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WO1993005109A1 - Preparation de compositions de polyurethanes - Google Patents

Preparation de compositions de polyurethanes Download PDF

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Publication number
WO1993005109A1
WO1993005109A1 PCT/US1992/005906 US9205906W WO9305109A1 WO 1993005109 A1 WO1993005109 A1 WO 1993005109A1 US 9205906 W US9205906 W US 9205906W WO 9305109 A1 WO9305109 A1 WO 9305109A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
containing compound
polyol
fluoroaliphatic group
group
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
PCT/US1992/005906
Other languages
English (en)
Inventor
John C. Clark
James E. Sax
John A. Temperante
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of WO1993005109A1 publication Critical patent/WO1993005109A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • 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
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

  • This invention relates to methods of making polyurethane compositions and shaped articles thereof with low surface energy surfaces.
  • polyurethane precursor compositions therefor comprising polyisocyanate, polyol, and fluoroaliphatic group-containing compound.
  • Polyurethanes are extremely important and useful with a wide range of applications. Shaped articles of polyurethane such as pellets and films, however, can have problems with mold release and self-adhesion or "blocking". For example, it can be difficult to separate layers of polyurethane film from one another, and pellets of polyurethane are often not free-flowing and may clump together and thereby make processing of the pellets very difficult.
  • Flow-control and mold-release additives such as silica, silicone, and calcium stearate have been used to impart non-blocking properties to polyurethane films - see, for example, E. N. Doyle, "The Development and Use of Polyurethane Products," pp. 75, 77, 274-275, McGraw-Hill (1971).
  • Japanese Pat. Nos. 59[1984]-157190 (Matsuo et al.) and 59[1984]-213716 (Noritake et al.) describe the use of certain active hydrogen group-containing fluorochemicals as internal mold-release agents for reaction injection molding of polyurethanes.
  • U.S. Pat. No. 5,025,052 describes certain fluoroaliphatic-containing oxazolidinones useful as melt additives in thermoplastic polymers, for example polyurethanes, the additives imparting low surface energy to fibers, films, and molded articles made from such polymers.
  • the present invention in one aspect, provides a method for the preparation of polyurethane compositions from which shaped articles, such as films, can be made with low surface energy, said method comprising polymerizing a mixture comprising polyisocyanate, polyol, and fluoroaliphatic group-containing compound such as a fluoroalkyl oxazolidinone.
  • Said fluoroaliphatic group-containing compound which is thus present during the polymerization, is free of moieties (for example, active hydrogen atoms) reactive with either of said polyisocyanate or polyol during the polymerization (viz. , under urethane bond forming conditions, e.g. 200°C) that is, it is inert or non-reactive.
  • the compound is partially miscible with the resulting polyurethane product.
  • partially miscible means that the fluoroaliphatic group-containing compound is miscible with, or soluble in, the resulting polyurethane at polymerizing or shaping temperatures and is less miscible with the resulting polyurethane at use or room temperatures.
  • the resulting polyurethane composition may conveniently be shaped or formed, for example by reaction injection molding or extrusion, into a variety of shaped articles, for example, fiber, pellets, and film.
  • the shaped articles may be in the form of foamed polyurethane or dense (not foamed) polyurethane.
  • the fluoroaliphatic group-containing compound imparts desirable properties to the surfaces of such articles, for example, low surface energy, which precludes the films and pellets from blocking or sticking together.
  • the fluoroaliphatic group-containing compound does not react with the polyisocyanate or polyol during the polyurethane polymerization process and appears to be free to migrate to some extent to the surface of the polyurethane article. In addition, it is believed that the migration is enhanced by the partial miscibility of the compound. In contrast, it is known that compounds which are immiscible with a polymer will form a second phase dispersed within the polymer and do not migrate as well to the surface as would an evenly distributed, dissolved or partially miscible compound. Also, compounds which remain equally miscible in a polymer at all relevant temperatures have less driving force to migrate to the surface and do not migrate as well as an initially dissolved compound which becomes less miscible at use temperatures than at polymerizing or processing temperatures.
