[go: up one dir, main page]

EP0464141A4 - Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same - Google Patents

Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same

Info

Publication number
EP0464141A4
EP0464141A4 EP19900905858 EP90905858A EP0464141A4 EP 0464141 A4 EP0464141 A4 EP 0464141A4 EP 19900905858 EP19900905858 EP 19900905858 EP 90905858 A EP90905858 A EP 90905858A EP 0464141 A4 EP0464141 A4 EP 0464141A4
Authority
EP
European Patent Office
Prior art keywords
polyol
component
composition
diisocyanate
extender
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP19900905858
Other languages
English (en)
Other versions
EP0464141A1 (fr
Inventor
Bert A. Ross
John R. Damewood
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reeves Brothers Inc
Original Assignee
Reeves Brothers Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/326,183 external-priority patent/US5013811A/en
Priority claimed from US07/326,865 external-priority patent/US5001208A/en
Application filed by Reeves Brothers Inc filed Critical Reeves Brothers Inc
Publication of EP0464141A1 publication Critical patent/EP0464141A1/fr
Publication of EP0464141A4 publication Critical patent/EP0464141A4/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8038—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3225
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols

Definitions

  • the present invention relates to the preparation of linear thermoplastic polyurethane elastomers of a polyol component, at least one extender component, and a diisocyanate compound by initially reacting the diisocyanate compound with the extender to form a modified diisocyanate component prior to reacting this component with the polyol component and other extenders, if any.
  • polyurethane elastomers are utilized in a wide array of products and applications, including producing industrial coated fabrics.
  • these polyurethanes are generally linear polymers exhibiting elastomeric characteristics of high tensile strength and elongation.
  • linear polyurethanes are quite varied in their final properties as a result of the large number of permutations that can be applied to the three main components that are used in their manufacture. These components are polyols, polyisocyanates, and one or more extenders (generally diols) .
  • Some examples of these compounds are: polyether, polyester, polycaprolactone, polycarbonate, and polybutadiene polyols; toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, naphthalene diisocyanate; xylene diisocyanate, hexane diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate; and 1,4- butanediol, 1,6-hexanediol, and 1,3-butanediol extenders.
  • polyurethane elastomers which are considered top of the line with respect to performance, include, for example, polytetramethylene glycol (polyether) polyurethanes and poly(butane adipates or hexane adipates) ester polyurethanes.
  • polyether polyurethanes exhibit good hydrolytic stability and low temperature properties but are generally poor for fuel resistance and oxidation resistance
  • the polyester polyurethanes are tough with good abrasion resistance, oxidation resistance and fuel resistance, but not particularly resistant to hydrolysis.
  • the polyesters are generally considered to represent the best compromise of physical properties and chemical resistance of the various polyurethanes.
  • polyurethanes based on polycarbonate polyols in the market. It is well known that these polycarbonate polyurethanes have very good hydrolytic stability and generally have good to very good resistance to other degradation forces; however, they are usually too hard, rigid and brittle for use in industrial coated fabrics.
  • polyurethane elastomers can be produced from a diol mixture of a polycarbonate diol and a polyoxytetramethylene glycol, and/or a polydimethyl siloxane glycol; an organic diisocyanate and a chain extension compound.
  • Practical Example 4 of Table I lists a porous polyurethane film formed from an 80/20 mixture of polycarbonate diol and polyoxytetra methylene glycol; 4,4'- diphenyl methane diisocyanate and 1,4-butylene glycol, while Practical Example 1 illustrates a film formed from a 50/25/25 mixture of polycarbonate diol/polyoxytetra methylene glycol/polydimethylsiloxane glycol; 4,4'-diphenyl methane diisocyanate and ethylene glycol.
  • These porous films can be used in the manufacture of artificial leather or suede articles.
  • Japanese Patent Specification Sho(61)-151235 discloses the preparation of aliphatic polycarbonate polyol from various mixtures of dialkyl carbonates and glycols. These polyols are described as having low color adhesion an smooth reactivity with isocyanates. Neither reference suggests that these materials can be used as or in the production of polyurethane elastomers for industrial coated fabrics.
