hydroxy groups, said polyester having a hydroxyl number from 40-100 and an acid number from 0-7, and (b) an arylene diisocyanate, and (2) a curing agent consisting essentially of an ester of a poly-hydrix alcohol of two or three hydroxy groups and a hydroxy A
1~15894 and/or epoxy aliphatic acid of at least 12 carbon atoms.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A. Prepolymer Suitable prepolymer compositions used in the present invention are prepared by reacting an active-hydrogen contain-ing polymeric material within particular molecular weight and acid number ranges with a controlled amount of a diisocyanate, with the diisocyanate being present in greater than stoichio-metric amounts. Examples of active-hydrogen containing polymeric materials which may be used are polyesters, castor oil, polyester amides and polyalkylene ether glycols. Pre-polymer compositions prepared by reacting a diisocyanate with active-hydrogen containing materials are more fully disclosed in United States Patent Nos. 2,625,531; 2,625,532; 2,625,535;
2,692,873 and 2,702,797.
The organic diisocyanates used in the preparation of the prepolymer compositions are those which are known in the art to be useful in the preparation of such compositions by reac-tion with active-hydrogen containing materials. Arylene diisocyanates as represented by the diisocyanates of the benzene and naphthalene series or mixtures of these compounds are preferred. Illustrative of arylene diisocyanates that may be employed are the following: tolylene diisocyanate (2,4/2,6), toluene 2,4 diisocyanate, toluene 2,6 diisocyanate, m-phenylene diisocyanate, xenylene 4,4'-diisocyanate, naph-thalene 1,5'-diisocyanate, 3,3'-bitolylene 4,4'-diisocyanate, diphenylene methane 4,4'-diisocyanate, 4-chlorophenylene 2,4-diisocyanate, dianisidine diisocyanate, diphenylene ether 4,4'-diisocyanate, and polymeric isocyanates such as poly-methylene polyphenylene isocyanate. Other arylene diiso-cyanates which are useful include lower alkyl substitutedderivates, halogen substit~ted derivatives and also alkoxy Il ..~ ,.~
1 substitutcd derivatives. Other aromatic hydrocarbon diisocyanates 2 as well as alipllatic isocyanates may be used.
8 Suitable active-hydrogen containing polymeric materials used 4 in prcparing the prepolymer include castor oil, a glycol or a 6 polyglycol monoester of a hydroxy carboxylic acid of at least 6 12 carbon atoms, polyalkylene ether glycols, and mixtures of any q of the foregoing.
8 The glycol and polyglycol monoesters of hydro~y carboxylic ~ acids of at least 12 carbon atoms are prepared by reacting a hydroxy carboxylic acid of at least 12 carbon atoms with dihydric 11 lower aliphatic alcohols or ether alcohols, such as ethylene 12 glycol, propylene glycol, hexylene glycol, diethylene glycol, 13 dipropylene glycol, hexamethylene g]ycol, and polyethylene and 14 polypropylene glycols, according to procedures well-~no~n in the 16 ¦ prior art such as direct esterification. These hydroxy mono-16 ¦ carboxylic acids may be saturated or unsaturated. Illustrative lq ¦ of this class of hydroxy acids are the following: ricinoleic 18 ¦ acid, 12-hydroxy stearic acid, hydroxy palmitic acid, hydroxy 19 ¦ pentadecanoic acid, hydroxy myristic acid, hydroxy cerotic acid, 20 I etc.
21 ¦ The preferred esters used in the preparation of these pre-22 ¦ polymers are propylene glycol monoricinoleate, ethylene glycol 23 ¦ monoricinoleate, and propylene glycol 12-hydroxy stearate. Also a4 ¦ other esters are useful in the preparation of the prepolymers in-25 ¦ cluding diethylene glycol monoricinoleate, polyethylene glycol 26 ¦ monoricinoleate, dipropylene glycol monoricinoleate, polypropylene 27 ¦ glycol 12-hydroxy stearate, propylene glycol hydroxy palmitate, 28 ¦ etc.
2g The esters of the hydroxy carboxylic acids of at least 12 carbon atoms may be used in a weight proportion with castor oil 31 I of about 80 to 40~ of the ester to al-out 20 to 6noO castor oil, 32 I the preferred proportion being about 61 to 6~. of the ester to 11 ` 11158~4 1 about 39 to 37% castor oil.
2 It has also been found that about 2 to 9 NCO equivalents of 8 the organic diisocyanate per equivalent of hydroxy group in the 4 mixture of castor oil and the ester provide a use~ul range of prepolymer compositions.
6 The castor oil that may be used to prepare the prepolymers q can be represented by any commercial grade of castor oil. The 8 preferred grade of castor oil is a low acid low volatile grade 9 available commercially as a DB castor oil obtained from NL
1~ Industries Inc.
1~ The polyalkylene ether polyols used to prepare the prepolymer 12 are polyoxypropylene derivatives of propylene glycol trimethylol-13 propane glycerine or pentaerythritol. The prèferred polyoxy-14 propylene polyols used in the preparation of the prepolymers are the 200 to 800 molecular weight derivatives of propylene glycol 16 and the 700 to 3000 molecular weight derivatives of trimethylol-17 propane. The preparation of these polyalkylene ether glycols and 18 their reaction with organic diisocyanates to produce prepolymer 19 compositions can be carried out according to United States Patents 2 702 797 and 2 692 873.
21 The preferred prepolymers for example can ~e prepared by æ combining DB castor oil polyoxypropylene glycol and an arylene 23 diisocyanate. The mixture should be heated for four hours at 24 70C. However other temperatures from about 20C. to 100C.
may be satisfactorily employed.
26 The polyesters reacted ~.ith the or~anic diisoc~Tanate can be 27 prepared by the reaction of two bifunctional reactants one bein~
28 a dibasic carboxylic acid and the other a glycol. The polyester 29 amides can be prepared by the reaction of a dibasic carboxylic ~0 acid with diamines or amino alcohols. The polyesters preferably 31 have a hydroxy numl)er from ahout 4~ to ahout lO0 and an acid 32 nu-nler ~rom () to 7.
Il "~ 15894 ~`~
l Illustrative of the dibasic carboxylic acids, preferably 2 those whose carboxyl &roups are attached to terminal carbons 8 that may be used in the preparation of the polyesters and poly-4 ester amides, include succinic, glutaric, adipic, pimelic, maleic, malonic, fumaric, terephthalic, citric, etc. Among the glycols 6 which may be used in the formation of the polyesters are ethylene q glycol, propylene glycol, 1,3-tolylene glycol, triethylene glycol, 8 butylene glycol, hexamethylene glycol, decamethylene glycol, and 9 glycerine monoethers. Among the diamines which are useful in the formation of the polyester amides are those which contain at 11 least one primary amino group, including as representative ex-12 amples, ethylene diamine, propylene diamine, tetramethylene ~ diamine, m-phenylene diamine and 3,3'-diaminodipropyl ether.
