WO1991000304A1 - Procede de polymerisation a l'etat de fusion pour la production de polyurethanes - Google Patents

Procede de polymerisation a l'etat de fusion pour la production de polyurethanes Download PDF

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Publication number
WO1991000304A1
WO1991000304A1 PCT/US1990/002869 US9002869W WO9100304A1 WO 1991000304 A1 WO1991000304 A1 WO 1991000304A1 US 9002869 W US9002869 W US 9002869W WO 9100304 A1 WO9100304 A1 WO 9100304A1
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Prior art keywords
zone
high shear
process according
polyol
shear mixing
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PCT/US1990/002869
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English (en)
Inventor
Henry W. Bonk
Augustin T. Chen
Benjamin S. Ehrlich
Laverne W. Ellerbe
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The Dow Chemical Company
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Publication of WO1991000304A1 publication Critical patent/WO1991000304A1/fr

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    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • 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
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Definitions

  • This invention relates to polyurethanes and is more particularly concerned with a process for the preparation of high flexural modulus polyurethane plastics by reactive extrusion.
  • thermoset and thermoplastic polyurethane polymers introduced novel classes of both thermoset and thermoplastic polyurethane polymers to the plastics molding art. These materials are characterized by high impact resistance, stiffness, and other structural strength properties similar to nylon and other engi ⁇ neering thermoplastics. Additionally, some members of this group of new materials have exceptionally high Tg values, as high as 165°C. The advent of these materials has provided the molding industry with excellent alter ⁇ native engineering thermoplastic material choices. Notably, some of these polyurethanes are thermoplastic and contain little or no soft segment because of either the very minor amount, or, complete absence, of high molecular weight polyol in their formulations.
  • thermo la tic nature and, similarly, to the well known softer thermoplastic polyurethanes, these materials lend themselves to manufacture by the reactive extrusion process.
  • This method is preferable because of its economic advantages in terms of simply adding the necessary ingredients into a screw extruder in the absence of solvents and continuously, but rapidly, producing a finished product in the form of desirable profiles or pellets.
  • Such continuous methods are preferably carried out in multi-shaft screw extruders, more preferably twin-screw extruders.
  • U.S. Patent 3,642,964 and its German counter ⁇ part DE 2059570 were the first disclosures to the continuous reactive extrusion of soft thermoplastic polyurethanes in twin-screw extruders.
  • This teaching called for high shear mixing zones in the extruder barrel with each zone having a series of kneading blocks which can have various configurations. More than one such mixing zone or series of blocks is employed on each of the twin-screw shafts.
  • the plurality of mixing zones are either separated by conveying screws or else conneoted as one long multi-zone depending on the manufacturer's design of the extruder.
  • U.S. Patent 3,963,679 discloses a process quite similar to the one described above in employing the extrusion apparatus set forth in Figure 1 of its disclosure. Primarily, this method differs from that of U.S. Patent 3*642,964 supra in requiring that the poly ⁇ urethane forming mixture be subjected to its first l ⁇ shear mixing during the time it has a viscosity of 10,000 to 100,000 centipoise (10 to 100 Pa « s). This limitation is paramount to the invention disclosed because when only a single kneading zone is employed after the viscosity has surpassed the upper viscosity limit (Example 1b, column 14) the product was inhomogeneous.
  • U.S. Patent 4,245,081 discloses the continuous preparation using the procedures described in U.S. Patents 3,642,964 and
  • U.S. Patents 4,261,946 and 4,342,847 each disclose essentially the same process differing only in the component proportions.
  • the former is directed to modifying 70 to 98 parts of a thermoplastic polymer with 2 to 30 parts of polyurethane forming components.
  • the procedure is accomplished by adding the thermoplastic polymer, inclusive of preformed polyurethane, and the poly ⁇ urethane forming ingredients to the first and second inlets respectively of an extruder.
  • the polyurethane formed in situ in the extruder is inclusive of both those with and without soft segments.
  • the latter has the preformed thermoplastic polymer at 4 to 65 parts with the polyurethane forming components at 35 to 96 parts.
  • Both patents disclose the use of the same twin-screw technology described in U.S. Patent 3,963,679 supra.
