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
  • C08G18/28—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
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—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
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
• • 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
  • C08G18/6552—Compounds of group C08G18/63
  • C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6564—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
• • 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
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0033—Foam properties having integral skins
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/0066—≥ 150kg/m3
• • 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
  • C08G2410/00—Soles
• • 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

Definitions

• This invention relates to the manufacture of microcellular polyurethane elastomers having wide applicability in the footwear and automotive industries.
• Polyurethane microcellular elastomers are employed in a wide number of end use applications as in the shoe and automotive industries, for example, in the manufacture of shoe soles, bumpers for automotive applications, arm rests of integral skin foams, and the like. In a number of applications a proper balance of physical properties is required in order to achieve optimum results for the intended commercial use.
• microcellular urethane elastomers from polyether polyols and prepolymers from 4,4' -diphenylmethane diisocyanate (4,4'-MDl) is well known in the art.
• the reason such elastomer products are not made by means of the "one-shot" process is due to the fact that the isocyanate reactant, 4,4'-MDI, is not readily miscible in the polyether polyol/glycol chain extender/blowing agent mixtures commonly employed.
• pure 4,4'-MDI has a melting point of approximately 40°C., and at such temperatures the handling of these materials becomes difficult in many of the end use applications illustrated above.
• Typical polyisocyanate products that f ind wide us e in the ab oves aid f ie lds are the quas i-prepolymers from di(propylene glycol) or dipropylene glycol/tripropylene glycol mixtures and 4,4'-diphenylmethane diisocyanate having equivalent weights of about 180-185.
• These quasi-prepolymers find extensive use in footwear and automotive applications, but they suffer from the above-mentioned drawbacks inasmuch as their melting points are approximately 17o-25°G., where they exhibit a tendency for dimer and trimer formation.
• the high NCO equivalent weights of the polyisocyanate component requires that the "resin" component be a polyol blend comprising high levels of chain extender, e.g., ethylene glycol or 1, 4-butanediol.
• chain extender e.g., ethylene glycol or 1, 4-butanediol.
• the required resin blend of polyether polyol/chain extender/ fluorocarbon blowing agent generally becomes quite incompatible thereby imposing significant processing problems and limitations on such systems.
• the invention provides for improved integral skin microcellular polyether polyurethane elastomers of a wide specific gravity range, e.g., about 0.4 gm/cm 3 to about 0.7 gm/cm 3 , which are characterized by a combination of properties such as Shore A hardness and compression modulus values, tensile and tear strengths as well as resiliency or rebound of the skin as well as core portions of said elastomers that significantly exceed the same combination of properties found in conventional integral skin microcellular polyether polyurethane elastomers of equivalent specific gravity.
• improved integral skin microcellular polyether polyurethane elastomers of relatively low specific gravities can be prepared which are characterized by a combination of physical and mechanical properties, e.g., tensile strength and elongation, Die C tear and split tear, dynamic flex properties at room temperature and at low temperatures, Shore A skin and core hardness, load bearing performance, heat resistance, as well as oil resistance which are substantially equivalent or even better to the same combination of properties characterizing the conventional integral skin microcellular polyether elastomers of higher specific gravities.
• This latter discovery affords marked economic advantages since the raw material requirements to produce the improved elastomers can be as much as 20-30 percent lower than the conventional elastomers, the combination of properties of both types of elastomers being approximately equivalent.
• integral skin microcellular polyether polyurethane elastomers which exhibit a combination of outstanding low temperature dynamic flex properties and green strength at the time of demold, at s pe c i f i c gravities approximating 0.4-0.5 gm/cm 3 , and higher, which properties heretofore have not been attainable in integral skin polyurethane elastomers from comparable conventional polyether polyol systems.
• green strength denotes the basic integrity and strength of the polyurethane polymer at demold.
• the polymer skin of a molded item should possess sufficient tensile modulus and elongation and tear strength to survive a 90 to 180 degree bend without exhibiting surface cracks.
• the prior art processes oftentimes require 3-4 minutes minimum demold times to attain this characteristic.
• the novel multi-component systems provide up to 150 seconds improvement in minimum demold times. That is to say, demold times of about 1.5 to about 2.5 minutes are achievable while providing integral skin microcellular products having outstanding low temperature dynamic flex and green strength characteristics.
• isocyanate index is the quotient obtained by dividing the equivalents of NCO by the sum of the equivalents of active hydrogen group(s), multiplied by 100. In the practice of the present inventions the isocyanate index is expressed as a number approximating 100 as will be developed hereinafter.
• the outstanding properties characterizing the microcellular polyether elastomers of the invention can be achieved using multi-component systems, e.g., two and three component systems, over a surprisingly wide isocyanate index range of from ab out 94 t o ab ou t 105 , and desirably from 97 to 103.
• variations outside the conventional narrow index range during manufacturing operations can result in higher reject rates (of molded product), lower production, and product of poor quality and inferior properties.
• the systems of the present invention are characterized by their ability to offer the fabricator greater process latitude during manufacturing operations by virtue of their broad isocyanate index range.
• a still further object is to provide unique microcellular polyether polyurethane elastomers which are characterized by a combination of mechanical properties such as spit tear, tensile and ultimate elongation which exceed, measured at equivalent densities and manufactured at equivalent NCO indices, the mechanical properties of conventional microcellular polyether polyurethane elas tomers.
• a still further object of the invention is to provide unique integral skin microcellular polyether elastomers of low density, characterized by a combination of the above- said mechanical properties, which approximate or exceed the comparable properties of conventional integral skin microcellular polyether elastomers having significantly higher densities, e.g., of the order of 20-30% higher density values.
• a yet further object of the invention is to provide integral skin microcellular polyether polyurethane elastomers of specific densities below 0.55 gm/c ⁇ w. desirably from about 0.5 to about 0.4 gm/cma 3 , and perhaps slightly lower, which are void of sink marks (shrinkage) and inferior skin surface which often characterize conventional microcellular polyether polyurethane elastomers of equivalent specific densities.