  • isocyanate and polyisocyanat compounds are available for use in the preparation of polyurethane elastomers.
  • the particular isocyanate is selected to facilitate preparation of the polyurethane for the intended application.
  • isocyanates which are liquid at room temperature are prepared for ease of handling.
  • MDI Diphenyl methane diisocyanate
  • a liquid MDI composition can be prepared, for example, by partially reacting solid MDI with a glycol, diol or other polyol. Generally, about 10 to 35% of the isocyanate groups are reacted with the polyol.
  • a number of U.S. patents illustrate this concept, including U.S. Patents 3,883,571, 4,115,429, 4,118,411, 4,229,347, 4,490,300, 4,490,301, 4,539,156, 4,539,157 and 4,539,158.
  • Such liquid diisocyanates are stated as being useful for forming polyurethanes for a wide variety of applications. None of these modified diisocyanate compositions have, however, been utilized to prepare linear thermoplastic polyurethane elastomers which have lower temperature processing characteristics compared to similar compositions prepared from solid MDI.
  • the invention relates to improvements in the preparation of a linear thermoplastic polyurethane elastome composition prepared from a polyol component, a diisocyanat compound, and first and second extender components.
  • the processing temperature of the polyurethane is lowered by initially reacting the diisocyanate compound with the first extender in a molar ratio of above 2:1 to form a modified diisocyanate component having a functionality of about 2 prior to reacting the modified diisocyanate component with the polyol and second extender components.
  • a linear thermoplastic polyurethane elastomer composition is formed which has lower temperature processing characteristics compared to similar compositions wherein the diisocyanate compound is not modified.
  • the polyol component may be a polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyester polyol, polybutadiene polyol or mixtures thereof, and the first extender component is generally a polyol or amine compound having a molecular weight of less than about 500.
  • the first extender component comprises a diol.
  • the second extender component is included for optimum results.
  • the diisocyanate compound is modified so that the modified diisocyanate component has an NCO content of between about 14 and 33%, and preferably between about 20 and 26%.
  • the most advantageous diisocyanate compound is one that primarily comprises 4,4'-diphenyl methane diisocyanate, with the first extender component being a polyol or a ine compound having a molecular weight between about 60 and 250, such as 1,4-butane diol, tripropylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, 1,6-hexane diol, 1,3-butane diol, neopentyl glycol, ethylene diamine or mixtures thereof.
  • the present invention also relates to a linear thermoplastic polyurethane elastomer compositions comprising a mixture of a polycarbonate polyol and a polyether polyol; a diisocyanate compound; and first and second extenders.
  • the diisocyanate compound is initially reacted with one of the extenders in a molar ratio of above 2:1 so as to form a modified diisocyanate component having a functionality of about 2 prior to reaction with the other components.
  • This modified diisocyanate component provides relatively low temperature processing properties to the composition, whereas the polyol mixture provides superior hydrolytic stability and low temperature flexibility to the composition.
  • the first extender component is a polyol or amine compound having a molecular weight of less than about 500, such as a diol, while the diisocyanate compound primarily comprises 4,4 '-diphenyl methane diisocyanate.
  • the first extender component is a polyol or amine compound having a molecular weight between about 60 and 250, such as 1,4-butane diol, tripropylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, 1,6- hexane diol, 1,3-butane diol, neopentyl glycol, ethylene diamine or mixtures thereof.
  • the polyether polyol and polycarbonate polyol are present in a relative amount of between 2:1 to 1:8.
  • the first extender is 1,4-butanediol and the second extender is tripropylene glycol
  • the modified diisocyanate component has an NCO content of between about 14 and 33%, preferably between about 20 and 26%.
  • the overall NCO/OH ratio of the entire composition is between about 0.95 and 1.05/1.
  • One preferred embodiment of this invention relates to a polyurethane elastomer based on a mixture of polycarbonate and polyether polyols, a modified diisocyanate component formed by reacting a diisocyanate compound with a low molecular weight extender such as tripropylene glycol, and a second extender of 1,4-butanediol.
