Polyurethane elastomers having improved physical properties and a process for the production thereof
32 claims: 2 independent, 30 dependent
- 1ES 2 284 992 T3 REIVINDICACIONES 1. Una composición de poliol que tiene un peso molecular medio en número entre 1000 aproximadamente y 3000 Da aproximadamente que comprende (1) al menos 60% en peso de un polioxipropilenpoliol que tiene un peso molecular entre 2000 aproximadamente y 12.000 Da aproximadamente, un contenido en restos de oxietileno internos o en bloque o en bloque/aleatorios no superior al 30% y un grado de insaturación inferior o igual a 0,02 meq/g y (2) entre el 5 y el 40% en peso de un poliol que tiene un peso molecular entre 400 aproximadamente y 1000 Da aproximadamente y un índice de polidispersidad superior a 1,1.
- 2La composición de poliol de la reivindicación 1 en la que el poliol (2) tiene un índice de polidispersidad superior o igual a 1,3.
- 3La composición de poliol de la reivindicación 1 en la que el poliol (2) tiene un índice de polidispersidad superior o igual a 1,6.
- 4La composición de poliol de la reivindicación 1 en la que el poliol (1) está presente en una cantidad entre el 70 y el 85% en peso.
- 5La composición de poliol de la reivindicación 1 que tiene un peso molecular medio de aproximadamente 2000 Da.
- 6La composición de poliol de la reivindicación 1 en la que el poliol (1) tiene un peso molecular medio en número entre 3000 aproximadamente y 8000 Da aproximadamente.
- 7La composición de poliol de la reivindicación 1 en la que el poliol (1) tiene un peso molecular medio en número entre 3000 aproximadamente y 6000 Da aproximadamente.
- 8La composición de poliol de la reivindicación 1 en la que el poliol (1) tiene un grado de insaturación inferior a 0,010 meq/g.
- 9La composición de poliol de la reivindicación 1 en la que el poliol (1) tiene un grado de insaturación inferior a 0,007 meq/g.
- 10La composición de poliol de la reivindicación 1 que incluye adicionalmente hasta el 20% en peso, en relación al poliol total, de un triol que tiene un peso molecular medio en número entre 250 aproximadamente y 7000 Da aproximadamente.
- 11La composición de poliol de la reivindicación 10 en la que el triol se selecciona del grupo constituido por propoxilatos de glicerina y trimetilolpropano y copolímeros de óxido de etileno/óxido de propileno de glicerina y trimetilolpropano.
- 12Un prepolímero o cuasi-prepolímero terminado en NCO que tiene un contenido en NCO entre el 3 aproximadamente y el 20% aproximadamente que es el producto de reacción de a) un diisocianato o poliisocianato y b) la composición de poliol de la reivindicación 1.
- 13El prepolímero de la reivindicación 12 en el que el diisocianato o poliisocianato es 4,4'-difenilmetanodiisocianato o una de sus mezclas isoméricas.
- 14El prepolímero de la reivindicación 12 en el que el diisocianato o poliisocianato es toluendiisocianato, isoforonadiisocianato, o 1,4-ciclohexanodiisocianato.
- 15El prepolímero de la reivindicación 12 en el que el diisocianato o poliisocianato es un isocianato modificado con urea, isocianato modificado con uretano;isocianato modificado con carbodiimida;isocianato modificado con alofanato;isocianato modificado con biuret o un isocianato modificado con uretonimina.
- 16El prepolímero de la reivindicación 12 en el que el poliol (1) tiene un peso molecular medio en número entre 3000 aproximadamente y 8000 Da aproximadamente.
- 17El prepolímero de la reivindicación 12 en el que el poliol (1) tiene un peso molecular medio en número entre 3000 aproximadamente y 6000 Da aproximadamente. ES 2 284 992 T3
- 18El prepolímero de la reivindicación 12 en el que el poliol (1) tiene un grado de insaturación inferior a 0,010 meq/g.
- 19El prepolímero de la reivindicación 12 en el que el poliol (1) tiene un grado de insaturación inferior a 0,007 meq/g.
- 20El prepolímero de la reivindicación 12 en el que el componente poliol incluye adicionalmente hasta el 20% en peso, en relación al peso total del componente poliol, de un triol que tiene un peso molecular medio en número entre 250 aproximadamente y 7000 Da aproximadamente.
- 21El prepolímero de la reivindicación 12 en el que el componente poliol incluye adicionalmente hasta el 20% en peso, en relación al peso total del componente poliol, de un triol que tiene un peso molecular medio en número de hasta 7000 Da seleccionado entre propoxilatos de glicerina y trimetilolpropano y copolímeros de óxido de etileno/óxido de propileno de glicerina y trimetilolpropano.
- 22El prepolímero de la reivindicación 12 en el que el diisocianato o poliisocianato es 4,4’-difenilmetanodiisocianato y el componente poliol comprende entre el 60 y el 95% en peso de polioxipropilenpoliol y entre el 5 y el 40% en peso de politetrametilenéterglicol.
- 23El prepolímero de la reivindicación 22 en el que hasta 20% en peso del componente poliol es un triol que tiene un peso molecular entre 250 aproximadamente y 7000 Da aproximadamente.
- 24Un poliuretano que comprende el producto de reacción del prepolímero de la reivindicación 12 y un extensor de cadena o un agente reticulante.
- 25Un poliuretano que comprende el producto de reacción del prepolímero de la reivindicación 22 con un extensor de cadena o un agente reticulante.
- 26Un poliuretano que comprende un producto de reacción del prepolímero de la reivindicación 22 con un extensor de cadena diol.
- 27Un poliuretano que comprende un producto de reacción del prepolímero de la reivindicación 22 con butanodiol.
- 28Un poliuretano que comprende el producto de reacción del prepolímero de la reivindicación 12 con butanodiol.
- 29Un elastómero preparado haciendo reaccionar (a) un prepolímero o cuasi-prepolímero terminado en NCO que es el producto de reacción de:(1) un diisocianato o poliisocianato y (2) un polioxipropilenpoliol que tiene un peso molecular entre 2000 aproximadamente y 12.000 Da aproximadamente, un contenido en restos de oxietileno internos o en bloque o en bloque/aleatorios no superior al 30% y un grado de insaturación inferior o igual a 0,02 meq/g y (b) un poliol que tiene un peso molecular entre 400 aproximadamente y 1000 Da aproximadamente y un índice de polidispersidad superior a 1,1 y (c) un extensor de cadena en cantidades tales que el elastómero contiene entre el 60 y el 95% en peso del poliol (2) y entre el 5 y el 40% en peso del poliol (b).
- 30Un elastómero de poliuretano producido haciendo reaccionar (a) un diisocianato o poliisocianato con (b) la composición de poliol de la reivindicación 1 en un procedimiento directo a un índice de isocianato entre 70 y 130.
- 31El elastómero de poliuretano producido haciendo reaccionar (a) un cuasi-prepolímero isocianato terminal producido a partir de una fracción de la composición de poliol de la reivindicación 1 con (b) el resto de la composición de poliol de la reivindicación 1 en un procedimiento directo a un índice de isocianato entre 70 y 130. ES 2 284 992 T3
- 32Un procedimiento directo para la producción de un elastómero de poliuretano que comprende (1) la introducción (a) de una primera corriente que comprende la composición de poliol de la reivindicación 1 y un extensor de cadena y (b) una segunda corriente que comprende un diisocianato o poliisocianato en un reactor y (2) permitir que los contenidos del reactor reaccionen.
