CA1327093C - Polyurethane syntactic foam modeling stock - Google Patents
Polyurethane syntactic foam modeling stockInfo
- Publication number
- CA1327093C CA1327093C CA000598699A CA598699A CA1327093C CA 1327093 C CA1327093 C CA 1327093C CA 000598699 A CA000598699 A CA 000598699A CA 598699 A CA598699 A CA 598699A CA 1327093 C CA1327093 C CA 1327093C
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- polyurethane
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing 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
- C08G18/40—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Polyurethane Syntactic Foam Modeling Stock Abstract of the Disclosure Polyurethane syntactic foam compositions having high glass transition temperatures and low coefficients of thermal expansion suitable for use in tooling applications as modeling stock are prepared from polymeric isocyanate, an amine-based polyol, a polyether triol, molecular sieve material and hollow microspheres.
Description
3271~3 K-17026/=/CGC 1347 Polyurethane Syntactic Foam Modelin~ Stock Acceptable modeling stock must have such properties that its dimensionsare essentially unchanged over a wide variation in environmental condi-tions (temperature, humidity) so that the dimensions of a workpiece made from such stock can meet the increasingly stringent specifications imposed by end-use considerations such as those of the aerospace industry.
Laminated wood modeling stock and plaster models exhibit numerous disadvantages. For example, wood models made from such stock swell and warp when exposed to adverse weather conditions, especially high tem-perature and humidity causing the parts and tools made from such wood models to be out of tolerance. Plaster models are fragila.
Metals, particularly aluminium, clearly overcome the problems associated with laminated wood modeling stock, but metal is relatively expensive, hsavy and difficult as well as slow to machine to ths desired shape.
Nonetheless9 a metal such as aluminium has been the standard modeling "
stock of preparing large workpieces of exact dimensions.
Attempt~ to overcsme the problems associated with aluminium, have focused .
on hand lay-up epoxy la~inate struc~ures. These structures have the disadvantages of being very costly and labor intensive in their construc-tion requirements and not belng adaptable to robotic construction coupled with the built-in inescapable flaws where adjoining edges of cloth in sait laminates occur. These disadvantages would be exacerbated in the preparation of very large workpieces.
Laminated wood modeling stock and plaster models exhibit numerous disadvantages. For example, wood models made from such stock swell and warp when exposed to adverse weather conditions, especially high tem-perature and humidity causing the parts and tools made from such wood models to be out of tolerance. Plaster models are fragila.
Metals, particularly aluminium, clearly overcome the problems associated with laminated wood modeling stock, but metal is relatively expensive, hsavy and difficult as well as slow to machine to ths desired shape.
Nonetheless9 a metal such as aluminium has been the standard modeling "
stock of preparing large workpieces of exact dimensions.
Attempt~ to overcsme the problems associated with aluminium, have focused .
on hand lay-up epoxy la~inate struc~ures. These structures have the disadvantages of being very costly and labor intensive in their construc-tion requirements and not belng adaptable to robotic construction coupled with the built-in inescapable flaws where adjoining edges of cloth in sait laminates occur. These disadvantages would be exacerbated in the preparation of very large workpieces.
- 2 - ~ 3 2 7~3 Improved epoxy resin modeling stock is reflected in U.S. 4,528,305 in terms of machinability with computer aided cutting equipment and physical characteristics approaching those of aluminium. However, such systems still suffer from the need for multiple processing operations, higher cost and particularly extended cycle times in the mold. Other thermo-setting resins, such as unsaturated polyesters, formaldehyde condensates and preferably epoxy systems are identified in U.S. 4,595,623.
By way of further background information, U.S. 3,886,846 describes a method of testing the accuracy of a cutting machine tool control program.
This patent relates to the now common practice of preparing a "control program" py punched card, magnetic tape or computer disc, on a machine tool to make a prototype workpiece. The control program thus prepared is then available to control the preparation of such workpieces on any similar machine tool. The invention of U.S. 3,886,846 provides a less expensive, easily machined, thermosetting plastics block as a working stock to test whether the control program applied to the machine tool to be used to manufacture the actual work pieces will in practice machine the working stock to the desired dimensions. This allows for savings in time and expense in testing the control programs. The thermosetting plastic block i5 cast polyurethane foam or extended polyester which is glued together with standard epoxy putty.
In addition, block material prepared from polyurethane foam is commer-ciall~ available for use as a modeling stock. Despite the major improve-ments provided by this material, higher glass transition temperatures, lower coefficients of thermal expansion closer to materials utili~ed for composite parts and further improved physical proper~ies are still required in view of the greater physical and configurational demands b~ing placed on composite parts.
The object of the instant invention is to provide a synthatic modaling material approaching composite part materials in lts coefficient of thermal linear e~pansion and having the advantages of lower cost, improved physical properties, simpler and quicker processing, and the like.