  • the addition of the fluoroaliphatic group-containing compound to the polyol-polyisocyanate reaction mixture before the completion of the polymerization thereof imparts surface properties to the polyurethane articles made therefrom which are comparable to that resulting when fluoroaliphatic group-containing compounds are mixed with a melt of a polyurethane, that is, added after the polymerization is complete. Addition of fluoroaliphatic group-containing compound into the polyurethane precursor mixture, rather than after the polymerization, results in elimination of some processing steps.
  • the fluoroaliphatic group-containing compounds useful in this invention can be normally liquid or solid (including meltable solids) and they are stable at the polymerizing and shaping temperatures.
  • the fluoroaliphatic group-containing compound is partially miscible in an amount sufficient to impart desired properties to the surfaces of resulting shaped polyurethane articles, said amount generally being 0.05 to 10% by weight, preferably from 0.2 to 10% by weight.
  • polyurethane compositions may be conveniently prepared by reactive extrusion polymerization, a method of polymer preparation that has grown in importance recently. See, for example, C. Tzoganakis, "Reactive Extrusion of polymers: A Review", Advances in Polymer Technology Methods. Vol. 9, No. 4, pp 321-330 (1989) .
  • the fluoroaliphatic group-containing compound can be first mixed with either the polyol or the polyisocyanate, or alternatively, be fed as a powder from a solids weigh-feeder, or as a liquid, into the throat of the twin-screw extruder at the same, or at a different, location as where the polyol and polyisocyanate streams are entering.
  • the polyurethane compositions may also conveniently be prepared by reaction injection molding and the resulting shaped and cured article can be readily released from the mold, the fluoroaliphatic group-containing compound acting as an internal mold-release agent.
  • Shaped articles made by the methods of this invention possess surfaces with excellent anti-blocking properties, for example, pellets can be prepared which are free-flowing, or films can be prepared which have interlayer adhesion as low as 100 grams/2.54 cm.
  • the resulting polyurethane composition, or product can be extruded in the form of a fiber which can be pelletized into particles that are free-flowing and can be used in a standard extrusion operation to form various articles of various shapes, such as gaskets.
  • a polyurethane film of this invention can be made by the conventional blown-film process. Such a process and equipment therefor are described, for example, in S. Middleman, "Fundamentals of Polymer Processing", pp 249-260, McGraw-Hill (1977), which descriptions are incorporated herein by reference. In the blown-film process, often an initial bubble is collapsed and then re-opened for post-processing steps or slitting.
  • compositions of this invention are beneficial for such a blown-film process because a polyurethane film with high interlayer adhesion cannot be reopened after the collapsing step.
  • the polyurethane films of this invention have lower surface energy and consequently reduced solvent wettability.
  • the fibers of this invention will have enhanced soil and stain resistance.
  • the presence of the fluoroaliphatic group- containing compound allows otherwise normally tacky polyurethanes to be processed on conventional equipment.
  • the method of this invention provides a convenient method for the production of polyurethanes with low glass transition temperatures (T g ) for example less than -50°C, which would otherwise be difficult to produce.
  • a class of the fluoroaliphatic group-containing compounds useful in this invention can be represented by Formula I:
  • R f is a fluoroaliphatic group or radical and y is l or 2, the compound thus containing 1 or 2 of such groups.
  • R f is saturated, mono-valent and has at least 4 fully-fluorinated carbon atoms. It can be straight, branched, or, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals.
  • the skeletal chain in the fluoroaliphatic group can include catenary hetero atoms bonded only to carbon atoms or the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the R f radical.