• microcellular polyether polyurethane elastomers such as molded integral skin articles, e.g., unit (shoe) soles, characterized by specific gravities in the range approximating 0.4 to about 0.7 gm/cm 3 and a favorable combination of properties as aforesaid (compared with conventional elastomers of equivalent specific gravities heretofore produced in the industry) can be prepared by reacting (a) unique, normally-liquid quasi- polyether prepolymers, (b) an ethylene oxide capped polyether polyol, (c) a chain extender, (d) blowing agent(s), (e) in the presence of polymer particles that are stably dispersed in said polyether polyol (b) above or in said quasi-polyether prepolymer (a) above or in both (b) and (a), desirably in the presence of a catalyst and cell regulating agent and o p t iona l ly , known
• the polyisocyanates used in the preparation of the unique normally-liquid quasi-polyether prepolymers preferably are a mixture of (a) a normally-solid diphenylmethane diisocyanate (MDX), in particular 4,4'-and/or 2,4'-diphenylmethane diisocyanate which are solid at room temperature plus minor quantities of (b) the carbodiimide of MDI, or the carbodiimide of tolylene diisocyanate (TDl), and/or mixtures thereof, and/or (c) the corresponding uretone imine t r i i s o c graphical t e of MDI, or the corresponding uretone imine triisocyanate of TDI, and/or mixtures thereof.
• MDX normally-solid diphenylmethane diisocyanate
• TDl carbodiimide of tolylene diisocyanate
• mixtures thereof preferably are a mixture of (a) a normally-solid di
• Suitable polymer dispersion include the polymer/polyether polyols such as described in U.S. Patent Nos. 3,304,273 and 3,383,351 to S t amb erger and in U.S. Pat. No.
• polymer/quasi-polyether prepolymers obtained by the reaction of polymer/polyether polyols with the above polyisocyanate mixture comprising the isocyanate compound, carbodiimide and/or uretone imine; or the polymer / quasi-polyether prepolymers resulting from the reaction of a polymer dispersion in said polyisocyanate mixture with normal polyether polyols and/or polymer/ polyether polyols following the procedures of U.S. 4,283,500 to Armstrong et al.
• normal polyether polyols indicates that such polyols do not contain particles of polymer dispersed therein.
• polymer/polyether polyol refers to a stable dispersion of polymer in the polyether polyol. Compatible mixtures of normal polyether polyols, of polymer/polyether polyols, and of both types of polyols are included within the scope of the invention.
• the polyether polyol(s) can be termed a poly (oxyethyleneoxypropylene) polyol (s) which is discussed and characterized in greater detail at a later section.
• the invention in a preferred form, provides for improved integral skin microcellular polyether polyurethane elastomers with specific gravities of from about 0.4 to 0.7 gm/cm 3 '
• Such elastomers are obtained by reacting a formulation comprising: (a) liquid quasi-polyoxyethyleneoxypropylene prepolymers having a crystalline point below about 13°C, desirably below about 10°C., preferably below about 5°C., and generally no lower than about -20°C., which result from the reaction of (1) a mixture consisting essentially of (i) a normally-solid (at room temperature) diphenylmethane diisocyanate, preferably 4,4'- and 2,4'-diphenylmethane diisocyanate, with small amounts of (ii) the carbodiimide of diphenylmethane diisocyanate, or the carbodiimide of tolylene diisocyanate, and/or mixtures thereof, and (iii) the corresponding
• molded integral skin microcellular polyether elastomer products such as shoe soles, automotive arm rests, etc., prepared from novel multi- component systems in which a stably dispersed polymer content as low as 1 to 2% by weight, based on the total weight of the system, results in a favorable and improved combination of mechanical strength properties, such as compression modulus, tensile, tear strength, and/or abrasion resistance and the like.
• a practical upper limit of polymer content in the system takes into consideration the viscosity and its effect on mixing prior to introduction into the mold, phase separation due to incompatibility, and other factors.
• a suitable upper limit may well be as high as 20-25% by weight, and even higher, based on the weight of the system.
• systems having a polymer content in the range of about 2-3% to about 15-18% by weight generally embraces the integral skin elastomers which are characterized by the improved physical and mechanical properties discussed herein.
• improved integral skin microcellular polyether polyurethane elastomer articles e.g., shoe soles, having specific gravities of from about 0.7 to about 0.4 gm/cm 3 , preferably below 0.55 gm/cm 3 , and preferably still from about 0.5 to about 0.4, and slightly lower, which are characterized inter alia by Shore A hardness values of about 50 to about 90, outstanding low temperature dynamic flexural properties (measured by Ross Flex, for example, at -18°C), excellent green strength, as well as a favorable combination of other mechanical properties, can be produced by reacting a formulation comprising:
• liquid quasi-polyoxyethyleneoxypropylene prepolymers having an NCO equivalent weight in the range of from about 200 to 280 prepared by reacting a mixture of (i) normally solid 4,4'- and/or 2,4'- and/or 2,2'- and/or 4,2'-diphenylmethane diisocyanate (MDl) and (ii) an equil-ibrium mixture of the diisocyanate carbodiimide of MDI and the triisocyanato uretone imine of MDI, said mixture having an NCO equivalent weight in the range of from an NCO equivalent weight of from 125.5 to 137, preferably from about 126 to 135, preferably still from 126-127 to about 130-132; with (ii) an ethylene oxide capped polyol of the group consisting of poly(oxyethyleneoxypropylene) polyols and polymer/poly(oxyethyleneoxypropylene) polyols and mixtures thereof having the characteristics described previously;
• reaction taking place in the presence of a halocarbon blowing agent and at an NCO index number in the range of from 94 to 104; and preferably
• the polymer content being upwards to about 20% by weight, suitably about 2-3 to about 15-18% by weight, based on the weight of the system.
• water as a secondary blowing agent does not circumvent shrinkage of conventional integral skin microcellular polyether polyurethanes in the density range of 0.4 up to about 0.55 gm/cm 3 .
• the utilization of water as a secondary blowing agent oftentimes also results in cream lines visible on the molded part. Such lines make painting of the part difficult and are objectionable.
• improved integral skin mic ro ce l lul ar polyether elastomers can be manufactured from systems in which blowing is effected without the use of water as a secondary blowing agent, i.e., blowing is preferably effected with halo carbons, as will be discussed hereinafter.
• the resulting improved integral skin elastomer products have specific gravities as low as about 0.4 gm/cm 3 and upwards to about 0.7gm/cm 3 , preferably below 0.55 to about 0.4 gm/cm 3 , and exhibit an excellent smooth surface appearance essentially devoid of blemishes and extremely suitable for painting and lacquering.