~ 3 - 1327~3 It has now been surprisingly discovered that a polyurethane syntactic foam formulation prepared from a polymeric isocyanate, an amine based polyol, z polyether triol, a molecular sieve and hollow microspheres provides the aforementioned performance benefits. Thus, the foam can be readily used as modeling stock at ambient and elevated temperatures. It is available for use with computer aided design methods for the produc-tion of tools for composite part manufacturs. Of particular interest, the material allows for the substantial reduction in operating steps required for final tool production. Whereas conventional procedures require mylars (transparent engineering drawings) to produce templates to produce master models ~y the conventional technique known as "splining", plaster or room temperature epoxy "splash" to provide a negative which, in turn, is utilized to make a high temperature intermediate, use of the intermediate to prepare a prepreg curing tool, and finally use of the latter to make a composite part, and whereas even the improved systems only eliminate the mylars and template operations, the improved model stock of this inven-tion utilizes computer-aided design data to directly make the high temperature intermediate. Thus, mylars, templates master models and splashes are totally eliminated.
In addition, the instant polyurethane materials exhibit higher glass transition temperatures to facilitate their use at elevated temperatures.
They exhibit reduced coefficients of thermal expansion and coefficients which are closer in value to that of materials utilized to make composite parts. The materials further show improved mechanical strength to permit their use under autoclave pressures and temperatures.
Subject of the invention is a curable polyur~thane composition comprising a blend o~ (a~ from 30-55 % of a polymeric isocyanate, ~b) from 9-35 % of an amine-based pol~ol, (c) from 5-40 % of a polyether triol, (d) from 3-10 % of a molecular sieve and (e) from 10-40 % of a hollow microsphere filler, all percsntages being by weight of ths total composition.
The product obtained by curing the instant compositions provides the indicated el~vated glass transition temperatures and the low coefficients of thermal expansion.
By way of further background information, U.S. 3,886,846 describes a method of testing the accuracy of a cutting machine tool control program.
This patent relates to the now common practice of preparing a "control program" py punched card, magnetic tape or computer disc, on a machine tool to make a prototype workpiece. The control program thus prepared is then available to control the preparation of such workpieces on any similar machine tool. The invention of U.S. 3,886,846 provides a less expensive, easily machined, thermosetting plastics block as a working stock to test whether the control program applied to the machine tool to be used to manufacture the actual work pieces will in practice machine the working stock to the desired dimensions. This allows for savings in time and expense in testing the control programs. The thermosetting plastic block i5 cast polyurethane foam or extended polyester which is glued together with standard epoxy putty.
In addition, block material prepared from polyurethane foam is commer-ciall~ available for use as a modeling stock. Despite the major improve-ments provided by this material, higher glass transition temperatures, lower coefficients of thermal expansion closer to materials utili~ed for composite parts and further improved physical proper~ies are still required in view of the greater physical and configurational demands b~ing placed on composite parts.
The object of the instant invention is to provide a synthatic modaling material approaching composite part materials in lts coefficient of thermal linear e~pansion and having the advantages of lower cost, improved physical properties, simpler and quicker processing, and the like.
~ 3 - 1327~3 It has now been surprisingly discovered that a polyurethane syntactic foam formulation prepared from a polymeric isocyanate, an amine based polyol, z polyether triol, a molecular sieve and hollow microspheres provides the aforementioned performance benefits. Thus, the foam can be readily used as modeling stock at ambient and elevated temperatures. It is available for use with computer aided design methods for the produc-tion of tools for composite part manufacturs. Of particular interest, the material allows for the substantial reduction in operating steps required for final tool production. Whereas conventional procedures require mylars (transparent engineering drawings) to produce templates to produce master models ~y the conventional technique known as "splining", plaster or room temperature epoxy "splash" to provide a negative which, in turn, is utilized to make a high temperature intermediate, use of the intermediate to prepare a prepreg curing tool, and finally use of the latter to make a composite part, and whereas even the improved systems only eliminate the mylars and template operations, the improved model stock of this inven-tion utilizes computer-aided design data to directly make the high temperature intermediate. Thus, mylars, templates master models and splashes are totally eliminated.
In addition, the instant polyurethane materials exhibit higher glass transition temperatures to facilitate their use at elevated temperatures.
They exhibit reduced coefficients of thermal expansion and coefficients which are closer in value to that of materials utilized to make composite parts. The materials further show improved mechanical strength to permit their use under autoclave pressures and temperatures.
Subject of the invention is a curable polyur~thane composition comprising a blend o~ (a~ from 30-55 % of a polymeric isocyanate, ~b) from 9-35 % of an amine-based pol~ol, (c) from 5-40 % of a polyether triol, (d) from 3-10 % of a molecular sieve and (e) from 10-40 % of a hollow microsphere filler, all percsntages being by weight of ths total composition.
The product obtained by curing the instant compositions provides the indicated el~vated glass transition temperatures and the low coefficients of thermal expansion.
- 4 - ~327~93 The polyisocyanates (a) which are applicable to the instant invention include any of those commonly employed in making polyurethane plastics including polyarylisocyanates such as polymethylene polyphenyl iso-cyanate, 4,4'-diphenylmethane diisocyanate and modifications thereof e.g.
containing carbodiimide linkages, toluene diisocyanate, phenylindane diisocyanate, aliphatic polyisocyanates such as hexamethylene diiso-cyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diiso-cyanate, and blends thereof. Preferred polyisocyanates (a) are poly-methylene polyphenyl isocyanates.