14 Primary amino alcohols useful in the formation of polyamides in-clude 3-aminopropanol, 6-aminohexanol, 4-aminobutanol, etc.
16 B. Cross-Linking Agent 17 According to this invention, it has been found that esters 18 of polyilydric alcohols containing t~o or three hydroxy groups 19 and an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule, are useful in 21 curing prepolymer compositions, wherein the resulting product has æ physical and electrical properties superior to the prepolymer 23 compositions cured with conventional curing agents. The hydroxy 24 and/or epoxy aliphatic acids of at least i2 carhon atoms that form an ester, when reacted with polyhydric alcohols of tl~o or 26 three hydroxy groups, may be saturated or unsaturated. Illustra-27 tive of this class of h~droxy acids are the follo-~in&: ricinoleic 28 acid, 12-hydroxy stearic acid, hydroxy palmitic acid, hyclroxy 29 pentadecanoic acid, hydroxy myristic acid, and hydroxy cerotic acid, as well as epoxy derivatives of these acids. The length of 31 the carbon chain of the hydro~y ancl/or epoxy alipllatic acicls is a2 ¦ only limited to the extent tllat commerciall~ there are arailahle ¦ -G-Il t ~ ~
1 aliphatic acids having about 22 carbon atoms. Ilo\~evcr, hydroxy 2 aliphatic acids having more than 22 carbon atoms are also con-8 templated. -4 Among the polyhydric alcohols, containing two or three 6 hydroxy groups, that may be reacted with hydroxy and/or epoxy B aliphatic acids to form an ester, are the following: ethylene q glycol, propylene glycol, glycerol, diethylene glycol, dipropylene 8 glycol, trimethylolpropane (TMP), trimethylolethane (T~E) and 9 the like.
The esters which are useful as curing agents for the pre-11 polymers are prepared according to known procedures such as lP direct esterification resulting from reaction of a hydroxy and/or 1~ epxoy aliphatic acid with a polyhydric alcohol containing two or 4 three hydroxy groups. Other well-known processes for producing 16 esters can also be employed. The preferred curing agents for 16 the prepolymers are ethylene glycol monoricinoleate, trimethylol-17 propane monoricinoleate and trimethylolethane monoricinoleate as 18 well as the di and tri esters, and mixtures of these esters.
Other esters which can be used include propylene glycol mono-ricinoleate, dipropylene glycol monoricinoleate, glycerol mono-21 ricinoleate and the like, as well as any other esters l~hich 22 would result from the reaction of the above enumerated polyhydric æ. alcohols and aliphatic acids.
24 It ~as also discovered that oxidatively polymerized castor oil, i.e., "blown" castor oil, can be used as part of the cura-26 tive mixture for purposes of improving flexibility even greater 27 than other~ise obtained without the polymerized or "blown" castor `2g oil.
29 The cured polyurethane products of this invention are particularly useful for potting and encapsulating electronic 31 components sucll as, for example, for potting underscas sonar 82 cguipment. Thc products arc also uscful in coating systems and, ll f ~ 1~15894 ~
1 ¦ particularly, for potting hollow fibcrs of 1uicl scparatory de-2 ¦ viccs employed for ultra-filtration, reverse osmosis and hemo-8 ¦ dialysis, etc. For instance, hollow fiber separatory dcvices are 4 ¦ e~ployed for dialysis, ultra-filtration, reverse osmosis, hemo-¦ dialysis, hemoultrafiltration, blood oxygenation. In general, 6 ¦ the separatory device consists of a plurality of fine hollow q ¦ fibers whose end portions are potted in a tube-sheet and whose 8 ¦ open fiber ends terminate in a tube-sheet face which provides 9 ¦ liquid access to the interior of the fibers. The separatory 10 ¦ elements are sealed within a casing to form a separatory cell 11 ¦ having one or more liquid ports which allow for the passage of 12 ¦ one fluid through the fibers and another around the fibers with-13 ! out mixing of the two fluids. The separatory element may have 14 ¦ two tube-sheets or a single tube-sheet, in which latter case 16 ¦ the fibers are doubled back so that all the ends terminate to-16 ~ gether. The general configuration of the separatory element and 17 ¦ separatory cell is similar to a tube-and-shell heat exchanger.
18 ¦ Patents representative of the art of hollow fiber separatory 19 ¦ devices include U.S. Patent Nos. 2,972,349; 3,228,876; 3,228,877;
ao ¦ 3,422,008; 3,423,491; 3,339,341; 3,503,515 and the like.
21 ¦ The tube-sheet material should fill the space between the 22 ¦ hollow fibers and yet not deform them. ~loreover, the cut edge 23 ¦ f the hollow fibers must remain substantially circular after a4 ¦ cutting. ~urther, it must be easy to handle and must fabricate 25 ¦ into a strong unit. And, of course, it must be nontoxic when 26 ¦ used in biomedical applications. The cured polyurethane product 27 ¦ of the present invention is especially useful as a tube-sheet æ ¦ material.
29 ¦ ~lany of the separatory devices described above must be ~0 ¦ flushed ~Yith ethanol prior to use. As a result, the tube-sheet 31 matcrial must have good alcohol resistance but must not be so æ hard or stiff as to be difficult to cut. It has hcen une~lcctedly ~ , .. .. ~
ll ~115B94 ' ~ ~
1 found that the csters of polyhydric alcohols containing two or2 three hydroxy groups and an aliphatic acid of at least 12 carbon 8 atoms and one or more hydroxy and/or epoxy groups per molecule 4 when used to curc the prepolymers of the instant in~cntion have 8 a unique combination of superior flexibility and excellent B ethanol resistance.
q The principle and practice of the invention will now be 8 illustrated by the following Examples which are only exemplary 9 thereof and it is not intended that the invention be limited ~0 thereto since modifications in technique and operation will be 11 apparent to anyone skilled in the art. All parts and percentages la expressed in the follo~ing Examples are by weight unless other-U wise indicated.
14 The polymcrs and shaped structures thereof prepared in the following Examples l~ere evaluated in accordance with the follow-16 ing procedures:
17 HARD.N'ESS
18 Th:e Shore D durometer readings were determined in accordance 19 with AST~I D 2240. The evaluated samples were cured for 16-20 hours at room temperature, plus 2 hours at 75C., plus 5-7 days 21 at room temperature.
a3 The ethanol resistance of the cured polymer samples ~as 24 determined in accordance with AST~I D 543. The evaluated samples were cured 16-20 hours at room temperature, plus 8 hours at 75C.