Independent claims32
338 paragraphs in 39 sections, as filed
ES 2 284 992 T3
DESCRIPTION
Polyurethane elastomers that have improved physical properties and process for their production.
Background of the invention
The present invention relates to polyurethane elastomers and a process for their production. More particularly, the present invention relates to polyurethane elastomers having improved physical properties, to the polyol component and to the terminal isocyanate prepolymer or quasi-prepolymer used to produce such elastomers, and to a direct process for producing polyurethane elastomers from these materials. . Preferably, these elastomers are prepared by chain extension of a terminal isocyanate prepolymer or quasi-prepolymer prepared from a polyol component having a number average molecular weight between about 1000 and about 3000 Da. This polyol component includes a low molecular weight polyol having a high polydispersity index and a polypropylene glycol with a low monol content.
Polyurethane elastomers are widely used in applications as diverse as gaskets and precipitate materials, medical devices, ski boots, rubber buffers, and conveyor rollers, to name a few. Due to their strength, toughness, and other properties, elastomers prepared from isocyanate terminal prepolymers or quasi-prepolymers incorporating polytetramethylene ether glycol (PTMeG), polycaprolactone, and polyolsters are predominantly used for demanding applications.
However, PTMEG, polycaprolactone, and polyesters tend to be expensive starting materials. As a result, polyurethane elastomers made from these polyol components are also premium priced products.
Polyoxypropylene diols have been suggested as possible substitutes for PTMEG in elastomeric prepolymer formulations, however, the properties of the elastomers thus produced are not comparable with those achieved with PTMEG.
The patent literature teaches the benefits of using polyoxypropylene diols with a low content of unsaturations but also recognizes that the production of elastomers with such polyols gives products that have low modulus values, low hardness values, compression deflection and resistance to abrasion. low and have processing problems.
One approach that has been taken to improve these physical properties and reduce or eliminate the processing problems encountered with such low unsaturation polyols is the use of a polyol blend. US Pat. 5,648,447, for example, describes polyurethane elastomers produced from a prepolymer prepared with a polyol component containing PTMEG and between 5 and 35% equivalent of a low monol chain-extending polyoxypropylene polyol. with an aliphatic diol or an aromatic amine. However, this patent teaches that if more than 35 equivalent% polyoxypropylene diol is used with a low monol content, the tensile strength of the elastomer decreases rapidly and the elongation values are worse than those for elastomers prepared using only polyoxypropylene diol with a low monol content. The economic benefit of using polyoxypropylene diols with a low monol content is therefore not fully achieved due to the requirement that less than 35 equivalent% of that diol must be used if tensile strength and elongation values are to be maintained.
It has also been found that approximately 20% more isocyanate (specifically, MDI) is needed in systems such as those described in US 5,648,447 to achieve the same degree of hardness as obtained using comparable PTMEG systems. . Furthermore, optimum mechanical properties are achieved only if the chain extension of the prepolymer is sufficiently catalyzed so that the lifetime of the system is about 2 minutes or less. Elastomers that require processing times greater than 2 minutes therefore cannot be produced with such systems without sacrificing the mechanical properties of the elastomeric product.
Among the known processes used to produce polyurethane elastomers, direct processes are considered to be particularly advantageous. US Patents 5,668,239 and 5,739,253, for example, each describe a direct process for the production of polyurethane / urea elastomers from isocyanate terminal prepolymers, polyol ethers, and a chain extender.
It would therefore be advantageous to develop an elastomer-forming composition in which a significant amount of the polyol component employed is a low monol content polyoxypropylene diol that produces elastomers having comparable hardness, modulus, compression deflection, abrasion resistance, and processability. to those of elastomers currently produced exclusively with traditional high performance polyols. Summary of the invention
It is an object of the present invention to provide a polyol component useful for producing polyurethane elastomers having good processing characteristics and physical properties, even when time
ES 2 284 992 T3 processing time is greater than 2 minutes, which includes a significant amount of polyoxypropylene diol with a low cost monol content.
It is another object of the present invention to provide an NCO terminated prepolymer or quasi-prepolymer useful for the production of polyurethane elastomers having characteristics comparable to those of elastomers produced solely with high performance polyols such as PTMEG, polycaprolactones and polyesters.
It is another object of the present invention to provide polyurethane elastomers characterized by good properties of hardness, modulus, elongation, resistance to abrasion and compression.
It is a further object of the present invention to provide an economical process for the production of polyurethane elastomers having good mechanical properties in which the processing of the elastomer-forming materials does not require unacceptably short reaction times.
These and other objects that will be apparent to those skilled in the art are achieved through the use of a polyol component that is a preparation or mixture having a number average molecular weight of between about 1000 and about 3000 Daltons. This polyol component should include: (1) a significant amount (i.e., greater than 60% by weight, relative to the total weight of the polyol component) of a low monol content polyoxypropylene polyol having a number average molecular weight of between about 2000 and 12,000 Da and a degree of unsaturation less than or equal to 0.02 meq / g and (2) a small amount (i.e. less than 40% by weight, relative to the total polyol component) of a low molecular weight polyol having a high polydispersity index (that is, the polydispersity index is greater than 1.1). This polyol component is reacted with an isocyanate, a terminal isocyanate prepolymer or a terminal isocyanate quasi-prepolymer. The elastomers produced in accordance with the present invention are most preferably synthesized by chain extension of a terminal isocyanate prepolymer or quasi-prepolymer prepared by reacting a stoichiometric excess of one or more di- or polyisocyanates with at least a fraction of the polyol component or one of the polyols of the polyol component.
Description of preferred embodiments
The polyurethane elastomers produced in accordance with the present invention are preferably prepared by chain extension of an isocyanate terminal prepolymer or quasi-prepolymer with one or more conventional chain extenders. The terminal isocyanate prepolymer can be prepared by reacting one or more of the polyisocyanates with a polyol component having a number average molecular weight of between about 1000 and about 3000 Daltons. This polyol component includes (1) a low monol content polyoxypropylene polyol, and (2) a low molecular weight polyol having a polydispersity index greater than 1.1. Quasi-prepolymers formed by first reacting an isocyanate with a small amount of the total polyol component (eg, 10% equivalent) are reacted with the part of the elastomeric formulation resin (part B) that contains the remainder of the polyol component. and a chain extender for producing elastomers in accordance with the present invention. The elastomers of the present invention can be produced by any of the processes known to those skilled in the art, including direct processes.
Useful isocyanates by themselves and for the preparation of isocyanate terminal prepolymers and isocyanate terminal quasi-prepolymers for the production of elastomers in accordance with the present invention include any of the known aromatic, aliphatic, and cycloaliphatic di- or polyisocyanates. Examples of suitable isocyanates include: 2,4- and 2,6-toluene diisocyanates and their isomeric mixtures, particularly an 80:20 mixture of the 2,4- and 2,6- isomers; 2,2'-, 2,4'- and particularly 4,4'-methylenediphenylenedisocyanates and their isomeric mixtures; polyphenylenepolymethylene polyisocyanates (poly-MDI, PMDI); the saturated cycloaliphatic analogs of PMDI such as 2,4-, and 2,6-methylcyclohexanediisocyanate and 2,2'-, 2,4'-, and 4,4'-methylenedicyclohexylene diisocyanate and their other isomers; isophorone diisocyanate; 1,4-diisocyanatobutane, 1,5-diisocyanatopentane; 1,6-diisocyanatohexane; 1,4-cyclohexanediisocyanate; and the like.