Preferred polyether triols (c) include aliphatic alkylene glycol polymers having an alkylene unit composed of at least two carbon atoms. Typical ones are prepared through the polymerization of such alkylene oxides as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, and di- and polyfunctional alcohols such as water, propylene glycol, glycerol, trimethylol propane, hexanetriol, pentaerythritol and sucrose.
Applicable materials will generally have molecular weights ranging from A~ 400-7000. Typical polyether triols are for example available from Olin Corp. under the designation POLY-G 30-280, from ~ASF under the *
designation PLURACOL TP-440 or from Union Carbide Corp. under the designation NIAX Polyol HPP.
The amine-based polyols ~b) generally have an equivalent weight of from 30 to 6000 and a viscosity of from 1.0 to 20000 mPa-s at 25C-60C. A
wide variety of aromatic and ~liphatic polyamines may form part of the amine-based polyols, such di- and polyamines including ethylenediamine, triethanolamine and toluenediamine, to be reacted with, for example, the alkyIene oxides notsd above. Pre~erred polyols (b) are ~hose derived from an aliphatic or an aromatic diamine. Also preferred are amine-based triols. Typical amine-based polyols are available for example fr~m Texaco Corp. under the designation THANQL SF 26S, from BASF Corp. under the designation PLURACOL 355 and from Carbochimiqus S.A. under the designation TERCAPUR G-200.
~rra de ~ a r~
~ 5 ~ 1 ~2 70 9~
The molecular sieve (d) functions as a moisture scavenger which reducesfoaming in the molding process and yields a product of uniform density.
Such sieves are well known to those skilled in the art, being zeolites with open-network structures.
The syntactic foam composites prepared in accordance with the present invention contain a relatively uniform distribution of hollow micro-spheres. Hollow microspheres are usually hollow thermoplastic spheres composed of acrylic-type resins such as polymethylmethacrylate, acrylic modified styrene, polyvinylidene chloride or copolymers of styrene and methyl methacrylate; phenolic resins; or hollow glass, silica, ceramic or carbon spheres that are very light in weight and act as a lightweight filler in the syntactic foam. Glass microspheres are preferred. These microspheres preferably have a diameter in the range of about 5 to about 250 micrometers. Methods for the production of these hollow microspheres are well known in the art. Such microspheres are readily available commercially. These hollow microspheres can be compressed somewhat when subjected to external pressure. However, they are relatively fragile and will collapse or fracture at high pressures. Therefore there is a pressure range under which the microspheres can effectively operate. It has be~n determined that when hollow glass microspheres are employed in the practice of the present invention, syntactic foam composites can be molded at pressures up to the limit of ths hollow microspheres without fracture, with molding pressures in the range of about 4.83 to about 6.21 MPa (about 700 to about 900 psi) being preferred. The hollow microspheres facilitate machining of the stock, lead to reduced density and, most importantly, serve to reduce the cosfficient of thermal axpansion.
Ths polyurethane systems of this invention are prepared by admixing thepolyisocyanate with the polyols. The molecular sieve and microspheres as well as optional additives are generally included with the polyols.
Generally stoichiometric amounts of polyisocyanate and polyol are utili~ed, with the possibility of deviating from the stoichiometric amount by utilizing up to about 25 % excess isocyanate or up to about 2 %
excess polyol. Solid, thermoset polyurethane elastomers are obtained - 6 - ~ 327~93 within about 20-40 minutes at room temperature. Post-curing/annealing may then occur for up to about 48 hours or longer at ambient temperatures and then up to about 20 hours at 130-140C.
In the compositions of the invention the polymeric isocyanate (a) is present in a concentration of pre~erably 40-45 %; the amine-based polyol (b) of preferably 15-30 % and most preferably 20-25 %; the polyether triol (c) of preferably 5~20 % and most preferably 10-15 %; the molecular sieve (d) of preferably 5-8 %; and the microspheres (e) of preferably 10-20 %; these percentages being based on the weight of the total composition. The relationship of the polyols is of particular significance in order to achieve high glass transition temperatures and proper reactivity, i.e. control of the reaction. Higher levels of ths amine-based polyol generally yield higher glass transition temperatures.
Various optional ingredients may be included in the system. For example, catalysts are known to those skilled in the art and may comprise, for example, heavy metals utilized in amounts of about 0.1 % metal, by weight of polyol, e.g. organo tin, organo zinc, mercury, bismuth and lead compounds. Tertiary amines may also be utilized.