• the invention in further preferred aspects, utilizes novel normally-liquid quasi-polyether prepolymers having a crystalline point below about 13°C., desirably below about 10oC, preferably below about 5°C., and generally no lower than about -20°C, in the preparation of the novel integral skin microcellular polyether polyurethanes, said quasi-polyether prepolymers being prepared by reacting (1) a mixture consisting essentially of (i) a normally-solid (at room temperature) diphenylmethane diisocyanate, preferably 4,4'- and 2,4'-diphenylmethane diisocyanate, and (ii) the carbodiimide of diphenylmethane diisocyanate or the carbodiimide of tolylene diisocyanate or mixtures thereof, and/or (iii) the corresponding triisocyanato uretone imine of diphenylmethane diisocyanate or the corresponding triisocyanato uretone imine of to
• the carbodiimide of MDI can be represented by the formula:
• Normally solid, relatively high purity 4,4'-MDI e.g., purity of about 90% by weight and upwards to 97-98% by weight, and higher
• a minor quantity of the above-described carbodiimide(s) and/or corresponding uretone imine(s) suitably an equilibrium mixture of the carbodiimide and the ure tone imine, can be characterized by their NCO equivalent weight.
• Suitable mixtures consisting essentially of normally solid, relatively pure 4,4'-MDI, the corresponding carbodiimide of 4,4'-MDI and/or corresponding uretone imine of 4,4'-MDI, desirably possess an NCO equivalent weight of from 125.5 and upwards to 137, preferably from about 126 to 135, preferably still from 126-127 to about 130-132.
• TDI diisocyanato carbodiimide of TDI and/or the triisocyanato uretone imine of TDI.
• relatively minor amounts of TDI in a virtually inert medium of diphenylmethane diisocyanate can be selectively converted to the carbodiimide of TDI and/or uretone imine of TDI by the catalytic process described in U.S. Pat. No. 4,294,719 to Wagner et al whereby there is obtained a liquid mixture of MDI and the diisocyanato carbodiimide and/or triisocyanato uretone imine of TDI.
• Mixtures of 4,4'-MDI and small quantities of carbodiimide of TDI and/or uretone imine of TDI which are highly desirable in the practice of various embodiments of the invention are characterized by an NCO equivalent weight in the range of from about 125.5 to about 132, preferably from about 126 to about 129-130.
• capped polyols which have a relatively high percentage of primary hydroxyl groups, e.g., greater than 50-60% primary hydroxyl and upwards to 90%, preferably at least about 75%, as the polyol ingredient of the polyol resin as well as in the preparation of the novel quasi-prepolymers.
• ethylene oxide As a cap for the poly ( oxyethyleneoxypropylene)- polyol.
• ethylene oxide There is a useful upper limit since the formation of stable polymer/polyols with relatively high ethylene oxide caps may prove commercially difficult to prepare. A cap of about 25-30% ethylene oxide is therefore believed to be a practical upper limit.
• the ethylene oxide cap represents about 10-15 to about 20-25% by weight of the capped polyol.
• the internal distribution of ethylene oxide in the polyol chain generally can range from 0% by weight to about 40% by weight of the capped polyol. In general, the total ethylene oxide content does not exceed 50% by weight based on the weight of the polyol.
• the remainder of the capped polyol consists essentially of oxypropylene.
• the portion of internal ethylene oxide may be randomly located in the polymer chain or it may be present as one or more blocks. It is preferred that any internal ethyleneoxy groups be distributed in random fashion in the chain.
• the preparation of the normal polyether polyols can be carried out in accordance with well-known techniques comprising the reaction of the polyhydric starter being employed and the propylene and ethylene oxides in the presence of an oxyalkylation catalyst.
• the catalyst is an alkali metal hydroxide such as, for example, potassium hydroxide.
• the oxyalkylation of the polyhydric initiator may be carried out at temperatures ranging from about 90°C to about 150°C and usually at an elevated pressure up to about 200 p.s.i.g., employing sufficient amounts of the propylene and ethylene oxides and adequate reaction time to obtain a polyol of the desired molecular weight which is conveniently followed during the course of the reaction by standard hydroxyl number determinations.
• the ethylene and/or propylene oxide reactants may be fed to the reaction system sequentially to provide chains containing respective blocks of the different oxyalkylene units or they may be fed simultaneously to provide substantially random distribution followed by appropriate capping with ethylene oxide.
• any suitable dihydric and/or trihydric initiator(s) may be employed.
• diols propylene glycol, water, ethylene glycol, 1,3-propanediol, dipropylene glycol, diethylene glycol, 1,4-butanedio l , neopentyl glyco l , ani l ine , te trahydro furan , N-methyldiethanolamine, or the like can be utilized.
• triols glycerine, trimethylolpropane, triethanolamine, trimethylolethane, 1,2,6-hexanetriol, or the like may advantageously be employed.
• Other useful initiators are well-known in the art.
• polymer/polyols which are useful in the preparation of the novel normally-liquid quasi-prepolymers and preferred as reactants in the preparation of the improved integral skin microcellular elastomer products are well known in the art and commercially available.
• the polymer/polyols may be prepared by polymerizing a vinyl monomer or monomers in situ in the normal ethylene oxide capped polyols. Any vinyl monomer may be used, and useful monomers are described in various prior patents, including U.S. Patent Nos. 3,304,273 and 3,383,351 to Stamberger, the disclosures of which are incorporated by reference as if set out in full text herein.
• acrylonitrile with or without a comonomer (s), e.g., methyl methacrylate, vinyl acetate, ethy l acrylate , etc .
• polymer/polyols which are suitable in the practice of the invention(s) include stable dispersions of polyureas and polyhydrazodicarbonamides in the ethylene oxide capped polyether polyol medium. These polymer/polyols products, as indicated previously, are obtained by the polyaddition of isocyanate compounds with polyamines, hydrazines and/or hydrazides in the abovesaid normal polyol medium.
• the isocyanate compounds can be monoisocyanates or polyisocyanates and include acyclic, alicyclic, aromatic and heterocyclic isocyanates. Polyisocyanates are preferred.
• Illustrative isocyanate compounds include 2,4- and 2,6-tolylene diisocyanate (preferred), 1,3- and 1,4-phenylene diisocyanate, 4,4'- and/or 2,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, phenyl isocyanate and the like.
• Suitable polyamines include the polyvalent primary and/or secondary acyclic, alicyclic or aromatic amines such as ethy lenediamine, propylenediamine, triethylenediamine, piperazine and the like.
• Illustrative hydrazines and hydrazides include hydrazine (preferred), hydrazine hydrate (preferred), methylhydrazine, dihydrazide, semicarbazide and the like.
• hydrazine hydrazine
• hydrazine hydrate hydrazine hydrate
• methylhydrazine dihydrazide
• semicarbazide a commercially available.