Modified di- and polyisocyanates can also be used in the practice of the present invention. Suitable modified isocyanates include: urea modified isocyanates, biuret modified isocyanates; urethane-modified isocyanates; isocyanurate modified isocyanates; allophanate-modified isocyanates; carbodiimide modified isocyanates; uretdione-modified isocyanates; uretonimine-modified isocyanates; and the like. Such modified isocyanates are commercially available, and are prepared by reacting an isocyanate with a less than stoichiometric amount of an isocyanate reactive compound, or with itself. For example, urea-modified isocyanates and urethane-modified isocyanates can be prepared by reacting a di- or polyisocyanate with small amounts of water or a diamine, or with a glycol, respectively. Carbodiimide, uretonimine, and isocyanurate modified isocyanates are prepared by inter-reacting isocyanates with themselves in the presence of a suitable catalyst.
Particularly preferred isocyanates among those listed above are toluene diisocyanates (TDI), methylenediphenylene diisocyanates (preferably 4,4'-MDI), carbodiimide-modified MDI, and aliphatic and cycloaliphatic isocyanates (particularly 1,6-diisocyanatehexane and isophorone diisocyanate; the various methylisoxy isocyanate3;
ES 2 284 992 T3 cyanates; and the various methylenedicyclohexylene diisocyanates. Isocyanate mixtures are also suitable, in particular mixtures of TDI and MDI, and mixtures of carbodiimide modified MDI and MDI.
Low molecular weight polyols having a polydispersity index greater than 1.1 that are useful in the present invention include any of the known polyols that satisfy the following criteria: (1) The number average molecular weight is between about 400 and 1000 Daltons approximately; and (2) the ratio of the weight average molecular weight to the number average molecular weight (polydispersity index) is greater than 1.1, preferably greater than 1.2, and most preferably greater than 1.3. Suitable polyols include polyethers and polyolsters that satisfy the criteria listed above. These low molecular weight, high dispersity polyols are typically difunctional. Small amounts of polyols of higher functionality may also be included (for example, less than about 20% by weight, preferably less than 10% by weight, and most preferably less than 5% by weight, relative to the total polyol having a polydispersity index greater than 1.1) that satisfy the criteria listed above.
The number average molecular weight of the polyol having a polydispersity index greater than 1.1 may be between about 400 and about 1000 Da, preferably between about 500 and about 1000 Da, and most preferably between about 600 and 1000 Da. about. Molecular weights and equivalent weights expressed herein in Da (Daltons) refer to number average molecular weights and number average equivalent weights, unless otherwise specified.
The low molecular weight polyol having a high polydispersity index is generally included in the polyol component of the present invention in an amount between 5 and 40% by weight, preferably between 10 and 30% by weight, and of most preferably between 15 and 25% by weight.
Specific examples of suitable polyols with a high polydispersity index and a low molecular weight that are useful in the practice of the present invention include polytetramethylene ether glycols and polyolsters that satisfy the criteria listed above. Polytetramethylene ether glycols having molecular weights between about 400 and about 1000 Da and a polydispersity index of at least 1.3 are preferred.
Polytetramethylene ether glycols (PTMEG) that satisfy the criteria listed above are commercially available. PTMEGs are typically prepared by the ring-opening polymerization of tetrahydrofuran, generally in the presence of a Lewis acid catalyst. PTMEG polyols have a relatively high methylene to oxygen ratio and offer low water absorption and good hydrolytic stability. PTMEGs having molecular weights between about 400 and about 1000 Da, preferably between about 500 and about 1000 Da, and a polydispersity index equal to or greater than 1.3 are particularly useful.
Polyolsters are also commercially available. Such polyolsters can be broadly classified as homopolymeric and co- and terpolymeric, although some of these terms are used interchangeably. Homopolymeric polyesters are prepared by polymerizing a monomer that contains both hydroxyl and carboxylic acid functions or their chemical equivalents. The most common homopolymeric polyester is polycaprolactone, prepared by ring-opening polymerization by inter-transesterification of ε-caprolactone. Polycaprolactone polyesters have a uniform head / tail structure that promotes crystallinity. Other lactones and molecules that have both hydroxyl and carboxylic acid functions are suitable for preparing polycaprolactone polyols. The addition of other difunctional or higher functional molecules, hydroxyl functional or carboxylic acid functional, can be used to modify the functionality or structure of the polycaprolactone polyols.
Co- or terpolyester polyols are also commercially available, and are the reaction product of a stoichiometric excess of a diol and a dicarboxylic acid or one of their esterifiable derivatives. When a single diol and a single dicarboxylic acid are reacted, the resulting product is a copolyester, often simply referred to as "polyester." Examples of such co-polyesters are: polyethylene adipate, a polyester formed from ethylene glycol and adipic acid; polybutylene adipate, a polyester formed from 1,4-butanediol and adipic acid; polyethylene terephthalate, a polyester formed from ethylene glycol and terephthalic acid or an esterifiable or transesterifiable derivative such as dimethylterephthalate; and the like. When two or more glycols and / or two or more dicarboxylic acids are used in the polyesterification reaction, terpolyesters are produced. An example of such a terpolyester is polyethylenebutylene adipate, prepared from a mixture of ethylene glycol, 1,4-butanediol, and adipic acid. Trifunctional or higher functional polyols and trifunctional or higher functional carboxylic acids can be added, generally in small amounts, to prepare polyols with average functionalities greater than two.
Homopolymeric polyolsters such as polycaprolactone, and copolyester polyols formed from a diol and a dicarboxylic acid are also useful in the practice of the present invention.
The low monol content polyoxypropylene polyol used in combination with the low molecular weight polyol having a polydispersity index greater than 1.1 is a key feature of the polyol component compositions of the present invention. Traditionally, polyoxypropylene polyols have been prepared by the base catalyzed oxypropylation of a suitably hydric oxyalkylatable starter molecule in the presence of a basic oxypropylation catalyst such as sodium or potassium hydroxide or a corresponding alkoxide. Under basic oxyalkylation conditions, part of the introduced propylene oxide rearranges to form an alcohol
ES 2 284 992 T3 allylic, an unsaturated functional monohydroxyl compound that itself serves as an additional oxyalkylatable starter molecule. As this rearrangement proceeds during the course of oxyalkylation, both the measured functionality and the molecular weight distribution of the product change.