2B and cooled to room temperature.
27 PREPOLY~IER PRFPARATION
28 A. A mixture of 204 grams of a 40~ molecular weight poly-29 oxypropylene glycol, 205 grams of castor oil, and 795 grams of 4,4'diphenylene methane diisocyanate (~IDI) ~ere charged to the ~1 reactor under a nitrogen blanket and witll agitation. The tempera-32 ture was slo-.]y raisc(1 to 75C. and maint~ine(l at 70-80C. for 1115894 ~ ~
1 7 hours, cooling t~l~en necessary. The resulting prepolymer had 2 an NCO content of about 16.2% and a viscosity of about 6000 cps.
8 B. Following the procedure of paragraph A above, a pre-4 polymer was preparecl based u~on:
~ 1560 molecular weight polyoxypropylene triol derived from tri-8 methylolproyane....... 519 grams q Polyoxypropylene glycol (400 molecular weight).......... 343 grams 8 4,4'diphenylene methane diisocyanate.................... 1331 grams 9 This prepolymer had an NCO content of about 15~ and a viscosity of about 32,000 cps.
11 The prepolymer compositions are cured by adding a curing 12 agent comprising an ester of a polyhydric alcohol having 2 or 1~ 3 hydroxyl groups and an aliphatic acid of at least 12 carbon 14 atoms and one or more hydroxy and/or epoxy groups or blends of 16 such esters to obtain an elastomeric product. The curing process 16 may be carried out at room temperature or at elevated temperature.
lq The following is an outline of the procedure that can be 18 used to prepare room temperature cure and heat cured urethane 19 elastomers:
Procedure for Room Tem~erature Cure 21 The curing agent and prepolymer are mixed in the correct 22 proportions until completely homogeneous. The mixture is then 23 degassed from 3 to 5 minutes at 5mm mercury pressure. The de-24 gassed mixture is then poured into molds ancl allowed to cure at room temperature.
26 Procedure for ~leat Cure 27 The prepolymer and curing agent are separately degassed for 28 about 30 minutes at 5mm mercury pressure or at least until all 29 the foam, which initially appears, collapses. The prepolymer and curing agent may be heated to facilitate degassing. The pre-
BACKGROUND OF INVENTION
Polyurethane compositions obtained by reacting a suitable 12 prepolymer of an organic diisocyanate and a curing agent such as a polyalkylene glycol are generally well-known. Ordinarily, the 14 organic diisocyanate is reacted with a suitable polyfunctional 1~ compound that contains active hydrogen groups to provide a pre-16 polymer composition. The prepolymer is thereafter reacted with 17 a suitable curing or cross-linking agent to provide the poly-18 urethan:e composition. For instance, U.S. Patent No. 3,362,921 1~ discloses an elastomeric polyurethane derived from a prepolymer obtained by reacting castor oil and an organic diisocyanate such 21 as toluene diisocyanate. The resulting prepolymer is cross-22 linked by reaction with a suitable ester of a polyhydric alcohol 28 which contains at least four hydroxy groups, e.g., pentaerythritol 24 monorlcinoleate. U.S. Patent No. 3,362,921 discloses that it is essential to utilize a cross-linking or curing agent derived from 26 esters of polyhydric alcohols that contain at least four hydroxy 27 groups in order to obtain a cured polyurethane having desirable 28 elastomeric properties for potting applications.
THE INVENTION
According to the present invention, there is provided a 31 polyurethane composition obtained by reacting a diisocyanate pre-82 polymer ~-rith an ester of a polyhydric alcohol ~hich contains t~o 1~5894 or three hydroxy groups and an aliphatic acid of at least 12 carbon atoms and one or more epoxy and/or hydroxy groups per molecule.
Thus, one feature of the invention is a hollow fiber separatory device comprising a hollow fiber bundle consisting of a plurality of fine hollow fibers whose end portions are potted in a tube-sheet and whose open fiber ends terminate in a tube-sheet face, the resulting bundle being sealed within a casing to form a separatory cell having one or more fluid ports which allow for the passage of one fluid through the fibers and another around the fibers without mixing of the two fluids, said tube-sheet comprising a cured polyurethane composition consisting essentially of:
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol wih at least one mole per polyol hydroxy group of an organic diisocyanate, and B. A cross-linking agent comprising the ester of i. a polyhydric alcohol containing two or three hydroxy groups, and ii. an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule and blends of said ester and blown castor oil.
Another feature is a cured polyurethane comprising the reaction product of: (1~ the product of the reaction of (a) a polyester prepared from bifunctional ingredients including at least one dibasic carboxylic acid and at least one bifunction-al reactant in which the functional groups are hydroxy groups, said polyester having a hydroxyl number from 40-100 and an acid number from 0-7, and (b) an arylene diisocyanate, and (2) a curing agent consisting essentially of an ester of a poly-hydrix alcohol of two or three hydroxy groups and a hydroxy A
1~15894 and/or epoxy aliphatic acid of at least 12 carbon atoms.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A. Prepolymer Suitable prepolymer compositions used in the present invention are prepared by reacting an active-hydrogen contain-ing polymeric material within particular molecular weight and acid number ranges with a controlled amount of a diisocyanate, with the diisocyanate being present in greater than stoichio-metric amounts. Examples of active-hydrogen containing polymeric materials which may be used are polyesters, castor oil, polyester amides and polyalkylene ether glycols. Pre-polymer compositions prepared by reacting a diisocyanate with active-hydrogen containing materials are more fully disclosed in United States Patent Nos. 2,625,531; 2,625,532; 2,625,535;
2,692,873 and 2,702,797.
The organic diisocyanates used in the preparation of the prepolymer compositions are those which are known in the art to be useful in the preparation of such compositions by reac-tion with active-hydrogen containing materials. Arylene diisocyanates as represented by the diisocyanates of the benzene and naphthalene series or mixtures of these compounds are preferred. Illustrative of arylene diisocyanates that may be employed are the following: tolylene diisocyanate (2,4/2,6), toluene 2,4 diisocyanate, toluene 2,6 diisocyanate, m-phenylene diisocyanate, xenylene 4,4'-diisocyanate, naph-thalene 1,5'-diisocyanate, 3,3'-bitolylene 4,4'-diisocyanate, diphenylene methane 4,4'-diisocyanate, 4-chlorophenylene 2,4-diisocyanate, dianisidine diisocyanate, diphenylene ether 4,4'-diisocyanate, and polymeric isocyanates such as poly-methylene polyphenylene isocyanate. Other arylene diiso-cyanates which are useful include lower alkyl substitutedderivates, halogen substit~ted derivatives and also alkoxy Il ..~ ,.~
1 substitutcd derivatives. Other aromatic hydrocarbon diisocyanates 2 as well as alipllatic isocyanates may be used.