• U.S. Patent No. 4,042,537 to Dahm which exemplifies this technology is incorporated by reference into this specification as if set out in full text herein.
• Liquid ethylene oxide capped polyols used as a reactant in the fabrication of the integral skin elastomer products are characterized by a hydroxyl equivalent we ight o f about 750 to about 3000 , preferably from about 850 to about 2500, and preferably still from about 1000 to about 2250; and a hydroxyl functionality of 2 to 3, preferably from about 2.1-2.2 to about 2.8-3.0, and preferably still from about 2.3-2.5 to about 2.7-3.0.
• the polymer/polyol may be blended with the normal polyol to reduce the polymer content to a desired level. Blending may be feasible when relatively low amounts of polymer content are desired due to the economic penalty involved in forming polymer/polyols with such relatively low polymer content initially. It should be noted, however, that the normal polyol used for blending may effect polymer stability; it will be desirable, therefore, to select the polyol to avoid this disadvantage.
• the manufacture of shoe soles of relatively high Shore A hardness can generally be obtained by introducing sufficient hard segments into the microcellular elastomer. This may be accomplished by increasing the amount of chain extender, e.g., ethylene glycol or 1,4-butanediol, in the resin.
• chain extender e.g., ethylene glycol or 1,4-butanediol
• the increase in the Shore A hardness property generally results in a decrease in low temperature flexibility and cut growth resistance of the elastomer.
• the decrease in these physical properties appears to be attributable to a decrease in the percentage of relatively long chain (soft) segments in the elastomer.
• Another disadvantage becomes apparent since compatibility of the polyol/chain extender mixture in the resin decreases with increasing amounts of the short chain extender.
• Package A contains the novel quasi-poly(oxyethyleneoxypropylene) prepolymer and Package B comprises a compatible mixture of poly(oxyethyleneoxypropylene) polyol, a difunctional chain extender, and a halogenated hydrocarbon blowing agent, with the following provisos: (1) the poly(oxyethyleneoxypropylene) segment of the quasi-prepolymer (Package A) is derived from a normal ethylene oxide capped polyol and/or a polymer/ethylene oxide capped polyol; (2) the poly (oxyethyleneoxypropylene) polyol (Package B) is a normal ethylene oxide capped polyol and/or a polymer/ethylene oxide capped polyol; and preferably (3) the total polymer content of said multi-component system contains upwards to about 20-25% by weight of stably dispersed polymer, based on the weight of the system, suitably upwards to about 30-35% by weight of polymer
• Polyfunctional chain extenders characterized by hydroxyl groups and/or amino groups which contain amino hydrogen atoms are especially useful in the practice of the invention and include the glycols, amino alcohols, and diamines.
• Typical glycols are illustrated by the alkanediols of the formula HO (CH 2 ) n OH, wherein n is 2 to 10 or more, e.g., ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, and the like.
• glycols that are suitable include diethylene glycol, thiodiglycol, triethylene glycol, tetraethylene glycol, p-xylylenediol, quinitol, neopentylene glycol, dihydroxyethylhydroquinone, and mixtures thereof, and the like. It is also possible to use glycols characterized by hetero atoms such as nitrogen and/or sulfur; double bonds; and bromine or other halogen atoms.
• N-methyldiethanolamine N-t-butyl ⁇ diethanolamine, di-beta-hydroxyethylaniline, triisopro ⁇ panolamine, di-beta-hydroxyethyl sulfide, 2-butene-1,4-diol, 2,3-dibromo-1,4-butanediol, di-beta-hydroxyethylurea, and di-beta-hydroxyethyl urethane.
• tertiary amines such as bis (dimethylaminoethyl) ether
• tertiary phosphines such as trialkylphosphines, dialkylbenzylphosphines, and the like;
• (e) chelates of various metals such as those which can be obtained from acetylacetone, benzoylace tone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetone-imine, bis- acetylacetonealkylenediimines, salicyaldehydeimine, and the like, with various metals such as Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or such ions as MoO 2 ++, UO 2 ++, and the like;
• salts of organic acids with a variety of metals such as alkali metals, alkaline earth metals, Al , Sn, Pb , Mn , Co, Ni, and Cu, including, for example, sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannous oleate, lead octoate, metallic driers such as manganese and cobalt naphthenate, and the like;
• dialkyltin salts of carboxylic acids e.g., dibutyltin diacetate, dibutyltin dilaurate, dibuty l t in maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-bis(6-methylaminocaproate), and the like.
• Dialkyltin mercaptides may also be utilized.
• a trialkyltin hydroxide dialkyltin oxide, dialkyltin dialkoxide, or dialkyltin dichloride.
• the tertiary amines may be used as primary catalysts for accelerating the reactive hydrogen/isocyanate reaction or as secondary catalysts in combination with one or more of the above noted metal catalysts.
• Metal catalysts, or combinations of metal catalysts, may also be employed as the accelerating agents, without the use of amines.
• the catalysts are employed in catalytically significant quantities, for example, from about 0.001 percent to about 2 percent, based on weight of the reaction mixture.
• Blowing agents which can be utilized to prepare the microcellular elastomers of the present invention include the halogenated hydrocarbons, in particular, the fluorocarbons such as trichlorofluoromethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trifluoro-1,2,2-trichloroethane, difluorodichloromethane, and mixtures of the same and other halogenated hydrocarbons. It is also feasible to use mixtures of low boiling hydrocarbons, ethers, and ketones with halogenated hydrocarbons. Additional blowing agents are well known in the art.
• blowing is effected in the absence of water as a secondary blowing agent and preferably in the presence of a halocarbon as a primary blowing agent thereby obtaining the advantages noted previously, e.g., integral skin microcellular polyether elastomer products exhibiting an excellent smooth surface, essentially devoid of blemishes, and extremely suitable for painting and lacquering.
• a very small amount of water as a secondary blowing agent may be tolerated in the system, particularly in the manufacture of integral skin microcellular polyether elastomers of high specific gravities, if so desired.
• additives which may be used include surface active agents, cell regulating agents, stabilizers, dyes, and the like.
• Suitable eraulsifiers include the sodium salts of castor oil sulphonates or salts of fatty acids with amines, such as diethylamine oleate or diethanolamine stearate.
• Alkali metal or ammonium salts of sulphonic acids for example, of dodecy lbenzenesulphonic acid or dinaphthylmethanedisulphonic acid, or of fatty acids, such as ricinoleic acid or of polymeric fatty acids, may also be used as surface active additives.
