US20080103217A1 - Polyether ester elastomer composition - Google Patents

Polyether ester elastomer composition Download PDF

Info

Publication number
US20080103217A1
US20080103217A1 US11/590,456 US59045606A US2008103217A1 US 20080103217 A1 US20080103217 A1 US 20080103217A1 US 59045606 A US59045606 A US 59045606A US 2008103217 A1 US2008103217 A1 US 2008103217A1
Authority
US
United States
Prior art keywords
polyether ester
elastomer composition
ester elastomer
ether glycol
polytrimethylene ether
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.)
Abandoned
Application number
US11/590,456
Other languages
English (en)
Inventor
Hari Babu Sunkara
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.)
EIDP Inc
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US11/590,456 priority Critical patent/US20080103217A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUNKARA, HARI BABU
Priority to DE112007002474T priority patent/DE112007002474T5/de
Priority to CN200780040870XA priority patent/CN101535371B/zh
Priority to PCT/US2007/022988 priority patent/WO2008054777A2/en
Priority to KR1020097008179A priority patent/KR20090082362A/ko
Priority to CA002662834A priority patent/CA2662834A1/en
Priority to JP2009534707A priority patent/JP2010508394A/ja
Priority to BRPI0716362 priority patent/BRPI0716362A2/pt
Publication of US20080103217A1 publication Critical patent/US20080103217A1/en
Priority to US12/899,117 priority patent/US20110021697A1/en
Priority to US14/672,015 priority patent/US10507480B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/02—Spray pistols; Apparatus for discharge
    • B05B7/04—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge
    • B05B7/0416—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing one gas and one liquid
    • B05B7/0483—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing one gas and one liquid with gas and liquid jets intersecting in the mixing chamber
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • thermoplastic polyether ester elastomers comprising polytrimethylene ether ester soft segment and polyethylene terephthalate ester hard segment containing nucleating agents, and manufacture and use thereof.
  • TPEs Thermoplastic elastomers
  • thermoplastics which may be reformed upon heating
  • 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.
  • 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.
  • 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.
  • Additives such as crystallization nucleants and plasticizers that improve crystallization rates of polyesters are in a general sense known.
  • 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.
  • 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.
  • 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.
  • 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.
  • This invention is directed to a polyether ester elastomer composition
  • 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.
  • the polyether ester is prepared by the steps of:
  • the polyether ester is prepared by the steps of:
  • the invention also relates to shaped articles prepared from the polyether ester, such as fibers and films.
  • Polyether esters containing the nucleating agents in accordance with the present invention exhibit short crystallization half times (t 1/2 ) and early onsets of crystallization as measured by differential scanning calorimeter (DSC) in the heating and cooling cycle.
  • Crystallization half time is the time needed for the degree of crystallinity to reach half of its ultimate value. The higher the onset crystallization temperature (Trc), the faster the crystallization rate.
  • the presence of the nucleating agent used in accordance with the present invention lowers the crystallization half time of the polymer and speeds up the onset of the crystallization time (as well as the early appearance of the crystallization peak temperature) during the cooling phase of the polymer, all as measured by DSC analysis, to the extent necessary to effectively utilize the polymer in a variety of end-use applications.
  • a further result achieved by the practice of this invention is the improvement of physical properties of polyester polymers by increasing the crystallization rate and increasing the crystallinity.
  • compositions of this invention are compared to the same polyether ester polymers containing no nucleating agent, the polymers containing nucleating agent exhibit lower crystallization half times and earlier onsets of the crystallization time (early arrival of the crystallization peak temperature) during the cooling phase. It has also been found that the polyether ester comprising polytrimethylene ether ester soft segment and polyethylene ester hard segment exhibits improvement in brittleness, heat resistance and impact resistance.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • the polyether ester elastomer preferably comprises:
  • the polyether ester elastomer preferably has an inherent viscosity of at least about 0.6 dl/g, more preferably at least about 1.0 dl/g, and preferably up to about 2.4 dl/g, more preferably up to about 1.9 dl/g.
  • dicarboxylic acid equivalent is meant dicarboxylic acids and their equivalents, which are compounds that perform substantially like dicarboxylic acids in reaction with polymeric glycols and diols, as would be generally recognized by a person of ordinary skill in the relevant art.
  • dicarboxylic acid equivalents for the purpose of the present invention include, for example, mono- and diesters of dicarboxylic acids, and diester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides.
  • the 1,3-propanediol is obtained biochemically from a renewable source (“biologically-derived” 1,3-propanediol).
  • the biologically-derived 1,3-propanediol, and PO3G and elastomers based thereon may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing.
  • This method usefully distinguishes chemically-identical materials, and apportions carbon in the copolymer by source (and possibly year) of growth of the biospheric (plant) component.
  • the isotopes, 14 C and 13 C bring complementary information to this problem.