  • the modified diisocyanate and the second extender enable the polymer to have low temperature processing properties compared to those wherein the diisocyanate is not modified.
  • This polymer also has hydrolytic stability which is vastly superior to conventional polyester polyurethanes.
  • This polymer also has elastomeric characteristics and other physical properties which render it suitable for use in coated fabric manufacturing processes and resultant products produced therefrom.
  • the polyether polyol and polycarbonate polyol can be used in any relative amounts provided that each are present in the composition. It has been found convenient to use a polyether polyol: polycarbonate polyol ratio in the range of between 2:1 to 1:8.
  • tripropylene glycol and 1,4-butanediol other low molecular weight extenders can be used.
  • polyols having a molecular weight of between about 60 and 500 (and preferably less than 250) have been found to be advantageous, although amines such as ethylene diamine can also be used.
  • Specific polyols include diols such as 1,3-butanediol, ethylene glycol, tripropylene glycol, dipropylene glycol, propylene glycol, and neopentyl glycol, triols such as tri ethyol propane, as well as mixtures of these components, can be used.
  • Any diisocyanate compound is suitable with those based on 4,4 '-diphenyl methane diisocyanate being preferred.
  • Toulene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, xylene diisocyanate and cyclohexane diisocyanate can also be used, if desired, but these compounds are generally more expensive or slower reacting.
  • Such diisocyanate compounds are converted to a modified diisocyanate component as previously described.
  • the relative amount of modified diisocyanate to polyol ranges from above 2:1 to 20:1, and preferably between about 2.5:1 and 8:1.
  • the second extender compound is included in an amount to achieve a final NC0:0H ratio of between about 0.95 to 1.05/1.
  • the Examples illustrate preferred ratios of components for use in the preparation of linear polyurethanes in accordance with this invention.
  • Another preferred embodiment of the invention relates to the manufacture of any type of polyurethane elastomer prepared from the modified diisocyanate component to significantly lower the temperature requirements for processing the polyurethane on heat processing equipment, i.e., calenders, extruders, injection molding apparatus, etc.
  • This modification includes reacting diisocyanate compound with a low molecular weight extender (i.e., polyol or amine compound, to form a modified diisocyanate component, prior to preparing the polyurethane with the other components.
  • a low molecular weight extender i.e., polyol or amine compound
  • MDI diisocyanate compounds primarily based on 4,4'-diphenyl methane diisocyanate which are preferred for use in this invention.
  • liquid MDI will be used to designate an essentially difunctional modified MDI component prepared from the reaction of a low molecular weight polyol with an MDI compound to form a modified diisocyanate composition which is liquid at room temperature.
  • the low molecular weight extender used to modify the diisocyanate compound generally includes diols, triols or amines having a molecular weight below about 500, but any polyol which enables the diisocyanate compound to possess a functionality of about 2 and an NCO content of between about 14 and 33%, preferably between 20 and 26%, after modification, would be acceptable.
  • any polyol component can be used for reaction with the liquid MDI component, including polyether, polyester, polycaprolactone, polycarbonate or polybutadiane polyols or mixtures thereof.
  • a preferred polyol component is mixture of a polyether polyol and polycarbonate polyol.
  • extenders also being a polyol or amine compound, preferably one of relatively low molecular weight (i.e., less than about 500). It is also possible to utilize unsaturated polyols as extenders, such as low molecular weight diols which include one or more double bonds. However, any conventional extender known to those skilled in the art can be used, depending upon the results desired.
  • the present invention demonstrates how various polycarbonate and polyether polyols, modified diisocyanate components and extenders may be blended over a wide range to allow the design of polyurethane polymers having different physical characteristics and properties. This makes it possible to custom design a polymer for a particular application.