• Suitable foam stabilizers include polyether siloxanes, especially those which are water-soluble. These compounds are generally synthesized in such a way that a copolymer of ethylene oxide and propylene oxide is attached to a polydimethylsiloxane radical. Foam stabilizers of this type are described, for example, in U.S. Pat. Nos. 2,834,748; 2,917,480; and 2,629,308.
• Cell regulating agents which are useful include the polydimethylsiloxanes having viscosities of from about 2 to about 100 centistokes at 25°C; polyphenylmethylsiloxanes like the products described in U.S. Pat. No. 4,042,537; mineral oils, polyether polyols comprising copolymers and block copolymers of ethylene and propylene oxides; and the like.
• Such polyether polyols can be linear or branched copolymers and block copolymers having molecular weights of, for example, from 1000 or lower to 6000 or higher.
• the preferred polyether polyols are linear copolymers and block copolymers having molecular weights of from about 2000 to about 3500. They can be utilized in proportions from 1 to as high as 20 parts per 100 parts of the polyol.
• Preferred cell regulating agents are the polydimethyls iloxanes having viscosities of from about 5 to about 20 centistokes at 25°C.
• these products include DC 200 fluids (available from Dow Corning Corporation), having viscosities of from about 5 to about 100 centistokes at 25°C, and also Dow Corning Fluid DCF-1-1630, having a viscosity of about 3.5 centistokes at 25oC. (the viscosity being an indicator of the molecular weight of these silicon fluids).
• DC 200 fluid 5 cs has a molecular weight of 680, 10 cs oil corresonds to 1000, 20 cs to 1600, 50 cs to 3200, and 100 cs to 5000 molecular weight.
• integral skin microcellular polyether elastomer articles such as shoe soles
• an aspect which is highly preferred, either of two commonly employed sole making processes are satisfactory.
• the left and right foot soles are cast as unit soles, removed from the cast, and then attached to the shoe uppers by a suitable adhesive.
• the shoe uppers i.e., left and right foot
• the formulation is injected into the mold cavity defined by the shoe uppers and the mold walls.
• the multi-package system is employed.
• Package A contains the unique normally-liquid quasi-polyether prepolymer and Package B contains a compatible blend of polyether polyol, chain extender, blowing agent, and optionally other additives.
• a further Package C may contain such additives as pigments, cell regulating agent, plasticizer, etc., as in a three package system.
• the shoe manufacturer does the actual metering, mixing and dispensing of the materials on the premises, the multi-package system, tailored to meet the manufacturer's requirements, is oftentimes purchased by the manufacturer of finished unit soles and/or shoes from the systems supplier.
• novel integral skin microcellular poly(oxyethyleneoxypropylene) polyurethane elastomer products in a preferred form, (a) consist essentially of divalent diphenylenemethane groups interconnected with divalent and trivalent oxyethyleneoxypropylene groups through urethane
• divalent extender groups consisting essentially of 2-6 carbon atoms and hydrogen atoms and optionally 1-2 oxy(-O-) atoms and/or 1-2 amino nitrogen atoms, said divalent extender groups being connected to said divalent diphenylenemethane groups
• urethane linkages and/or ureylene (-NHCNH-) linkages and characterized by the following properties: (b) a density below 0.55 gm/cc, preferably from about 0.4 to 0.55 gm/cc, and preferably still from about 0.4 to about 0.5 gm/cc; (c) Shore A hardness of from 50-90, preferably from about 50-85, preferably still from about 55-85, ASTM-2230; (d) 0% cutgrowth (-20°C) at 10 3 x 100 cycles, ASTM-1052; (e) excellent green strength at a demold time of 2.5 minutes characterized in that said integral skin microcellular product in the form of a 6" x 8" x 0.25" molded plaque is capable of withstanding a 180 degree bend without development of visual surface cracks at the bend of said plaque; (f) Tabor ab ras ion loss at 5000 cycles of less than about 500 mg, preferably less than about 350 mg, and preferably s t i
• Highly desirable divalent extender groups which characterize the novel integral skin elastomer products include the C 2 -C 6 alkylenes, in particular, the -CH 2 CH 2 - and -CH 2 CH 2 CH 2 CH 2 - groups; the C 2 -C 6 oxaalkylenes such as the -C 2 H 4 OC 2 H 4 - group; and the azaC 2 -C 6 alkylenes such as -CH 2 CH 2 N-, and the like.
• a specimen of the novel integral skin microcellular elastomer in the shape of a disc (4 1/2" in diameter and 1/4" or 1/2" thickness) is first conditioned (pre-abraded) for 1000 cycles at room temperature using Wheel H-22.
• the specimen is then cleaned of abraded particles, weighed, again subjected to abrasion for 5000 cycles at room temperature using Wheel H-22.
• the abraded material is weighed and expressed as milligrams (mg) of specimen loss through the abrasion operation.
• the cycle speed of the wheel is 70 1 revolutions per minute.
• a vertical force or weight of 1000 grams is imposed on the arm of the abrader. Hardness;
• Hand foams are prepared by weighing all the ingredients of the polyol component (e.g., polyol(s), extender(s), surfactant(s), catalyst(s), blowing agent(s), etc.) as required, into a polyethylene lined paper cup. These ingredients are then mixed well. The required amount of quasi-prepolymer is then added into the polyol component and mixed at high speed for 8 to 10 seconds. The mixture is then cast into a clean cup or a mold as required.
• the polyol component e.g., polyol(s), extender(s), surfactant(s), catalyst(s), blowing agent(s), etc.
• Cream Time The time interval between the final mixing and the point at which the mixture turns creamy or cloudy and starts to expand.
• Rise Time The time interval between the liquid mixture poured into the container (mold) and the completion of expansion of the foaming mass.
• Tack Free The time interval between pouring the Time: liquid mixture and the time that the surface of the foam can be touched with a finger without sticking. Snap Time: When the reacted polymer can no longer be separated when pinched between two fingers and pulled.
• Free Blowing The density in lbs./ft. 3 of a foam that Density: is allowed to rise in an open cup and is determined by cutting the cap of the foam flush with top of the cup and using the following equation:
• Isocyanate A high-purity grade of diphenylmethane diisocyanate containing approximately 98% 4,4'-diphenylmethane diisocyanate and 2% 2,4'-diphenylmethane diisocyanate. The average isocyanate equivalent weight is 125.
