CA1221791A - Castable polyurethane systems - Google Patents
Castable polyurethane systemsInfo
- Publication number
- CA1221791A CA1221791A CA000472955A CA472955A CA1221791A CA 1221791 A CA1221791 A CA 1221791A CA 000472955 A CA000472955 A CA 000472955A CA 472955 A CA472955 A CA 472955A CA 1221791 A CA1221791 A CA 1221791A
- Authority
- CA
- Canada
- Prior art keywords
- polyol
- amine
- prepolymer
- polyether
- polyisocyanate
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
Abstract
Abstract of the Disclosure Castable Polyurethane Systems A castable polyurethane system comprising the reaction product of (a) a polyisocyanate prepolymer prepared by reacting an excess of a polyisocyanate compound with an amine-based polyol and (b) a polyol, said polyurethane systems being clear, hard, easily cast, impact resistant, heat resistant and appropriate for a number of applicable uses.
Description
7~3~
3-14748/CGC 10~7J=
Cartable Polyurethane Systems The Chemistry of combining polyisocyanates and polyols to form prepolymers and the chemistry of curing the prepolymer with active hydrogen containing compounds are well known. The resulting polyp urethane systems have been used for a variety of applications such as casting resins coatings, encapsulant and for general polyp urethane elastomeric uses. Unfortunately preexisting systems have not exhibited optimum properties for certain of these uses, part-ocularly for casting purposes and the preparation of clear prototype products. These required properties include clarity, minimum color, heat resistance, minimum shrinkage, hardness, impact resistance and low viscosity to facilitate mixing and pouring of the system. It is to be noted that existing, easily cast urethanes ego. non-prepoly-men, two-component, plasticized systems have not exhibited the required clarity, absence of color and stability to be effectively utilized for clear casting purposes.
.
In an effort to monomial these difficulties, resort has been had to various acrylic (e.g. LUCITE from Dupont and epoxy systems.
Although acrylics provide the desired clarity, they generally are available only in sheet form and must be machined to various shapes, thereby making it rather difficult to fabricate to specific and more intricate shapes. Such acrylic products also exhibit high shrinkage.
Correspondingly, epoxy systems are brittle and lose their clarity with the passage of time.
I
It is therefore the primary object of this invention to prude clear, cartable polyurethane systems which are applicable for a broad range of utilities.
It is another object to provide such systems which eliminate or substantially reduce the disadvantages encountered with prior art systems.
Various other objects and advantages of this invention will be readily apparent from the following detailed description thereof.
It has now been surprisingly discovered that by combining specific polyisocyanate prepolymers and polyols, polyurethane systems are obtained which are well suited for a number of end use applications, particularly for casting and prototype fabrication operations.
Thus, the invention relates to substantially clear, cartable polyurethane systems comprising the reaction product of (a) a polyisocyanate prepolymer comprising the reaction product of an excess of an aliphatic or cycloaliphatic polyisocyanate compound and an amine-based polyol, and (b) at least an amine-based polyol, a polyether polyol or mixtures thereof (hardener).
These systems thus exhibit clarity, heat resistance, low shrinkage, high hardness, impact resistance and sufficiently high heat deflect lion temperatures. They exhibit relatively low mixed viscosities which facilitate their ease of mixing and pouring. The systems are also readily compatible with a variety of optional additives such, for example, as light stabilizers which allows for prolonged light stability without evidence of color formation and/or degradation.
The polyurethane systems of the present invention are prepared by reacting approximately stoichiometric amounts of a polyisocyanate prepolymer (a) with a polyol (b).
The polyisocyanate prepolymer (a) is in turn prepared by reacting an excess of a polyisocyanate compound with a amine-based polyol in a manner well known in the art. For purposes of this invention, the term "prepolymer" is intended to reflect the products of the latter reaction. The polyisocyanate prepolymer is then reacted with the polyol in the presence of optional additives to form the puller-than system.
The polyisocyanate compound which is used in the preparation of the polyisocyanats prepolymer is preferably a liquid aliphatic or cycloaliphatic polyisocyanate. Typical of such polyisocyanate compounds are 3-isocyanatomethyl 3,5,5-trimethylcyclohexyl issues-Nate (isophorone diisocyanate), I ethylene bis-(cyclohexyliso-Senate), hexamethylene diisocyanate, Burt of hexamethylene diisocyanate, 1,3-cyclohexane bis(methylisocyanate), trim-thylhexamethylene diisocyanate and combinations thereof, as well as related aliphatic and cycloaliphatic polylsocyanates which may be substituted with other organic or inorganic groups that do not adversely affect the course of the reaction. The 4,4'-methylene bis(cyclohe~ylisocyanate), hexamethylene diisocyanate and isophorone diisocyanate are preferred.
The term "aliphatic~', as used herein, includes those carbon chains which are substantially non-aromatic in nature. They may be sat-rated or unsaturated, unbranched, branched or cyclic in configu-ration and may contain various substituents. Such aliphatic issues-antes generally have an equivalent weight of from 60 to 160 and a viscosity of 1.0 to 1500.0 ma s at 25~. Exemplary of liquid long chain aliphatic polyisocyanates are dodecyl diisocyanate, tridecyl diisocyanate, and the like.
socyanate terminated prepolymers are available from PUN Plastics such as RP-6414~ based on DESMODUR To (Mob, a cycloaliphatic lsocyanate.