Other optional additives include anti-foaming agents such as glycerine,an ethyl acrylate-2-~thylhexyl acrylate copolymer, dimethyl siloxane copolymers and silicones; wetting agents such as solutions of a salt of unsaturated polyamine amides and high molecular weight esters, neoalkoxy zirconate and titanate or coordinate titanate coupling agents; anti-oxidants such as esters of B-t3,5-di-tert.butyl-4-hydroxyphenYl)-propionic acid with monohydric or polyhydric alcohols, for example, methanol, octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethylene-glycol, diethyleneglycol, trieshyleneglycol, pentaerythritol; tris-hydroxyethyl isocyanurate, and di-hydroxyethyl oxalic acid diamide; UV
absorbers and light stabilizers such as 2-(2'-hydroxyphenyl)benzo-triazoles and sterically hindered amines as bis-(2,2,6,6-tetramethyl-piparidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acidi c~ndensation - 7 - ~ ~2709 product of N,N'-~2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert.octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetra-methylpiperidyl)-nitrilotriacetata, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarbonic acid and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl piperazinone); plasticizers such as phthalates, adipates, glutarates, epoxidized vegetable oils, and the like;
fungicides; pigments; dyes; reactive dyes; flame retardants; and the like.
Additional fillers or combinations of fillers may also be present such as calcium carbona~e, mica, glass fibers, silica-alumina ceramic alloy, hydrated alumina silicates, calcium sulfate, talc and solid microspheres.
These optional fillers can be used in concentrations which replace up to a maximum of about 85 %, by weight, of the hollow microsphers content.
. .
Another subject of the invention is the shaped articl~ comprising the instant polyurethane composition subsequent to the curing thereof.
,, In order to meet the overall requirements for an acceptable cured polyurethane foam modeling stock, the cured composition should have a glass transition temperature (Tg) over 100C and preferably over 125C, and a coefficient of thermal expansion (CTE) of less than 70 x 10 6 cm/cm/C in the -30- 30C range and preferably less than 50 x 10 6 cm/cm/C, and less and 80 x 10 6 cm/cm/C in the 25-100C
range and preferably less than 60 x 10 6 cm/cm/C.
As previously noted, these cured polyurethanes function as modeling stock and are readily machinable by conventional tools or computer-aided design data to produce master models. They exhibit improved perormance over a commercial polyurethane matarial in terms of ~igher glass transition temperatures, reduced CTE, facilitating their use with larga models and achieving closer proximity to the CTE of composite material parts (e.g.
graphite composite part 2 6.0 x 10 6 cm/cm/C in the 25-100C range~ and increased strength characteristics. They are easier and more economical to fabricate than ~nown epoxy model blocks. Of particular signi~icancs, . .
, ~
2.
;
.
- 8 - ~ 32 7 ~93 the number of steps required to go from conception to final tool produc-tion is reduced to two from the six steps prevalent in current technology.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts given are by weight unless otherwise specified.
Example 1 This example illustrates the preparation oE typical poly-urethane systems of the invention.
Each of the formulations noted in the table below is prepared by charging the polyols and molecular sieve paste to a Hobart blender, mixing for 1-2 minutes at low speed, admixing the filler and stirring until wet and then mixing at low speed for an additional seven minutes.
The various castings are prepared by weighing fifty grams of the filled polyol formulation into a container, adding the indicated amount of isocyanate, mixing for approximately two minutes, casting a 1.3 cm x l.3 cm x 26.7 cm bar, retaining the bar for 78 hours at room temperature and post-curing/annealing for 20 hours at 130C. The sample siza for post-cure testing is 0.64 cm x 1.14 cm x l0.2 cm.
Each of the systems prior to casting and curing is evaluated as follows:
) Gel Time and % E~ansion - Two hundred grams of filled polyol are mixed with the indicated amount of isocyanate for one minute. Thereafter, 300 grams of ths mixed formulation are poured into a beaker, the initial height is marked, gelation is checked with a wooden probe and, after gelation, the final height is marked. "Gel Time" is noted as the time elapsed from the start of mixing until initial formation of a llardened mass. "% Expansion" is the height change divided by the initial height times 100.
Each of the cured bars is evaluated as follows:
~3~7093 Density - FTMS 406, Method 5012 (a method for determining the specific gravity of a solid from weight and volume measurements).
Glass Transition Temperature (Tg) - ASTM D-4065 using a DuPont 9900 DMA 982 using the Loss Modulus Curve.
Estimated Use Temperature - ASTM D-4065 using a DuPont 9900 DMA 982 using the Storage Modulus Curve.
Coefficient of Thermal Expansion (CTE) - ASTM D-3386 using a DuPont 9900 TMA 943 with samples annealed for one hour at 130C prior to testing.
parts by weight Polyol System 1 2 3 4 Amine-based trioll 39.5 45.5 36.436.4 Polyether triol2 21.2 15.2 24.324.3 Molecular sieve paste3 11.8 11.8 11.811.8 Hollow Glass microballoons 27.5 27.527.5 5.5 (20-130 ~m size) Mica - - - 11.0 Milled glass fibers - - - 11.0 PolYisocYanate Polymethylens polyphenyl76/10077110075/10075/100 isocyanats with an average fuctional~ty of 2.7 (isocyanate/
polyol system weight ratio) Mixed Properties Gcl Time (min.) ~6.54.5-5.0 6.8~7.0 % Expansion nil nil nil nil ~o 1327093 Cured Properties Density (g/ml) 0.80680.7971 0.80901.126 Tg (C) 141.9144.3 141.9144.8 Estimated Use Temp. (C) 121.6122.6 122.5125.2 TCE (10 cm/cmlC) -30- 30C 44.2546.05 45.1 52.5 25-100C 49.8549.95 49.6557.6 l-TERCAPUR G-200 from Carbochimique S.A.