  • modified MDIs there are several different types of modified MDIs presently on the market, but the types suitable for use in this invention are essentially difunctional.
  • the preferred liquid MDI components are made by reacting an MDI compound with a small amount of a diol such as tripropylene glycol or a mixture of diols.
  • the material resulting from this sligh extension of the MDI compound is a liquid at room temperature while, as noted above, the original MDI compoun is a solid at such temperatures. This makes the liquid MDI substantially easier to handle and process, while retaining generally equivalent performance to the unmodified MDI compound.
  • isocyanates having a functionality which is much greater than two are not particularly suitable for use in this invention, since they promote crosslinking rather than linearity in the resultant polyurethane polymer.
  • the functionality of these compounds should be above 1.9 but below 2.2, with the preferred modified diisocyanate components being those having a functionally of approximately 2 so as to facilitate the preparation of linear polyurethanes.
  • the use of the modified diisocyanate components of this invention enables a polyurethane having lower temperature processing characteristics to be achieved
  • the temperature difference can be as great as 30 to 40 ⁇ F below that of a corresponding formulation wherein the diisocyanate compound is not modified.
  • greater temperature reductions are achieved when the polyurethane i manufactured in a specific manner.
  • the polyurethanes of the invention are made by the conventional "one shot” technique, a slight reduction on the order of about 3-4 degrees is obtained: this representing only about 10% of the maximum reduction which could be achieved.
  • solid MDI is used t prepare an isocyanate prepolymer with the high molecular weight polyol prior to reacting this prepolymer with the mixed extenders, a temperature reduction of about 4-5 degrees (i.e., about 15% of the maximum) is achieved.
  • Substantial reductions in the temperature processability of the resulting polyurethane can be achieve by following one of the following methods of manufacture.
  • the isocyanate is pre-reacted with one of the extenders to form a modified isocyanate component prior to reaction with a mixture of the high molecular weight polyol and other extenders.
  • This enables a temperature reduction of about 20 to 25 degrees to be achieved (i.e., about 60% of the optimum) .
  • the optimum temperatur reduction is achieved by sequentially reacting the modified isocyanate component first with the high molecular weight polyol followed by reaction with the second extender.
  • a temperature reduction of 30 to 40 degrees is possible, with the formation of a clear polyurethane polymer.
  • MDI modified as disclosed herein, is the most advantageous diisocyanate for use in preparing the polyurethanes of this invention, although the other isocyanates mentioned above can instead be used, if desired.
  • an isophorone diisocyanate can be used to achieve better results than MDI.
  • toluene diisocyanate can be used, but it is less reactive than MDI.
  • amine extenders rather than polyol or diol extenders, should be used.
  • One skilled in the art can select the best combination of ingredients for any particular formulation.
  • linear polyurethane elastomers are preferably made using a two step solution polymerization technique.
  • Predried toluene, dimethyl formamide and the isocyanate are charged to a 3000 ml reactor (in some cases a 15,000 ml reactor was used).
  • a given weight of polyol(s), the amount needed to achieve the desired prepolymer NCO/OH value, is dissolved in additional dry toluene.
  • the reactor is then prepurged with dry nitrogen and maintained under a positive low pressure of dry nitrogen for the full reaction time.
  • the isocyanate containing solution is preheated to 65- 75°C (depending on anticipated exotherm) , and the solution of polyols is slowly added by a continuous stream (over one-half hour) to the reactor. The temperature is allowed to rise to 80-90 ⁇ C (depending on system) and is maintained at this temperature for an additional two hours.
  • the desired extender diol is preweighed and dissolved in dry dimethyl formamide.
  • the reactor is cooled to 60-65°C and two 7-10 gram samples of the reaction mixture are removed and analyzed for NCO content.
  • the diol is then charged to the reactor, and the temperature raised (partly by the exotherm of extension) to 85-90°C and maintained at this temperature for two hours.
  • a sample of the polymer is dried and an IR spectrum was run. If free NCO is detected in the spectrum, the reaction is continued for another hour.