The amine-based polyols which are reacted with the polyisocyanate prepolymer generally have an equivalent weight of from 30 to 6'000 and a viscosity of from 1.0 to 20'000 ma s at 25~C-60C. A wide variety of aromatic and aliphatic dominoes may form part of the amine-based polyol3, such polyols including N,N-bis(2-hydroxypro-Pyle aniline, and, preferably, N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine and polymers of ethylene Damon, propylene oxide and ethylene oxide. A typical aromatic amine-based polyol is available from Upjohn under the designation ISONOL 100~, a typical aliphatic amine-based polyol is available from BASS under the designation QUADRILLE and a typical ethylene diaminelpropylene oxide/ethylene oxide polymer is available from BASS under the designation PLURACOL 355~.
Preferred concentration ranges for the respective components of the prepolymer are 85-95 % by weight of polyisocyanate and 5-15 % by weight polyol to form a resin prepolymer of 20-55 % by weight polymer dissolved in 45-80 % by weight excess polyisocyanate, and preferably 30 to 40 %, by weight, polymer in 60 to 70 %, by weight, excess polyisocyanate.
The polyol hardener system (b) consists at least of an amine-based polyol, a polyether polyol or blends of these polyol8. Suitable amine-based polyols have been mentioned above. N,N-bis(2-hydroxypro-pyl~anilins,N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediaminno and polymers of ethylene diaminelpropylene oxidelethylene oxide are preferred.
Suitable polyether polyols (b) include alkaline glycol polymers having an alkaline unit composed of at least two carbon atoms. These aliphatic alkaline glycol polymers are exemplified by polyoxypro-pylon glycol and polytetramethylene ether glycol. Do-, in- and I
tetrafunctional compounds are also suitable, the trifunctional compounds being exemplified by the reaction product of glycerol or trimethylol propane and propylene oxide. A typical polyether polyol is available prom Union Carbide under the designation PPG-425~. The trifunctional compounds are preferred. Suitable polyether polyols will generally have molecular weights of from 60-7'000 with the dills ranging from 60-200, the trios from 400-7'000 and the petrols from 400-600. The preferred polyol (b) is a blend of amine-based polyol and at least one polyether polyol, said polyether polyol being present in weight ratios ranging from 1:1 to 1:9 and pro-fireball 1:2 to 1:4.
As previously noted, the polyurethane systems of this invention are prepared by admixing the prepolymer with the polyol hardener.
Catalysts and optional additives may be included with the hardener system. Generally, stoichiomet~ic amounts of prepolymer (a and polyol (b) are utilized, with the possibility of deviating from the stoichiamet~ic amount by utilizing up to about 25 % excess propel-men (a) or up to about 2 % excess polyol (b). Solid, thermoses polyurethane elastomers are obtained within about 40 minutes at room temperature.
Preferably, the prepolymer (a) and the polyol (b) are present in equal amounts by weight.
Particularly preferred are polyurethane systems wherein the propel-men (a) is the reaction product of 4,4'-methylene bis(cyclohexyliso-Senate) and N,N,N',N'-tetra~is(2-hydroxypropyl) ethylenediamine, and the polyol (b) is a blend ox N,N~N',N'-tetrakis(2-hydroxypro-pyl)ethylenediamlne,`a polyether trio having a molecular weight of ~15 and a polyether troll having a molecular weight of 4'500.
Catalysts are known to those skilled in the art and may comprise, for example, heavy metals utilized in amounts ox about 0.1 % metal, by weight of hardener, e.g. organ tin, organ zinc, mercury and lead compounds. Tertiary amine may also be utilized.
Optional additives include anti-foaming agents such as glycerine, an ethyl acrylate-2-ethylhexyl assault copolyme}, dim ethyl selection copolymers and silicones; antioxidant such as esters of B-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with mandrake an polyhydric alcohols, for example, methanol, octadecanol, 1,6-hexane-dill, neopentylglycol, thiodiethyleneglycol, diethyleneglycol, triethyleneglycol, pentaerythritol~ tris-hydroxyethyl isocyanurate, and di-hydroxyethyl oxalic acid doomed; US absorbers and light stabilizers such as 2-(2'-hydroxyphenyl)benzotriazoles and stern-gaily hindered amine such as bis-(2,2,6,6-tetramethylpiperidyl)-subacute, Boyce 9 6,6-pentamethylpiperidyl)-sebacate, 2-n-butyl-
3-14748/CGC 10~7J=
Cartable Polyurethane Systems The Chemistry of combining polyisocyanates and polyols to form prepolymers and the chemistry of curing the prepolymer with active hydrogen containing compounds are well known. The resulting polyp urethane systems have been used for a variety of applications such as casting resins coatings, encapsulant and for general polyp urethane elastomeric uses. Unfortunately preexisting systems have not exhibited optimum properties for certain of these uses, part-ocularly for casting purposes and the preparation of clear prototype products. These required properties include clarity, minimum color, heat resistance, minimum shrinkage, hardness, impact resistance and low viscosity to facilitate mixing and pouring of the system. It is to be noted that existing, easily cast urethanes ego. non-prepoly-men, two-component, plasticized systems have not exhibited the required clarity, absence of color and stability to be effectively utilized for clear casting purposes.
.
In an effort to monomial these difficulties, resort has been had to various acrylic (e.g. LUCITE from Dupont and epoxy systems.
Although acrylics provide the desired clarity, they generally are available only in sheet form and must be machined to various shapes, thereby making it rather difficult to fabricate to specific and more intricate shapes. Such acrylic products also exhibit high shrinkage.
Correspondingly, epoxy systems are brittle and lose their clarity with the passage of time.
I
It is therefore the primary object of this invention to prude clear, cartable polyurethane systems which are applicable for a broad range of utilities.
It is another object to provide such systems which eliminate or substantially reduce the disadvantages encountered with prior art systems.
Various other objects and advantages of this invention will be readily apparent from the following detailed description thereof.