2-PLURACoL TP-440 from BASF
3-PURMOL 3A Paste from Zeochem These data thus illustrate the excellent performance characteristics of the instant systems.
Example 2: This example illustra~es the use of different amine based triols and different polyol ratios.
In each instance, the polyols are mixed for two minutes and the required amount of polymethylene polyphenyl isocyanats is added with mixing for two minutes. A 1.3 cm x 1.3 cm x 26.7 cm bar is cast, left for 2~-96 hours at room temperature and post-cured/annealed for twenty hours at 130C. The sample size for testing is 0.64 cm x 1.14 cm x 10.2 cm.
Polyether triolJ
~mine-based Weight Ratio Estimated Use triol ) ~eight Ratio (iso:polyol) Tg (C) Temp. (C~
:
2/1 60:40 114:100136.4 121.4 211 50:50 117:100139.1 123.4 2/1 25:75 124:100145.3 129.3 2/4 50:50 120:100150.5 129.8 214 25:75 128:1001~0.6 143.6 2/5* 50:50 136:100141.7 124.4 2/5* 25:75 152:100141.1 124.1 2/6* 50:50 128:10012Y.8 110.0 2/6* 25:75 141:100151.6 129.4 a) For triols 1 and 2 see Example 1. Triols 4, 5 and 6 are as follows:
4- NIAX Polyol HPP - 520 from Union Carbids Corp.
containing carbodiimide linkages, toluene diisocyanate, phenylindane diisocyanate, aliphatic polyisocyanates such as hexamethylene diiso-cyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diiso-cyanate, and blends thereof. Preferred polyisocyanates (a) are poly-methylene polyphenyl isocyanates.
Preferred polyether triols (c) include aliphatic alkylene glycol polymers having an alkylene unit composed of at least two carbon atoms. Typical ones are prepared through the polymerization of such alkylene oxides as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, and di- and polyfunctional alcohols such as water, propylene glycol, glycerol, trimethylol propane, hexanetriol, pentaerythritol and sucrose.
Applicable materials will generally have molecular weights ranging from A~ 400-7000. Typical polyether triols are for example available from Olin Corp. under the designation POLY-G 30-280, from ~ASF under the *
designation PLURACOL TP-440 or from Union Carbide Corp. under the designation NIAX Polyol HPP.
The amine-based polyols ~b) generally have an equivalent weight of from 30 to 6000 and a viscosity of from 1.0 to 20000 mPa-s at 25C-60C. A
wide variety of aromatic and ~liphatic polyamines may form part of the amine-based polyols, such di- and polyamines including ethylenediamine, triethanolamine and toluenediamine, to be reacted with, for example, the alkyIene oxides notsd above. Pre~erred polyols (b) are ~hose derived from an aliphatic or an aromatic diamine. Also preferred are amine-based triols. Typical amine-based polyols are available for example fr~m Texaco Corp. under the designation THANQL SF 26S, from BASF Corp. under the designation PLURACOL 355 and from Carbochimiqus S.A. under the designation TERCAPUR G-200.
~rra de ~ a r~
~ 5 ~ 1 ~2 70 9~
The molecular sieve (d) functions as a moisture scavenger which reducesfoaming in the molding process and yields a product of uniform density.
Such sieves are well known to those skilled in the art, being zeolites with open-network structures.
The syntactic foam composites prepared in accordance with the present invention contain a relatively uniform distribution of hollow micro-spheres. Hollow microspheres are usually hollow thermoplastic spheres composed of acrylic-type resins such as polymethylmethacrylate, acrylic modified styrene, polyvinylidene chloride or copolymers of styrene and methyl methacrylate; phenolic resins; or hollow glass, silica, ceramic or carbon spheres that are very light in weight and act as a lightweight filler in the syntactic foam. Glass microspheres are preferred. These microspheres preferably have a diameter in the range of about 5 to about 250 micrometers. Methods for the production of these hollow microspheres are well known in the art. Such microspheres are readily available commercially. These hollow microspheres can be compressed somewhat when subjected to external pressure. However, they are relatively fragile and will collapse or fracture at high pressures. Therefore there is a pressure range under which the microspheres can effectively operate. It has be~n determined that when hollow glass microspheres are employed in the practice of the present invention, syntactic foam composites can be molded at pressures up to the limit of ths hollow microspheres without fracture, with molding pressures in the range of about 4.83 to about 6.21 MPa (about 700 to about 900 psi) being preferred. The hollow microspheres facilitate machining of the stock, lead to reduced density and, most importantly, serve to reduce the cosfficient of thermal axpansion.