  • the reaction solution is then allowed to cool to room temperature overnight and stored in a container until it ca be tested. All mixtures were designed to yield a solution of 30% by weight of polymer dissolved in a 60/40 mixture of toluene/DMF.
  • This solution cooking technique provides an easy way o making this polymer, but it is difficult to evaluate the physical properties of such solutions.
  • the solution collected from an individual cook is spread coated onto release paper and dried at 300 ⁇ F to remove the solvent. This film can then be stripped from the paper and used to conduct various physical property tests.
  • One gram of cadmium stearate was added to 200 grams of dried polymer and intimately mixed on a two roll rubber mill.
  • a 0.040 inch slab of polymer was removed from the mill and was used to make tensile specimens. This was done by pressing the slab between two polished plates in a heate abash press for 15 minutes at sufficient temperature and pressure to yield a 0.010 - 0.014 inch film. Temperatures and pressures varied depending upon the particular formulation. The press was cooled to room temperature and the film was removed from between the plates. From this film, five samples were cut in the size of one inch by six inches. These were then tested on an Instron and averages of 100% modulus, 200% modulus, tensile strength, and elongation were calculated from the test results. The temperature for the milling and pressing operations were observed and found to be related to formulation changes.
  • a three to five gram sample of polymer was finely chopped and used to determine the temperature at which the polymer would flow at a measurable rate and to determine the rate itself on a Kayness, Inc. extrusion plasto eter Model D-0051.
  • a measurable rate was defined as greater than 0.15 grams per 10 minutes. Thus at temperatures below the flow temperature, neither fusion of the polymer nor flow greater than 0.15 grams is achieved.
  • the flow rate is defined as the number of grams extruded from the barrel of the plastometer in a period of ten minutes.
  • Table I illustrates the effect that modified liquid MDI components have on flow temperature of various polyurethanes compared to those made from the corresponding unmodified MDI compound.
  • the table lists six polyurethanes made with various polyols, including some mixtures of polyols. Each two examples represent a polyurethane made from liquid MD and its analog made from the corresponding MDI unmodified, solid component. As shown in the table, the percent hard segment is equivalent in each comparison. Examples 1, 3, 5, 7 9 and 11 are in accordance with the present invention, while Examples 2, 4, 6, 8, 10 and 12 are included for comparison. I all cases, the liquid MDI polymer has a lower flow temperature than its solid MDI analog. Flow temperature is that temperature at which a measurable flow is first observed when tested on an extrusion plastometer.
  • liquid MDI components Since flow temperature is a measure of the temperature at which the polymer may be processed on calendering and extrusion equipment, the use of the liquid MDI components allows the making of polymers which process at lowe temperatures, and therefore are easier to process and manufacture into articles such as calendered sheets for coated fabrics. The results demonstrate that all experimental polymers made with liquid MDI components exhibited lower milling temperatures than those of their solid MDI analogs.
  • Table I illustrates polyurethanes made wit polyether, polyester, and polycarbonate polyols, it would be expected that this improvement would be present regardless of the specific type of polyol used.
  • Table III compares polycarbonate polyurethanes mad from liquid MDI components against those made with solid MDI components. Examples 17-19 are in accordance with the invention, while Examples 20-22 are comparative. It can be seen from the data that polyurethane polymers made using liqui MDI exhibit better physical properties, particularly tensile strength, compared to those made with solid MDI. Flow temperatures were not specifically measured on the liquid MDI polymers, but processing on the mill was found to be significantly better than for polymers made with the comparabl unmodified, solid MDI compounds.
  • liquid MDI allow the production of polyurethane elastomers having a higher percent hard segment. This is advantageous because in general the urethane linkages are much more stable to various degradation forces (i.e. hydrolysis, oxidation, etc.) than are ether, ester or other bonds in the polyol backbone.
  • Polyurethane elastomers made from an aliphatic polycarbonate polyol, liquid MDI and 1,4-butanediol were prepared as shown in Table III, Examples 17-19.
