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    • 专利摘要:
    "thermoplastic polyurethane, processes for making a molded article, for making a thermosetting tube, for making a coated electrical wire, and wire and cable construction. the tpu of this invention contains unsaturation in a polymeric backbone. unsaturation can be present in the flexible segment or in the rigid segment or in both the flexible and rigid segments of the tpu. the tpu can be molded as a thermoplastic, and can be subsequently crosslinked. in one embodiment, the tpus of this invention are the reaction product of ( 1) a hydroxyl ending intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds. thermoplastic that is crosslinkable by electron beam irradiation is composed of the reaction product of (1) a saturated hydroxyl terminated intermediate, (2) an unsaturated hydroxyl terminated intermediate, wherein the unsaturated hydroxyl-terminated intermediate contains carbon-carbon double bonds, (3) a polyisocyanate, and (4) a saturated glycol chain extender.
    公开号:BR112012017883B1
    申请号:R112012017883-0
    申请日:2011-01-21
    公开日:2021-08-03
    发明作者:Umit G. Makal；Louis J. Brandewiede；George H. Loeber
    申请人:Lubrizol Advanced Materials, Inc；
    IPC主号:
    专利说明:

    field of invention
    [001] The present invention relates to thermoplastic polyurethane (TPU) compositions that can be formed into useful articles by injection molding, blow molding, or extrusion and that can subsequently be crosslinked. In one embodiment, crosslinking of the TPU is accomplished by exposing crosslinkable portions polymerized in the TPU to electron beam irradiation. Thermosetting articles having excellent chemical resistance, dimensional stability, curing properties, heat resistance, oxidative resistance, and creep resistance are formed from the crosslinked TPUs. Fundamentals of Invention
    [002] TPUs (Polyurethane Thermoplastics) are currently being used to manufacture a wide variety of products for many applications by various melt processing techniques such as injection molding and extrusion. For example, TPUs are commonly used in the manufacture of seals, gaskets, catheters, wires and cables. These TPUs are typically made by reacting (1) a hydroxyl-terminated polyether or hydroxyl-terminated polyester, (2) a chain extender, and (3) an isocyanate compound. Various types of compounds for each of the three reagents are disclosed in the literature. These TPUs are segmented polymers having flexible segments and rigid segments. This characteristic is responsible for its excellent elastic properties. The flexible segments are derived from hydroxyl-terminated polyether, polyester, polycarbonate, or polycaprolactone(s) and the rigid segments are derived from the isocyanate and the chain extender. The chain extender is typically one of a variety of glycols, such as 1,4-butanediol. For example, United States Patent 5,959,059 discloses a TPU made from a hydroxyl terminated polyether, a glycol chain extender, and a diisocyanate. This TPU is described as being useful for making fibers, golf ball cores, recreation wheels, and other uses.
    [003] In many applications, it is desirable or even critical for the TPU used in the manufacture of articles to present good chemical resistance, dimensional stability, stiffness properties, thermal resistance, oxidative resistance, and creep resistance. These physical and chemical characteristics are important in articles that are exposed to chemicals, solvents, and/or elevated temperatures. For example, it is often important for seals, gaskets, wires and cables that are used in industrial applications to possess these desirable characteristics. This is particularly the case in automotive under-the-hood applications where the part made with the TPU may well be exposed to high temperatures and organic liquids such as gasoline and engine oil. For example, ignition cables and other wires used in automotive applications need to be resistant to both oil and heat. Seals and gaskets used in internal combustion machines, heavy equipment, appliances, and countless other applications also need to be resistant to heat and solvents.
    [004] Crosslinking of a thermoplastic polymer in a redethermofix is a known technique to improve chemical resistance, dimensional stability, stiffness properties, thermal resistance, oxidative resistance, and creep resistance. However, thermosetting resins cannot be processed using standard melt processing techniques such as injection molding, blow molding, and extrusion. In general, thermosets are molded to the desired shape and cured to the mold shape using a more labor-intensive, time-consuming and expensive curing technique. Additionally, defective thermoset parts and scrap cannot be recycled and remolded like thermoplastics. This leads to polymer waste which also increases total cost and has a detrimental impact on the environment.
    [005] There is a need for a TPU that can be melt processed into a desired shape by injection molding, blow molding, extrusion, or the like, and then crosslinked into a thermoset network. It is, of course, important that the thermoset network exhibit good chemical, solvent and thermal resistance, which is characterized by good dimensional stability, stiffness properties, oxidative resistance, and creep resistance. This TPU could be used beneficially in manufacturing a wide range of component parts and articles of manufacture having improved chemical and physical characteristics. For example, this polymer could advantageously be used in the manufacture of seals, gaskets, wires, cables, hoses, tubes, and other industrial and consumer products with improved thermal, chemical and solvent resistances. There is, therefore, a need for a TPU composition that can be molded into articles useful as a thermoplastic, but that has the physical and chemical properties of a thermostable TPU. Summary of the invention.
    [006] The TPU of this invention contains a small amount of unsaturation in its polymeric backbone, can be molded as a thermoplastic, and can be subsequently crosslinked by exposure to electron beam irradiation in thermostable articles having excellent chemical resistance, dimensional stability, properties stiffness, heat resistance, oxidative resistance, and creep resistance. The TPUs of this invention are the reaction product of (1) a hydroxyl terminated intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon double bonds. -carbon.
    [007] The present invention further discloses a process for manufacturing a molded article comprising (a) heating a thermoplastic polyurethane composition to a temperature above the melting point of the thermoplastic polyurethane composition, wherein the thermoplastic polyurethane composition is composed the reaction product of (1) a hydroxyl-terminated intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds; (b) injecting the thermoplastic polyurethane composition into a mold; (c) cooling the thermoplastic polyurethane composition in the mold to a temperature below the melting point of the thermoplastic polyurethane composition to produce the molded article; (d) removing the molded article from the mold; and (e) exposing the molded article to electron beam irradiation to crosslink the thermoplastic polyurethane composition into a thermostable.
    [008] The subject invention also discloses a process for manufacturing a thermosetting tube comprising (a) heating a thermoplastic polyurethane composition to a temperature above the melting point of the thermoplastic polyurethane composition, wherein the thermoplastic polyurethane composition is composed of the reaction product of (1) a hydroxyl-terminated intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) a glycol chain extender containing carbon-carbon double bonds; (b) extruding the thermoplastic polyurethane composition into a hot extruded tube; (c) cooling the hot extruded tube to a temperature below the melting point of the thermoplastic polyurethane composition to produce an uncured extruded tube; and (d) exposing the uncured extruded tube to electron beam irradiation to crosslink the thermoplastic polyurethane composition into a thermoset and produce the thermoset tube.
    [009] The present invention further discloses a process for manufacturing a coated electrical wire comprising (a) passing a metallic wire through a pipe-type transverse head matrix; (b) extruding the thermoplastic polyurethane composition which is composed of the reaction product of (1) a hydroxyl terminated intermediate, (2) a polyisocyanate, (3) a saturated glycol chain extender, and (4) an extender of glycol chain containing carbon-carbon double bonds in a tube surrounding the metallic wire exiting the pipe-type crosshead matrix at a speed slower than that at which the wire is exiting the pipe-type crosshead matrix; (c) applying a vacuum to the matrix cavity so as to cause the thermoplastic polyurethane composition tube to collapse onto the wire as it exits the pipe-like crosshead matrix to produce a wire having an uncured coating about it; and (d) exposing the wire having the uncured coating thereon to electron beam irradiation to crosslink the thermoplastic polyurethane composition into a thermostable and produce the coated electrical wire.