• NIAX POLYOL UNION CARBIDE CORPORATION 12-56 A poly (oxypropyleneoxye thylene) glycol having a molecular weight of about 2000, a hydroxyl equivalent weight of about 1000, an average hydroxyl number of 56, and an ethylene oxide content of about 30% by weight. The ethyleneoxy units are predominantly end-capped.
• NIAX POLYOL UNION CARBIDE CORPORATION E-351 A poly(oxypropyleneoxyethylene) glycol having a molecular weight of about 2800, an ethyleneoxy end cap of about 15% by weight, an average hydroxyl number of 40, and a hydroxyl equivalent weight of about 1400.
• NIAX POLYOL UNION CARBIDE CORPORATION 24-32 A polymer polyol comprising about
• This polymer diol has a molecular weight of about 3500, a hydroxyl equivalent weight of about 1750, and an average hydroxyl number of 32.
• NIAX POLYOL UNION CARBIDE CORPORATION 34-28 A polymer polyol comprising about
• a glycerine-started poly(oxypropyleneoxyethylene) triol having about 15% by weight ethyleneoxy end caps, an average hydroxyl number of 28, a hydroxyl equivalent weight of about 2000, and 10% by weight each, of styrene and acrylonitrile as a vinyl polymer thereof.
• a poly(oxypropyleneoxyethylene) glycol having a molecular weight of about 3000, an ethylene oxide content of about 50% by weight, a portion of the ethylene oxide therein copolymerized with propylene oxide, and the balance present as ethyleneoxy end caps, and possessing a hydroxyl equivalent weight of about 1500.
• a polymer polyol comprising about 80% by weight of a poly(oxypropyleneoxyethylene)triol having about 15% by weight ethyleneoxy end caps, and 20% by weight of a mixture of styrene and acrylonitrile as a vinyl polymer, and having a hydroxyl equivalent weight of about 2000.
• CARPOL 2040 CARPENTER CHEMICAL COMPANY A poly (oxypropyleneoxyethylene) diol having a molecular weight of about 2000, a hydroxyl equivalent weight of about 1000, and containing about 40% by weight of oxyethylene units. Said units are partially internal copolymers with oxypropylene units and partially oxyethylene end caps.
• CARPOL 2050 CARPENTER CHEMICAL COMPANY A poly(oxypropyleneoxyethylene) diol having a molecular weight of about 2000, a hydroxyl equivalent weight of about 1000, and containing about 50% by weight of oxyethylene units, said units are partially internal copolymers with oxypropylene units and partially oxyethylene end caps.
• L-5302 UNION CARBIDE CORPORATION Surfactant A polyoxyalkylene-polysiloxane surfactant having a specific gravity of 1.02 at 25/25°C, and a viscosity of 850 cs at 25oC.
• L-5303 UNION CARBIDE CORPORATION Surfactant A polyoxyethylene-polysiloxane surfactant having a specific gravity of 1.02 at 25/25°C, and a viscosity of 300 centistokes (cs) at 25°C.
• L-5305 UNION CARBIDE CORPORATION Surfactant A polyoxyethylene-polysiloxane surfactant having a specific gravity of 1.06 at 25/25°C, and a viscosity of 150 cs at 25°C.
• L-5307 UNION CARBIDE CORPORATION Surfactant A polyoxyethylene-polysiloxane surfactant having a specific gravity of 0.995 at 25/25°C, and a viscosity of 175 cs at 25°C.
• L-5309 UNION CARBIDE CORPORATION Surfactant A polyoxyethylene-polysiloxane surfactant having a specific gravity of 1.00 at 25/25°C, and a viscosity of 225 cs at 25°C. L-6202 UNION CARBIDE CORPORATION
• Surfactant A polyoxyethylene-polyoxypropylene- polydimethyls iloxane surfactant having a specific gravity of 1.03 at 25/25°C, and a viscosity of 1300 cs at 25°C. L-520 UNION CARBIDE CORPORATION
• Surfactant A poly(oxyethyleneoxypropylene)- polysiloxane surfactant having a specific gravity of 1.03 at 25/25°C, and a viscosity of 1100 cs at 25°C. L-540 UNION CARBIDE CORPORATION
• Surfactant A polyoxyethylene-polyoxypropylene- polydiraethylsiloxane surfactant having a specific gravity of 1.02 at 25/25°C, and a viscosity of 1200 cs at 25°C. L-548 UNION CARBIDE CORPORATION
• Surfactant A polyoxyethylene-polyoxypropylene- polydiraethylsiloxane surfactant having a specific gravity of 1.03 at 25/25°C, and a viscosity of 1250 cs at 25°C. L-550 UNION CARBIDE CORPORATION
• Surfactant A polyoxye thylene-polyoxypropylene- polydimethyls iloxane surfactant having a specific gravity of 1.03 at 25/25°C, and a viscosity of 1800 cs at 25°C. L-5710 UNION CARBIDE CORPORATION
• Surfactant A polyoxyethy lene-polyoxypropylene- polydimethyIs iloxane surfactant having a specific gravity of 1.040 at
• SURFACTANT DOW CORNING CORPORATION 191 A polyoxyalkylene-polysiloxane surfactant.
• SURFACTANT DOW CORNING CORPORATION 196 A polyoxyalkylene-polysiloxane surfactant.
• NIAX A-1 UNION CARBIDE CORPORATION Catalyst A liquid blend catalyst consisting of 70% by weight of bis(dimaethylaminoethyl) ether and 30% by weight dipropylene glycol.
• DMS A low molecular weight polydimethylsiloxane having a viscosity of 3.5 cs at 25°C, and a specific gravity of 0.916 at 25/25°C.
• FREON 11A E. I. duPONT deNEMOURS, INC. A stabilized version of trichlorofluorome thane.
• BROWN PIGMENT BI-ANGLE CHEMICAL CO., INC. About 40% by weight brown pigment in polyoxyalkylene ether polyol, further designated as Peanut 0-207-2BSP.
• PIGMENT WHITE PIGMENT DISPERSIONS, INC. 3100 A titanium dioxide pigment dispersed in a low molecular weight polyester diol (about 40% by weight solids).
• the following Examples are illustrative of the invention but are not to be construed as to limiting the scope thereof in any manner. In the specification, the following should be noted:
• Room temperature refers to a temperature of 20°C-23°C unless a different temperature is indicated.
• Percent refers to percent by weight unless indicated otherwise.
• Parts refers to parts by weight unless indicated otherwise.
• MDI refers to diphenylmethane diisocyanate.