It has now been surprisingly discovered that by combining specific polyisocyanate prepolymers and polyols, polyurethane systems are obtained which are well suited for a number of end use applications, particularly for casting and prototype fabrication operations.
Thus, the invention relates to substantially clear, cartable polyurethane systems comprising the reaction product of (a) a polyisocyanate prepolymer comprising the reaction product of an excess of an aliphatic or cycloaliphatic polyisocyanate compound and an amine-based polyol, and (b) at least an amine-based polyol, a polyether polyol or mixtures thereof (hardener).
These systems thus exhibit clarity, heat resistance, low shrinkage, high hardness, impact resistance and sufficiently high heat deflect lion temperatures. They exhibit relatively low mixed viscosities which facilitate their ease of mixing and pouring. The systems are also readily compatible with a variety of optional additives such, for example, as light stabilizers which allows for prolonged light stability without evidence of color formation and/or degradation.
The polyurethane systems of the present invention are prepared by reacting approximately stoichiometric amounts of a polyisocyanate prepolymer (a) with a polyol (b).
The polyisocyanate prepolymer (a) is in turn prepared by reacting an excess of a polyisocyanate compound with a amine-based polyol in a manner well known in the art. For purposes of this invention, the term "prepolymer" is intended to reflect the products of the latter reaction. The polyisocyanate prepolymer is then reacted with the polyol in the presence of optional additives to form the puller-than system.
The polyisocyanate compound which is used in the preparation of the polyisocyanats prepolymer is preferably a liquid aliphatic or cycloaliphatic polyisocyanate. Typical of such polyisocyanate compounds are 3-isocyanatomethyl 3,5,5-trimethylcyclohexyl issues-Nate (isophorone diisocyanate), I ethylene bis-(cyclohexyliso-Senate), hexamethylene diisocyanate, Burt of hexamethylene diisocyanate, 1,3-cyclohexane bis(methylisocyanate), trim-thylhexamethylene diisocyanate and combinations thereof, as well as related aliphatic and cycloaliphatic polylsocyanates which may be substituted with other organic or inorganic groups that do not adversely affect the course of the reaction. The 4,4'-methylene bis(cyclohe~ylisocyanate), hexamethylene diisocyanate and isophorone diisocyanate are preferred.
The term "aliphatic~', as used herein, includes those carbon chains which are substantially non-aromatic in nature. They may be sat-rated or unsaturated, unbranched, branched or cyclic in configu-ration and may contain various substituents. Such aliphatic issues-antes generally have an equivalent weight of from 60 to 160 and a viscosity of 1.0 to 1500.0 ma s at 25~. Exemplary of liquid long chain aliphatic polyisocyanates are dodecyl diisocyanate, tridecyl diisocyanate, and the like.
socyanate terminated prepolymers are available from PUN Plastics such as RP-6414~ based on DESMODUR To (Mob, a cycloaliphatic lsocyanate.
The amine-based polyols which are reacted with the polyisocyanate prepolymer generally have an equivalent weight of from 30 to 6'000 and a viscosity of from 1.0 to 20'000 ma s at 25~C-60C. A wide variety of aromatic and aliphatic dominoes may form part of the amine-based polyol3, such polyols including N,N-bis(2-hydroxypro-Pyle aniline, and, preferably, N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine and polymers of ethylene Damon, propylene oxide and ethylene oxide. A typical aromatic amine-based polyol is available from Upjohn under the designation ISONOL 100~, a typical aliphatic amine-based polyol is available from BASS under the designation QUADRILLE and a typical ethylene diaminelpropylene oxide/ethylene oxide polymer is available from BASS under the designation PLURACOL 355~.
Preferred concentration ranges for the respective components of the prepolymer are 85-95 % by weight of polyisocyanate and 5-15 % by weight polyol to form a resin prepolymer of 20-55 % by weight polymer dissolved in 45-80 % by weight excess polyisocyanate, and preferably 30 to 40 %, by weight, polymer in 60 to 70 %, by weight, excess polyisocyanate.
The polyol hardener system (b) consists at least of an amine-based polyol, a polyether polyol or blends of these polyol8. Suitable amine-based polyols have been mentioned above. N,N-bis(2-hydroxypro-pyl~anilins,N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediaminno and polymers of ethylene diaminelpropylene oxidelethylene oxide are preferred.
Suitable polyether polyols (b) include alkaline glycol polymers having an alkaline unit composed of at least two carbon atoms. These aliphatic alkaline glycol polymers are exemplified by polyoxypro-pylon glycol and polytetramethylene ether glycol. Do-, in- and I
tetrafunctional compounds are also suitable, the trifunctional compounds being exemplified by the reaction product of glycerol or trimethylol propane and propylene oxide. A typical polyether polyol is available prom Union Carbide under the designation PPG-425~. The trifunctional compounds are preferred. Suitable polyether polyols will generally have molecular weights of from 60-7'000 with the dills ranging from 60-200, the trios from 400-7'000 and the petrols from 400-600. The preferred polyol (b) is a blend of amine-based polyol and at least one polyether polyol, said polyether polyol being present in weight ratios ranging from 1:1 to 1:9 and pro-fireball 1:2 to 1:4.
As previously noted, the polyurethane systems of this invention are prepared by admixing the prepolymer with the polyol hardener.
Catalysts and optional additives may be included with the hardener system. Generally, stoichiomet~ic amounts of prepolymer (a and polyol (b) are utilized, with the possibility of deviating from the stoichiamet~ic amount by utilizing up to about 25 % excess propel-men (a) or up to about 2 % excess polyol (b). Solid, thermoses polyurethane elastomers are obtained within about 40 minutes at room temperature.
Preferably, the prepolymer (a) and the polyol (b) are present in equal amounts by weight.