Ths polyurethane systems of this invention are prepared by admixing thepolyisocyanate with the polyols. The molecular sieve and microspheres as well as optional additives are generally included with the polyols.
Generally stoichiometric amounts of polyisocyanate and polyol are utili~ed, with the possibility of deviating from the stoichiometric amount by utilizing up to about 25 % excess isocyanate or up to about 2 %
excess polyol. Solid, thermoset polyurethane elastomers are obtained - 6 - ~ 327~93 within about 20-40 minutes at room temperature. Post-curing/annealing may then occur for up to about 48 hours or longer at ambient temperatures and then up to about 20 hours at 130-140C.
In the compositions of the invention the polymeric isocyanate (a) is present in a concentration of pre~erably 40-45 %; the amine-based polyol (b) of preferably 15-30 % and most preferably 20-25 %; the polyether triol (c) of preferably 5~20 % and most preferably 10-15 %; the molecular sieve (d) of preferably 5-8 %; and the microspheres (e) of preferably 10-20 %; these percentages being based on the weight of the total composition. The relationship of the polyols is of particular significance in order to achieve high glass transition temperatures and proper reactivity, i.e. control of the reaction. Higher levels of ths amine-based polyol generally yield higher glass transition temperatures.
Various optional ingredients may be included in the system. For example, catalysts are known to those skilled in the art and may comprise, for example, heavy metals utilized in amounts of about 0.1 % metal, by weight of polyol, e.g. organo tin, organo zinc, mercury, bismuth and lead compounds. Tertiary amines may also be utilized.
Other optional additives include anti-foaming agents such as glycerine,an ethyl acrylate-2-~thylhexyl acrylate copolymer, dimethyl siloxane copolymers and silicones; wetting agents such as solutions of a salt of unsaturated polyamine amides and high molecular weight esters, neoalkoxy zirconate and titanate or coordinate titanate coupling agents; anti-oxidants such as esters of B-t3,5-di-tert.butyl-4-hydroxyphenYl)-propionic acid with monohydric or polyhydric alcohols, for example, methanol, octadecanol, 1,6-hexanediol, neopentylglycol, thiodiethylene-glycol, diethyleneglycol, trieshyleneglycol, pentaerythritol; tris-hydroxyethyl isocyanurate, and di-hydroxyethyl oxalic acid diamide; UV
absorbers and light stabilizers such as 2-(2'-hydroxyphenyl)benzo-triazoles and sterically hindered amines as bis-(2,2,6,6-tetramethyl-piparidyl)-sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acidi c~ndensation - 7 - ~ ~2709 product of N,N'-~2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert.octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetra-methylpiperidyl)-nitrilotriacetata, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarbonic acid and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethyl piperazinone); plasticizers such as phthalates, adipates, glutarates, epoxidized vegetable oils, and the like;
fungicides; pigments; dyes; reactive dyes; flame retardants; and the like.
Additional fillers or combinations of fillers may also be present such as calcium carbona~e, mica, glass fibers, silica-alumina ceramic alloy, hydrated alumina silicates, calcium sulfate, talc and solid microspheres.
These optional fillers can be used in concentrations which replace up to a maximum of about 85 %, by weight, of the hollow microsphers content.
. .
Another subject of the invention is the shaped articl~ comprising the instant polyurethane composition subsequent to the curing thereof.
,, In order to meet the overall requirements for an acceptable cured polyurethane foam modeling stock, the cured composition should have a glass transition temperature (Tg) over 100C and preferably over 125C, and a coefficient of thermal expansion (CTE) of less than 70 x 10 6 cm/cm/C in the -30- 30C range and preferably less than 50 x 10 6 cm/cm/C, and less and 80 x 10 6 cm/cm/C in the 25-100C
range and preferably less than 60 x 10 6 cm/cm/C.
As previously noted, these cured polyurethanes function as modeling stock and are readily machinable by conventional tools or computer-aided design data to produce master models. They exhibit improved perormance over a commercial polyurethane matarial in terms of ~igher glass transition temperatures, reduced CTE, facilitating their use with larga models and achieving closer proximity to the CTE of composite material parts (e.g.
graphite composite part 2 6.0 x 10 6 cm/cm/C in the 25-100C range~ and increased strength characteristics. They are easier and more economical to fabricate than ~nown epoxy model blocks. Of particular signi~icancs, . .
, ~
2.
;
.
- 8 - ~ 32 7 ~93 the number of steps required to go from conception to final tool produc-tion is reduced to two from the six steps prevalent in current technology.
The following examples illustrate the preferred embodiments of the invention. In these examples, all parts given are by weight unless otherwise specified.
Example 1 This example illustrates the preparation oE typical poly-urethane systems of the invention.
Each of the formulations noted in the table below is prepared by charging the polyols and molecular sieve paste to a Hobart blender, mixing for 1-2 minutes at low speed, admixing the filler and stirring until wet and then mixing at low speed for an additional seven minutes.