  • a fully fluorinated group is preferred, but hydrogen or chlorine atoms may be present as substituents provided that not more than one atom of either is present for every two carbon atoms.
  • R f can contain a large number of carbon atoms, compounds where R f is not more than 20 carbon atoms will be adequate and preferred since larger radicals usually represent a less efficient utilization of the fluorine than is possible with shorter chains. Fluoroaliphatic groups containing from about 6 to about 12 carbon atoms are most preferred. Generally R f will contain 40 to 78 weight percent fluorine.
  • the terminal portion of the R f group preferably has at least four fully fluorinated carbon atoms, e.g., CF 3 CF 2 CF 2 CF 2 -, and the preferred compounds are those in which the R f group is fully or substantially completely fluorinated, as in the case where R f is perfluoroalkyl, e.g. CF 3 (CF 2 ) n -.
  • Suitable R f groups include for example, C 8 F 17 -, C 6 F 13 CH 2 CH 2 -, F 5 SC 3 F 6 -, and C 10 F 21 CH 2 CH 2 -.
  • R is an organic group which can contain from 2 to 35 carbon atoms. R preferably contains from 12 to 25 carbon atoms. R is such that the fluoroaliphatic group-containing compound is partially miscible with the polyurethane resulting from polymerization of the polyisocyanate-polyol mixture containing such compound. Such miscibility can be confirmed by testing the mixture or blend of the polyurethane and fluoroaliphatic group-containing compound, for example, testing the melting point, modulus, phase separation or cloud-point, or by differential scanning calorimetry (DSC) , of the mixture or blend - see, for example, the techniques described in D. Paul, and S. Newman, "Polymer Blends", Vol.
  • DSC differential scanning calorimetry
  • R f group in the fluoroaliphatic group- containing compound used in this invention, the larger will the R group have to be in order for the compound to be partially miscible in the polyurethane.
  • Suitable R groups include, for example, ⁇ C 18 H 37
  • a preferred class of the fluoroaliphatic group- containing compounds useful in this invention are those where R comprises one or more oxazolidinone moieties. See, for example, the fluoroaliphatic group-containing compounds described in U.S. Pat. No. 5,025,052 (Crater et al.) , which description is incorporated herein by reference.
  • Suitable R groups include, for example:
  • Q is a linking group and Z is 0 or 1. Note that when z is 0, Q is absent and R f and R are joined by a covalent bond. Q and R together preferably contain from 5 to 35 carbon atoms.
  • the linking group, Q can comprise a hetero atom-containing group, e.g., a group containing -S-, -0-, and or -NCH 3 -, or a combination of such groups, for example -CO-, -C0NR-, -S0 2 -, S0 2 N(CH 3 )-, -C 3 H 5 C1-, or -OC 2 H 4 -.
  • Q is free of groups reactive with polyisocyanate or polyol.
  • polyisocyanate and polyol can be reacted, in the presence of or in admixture with the fluoroaliphatic group-containing compound, in a conventional polyurethane polymerization manner in the presence of catalyst.
  • Polyols useful in the present invention include diols of a polyester, polyether such as poly(oxyalkylene) , silicone diols, or a combination thereof, such as those described for example in U.S. Pat. No. 4,948,859 (Echols et al.).
  • Polyisocyanates useful in the present invention include conventional aliphatic or aromatic polyisocyanates used in making polyurethanes, for example, toluene diisocyanate.
  • Other useful polyisocyanates which can be used are hexamethylene-1,6,-diisocyanate, diphenylmethane-4,4'-diisocyanate, meta- or para-phenylene diisocyanate, and 1,5-naphthalene diisocyanate.
  • Polymeric polyisocyanates can also be used, such as methylene bis(4-phenyl)iso ⁇ yanate and polyaryl polyisocyanate.
  • Fluoroaliphatic group-containing compounds were incorporated into a reactive polyurethane precursor mixture of polyol and polyisocyanate during reactive extrusion polymerization of the mixture.
  • the resulting polyurethanes were shaped into pellets and films which were tested for non-blocking and other properties.
  • Example 2 Pellets and film were prepared as in Example 1 except 1.0 wt% of the fluorochemical oxazolidinone of Example 1 was used instead of 0.5 wt.%.
  • Example 4 Example 4
  • Example 3 Pellets and film were prepared as in Example 3 except using 0.5 wt.% of the fluorochemical oxazolidinone of same structure as in Example 1 except that the fluorochemical oxazolidinone was prepared from