  • a mixture of polycarbonate polyols was used in Example 38 of table IV.
  • Excellent physical properties, particularly tensile strength and elongation, were achieved in these formulations.
  • tensile curves it was observed that these polymers were more plastic than elastomeric in character
  • these polymers could be described as hard and tough with a high yield value as illustrated by the 100% modulus values.
  • evaluation of films of the polycarbonate based polyurethane polymers exhibited poor cold crack properties.
  • a copolyol was introduced into the system, as shown in Examples 23-37 of Tables IV (A & B) .
  • a polytetramethylene glycol (“PTMG”) polyol was found to have the compatibility with the specific polycarbonate polyols used, with the molecular weight of 1000 and 2000 each found to be suitable.
  • Table V (A&B) compares two formulations which are similar with the exception of the introduction of 20% PTMG polyether polyol into the polymer (Example 40) . Again the changes in physical properties can be observed.
  • T of the formulations of these examples was determined by mechanical spectrometry (M.S.) and differential scanning calorimetry (DSC) to be as follows:
  • Examples 41-45 Table VI (A&B) illustrates the reproducibilit of the invention by listing several formulations which were made at different times on different days.
  • Example 40 In both cases, the formula of Example 40 was used.
  • the one-shot experiment was conducted by weighing the polyols and diol into a plastic container and mixing well under nitrogen. The appropriate amount of LF-179 was then added, mixed well, capped under nitrogen and placed in an oven at 90 ⁇ C overnight.
  • the prepolymer approach was conducted by mixing th polyols thoroughly with an excess of isocyanate (per formula) , followed by capping and heating for two hours at 85 ⁇ C. After removing the sample from the oven, an appropriate amount of diol was added, quickly mixed, capped and returned to a 90 ⁇ C oven overnight.
  • Table VII gives a comparison of a solution coo to a one-shot and a prepolymer cook. In all cases, flow temperature is still lower than a comparable unmodified MDI polymer and physical properties are very similar. Working these polymers on a rubber mill indicates that the prepolymer approach may actually yield a lower temperature processing polymer than the one-shot approach. Also, the prepolymer approach provides a much clearer polymer which is a sign of better uniformity and compatibility. Therefore the prepolymer approach is preferred although the one-shot approach will indeed yield acceptable polymers and, it is seen that a new linear polyurethane elastomers useful for a wide variety of applications can be prepared.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NCO/OH ratio.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NCO/OH ratio.
  • Each formulation contains 1, -butane diol as an extender as necessary to achieve the final NCO/OH ratio.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NCO/OH ratio.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NCO/OH ratio.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NC0/0H ratio.
  • Equivalent and weight ratio refer to the ratio of primary to secondary polyol by equivalents or weight, respectively.
  • Each formulation contains 1,4-butane diol as an extender in an amount necessary to achieve the final NCO/OH ratio.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des élastomères de polyuréthane linéaires d'un composant polyol, au moins deux diluants, et un composé de diisocyanate sont préparés en faisant réagir le composé de diisocyanate avec l'un des diluants pour former un composant de diisocyanate modifié ayant une fonctionnalité d'environ 2 avant de faire réagir ce composant modifié avec les autres composants de l'élastomère. Un composant de polyol préféré comprend un mélange d'un polyol de polycarbonate et un polyol de polyéther. Ces nouveaux élastomères possèdent une combinaison unique de caractéristiques telles que la stabilité hydrolitique, la résistance et la flexibilité, et peuvent être traités à des températures plus basses que les températures de traitement d'élastomères préparés à partir de compositions semblables dans lesquelles le composé isocyanate n'est pas modifié.
EP19900905858 1989-03-20 1990-03-19 Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same Ceased EP0464141A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/326,183 US5013811A (en) 1989-03-20 1989-03-20 Use of modified diisocyanates for preparing linear thermoplastic polyurethane elastomers having improved properties
US07/326,865 US5001208A (en) 1989-03-20 1989-03-20 Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols
US326183 1989-03-20
US326865 1989-03-20