Continued introduction of monofunctional species decreases overall functionality, and thus a diol initiated polyol with an equivalent weight of 2000 Da may contain 40 to 50 mole% or more of monofunctional species. As a result, the "nominal" or "theoretical" functionality of the two, due to difunctionality of the diol initiator, can be reduced to about 1.6 or 1.7 or less. The relative amount of monol present is generally determined by measuring the unsaturation of the polyol, expressed as milliequivalents (meq) of unsaturation per gram of polyol, hereinafter "meq / g". Unsaturation is measured according to ASTMD-2849-69 "Testing Urethane Foam Polyol Raw Materials". Conventional base-catalyzed polyoxypropylene diols in the 2000 Da equivalent weight range generally have unsaturations measured in the range of 0.07 to 0.12 meq / g. Due to the high level of unsaturation and the high level of monofunctional species that reflects unsaturation, the practical equivalent weight of polyoxypropylene diols produced by conventional base-catalyzed processes is limited to about 2000 Da.
Various procedures have been proposed to decrease unsaturation and the amount of monofunctional species. To decrease unsaturation, cesium and rubidium hydroxides have been used in place of the cheaper sodium and potassium hydroxides (see, for example, US Patent 3,393,243). Barium and strontium hydroxides have also been used (see, for example, US Patents 5,010,187 and 5,114,619). The use of metal carboxylate catalysts such as calcium naphthenate, with or without tertiary amines as cocatalysts is described in US Patent 4,282,387. Such catalysts are claimed to have reduced polyol unsaturation to the range of 0.04 meq / g. However, the cost of such catalysts and the limited improvement in the level of unsaturation attributable to their use makes the commercial use of these catalysts unattractive.
Double metal cyanide complex catalysts such as those described in US Patent 5,158,922 have made it possible to produce polyethers having a degree of unsaturation in the range of 0.015 to 0.018 meq / g. These DMC catalysts have been improved to such an extent that polyols with exceptionally low levels of unsaturation can be obtained, eg, in the range of 0.002 to 0.007 meq / g (see, eg, US Pat. 5,470,813 and 5,482,908). Although measurable unsaturation implies at least some monol content, the low molecular weight species that would be expected to be produced are difficult to detect with conventional size exclusion chromatography. Furthermore, the polydispersities of the products are exceptionally low, so that the polyols are considered to be virtually monodisperse.
The polyoxypropylene polyols useful in the present invention are limited to those that have a low monol content. Specifically, the monol content in terms of unsaturation of the polyol should be less than about 0.02 meq / g, preferably less than 0.010 meq / g, and most preferably about 0.007 meq / g or less. Polyoxyalkylene polyols are preferably difunctional, although small amounts of polyols with higher functionality can also be used. The term "polyoxypropylene polyol" as used herein includes polyoxypropylene diols containing up to about 20% by weight of trifunctional or higher functional polyoxypropylene species. Polyoxypropylene diols are preferably homopolyoxypropylene diols. However, random, block, or block / random copolymer diols containing up to 30% by weight of oxyethylene moieties, preferably no more than 20% by weight of oxyethylene moieties, can also be used. Polyoxypropylene polyols containing small amounts of higher alkylene oxide derived moieties, particularly those derived from 1,2- and 2,3-butylene oxide may also be present in small amounts (ie, less than 10% by weight). The term "polyoxypropylene polyol" also includes such polyoxyalkylene copolymers derived predominantly from propylene oxide. Preferably, the polyoxypropylene polyols are all substantially derivatives of propylene oxide, and most preferably substantially difunctional. The molecular weights of the low polyoxypropylene polyols can range from about 2,000 Da to about 12,000 Da, preferably about 3,000 to about 8,000 Da, and most preferably about 3,000 to about 4,500 Da.
The polyol component used in the practice of the present invention has an average molecular weight between about 1000 and about 3000 Da, preferably between about 1000 and about 2500 Da, most preferably between about 1000 and about 2000 Da. The average degree of unsaturation of the polyol component is generally less than 0.02 meq / g, preferably less than 0.01 meq / g, most preferably less than 0.007 meq / g. The amounts of low molecular weight polyol having a polydispersity index greater than 1.1 and a polyoxypropylene polyol with a low monol content and any other isocyanate reactive material present in the polyol component are such that the total polyol component will have a weight average molecular weight and an average degree of unsaturation within these specified ranges. However, the low monol content polyoxypropylene polyol should comprise at least 60% by weight, preferably at least 70% by weight, most preferably at least 75% by weight of the total polyol component.
The isocyanate terminal prepolymers or quasi-prepolymers of the present invention will generally have an isocyanate group content expressed in weight percent (% NCO) of between 3 and 20% of NCO, preferably between 4 and 14% of NCO. , and most preferably between 4 and 10% NCO. The prepolymers can be prepared by any of the conventional techniques. For example, a suitable terminal isocyanate prepolymer can be obtained by reacting a mixture of a low molecular weight polyol having a poly5
ES 2 284 992 T3 dispersity greater than 1.1 and a low monol content polyoxypropylene polyol with a sufficient stoichiometric excess of isocyanate to provide the desired isocyanate group content. It is also possible to use a prepolymer mixture formed, for example, by reacting an isocyanate with a stoichiometric excess of only the low molecular weight polyol having a polydispersity greater than 1.1 to form a first prepolymer and reacting an excess of isocyanate with the low monol content polyoxypropylene polyol to form a second prepolymer and the combination of these two prepolymers. The reactive components of the prepolymer are preferably reacted under a nitrogen atmosphere at temperatures in the range of room temperature to about 100 ° C, preferably in the range of 40 ° C to 80 ° C. Urethane group promoting catalysts such as tin catalysts can be added if desired, but are not ordinarily necessary. The processes for preparing prepolymers are well known, and can be found, for example, in the Polyurethane Handbook, G. Oertel, Ed., Hanser Publications, Munich, 1985, or the treatise by JH Saunders and KC Frisch, Polyurethanes Chemistry and Technology, Interscience Publishers, New York, 1963.
Chain extenders useful in the preparation of elastomers according to the present invention include the usual diol chain extenders such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol , O, O'-bis (2-hydroxyethyl) -hydroquinone, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, and the like. Ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol are preferred. 1,4-butanediol is particularly preferred.
Small amounts of crosslinking agents such as glycerin, trimethylolpropane, diethanolamine, and triethanolamine can be used in conjunction with the diol chain extenders, but are not preferable.
Aromatic amine chain extenders are also useful in the practice of the present invention. Preferred amine chain extenders are aromatic amines such as the various toluenediamines and methylenedianilines, and particularly substituted aromatic amines that provide slower reactions attributable to electronic or steric effects, such as MOCA (4,4'-methylene-bis-o-chloroaniline ), M-CDEA (4,4'-methylenebis (3-chloro-2,6-diethylaniline) and the various aralkylated toluenediamines and methylenedianilines Mixtures of various types of chain extenders can also be used.
The terminal isocyanate prepolymers are reacted with chain extenders and optionally crosslinking agents at an isocyanate number between 70 and 130, preferably between 90 and 110, and most preferably between 95 and 105. The elastomers formed by this reaction preferably have a hardness in the range of Shore A 50 to Shore D 60, preferably between Shore A 60 and Shore A 95. Both harder and softer elastomers can also be prepared. The prepolymer can be cured with heat, with the aid of catalysts such as dibutyltin diacetate, stannous octoate, or dibutyltin dilaurate, amine catalysts, or a combination thereof. If microcellular elastomers are desired, a small amount of physical or chemical blowing agents can be added, particularly water; or the curing elastomer can be foamed by intensive mixing with air, nitrogen, or CO<sub>2</sub>; or CO can be incorporated<sub>2</sub> liquid in the reactive mixture of the curable elastomer. Water is a preferred blowing agent and is preferably used in an amount that provides a microcellular elastomer having a density in the range 0.15-0.8 g / cm.<sup>3</sup>, preferably between 0.2 and 0.5 g / cm<sup>3</sup>.