8 Suitable active-hydrogen containing polymeric materials used 4 in prcparing the prepolymer include castor oil, a glycol or a 6 polyglycol monoester of a hydroxy carboxylic acid of at least 6 12 carbon atoms, polyalkylene ether glycols, and mixtures of any q of the foregoing.
8 The glycol and polyglycol monoesters of hydro~y carboxylic ~ acids of at least 12 carbon atoms are prepared by reacting a hydroxy carboxylic acid of at least 12 carbon atoms with dihydric 11 lower aliphatic alcohols or ether alcohols, such as ethylene 12 glycol, propylene glycol, hexylene glycol, diethylene glycol, 13 dipropylene glycol, hexamethylene g]ycol, and polyethylene and 14 polypropylene glycols, according to procedures well-~no~n in the 16 ¦ prior art such as direct esterification. These hydroxy mono-16 ¦ carboxylic acids may be saturated or unsaturated. Illustrative lq ¦ of this class of hydroxy acids are the following: ricinoleic 18 ¦ acid, 12-hydroxy stearic acid, hydroxy palmitic acid, hydroxy 19 ¦ pentadecanoic acid, hydroxy myristic acid, hydroxy cerotic acid, 20 I etc.
21 ¦ The preferred esters used in the preparation of these pre-22 ¦ polymers are propylene glycol monoricinoleate, ethylene glycol 23 ¦ monoricinoleate, and propylene glycol 12-hydroxy stearate. Also a4 ¦ other esters are useful in the preparation of the prepolymers in-25 ¦ cluding diethylene glycol monoricinoleate, polyethylene glycol 26 ¦ monoricinoleate, dipropylene glycol monoricinoleate, polypropylene 27 ¦ glycol 12-hydroxy stearate, propylene glycol hydroxy palmitate, 28 ¦ etc.
2g The esters of the hydroxy carboxylic acids of at least 12 carbon atoms may be used in a weight proportion with castor oil 31 I of about 80 to 40~ of the ester to al-out 20 to 6noO castor oil, 32 I the preferred proportion being about 61 to 6~. of the ester to 11 ` 11158~4 1 about 39 to 37% castor oil.
2 It has also been found that about 2 to 9 NCO equivalents of 8 the organic diisocyanate per equivalent of hydroxy group in the 4 mixture of castor oil and the ester provide a use~ul range of prepolymer compositions.
6 The castor oil that may be used to prepare the prepolymers q can be represented by any commercial grade of castor oil. The 8 preferred grade of castor oil is a low acid low volatile grade 9 available commercially as a DB castor oil obtained from NL
1~ Industries Inc.
1~ The polyalkylene ether polyols used to prepare the prepolymer 12 are polyoxypropylene derivatives of propylene glycol trimethylol-13 propane glycerine or pentaerythritol. The prèferred polyoxy-14 propylene polyols used in the preparation of the prepolymers are the 200 to 800 molecular weight derivatives of propylene glycol 16 and the 700 to 3000 molecular weight derivatives of trimethylol-17 propane. The preparation of these polyalkylene ether glycols and 18 their reaction with organic diisocyanates to produce prepolymer 19 compositions can be carried out according to United States Patents 2 702 797 and 2 692 873.
21 The preferred prepolymers for example can ~e prepared by æ combining DB castor oil polyoxypropylene glycol and an arylene 23 diisocyanate. The mixture should be heated for four hours at 24 70C. However other temperatures from about 20C. to 100C.
may be satisfactorily employed.
26 The polyesters reacted ~.ith the or~anic diisoc~Tanate can be 27 prepared by the reaction of two bifunctional reactants one bein~
28 a dibasic carboxylic acid and the other a glycol. The polyester 29 amides can be prepared by the reaction of a dibasic carboxylic ~0 acid with diamines or amino alcohols. The polyesters preferably 31 have a hydroxy numl)er from ahout 4~ to ahout lO0 and an acid 32 nu-nler ~rom () to 7.
Il "~ 15894 ~`~
l Illustrative of the dibasic carboxylic acids, preferably 2 those whose carboxyl &roups are attached to terminal carbons 8 that may be used in the preparation of the polyesters and poly-4 ester amides, include succinic, glutaric, adipic, pimelic, maleic, malonic, fumaric, terephthalic, citric, etc. Among the glycols 6 which may be used in the formation of the polyesters are ethylene q glycol, propylene glycol, 1,3-tolylene glycol, triethylene glycol, 8 butylene glycol, hexamethylene glycol, decamethylene glycol, and 9 glycerine monoethers. Among the diamines which are useful in the formation of the polyester amides are those which contain at 11 least one primary amino group, including as representative ex-12 amples, ethylene diamine, propylene diamine, tetramethylene ~ diamine, m-phenylene diamine and 3,3'-diaminodipropyl ether.
14 Primary amino alcohols useful in the formation of polyamides in-clude 3-aminopropanol, 6-aminohexanol, 4-aminobutanol, etc.
16 B. Cross-Linking Agent 17 According to this invention, it has been found that esters 18 of polyilydric alcohols containing t~o or three hydroxy groups 19 and an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule, are useful in 21 curing prepolymer compositions, wherein the resulting product has æ physical and electrical properties superior to the prepolymer 23 compositions cured with conventional curing agents. The hydroxy 24 and/or epoxy aliphatic acids of at least i2 carhon atoms that form an ester, when reacted with polyhydric alcohols of tl~o or 26 three hydroxy groups, may be saturated or unsaturated. Illustra-27 tive of this class of h~droxy acids are the follo-~in&: ricinoleic 28 acid, 12-hydroxy stearic acid, hydroxy palmitic acid, hyclroxy 29 pentadecanoic acid, hydroxy myristic acid, and hydroxy cerotic acid, as well as epoxy derivatives of these acids. The length of 31 the carbon chain of the hydro~y ancl/or epoxy alipllatic acicls is a2 ¦ only limited to the extent tllat commerciall~ there are arailahle ¦ -G-Il t ~ ~
1 aliphatic acids having about 22 carbon atoms. Ilo\~evcr, hydroxy 2 aliphatic acids having more than 22 carbon atoms are also con-8 templated. -4 Among the polyhydric alcohols, containing two or three 6 hydroxy groups, that may be reacted with hydroxy and/or epoxy B aliphatic acids to form an ester, are the following: ethylene q glycol, propylene glycol, glycerol, diethylene glycol, dipropylene 8 glycol, trimethylolpropane (TMP), trimethylolethane (T~E) and 9 the like.