Publications (2)

Publication Number Publication Date
EP0464141A1 EP0464141A1 (fr) 1992-01-08
EP0464141A4 true EP0464141A4 (en) 1992-05-20

Family

ID=26985288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900905858 Ceased EP0464141A4 (en) 1989-03-20 1990-03-19 Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same

Country Status (6)

Country Link
EP (1) EP0464141A4 (fr)
JP (1) JPH04504138A (fr)
KR (1) KR920701290A (fr)
AU (1) AU642409B2 (fr)
CA (1) CA2047678A1 (fr)
WO (1) WO1990011309A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU664158B2 (en) * 1990-09-12 1995-11-09 Polymedica Industries, Inc Biostable polyurethane products
DE4217362A1 (de) * 1992-05-26 1993-12-02 Bayer Ag Thermoplastisch verarbeitbare Polyurethan-Elastomere mit verbessertem Verarbeitungsverhalten und Verfahren zur Herstellung
DE9317924U1 (de) * 1993-11-23 1994-02-10 W.L. Gore & Associates Gmbh, 85640 Putzbrunn Flachdichtung für Kraftstofftanks
AU2014265117B2 (en) * 2010-09-16 2016-05-26 Baker Hughes Incorporated Polymer foam cell morphology control and use in borehole filtration devices
CN103827207B (zh) 2011-07-25 2017-07-11 诺沃梅尔公司 用于聚氨酯的脂族聚碳酸酯
JP6811531B2 (ja) 2012-11-07 2021-01-13 サウジ アラムコ テクノロジーズ カンパニー 高強度ポリウレタンフォーム組成物及び方法
JP6341405B2 (ja) * 2013-10-22 2018-06-13 Dic株式会社 ウレタン組成物及びウレタンエラストマー成形品
DE102013021027A1 (de) * 2013-12-17 2015-06-18 Carl Freudenberg Kg Thermoplastisches Polyurethan für Dichtungsanwendungen
JP2021524530A (ja) * 2018-07-12 2021-09-13 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ ガラス繊維強化ｔｐｕ
CN114891181B (zh) * 2022-05-26 2024-03-12 浙江华峰合成树脂有限公司 一种聚氨酯树脂及其镜面合成革
CN117229471A (zh) * 2023-11-15 2023-12-15 长春设备工艺研究所 聚氨酯弹性体的改性方法及其3d打印温度参数优化方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2523987A1 (de) * 1974-06-04 1976-01-02 Stassfurt Veb Chemieanlagenbau Verfahren zur herstellung thermoplastisch verformbarer polyurethanelastomerer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2221756C3 (de) * 1972-05-04 1980-06-26 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von lösungsmittelbeständigen, lichtechten, knick- und reibfesten Polyurethanüberzügen auf textlien Substraten, Leder oder Kunstleder oder von Folien
DE2906113C2 (de) * 1979-02-17 1985-06-13 Fa. Carl Freudenberg, 6940 Weinheim Verwendung von feindispersen Polyurethanharnstoffen als Heißsiegelkleber zur Herstellung von heißsiegelbaren Einlagestoffen
US4306052A (en) * 1980-09-25 1981-12-15 The Upjohn Company Thermoplastic polyester polyurethanes
JPS57205469A (en) * 1981-06-10 1982-12-16 Toyo Ink Mfg Co Ltd Solventless polyurethane adhesive for dry laminate
JPS61179733A (ja) * 1985-02-05 1986-08-12 旭硝子株式会社 積層体およびその製造方法
FR2577934B1 (fr) * 1985-02-26 1988-01-08 Saint Gobain Vitrage Couche adhesive a base de polyurethane et son utilisation dans les vitrages feuilletes
DE3622609A1 (de) * 1986-07-05 1988-01-07 Bayer Ag Verfahren zur herstellung von fluessig-kristallinen nco-polyurethanpraepolymeren und deren verwendung
DE3628141A1 (de) * 1986-08-19 1988-02-25 Bayer Ag Lineare polyurethan-elastomere und verfahren zu ihrer herstellung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2523987A1 (de) * 1974-06-04 1976-01-02 Stassfurt Veb Chemieanlagenbau Verfahren zur herstellung thermoplastisch verformbarer polyurethanelastomerer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of WO9011309A1 *
WORLD PATENTS INDEX LATEST Week 8733, Derwent Publications Ltd., London, GB; AN 87-233021 & JP-A-62 158 712 (TOYO RUBBER) 14 July 1987 *