Particularly preferred are polyurethane systems wherein the propel-men (a) is the reaction product of 4,4'-methylene bis(cyclohexyliso-Senate) and N,N,N',N'-tetra~is(2-hydroxypropyl) ethylenediamine, and the polyol (b) is a blend ox N,N~N',N'-tetrakis(2-hydroxypro-pyl)ethylenediamlne,`a polyether trio having a molecular weight of ~15 and a polyether troll having a molecular weight of 4'500.
Catalysts are known to those skilled in the art and may comprise, for example, heavy metals utilized in amounts ox about 0.1 % metal, by weight of hardener, e.g. organ tin, organ zinc, mercury and lead compounds. Tertiary amine may also be utilized.
Optional additives include anti-foaming agents such as glycerine, an ethyl acrylate-2-ethylhexyl assault copolyme}, dim ethyl selection copolymers and silicones; antioxidant such as esters of B-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionic acid with mandrake an polyhydric alcohols, for example, methanol, octadecanol, 1,6-hexane-dill, neopentylglycol, thiodiethyleneglycol, diethyleneglycol, triethyleneglycol, pentaerythritol~ tris-hydroxyethyl isocyanurate, and di-hydroxyethyl oxalic acid doomed; US absorbers and light stabilizers such as 2-(2'-hydroxyphenyl)benzotriazoles and stern-gaily hindered amine such as bis-(2,2,6,6-tetramethylpiperidyl)-subacute, Boyce 9 6,6-pentamethylpiperidyl)-sebacate, 2-n-butyl-
2-(3,5-di-tert.butyl-~-hydroxybenzyl) Masonic acid Boyce-pentamethylpiperidyl)ester, the condensation product of l-hydroxy-ethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and 4-tert.octylamino-2,6-dichloro-1,3,5-s-treason, Tracy 3 6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-3-piperidyl)-1,2,3,44-butane-tetracarb-oxylic acid and1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperray xenon); plasticizers such as phthalates, adipates, glutarates, epoxidized vegetable oils, and the like; fungicides; pigments; dyes;
reactive dyes; moisture scavengers; and the like. Preferably, one or more light stabilizers and antioxidant are used as optional add-lives.
The invention also relates to shaped articles obtained after curing the polyurethane systems as defined above.
As previously noted, the polyurethane possess the desired properties for a wide range of utilities, with primary emphasis on molding and prototype fabrication. Thus, the resulting systems are water-clear, heat resistant, hard and impact resistant. The exhibit sufficiently low mixed viscosities to facilitate mixing, pouring and air bubble diffusion, thereby allowing for the formation of bubble free castings of both simple and intricate shapes. The resulting ~:2~7~
molded products exhibit low shrinkage during molding and subsequent thereto. Systems containing light stabilizers exhibit prolonger stability without encountering significant color formation and/or degradation.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts given are by weight unless otherwise specified.
Example l: This example illustrates the preparation of a typical polyurethane system of this invention.
Prepolymer (A) parts 4,4'-methylene bis(cyclohexylisocanate) 3720 N,N,N',N'-tetrakls(2-hydroxypropyl)ethylenediaminee 280 The components are charged to a flask equipped with a nitrogen inlet, a mechanical stirrer and a thermometer, which is attached to a vacuum pump. The contents are heated to 80~C with mixing under vacuum, then reacted or 1 hour at 80C under nitrogen. The product is characterized by an NC0 content of 24.7 %, by weight.
Hardener (~) - parts N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediaminee 300 polyether trio (MISS) 200 polyether trio (MOE) 496 ethyl acrylate/2-ethylhexyl acrylate copolymer 0.5 bis(1,2,2,6,6-pentamethyl-4-piperidyl)-~ebacate 12.5 2(2'-hydroxy-3',5'~di-tert.amylphenyl)-benzotriazoowe 12.5 dibutyl tin dilaurate 0.
MY = molecular weight.
I
1- POSY G 30-208~ from Olin Corp.
2- POSY G 85-36~ from Olin Corp.
The ingredients are charged to a flask, heated to 100~C under vacuum and the temperature is maintained until a moisture level of 0.04 %
is reached. The mixture is cooled to 70~C and the catalyst then admixed therewith.
Polyurethane No. 1 parts Prepolymer A 100 Hardener H 100 A mix of the two is prepared with the excellent properties thereof being illustrated in subsequent example.
Prepolymer B C D
(parts) 4,4'-methylene-bis~cyclo-hexylisocyanate) 910 - 704 isophorone diisocyanate - 90 polymer of ethylenediamine/
propylene oxide/ethylene oxide 90 10 N,N,N',N'-tetrakis(2-hy-droxypropyl)-ethylened~amine - - 96 reaction temperature I 70-83 80-84 80 reaction time (minutes) 30 10 60 NC0 content (%) 25.9 35.05 22.5 These prepolymers are prepared according to the procedure of Example 1.
~2~7~1 _ 9 _ Example 3:
Hardener J K L M N O
(parts) N,N,N',N'-tetra~is- 900 - 90 - - 600 50 (2~hydroxypropyl) ethylenediamine polyether trio 600 85 59.4 56 88.8 400 50 (MOE
polyether trio - - 60 (MOE) pithier trio 1498 - 90.6 - - 983 (MOE) 2 Dick alkyd) 14.6 phthalate phenol mercuric pro- - 0.4 - - 0.2 - -pinnate dibutyl tin dilaurate 1.5 - 0.15 0.1 - 1.8 dipropylene glycol - - - 19 11 triethylenediamlne - 0.5 ballpoint - 5 methyl-4-piperidyl)-subacute 2(2'-hydroxy-3',5'-dl- - - - - - 5 tert.amylphenyl)benzo-` triazole tetrakiæ(methylene(3,5-di-tert.butyl-4-hydroxy-hydro-cinnamate)methane - - - - - 5 reaction temperature (US) lo RUT 100 RUT RUT 100 100
reactive dyes; moisture scavengers; and the like. Preferably, one or more light stabilizers and antioxidant are used as optional add-lives.