The esters which are useful as curing agents for the pre-11 polymers are prepared according to known procedures such as lP direct esterification resulting from reaction of a hydroxy and/or 1~ epxoy aliphatic acid with a polyhydric alcohol containing two or 4 three hydroxy groups. Other well-known processes for producing 16 esters can also be employed. The preferred curing agents for 16 the prepolymers are ethylene glycol monoricinoleate, trimethylol-17 propane monoricinoleate and trimethylolethane monoricinoleate as 18 well as the di and tri esters, and mixtures of these esters.
Other esters which can be used include propylene glycol mono-ricinoleate, dipropylene glycol monoricinoleate, glycerol mono-21 ricinoleate and the like, as well as any other esters l~hich 22 would result from the reaction of the above enumerated polyhydric æ. alcohols and aliphatic acids.
24 It ~as also discovered that oxidatively polymerized castor oil, i.e., "blown" castor oil, can be used as part of the cura-26 tive mixture for purposes of improving flexibility even greater 27 than other~ise obtained without the polymerized or "blown" castor `2g oil.
29 The cured polyurethane products of this invention are particularly useful for potting and encapsulating electronic 31 components sucll as, for example, for potting underscas sonar 82 cguipment. Thc products arc also uscful in coating systems and, ll f ~ 1~15894 ~
1 ¦ particularly, for potting hollow fibcrs of 1uicl scparatory de-2 ¦ viccs employed for ultra-filtration, reverse osmosis and hemo-8 ¦ dialysis, etc. For instance, hollow fiber separatory dcvices are 4 ¦ e~ployed for dialysis, ultra-filtration, reverse osmosis, hemo-¦ dialysis, hemoultrafiltration, blood oxygenation. In general, 6 ¦ the separatory device consists of a plurality of fine hollow q ¦ fibers whose end portions are potted in a tube-sheet and whose 8 ¦ open fiber ends terminate in a tube-sheet face which provides 9 ¦ liquid access to the interior of the fibers. The separatory 10 ¦ elements are sealed within a casing to form a separatory cell 11 ¦ having one or more liquid ports which allow for the passage of 12 ¦ one fluid through the fibers and another around the fibers with-13 ! out mixing of the two fluids. The separatory element may have 14 ¦ two tube-sheets or a single tube-sheet, in which latter case 16 ¦ the fibers are doubled back so that all the ends terminate to-16 ~ gether. The general configuration of the separatory element and 17 ¦ separatory cell is similar to a tube-and-shell heat exchanger.
18 ¦ Patents representative of the art of hollow fiber separatory 19 ¦ devices include U.S. Patent Nos. 2,972,349; 3,228,876; 3,228,877;
ao ¦ 3,422,008; 3,423,491; 3,339,341; 3,503,515 and the like.
21 ¦ The tube-sheet material should fill the space between the 22 ¦ hollow fibers and yet not deform them. ~loreover, the cut edge 23 ¦ f the hollow fibers must remain substantially circular after a4 ¦ cutting. ~urther, it must be easy to handle and must fabricate 25 ¦ into a strong unit. And, of course, it must be nontoxic when 26 ¦ used in biomedical applications. The cured polyurethane product 27 ¦ of the present invention is especially useful as a tube-sheet æ ¦ material.
29 ¦ ~lany of the separatory devices described above must be ~0 ¦ flushed ~Yith ethanol prior to use. As a result, the tube-sheet 31 matcrial must have good alcohol resistance but must not be so æ hard or stiff as to be difficult to cut. It has hcen une~lcctedly ~ , .. .. ~
ll ~115B94 ' ~ ~
1 found that the csters of polyhydric alcohols containing two or2 three hydroxy groups and an aliphatic acid of at least 12 carbon 8 atoms and one or more hydroxy and/or epoxy groups per molecule 4 when used to curc the prepolymers of the instant in~cntion have 8 a unique combination of superior flexibility and excellent B ethanol resistance.
q The principle and practice of the invention will now be 8 illustrated by the following Examples which are only exemplary 9 thereof and it is not intended that the invention be limited ~0 thereto since modifications in technique and operation will be 11 apparent to anyone skilled in the art. All parts and percentages la expressed in the follo~ing Examples are by weight unless other-U wise indicated.
14 The polymcrs and shaped structures thereof prepared in the following Examples l~ere evaluated in accordance with the follow-16 ing procedures:
17 HARD.N'ESS
18 Th:e Shore D durometer readings were determined in accordance 19 with AST~I D 2240. The evaluated samples were cured for 16-20 hours at room temperature, plus 2 hours at 75C., plus 5-7 days 21 at room temperature.
a3 The ethanol resistance of the cured polymer samples ~as 24 determined in accordance with AST~I D 543. The evaluated samples were cured 16-20 hours at room temperature, plus 8 hours at 75C.
2B and cooled to room temperature.
27 PREPOLY~IER PRFPARATION
28 A. A mixture of 204 grams of a 40~ molecular weight poly-29 oxypropylene glycol, 205 grams of castor oil, and 795 grams of 4,4'diphenylene methane diisocyanate (~IDI) ~ere charged to the ~1 reactor under a nitrogen blanket and witll agitation. The tempera-32 ture was slo-.]y raisc(1 to 75C. and maint~ine(l at 70-80C. for 1115894 ~ ~
1 7 hours, cooling t~l~en necessary. The resulting prepolymer had 2 an NCO content of about 16.2% and a viscosity of about 6000 cps.
8 B. Following the procedure of paragraph A above, a pre-4 polymer was preparecl based u~on:
~ 1560 molecular weight polyoxypropylene triol derived from tri-8 methylolproyane....... 519 grams q Polyoxypropylene glycol (400 molecular weight).......... 343 grams 8 4,4'diphenylene methane diisocyanate.................... 1331 grams 9 This prepolymer had an NCO content of about 15~ and a viscosity of about 32,000 cps.
11 The prepolymer compositions are cured by adding a curing 12 agent comprising an ester of a polyhydric alcohol having 2 or 1~ 3 hydroxyl groups and an aliphatic acid of at least 12 carbon 14 atoms and one or more hydroxy and/or epoxy groups or blends of 16 such esters to obtain an elastomeric product. The curing process 16 may be carried out at room temperature or at elevated temperature.
lq The following is an outline of the procedure that can be 18 used to prepare room temperature cure and heat cured urethane 19 elastomers:
Procedure for Room Tem~erature Cure 21 The curing agent and prepolymer are mixed in the correct 22 proportions until completely homogeneous. The mixture is then 23 degassed from 3 to 5 minutes at 5mm mercury pressure. The de-24 gassed mixture is then poured into molds ancl allowed to cure at room temperature.
26 Procedure for ~leat Cure 27 The prepolymer and curing agent are separately degassed for 28 about 30 minutes at 5mm mercury pressure or at least until all 29 the foam, which initially appears, collapses. The prepolymer and curing agent may be heated to facilitate degassing. The pre-
3~ polymer ancl curing agent are then thorollghly mixed, in the proper 32 portion, ancl then re-evacuatecl at 60C. for a~out 5 minutes at 11 lllS894 1 ¦ 5mm mercury pressure to remove air intro~uced during mixing. The 2 ¦ degassed mixture is then poured into molds and cured for 4 hours 8 ¦ at 100C.
4 ¦ In examples 1-16 below, the heat curing proccdure ~as used ¦ to illustrate the cured urethane elastomers of the present in-6 ¦ vention. The amounts of the agents in Examples 1-16 are ex-7 ¦ pressed in parts by weight.
8 ¦ EXA~IPLE 1 9 ¦ Prepolymer A 272 0 ¦ Trimethylolpropane monoricinoleate 220 11 ¦ NCO/OH ratio 1.1 12 ¦ EXA~IPLE 2 13 ¦ Prepolymer A 272 14 ¦ Trimethylolpropane triricinoleate 391 16 ¦ NCO/OI~ ratio 1.1 16 I EXA~IPLE 3 17 ¦ Prepolymer A 272 18 ¦ Trimethylolpropane monoricinoleate 154 1~ ¦ Trimethylolpropane triricinoleate 117 20 ¦ NCO/OH ratio 1.1 21 I EXA~IPLE 4 22 ¦ Prepolymer A 272 23 ¦ Trimethylolpropane monoricinoleate 132 24 ¦ Trimethylolpropane triricinoleate 156 25 ¦ NCO/OH ratio 1.1 26 ¦ EXA~IPLE 5 27 ¦ Prepolymer A 272 28 ¦ Trimethylolethane monoricinoleate 221 80 ¦~ N O/OII ra~i~ I.I
82 ~ ' I
~15894 1 EXA~IPLE 6 2 Prepolymer A 272 8 Propylene glycol monoricinoleate 193 4 NCO/OH ratio 1.1 ~ EXA~IPLE 7 6 Prepolymer A 272 q Ethylene glycol monoricinoleate 215 8 NCO/OH ratio 1.1 EXA~IPLE 8 Prepolymer A 272 11 Glycerol monoricinoleate 162 12 NCO/OH ratio 1.1 13 EXA~IPL~ 9 (Control E,xamplc) 14 Prepolymer A 272 16 Castor Oil 342 16 NCO/OH ratio 1.1 lq EXA~IPLE 10 (Control Example) 18 Prepolymer A - 272 19 Pentaerythritol monoricinoleate 169 20 NCO/OII ratio 1.1 21 EXA~IPLE 11 22 Prepolymer B 302 23 Propylene glycol monoricinoleate 193 2~ NCO/OH ratio 1.1 25 EXA~IPLE 12 26 Prepolymer B 302 27 Ethylene glycol monoricinoleate 215 2B NCO/OH ratio 1.1 29 EX~IPLE 13 (Control Example) 80 Prepolymer B 302 31 Pentaerythritol monoricinoleate 169 82 NICO/OII ratio 1.1 ~ EX,~I~I}'LE 14 (Colltlol Ixample) 2 rrepolymer B 302 8 Castor oil 342 4 NC0/O~ ratio 1.1 EXA~IPLE 15 6 Prepolymer A 272 q Ethylene glycol monoricinoleate 151 8 Blown castor oil 105 9 NCO/OII ratio 1.1 EXA~PLE 16 11 Prepolymer A 272 12 Ethylene glycol monoricinoleate 173 18 Blown castor oil 70 14 NCO/OII ratio 1.1 Examples 1-16 were cured at room temperature for 16-20 16 hours plus ~ hours at 75C., cooled to room temperature and then 17 microtomed. The microtomed sections were microscopically ex-18 amined for contact of the potting compound to the hollow fibers 19 and for retention of the fiber geometry. In all c'ases the contact to the hollow fibers was judged to be excellent and the 21 fiber ends maintained their geometry. The hardness and alcohol aæ resistance properties of the polymers of the above Examples are 23 ¦ listed in the Table below.
¦ As can be seen from the Table, althougll the polymers of 25 ¦ Control Examples 10 and 13 exhibit good alcohol resistance, 26- ¦ these polymers are too hard or inflexible. Also, the polymers 27 ¦ of Control Examples 9 and 14 exhibit good flexibility, but these 28 polymers have poor alcohol resistance. The Examples of the 2g invention exhibit tlle unique and unexpected combination of good flexibility and excellent alcohol resistance.
-~3-I f ~ 15894 1 ~n 2 ~Dl U~l o 6 ,. ~ ~ o q ~1 ~
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8 ¦ EXA~IPLE 1 9 ¦ Prepolymer A 272 0 ¦ Trimethylolpropane monoricinoleate 220 11 ¦ NCO/OH ratio 1.1 12 ¦ EXA~IPLE 2 13 ¦ Prepolymer A 272 14 ¦ Trimethylolpropane triricinoleate 391 16 ¦ NCO/OI~ ratio 1.1 16 I EXA~IPLE 3 17 ¦ Prepolymer A 272 18 ¦ Trimethylolpropane monoricinoleate 154 1~ ¦ Trimethylolpropane triricinoleate 117 20 ¦ NCO/OH ratio 1.1 21 I EXA~IPLE 4 22 ¦ Prepolymer A 272 23 ¦ Trimethylolpropane monoricinoleate 132 24 ¦ Trimethylolpropane triricinoleate 156 25 ¦ NCO/OH ratio 1.1 26 ¦ EXA~IPLE 5 27 ¦ Prepolymer A 272 28 ¦ Trimethylolethane monoricinoleate 221 80 ¦~ N O/OII ra~i~ I.I
82 ~ ' I
~15894 1 EXA~IPLE 6 2 Prepolymer A 272 8 Propylene glycol monoricinoleate 193 4 NCO/OH ratio 1.1 ~ EXA~IPLE 7 6 Prepolymer A 272 q Ethylene glycol monoricinoleate 215 8 NCO/OH ratio 1.1 EXA~IPLE 8 Prepolymer A 272 11 Glycerol monoricinoleate 162 12 NCO/OH ratio 1.1 13 EXA~IPL~ 9 (Control E,xamplc) 14 Prepolymer A 272 16 Castor Oil 342 16 NCO/OH ratio 1.1 lq EXA~IPLE 10 (Control Example) 18 Prepolymer A - 272 19 Pentaerythritol monoricinoleate 169 20 NCO/OII ratio 1.1 21 EXA~IPLE 11 22 Prepolymer B 302 23 Propylene glycol monoricinoleate 193 2~ NCO/OH ratio 1.1 25 EXA~IPLE 12 26 Prepolymer B 302 27 Ethylene glycol monoricinoleate 215 2B NCO/OH ratio 1.1 29 EX~IPLE 13 (Control Example) 80 Prepolymer B 302 31 Pentaerythritol monoricinoleate 169 82 NICO/OII ratio 1.1 ~ EX,~I~I}'LE 14 (Colltlol Ixample) 2 rrepolymer B 302 8 Castor oil 342 4 NC0/O~ ratio 1.1 EXA~IPLE 15 6 Prepolymer A 272 q Ethylene glycol monoricinoleate 151 8 Blown castor oil 105 9 NCO/OII ratio 1.1 EXA~PLE 16 11 Prepolymer A 272 12 Ethylene glycol monoricinoleate 173 18 Blown castor oil 70 14 NCO/OII ratio 1.1 Examples 1-16 were cured at room temperature for 16-20 16 hours plus ~ hours at 75C., cooled to room temperature and then 17 microtomed. The microtomed sections were microscopically ex-18 amined for contact of the potting compound to the hollow fibers 19 and for retention of the fiber geometry. In all c'ases the contact to the hollow fibers was judged to be excellent and the 21 fiber ends maintained their geometry. The hardness and alcohol aæ resistance properties of the polymers of the above Examples are 23 ¦ listed in the Table below.
¦ As can be seen from the Table, althougll the polymers of 25 ¦ Control Examples 10 and 13 exhibit good alcohol resistance, 26- ¦ these polymers are too hard or inflexible. Also, the polymers 27 ¦ of Control Examples 9 and 14 exhibit good flexibility, but these 28 polymers have poor alcohol resistance. The Examples of the 2g invention exhibit tlle unique and unexpected combination of good flexibility and excellent alcohol resistance.
-~3-I f ~ 15894 1 ~n 2 ~Dl U~l o 6 ,. ~ ~ o q ~1 ~
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28 ~1 ~3 o ~ _, . ~ E
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Claims (9)
1. A hollow fiber separatory device comprising a hollow fiber bundle consisting of a plurality of fine hollow fibers whose end portions arc potted in a tube-sheet and whose open fiber ends terminate in a tube-sheet face, the resulting bundle being sealed within a casing to form a separatory cell having one or more fluid ports which allow for the passage of one fluid through the fibers and another around the fibers without mixing of the two fluids, said tube-sheet comprising a cured polyurethane composition consisting essentially of:
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol with at least one mole per polyol hydroxy group of an organic diisocyanate, and B. A cross-linking agent comprising the ester of i. a polyhydric alcohol containing two or three hydroxy groups, and ii. an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule and blends of said ester and blown castor oil.
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol with at least one mole per polyol hydroxy group of an organic diisocyanate, and B. A cross-linking agent comprising the ester of i. a polyhydric alcohol containing two or three hydroxy groups, and ii. an aliphatic acid of at least 12 carbon atoms and one or more hydroxy and/or epoxy groups per molecule and blends of said ester and blown castor oil.
2. The device of Claim 1 wherein the organic diisocyanate of the prepolymer is diphenylene methane 4,4'-diisocyanate.
3. The device of Claim 1 wherein the polyurethane composi-tion consists essentially of:
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol with at least one mole per polyol hydroxy group of toluene 2,4-diiso-cyanate, toluene 2,6-diisocyanate or their mixtures, diphenylene methane 4,4'-diisocyanate, or m-phenylene diisocyanate, and B. A cross-linking agent comprising the mono-ester and/or diester of ethylene glycol and ricinoleic acid or a mono, di or tri ester of ricinoleic acid and trimethylol-propane or trimethylolethane or mixtures of the mono, di or tri esters.
A. A prepolymer which comprises the reaction product of castor oil and polyoxypropylene glycol with at least one mole per polyol hydroxy group of toluene 2,4-diiso-cyanate, toluene 2,6-diisocyanate or their mixtures, diphenylene methane 4,4'-diisocyanate, or m-phenylene diisocyanate, and B. A cross-linking agent comprising the mono-ester and/or diester of ethylene glycol and ricinoleic acid or a mono, di or tri ester of ricinoleic acid and trimethylol-propane or trimethylolethane or mixtures of the mono, di or tri esters.
4. A cured polyurethane comprising the reaction product of:
(1) the product of the reaction of (a) a polyester prepared from bifunctional ingredients including at least one dibasic carboxylic acid and at least one bifunctional reactant in which the function-al groups are hydroxy groups, said polyester having a hydroxyl number from 40-100 and an acid number from 0-7, and (b) an arylene diisocyanate, and (2) a curing agent consisting essentially of an ester of a polyhydric alcohol of two or three hydroxy groups and a hydroxy and/or epoxy aliphatic acid of at least 12 carbon atoms.
(1) the product of the reaction of (a) a polyester prepared from bifunctional ingredients including at least one dibasic carboxylic acid and at least one bifunctional reactant in which the function-al groups are hydroxy groups, said polyester having a hydroxyl number from 40-100 and an acid number from 0-7, and (b) an arylene diisocyanate, and (2) a curing agent consisting essentially of an ester of a polyhydric alcohol of two or three hydroxy groups and a hydroxy and/or epoxy aliphatic acid of at least 12 carbon atoms.
5. The cured polyurethane of Claim 4 wherein the curing agent is ethylene glycol monoricinoleate, trimethylolpropane or trimethylolethane esters of ricinoleic acid or mixtures thereof.
6. A cured polyurethane consisting essentially of the re-action product of (1) the product of the reaction of a poly-alkylene ether glycol having a molecular weight of at least about 200, a polyalkylene ether triol having a molecular weight of at least 1500 and an arylene diisocyanate wherein the arylene diiso-cyanate is used in an amount ranging from about 2 equivalents to 12 equivalents per equivalent of polyalkylene ether glycol and (2) a curing agent consisting essentially of an ester of a poly-hydric alcohol containing two or three hydroxy groups and a hydroxy and/or epoxy aliphatic acid of at least 12 carbon atoms.
7. The cured polyurethane of Claim 6 wherein the poly-alkylcne ether glycol is polyoxypropylene glycol.
8. Thc cured polyurethane of Claim 6 wherein the curing agent is ethylene glycol monoricinoleate, trimethylolpropane or trimethylolethane esters of ricinoleic acid or mixtures thereof.
9. A cured polyurethane consisting essentially of the re-action product of (1) the product of the reaction of castor oil, an alkyl glycol ester of a hydroxy carboxylic acid of at least 12 carbon atoms and an arylene diisocyanate which comprises re-acting from about 2 to about 3 NCO equivalents of the diisocyanate per equivalent of hydroxy group in the mixture of castor oil and ester, wherein the ester and castor oil are used in a weight pro-portion of about 80% to 40% of the ester to about 20% to 60%
castor oil, said reaction of castor oil, ester and diisocyanate being carried out at a temperature from about 20°C. to 100°C., and (2) a curing agent consisting essentially of an ester of a polyhydric alcohol containing two or three hydroxy groups and a hydroxy and/or epoxy aliphatic acid of at least 12 carbon atoms.
castor oil, said reaction of castor oil, ester and diisocyanate being carried out at a temperature from about 20°C. to 100°C., and (2) a curing agent consisting essentially of an ester of a polyhydric alcohol containing two or three hydroxy groups and a hydroxy and/or epoxy aliphatic acid of at least 12 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73938076A | 1976-11-05 | 1976-11-05 | |
| US739,380 | 1976-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115894A true CA1115894A (en) | 1982-01-05 |
Family
ID=24972021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA287,732A Expired CA1115894A (en) | 1976-11-05 | 1977-09-28 | Polyurethane composition and articles thereof |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5358599A (en) |
| AU (1) | AU516475B2 (en) |
| BE (1) | BE860451A (en) |
| CA (1) | CA1115894A (en) |
| DE (1) | DE2749491A1 (en) |
| ES (1) | ES463841A1 (en) |
| FR (2) | FR2378053A1 (en) |
| GB (1) | GB1557895A (en) |
| IT (1) | IT1115397B (en) |
| NL (1) | NL7712189A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1114714B (en) * | 1978-03-25 | 1986-01-27 | Akzo Nv | POLYURETHANE INCORPORATION MASS AND RELATED PRODUCTION PROCESS |
| US4256617A (en) * | 1979-11-01 | 1981-03-17 | Nl Industries, Inc. | Catalyzed non-toxic polyurethane forming compositions and separatory devices employing the same |
| DE3147025A1 (en) * | 1981-11-27 | 1983-06-01 | Akzo Gmbh, 5600 Wuppertal | EMBEDDING BASED ON QUICK REACTIVE POLYURETHANE CASTING RESIN |
| JPS60115616A (en) * | 1983-11-26 | 1985-06-22 | Toyobo Co Ltd | Production of thermoplastic polyurethane resin |
| DE3411361A1 (en) * | 1984-03-28 | 1985-10-10 | Akzo Gmbh, 5600 Wuppertal | EMBEDDING MATERIAL, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3912531C2 (en) * | 1989-04-17 | 1998-08-27 | Basf Ag | Crystal-clear, steam-sterilizable, compact polyurethane casting compounds, process for their production and their use, in particular for medical technical articles |
| DE3927244A1 (en) * | 1989-08-18 | 1991-02-21 | Basf Ag | TRANSPARENT, COMPRESSABLE, STEAM-STEAMABLE, COMPACT POLYURETHANE POWDERING, PROCESS FOR THEIR PRODUCTION AND THEIR USE, IN PARTICULAR FOR MEDICAL TECHNICAL ITEMS |
| DE4134693A1 (en) * | 1991-10-21 | 1993-04-22 | Basf Ag | TRANSPARENT, STEAM-STEAMABLE, NON-CYTOTOXIC, COMPRISINGLY COMPACT POLYURETHANE POWDERING, PROCESS FOR THEIR PRODUCTION AND THEIR USE, ESPECIALLY FOR MEDICAL-TECHNICAL ITEMS |
| WO2020004212A1 (en) * | 2018-06-26 | 2020-01-02 | Nok株式会社 | Method for producing porous hollow fiber membrane for humidification |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2772245A (en) * | 1952-04-26 | 1956-11-27 | Lockheed Aircraft Corp | Resilient cellular resin products |
| US3362921A (en) * | 1965-03-24 | 1968-01-09 | Baker Castor Oil Co | Novel elastomeric products obtained from prepolymer compositions |
| US3483150A (en) * | 1967-02-15 | 1969-12-09 | Arthur Ehrlich | Polyurethane prepolymers and elastomers |
| US3962094A (en) * | 1973-09-18 | 1976-06-08 | The Dow Chemical Company | Hollow fiber separatory device |
-
1977
- 1977-09-28 CA CA287,732A patent/CA1115894A/en not_active Expired
- 1977-09-28 IT IT2803377A patent/IT1115397B/en active
- 1977-09-30 AU AU29276/77A patent/AU516475B2/en not_active Expired
- 1977-10-26 FR FR7732334A patent/FR2378053A1/en active Granted
- 1977-11-02 JP JP13095777A patent/JPS5358599A/en active Pending
- 1977-11-03 BE BE182328A patent/BE860451A/en not_active IP Right Cessation
- 1977-11-04 ES ES463841A patent/ES463841A1/en not_active Expired
- 1977-11-04 NL NL7712189A patent/NL7712189A/en not_active Application Discontinuation
- 1977-11-04 DE DE19772749491 patent/DE2749491A1/en not_active Withdrawn
- 1977-11-04 GB GB4607077A patent/GB1557895A/en not_active Expired
-
1978
- 1978-03-30 FR FR7809269A patent/FR2377825A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BE860451A (en) | 1978-03-01 |
| IT1115397B (en) | 1986-02-03 |
| AU516475B2 (en) | 1981-06-04 |
| AU2927677A (en) | 1979-04-05 |
| JPS5358599A (en) | 1978-05-26 |
| DE2749491A1 (en) | 1978-05-18 |
| FR2378053B1 (en) | 1982-01-08 |
| FR2377825A1 (en) | 1978-08-18 |
| FR2377825B1 (en) | 1981-07-03 |
| ES463841A1 (en) | 1979-01-01 |
| FR2378053A1 (en) | 1978-08-18 |
| GB1557895A (en) | 1979-12-12 |
| NL7712189A (en) | 1978-05-09 |
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