Also Published As

Publication number Publication date
AU642409B2 (en) 1993-10-21
AU5355190A (en) 1990-10-22
KR920701290A (ko) 1992-08-11
JPH04504138A (ja) 1992-07-23
CA2047678A1 (fr) 1990-09-21
EP0464141A1 (fr) 1992-01-08
WO1990011309A1 (fr) 1990-10-04

Similar Documents

Publication Publication Date Title
US5001208A (en) Linear polyurethane elastomer compositions based on mixed polycarbonate and polyether polyols
US5013811A (en) Use of modified diisocyanates for preparing linear thermoplastic polyurethane elastomers having improved properties
Rogulska et al. Studies on thermoplastic polyurethanes based on new diphenylethane-derivative diols. II. Synthesis and characterization of segmented polyurethanes from HDI and MDI
US4376834A (en) Polyurethane prepared by reaction of an organic polyisocyanate, a chain extender and an isocyanate-reactive material of m.w. 500-20,000 characterized by the use of only 2-25 percent by weight of the latter material
EP1805239B1 (fr) Elastomere polyurethanne de grande transparence
CA2168938C (fr) Resine de polyurethanne thermoplastique
CN109438646B (zh) 聚氨酯弹性体组合物、聚氨酯弹性体及其制备方法
US5070172A (en) Process for producing polyurethane
EP0464141A4 (en) Linear polyurethane elastomer compositions and use of modified diisocyanates for preparing same
US5096992A (en) Use of modified diisocyanates for preparing linear thermoplastic polyurethane elastomers having improved properties
US6022939A (en) Thermoplastic polyurethanes with improved melt flow
CN110498900A (zh) 高黑色展色性革用聚氨酯树脂及其制备方法
CA2404753A1 (fr) Elastomeres de polyurethane thermoplastiques (tpus) prepares avec un segment souple de carbonate de polytrimethylene
JP2003504520A (ja) 高い弾性回復および低い応力緩和を有するポリウレタンエラストマー製の溶融加工が可能で漂白耐性のある耐久性繊維
CN100336839C (zh) 热塑性聚氨酯
CN109337035B (zh) 高耐甲苯性超细纤维合成革用聚氨酯树脂及其制备方法
CA2165617C (fr) Polyurethanes thermoplastiques a fluage ameliore
CA3153627A1 (fr) Composition de polyurethane thermoplastique
JP3980068B2 (ja) ポリウレタン
KR101955499B1 (ko) 아자이드계 탄성체 및 이의 제조방법
Kultys Sulfur‐Containing Polyesters, 9. The Synthesis and Characterization of New Diphenylmethane‐Derivative Thiopolyester Diols and Their Use for the Preparation of Thermoplastic Polyurethanes
JPS60199017A (ja) 熱可塑性ポリウレタンの製造法
JP2025114006A (ja) 硬化性組成物及び合成皮革
KR20250164278A (ko) 폴리우레탄 수지 조성물
JP2024046145A (ja) 合成皮革用ポリウレタン樹脂及び合成皮革

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19910930

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

A4 Supplementary search report drawn up and despatched

Effective date: 19920402

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930916

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19951217