  • U.S. Patent 4,595,709 discloses a method for converting toluene diisocyanate distillation residues to useful polyurethane polyaddition products containing urethane groups by continuously reacting the residues with low molecular weight compounds containing hydroxyl groups. The reaction is carried out in multiple-screw extruders using the extrusion technology of U.S. Patent 3,963,679 cited supra.
  • the present invention is directed to an improved reactive extrusion process for the continuous preparation of a polyurethane having a Tg greater than 80°C from a reaction mixture comprising a polyisocyanate and at least one polyol component by passing said reac ⁇ tion mixture through a twin-screw extruder having besides the feed zone, zones of high shear mixing and a metering zone, wherein the improvement comprises limit ⁇ ing the high shear mixing to a single zone.
  • the polyurethanes prepared in accordance with the present invention are substantially free of bubble formation and, surprisingly, are found to be much lighter in color than those same chemically constituted polyurethanes but prepared by the prior art method.
  • the difference in color is t-eadily detected by comparing Yellowness Index determinations for the respective samples when measured in accordance with ASTM Test Method D-1925.
  • the present reactive extrusion process can be carried out at much lower L/D ratios than prior art extrusion methods.
  • L/D ratio refers to the overall length of the twin-screw extruder barrel divided by the barrel diameter, usually measured in millimeters (mm). In running at lower L/D ratios which means shorter barrels, this translates to an additional benefit of lowered energy consumption compared with prior art methods.
  • the polyurethanes produced in accordance with the present process are made up of either all hard segments or hard segments with only a minor proportion of soft segments arising from the small amount of high molecular weight polyol used which is discussed in the art cited supra. They are characterized by the following properties: high impact resistance of at least 1 ft. lb. per inch (53 J/m), preferably at least 3 ft. lbs.
  • those polyurethanes prepared with non-aromatic polyisocyanates are characterized by having essentially optical clarity and light stability.
  • the products produced in accordance with the present invention find utility, for example, in the molding of under the hood auto and truck parts such as distributor covers, filter bowels, air-filter units and covers, containers and covers for electronic circuitry, medical devices requiring transparency and autoclavability, surgical instrument trays and containers for steam sterilization.
  • FIG 1 shows in schematic form one typical embodiment of the process of the invention.
  • the reactive extrusion process in accordance with the present invention is directed primarily to certain specific classes of hard, high temperature resistant polyurethanes defined above. All of the reactants, components, ingredients, and catalysts and proportions therefor have already been set forth in detail in U.S. Patents 4,376,834; 4,567,236; and
  • compositions include both thermoplastic in ection-moldable resins and thermoset resins.
  • thermoplastic in ection-moldable resins are obtained when polyisocyanates, extenders and polyols of functionalities greater than two are employed as taught in the previously mentioned patents.
  • Thermoplastic products are obtained by employing substantially difunctional polyisocyanates and difunctional extenders and, if used, polyols having functionalities preferably not exceeding about 4. Since the amount by weight of the polyol employed is relatively small, it is thus possible to employ such components having functionalities greater than two without detracting from the thermoplasticity of the polymer.
  • the thermoplastic materials are greatly preferred and in this connection the following sets forth some of the more preferred reactants which can be employed.
  • Illustrative isocyanates but non-limiting thereof are methylenebis(phenyl isocyanate) including the 4,4'-isomer, the 2,4'-isomer and mixtures thereof, m- and p-phenylene diisocyanates, chlorophenylene diisocyanates, ⁇ , ⁇ '-xylylene diisocyanate, 2,4- and 2,6- -toluene diisocyanate and the mixtures of these latter two isomers which are available commercially, tolidine diisocyanate, hexamethylene diisocyanate, 1,5- -naphthalene diisocyanate and isophorone diisocyanate; cycloaliphatic diisocyanates such as methylenebis(cyclohexyl isocyanate) including the 4,4'- -isomer, the 2,4'-isomer and mixtures thereof, and all the geometric isomers thereof including trans/trans, cis/trans, cis/cis and
  • modified forms of methylenebis(phenyl isocyanate By the latter are meant those forms of methylenebis(phenyl isocyanate) which have been treated to render them stable liquids at ambient temperacu ⁇ e (circa 20°C). Such products include those which have been reacted with a minor amount (up to about 0.2 equivalents per equivalent of polyisocyanate) of an aliphatic ⁇ .lycol or a mixture of aliphatic glycols such as the modified methylenebis(phenyl isocyanates) described in U.S. Patents 3,394,164; 3,644,457; 3,883,571; 4,031,026; 4,115,429; 4,118,411; and 4,299,347.