The various castings are prepared by weighing fifty grams of the filled polyol formulation into a container, adding the indicated amount of isocyanate, mixing for approximately two minutes, casting a 1.3 cm x l.3 cm x 26.7 cm bar, retaining the bar for 78 hours at room temperature and post-curing/annealing for 20 hours at 130C. The sample siza for post-cure testing is 0.64 cm x 1.14 cm x l0.2 cm.
Each of the systems prior to casting and curing is evaluated as follows:
) Gel Time and % E~ansion - Two hundred grams of filled polyol are mixed with the indicated amount of isocyanate for one minute. Thereafter, 300 grams of ths mixed formulation are poured into a beaker, the initial height is marked, gelation is checked with a wooden probe and, after gelation, the final height is marked. "Gel Time" is noted as the time elapsed from the start of mixing until initial formation of a llardened mass. "% Expansion" is the height change divided by the initial height times 100.
Each of the cured bars is evaluated as follows:
~3~7093 Density - FTMS 406, Method 5012 (a method for determining the specific gravity of a solid from weight and volume measurements).
Glass Transition Temperature (Tg) - ASTM D-4065 using a DuPont 9900 DMA 982 using the Loss Modulus Curve.
Estimated Use Temperature - ASTM D-4065 using a DuPont 9900 DMA 982 using the Storage Modulus Curve.
Coefficient of Thermal Expansion (CTE) - ASTM D-3386 using a DuPont 9900 TMA 943 with samples annealed for one hour at 130C prior to testing.
parts by weight Polyol System 1 2 3 4 Amine-based trioll 39.5 45.5 36.436.4 Polyether triol2 21.2 15.2 24.324.3 Molecular sieve paste3 11.8 11.8 11.811.8 Hollow Glass microballoons 27.5 27.527.5 5.5 (20-130 ~m size) Mica - - - 11.0 Milled glass fibers - - - 11.0 PolYisocYanate Polymethylens polyphenyl76/10077110075/10075/100 isocyanats with an average fuctional~ty of 2.7 (isocyanate/
polyol system weight ratio) Mixed Properties Gcl Time (min.) ~6.54.5-5.0 6.8~7.0 % Expansion nil nil nil nil ~o 1327093 Cured Properties Density (g/ml) 0.80680.7971 0.80901.126 Tg (C) 141.9144.3 141.9144.8 Estimated Use Temp. (C) 121.6122.6 122.5125.2 TCE (10 cm/cmlC) -30- 30C 44.2546.05 45.1 52.5 25-100C 49.8549.95 49.6557.6 l-TERCAPUR G-200 from Carbochimique S.A.
2-PLURACoL TP-440 from BASF
3-PURMOL 3A Paste from Zeochem These data thus illustrate the excellent performance characteristics of the instant systems.
Example 2: This example illustra~es the use of different amine based triols and different polyol ratios.
In each instance, the polyols are mixed for two minutes and the required amount of polymethylene polyphenyl isocyanats is added with mixing for two minutes. A 1.3 cm x 1.3 cm x 26.7 cm bar is cast, left for 2~-96 hours at room temperature and post-cured/annealed for twenty hours at 130C. The sample size for testing is 0.64 cm x 1.14 cm x 10.2 cm.
Polyether triolJ
~mine-based Weight Ratio Estimated Use triol ) ~eight Ratio (iso:polyol) Tg (C) Temp. (C~
:
2/1 60:40 114:100136.4 121.4 211 50:50 117:100139.1 123.4 2/1 25:75 124:100145.3 129.3 2/4 50:50 120:100150.5 129.8 214 25:75 128:1001~0.6 143.6 2/5* 50:50 136:100141.7 124.4 2/5* 25:75 152:100141.1 124.1 2/6* 50:50 128:10012Y.8 110.0 2/6* 25:75 141:100151.6 129.4 a) For triols 1 and 2 see Example 1. Triols 4, 5 and 6 are as follows:
4- NIAX Polyol HPP - 520 from Union Carbids Corp.
5- THANOL SF 265 from Texaco Corp.
6- POLY-G 37-600 from Olin Corp.
*-foaming occured 11- ~.3~7093 Example 3: The following formulations are prepared by charging the polyol blend ingredients into a Hobart blender and mixing at low speed for ten minutes. Formulations containing calcium stearate are prepared by mixing the amine-based triol, molecular sieve paste and calcium stearate in the Hobart blender for twenty minutes at low speed to disperse the stearate and then adding the remaining ingredients and mixing for an additional ten minutes at low speed. The castings are prepared by weighing filler and polyol blend to 100 grams in a container and mixing for two minutes or until the filler(s) is wet out, adding the indicated amount of isocyanate, mixing for approximately two minutes, casting a 1.3 cm x 1.3 cm x 26.7 cm bar, retaining the-bar for 20-24 hours at room temperature and post-curing/annealing for 20 hours at 130C. The sample size for testing is 0.64 cm x 1.14 cm x 10.2 cm. Test procedures are described in Example 1.
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In summary, this invention provides novel improved polyurethane systemsfor use as modeling stock. Variations may be made in procedures, propor-tions and materials without departing from the scope of the invention as defined by the following claims.