The invention also relates to shaped articles obtained after curing the polyurethane systems as defined above.
As previously noted, the polyurethane possess the desired properties for a wide range of utilities, with primary emphasis on molding and prototype fabrication. Thus, the resulting systems are water-clear, heat resistant, hard and impact resistant. The exhibit sufficiently low mixed viscosities to facilitate mixing, pouring and air bubble diffusion, thereby allowing for the formation of bubble free castings of both simple and intricate shapes. The resulting ~:2~7~
molded products exhibit low shrinkage during molding and subsequent thereto. Systems containing light stabilizers exhibit prolonger stability without encountering significant color formation and/or degradation.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts given are by weight unless otherwise specified.
Example l: This example illustrates the preparation of a typical polyurethane system of this invention.
Prepolymer (A) parts 4,4'-methylene bis(cyclohexylisocanate) 3720 N,N,N',N'-tetrakls(2-hydroxypropyl)ethylenediaminee 280 The components are charged to a flask equipped with a nitrogen inlet, a mechanical stirrer and a thermometer, which is attached to a vacuum pump. The contents are heated to 80~C with mixing under vacuum, then reacted or 1 hour at 80C under nitrogen. The product is characterized by an NC0 content of 24.7 %, by weight.
Hardener (~) - parts N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediaminee 300 polyether trio (MISS) 200 polyether trio (MOE) 496 ethyl acrylate/2-ethylhexyl acrylate copolymer 0.5 bis(1,2,2,6,6-pentamethyl-4-piperidyl)-~ebacate 12.5 2(2'-hydroxy-3',5'~di-tert.amylphenyl)-benzotriazoowe 12.5 dibutyl tin dilaurate 0.
MY = molecular weight.
I
1- POSY G 30-208~ from Olin Corp.
2- POSY G 85-36~ from Olin Corp.
The ingredients are charged to a flask, heated to 100~C under vacuum and the temperature is maintained until a moisture level of 0.04 %
is reached. The mixture is cooled to 70~C and the catalyst then admixed therewith.
Polyurethane No. 1 parts Prepolymer A 100 Hardener H 100 A mix of the two is prepared with the excellent properties thereof being illustrated in subsequent example.
Prepolymer B C D
(parts) 4,4'-methylene-bis~cyclo-hexylisocyanate) 910 - 704 isophorone diisocyanate - 90 polymer of ethylenediamine/
propylene oxide/ethylene oxide 90 10 N,N,N',N'-tetrakis(2-hy-droxypropyl)-ethylened~amine - - 96 reaction temperature I 70-83 80-84 80 reaction time (minutes) 30 10 60 NC0 content (%) 25.9 35.05 22.5 These prepolymers are prepared according to the procedure of Example 1.
~2~7~1 _ 9 _ Example 3:
Hardener J K L M N O
(parts) N,N,N',N'-tetra~is- 900 - 90 - - 600 50 (2~hydroxypropyl) ethylenediamine polyether trio 600 85 59.4 56 88.8 400 50 (MOE
polyether trio - - 60 (MOE) pithier trio 1498 - 90.6 - - 983 (MOE) 2 Dick alkyd) 14.6 phthalate phenol mercuric pro- - 0.4 - - 0.2 - -pinnate dibutyl tin dilaurate 1.5 - 0.15 0.1 - 1.8 dipropylene glycol - - - 19 11 triethylenediamlne - 0.5 ballpoint - 5 methyl-4-piperidyl)-subacute 2(2'-hydroxy-3',5'-dl- - - - - - 5 tert.amylphenyl)benzo-` triazole tetrakiæ(methylene(3,5-di-tert.butyl-4-hydroxy-hydro-cinnamate)methane - - - - - 5 reaction temperature (US) lo RUT 100 RUT RUT 100 100
3- TYPE 4542~ from BASS RUT = room temperature .
These hardeners are prepared by the general procedure of Example 1.
Example 4: The following polyurethane systems of this invention are made by the general procedure of Example 1.
Prepolymer A B C A D A A A A
Hardener H J H M M L I K N
Weight ratio (P/H) 100/100 80/100 80/100 100/90 100/80 100/75 100/100 100/100 100/100 The resulting systems are then subjected to the following test procedures to identify physical and performance characteristics.
Viscosity - determined on a Brook field RVF viscometer using spindle No. 3 at 20 rum (revolutions per minute). The samples are mixed for two minutes and the viscosity reading is taken three minutes after start of mixing. All samples are at room temperature (23-25~C).
Hardness - Shore D Hardness measured by the ASTM standard test method D 2240-81.
- determined according to I, ASTM-D 648-82 using a load of 18.56 kg/cm on a sample size 1.27 cm x 1.27 cm x 12.7 cm.
Impact Strength - Issued impact determined utilizing ASTM D 256-1, Method A, on a 1.27 cm x 1.27 cm x 6.3 cm specimen.
The results of these determinations are noted in the following table:
~;~217~
Polyurethane No.
viscosity 300 -- ~00 2720 -- 1655 1475 1395 (ma so Shore D 77 50 55 76 79 -- 72 73 77 hardness HUT (~C)54 39 37 34 44 48 54 ART cure) (16 ho cure 6B -- -- -- 49 -- -- -- 68 at 80~C) Issued impact 1.3 -- -- 0.72 -- -- 1.2 1.09 1.3 The excellent properties of these systems are thus evident.
example 5: This example illustrates the casting capability of the polyurethane systems of this invention.
A silicone mold for a perfume bottle prototype is utilized. 50 parts prepolymer A and 50 parts hardener H are weighed into a metal can.
The can contents are mixed by hand for 2 minutes and then placed on a vacuum desiccator. The sample is held under a 4000 Pa vacuum for 5 minutes at which time nearly all the entrapped air has been removed. The de-aired mixture is carefully poured into the mold to avoid entrapping air bubbles. The mold is allowed to stand at room temperature (23-25~C) for 16-24 hours. The completed bottle is removed from the mold. The entire procedure is done at room temperature (23-25~C?. Several clear, shrink-free, bubble-free, castings are obtained using this method.
In summary, this invention provides novel clear, cartable polyurethane systems. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
These hardeners are prepared by the general procedure of Example 1.
Example 4: The following polyurethane systems of this invention are made by the general procedure of Example 1.
Prepolymer A B C A D A A A A
Hardener H J H M M L I K N
Weight ratio (P/H) 100/100 80/100 80/100 100/90 100/80 100/75 100/100 100/100 100/100 The resulting systems are then subjected to the following test procedures to identify physical and performance characteristics.
Viscosity - determined on a Brook field RVF viscometer using spindle No. 3 at 20 rum (revolutions per minute). The samples are mixed for two minutes and the viscosity reading is taken three minutes after start of mixing. All samples are at room temperature (23-25~C).
Hardness - Shore D Hardness measured by the ASTM standard test method D 2240-81.
- determined according to I, ASTM-D 648-82 using a load of 18.56 kg/cm on a sample size 1.27 cm x 1.27 cm x 12.7 cm.
Impact Strength - Issued impact determined utilizing ASTM D 256-1, Method A, on a 1.27 cm x 1.27 cm x 6.3 cm specimen.
The results of these determinations are noted in the following table:
~;~217~
Polyurethane No.
viscosity 300 -- ~00 2720 -- 1655 1475 1395 (ma so Shore D 77 50 55 76 79 -- 72 73 77 hardness HUT (~C)54 39 37 34 44 48 54 ART cure) (16 ho cure 6B -- -- -- 49 -- -- -- 68 at 80~C) Issued impact 1.3 -- -- 0.72 -- -- 1.2 1.09 1.3 The excellent properties of these systems are thus evident.
example 5: This example illustrates the casting capability of the polyurethane systems of this invention.
A silicone mold for a perfume bottle prototype is utilized. 50 parts prepolymer A and 50 parts hardener H are weighed into a metal can.
The can contents are mixed by hand for 2 minutes and then placed on a vacuum desiccator. The sample is held under a 4000 Pa vacuum for 5 minutes at which time nearly all the entrapped air has been removed. The de-aired mixture is carefully poured into the mold to avoid entrapping air bubbles. The mold is allowed to stand at room temperature (23-25~C) for 16-24 hours. The completed bottle is removed from the mold. The entire procedure is done at room temperature (23-25~C?. Several clear, shrink-free, bubble-free, castings are obtained using this method.
In summary, this invention provides novel clear, cartable polyurethane systems. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Claims (14)
1. A substantially clear, castable polyurethane system comprising the reaction product of (a) a polyisocyanate prepolymer comprising the reaction product of an excess of an aliphatic or cycloaliphatic polyisocyanate compound and an amine-based polyol, and (b) at least an amine-based polyol, a polyether polyol or mixtures thereof.
2. The system of claim 1, wherein said polyisocyanate in said prepolymer is 4,4'-methylene bis(cyclohexylisocyanate), hexamethy-lene diisocyanate or isophorone diisocyanate.
3. The system of claim 1, wherein said amine-based polyol is N,N-bis(2-hydroxypropyl)aniline, N,N,N',N'-tetrakis(2-hydroxypro-pyl)ethylenediamine or a polymer of ethylene diamine/propylene oxide/ethylene oxide.
4. The system of claim 1, wherein the prepolymer contains 85-95 %
polyisocyanate and 5-15 % amine-based polyol to form a prepolymer system of 20-55 % polymer dissolved in 45-80 % polyisocyanate, all percentages being on a weight basis.
polyisocyanate and 5-15 % amine-based polyol to form a prepolymer system of 20-55 % polymer dissolved in 45-80 % polyisocyanate, all percentages being on a weight basis.
5. The system of claim 1, wherein said polyether polyols have a molecular weight of from 60-7'000.
6. The system of claim 5, wherein said polyether polyol is an alkylene glycol polymer having an alkylene unit composed of at least two carbon atoms or a di , tri- or tetra-functional polyol compound.
7. The system of claim 6, wherein said polyether polyol is a trifunctional polyol compound.
8. The system of claim 1, wherein said component (b) is a blend of an amine-based polyol and at least one polyether polyol, said amine-based polyol and said polyether polyol being present in a weight ratio of from 1:1 to 1:9.
9. The system of claim 8, wherein said polyether polyol is a trifunctional polyol compound.
10. The system of claim 1, wherein components (a) and (b) are present in stoichiometric amounts up to a 25 % excess of component (a) or a 2 % excess of component (b).
11. The system of claim 1 which also contains one or more light stabilizers and antioxidants.
12. The system of claim 1, wherein said prepolymer (a) is the reaction product of 4,4'-methylene bis(cyclohexylisocyanate) and N,N,N',N'-tetrakis(2-hydroxypropyl) ethylenediamine, and said polyol (b) is a blend of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenedi-amine, a polyether triol having a molecular weight of 615 and a polyether triol having a molecular weight of 4'500.
13. The system o claim 10, wherein said prepolymer (a) and said polyol (b) are present in equal amounts by weight.
14. A shaped article comprising the polyurethane system of claim 1 subsequent to the curing thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/574,823 US4476292A (en) | 1984-01-30 | 1984-01-30 | Castable polyurethane systems |
| US574,823 | 1984-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221791A true CA1221791A (en) | 1987-05-12 |
Family
ID=24297796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472955A Expired CA1221791A (en) | 1984-01-30 | 1985-01-28 | Castable polyurethane systems |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4476292A (en) |
| JP (1) | JPS60179416A (en) |
| CA (1) | CA1221791A (en) |
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| US4677157A (en) * | 1985-06-03 | 1987-06-30 | Richard Jacobs | Preparing urethane polymer mixing isocyanate and premix of hydroxylated tertiary amine providing a crystalline polymer phase and polyol providing an amorphous polymer phase interdispersed with crystalline phase |
| WO1986007069A1 (en) * | 1985-05-31 | 1986-12-04 | Richard Jacobs | Bumper repair composition |
| JPH0780737B2 (en) * | 1985-05-31 | 1995-08-30 | ポ−ト−ス，ドン・ディ− | Tooth restoration formulation, structure and method |
| US4729925A (en) * | 1986-12-22 | 1988-03-08 | Eastman Kodak Company | Polyurethane elastomers comprising a charge-control agent and shaped elements therefrom |
| US4762941A (en) * | 1986-12-22 | 1988-08-09 | Eastman Kodak Company | Polyurethane elastomers comprising a charge control agent and shaped elements therefrom |
| US4808690A (en) * | 1988-02-29 | 1989-02-28 | Loral Corporation | High heat distortion temperature transparent polyurethanes |
| US5252697A (en) * | 1989-08-28 | 1993-10-12 | Richard Jacobs | Tooth restoration composition, structures and methods |
| US5011739A (en) * | 1989-10-02 | 1991-04-30 | Eastman Kodak Company | Moisture stable biasable transfer members and method for making same |
| US5212032A (en) * | 1991-11-26 | 1993-05-18 | Eastman Kodak Company | Moisture stable polyurethane biasable transfer members |
| US5250357A (en) * | 1991-11-26 | 1993-10-05 | Eastman Kodak Company | Moisture stable elastomeric polyurethane biasable transfer members |
| US5217838A (en) * | 1991-11-26 | 1993-06-08 | Eastman Kodak Company | Moisture stable biasable transfer members |
| US5554474A (en) | 1994-06-30 | 1996-09-10 | Eastman Kodak Company | Conductive substrate bearing a elastomeric polyurethane coating containing a conductivity control agent |
| US5541001A (en) | 1994-06-30 | 1996-07-30 | Eastman Kodak Company | Polyurethane biasable transfer members having improved moisture stability |
| US5571457A (en) | 1994-08-31 | 1996-11-05 | Eastman Kodak Company | Biasable transfer compositions and members having extended electrical life |
| US5962617A (en) * | 1995-02-02 | 1999-10-05 | Simula Inc. | Impact resistant polyurethane and method of manufacture thereof |
| US6127505A (en) * | 1995-02-02 | 2000-10-03 | Simula Inc. | Impact resistant polyurethane and method of manufacture thereof |
| US7214757B2 (en) | 2000-03-09 | 2007-05-08 | Eastman Kodak Company | Polyurethane elastomers and shaped articles prepared therefrom |
| DE10150558A1 (en) * | 2001-10-15 | 2003-04-17 | Bayer Ag | Process for the production of solid polyurethane moldings |
| US7034470B2 (en) * | 2002-08-07 | 2006-04-25 | Eastman Kodak Company | Serially connecting OLED devices for area illumination |
| US6693296B1 (en) | 2002-08-07 | 2004-02-17 | Eastman Kodak Company | OLED apparatus including a series of OLED devices |
| US20060074147A1 (en) * | 2004-10-06 | 2006-04-06 | Mayo Michael A | Cast material having color effect |
| US7602118B2 (en) * | 2005-02-24 | 2009-10-13 | Eastman Kodak Company | OLED device having improved light output |
| US7276848B2 (en) | 2005-03-29 | 2007-10-02 | Eastman Kodak Company | OLED device having improved light output |
| US20060290276A1 (en) * | 2005-06-22 | 2006-12-28 | Eastman Kodak Company | OLED device having spacers |
| US7459850B2 (en) * | 2005-06-22 | 2008-12-02 | Eastman Kodak Company | OLED device having spacers |
| US7531955B2 (en) * | 2005-07-12 | 2009-05-12 | Eastman Kodak Company | OLED device with improved efficiency and robustness |
| US20070013293A1 (en) * | 2005-07-12 | 2007-01-18 | Eastman Kodak Company | OLED device having spacers |
| US7719182B2 (en) * | 2005-09-22 | 2010-05-18 | Global Oled Technology Llc | OLED device having improved light output |
| US7548021B2 (en) * | 2005-09-22 | 2009-06-16 | Eastman Kodak Company | OLED device having improved light output |
| US20070103056A1 (en) * | 2005-11-08 | 2007-05-10 | Eastman Kodak Company | OLED device having improved light output |
| US7508130B2 (en) * | 2005-11-18 | 2009-03-24 | Eastman Kodak Company | OLED device having improved light output |
| US7466075B2 (en) * | 2005-12-08 | 2008-12-16 | Eastman Kodak Company | OLED device having improved output and contrast with light-scattering layer and contrast-enhancement layer |
| US7710026B2 (en) | 2005-12-08 | 2010-05-04 | Global Oled Technology Llc | LED device having improved output and contrast |
| US7710022B2 (en) * | 2006-01-27 | 2010-05-04 | Global Oled Technology Llc | EL device having improved power distribution |
| US7594839B2 (en) * | 2006-02-24 | 2009-09-29 | Eastman Kodak Company | OLED device having improved light output |
| US7791271B2 (en) * | 2006-02-24 | 2010-09-07 | Global Oled Technology Llc | Top-emitting OLED device with light-scattering layer and color-conversion |
| US20070201056A1 (en) * | 2006-02-24 | 2007-08-30 | Eastman Kodak Company | Light-scattering color-conversion material layer |
| US7417370B2 (en) * | 2006-03-23 | 2008-08-26 | Eastman Kodak Company | OLED device having improved light output |
| US7564063B2 (en) * | 2006-03-23 | 2009-07-21 | Eastman Kodak Company | Composite electrode for light-emitting device |
| US20080012471A1 (en) * | 2006-06-29 | 2008-01-17 | Eastman Kodak Company | Oled device having improved light output |
| US7969085B2 (en) * | 2006-08-18 | 2011-06-28 | Global Oled Technology Llc | Color-change material layer |
| US20080042146A1 (en) * | 2006-08-18 | 2008-02-21 | Cok Ronald S | Light-emitting device having improved ambient contrast |
| US7834541B2 (en) * | 2006-10-05 | 2010-11-16 | Global Oled Technology Llc | OLED device having improved light output |
| US20080100202A1 (en) * | 2006-11-01 | 2008-05-01 | Cok Ronald S | Process for forming oled conductive protective layer |
| US7535646B2 (en) * | 2006-11-17 | 2009-05-19 | Eastman Kodak Company | Light emitting device with microlens array |
| US7646144B2 (en) * | 2006-12-27 | 2010-01-12 | Eastman Kodak Company | OLED with protective bi-layer electrode |
| US7750558B2 (en) * | 2006-12-27 | 2010-07-06 | Global Oled Technology Llc | OLED with protective electrode |
| US8174187B2 (en) * | 2007-01-15 | 2012-05-08 | Global Oled Technology Llc | Light-emitting device having improved light output |
| US7521270B2 (en) * | 2007-02-19 | 2009-04-21 | Eastman Kodak Company | OLED patterning method |
| US7662663B2 (en) * | 2007-03-28 | 2010-02-16 | Eastman Kodak Company | OLED patterning method |
| US7635609B2 (en) | 2007-04-16 | 2009-12-22 | Eastman Kodak Company | Patterning method for light-emitting devices |
| US20080261478A1 (en) * | 2007-04-17 | 2008-10-23 | Cok Ronald S | Patterning method for light-emitting devices |
| US7560747B2 (en) * | 2007-05-01 | 2009-07-14 | Eastman Kodak Company | Light-emitting device having improved light output |
| US7902748B2 (en) * | 2007-05-31 | 2011-03-08 | Global Oled Technology Llc | Electroluminescent device having improved light output |
| US7982396B2 (en) * | 2007-06-04 | 2011-07-19 | Global Oled Technology Llc | Light-emitting device with light-scattering particles and method of making the same |
| US7777416B2 (en) * | 2007-06-14 | 2010-08-17 | Global Oled Technology Llc | Light emitting device with microlens array |
| US20090004419A1 (en) * | 2007-06-29 | 2009-01-01 | Cok Ronald S | Multi-layer masking film |
| US20090081360A1 (en) * | 2007-09-26 | 2009-03-26 | Fedorovskaya Elena A | Oled display encapsulation with the optical property |
| US7674712B2 (en) * | 2007-10-22 | 2010-03-09 | Cok Ronald S | Patterning method for light-emitting devices |
| US8178644B2 (en) * | 2008-01-02 | 2012-05-15 | Polyplexx, Llc | Impact-resistant polyurethane |
| US8193018B2 (en) * | 2008-01-10 | 2012-06-05 | Global Oled Technology Llc | Patterning method for light-emitting devices |
| US20090278454A1 (en) * | 2008-05-12 | 2009-11-12 | Fedorovskaya Elena A | Oled display encapsulated with a filter |
| TWI429669B (en) * | 2009-11-18 | 2014-03-11 | Nippon Polyurethane Kogyo Kk | A polyurethane resin-forming composition, and a water-proof material for a steel plate |
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|---|---|---|---|---|
| US3781238A (en) * | 1971-08-04 | 1973-12-25 | Textron Inc | Aqueous chain extension of nco prepolymer with tertiary amino polyol using nonionic surfactant,and aqueous dispersion produced |
| BE794607A (en) * | 1972-01-28 | 1973-07-26 | Dow Chemical Co | SOLID RIGID POLYURETHANNES AND THEIR PREPARATION |
| US4045527A (en) * | 1974-09-23 | 1977-08-30 | Hitco | Polyurethane and composite thereof |
| US4028301A (en) * | 1975-05-01 | 1977-06-07 | The Dow Chemical Company | Solid, rapid-setting, rigid polyurethanes |
| DE2824003B2 (en) * | 1977-06-03 | 1980-09-04 | Thiokol Corp., Newtown, Pa. (V.St.A.) | Process for the production of molded polyurethane articles |
| US4387194A (en) * | 1982-07-22 | 1983-06-07 | General Motors Corporation | High solids internally U.V. stabilized melamine cured urethane paint |
-
1984
- 1984-01-30 US US06/574,823 patent/US4476292A/en not_active Expired - Lifetime
-
1985
- 1985-01-28 CA CA000472955A patent/CA1221791A/en not_active Expired
- 1985-01-30 JP JP60016383A patent/JPS60179416A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4476292A (en) | 1984-10-09 |
| JPS60179416A (en) | 1985-09-13 |
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