  • the modified methylenebis(phenyl isocyanates) also include those which have been treated so as to convert a minor proportion of the diisocyanate to the corresponding carbodiimide which then interacts with further diisocyanate to form uretone-imine groups, the resulting product being a stable liquid at ambient temperatures as described, for example, in U.S. Patent 3,384,653. Mixtures of any of the above-named polyiso ⁇ cyanates can be employed if desired.
  • a particularly preferred group of diisocyanates includes aromatic and cycloaliphatic diisocyanates and mixtures thereof as exemplified above.
  • Most preferred species within this group include methylenebis(phenyl isocyanate) including both 4,4'- and 2,4'-isomers and mixtures thereof with 4,4'- preferred, methylenebis- (cyclohexyl isocyanate) including the 4,4'- and 2,4'-isomers and mixtures thereof including all of the geometric isomers thereof with the 4,4*- preferred, and 4,4'-isopropylidenebis(cyclohexyl isocyanate).
  • the at least one polyol component called for above in its broadest scope will include the chain extender and any polyol if it be employed.
  • the difunctional extenders they are not strictly limited to hydroxyl-containing extenders but can include other active hydrogen materials such as amine groups or mixtures of such extender types.
  • the preferred extenders comprise at least one diol having a molecular weight of from 60 to 400. Included in this group are the aliphatic diols having 2 to 10 carbon atoms, inclusive of bis(hydroxyalkyl)cycloalkanes; and the cycloalkane diols described in U.S. Patent 4,822,827 as having 4 to 12 cycloaliphatic carbon atoms.
  • diols Illustrative of such diols are ethylene glycol, 1,3- -propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1,6- -hexanediol, 1 ,2-propanediol, 1,3-butanediol, 2,3- -butanediol, 1,3-pentanediol, 1,2-hexanediol, 3- -methylpentane-1 ,5-diol, 1 ,9-nonanediol, 2-methyloctane- -1,8-diol, 1 ,4-cyclohexanedimethanol, neopentyl glycol, hydroquinone bis(hydroxyethyl)ether, diethylene glycol, dipropylene glycol and tripropylene glycol including mixtures of two or more such diols; 1
  • Preferred for use in the present process are 1,4-butanediol, 1 ,5- oxanediol, 1 ,6-hexanediol, 1,4- -cyclohexanedimethanol, the cyclohexanediols including the 1,2-, 1,3-, and 1,4-isomers, and 4,4'-isopropyli- denebis(cyclohexanols) , and mixtures of the above in accordance with the teachings of the previously mentioned patents.
  • the expedient concentration for the polyol falls in the range of from 0 to 25 parts by weight per 100 parts of total urethane reactants based on (i) organic polyisocyanate, (ii) at least one chain extender and said polyol (iii).
  • an advantageous range is from 1 to 15 parts per 100 parts of reactants, and preferably from 1 to 5 parts.
  • Minimum requirements for the polyol component are a molecular weight of at least 500 and functionality of at least 2.
  • the molecular weight falls within a range of from 500 to 12,000 with a functionality of from 2 to not greater than 6; preferably the molecular weight and functionality are from 500 to 6,000 and from 2 to 4 respectively; most preferabl/ the functionality is from 2 to 3.
  • polyether polyols examples include polyether polyols, poly ⁇ ester polyolt;, hydroxy-terminated olycarbonates, hydroxy-terminated polybutadienes, hydroxy-terminated polybutadiene-acrylonitrile copolymers, hydroxy- -terminated copolymers of dialkyl siloxane and alkylene oxides such as, for example, ethylene oxide and propylene oxide, and mixtures in which any of the above polyols are employed as major component (greater than 50 percent w/w) with amine-terminated polyethers and amino- -terminated polybutadiene-acrylonitrile copolymers.