  • Example 5 Pellets and film were prepared as in Example 3 except using 0.5 wt.% of the fluorochemical oxazolidinone of structure
  • Pellets and film were prepared as in Example 3 except that the fluorochemical used was 0.5 wt.% of the immiscible perfluoroaliphatic compound polytetrafluoroethylene resin #203, commercially available from Scientific Polymer Products, Inc. , Ontario, N.Y.
  • Pellets and film were prepared as in Example 3 except that the fluorochemical used was 0.5 wt.% of an immiscible, perfluoroaliphatic, high molecular weight fluorocarbon elastomer composition of 3 wt.% calcium carbonate and 97 wt.% elastomer (commercially available from 3M Company as FLUORELTM 2211) .
  • Pellets of Examples 3-6 exhibited the same excellent free-flowing flow properties as the pellets of Examples 1 and 2. In contrast, pellets of Comparative Examples C2-C4 tended to adhere to one another and formed an agglomerated mass.
  • the amounts of fluorine at the surfaces of the above-described films were measured using electron spectroscopy for chemical analysis (ESCA) .
  • the bulk fluorine contents of the films were also measured.
  • the surface energy of the film samples were measured using the contact-angle method set forth in "Estimation of the Surface Free Energy of Polymers", Journal of Applied Polymer Science. Vol. 13, pp 174-177 (1969) using LubinolTM mineral oil (commercially available from Purepac Pharmaceutical Co., a division of Kalipharma, Inc.) and glycerin. The results are listed in Table 1.
  • the films were also characterized in terms of their non-blocking property by measurement of the force necessary to unwind a roll of film (“unwind force”) , and the force needed to peel a pressure sensitive adhesive tape, 3M Co. tape #STA-115, from the surface of the film (“peel force”) .
  • the unwind force test For the unwind force test, 5.08 cm wide film samples were wound onto 3 inch (7.6 cm) diameter cores.
  • the unwind test then consisted of mounting a 50 yard (45.7 meters) long roll of the film onto the stationary arm of a peel tester platen (model SP-102C-3M90, commercially available from Instrumentors Inc. , Strongsville Ohio) and connecting the free edge of the film to the force transducer on the peel tester base. The platen was then moved away from the base at a set speed. The roll of film was allowed to freely rotate on a low friction set of bearings. The force required to unwind the film from the roll was then measured and recorded according to the procedure described by the peel tester manual published by Instrumentors, Inc., Copyright 1987. The unwind force data obtained are shown in Table 2.
  • the fluoroaliphatic group-containing compounds useful in this invention are those which are partially miscible with the resulting polyurethane at temperatures under which the polyurethane preparation or processing actually occurs. Partial miscibility was demonstrated in a conventional manner by measuring cloud point temperatures and by observing the phase volumes of fluorochemical-polyurethane mixtures as a function of temperature and composition.
  • the mixture containing the fluorochemical of Example 1 showed partial miscibility as observed by large changes in phase volumes as a function of temperature. At high temperature, complete miscibility was achieved as the phase volume of the fluorochemical-rich phase became zero. Samples prepared with lower weight % of fluorochemical exhibited complete miscibility at lower temperatures. At lower fluorochemical levels, for example, 0.5 to 1.5%, phase separation will occur at lower temperatures, giving rise to a state of partial miscibility. This partial miscibility is an important requirement of the fluorochemical-polyurethane system.
  • the mixture containing the fluorochemical used in Example 5 had the extent of miscibility significantly reduced compared to the mixture containing the fluorochemical of Example 1, at a given temperature and concentration, as seen by cloud points which are much higher in temperature. Indeed, complete miscibility was not achieved with above 12.5% by weight fluorochemical at any temperature less than 325°C (a practical limit on the temperature due to degradation of the mixture as seen by darkening of the mixture) . However, partial miscibility was observed as manifested by the change in phase volumes. As the temperature was increased, the fluorochemical-rich phase decreased in volume, and as the temperature was lowered, the fluorochemical rich phase increased in volume. Below 12.5% by weight of fluorochemical, complete miscibility was achieved at experimentally accessible temperatures.