• 4,4'- and/or 2,4'- and/or 2,2'- and/or 4,2'-MDI refers to 4,4'- and/or 2,4'- and/or 2,2'- and/or 4,2'-diphenylmethane diisocyanate.
• TDI refers to tolylene diisocyanate.
• 80/20 TDI refers to an isomeric mixture of 80 parts of 2,4-to lyl ene diisocyanate and 20 parts of 2,6-tolylene diisocyanate.
• PU Foam refers to polyurethane foam.
• NCO index refers to NCO index number.
• pli refers to pounds per linear inch.
• a compatible liquid polyol resin or “compatible liquid mixture of ingredients comprising the polyol resin”, or language indicating such text, shall mean that the polyol resin package which includes the polyol, chain extender, blowing agent, and generally the catalyst and other additives, if desired, is a stable, liquid blend at room temperature, or if not compatible at room temperature the polyol resin is a compatible, stably dispersed liquid blend prior to its introduction into the mixing chamber of the dispenser.
• liquid polyol resins which can be utilized in the practice of preferred aspects of the invention include relatively minor amounts of chain extenders, e.g., small amounts generally ranging from about 5 to 13% by weight of extender based on the weight of the total polyol resin side.
• Example 1 A quasi-prepolymer was prepared by reacting 200 gms of PPG-2025** with 300 gms of Isonate 125 M** at 60-70°C, for 3 hours under an atmosphere of dry nitrogen. The reaction procedure comprised charging molten Isonate 125M to a reaction flask equipped with agitator, nitrogen inlet tube, dropping funnel and condenser. Heating was accomplished by means of an electric heating mantle.
• the molten Isonate 125M was heated to 55°-60°C., whereupon PPG- 2025 was added thereto, the reaction temperature being held between 60°-70°C. After completion of the PPG-2025 addition, the reactants were further heated at 60°-70oC for 3 hours.
• the resulting quasi-polyether prepolymer product was found to contain 18.5% NCO, corresponding to an isocyanate equivalent weight of 227.
• the warm quasi- prepolymer fluid was transferred to a glass container. Next day, the quasi-polyether prepolymer product was found to have crystallized at room temperature. The material became homogeneous by heating in an air circulating oven at 65oC. This quasi-prepolymer product is designated as Prepolymer 1.
• Example 2 In the manner described in Example 1, there were reacted 200 gms of PPG-2025**, and a mixture of 240 gms of Isonate 125M** and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.6% NCO, corresponding to an isocyanate equivalent weight of 226.
• the product was still liquid at room temperature after a period of 3 weeks. It is designated as Prepolymer 2.
• Example 2 In the manner described in Example 1, there were reacted 200 gms of Niax Polyol 12-56**, 240 gms of Isonate 125 M** and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.3% NCO, corresponding to an isocyanate equivalent weight of 230.
• the product remained liquid for several months at room temperature. it is designated as Prepolymer 3.
• Example 4 In an analogous manner described in Example 1, there were reacted 200 gms of Niax Polyol E-351**, 200 gms of Isonate 125 M**, and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.7% NCO, corresponding to an isocyanate equivalent weight of 225.
• the product was still liquid after a period of 3 months at room temperature. It is designated as Prepolymer 4.
• Example 5 In an analogous manner as described in Example 1, there were reacted 200 gms of Poly-G 55-37**, 240 gms of Isonate 125 M**, and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.6% NCO, corresponding to an isocyanate equivalent weight of 226.
• the product remained liquid for 3 months at room temperature until its use in subsequent foaming experiments. It is designated as Prepolymer 5.
• Example 6 In an analogous manner described in Example 1, there were reacted 200 gms of Voranol 4701**, 240 gms of Isonate 125M**, and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.8% NCO, corresponding to an isocyanate equivalent weight of 223.
• the product was still liquid after 5 months at room temperature until employed in subsequent foaming experiments. It is designated as Prepolymer 6.
• Example 7 In an analogous manner described in Example 1, there were reacted 200 gms of Carpol 2040**, 200 gms of Isonate 125 M**, and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.4% NCO, corresponding to an isocyanate equivalent weight of 228.
• the product remained liquid for 3 months at room temperature until its use in subsequent foaming experiments. It is designated as Prepolymer 7.
• Example 8 In an analogous manner as described in Example 1, there were reacted 200 gms of Carpol 2050**, 200 gms of Isonate 125 M**, and 30 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 18.3% NCO, corresponding to an isocyanate equivalent weight of 230.
• the product remained liquid at room temperature until its use about 3 months later. It is designated as Prepolymer 8.
• Example 9 In an analogous manner as described in Example 1, there were reacted 200 gms of NIAX Polyol 11-27**, 240 gms of Isonate 125M** and 30 gms of Isonate 143L**.
• the resulting liquid quasi-polyether prepolymer was found to contain 18.6% NCO, corresponding to an isocyanate equivalent weight of 226. It is designated as Prepolymer 9.
• Example 10 In an analogous manner as described in Example 1, there were reacted 200 gms of Niax Polyol E-351**, 360 gms of Isonate 125 M**, and 40 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain 20.4% NCO, corresponding to an isocyanate equivalent weight of 206.
• the product was clear and liquid after a period of 6 months at room temperature. It is designated as Prepolymer 10.
• Example 11 In an analogous manner as described in Example 1, there were reacted 200 gms of NIAX Polyol E-351**, 180 gms of Isonate 125M**, and 20 gms of Isonate 143L**.
• the resulting quasi-polyether prepolymer was found to contain an NCO content of 15.1%, corresponding to an isocyanate equivalent weight of 278.
• the product was found to remain liquid at a temperature of 15°-25oC for a period in excess of one year and exhibit no sign of dimer and trimer formation. It is designated as Prepolymer 11.
• the foams made from Prepolymers 3-11 resulted in good to excellent integral skin microcellular foams exhibiting no shrinkage. All the quasi-prepolymers that gave operable results contain ethyleneoxy end-blocks in their structure. It is believed that this results in the proper compatibility parameters for the diol extender, exhibiting proper reactivity level for good cure of the microcellular foam. Prepolymers 3-11 did not exhibit any dimer or trimer formation, although several had been prepared up to 6 months before a foam test was conducted, indicating the excellent and unexpected shelf-stability of these products.
• Examples 13-24 Eleven quasi-polyether prepolymers from Niax Polyol E-351**, Rubinate 44** and Rubinate LF-168** were prepared in the manner described in Example 1 supra. An additional quasi-prepolymer was also prepared without the use of Rubinate LF-168. Various properties of the resulting quasi-prepolymers were then determined, i.e., % NCO, viscosity, specific gravity, temperature at which quasi- prepolymer begins to crystallize, and NCO equivalent weight. The data are set forth in Table II infra.