  • polyether polyols are polyoxy- ethylene glycols, polyoxypropylene glycols which, optionally, have been capped with ethylene oxide resi ⁇ dues, random and block copolymers of ethylene oxide and propylene oxide, propoxylated tri- and tetrahydric alcohols such as glycerine, trimethylolpropane and pentaerythritol, which propoxylated compounds have been capped with ethylene oxide; polytetramethylene glycol, random and block copolymers of tetrahydrofuran and ethylene oxide and or propylene oxide, and products derived from any of the above reaction with di- or higher functional carboxylic acids or esters derived from said acids in which latter case ester interchange occurs and the esterifying radicals are replaced by polyether polyol radicals.
  • the preferred polyether polyols are random and block copolymers of ethylene and propylene oxide of functionality from 2 to 4, preferably, 2 to 3 and polytetram
  • the overall proportions of the components (i), (ii), and (iii) are such that the active hydrogen-containing components (ii) and (iii) balance the isocyanate component (i) so that stoichio ⁇ metric equivalency of the reactants is maintained.
  • the proportions are s.ich that the overall ratio of isocyanate groups to active hydrogen groups is in the range of from 0.90:1 to 1.10:1, preferably, from 0.95:1 to 1.05:1 and, more preferably, from 0.98:1 to 1.02:1.
  • a catalyst in the process. Any of the cata ⁇ lysts conventionally employed in the art to catalyze the reaction of an isocyanate with a reactive hydrogen- -containing compound can be employed for this purpose; see, for example, Saunders et al., Polyurethanes, Chemistry and Technology, Part I, Interscience, New York, 1963, pages 228-232; see also England et al., J. Applied Polymer Science, 4, 207-211, 1960.
  • Such catalysts include organic and inorganic acid salts of, and organometallic derivatives of, bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel cerium, molybdenum, vanadium, copper, manganese and zirconium, as well as phosphines and tertiary organic amines.
  • organotin catalysts are stannous octoate, stannous oleate, dibutyltin dioctoate and dibutyltin dilaurate.
  • Representative tertiary organic amine catalysts are triethylamine, triethylenediamine, N,N,N',N'-
  • the amount of catalyst employed is generally within the range of from 0.02 to 2.0 percent by weight based on the total weight of the reactants.
  • the one-shot procedure wherein all the reactants are brought together all at once in the extrusion apparatus, and the prepolymer or quasi-prepolymer techniques.
  • the use of a prepolymer technique would, of course, be limited primarily to those formulations employing the polyol component (iii) wherein part or all of the polyol is first reacted with isocyanate and the isocyanate prepolymer, then fed to the extrusion apparatus along with the extender.
  • the preferred method is the one-shot reaction.
  • the process can also include various additives such as impact modifiers, fillers and fiber glass; antioxidants, pigments, fire retardants, plasticizers, reinforcing agents and wax lubricants commonly employed in the art in such compositions. These may be added along with the reactants or at a later stage through a downstream feed port, or at a post reactor compounding step.
  • additives such as impact modifiers, fillers and fiber glass; antioxidants, pigments, fire retardants, plasticizers, reinforcing agents and wax lubricants commonly employed in the art in such compositions.
  • the process in accordance with the present invention is carried out by feeding the above ingre ⁇ transtruder into a commercial multi-screw extruder which is, generally speaking, a twin-screw extruder.
  • the screws can be co- or counter-rotating.
  • a co- -rotating and self-cleaning twin-screw extruder is employed.
  • the general procedures and extrusion equipment described in U.S. Patents 3.642,964 and 3,963,679 can be employed herein except for the novel exceptions discussed hereinbelow.
  • the reactive extrusion process is carried out within an overall temperature range of from 150°C to 280°C. That is to say, individual zones may not all be at the same temperatures but their individual values will fall within this range.
  • FIG 1 shows one schematic embodiment of the process wherein (A), (B), and (C) represent three separate reactant feed lines for the isocyanate component, polyol component, and catalyst component respectively. It is not essential that all three lines be utilized.
  • catalyst may be included in the (B) feed line; alternatively, and, if desired, the reactants may be mixed in a suitable mixing head before they are introduced into the extruder.
  • (A) represents a mixing head which includes all the reactants with catalyst or else the catalyst may be added separately as (B).
  • the reaction mixture viscosity should exceed 100,000 cps (100 Pa-s) before reaching the critical SINGLE HIGH SHEAR MIXING ZONE (hereinafter MIXING ZONE).
  • MIXING ZONE the critical SINGLE HIGH SHEAR MIXING ZONE
  • the gel time for the reactant systems should be less than about 10 seconds, preferably less than about 6 seconds and FEED ZONE temperatures can fall within a range of from 150°C to 250°C.
  • the FEED ZONE length and conveying screws are in no way critical to the present process and can be configured as in the previously mentioned U.S. patents. Actual barrel lengths for the FEED ZONE will be defined by the overall L/D (length/diameter) of the extruder which will be discussed in detail below.
  • such high shear mixing zones employ two series of broad edged multiple kneading elements or blocks mounted in intermeshing relationship on the pair of parallel mounted screws in the twin-screw extruder in each zone.
  • the individual kneading elements or blocks can be triangular, circular or elliptical as typically disclosed in the figures 2 through 7 of the '679 patent.
  • the dimensions are such that there is minimal radial clearance between the inner surface of the barrel and the perimeter edges of the blocks.
  • rotation of the screws subjects the reaction mixture to high shear forces. Additional mixing and application of high shear forces can be imparted, if desired, by mounting appropriate baffles but more usually reverse pitch kneading blocks.
  • conveying screws are present in the same extruder barrel sections which contain the zone of kneading blocks. What distinguishes the present process is the fact that the high shear mixing is carried out in just a single zone, o these multiple kneading elements and not a series of repetitive zones.
  • the actual length of the kneading elements within the single zone will fall within a range of from 50 mm to 240 mm, preferably from 80 to 180, and more preferably from 120 to 180 mm.
  • this clearance will fall within a range of from 0.05 mm to 0.6 mm, preferably from 0.1 to 0.4 mm.
  • Screw rotation expressed in rotations per minute (r.p.m.) will fall within a range of from 140 to 500 r.p.m., preferably 150 to 300 r.p.m.
  • Temperatures in the MIXING ZONE will be controlled within a range similar to the FEED ZONE with optionally a slightly higher range, that is to say, from 150°C to 280°C. Capability of cooling this zone should be provided in the event that exotherm could exceed the upper limit of 280°C.
  • the EXTRUSION ZONE sometimes called the METERING ZONE, can be configured similarly to the prior art with only conveying screws. Temperatures are advantageously controlled to a range of from 180°C to 280°C.
  • the reacted melt product is simply extruded at the end through any desired molding tool or die known to the art such as, for example, slot dies, profile-forming dies and rods.
  • the L/D ratio can fall within a range of from 10/1 to 44/1, preferably from 15/1 to 25/1, most preferably from 15/1 to 20/1.
  • Overall temperature control throughout the above L/D ranges, whether it be through heating and/or cooling in particular zones, will fall within the previously stated range of from 150°C to 280°C.
  • Overall residence times in the extruder when operating under these L/D, temperature, and r.p.m. conditions set forth above will fall within a range of from 5 to 45 seconds, preferably from 6 to 30 seconds, more preferably from 6 to 25 seconds.
  • the extruded polyurethanes can be in finally desired shape or else comminuted or pelletized for further molding or injection molding into desired articles.
  • the polymers as obtained need no further treatment, having attained their superior physical and mechanical properties as set forth in the three patents cited supra and already incorporated herein.
  • a Werner and Pfleiderer ZSK-53 self-cleaning, co-rotating twin-screw extruder was fitted with five barrels of which four had high shear mixing zones. Each of the latter zones were 240 mm in length but only 120 mm of this length was formed of the actual high shear kneading blocks themselves with the remainder given over to conveying screws. Radial clearance between extruder wall and outer diameter of the shearing edges of each kneading block was about 0.2 mm. Screw speed was con ⁇ trolled to 460 r.p.m. Extruder temperatures were con ⁇ trolled by five independent barrel heating or cooling zones.
  • Feed zone temperature was 225 ⁇ 5°C, with extrusion zone being 215 ⁇ 5°C and the intermediate zones including the four high shear mixing zones being 190 to 210°C.
  • a sheeting die, 200 mm width and 3 mm gap was flanged to the end of the extrusion zone.
  • Gel time of this reacting mixture determined by hand mixing the components rapidly in a beaker was less than 10 seconds.
  • the polymer was extruded onto a metal conveyor belt at 26°C, cooled and diced. At this point the solidified polymer was observed for the formation of bubbles. After drying at 115°C in a dehumidifying hopper dryer with a dew point below -28°C, the pellets were injection molded into test specimens. Their physical properties were determined according to ASTM test procedures with the results set forth in Table I.
  • Run 1 in accordance with the invention was carried out identically to the above comparison run in every respect except the reactants were fed into a downstream feed port.
  • the second feed port was located in the extruder barrel which was just prior to the last (i.e. fourth) high shear mixing zone. Feeding the reactants at this point shortened the barrel to 919 mm and reduced the L/D to 17.3/1. More importantly, the reaction mixture passed through a single zone of high shear mixing wherein the actual length of kneading blocks was 120 mm.
  • Notched Izod Izod impact strength measured on 1/8" and 1/4" (3.175 mm and 6.35 mm) thick samples in accordance with ASTM D256-56.
  • Yellowness Index determined using ASTM D-1925 standard at a two degree observer angle using a Pacific Scientific Spectrogard Color System, Silver Spring, Maryland 20910 with the illuminant uei ⁇ g simulated average daylight.
  • Bubble Formation refers to the qualitative visual observation of the extruded polymer for the formation of bubbles ; presence of a very few minute bubbles can be tolerated and the polymers classified as essentially a clear plastic, whereas the formation of a copious number of bubbles is not acceptable.
  • Example 1 this experiment describes comparison 2 and run 2 reactive extrusions wherein the same apparatus and conditions were employed herein with the exception of different reactant com- ponents .
  • the mixture pumped to the first feed port for comparison 2 which ran through the four mixing zones was as follows : a degassed and dehydrated mixture of 100 parts of an 85/15 mole ratio of 1 , 4-cyclohexane- dimethanol and hydrogenated bisphenol-A , 0.77 parts trisnonylphenyl phosphite , and 0.64 parts of Irganox 1010 ; 158.35 parts of melted 4 , 4 ' -methylenebis (phenyl isocyanate ) ; and 0.31 part of Fomrez UL-22.
  • the same three part ingredient mixture was fed into the downstream feed port for the L/D ratio of 17. 3/1 .
  • the ingredients were as follows: degassed and dehydrated mixture of 100 parts of 1,6- -hexanediol, 0.94 part trisn ⁇ nylphenyl phosphite, and 0.78 part of Irganox 1010; 213.8 part of melted 4,4'- -methylenebis(phenyl isocyanate); and 0.19 part of Fomrez UL-22.
  • This example describes the preparation of a hard thermoplastic polyurethane polymer in accordance with the present invention (run 4) and comparison 4.
  • the reaction mixture which was metered into the feed port in three streams in the following proportions in parts by weight was as follows: degassed and dehydrated mixture of 43.2 parts of 1 ,-4-cyclohexane- dimethanol, 23.6 parts of 1 ,6-hexanediol, 10.4 parts of a 650 molecular weight polytetramethylene glycol, 0.52 part of Irganox 1010, and 0.31 part of triphenyl phosphite; 130.79 parts of 4,4-methylenebis(phenyl isocyanate); and 0.10 part of a 50/50 weight mixture of stannous octoate and dioctyl phthalate.
  • the extruded product was fed onto a cool conveyor as described in the previous examples and diced.
  • the extruded material was clear transparent with only a few minute bubbles being detectable.
  • the injection molded product had the following properties set forth in Table IV.
  • Comparison 4 was carried out under essentially the same temperature conditions with identical ingredients to run 4 but using a twin-screw Werner and Pfleiderer extruder having an 83 mm diameter, equipped with three zones of high shear mixing and an L/D of 30.7/1.
  • run 4 provided a product with much superior molecular weight to the comparison run 4 and a measurably better yellow index and transmission. Notably, this was accomplished with much less power consumption as compared with comparison 4.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

On décrit un procédé d'extrusion réactive améliorée pour la préparation continue d'un polyuréthane dur présentant des valeurs Tg supérieures à 80°C. On fait réagir les ingrédients de polyisocyanate de polyol dans une boudineuse à deux vis limitée à une seule zone de mélange à cisaillement élevé. Ledit procédé empêche la formation de petites bulles dans les polyuréthanes extrudés ainsi que la formation de coloration jaune dans ce qui doit être essentiellement un polymère blanc à eau. De telles formations problématiques se présentent lors de la préparation desdits polyuréthanes durs lorsqu'on utilise les procédés de l'art antérieur, au cours desquels le mélange à cisaillement élevé s'effectue dans des zones multiples.