The reactive mixture of the terminal isocyanate prepolymer, chain extender (s), blowing agents, pigments, thermal and UV stabilizers, fillers, reinforcing agents, crosslinking agents, and other optional additives and adjuvants can be mixed thoroughly, injected into a suitable mold , extruded, or deposited onto a conveyor belt. If substantially all of the reactive components are difunctional, an elastomer extruded or deposited on the tape can subsequently be granulated or remelted (ie, that elastomer will be a thermoplastic polyurethane (TPU)). TPU can be fed into an extruder or other device, remelted, and injection molded, blow molded, etc., to form a wide variety of products.
In the quasi-prepolymer technique, a quasi-prepolymer is prepared from excess isocyanate and only a small fraction of the polyol component or a fraction of at least one polyol of the polyol component in the same way as the isocyanate terminal prepolymers described above. . However, because smaller amounts of polyol component react with the isocyanate, the content of the quasi-prepolymers in% NCO is higher than the% NCO of the prepolymers. Contained in isocyanate groups of between 14 and 20% NCO are typical for these quasi-prepolymers. When quasi-prepolymers are used, the remainder of the polyol component will be introduced together with the diol chain extender, as a mixture, or as a separate stream at the mix head.
A particularly useful quasi-prepolymer technique uses all or virtually all of the low-monol polyoxyalkylene diol and virtually no or no low-molecular-weight polyol having a polydispersity index greater than 1.1 during quasi-prepolymer preparation. . The quasi-prepolymer thus prepared is then subjected to chain extension with the low molecular weight polyol having a polydispersity greater than 1.1 and the chain extender supplying these two components in zone B of the formulation. The relative amounts of low molecular weight polyol having a polydispersity greater than 1.1 and polyoxyalkylene diol with a low monol content are adjusted between the amounts contained in the quasi-prepolymer and zone B so that the elastomeric product contains between the 60 to 95% by weight of low monol content polyoxyalkylene polyol relative to about 5 to about 40% by weight of low molecular weight polyol having an index of polydispersity greater than 1.1.
ES 2 284 992 T3
Direct techniques are also useful in the practice of the present invention. In the direct technique, the isocyanate component is not pre-reacted with any substantial fraction of the polyol component, the entire or virtually entire polyol component and chain extender are delivered to the mix head in a separate stream or streams of the isocyanate component. When using the direct process, it is desirable that a fraction of the polyol component is a protected polyoxyethylene polyoxypropylene diol with a low monol content, or that a small proportion of conventional polyoxypropylene diol with a high primary hydroxyl content is included in the formulation unless mold release and long cure times can be tolerated.
Having generally described this invention, a more thorough understanding can be obtained by reference to certain specific examples which are provided herein for illustrative purposes only and are not intended to be limiting unless otherwise specified.
Examples
The materials used in the Examples were the following:
POLYOL A Polytetramethylene ether glycol having an average molecular weight of 2000.
POLYOL B A propylene oxide-based diol having an average molecular weight of 4000 and a degree of unsaturation of 0.005 meq / g.
POLYOL C
POLYOL D
POLYOL E
A propylene oxide based diol having an average molecular weight of 4000, with 15% internal ethylene oxide and a degree of unsaturation of 0.005 meq / g.
A propylene oxide based diol having an average molecular weight of 4000, with 30% internal ethylene oxide and a degree of unsaturation of 0.005 meq / g.
A propylene oxide based diol having an average molecular weight of 4000, with 40% internal ethylene oxide and a degree of unsaturation of 0.005 meq / g.
POLYOL F A diol based on propylene oxide, with 10% random internal ethylene oxide having an average molecular weight of 3000 and a degree of unsaturation of 0.005 meq / g.
POLYOL G
A polydiol based on propylene oxide having an average molecular weight of 8000 and a degree of unsaturation of 0.005 meq / g.
POLYOL H A polyethylene glycol having an average molecular weight of 600 and a polydispersity index of 1.01.
POLYOL I A polytetramethylene ether glycol having an average molecular weight of 650 and a polydispersity index of 1.6.
POLYOL J A polypropylene glycol having an average molecular weight of 650 and a polydispersity index of 1.1 that is prepared by mixing 21.6% by weight of a polypropylene glycol having a molecular weight of 425 and 74.8% by weight of a polypropylene glycol having a molecular weight of 760.
POLYOL K A polypropylene glycol having a mean molecular weight of 650 and a polydispersity index of 1.65 that is prepared by mixing 5% by weight of a low unsaturation polypropylene glycol having a molecular weight of 4000 (commercially available from Bayer Corporation under the name Acclaim 4200), 15% by weight of a low unsaturation polypropylene glycol having a molecular weight of 2000 (commercially available from Bayer Corporation under the name Acclaim 2200), 30% by weight of a low unsaturation polypropylene glycol having a molecular weight of 1000 (commercially PPG-1000), 25% by weight of a low unsaturation polypropylene glycol having a molecular weight of 760 (commercially available from Bayer Corporation under the name PPG-725), 17% by weight of a low unsaturation polypropylene glycol which it has a molecular weight of 425 (commercially available from Bayer Corporation under the name PPG-425), and 8% by weight of tripropylene glycol.
POLYOL L A polytetramethylene ether glycol having an average molecular weight of 250 having a polydispersity index of 1.1.
POLYOL M
A diol based on propylene oxide, with 20% of a random internal oxyethylene moiety having an average molecular weight of 4000 and a degree of unsaturation of 0.005 meq / g.
BDO 1,4-Butanediol.
Isocyanate 4,4'-diphenylmethane diisocyanate.
ES 2 284 992 T3
Examples 1-5 and Comparative Examples C1-C7
Polyurethane elastomers were prepared by chain extending an NCO terminated prepolymer having an NCO content of 6% with 1,4-butanediol at an isocyanate number of 105. The isocyanate number was kept constant to facilitate comparison of the various formulations. Each tested prepolymer was prepared by reacting a stoichiometric excess of 4,4'-MDI with one or more polyether diols such that the polyol component had a mean equivalent weight of 1000 Da. In a comparative example, the prepolymer was prepared by reacting 4,4'-DMI with only one polyoxypropylene diol (ie, without PTMEG). The specific polyol components used to prepare these prepolymers and elastomers are given in Table 1A. The reaction mixture was then placed in a mold where it was allowed to cure for 16 hours at 105 ° C. The elastomers were then removed from the mold and conditioned for 4 weeks. The physical properties of the product polyurethane elastomers were then measured. The results are presented in Table 1B.