    [0010] In another embodiment of this invention, double bonds are incorporated into the thermoplastic polyurethane composition by polymerizing a hydroxyl terminated intermediate that contains double bonds in the polymer backbone. The present invention thus further discloses a thermoplastic polyurethane which is crosslinkable with electron beam radiation, wherein the thermoplastic polyurethane is composed of the reaction product of (1) a saturated hydroxyl terminated intermediate, (2) an unsaturated hydroxyl terminated intermediate , wherein the unsaturated hydroxyl-terminated intermediate contains carbon-carbon double bonds, (3) a polyisocyanate, and (4) a saturated glycol chain extender.
    [0011] In another embodiment of this invention, double bonds are incorporated into thermoplastic polyurethane using small amounts of both a hydroxyl terminated intermediate containing double bonds and a glycol chain extender containing double bonds. In this modality the TPU, which is crosslinkable with electron beam radiation, is composed of the reaction product of (1) a saturated hydroxyl terminated intermediate, (2) an unsaturated hydroxyl terminated intermediate, wherein the unsaturated hydroxyl terminated intermediate contains carbon-carbon double bonds, (3) a saturated glycol chain extender, (4) a glycol chain extender containing carbon-carbon double bonds, and (5) a polyisocyanate. This modality allows crosslinking to occur in both the rigid and flexible segments of the TPU polymer.
    [0012] The TPU compositions of this invention are of particular value when used in the manufacture of articles that benefit from improved chemical resistance, dimensional stability, stiffness properties, thermal resistance, oxidative resistance, and/or creep resistance. These crosslinkable TPUs can, for example, be used in the manufacture of flame retardant articles and composite structures. Brief description of the drawings
    [0013] The TPU of this invention can be used to coat electrical wires using the apparatus illustrated in the attached drawings.
    [0014] FIG. 1 is a fragmentary, diagrammatic perspective view of an apparatus that can be used to coat metallic wires in accordance with an embodiment of this invention.
    [0015] FIG. 2 is a cross-sectional view of the pipe-type crosshead die taken along line 2-2 of FIG. 1.
    [0016] FIG. 3 is an end view of the pipe-like crosshead die illustrated in FIG. 3 showing the end of the die from which the coated yarn exits. Detailed Description of the Invention
    [0017] The thermoplastic polyurethane of this invention contains unsaturation in its backbone which is capable of reacting to form crosslinks to produce a thermoset network. This unsaturation is introduced by incorporating glycols that contain carbon-carbon double bonds in the polymer as part of the chain extender or the hydroxyl terminated intermediate may have carbon-carbon double bonds. In some embodiments, both the chain extender (rigid segment component) and the hydroxyl terminated intermediate (flexible segment component) have double bonds. This allows crosslinking to occur on both the rigid and flexible segments of the TPU. These glycol chain extenders which contain carbon-carbon double bonds are typically in the form of allyl moieties, such as that present in trimethylolpropane monoallyl ether. In either case, when irradiated with electron beam radiation, the carbon-carbon double bonds inside the TPU react with each other to produce crosslinks between different polymer chains of the TPU, thus producing a crosslinked thermostable. Crosslinking used in TPU cure can be generated by exposure to electron beam irradiation, gamma rays, ultraviolet light (in the case of relatively light polymeric formulations), or by chemical free radical generators such as aliphatic and aromatic peroxides, azo compounds, photoinitiators, etc.
    [0018] The thermoplastic polyurethane of this invention can be the reaction product of (1) a hydroxyl terminated intermediate, (2) a polyisocyanate, and (3) a saturated glycol chain extender, and (4) a hydroxyl-terminated intermediate. glycol chain containing carbon-carbon double bonds. The technique under which these reagents are polymerized to synthesize thermoplastic polyurethane is conducted using conventional equipment, catalysts and procedures. However, the polymerization is carried out in a way that results in the desired characteristics for the polymer and the required molecular weight. The types and levels of hydroxyl terminated intermediate, polyisocyanate, and saturated glycol chain extender will be adjusted to obtain the desired set of chemical and physical characteristics for the polymer being synthesized. The polymerization technique used in preparing the TPUs of this invention are therefore conventional except that a glycol chain extender containing carbon-carbon double bonds replaces a portion of the saturated glycol chain extender that would normally be used in making the polymer.
    [0019] The hydroxyl-terminated intermediate (flexible segment components) used in the manufacture of thermoplastic polyurethane is a hydroxyl-terminated polyether intermediate, a hydroxyl-terminated polyester intermediate, hydroxyl-terminated polycarbonate intermediate, a hydroxyl-terminated polycaprolactone intermediate, and blends of the same. To inhibit crystallization, the hydroxyl-terminated intermediate can be (1) composed of repeating units that are derived from a branched glycol or (2) a random copolyether or random copolyester. For example, a hydroxyl terminated random copolyether intermediate can be synthesized by reacting two different alkyl diols or glycols with an alkylene oxide. Alternatively, the alkyl diol or glycol can be branched to inhibit crystallization.
    The alkyl diols or glycols used in making the hydroxyl terminated polyether intermediate will typically contain 2 to 12 carbon atoms and the alkylene oxide will typically contain 2 to 6 carbon atoms. The glycols that can be used in making the hydroxyl-terminated polyester intermediate can be aliphatic, aromatic, or combinations thereof, and typically contain a total of 2 to 8 carbon atoms. Some representative examples of glycols that can be used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2 ,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like. Some suitable glycols include ethylene glycol, 1,3-propanediol and 1,4-butanediol. Ethylene oxide and propylene oxide are representative examples of alkylene oxides that can be used in the synthesis of the hydroxyl functional polyether intermediate.
    [0021] A hydroxy-functional random copolyether intermediate that is useful in the practice of this invention can be produced by first reacting propylene glycol with propylene oxide followed by subsequent reaction with ethylene oxide. This results in the formation of poly(propylene-ethylene) glycol. Some representative examples of other useful hydroxy-functional polyether polyols include poly(ethylene) glycol, poly(propylene) glycol, and poly(tetramethylene ether) glycol, and the like.
    [0022] Poly(tetramethylene ether) glycol is a hydroxy-functional polyether polyol suitable for use in the manufacture of the thermoplastic polyurethane of this invention.
    [0023] Hydroxyl terminated random copolyester intermediates can be synthesized through (1) an esterification reaction of two different alkyl diols or glycols with one or more dicarboxylic acids or anhydrides, or (2) a transesterification reaction of two different alkyl diols or different glycols with one or more dicarboxylic acid esters. Alternatively, the alkyl diol or glycol can be branched to inhibit crystallization of the hydroxyl terminated copolyester intermediate
    [0024] The diols or glycols used in the manufacture of the hydroxyl-terminated polyester intermediate are the same diols or glycols that can be used in the synthesis of the hydroxyl-terminated polyether intermediate. The dicarboxylic acids used in making the hydroxyl-terminated copolyester intermediate can be aliphatic, cycloaliphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids that can be used alone or in mixtures generally have a total of 4 to 15 carbon atoms and include: succinic acid, glutatic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, acid phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Adipic acid is a suitable acid to use. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used to synthesize the intermediate by a transesterification reaction as explained above. Some representative examples of hydroxy-functional random copolyester polyols include poly(butylene hexylene adipate) glycol, poly(ethylene hexylene adipate) glycol, poly(propylene hexylene adipate) glycol, poly(ethylene butylene adipate) glycol, poly(butylene hexylene succinate) glycol , poly(butylene hexylene glutarate) glycol, poly(butylene hexylene pimelate) glycol, poly(butylene hexylene azelate) glycol, poly(butylene hexylene terephthalate) glycol, poly(butylene hexylene isophthalate) glycol, and the like. Poly(butylene hexylene adipate) glycol is a hydroxy-functional copolyester polyol suitable for use in synthesizing many TPUs in accordance with the practice of this invention.
    [0025] The hydroxyl-terminated polyether intermediate or the hydroxyl-terminated polyester intermediate used in the manufacture of the thermoplastic polyurethanes of this invention will typically have a number average molecular weight (Mn), determined by testing the terminal functional groups, which is in the range of about about 350 to about 10,000 in one aspect, from about 500 to about 5,000 in another aspect, from about 700 to about 4,000 in another aspect, and from about 1000 to about 3000 in yet another aspect. A blend of two or more hydroxyl terminated intermediates can be used to produce the TPU of this invention.
    Hydroxyl terminated polycarbonate intermediates are commercially available from Stahl USA of Peabody, MA. Suitable hydroxyl terminated polycarbonates can be prepared by reacting a glycol with a carbonate. U.S. Patent No. 4,131,731, incorporated herein by reference, describes hydroxyl-terminated polycarbonates, their preparation and how they can be used. These polycarbonates are typically linear. The number average molecular weight of hydroxyl-terminated polycarbonates is generally at least about 500 and typically not more than 3000.
    Hydroxyl terminated polycaprolactone intermediates are commercially available from companies such as, for example, Perstorp Polyols, Inc., Toledo, OH. Hydroxyl-terminated polycaprolactones can be formed by reacting a caprolactone with a glycol. Suitable caprolactones include ε-caprolactone and methyl ε-caprolactone. Suitable glycols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2- dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like. Methods for preparing hydroxyl terminated polycaprolactones are generally known to those of ordinary skill in the art.
    [0028] The polyisocyanate used in the synthesis of thermoplastic polyurethane can be selected among diisocyanates. Although aliphatic diisocyanates can be used, aromatic diisocyanates are typically used in polymer manufacture for most applications. Furthermore, the use of multifunctional isocyanate compounds, ie, tri-isocyanates, etc., which cause undesirable premature crosslinking, are generally avoided and thus the amount used, if any is used, is generally less than 4 mol percent in one aspect and less than 2 mole percent in another respect, based on the total moles of all the various isocyanates used. Diisocyanates include aromatic diisocyanates such as: 4,4'-methylenebis(phenyl isocyanate) (MDI); m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, and dicyclohexylmethane-4,4'-di - isocyanate. Dimers and trimers of the above diisocyanates as well as a blend of two or more diisocyanates can be used.
    [0029] The polyisocyanate used in this invention may be in the form of a low molecular weight polymer or oligomer with the end capped with an isocyanate. For example, the hydroxyl-terminated polyether intermediate described above can be reacted with an isocyanate-containing compound to create a low molecular weight polymer end capped with an isocyanate. In the TPU art, these materials are commonly referred to as prepolymers. These prepolymers typically have a number average molecular weight (Mn) in the range of about 500 to about 10,000.
    [0030] The molar ratio of the one or more diisocyanates to the total moles of the one or more hydroxyl-terminated intermediates and one or more chain extenders generally ranges from about 0.95 to about 1.05 in one aspect, and from about 0.98 to about 1.03 [moles per mole] in another aspect.
    [0031] The glycol chain extenders used in the manufacture of the thermoplastic polyurethane of this invention will be a combination of a saturated glycol chain extender and glycol chain extender containing carbon=carbon double bonds (unsaturated glycol chain extender). The unsaturated glycol chain extender 1 will typically represent about 2 percent by weight to about 100 percent by weight of the total amount of chain extender used in synthesizing the TPU of this invention. The total amount of chain extender is, of course, the sum of the total amount of saturated glycol and unsaturated glycol used in manufacturing the TPU. Thus, in this scenario, the unsaturated glycol chain extender will represent about 2 weight percent to about 100 weight percent and the saturated glycol chain extender will represent about 0 weight percent to about 98 weight percent of the total extender chain used in polymer synthesis. The unsaturated glycol chain extender will most typically represent about 5 percent by weight to about 50 percent by weight of the total amount of chain extender used in synthesizing the TPU. The unsaturated glycol chain extender will most typically represent about 8 percent by weight to about 50 percent by weight of the total amount of chain extender used in synthesizing the TPU. The unsaturated glycol will typically represent from about 0.5 weight percent to about 20 weight percent of the total weight of the TPU (total weight of hydroxyl terminated intermediate, polyisocyanate, saturated glycol chain extender, and glycol chain extender unsaturated). The unsaturated glycol most typically will represent from about 1 percent by weight to about 10 percent by weight of the total weight of the TPU. In another aspect, the unsaturated glycol will represent from about 1.5 weight percent to about 5 weight percent of the total weight of the TPU.
    [0032] The saturated chain extender that can be used in synthesizing the TPUs of this invention includes organic diols or glycols having from 2 to about 20 carbon atoms, such as alkane diols (straight and branched chain), cycloaliphatic diols, alkylaryl diols , and the like. Alkane diols that have a total of about 2 to about 12 carbon atoms are often used. Some representative examples of alkane diols that can be used include ethanediol, propane glycol, 1,6-hexanediol, 1,3-butanediol (1,3-BDO), 1,5-pentanediol, neopentylglycol (NPG), 2-butyl- 2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,4-butanediol. Dialkylene ether glycols, such as diethylene glycol and dipropylene glycol, can also be used as the chain extender. Examples of suitable cycloaliphatic diols include 1,2-cyclopentanediol, 1,4-cyclohexanedimethanol (CHDM) and the like. Examples of suitable alkylaryl diols include hydroquinone bis(P-hydroxyethyl) ether (HQEE), 1,4-benzenedimethanol, biphenol bisethoxy, bisphenol A ethoxylates, bisphenol F ethoxylates and the like. Still other suitable chain extenders are 1,3- bis(2-hydroxyethyl)benzene, el,2-bis(2-hydroxyethoxy)benzene. Mixtures of the chain extenders mentioned above can also be used.
    [0033] Saturated chain extenders with a functionality greater than 2 may also be used with the proviso that the resulting polymer retains the desired thermoplastic nature and other desired chemical and physical characteristics. Examples of such multifunctional chain extenders include trimethylolpropane, glycerin and pentraerythritol. Typically, multifunctional chain extenders are used in conjunction with difunctional chain extenders to introduce a limited amount of branching into the chain.
    [0034] Thus, the level of multifunctional chain extenders typically does not exceed 10 mole percent of the total amount of chain extenders used in the manufacture of thermoplastic polyurethane. It is more typical for the level of multifunctional saturated chain extenders to be limited to the range of 0.5 mol percent to 5 mol percent based on the total amount of chain extenders used in TPU fabrication. In many cases, the TPU will not have chain extenders having functionality greater than 2. In any case, saturated difunctional chain extenders will typically represent at least about 90 mole percent of the total amount of saturated chain extenders used in TPU synthesis.
    [0035] The saturated linear chain extenders that can be used for use in the fabrication of the TPUs of this invention can be represented by the structural formula
    where n represents an integer from 2 to 20 and where n typically represents an integer from 2 to 12. Thus, the linear chain extender will typically be selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4 - butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12- dodecanediol. However, it should be appreciated that various mixtures of diols can be used as the chain extender in the practice of this invention.
    [0036] The unsaturated glycol chain extender used in the manufacture of the TPUs of this invention are typically of the structural formula:
    wherein R1 groups may be the same or different and represent alkylene groups containing 1 to about 5 carbon atoms, wherein R2 represents a hydrogen atom or an alkyl group containing 1 to about 5 carbon atoms, and in that R3 represents an unsaturated hydrocarbyl group containing from 2 to about 10 carbon atoms. R1 will typically represent a divalent alkylene group containing 1 to 7 carbon atoms in one aspect of the invention and 1 to 3 carbon atoms in another aspect. In yet another aspect R1 can be represented by the formula: -(CH2)n'-. In many cases, R1 can be a methylene group. R2 will typically represent a methyl, ethyl, isopropyl, or a normal-propyl group. R3 is typically a monoallyl ether group, such as a monoallyl ether group of the structural formula: -(CH2)n'-O-CH2-CH=CH2, where n' in the above formula represents an integer from 1 to about 7 in one aspect and from 1 to 3 in another aspect. It is typical for n' to represent an integer from 1 to 3.
    [0037] In one aspect, the unsaturated glycol chain extender for use in the practice of this invention is trimethylolpropane monoallyl ether. Trimethylolpropane monoallyl ether has the structural formula:
    and is commercially available from many sources.
    [0038] In the embodiment of this invention where a hydroxyl terminated intermediate containing carbon-carbon double bonds is used to introduce double bonds into the TPU this will be used together with a saturated hydroxyl terminated intermediate in the TPU synthesis. In other words, the hydroxyl terminated intermediate used in making the TPU will be a mixture of saturated and unsaturated hydroxyl terminated intermediates. The unsaturated hydroxyl terminated intermediate will typically comprise from 1 to 100 weight percent of the total hydroxyl terminated intermediate with the saturated hydroxyl terminated intermediate representing 0 weight percent to 99 weight percent of the total hydroxyl terminated intermediate. In most cases, the unsaturated hydroxyl terminated intermediate will constitute 20 to 40 weight percent of the total hydroxyl terminated intermediate as the saturated hydroxyl terminated intermediate representing 60 weight percent to 80 weight percent of the total hydroxyl terminated intermediate. In one aspect, the unsaturated hydroxyl terminated intermediate constitutes 5 to 30 weight percent of the total hydroxyl terminated intermediate with the saturated hydroxyl terminated intermediate representing 70 weight percent to 95 weight percent of the total hydroxyl terminated intermediate.
    [0039] In one aspect of the invention, the unsaturated hydroxyl-terminated intermediate used in the manufacture of these TPUs is typically of the structural formula:
    where A independently represents -RiOH and a selected portion of the structure represented as follows:
    wherein R 1 , R 2 , R 3 and R 4 may be the same or different and represent divalent straight and branched alkylene moieties containing from 1 to about 10 carbon atoms. In one aspect, R1, R2, R3 and R4 independently are selected from methylene, ethylene, propylene, butylene, pentylene and hexylene moieties. In another aspect, R1 and R2 may contain 4 carbon atoms (eg, butylene) with R3 and R4 containing 1 carbon atom (eg, methylene). In yet another aspect, R1 is a divalent ether group represented by -R5-O-R5-, wherein R5 is independently selected from a divalent alkylene moiety containing 1 to 5 carbon atoms, and R2, R3 and R4 are as defined above . In one aspect of the invention, the n:m ratio ranges from about 0 to about 35, from about 1 to about 30 in another aspect, from about 5 to about 25 in yet another aspect, and from about 10 to about 20 in an additional aspect; ey is an integer in the range of about 1 to about 20.
    [0040] In another aspect of the invention, the unsaturated hydroxyl-terminated intermediate is the reaction product of the following components: a) from about 1.5 mol % to about 55 mol % of an unsaturated chain extender selected from a compound represented by the formula:
    b) from about 0 mol% to about 50 mol% of a diol selected from a compound represented by the formula:
    c) from about 45 to about 49 mol% of a diacid represented by the formula:
    where R1, R2, R3, and R4 are as previously defined. It will be recognized by the person skilled in the art that the total amount of each of the components forming the unsaturated hydroxyl-terminated intermediate will not exceed 100 mol%.
    [0041] A suitable unsaturated chain extender is trimethylolpropane monoallyl ether (TMPME).
    Suitable diols include but are not limited to ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and mixtures thereof.
    Suitable dicarboxylic acids that can be used alone or in mixtures generally include, but are not limited to succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, acid terephthalic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used to synthesize the intermediate by a transesterification reaction as previously discussed.
    [0044] In one aspect, the unsaturated hydroxyl-terminated intermediate can be manufactured by placing an unsaturated chain extender, a diol, and a diacid in a stirred reactor, heating the reaction medium to between about 120°C to about 200 °C at ambient pressure for about 3 to 8 hours, and removing any water generated. A transesterification catalyst such as tetra-(2-ethylhexyl) titanate is added and a vacuum (0-15 mm Hg) is optionally applied to the reaction medium to catalyze the reaction. The reaction medium is heated between about 180°C to about 210°C and generated water is continuously removed until an acid number below about 0.5 is obtained.
    [0045] The glycol chain extender containing carbon-carbon double bonds (unsaturated glycol chain extender) and/or the unsaturated hydroxyl terminated intermediate containing carbon-carbon double bonds can also be used to manufacture a very rigid TPU, often referred to as an engineering resin. Very rigid TPU is manufactured by reacting a polyisocyanate with a glycol chain extender, and optionally with up to 15 weight percent polyol (hydroxyl terminated intermediate). In one aspect, the very rigid TPU contains less than 5 percent by weight of polyol, and in another aspect zero polyol is present in the very rigid TPU polymer. Very hard TPU polymer has a durometer hardness greater than 60 Shore D in one aspect, greater than 80 Shore D in another aspect, and approximately 85 Shore D in an additional aspect. The glycol chain extenders, hydroxyl-terminated intermediates, and polyisocyanate used are the same as described above. Very rigid TPU polymer is predominantly made of rigid block segments in one aspect and is made all of rigid blocks in another aspect if no hydroxyl terminated intermediates are used. These types of TPU polymer, lacking carbon-carbon double bonds and therefore not cross-linked, are commercially available from Lubrizol Advanced Materials, Inc. under the brand names Isoplast® and HS-85.
    [0046] Replacing a portion of the saturated glycol chain extender with the glycol chain extender containing carbon-carbon double bonds and/or replacing a portion of the saturated hydroxyl terminated intermediate (if used) with the unsaturated hydroxyl terminated intermediate, the TPU rigid becomes capable of being crosslinked by exposure to electron beam radiation. Rigid crosslinked TPU will have improved properties such as reduced stiffness, reduced creep, and improved chemical resistance. These rigid products are useful in many applications such as medical applications and industrial applications. Retention dental impressions are an example of an application using rigid TPU.
    [0047] The process to produce the TPU polymer of this invention can use conventional TPU fabrication equipment. The hydroxyl-terminated polyether intermediate, the diisocyanate, the saturated chain extender and the unsaturated chain extender are generally added together and reacted according to standard polyurethane synthesis methodology. Typically, the components that form the TPU of the present invention are melt polymerized in a suitable mixer, such as an internal mixer known as a Banbury mixer, or in an extruder. In one process, the hydroxyl-terminated polyether intermediate is mixed with the glycol chain extender and added to the extruder as a blend. The diisocyanate is added separately to the extruder. Suitable polymerization or processing initiation temperatures of the diisocyanate are from about 100°C to about 200°C in one aspect, and from about 100°C to about 150°C in another aspect. Suitable polymerization initiation or processing temperatures of the blend of the hydroxyl-terminated polyether intermediate with the chain extender are from about 100°C to about 220°C in one aspect, and from about 150°C to 200°C in an additional aspect. Suitable mixing times to allow the various components to react and form the TPU polymers of the present invention are generally from about 2 to about 10 minutes in one aspect, and from about 3 to about 5 minutes in another aspect.
    [0048] A process to produce the TPU of this invention is the process referred to as a single-step polymerization process. In the one-step polymerization process which generally takes place in situ, a simultaneous reaction between three components takes place, i.e. the one or more hydroxyl-terminated polyether intermediates, the glycol, and the diisocyanate. The reaction is generally started at a temperature of about 90°C to about 120°C. As the reaction is exothermic, the reaction temperature generally rises to about 220°C to 250°C. In cases where ethylene glycol is used as the chain extender, it is important to limit the temperature of this exothermic reaction to a maximum of 235°C to avoid unwanted levels of foaming. The TPU polymer will come out of the reaction extruder and be pelletized. TPU pellets are normally stored in a heated vessel to continue the reaction and dry.
    [0049] It is often desirable to use catalysts such as stannous carboxylate or other metal carboxylates as well as tertiary amines. Examples of metal carboxylate catalysts include stannous octoate, dibutyltin dilaurate, phenyl mercuric propionate, lead octoate, iron acetylacetonate, magnesium acetylacetonate, and the like. Examples of tertiary amine catalysts include triethyleneamine, and the like. The amount of the one or more catalysts is low, generally from about 50 to about 100 parts by weight per million parts by weight of the final TPU polymer formed.
    [0050] The weight average molecular weight (Mw) of the TPU polymer, prior to being cross-linked, of the present invention is in the range of about 90000 to about 600000 Daltons in one aspect, from about 100,000 to about 300000 Daltons in another aspect, and from about 120,000 to about 250,000 Daltons in an additional aspect. The Mw of the TPU polymer is measured according to gel permeation chromatography (GPC) against polystyrene standard.
    [0051] When a higher molecular weight TPU polymer is desired, it can be obtained using a small amount of a crosslinking agent having an average functionality greater than 2.0 to induce crosslinking. The amount of crosslinking agent used is less than 2 mole percent of the total moles of chain extender in one aspect, and less than 1 mole percent in another aspect. One method of increasing the molecular weight in a TPU polymer is to replace less than 1 mole percent of the chain extender with trimethylolpropane (TMP).
    [0052] Crosslinking is accomplished by adding a crosslinking agent having an average functionality greater than 2.0 along with the hydroxyl terminated intermediate, the isocyanate compound, and chain extender into a reaction mixture to manufacture the TPU polymer. The amount of crosslinking agent used in the reaction mixture to make the TPU polymer will depend on the desired molecular weight and effectiveness of the particular crosslinking agent used. Usually less than 2.0 mol percent is used in one aspect, and less than 1.0 mol percent in another aspect, based on the total moles of chain extender used in making the TPU polymer. Crosslinking agent levels greater than 2.0 mole percent, based on total moles of chain extender, would be difficult for the fusion process. Therefore, the level of crosslinking agent used is from about 0.05 mol percent to about 2.0 mol percent based on total moles of chain extender.
    [0053] Crosslinking agents can be any monomeric or oligomeric materials that have an average functionality of more than 2.0 and have the ability to crosslink the TPU polymer. Such materials are well known in the art for thermosetting polyurethanes. In one aspect, crosslinking agents include trimethylolpropane (TMP) and pentaerythritol. Trimethylolpropane has been found to be a desirable crosslinking agent.
    [0054] The polymer TPUs of the present invention can be blended with various conventional additives or formulating agents, such as plasticizers, fillers, extenders, pigments, lubricants, UV absorbers, flame retardants, and the like. Fillers that can be used include talc, silicates, clays, calcium carbonate, and the like. The level of conventional additives will depend on the final properties and cost of the desired end application, as is well known to those skilled in the art of formulating TPUs. Additives can be added during the reaction to form TPU, but are usually added in a second formulation step.
    [0055] The TPUs of this invention can be used in the manufacture of a wide variety of consumer and industrial products having an improved level of thermal resistance, chemical resistance and solvent resistance. This is accomplished by melt processing the TPU to the desired structure and then exposing it to electron beam irradiation to crosslink it into a thermostable with that design. Virtually any melt processing method can be used to process the TPU into a desired uncured structure. TPU can be processed in melt extrusion, injection molding, compression molding, casting, melt spinning, film blowing, thermoforming, blow molding, and the like. For example, TPU can be extruded into a tube or hose of virtually any diameter. It can also be molded into the shape of a seal or gasket. After being formed into a desired shape the uncured TPU is then exposed to electron beam irradiation to crosslink it into a cured permanent structure.
    [0056] The TPU of this invention can beneficially be used to coat electrical wires that are exposed to high temperatures and organic solvents. This can be done by applying the TPU of this invention to the bare metal wire being coated using a pipe-type crosshead die. The metal will typically be aluminum or copper. To improve the adhesion between the TPU being applied and the bare wire, the bare wire is usually pre-heated before entering the pipe-type crosshead die.
    [0057] A vacuum is generally applied to the die cavity in the pipe-type transverse head die to make the thermoplastic composition tube being extruded from the die uniformly contact the bare wire exiting the head die piping-type cross section. The amount of vacuum or partial vacuum that needs to be applied to the die cavity to facilitate the newly formed extruded thermoplastic composition tube to properly contact the metallic wire will be determined by several factors, such as the speed of the wire. nu is coming out of the pipe-type cross-head array, the thickness of the coating being applied, the diameter of the wire wire, and the dimensions of the pipe-type cross-head array. Those skilled in the art will be able to determine the optimum amount of vacuum needed in their particular process.
    [0058] Using the process of this invention, bare metallic strands can be coated at relatively high speeds. It will generally be desirable to coat yarn at relatively high speeds due to economic considerations. Generally, wires will be treated at a rate of around 20 meters per minute to around 500 meters per minute. Typically, the wire being coated will pass through the pipe-type cross-head die at a speed of about 100 meters per minute to about 400 meters per minute. The exact speed at which the wire can be optimally coated can be determined by persons skilled in the art using standard engineering practices and will depend on the nature and design of the equipment being used, the thickness and type of wire being coated and the thickness of the coating being applied. It should be noted that the TPU tube being extruded from the pipe-type cross-head die will be extruded at a slower rate than that at which the bare metal wire is exiting the pipe-type cross-head die.
    [0059] The pipe-type crosshead array can be designed to coat wires with the TPU Composition in any desired thickness. Typically wires that will be manufactured into magnetic wires will be coated to a thickness between about 10 microns and about 100 microns. Typically, standard magnetic wires having a diameter of about 1 millimeter are coated to a thickness in the range of 15 microns to 35 microns. Magnetic wires having reinforced insulation generally have a coating thickness of 30 microns to 50 microns. As a general rule, the coating thickness on a magnetic wire will be less than about 5 percent of the diameter of the bare metal filament of the magnetic wire.
    [0060] An apparatus that can be used to coat metallic wire with the TPU of this invention to fabricate coated electrical wire is illustrated in FIG. 1. Apparatus 10 generally consists of a filament unwinding device 11, a filament preheater 12, and extruder 13 equipped with a pipe-like crosshead die 14, a quench bath 15, a beam source of electrons 19, and a device for winding filament 16. As shown in FIG. 1, bare wire filament 17 and coated wire 18 are broken at points 19 and 20. In bare wire filament breaking 19', when this apparatus is used to manufacture magnetic wire, conventional drawing equipment can be installed. Thus, an oversized bare strand filament 17 can be reduced to the desired size using drawing equipment before coating the bare strand filament. The filament preheater 12 in a specific embodiment of the process of this invention can include an annealer with which the effects of the process of drawing the bare filament filament or drawing it can be eliminated. In other specific embodiments where the apparatus 10 is being used to manufacture the coated wire 18, additional coating devices and hardeners can be inserted at the break point 20' so that successive coatings of various coating materials can be applied to the wire in advance. coated continuously.
    [0061] The device for unwinding the yarn 11 includes a spool 21 on which the bare yarn filament 17 is stored. The spool 21 is mounted on an axis 22 of the unwinding device 11 so as to rotate freely in the direction of the arrow 20. Operatively associated with the spool 21 there is a brake 23 which restricts the rotation of the spool 21 as the filament of yarn bare metal 17 is being pulled from it by the device for winding filament 16 so as to avoid entanglement. According to the process of this invention, it is highly possible that in an apparatus used for the commercial manufacture of electrical wire where bare wire filaments are being rolled, drawn or otherwise reduced in size, the device for unwinding the wire 11 may be completely eliminated, as the remaining apparatus can be used to coat the bare strand filament 17 continuously in a single pass as the bare strand filament is supplied from this rolling mill and drawing device. The spool 21 in this case can be replaced with one or more spools on which the bare yarn filament is transported from the rolling and drawing operation to the filament preheater 12. In cases where the device for unwinding the yarn 11 is eliminated and drawing and drawing equipment replaces it, it is important that an annealer be included at point 19 to eliminate the working effects of bare strand filament during the milling and drawing operations. In this operation depending on the temperature at which the bare wire filament 17 leaves the annealer, it is possible to eliminate the need for the filament preheater 12. The filament preheater 12 is only used to increase the temperature of the bare wire filament 17 prior to application of the coating material (TPU) by the pipe-type transverse head matrix 14. In the specific embodiment of this invention illustrated in FIG. 1, the device used to preheat the bare strand filament is the filament preheater 12. However, in other embodiments of the process of this invention, an annealer must be used to preheat the bare strand filament. The filament preheater 12 can be designed so as to heat the bare strand filament by passing it over hot rollers. In another embodiment, the filament preheater 12 may be designed to heat the bare wire filament simply containing a preferably tubular-shaped electrical resistance through which the bare wire filament passes before entering the pipe-like transverse head matrix. 14.
    [0062] The extruder 13 will normally be equipped with a material reservoir 24 to store the TPU composition that will be used to coat the bare metal wire filament. This will also be equipped with a pump 25 to transport the TPU composition from the material reservoir 24 to the pipe-type crosshead matrix 14. The pump 25 will usually be driven by a motor of the pump 26. Vacuum can be applied to the cavity of the matrix via a vacuum line 27. If desired, a vacuum pump can be connected directly to the pipe-type cross-head matrix 14.
    [0063] The pipe-type transverse head array 14 is most clearly illustrated in FIG. 2 and FIG. 3. The die cavity 28 through which the bare wire filament 17 passes extends the entire length of the pipe-type transverse head die. The TPU composition 30 used to coat the bare yarn filament 17 is pumped into the tube extrusion cavity 29. The bare yarn filament enters the die cavity 28 at the die cavity inlet opening 31 and exits the die at outlet opening 32. The TPU composition 30 exits the pipe-type crosshead array at the pipe outlet opening 33. After the TPU composition exits the pipe-type crosshead array through the pipe outlet 33, it collapses over and around the bare metallic wire coating it evenly. The TPU compound tube is extruded in such a way that it wraps the bare metal wire coming out of the pipe-type crosshead die and closes over it due to the vacuum being applied to die cavity 28 through the vacuum line 27. This collapse of the extruded TPU tube onto the wire filament 17 is also caused by the adhesion of the TPU composition to the bare metal wire being extruded. Due to the fact that the bare metallic wire is exiting the matrix at a higher speed than the thermoplastic composition is exiting the matrix as a tube that wraps the bare metallic wire, the thermoplastic composition tube is drawn and oriented to the as it is being applied to the wire.
    [0064] In the embodiment of this invention illustrated in FIG. 1, the hot coated wire 18 which came out of the pipe-like cross-head die 14 is rapidly cooled in a quench bath 15. This quench quench bath is not an essential element of the apparatus. For example, the newly coated yarn 18 could be allowed to cool simply by air-cooling for a sufficient period of time. However, since high speed is usually desirable, a sharp cooling bath will normally be used. The sudden cooling bath will normally use a cooling cold such as water. The quench bath can optionally contain various conditioners or colorants as desired.
    [0065] Before or after being cooled, the coated wire is exposed to electron beam irradiation provided by an electron beam source 19. The electron beam treatment is provided at an intensity and for a period of time sufficient to achieve the desired level of crosslinking needed to cure the TPU coating to the desired degree.
    [0066] The winding device 16 in many respects is similar to the unwinding device 11. The winding device 16 includes a spool 21 on which the coated wire 18 is wound for shipping. Bobbin 21 may be a conventional spool on which the coated yarn is shipped. Spools 21 are mounted for rotation on an axis 22 so as to be driven in the direction of arrow 34. Operatively connected to spool 21 there is a motor 35 which drives spool 21 and through it pulls the filament of bare wire 17 and coated wire 18 from the spool or spool 21 from unwinding device 11 finally to filament winding device 16.
    [0067] The TPU compositions of this invention, because of their flame retardant properties, abrasion resistance and good tensile strength, are particularly suitable for use as a housing for electrical conductors in wire and cable applications in construction, as a housing for shielded cable, industrial robotics equipment, cable with non-metallic jacket, cables for deep well pumps and other multi-conductor assemblies. A typical wire and cable construction will have at least one and will typically have multiple electrical conductors, usually 2 to 8 conductors, such as copper wire. Each conductor will typically be coated, typically by extrusion, with a thin layer of a polymeric insulating compound which may be TPU, polyvinyl chloride, polyethylene, cross-linked polyethylene, fluorocarbon polymers, and the like. Insulated multiple conductors can be wound with a metallic, fiberglass or other non-flammable textile material. The multiple conductors are then encased in a sheath material (i.e., the TPU Composition of this invention) to protect the electrical conductors. In most wire and cable end use applications, it is necessary for this covering material to be flame resistant in the event of a fire.
    [0068] Flame retardants used in TPU applications in wires and cables are well known in the literature and in the art. Exemplary flame retardants include non-halogenated flame retardants such as melamine, melamine derivatives such as melamine cyanurate, organic phosphates, organic phosphonates, and phosphorus-containing compounds. Halogenated flame retardants, such as chlorinated and brominated compounds, can also be used. Inorganic compounds such as aluminum trihydrate, antimony oxide, ammonium phosphate, ammonium polyphosphate, calcium carbonate, clay and talc can also be used as flame retardants. Often more than one flame retardant is used and often 3 or more flame retardants are combined in the TPU formulation.
    [0069] When used as a wire and cable jacket, the TPU of this invention would be extruded over the wire bundle and subsequently crosslinked by exposure to electron beam radiation to form a crosslinked jacket.
    [0070] This invention is illustrated by the following examples which are for illustrative purposes only and are not to be considered as limiting the scope of the invention or the manner in which it may be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.
    [0071] Examples 1 to 6 illustrate the synthesis of a hydroxyl-terminated intermediate that contains carbon-carbon double bonds. In these examples an unsaturated polyester diol intermediate is synthesized.
    [0072] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 232.23g (1.59 moles) of adipic acid (AA), 160.38g (1 .78 moles) of 1,4-butanediol (BDO) and 8.07g (0.046 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to a temperature of 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (0-15mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed until the acid number becomes less than 0.5 (3-5 hours). The final polyol has a hydroxyl number of 62.21 (~Mn of 1803.6 g/mol). Example 2
    [0073] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 212.66g (1.46 moles) of adipic acid (AA), 141.98g (1 .58 moles) of 1,4-butanediol (BDO) and 16.69g (0.096 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (0-15mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed until the acid number becomes less than 0.5 (3-5 hours). The final polyol has a hydroxyl number of 47.50 (~Mn of 2361.9 g/mol). Example 3
    [0074] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 240.18g (1.65 moles) of adipic acid (AA), 149.34g (, 66 moles) of 1,4-butanediol (BDO) and 38.93g (0.22 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (0-15mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed until the acid number becomes less than 0.5 (3-5 hours). The final polyol has a hydroxyl number of 83.45 (~Mn of 1344.58 g/mol). Example 4
    [0075] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 220.89g (1.51 moles) of adipic acid (AA), 116.08g (1 .29 moles) of 1,4-butanediol (BDO) and 81.07g (0.47 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to a temperature of 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (0-15mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed until the acid number becomes less than 0.5 (3-5 hours). The final polyol has a hydroxyl number of 68.12 (~Mn of 1647.1 g/mol). Example 5
    [0076] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 204.14g (1.40 moles) of adipic acid (AA) and 295.86g (1 .70 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to a temperature of 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (015mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed while the reaction is monitored by following the acid number (7 hours). The final polyol has an acid number of 4.98 and a hydroxyl number of 67.42 (~Mn of 1664.2 g/mol). Further reaction to reduce the acid number below 0.5 resulted in gelation. Example 6
    [0077] To a three-neck glass reactor equipped with a mechanical overhead stirrer, thermometer, column condenser, and receiver are added 417.32g (2.86 moles) of adipic acid (AA), 325.04g (3.063) moles) of diethylene glycol (DEG) and 38.47g (0.22 moles) of trimethylolpropane mono allyl ether (TMPME). The reaction medium is heated to a temperature of 150°C to 190°C at ambient pressure (5-6 hours) and the generated water is collected. Then 100 ppm of tetra-(2-ethylhexyl) titanate transesterification catalyst is added and a vacuum (0-15mmHg) is applied while the reaction medium is heated to 190°C to 200°C. The generated water is removed until the acid number becomes less than 0.5 (3-5 hours). The final polyol has a hydroxyl number of 68.00 (~Mn of 1650.0 g/mol). Examples 7-14
    [0078] Examples 7 to 14 illustrate synthesized crosslinkable TPUs with unsaturation present only in the chain extender (rigid segment). In these examples, a typical high temperature melt polymerization is used to prepare TPUs synthesized from the components shown in Table 1 below. The polyol glycol(s) is (are) melted at 120°C and mixed with the chain extender(s). The blend is mixed with molten 4,4'-diphenylmethane diisocyanate (MDI) and reacted at an initial temperature of 190°C. TPU polymerization is complete in 3 to 4 minutes. Compression molded boards are molded from TPU and cut into smaller pieces weighing 1-2 grams and subjected to Soxhlet extraction in THF (tetrahydrofuran) and dissolution in NMP solvent (N-methylpyrrolidone) to determine if TPU is soluble in these solvents.
    [0079] In the Soxhlet extraction procedure with THF, the sample TPU sample is immersed in the solvent and the extraction is performed at reflux for 6 hours. After extraction the sample is first placed in water to remove residual solvent and then placed in a convection oven at 105°C until constant weight is obtained indicating that all solvent has been removed. If the sample is dissolved or has a crosslink density (CD) value less than 60% the solubility in THF is classified as soluble, an indication of no or insufficient crosslinking present. If the CD value was greater than 60% the sample is classified as insoluble, an indication of the presence of crosslinking. CD values are calculated using the following equation: CD = 100 x (1 - [(Wi - Wf) / Wi]) where Wi and Wf are the initial and final dry weight of the sample before and after Soxhlet extraction, respectively. Since the samples are not irradiated crosslinking is null resulting in no solvent resistance. The results are shown in Table 1.
    [0080] For the determination of solubility in NMP, 1-2 gram samples of TPU are immersed in NMP for 7 days. After 7 days, if the sample is completely dissolved, it is considered soluble. If the sample does not dissolve, it is removed from the solution and placed in water to remove excess solvent and then placed in a convection oven at 140°C for 4 hours to remove any residual solvent. Samples in which brittleness properties are observed are classified as insoluble.
    1 MDI 4,4'-diphenylmethane diisocyanate (molecular weight 250.4 g/mol) 8 TMPME Trimethylolpropane monoallyl ether (molecular weight 175 g/mol) 9 THF Solvent Tetrahydrofuran10 NMP Solvent N-methylpyrrolidoneExamples 15-20
    [0081] Examples 15 to 20 illustrate crosslinkable TPUs synthesized with unsaturation present only in the hydroxyl-terminated polyester polyol intermediate (flexible segment). In these examples, a typical high temperature melt polymerization is used to prepare TPUs synthesized from the components shown in Table 2 below. The polyol glycol(s) is (are) melted at 120°C and mixed with the chain extender(s). The blend is mixed with molten 4,4'-diphenylmethane diisocyanate (MDI) and reacted at an initial temperature of 190°C. TPU polymerization is complete in 3 to 4 minutes. Compression molded boards are molded from TPU and cut into smaller pieces for solubility testing in THF and NMP as indicated in Examples 7-14. The results are shown in Table 2.
    1 MDI 4,4'-diphenylmethane diisocyanate (molecular weight 250.4 g/mol) 5 PCARB Poly(hexamethylene carbonate) glycol (molecular weight 2000 g/mol) 6 THF Solvent Tetrahydrofuran) 7 NMP Solvent (N- methylpyrrolidone) Examples 21-34
    [0082] Examples 21 to 34 illustrate synthesized crosslinkable TPUs with unsaturation present in the chain extender (rigid segment) and in the hydroxyl-terminated polyester polyol intermediate (flexible segment). In these examples, a typical high temperature melt polymerization is used to prepare TPUs synthesized from the components shown in Tables 3 and 4 below. The polyol glycol(s) is (are) melted at 120°C and mixed with the chain extender(s). The blend is mixed with molten 4,4'-diphenylmethane diisocyanate (MDI) and reacted at an initial temperature of 190°C. TPU polymerization is complete in 3 to 4 minutes. Compression molded boards are molded from TPU and cut into smaller pieces for solubility testing in THF and NMP as indicated in Examples 7-14. The results are shown in Tables 3 and 4.
    1 MDI 4,4'-diphenylmethane diisocyanate (molecular weight 250.4 g/mol) 2 PTMEG 1000 Poly(tetramethylene ether) glycol (molecular weight 1000 g/mol) 3 TMPME Trimethylolpropane monoallyl ether (molecular weight 175 g/mol) ) 4 THF Solvent Tetrahydrofuran) 5 NMP Solvent N-methylpyrrolidone Table 4
    1 MDI 4,4'-diphenylmethane diisocyanate (molecular weight 250.4 g/mol)2 PTMAG Poly(tetramethylene adipate) glycol (molecular weight 870 g/mol)3 P(TMA/HMA)G Poly(tetramethylene-co) -hexamethylene adipate) glycol (molecular weight 2500 g/mol)4 Poly(caprolactone) Polyol (molecular weight 2000 g/mol)5 PCARB Poly(hexamethylene carbonate) glycol (molecular weight 2000 g/mol)6 TMPME Trimethylolpropane monoallyl ether (weight molecular 175 g/mol) 7 THF Solvent Tetrahydrofuran 8 NMP Solvent N-methylpyrrolidone Examples 35-46
    [0083] In many cases, the solvent resistance of a polymer is related to its crosslink density. Generally, uncrosslinked polymers are susceptible to solvent attack (eg, they are soluble or partially soluble in a particular solvent system). Crosslinked polymers are commonly resistant to solvent attack. In these examples, compression molded plates are molded from selected TPUs synthesized in Examples 7 to 34 and are subsequently irradiated with dosages of 10 to 60 MRad (MR) of electron beam radiation. As a control, commercially available TPUs not containing crosslinkable unsaturated portions are similarly molded and irradiated. The irradiated plates were cut into 1-2 gram samples and subjected to solvent testing using THF and NMP as indicated in Examples 7 to 14. Generally, CD values are in the range of 55% to 66% for samples irradiated with 10 MR and in the range of 85% to 97% for samples irradiated with a dose of 20 MR and higher in the electron beam. All non-irradiated samples as well as the irradiated control polymers are soluble in THF and NMP indicating that no cross-linking has occurred. The results are shown in Table 5.

    1 Estane® 58315 TPU A polyether-based TPU made from MDI, polyether polyol, butanediol, being commercially available from Lubrizol Advanced Materials, Inc.2 Estane® 58271 TPU A polyester-based TPU made from MDI, polyester polyol, and butanediol, being commercially available from Lubrizol Advanced Materials, Inc. Examples 47-48
    [0084] In these examples, compression molded plates are molded from the TPUs synthesized in Examples 7 and 8 and are subsequently irradiated with dosages of 10 and 20 MRad (MR) of electron beam radiation. Dynamic Mechanical Analysis (DMA) is performed on irradiated TPUs in accordance with ASTM D5279-08. As a control, a commercially available TPU containing no crosslinkable unsaturated moieties is similarly tested. Temperature sweep runs are performed using a dynamic mechanical analyzer in torsional mode with a heating rate of 3°C/min and at 0.1% strain and frequency of 1 Hz.
    [0085] In addition, creep-recovery measurements are performed on the irradiated samples using the methodology presented in ASTM D2990 at 90°C. A constant load of 25000 Pa is applied to the samples and removed after 60 seconds allowing the sample to recover. Deformation not recovered after load removal is reported as % creep. DMA data and creep-recovery analysis are reported in Table 6.
    1Estane® 58315 TPU A polyether-based TPU made from MDI, polyether polyol, butanediol, being commercially available from Lubrizol Advanced Materials, Inc.Examples 49-50
    [0086] Compression molded plates (6 in. x 6 in. x 30mil) irradiated with an electron beam molded from the TPUs of Examples 12 and 34 are placed in a convection oven at 200°C for 6 hours. After 6 hours, the appearance and physical condition of the samples are determined by visual inspection. A commercially available TPU that does not contain crosslinkable unsaturated portions is similarly tested. The results are presented in Table 7.
    1Estane® 58315 TPU A polyether-based TPU made from MDI, polyether polyol, butanediol, being commercially available from Lubrizol Advanced Materials, Inc.Examples 51-52
    [0087] Percentage swelling (according to ASTM D471) is measured by placing irradiated samples of the TPUs synthesized in Examples 23 and 34 in Fuel C and measuring the weight gain/loss after 1 week of immersion in the fuel. Commercially available TPUs not containing crosslinkable unsaturated moieties are similarly tested. The results are shown in Table 8.
    1 Estane® 58887 TPU A polyether-based TPU made from MDI, polyether polyol, butanediol, being commercially available from Lubrizol Advanced Materials, Inc.2 Estane® 58219 TPU A polyether-based TPU made from MDI, polyether polyol, butanediol , being commercially available from Lubrizol Advanced Materials, Inc.
    权利要求:
    Claims (16)
    [0001]
    1. Crosslinkable thermoplastic polyurethane, characterized in that it comprises the reaction product of (1) an unsaturated hydroxyl-terminated compound, (2) an optional saturated hydroxyl-terminated compound, (3) a polyisocyanate, and (4) a saturated glycol chain extender, in which the unsaturated hydroxyl-terminated compound has the structural formula:
    [0002]
    2. Crosslinkable thermoplastic polyurethane according to claim 1, characterized in that it comprises the reaction product of (1) a compound terminated in unsaturated hydroxyl, (2) a compound terminated in saturated hydroxyl, (3) a polyisocyanate , and (4) a saturated glycol chain extender.
    [0003]
    3. Thermoplastic polyurethane according to claim 1 or 2, characterized in that R1 contains 4 carbon atoms, where R2 contains 4 carbon atoms, where R3 contains 1 carbon atom, and where R4 contains 1 atom of carbon.
    [0004]
    4. Thermoplastic polyurethane according to claim 1 or 2, characterized in that it additionally comprises (5) a glycol chain extender containing carbon-carbon double bonds.
    [0005]
    5. Thermoplastic polyurethane according to claim 4, characterized in that the glycol chain extender containing carbon-carbon double bonds has the structural formula:
    [0006]
    6. Thermoplastic polyurethane according to claim 5, characterized in that R3 of the glycol chain extender containing carbon-carbon double bonds is a monoallyl ether group of the structural formula: -(CH2)n'-O-CH2-CH= CH2, where n' represents an integer from 1 to 7.
    [0007]
    7. Thermoplastic polyurethane according to claim 6, characterized in that the glycol chain extender containing carbon-carbon double bonds is trimethylolpropane monoallyl ether.
    [0008]
    8. Thermoplastic polyurethane according to claim 4, characterized in that the glycol chain extender containing carbon-carbon double bonds is present in the thermoplastic polyurethane at a level in the range of 1 percent by weight to 10 percent by weight of the total weight of the TPU.
    [0009]
    9. Thermoplastic polyurethane according to claim 1 or 2, characterized in that the hydroxyl-terminated compound is selected from a hydroxyl-terminated polyether, a hydroxyl-terminated polyester, a hydroxyl-terminated polycarbonate, a hydroxyl-terminated polycaprolactone, and mixtures thereof.
    [0010]
    10. Thermoplastic polyurethane according to claim 1 or 2, characterized in that the hydroxyl-terminated compound is a hydroxyl-terminated random copolyester.
    [0011]
    11. Thermoplastic polyurethane according to claim 1 or 2, characterized in that said polyisocyanate is an aromatic diisocyanate.
    [0012]
    12. Thermoplastic polyurethane according to claim 11, characterized in that the aromatic diisocyanate is selected from 4,4'-methylenebis(phenyl isocyanate); m-xylene diisocyanate, p-xylene diisocyanate, phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-3,3'-dimethoxy-4,4'-di- isocyanate, and toluene diisocyanate.
    [0013]
    13. Thermoplastic polyurethane according to claim 11, characterized in that the aromatic diisocyanate is 4,4'-methylenebis(phenyl isocyanate).
    [0014]
    14. Thermoplastic polyurethane according to claim 10, characterized in that the hydroxyl-terminated polyester is poly(butylene hexylene adipate) glycol.
    [0015]
    15. Wire and cable, characterized in that they are obtainable from crosslinkable thermoplastic polyurethane as defined in any one of claims 1 to 14, by extrusion of said crosslinkable thermoplastic polyurethane onto a metallic conductor and subsequent crosslinking.
    [0016]
    16. Crosslinked thermoplastic polyurethane, characterized in that it is obtainable from crosslinkable thermoplastic polyurethane as defined in any one of claims 1 to 14, by exposure to electron beams, gamma, or ultraviolet irradiation.
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    同族专利:
    公开号 | 公开日
    CN102803331B|2015-05-20|
    US8865052B2|2014-10-21|
    US20150034361A1|2015-02-05|
    TW201139555A|2011-11-16|
    MY156671A|2016-03-15|
    EP2526137B1|2015-07-01|
    KR101914104B1|2018-11-01|
    KR20120123687A|2012-11-09|
    US9650477B2|2017-05-16|
    CA2786567A1|2011-07-28|
    US20110186329A1|2011-08-04|
    JP5757959B2|2015-08-05|
    IN2012DN06240A|2015-09-25|
    WO2011091196A1|2011-07-28|
    AU2011207272A1|2012-07-26|
    CA2786567C|2019-04-16|
    SG182341A1|2012-08-30|
    TWI490271B|2015-07-01|
    JP2013518147A|2013-05-20|
    BR112012017883A2|2020-07-28|
    MX2012008333A|2012-08-08|
    AU2011207272B2|2015-06-18|
    KR20170077290A|2017-07-05|
    EP2526137A1|2012-11-28|
    CN102803331A|2012-11-28|
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    法律状态:
    2020-08-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-10-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/01/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    US29743410P| true| 2010-01-22|2010-01-22|
    US61/297,434|2010-01-22|
    US61/297434|2010-01-22|
    PCT/US2011/021960|WO2011091196A1|2010-01-22|2011-01-21|Crosslinkable thermoplastic polyurethane|
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