PCT/US1990/002869 1989-06-27 1990-05-14 Procede de polymerisation a l'etat de fusion pour la production de polyurethanes WO1991000304A1 (fr)

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US372,498 1989-06-27

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EP0519734A2 (fr) * 1991-06-19 1992-12-23 MITSUI TOATSU CHEMICALS, Inc. Méthode pour la réaction d'uréthanisation
EP0708124A2 (fr) 1994-10-20 1996-04-24 BASF Schwarzheide GmbH Procédé de préparation de polyuréthanes thermoplastiques
US5679756A (en) * 1995-12-22 1997-10-21 Optima Inc. Optical thermoplastic thiourethane-urethane copolymers
CN1059478C (zh) * 1994-03-12 2000-12-13 陶宇 一种生产聚氨酯弹性纤维的方法
WO2006082183A1 (fr) * 2005-02-03 2006-08-10 Basf Aktiengesellschaft Procede pour produire en continu des elastomeres de polyurethanne thermoplastiques
WO2007112105A2 (fr) * 2006-03-24 2007-10-04 Century-Board Usa, Llc Extrusion de matériaux composites en polyuréthanne
WO2009086459A1 (fr) * 2007-12-28 2009-07-09 Bostik, Inc. Procédé continu pour la production de matériaux d'étanchéité et d'adhésifs de polyuréthane durcissant à l'humidité
WO2009143198A2 (fr) * 2008-05-23 2009-11-26 Lubrizol Advanced Materials, Inc. Composites tpu renforcés par des fibres
CN103228752A (zh) * 2010-10-01 2013-07-31 阿雷蒙公司 用于制造可热活化的粘合粒子的系统和方法
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
JP2014205854A (ja) * 2008-04-03 2014-10-30 サントル ナスィオナル ド ラ ルシェルシュ スィアンティフィク（セ．エン．エル．エス．） イソシアネートの連続的オリゴマー化の方法
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US9745224B2 (en) 2011-10-07 2017-08-29 Boral Ip Holdings (Australia) Pty Limited Inorganic polymer/organic polymer composites and methods of making same
US9752015B2 (en) 2014-08-05 2017-09-05 Boral Ip Holdings (Australia) Pty Limited Filled polymeric composites including short length fibers
EP3058018B1 (fr) 2013-10-18 2017-09-13 Basf Se Procédé de fabrication d'élastomères thermoplastiques expansés
US9988512B2 (en) 2015-01-22 2018-06-05 Boral Ip Holdings (Australia) Pty Limited Highly filled polyurethane composites
US10030126B2 (en) 2015-06-05 2018-07-24 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with lightweight fillers
US10086542B2 (en) 2004-06-24 2018-10-02 Century-Board Usa, Llc Method for molding three-dimensional foam products using a continuous forming apparatus
US10138341B2 (en) 2014-07-28 2018-11-27 Boral Ip Holdings (Australia) Pty Limited Use of evaporative coolants to manufacture filled polyurethane composites
US10472281B2 (en) 2015-11-12 2019-11-12 Boral Ip Holdings (Australia) Pty Limited Polyurethane composites with fillers

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US4948859A (en) * 1988-10-28 1990-08-14 Minnesota Mining And Manufacturing Company Extruder polymerization of polyurethanes
CN102719901A (zh) * 2012-06-28 2012-10-10 东华大学 一种变径螺杆熔融挤出机的聚酯纺丝方法

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Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0519734A2 (fr) * 1991-06-19 1992-12-23 MITSUI TOATSU CHEMICALS, Inc. Méthode pour la réaction d'uréthanisation
EP0519734A3 (en) * 1991-06-19 1993-02-03 Mitsui Toatsu Chemicals, Inc. Method of urethanating reaction
CN1059478C (zh) * 1994-03-12 2000-12-13 陶宇 一种生产聚氨酯弹性纤维的方法
EP0708124A2 (fr) 1994-10-20 1996-04-24 BASF Schwarzheide GmbH Procédé de préparation de polyuréthanes thermoplastiques
US5679756A (en) * 1995-12-22 1997-10-21 Optima Inc. Optical thermoplastic thiourethane-urethane copolymers