ro
<td>C7</td><td> 1</td><td> 9*08</td><td> 1</td><td> 1</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td> 19,4</td><td> 1</td><td> 1</td><td></td><td>oo</td><td> 37,0</td><td> 2,96</td>
<td> 90</td><td> 1</td><td> 82,4</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 17,6</td><td></td><td> 1</td><td> 1</td><td> 1</td><td>or_</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td>C5</td><td> 1</td><td> 93,3</td><td></td><td></td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 1</td><td></td><td></td><td> 6,7</td><td></td><td>tT oo '</td><td> 37,0</td><td> 2,96</td>
<td>m</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 39,7</td><td> 39,7</td><td></td><td> 20,7</td><td></td><td> 1</td><td> 1</td><td> 1,6</td><td>'T oo '</td><td> 37,0</td><td> 2,96</td>
<td></td><td></td><td> 1</td><td></td><td></td><td></td><td> 86,2</td><td> 1</td><td></td><td> 13,8</td><td> 1</td><td> 1</td><td> 1</td><td>CO</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td>C4</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 80,6</td><td></td><td> 1</td><td> 1</td><td> 19,4</td><td> 1</td><td> 1</td><td> 1</td><td> 1,6</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td>co</td><td> 1</td><td> 1</td><td></td><td> 80,6</td><td></td><td> 1</td><td></td><td> 1</td><td> 19,4</td><td></td><td> 1</td><td> 1</td><td>co_</td><td> 8,4</td><td> 37,0</td><td> 2,06</td>
<td>CN</td><td> 1</td><td> 1</td><td> 9*08</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 19,4</td><td> 1</td><td> 1</td><td> 1</td><td> 1,6</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td> -</td><td> 1</td><td> 9*08</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 19,4</td><td> 1</td><td> 1</td><td> 1</td><td>co_</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td>C3</td><td> 40</td><td> 09</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td></td><td></td><td>oo '</td><td> 32,4</td><td> 3,70</td>
<td>C2</td><td> 1</td><td> 100</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 1</td><td> 7,9</td><td> 29,3</td><td> 4,70</td>
<td>OR</td><td> 100</td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 1</td><td> 1</td><td></td><td></td><td> 1</td><td> 8,4</td><td> 37,0</td><td> 2,96</td>
<td>Example</td><td>Polyol A</td><td>Polyol B</td><td>Polyol C</td><td>Polyol D</td><td>LU OR OR Q_</td><td>Polyol F</td><td>Polyol G</td><td>Polyol H</td><td>Polyol 1</td><td>Polyol J</td><td>Polyol K</td><td>Polyol L</td><td>Mw / Mn low polyol P.M</td><td>% p BDO</td><td>%floor</td><td>NCO / OH</td>
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN - ON
CL E ro
IES 2 284 992 T3
<td>C7</td><td>or 00</td><td> 58</td><td> 2318</td><td> 687</td><td> 573</td><td> 800</td><td> 1025</td><td> 1266</td><td> 417</td>
<td>C6</td><td> 77</td><td> 99</td><td>1922 _I</td><td> 474 |</td><td> 454</td><td> 705</td><td>ί 1015</td><td> 1453</td><td> 169</td>
<td>C5</td><td> 83</td><td> 62</td><td> 2215</td><td> 581</td><td> 696</td><td> 992</td><td> 1257</td><td>1552 I</td><td> 204</td>
<td>tn</td><td> 79</td><td> 09</td><td> 3202</td><td> 816</td><td> 612</td><td> 828</td><td> 1040</td><td>i 1212</td><td> 419</td>
<td>Ν '</td><td> 76</td><td>........ θ? .........- i</td><td> 2972</td><td> 703</td><td> 586</td><td> 834</td><td> 1098</td><td>i 1415 I</td><td> 375</td>
<td>C4</td><td> 76</td><td> 65,5</td><td>or OO 00</td><td> 579</td><td> 390</td><td> 586</td><td> 822</td><td> 1119</td><td> 273</td>
<td>co</td><td> 80</td><td> 64</td><td> 3556</td><td> 642</td><td> 636</td><td> 917</td><td> 1237</td><td>1653 I</td><td> 269</td>
<td>CN</td><td> 80</td><td> 63</td><td> 3649</td><td> 687</td><td> 625</td><td> 893</td><td> 1180</td><td> 1521</td><td> 259</td>
<td> -</td><td> 79</td><td> 64</td><td> 3661</td><td> 785</td><td> 665</td><td> 926</td><td> 1180</td><td> 1463</td><td> 402</td>
<td>C3</td><td> 80</td><td> 72</td><td> 3450</td><td> 760</td><td> 610</td><td> 860</td><td> 1120</td><td> 1400</td><td> 400</td>
<td>C2</td><td> 75</td><td> 69</td><td> 3325</td><td> 930</td><td> 506 . ... .....-</td><td> 729</td><td> 952</td><td> 1190</td><td> 389</td>
<td>or</td><td> 84</td><td></td><td> 6320</td><td> 551</td><td> 763</td><td> ¡ 1040</td><td> 1430</td><td> 2096</td><td> 374</td>
<td>Ex./Pr.</td><td>Shore A hardness<sup>1</sup></td><td>CM xi ω I heard H.H</td><td>Beef. Trace.<sup>3</sup></td><td>c or UI χΡ</td><td>ro in . '' S § 8 2 T—</td><td>ro co Ό 2 CN</td><td>ro . -S IT θ ' S or 5 or 2 co</td><td>ro co 1 8 2 Ν '</td><td>Res. Al Desg.<sup>9</sup></td>
ES 2 284 992 T3
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<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td colspan="3"></td><td colspan="2"> 210,1</td><td colspan="2"> 75</td><td colspan="2"> 166</td><td colspan="2"> 261</td><td colspan="2"> 486</td>
<td>co</td><td></td><td></td><td>p</td><td></td><td>CD</td><td></td><td>oo</td><td></td><td></td><td></td><td></td><td></td>
<td>LD</td><td></td><td></td><td>'F</td><td></td><td>CO</td><td></td><td></td><td></td><td>T ~</td><td></td><td>V</td><td></td>
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<td>T "</td><td></td><td></td><td>or</td><td></td><td>cu</td><td></td><td> 00</td><td></td><td></td><td></td><td>co</td><td></td>
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<td></td><td></td><td></td><td>s-</td><td></td><td></td><td></td><td>cu</td><td></td><td>co</td><td></td><td>LD</td><td></td>
<td>r- rC</td><td></td><td></td><td>st Οθ "</td><td></td><td colspan="2" rowspan="2"> 06</td><td> 95</td><td></td><td>co or</td><td></td><td> ¡50</td><td></td>
<td></td><td></td><td></td><td>h-</td><td></td><td></td><td></td><td>co</td><td></td><td>UJ</td><td></td>
<td> 5,0</td><td></td><td></td><td>or</td><td></td><td colspan="2" rowspan="2"> 83</td><td> 77</td><td></td><td> 76</td><td></td><td>co or</td><td></td>
<td>co</td><td></td><td></td><td></td><td></td><td></td><td></td><td>cu</td><td></td><td>IT</td><td></td>
<td>cq</td><td></td><td></td><td>p 00 *</td><td></td><td colspan="2" rowspan="2"> 96</td><td> 07</td><td></td><td> 23</td><td></td><td>co 00</td><td></td>
<td>cu</td><td></td><td></td><td>oo</td><td></td><td>cu</td><td></td><td>co</td><td></td><td>IT</td><td></td>
<td>° o</td><td></td><td></td><td>co_</td><td></td><td>CD</td><td></td><td>CD</td><td></td><td>ID</td><td></td><td>cu</td><td></td>