• Examples 31-36 Five quasi-polyether prepolymers from Niax Polyol 11-27**, Rubinate 44** and Rubinate LF-168** were prepared in the manner described in Examples 1 supra. An additional quasi-prepolymer was also prepared without the use of Rubinate LF-168. Various properties of the resulting quasi-prepolymers were then determined, i.e., % NCO, viscosity, specific gravity, temperature at which quasi-prepolymer begins to crystallize, and NCO equivalent weight. The data are set forth in Table IV infra.
• the molded plaques were prepared by pre-blending a polyol blend including polyether polyols, chain extenders, catalysts, surfactants, and blowing agent, and reacting said blend with the equivalent amount of the applicable quasi-prepolymers that had been prepared according to the procedures described in the abovesaid Examples.
• the reacting foaming mass was transferred into a preheated aluminum mold having dimensions of 6" x 8" x 0.25"; the properly vented mold was closed and placed into a press whose platens were preheated to about 50oC-60oC. After several minutes, the molded plaques were removed, allowed to stand at room temperature for 2-3 days and were then examined for the physical properties listed hereinbelow.
• the polyol blend comprised the following ingredients
• a series of comparative machine foams were prepared from the above-identified Prepolymers A and B, and with a prior art prepolymer designated as Airflex 100 Isocyanate**.
• Airflex 100 Isocyanate** a prior art prepolymer designated as Airflex 100 Isocyanate**.
• all ingredients with the exception of the Prepolymers A or B or AIRFLEX 100 Isocyanate (Formulations 64-70 of Table VII infra) were premixed to form the so-called "polyol resin" stream.
• the second stream consisted either of Prepolymer A, Prepolymer B, or Airflex 100 Isocyanate.
• the formulations containing dispersed vinyl polymer exhibited consistently better abrasion properties.
• abrasion properties are about as good as is normally experienced with polyester formulations, known to be outstanding in this respect.
• the abrasion tests conducted in this test series were of the nature normally selected for athletic footwear; hence, the results are indeed surprising.
• other mechanical properties such as tensile and tear strength are also judged good to excellent.
• L-5309** a low potency surfactant
• others of this type such as L-5303**, L-5305** and L-5307** as well as their competitive products from other manufacturers can also be employed.
• DMS** low molecular weight polydimethyls iloxanes
• EXAMPLES 74-84 A series of hand foams from Prepolymer A (Example 62 supra) were prepared to further illustrate the wide operating latitude afforded by the novel prepolymers of the present invention.
• two polyether polyols one containing about 28% by weight of dispersed vinyl polymer, the other containing no dispersed polymer (Pluracol WUC-25230**) were foamed employing different ratios of the non-vinyl polyether polymer and the vinyl polymer/polyether polyols.
• Excellent integral skin microcellular foams resulted over the entire composition range (Table IX, Formulations 74-84), further establishing the excellent operating latitude of novel liquid quasi-prepolymers.
• the so-called high potency siloxane block copolymer surfactants are particularly useful as cell regulators for the microcellular foam process of the present invention.
• low potency surfactants of the type disclosed in U.S. Patent No. 3,741,917 are useful for the purpose of the present invention
• the high potency surfactants are preferred (typical low potency surfactants employed in the present invention comprise L-5303**, L-5305**, L-5307** and L-5309**).
• Suitable high potency surfactants include L-520**, L-6202**, L-540**, L-548**, L-550** and L-560 (available from Union Carbide Corporation).
• the high potency surfactants normally yield integral skin microcellular foams, characterized by severe shrinkage, from systems comprising the polyether polyols utilized in the present invention in combination with the polyether prepolymers utilized in the prior art shoe sole formulations.
• the preferred high potency surfactants utilized in the present invention comprise siloxane block copolymer surfactants having molecular weights in the range of from about 3000 to about 9000, a siloxane content of from 30% to about 70% by weight based on the weight of the copolymer.
• the polyether segment(s) of said copolymer surfactant has an oxypropylene content of from 70% to about 30°% by weight and an oxyethylene content of from about 30% to about 70% by weight based on the weight of said polyether segment(s) of the polysiloxane-polyoxy-alkylene copolymer.
• the high potency copolymer surfactants which can be utilized in the practice of preferred embodiments of the present invention can contain tetrafunctional, trifunctional, difunctional and monofunctional siloxane groups, or combinations of such siloxane groups and they can have the same or different substituents bonded to the Si atom as, for example, methyl, ethyl, phenyl, etc.
• the polyether portions or blocks of polysiloxane copolymers represent oxyaIkylene groups comprising oxyethylene/oxypropylene copolymer groups, with the proviso that at least 70% by weight, preferably 40-60% by weight, are ethyleneoxy groups to give the oxyalkylene block a desired amount of hydrophilicity.
• the oxyalkylene groups consist essentially of oxyethylene and oxypropylene groups copolymerized in random manner.
• copolymer surfactants useful in the practice of the invention can be hydrolyzable polyoxyalkylene-polysiloxanes in which Si is bonded to carbon through the oxy (-O-) group, i.e, Si-O-C , or they can be the non-hydrolyzable polyoxyalkylene-polysiloxanes in which Si is monovalently bonded directly to carbon, i.e., Si-C .
• Table X infra (Formulations 95-96) demonstrates the usefulness of high potency surfactants in producing outstanding integral skin microcellular foams without shrinkage being observed.
• Table X infra a number of other high efficiency surfactants, e.g., Dow corning 191** and 196**, also have been tested successfully. Data and results are recorded in Table X infra.
• Similar microcellular polyurethane foams of excellent structure were prepared from various blends of Niax Polyol 11-27** and Niax Polyol 34-28**. Such products are particularly suitable for the molding of integral skin components such as automotive arm rests, tractor and bicycle seats, and the like.

Applications Claiming Priority (2)

Publications (2)

Family

ID=24379449

Family Applications (1)

Country Status (3)

Families Citing this family (10)

Citations (5)

Family Cites Families (6)

• 1985
  • 1985-03-29 EP EP19850901865 patent/EP0175773A4/de not_active Withdrawn
  • 1985-03-29 AU AU41198/85A patent/AU4119885A/en not_active Abandoned
  • 1985-03-29 WO PCT/US1985/000550 patent/WO1985004410A1/en not_active Application Discontinuation

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events