US10889035B2 (en) 2004-06-24 2021-01-12 Century-Board Corporation Method for molding three-dimensional foam products using a continuous forming apparatus
US10086542B2 (en) 2004-06-24 2018-10-02 Century-Board Usa, Llc Method for molding three-dimensional foam products using a continuous forming apparatus
WO2006082183A1 (fr) * 2005-02-03 2006-08-10 Basf Aktiengesellschaft Procede pour produire en continu des elastomeres de polyurethanne thermoplastiques
US8287788B2 (en) 2005-02-03 2012-10-16 Basf Aktiengesellschaft Method for the continuous production of thermoplastically-processable polyurethane elastomers
CN101115780B (zh) * 2005-02-03 2010-07-28 巴斯福股份公司 连续生产可热塑加工的聚氨酯弹性体的方法
WO2007112105A2 (fr) * 2006-03-24 2007-10-04 Century-Board Usa, Llc Extrusion de matériaux composites en polyuréthanne
US9139708B2 (en) 2006-03-24 2015-09-22 Boral Ip Holdings Llc Extrusion of polyurethane composite materials
WO2007112105A3 (fr) * 2006-03-24 2008-04-10 Century Board Usa Llc Extrusion de matériaux composites en polyuréthanne
US9512288B2 (en) 2006-03-24 2016-12-06 Boral Ip Holdings Llc Polyurethane composite materials
AU2008345105B2 (en) * 2007-12-28 2014-08-07 Bostik, Inc. A continuous process for the production of moisture-cure, polyurethane sealants and adhesives
US8734609B2 (en) 2007-12-28 2014-05-27 Bostik, Inc. Continuous process for the production of moisture-cure, polyurethane sealants and adhesives
WO2009086459A1 (fr) * 2007-12-28 2009-07-09 Bostik, Inc. Procédé continu pour la production de matériaux d'étanchéité et d'adhésifs de polyuréthane durcissant à l'humidité
JP2014205854A (ja) * 2008-04-03 2014-10-30 サントル ナスィオナル ド ラ ルシェルシュ スィアンティフィク（セ．エン．エル．エス．） イソシアネートの連続的オリゴマー化の方法
WO2009143198A3 (fr) * 2008-05-23 2010-01-07 Lubrizol Advanced Materials, Inc. Composites tpu renforcés par des fibres
US9068076B2 (en) 2008-05-23 2015-06-30 Lubrizol Advanced Materials, Inc. Fiber reinforced TPU composites
WO2009143198A2 (fr) * 2008-05-23 2009-11-26 Lubrizol Advanced Materials, Inc. Composites tpu renforcés par des fibres
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
CN103228752B (zh) * 2010-10-01 2015-10-14 阿雷蒙公司 用于制造可热活化的粘合粒子的系统和方法
CN103228752A (zh) * 2010-10-01 2013-07-31 阿雷蒙公司 用于制造可热活化的粘合粒子的系统和方法
US9745224B2 (en) 2011-10-07 2017-08-29 Boral Ip Holdings (Australia) Pty Limited Inorganic polymer/organic polymer composites and methods of making same
EP3058018B1 (fr) 2013-10-18 2017-09-13 Basf Se Procédé de fabrication d'élastomères thermoplastiques expansés
US11142625B2 (en) 2013-10-18 2021-10-12 Basf Se Process for production of expanded thermoplastic elastomer
US10138341B2 (en) 2014-07-28 2018-11-27 Boral Ip Holdings (Australia) Pty Limited Use of evaporative coolants to manufacture filled polyurethane composites
US9752015B2 (en) 2014-08-05 2017-09-05 Boral Ip Holdings (Australia) Pty Limited Filled polymeric composites including short length fibers
US9988512B2 (en) 2015-01-22 2018-06-05 Boral Ip Holdings (Australia) Pty Limited Highly filled polyurethane composites
US10030126B2 (en) 2015-06-05 2018-07-24 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with lightweight fillers
US10472281B2 (en) 2015-11-12 2019-11-12 Boral Ip Holdings (Australia) Pty Limited Polyurethane composites with fillers

Also Published As

Publication number Publication date
AU5949390A (en) 1991-01-17
CA2019877A1 (fr) 1990-12-27

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