<td>or</td><td></td><td></td><td>h-</td><td></td><td>V ™</td><td></td><td>St</td><td></td><td></td><td></td><td>co</td><td></td>
<td>cu</td><td></td><td></td><td>CT)</td><td></td><td></td><td></td><td>CU</td><td></td><td>CO</td><td></td><td>co</td><td></td>
<td></td><td></td><td></td><td>st</td><td></td><td></td><td></td><td></td><td></td><td>st</td><td></td><td>cu</td><td></td>
<td>co'</td><td></td><td></td><td></td><td></td><td>or</td><td></td><td>cu</td><td></td><td>co</td><td></td><td>oo</td><td></td>
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<td></td><td></td><td></td><td>p</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
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<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>p</td><td></td><td></td><td></td><td></td><td rowspan="2"> 68</td><td></td><td></td><td></td><td></td><td></td><td>co</td><td></td>
<td>CD</td><td></td><td></td><td>C \ l 00</td><td></td><td></td><td>co</td><td></td><td> 26</td><td></td><td>CT) • st</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
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<td>Φ</td><td></td><td></td><td></td><td></td><td>or</td><td></td><td>or</td><td></td><td>OR</td><td></td><td>or</td><td></td>
<td></td><td></td><td>OR</td><td></td><td> £</td><td>OR</td><td></td><td>OR</td><td></td><td>OR</td><td></td><td>OR</td><td></td>
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<td></td><td>cn Ό</td><td></td><td></td><td></td><td> 2</td>
<td></td><td>cn</td><td></td><td> 1—</td><td> 1—</td><td> 1—</td>
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<td></td><td>cn</td><td></td><td> <</td><td> <</td><td> <</td>
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<td></td><td>cn</td><td></td><td>Ό</td><td>Ό</td><td>n</td>
<td></td><td>σ</td><td></td><td> 2</td><td>in</td><td> 2</td>
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ES 2 284 992 T3
400% modulus, pounds per square inch (ASTM D412)
Tear strength, pounds per linear inch (ASTM D624) <sup>3</sup> Compression Remaining,% (ASTM D395, Method B) 'Taber Abrasion, loss mg / 1000 revolution
- Compression Deflection: Tension at 5% compression, psi (ASTM D575, Method A)
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ES 2 284 992 T3
As can be seen from Tables 1A and 1B, Comparative Example C-2 shows that when a low monol content polyoxypropylene diol having a molecular weight of 4000 is used as the sole polyol, the elastomeric product was softer than that prepared. only with PTMEG-2000 (Example C-1). The C2 elastomer also had lower modulus properties, poor abrasion resistance, and low compression deflection (under load). During the chain extension procedure, the elastomer prepared from the composition of Example C-2 was also found to have poor green strength.
To improve the quality of elastomers prepared with low monol content polyoxyalkylenediols, a mixture of the low monol content diol having a molecular weight of 4000 and PTMEG-2000 was used in Comparative Example C-3. Although the elastomer made from this blend had an increase in Shore A hardness, abrasion resistance was still unacceptable. The large amount of high cost PTMEG used in this formulation makes the use of this mixture commercially unattractive.
Blends of low monol polyoxyalkylene glycol with a low molecular weight polyol were also tested to determine whether the inclusion of the low molecular weight polyol would improve the physical properties of elastomers made from those blends.
When the low molecular weight polyol employed had a polydispersity (measured by size exclusion chromatography) of less than 1.1 (see Comparative Examples C-5, C-6 and C-7), the resulting elastomer had a resistance to corrosion. low stress and abrasion resistance. Additionally, some of those elastomers (Examples C-5 and C-6) had very poor tear strength.
When a low molecular weight polyol having a broad molecular weight distribution (that is, a polydispersity index greater than 1.1) was used with the low monol content polyoxyalkylene glycol (see Examples 1-5), the resulting elastomers they had improved hardness, modulus, compression deflection, tensile strength, and abrasion resistance. Its processability, determined by green resistance, was also vastly improved.
In Examples 1-3 and Comparative Example C-4, a low monol content diol having a molecular weight of 4000 was used as the high molecular weight polyol. The percentage of random internal oxyethylene moieties present in this high molecular weight polyol ranged from 0% (Example 1) to 15% (Example 2) to 30% (Example 3) and 40% (Example C-4 ). POLYOL I (having a polydispersity index of about 1.6) was also used as the low molecular weight polyol in each of Examples 1, 2, 3 and C-4. From the properties of these elastomers presented in Table 1B, it is apparent that the use of a high molecular weight polyol having 40% random internal oxyethylene moieties results in an elastomer with reduced mechanical properties such as strength. to tension, elongation, modulus, and remaining compression.
In Example 4, a low monol content diol having a molecular weight of 3000 and containing 10% random internal oxyethylene moieties was used in combination with an amount of POLYOL I sufficient to result in a molecular weight medium for the mixture of 2000 Da. In Example 5, a 50/50 mixture of a low monol content diol having a molecular weight of 3000 containing 10% random internal oxyethylene moieties and a low monol content polyoxypropylene glycol having a 8000 Da molecular weight as a high molecular weight fraction of the polyol component. The elastomers produced from such a high molecular weight low monol polyol and the low molecular weight polyol having a polydispersity index greater than 1.1 had excellent processing properties and characteristics. The abrasion resistance of the elastomers produced in Examples 4 and 5 was particularly good.
Examples 6-9 and Comparative Examples C-8-C-13
Terminal isocyanate prepolymers were prepared in the same manner as those prepared in Examples 15 and C-1-C-7 and then chain extended to form elastomers. However, the prepolymers used in these Examples 6-9 and C-8-C-13 had an NCO content of 8%. The specific amounts of the specific materials used to produce these elastomers are given in Table 2A. The properties of the elastomers produced in these Examples are presented in Table 2B.