*-foaming occured 11- ~.3~7093 Example 3: The following formulations are prepared by charging the polyol blend ingredients into a Hobart blender and mixing at low speed for ten minutes. Formulations containing calcium stearate are prepared by mixing the amine-based triol, molecular sieve paste and calcium stearate in the Hobart blender for twenty minutes at low speed to disperse the stearate and then adding the remaining ingredients and mixing for an additional ten minutes at low speed. The castings are prepared by weighing filler and polyol blend to 100 grams in a container and mixing for two minutes or until the filler(s) is wet out, adding the indicated amount of isocyanate, mixing for approximately two minutes, casting a 1.3 cm x 1.3 cm x 26.7 cm bar, retaining the-bar for 20-24 hours at room temperature and post-curing/annealing for 20 hours at 130C. The sample size for testing is 0.64 cm x 1.14 cm x 10.2 cm. Test procedures are described in Example 1.
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In summary, this invention provides novel improved polyurethane systemsfor use as modeling stock. Variations may be made in procedures, propor-tions and materials without departing from the scope of the invention as defined by the following claims.
Claims (10)
1. A curable polyurethane composition comprising a blend of (a) from 30-55 % of a polymeric isocyanate, (b) from 9-35 % of an amine-based polyol, (c) from 5-40 % of a polyether triol, (d) from 3-10 % of a molecular sieve and (e) from 10-40 % of a hollow microsphere filler, all percentages being by weight of the total composition.
2. The composition of claim 1, wherein component (a) is present in a concentration of from 40-45 %, component (b) from 15-30 %, component (c) from 5-20 %, component (d) from 5-8 %, and component (e) from 10-20 %, all percentages being by weight of the total composition.
3. The composition of claim 1, wherein component (a) is a polymethylene polyphenyl isocyanate.
4. The composition of claim 1, wherein component (b) is an amine-based triol.
5. The composition of claim 1, wherein component (c) is an aliphatic alkylene glycol polymer having an alkylene unit of at least two carbon atoms.
6. The composition of claim 1, wherein component (e) is hollow glass microspheres having a diameter of from 5-250 micrometers.
7. The composition of claim 1, which also contains at least one other filler selected from the group consisting of calcium carbonate, mica, glass fibers, silica-alumina ceramic alloy, hydrated alumina silicate, calcium sulfate, talc and solid microspheres.
8. The composition of claim 7, wherein said at least one other filler replaces up to 85 %, by weight, of the hollow microsphere content.
9. A shaped article comprising the polyurethane composition of claim 1 subsequent to the curing thereof.
10. The article of claim 9 having a glass transition temperature over 100°C coupled with a coefficient of thermal linear expansion of less than70 x 10-6 cm/cm/°C in the -30- 30°C range and of less than 80 x 10-6 cm/cm/°C in the 25-100°C range.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US190,796 | 1988-05-06 | ||
| US07/190,796 US4916173A (en) | 1988-05-06 | 1988-05-06 | Polyurethane syntactic foam modeling stock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1327093C true CA1327093C (en) | 1994-02-15 |
Family
ID=22702816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000598699A Expired - Fee Related CA1327093C (en) | 1988-05-06 | 1989-05-04 | Polyurethane syntactic foam modeling stock |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4916173A (en) |
| EP (1) | EP0341210B1 (en) |
| JP (1) | JPH01318067A (en) |
| CA (1) | CA1327093C (en) |
| DE (1) | DE68904590T2 (en) |
| ES (1) | ES2054083T3 (en) |
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| US4526906A (en) * | 1983-09-06 | 1985-07-02 | Wegner Development Company | Non-burning, non-dripping instant set microcellular polyurethanes |
| US4528305A (en) * | 1984-04-13 | 1985-07-09 | Ciba-Geigy Corporation | Epoxy resin modeling stock |
| US4518718A (en) * | 1984-05-18 | 1985-05-21 | The United States Of America As Represented By The United States Department Of Energy | Rigid zeolite containing polyurethane foams |
-
1988
- 1988-05-06 US US07/190,796 patent/US4916173A/en not_active Expired - Lifetime
-
1989
- 1989-04-27 ES ES89810318T patent/ES2054083T3/en not_active Expired - Lifetime
- 1989-04-27 EP EP89810318A patent/EP0341210B1/en not_active Expired - Lifetime
- 1989-04-27 DE DE8989810318T patent/DE68904590T2/en not_active Expired - Fee Related
- 1989-05-04 CA CA000598699A patent/CA1327093C/en not_active Expired - Fee Related
- 1989-05-06 JP JP1113994A patent/JPH01318067A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4916173A (en) | 1990-04-10 |
| ES2054083T3 (en) | 1994-08-01 |
| DE68904590T2 (en) | 1993-07-29 |
| EP0341210B1 (en) | 1993-01-27 |
| EP0341210A1 (en) | 1989-11-08 |
| JPH01318067A (en) | 1989-12-22 |
| DE68904590D1 (en) | 1993-03-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |