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  Polyether ester elastomer compositionUSPTO Application #: 20080103217Title: Polyether ester elastomer composition Abstract: Disclosed are polyether ester elastomer compositions having polytrimethylene ether ester soft segments and polyethylene ester hard segments and containing a nucleating agent. Shaped articles can be made from these compositions, particularly molded articles, films and fibers. (end of abstract) Agent: E I Du Pont De Nemours And Company Legal Patent Records Center - Wilmington, DE, US Inventor: Hari Babu Sunkara USPTO Applicaton #: 20080103217 - Class: 516 53 (USPTO) The Patent Description & Claims data below is from USPTO Patent Application 20080103217. Brief Patent Description - Full Patent Description - Patent Application Claims
FIELD OF THE INVENTION [0001]This invention relates to thermoplastic polyether ester elastomers comprising polytrimethylene ether ester soft segment and polyethylene terephthalate ester hard segment containing nucleating agents, and manufacture and use thereof. BACKGROUND OF THE INVENTION [0002]Thermoplastic elastomers (TPEs) are a class of polymers which combine the properties of two other classes of polymers, namely thermoplastics, which may be reformed upon heating, and elastomers which are rubber-like polymers. One form of TPE is a block copolymer, usually containing some blocks whose polymer properties usually resemble those of thermoplastics, and some blocks whose properties usually resemble those of elastomers. Those blocks whose properties resemble thermoplastics are often referred to as "hard" segments, while those blocks whose properties resemble elastomers are often referred to as "soft" segments. It is believed that the hard segments provide properties similar to chemical crosslinks in traditional thermosetting elastomers, while the soft segments provide rubber-like properties. [0003]Polyether ester thermoplastic elastomers comprising polytrimethylene ether ester soft segments and tetramethylene ester hard segments are known, for example, from U.S. Pat. No. 6,562,457. Polyether ester thermoplastic elastomers comprising polytrimethylene ether ester soft segments and trimethylene ester hard segments are known, for example, from U.S. Pat. No. 6,599,625. The polyether ester thermoplastic elastomers disclosed in these publications and useful, for example, in making fibers, films and other shaped articles. [0004]Polyether ester thermoplastic elastomers comprising polytrimethylene ether ester soft segments, in particular polytrimethylene terephthalate, and polyethylene ester hard segments, in particular polyethylene terephthalate, have also been described US 20050282966A1. These flexible materials have a potential advantage for some uses because the melting point and thermal stability of the polyethylene terephthalate hard segments is higher than those of the hard segments based on tetramethylene or trimethylene esters. Their utility, however, has been limited, particularly in engineering resin applications, because of their relatively low rates of crystallization. In fact, the unmodified polyether ester comprising polytrimethylene ether terephthalate soft segment and polyethylene terephthalate hard segment is unsuitable for most injection molding applications. Low crystallization rates cause the polymer to be difficult to pelletize or flake, difficult to spin into fibers, and difficult to process into shaped articles by such methods as thermoforming, injection molding and blow molding, because ejection from the mold of an insufficiently crystallized molding would mean that the article could continue to crystallize when in service with appropriate volume changes. [0005]Additives such as crystallization nucleants and plasticizers that improve crystallization rates of polyesters are in a general sense known. For example, U.S. Pat. No. 6,245,844 discloses polyester compositions comprising poly(trimethylene dicarboxylate) and a nucleating agent that is a mono sodium salt of a dicarboxylic acid selected from the group consisting of monosodium terephthalate, monosodium naphthalene dicarboxylic acid, and monosodium isophthalate. It is, however, also generally known that a specific additive that works very efficiently for a particular polyester may not work well for others. [0006]U.S. Pat. No. 3,761,450 describes molding compositions based on linear saturated polyesters comprising small amounts of lithium and/or sodium salts of polycarboxylic acids to bring about a high crystallinity in the heated mold after a short time. Polyesters and salts of polycarboxylic acids are disclosed generally. Poly(ethylene terephthalate) and disodium 1,10-dodecanedicarboxylate are exemplified. [0007]U.S. Pat. No. 5,264,477 discloses an improved melt processable liquid crystalline polyester composition capable of forming an anisotropic melt phase and having an improved heat distortion temperature under a load by using 0.05 to 1.0 wt % of a divalent metal salt of an aromatic dicarboxylic acid, wherein the metal is zinc, calcium, cadmium, barium or mixtures thereof. [0008]U.S. Pat. No. 4,380,621 discloses fast crystallizing polyesters in which at least some of the acid end groups of the polyester have the formula --COO.sup.-M.sup.+, wherein M.sup.+ is an alkaline metal ion. Poly(ethylene terephthalate) and poly(butylene terephthalate) are disclosed as polyesters. Sodium containing species exemplified include sodium hydroxide, sodium benzoate and sodium o-chlorobenzoate. [0009]There remains a need for nucleating agents that can improve the rate of crystallization of polyether ester thermoplastic elastomers comprising polytrimethylene ether ester soft segments and polyethylene ester hard segments and thereby take advantage of their high melting points in production of fibers, films and other shaped articles. SUMMARY OF THE INVENTION [0010]This invention is directed to a polyether ester elastomer composition comprising (i) a polyether ester elastomer based on a polytrimethylene ether ester soft segment and a polyethylene ester hard segment; and (ii) a nucleating agent selected from the group consisting of an alkali metal salt, an alkaline earth metal salt and mixtures thereof. [0011]The amount of nucleating agent utilized is such that the polyether ester containing nucleating agent exhibits a lower crystallization half time and earlier onset of the crystallization time during the cooling phase of molding, as compared to the same polyether ester without nucleating agent (an "effective amount"). [0012]In one preferred embodiment of the invention, the polyether ester composition is prepared by the steps of providing and reacting: [0013](a) a polytrimethylene ether glycol ("PO3G"); [0014](b) ethylene glycol; and [0015](c) a dicarboxylic acid equivalent, in the presence of the nucleating agent. [0016]In another preferred embodiment of the present invention, the polyether ester is prepared by the steps of: [0017](a) heating [0018](i) a polymeric ether glycol component comprising at least about 50 wt % PO3G, [0019](ii) terephthalic acid and/or dimethyl terephthalate, [0020](iii) a molar excess of a diol component comprising at least about 75 mole % ethylene glycol, and [0021](iv) a nucleating agent selected from the group consisting of an alkali metal salt, an alkaline earth metal salt and mixtures thereof,in the presence of a catalyst at a temperature in the range of from about 150.degree. C. to about 250.degree. C. while removing water or methanol by-product to form a precondensation product; and [0022](b) polymerizing the precondensation product under vacuum at temperature in the range of from about 220.degree. C. to about 290.degree. C. while removing excess diol to form a polyether ester having polytrimethylene ether terephthalate soft segment and polyethylene terephthalate hard segment. [0023]In yet another preferred embodiment, the polyether ester is prepared by the steps of: [0024](a) heating [0025](i) a polymeric ether glycol component comprising at least about 50 wt % PO3G, [0026](ii) terephthalic acid and/or dimethyl terephthalate, and [0027](iii) a molar excess of a diol component comprising at least about 75 mole % ethylene glycol,in the presence of a catalyst at temperature in the range of from about 150.degree. C. to about 250.degree. C. while removing water and/or methanol by-product to form a precondensation product; Continue reading... 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