ES 2 284 992 T3
Table 2A
<td>σ></td><td> 1</td><td>CN or 00</td><td> 1</td><td> 1</td><td></td><td></td><td> 1</td><td> 1</td><td> 19,8</td><td> 1</td><td> 1,65</td><td> 12,5</td><td> 50,0</td><td> 3,50</td><td> 8,00</td>
<td>C13</td><td> (</td><td> 1</td><td> 80,6</td><td> •</td><td></td><td> 1</td><td> 1</td><td> 19,4</td><td> 1</td><td> 1</td><td> -</td><td> 12,1</td><td> 47,7</td><td> 3,83</td><td> 8,00</td>
<td>C12</td><td> 1</td><td> 1</td><td> 82,4</td><td>t</td><td> 1</td><td> 17,6</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td><O</td><td>I HEARD ▼ -</td><td> 47,7</td><td> 3,83</td><td> 8,00</td>
<td>C11</td><td> 1</td><td> 1</td><td> 93,5 2</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 6,48</td><td>T "</td><td>t ™ (N</td><td> 47,7</td><td> 3,83</td><td> 8,00</td>
<td>oo</td><td> 1</td><td> 86,62</td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 13,38</td><td> 1</td><td></td><td> 1</td><td><q V—</td><td><N</td><td> 47,7</td><td> 3,83</td><td> 8,00</td>
<td>C10</td><td> 1</td><td></td><td></td><td> 1</td><td> 80,6</td><td> 1</td><td> 19,4</td><td></td><td> 1</td><td> 1</td><td>CO</td><td> 12,1</td><td> 47,7</td><td> 3,83</td><td>or or oo</td>
<td>h-</td><td></td><td> 1</td><td></td><td> 9*08</td><td> 1</td><td></td><td> 19,4</td><td> 1</td><td> 1</td><td> 1</td><td><q v—</td><td> 12,1</td><td> 47,7</td><td> 3,83</td><td> 8,00</td>
<td>co</td><td> 1</td><td> 1</td><td> 80,76</td><td> 1</td><td> 1</td><td></td><td> 19,24</td><td> 1</td><td></td><td> 1</td><td> 1,6</td><td> 12,1</td><td> 47,7</td><td> 3,87</td><td> 8,00</td>
<td>C9</td><td> 1</td><td> 1</td><td> 100</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td>Tt</td><td> 39,5</td><td> 6,22</td><td> 8,00</td>
<td>C8</td><td> 100</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td></td><td> 1</td><td> 1</td><td>t</td><td> 12,1</td><td> 47,7</td><td> 3,87</td><td> 8,00</td>
<td>Ex./Mat.</td><td>< or or 0.</td><td>Polyol F</td><td>Polyol B</td><td>Polyol M</td><td>LU OR OR CL</td><td>Polyol H</td><td>Polyol 1</td><td>Polyol J</td><td>Polyol K</td><td>_J or or CL</td><td>Mw / Mn low polyol P.M</td><td>% p BDO</td><td>%floor</td><td>NCO / OH</td><td>% of</td>
ES 2 284 992 T3 or
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ES 2 284 992 T3
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<td></td><td> 10,0</td><td> 203, 8</td><td> 139</td><td> 289</td><td> 433</td><td> 760</td>
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ES 2 284 992 T3
Prepolymers with a higher NCO content generally produce harder elastomers. The elastomer produced from the prepolymer made with POLYOL A (Example C-8) had a Shore A hardness of 90. The elastomer produced from the prepolymer prepared with POLYOL B alone (i.e. without PTMEG) (Example C-9), was softer than that prepared in Example C-8 and had lower modulus characteristics, poor resistance to abrasion and low compression deflection (under load). The disadvantages of using only a high molecular weight polyol such as POLYOL A are evidenced by the fact that even though the elastomer produced in Example C-8 was prepared from a prepolymer having a higher NCO content, the tensile strength of the elastomer was still 7% lower than that of the elastomer produced in Example C-2.
In contrast, elastomers produced with a polyol component including both a high molecular weight low monol polyoxyalkylene glycol and a low molecular weight polyol having a polydispersity greater than 1.1 had highly mechanical properties and processing characteristics. improved.
In Examples 6, 7 and Comparative Example C-10, a diol with a low monol content was used having a molecular weight of 4000 and an internal oxyethylene residue content of 0% (Example 6), 20% ( Example 7) or 40% (Example C-10) as a high molecular weight polyol. POLYOL I was used as the low molecular weight polyol in each of these examples. As is evident from Table 2B, the elastomers produced in Examples 6 and 7 had properties of hardness, tensile strength, modulus, abrasion resistance, and compression deflection that were superior to those of the elastomers produced in Comparative Example C-9. The elastomer produced in Comparative Example C-10 with a high molecular weight polyol having an internal oxyethylene residue content greater than 30% had poorer mechanical properties, particularly tensile strength, elongation, modulus, tear resistance and compression deflection than elastomers produced in Examples 6 and 7.
In Example 8, the high molecular weight polyol component used was a low monol content diol having 10% random internal oxyethylene moieties and a molecular weight of 3000. Enough POLYOL I was mixed with this high polyol. molecular weight (POLYOL F) to result in an overall average molecular weight of 2000 Da. Although reducing the blend from a molecular weight of 3000 to 2000 Da resulted in a slightly softer elastomer, the use of this blend resulted in a polyol component from which elastomers were prepared having a tensile strength, excellent tear resistance and abrasion resistance.
Comparative Examples C-11, C-12 and C-13 demonstrate that the use of low molecular weight polyols having a low polydispersity index (i.e., a polydispersity of 1.1 or less) did not produce elastomers having acceptable processing properties and characteristics. The elastomers produced in Comparative Examples C-11, C-12 and C-13 exhibited low tensile strength and poor abrasion resistance.
In Example 9, the polyol component included a low molecular weight polypropylene glycol (POLYOL K) having a polydispersity index of 1.65 and a high molecular weight polyol with a low unsaturation content (POLYOL F). The elastomer produced from this polyol component had excellent tensile strength, abrasion resistance and other properties.
Although the invention has been previously described in detail for illustrative purposes, it should be understood that that detail is for this purpose only and that variations may be made therein by those skilled in the art without departing from the spirit and scope of the invention except as what may be limited by the claims.
Contents39
5 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5
24 members in 11 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 20020094238 | United States of America | – | |
| 9423802 | United States of America | A | |
| 9423802 | United States of America | A | |
| 9423803003255 | – | – | – |
| US20020094238 | – | – | – |
Members24
| Document | Office | Kind | |
|---|---|---|---|
| CA2420833A1 | Canada | A1 | |
| EP1342740A1 | European Patent Office (EPO) | A1 | |
| US2003176615A1 | United States of America | A1 | |
| KR20030074157A | Republic of Korea | A | |
| CN1443793A | China | A | |
| JP2003286326A | Japan | A | |
| MXPA03001992A | Mexico | A | |
| US6824703B2 | United States of America | B2 | |
| US2005027096A1 | United States of America | A1 | |
| US7045650B2 | United States of America | B2 | |
| US2006149021A1 | United States of America | A1 | |
| EP1342740B1 | European Patent Office (EPO) | B1 | |
| CN1310992C | China | C | |
| AT359310T | Austria | T | |
| ATE359310T1 | Austria | T1 | |
| DE60313068D1 | Germany | D1 | |
| DK1342740T3 | Denmark | T3 | |
| ES2284992T3This record | Spain | T3 | |
| DE60313068T2 | Germany | T2 | |
| JP2008208386A | Japan | A | |
| US7511111B2 | United States of America | B2 | |
| JP4272453B2 | Japan | B2 | |
| CA2420833C | Canada | C | |
| JP2014088583A | Japan | A |
Numbers
- Publication
- 2284992
- Publication, DOCDB
- 2284992
- Publication, EPODOC
- ES2284992T
- Application
- 3003255
- Application, DOCDB
- 03003255
- Application, EPODOC
- ES20030003255T
Titles2
- Spanish
- ELASTOMEROS DE POLIURETANO QUE TIENEN PROPIEDADES FISICAS MEJORADAS Y PROCEDIMIENTO PARA SU PRODUCCION.
- English
- POLYURETHANE ELASTOMEROS THAT HAVE IMPROVED PHYSICAL PROPERTIES AND PROCEDURE FOR THEIR PRODUCTION.
Classification
- CPC, 2
- C08G18/4808
- C08G18/42
- IPC, 5
- C08G18 48
- C08L71 02
- C08G18 10
- C08G18 66
- C08G65 28