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

Abstract

Procédé destiné à préparer des compositions de polyuréthanes consistant à polymériser un mélange comprenant du polyisocyanate, du polyol, et un composé contenant un groupe fluoroaliphatique non réactif. Des articles façonnés, tels que des boulettes et des films, comprenant lesdites compositions de polyuréthanes présentent des propriétés superficielles de faible énergie, telles que la non-adhésion.
PCT/US1992/005906 1991-09-05 1992-07-15 Preparation de compositions de polyurethanes Ceased WO1993005109A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75508791A 1991-09-05 1991-09-05
US755,087 1991-09-05

Publications (1)

Publication Number Publication Date
WO1993005109A1 true WO1993005109A1 (fr) 1993-03-18

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PCT/US1992/005906 Ceased WO1993005109A1 (fr) 1991-09-05 1992-07-15 Preparation de compositions de polyurethanes

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4309139A1 (de) * 1993-03-22 1994-09-29 Bayer Ag Verfahren zur Herstellung von Pulvern und anderen Klein- und Kleinstteilchen
US5459188A (en) * 1991-04-11 1995-10-17 Peach State Labs, Inc. Soil resistant fibers
WO1999016806A1 (fr) * 1997-10-01 1999-04-08 The Dow Chemical Company Extrusion reactive de polymeres liquides pouvant etre façonnes sur mesure
WO2006065385A1 (fr) * 2004-12-15 2006-06-22 3M Innovative Properties Company Diesters fluores en tant qu'additifs repulsifs pour polymere a l’etat fondu

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2034166A1 (de) * 1969-07-10 1971-01-21 Minnesota Mining and Manufacturing Co., St. Paul. Minn. (V.St.A.) Verfahren zur Herstellung von Isocyanuraten, Polyisocyanuraten un<j Polyurethanen
EP0000927A1 (fr) * 1977-08-26 1979-03-07 Mobay Chemical Corporation Procédé pour la stabilisation de polyesteruréthanes thermoplastiques
EP0260011A2 (fr) * 1986-09-12 1988-03-16 Minnesota Mining And Manufacturing Company Oxazolidinones fluorochimiques
EP0308683A1 (fr) * 1987-08-31 1989-03-29 The B.F. Goodrich Company Utilisation de polyuréthane thermoplastique pour la préparation de feuilles soufflées

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2034166A1 (de) * 1969-07-10 1971-01-21 Minnesota Mining and Manufacturing Co., St. Paul. Minn. (V.St.A.) Verfahren zur Herstellung von Isocyanuraten, Polyisocyanuraten un<j Polyurethanen
EP0000927A1 (fr) * 1977-08-26 1979-03-07 Mobay Chemical Corporation Procédé pour la stabilisation de polyesteruréthanes thermoplastiques
EP0260011A2 (fr) * 1986-09-12 1988-03-16 Minnesota Mining And Manufacturing Company Oxazolidinones fluorochimiques
EP0308683A1 (fr) * 1987-08-31 1989-03-29 The B.F. Goodrich Company Utilisation de polyuréthane thermoplastique pour la préparation de feuilles soufflées

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5459188A (en) * 1991-04-11 1995-10-17 Peach State Labs, Inc. Soil resistant fibers
DE4309139A1 (de) * 1993-03-22 1994-09-29 Bayer Ag Verfahren zur Herstellung von Pulvern und anderen Klein- und Kleinstteilchen
WO1999016806A1 (fr) * 1997-10-01 1999-04-08 The Dow Chemical Company Extrusion reactive de polymeres liquides pouvant etre façonnes sur mesure
WO2006065385A1 (fr) * 2004-12-15 2006-06-22 3M Innovative Properties Company Diesters fluores en tant qu'additifs repulsifs pour polymere a l’etat fondu
US7396866B2 (en) 2004-12-15 2008-07-08 3M Innovative Properties Company Fluorochemical diesters as repellent polymer melt additives

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