  • the radiocarbon dating isotope ( 14 C) with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil (“dead”) and biospheric (“alive”) feedstocks (Currie, L. A.
  • the fundamental definition relates to 0.95 times the 14 C/ 12 C isotope ratio HOxI (referenced to AD 1950). This is roughly equivalent to decay-corrected pre-Industrial Revolution wood.
  • HOxI referenced to AD 1950.
  • 13 C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism.
  • the major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary carboxylation, i.e., the initial fixation of atmospheric CO 2 .
  • Two large classes of vegetation are those that incorporate the “C 3 ” (or Calvin-Benson) photosynthetic cycle and those that incorporate the “C 4 ” (or Hatch-Slack) photosynthetic cycle.
  • C 3 plants, such as hardwoods and conifers, are dominant in the temperate climate zones.
  • the primary CO 2 fixation or carboxylation reaction involves the enzyme ribulose-1,5-diphosphate carboxylase and the first stable product is a 3-carbon compound.
  • C 4 plants include such plants as tropical grasses, corn and sugar cane.
  • an additional carboxylation reaction involving another enzyme, phosphenol-pyruvate carboxylase is the primary carboxylation reaction.
  • the first stable carbon compound is a 4-carbon acid, which is subsequently decarboxylated. The CO 2 thus released is refixed by the C 3 cycle.
  • Biologically-derived 1,3-propanediol, and compositions comprising biologically-derived 1,3-propanediol may be completely distinguished from their petrochemical derived counterparts on the basis of 14 C (f M ) and dual carbon-isotopic finger-printing, indicating new compositions of matter.
  • the ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both “new” and “old” carbon isotope profiles may be distinguished from products made only of “old” materials.
  • the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
  • the purified 1,3-propanediol preferably has the following characteristics:
  • the starting material for making PO3G will depend on the desired PO3G, availability of starting materials, catalysts, equipment, etc., and comprises “1,3-propanediol reactant.”
  • 1,3-propanediol reactant is meant 1,3-propanediol, and oligomers and prepolymers of 1,3-propanediol preferably having a degree of polymerization of 2 to 9, and mixtures thereof. In some instances, it may be desirable to use up to 10% or more of low molecular weight oligomers where they are available.
  • the starting material comprises 1,3-propanediol and the dimer and trimer thereof.
  • a particularly preferred starting material is comprised of about 90% by weight or more 1,3-propanediol, and more preferably about 99% by weight or more 1,3-propanediol, based on the weight of the 1,3-propanediol reactant.
  • PO3G can be made via a number of processes known in the art, such as disclosed in U.S. Pat. No. 6,977,291 and U.S. Pat. No. 6,720,459. A preferred process is as set forth in previously incorporated US 20050020805A1.
  • PO3G may contain lesser amounts of other polyalkylene ether repeating units in addition to the trimethylene ether units.
  • the monomers for use in preparing polytrimethylene ether glycol can, therefore, contain up to 50% by weight (preferably about 20 wt % or less, more preferably about 10 wt % or less, and still more preferably about 2 wt % or less), of comonomer polyols in addition to the 1,3-propanediol reactant.
  • Suitable comonomer polyols include aliphatic diols, for example, ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol; cycloaliphatic diols, for example, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbide; and polyhydroxy compounds, for
  • a preferred group of comonomer diols is selected from the group consisting of ethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, C 6 -C 10 diols (such as 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol) and isosorbide, and mixtures thereof.
  • Particularly preferred diols other than 1,3-propanediol include ethylene glycol, 2-methyl-1,3-propanediol and C 6 -C 10 diols.
  • poly(trimethylene-ethylene ether) glycol such as described in US 20040030095A1.
  • Preferred poly(trimethylene-ethylene ether) glycols are prepared by acid catalyzed polycondensation of from greater than 50 to about 99 mole % (preferably from about 60 to about 98 mole %, and more preferably from about 70 to about 98 mole %) 1,3-propanediol, and up to 50 to about 1 mole % (preferably from about 40 to about 2 mole %, and more preferably from about 30 to about 2 mole %) ethylene glycol.
  • the PO3G after purification has essentially no acid catalyst end groups, but may contain very low levels of unsaturated end groups, predominately allyl end groups, in the range of from about 0.003 to about 0.03 meq/g.
  • Such a PO3G can be considered to comprise (consist essentially of) the compounds having the following formulae (II) and (III):
  • m is in a range such that the Mn (number average molecular weight) is within the range of from about 200 to about 5000, with compounds of formula (III) being present in an amount such that the allyl end groups (preferably all unsaturation ends or end groups) are present in the range of from about 0.003 to about 0.03 meq/g.
  • the small number of allyl end groups in the PO3G are useful to control elastomer molecular weight, while not unduly restricting it, so that compositions ideally suited, for example, for fiber end-uses can be prepared.
  • the preferred PO3G for use in the invention has an Mn of at least about 250, more preferably at least about 1000, and still more preferably at least about 2000.
  • the Mn is preferably less than about 5000, more preferably less than about 4000, and still more preferably less than about 3500.
  • Blends of PO3Gs can also be used.
  • the PO3G can comprise a blend of a higher and a lower molecular weight PO3G, preferably wherein the higher molecular weight PO3G has a number average molecular weight of from about 1000 to about 5000, and the lower molecular weight PO3G has a number average molecular weight of from about 200 to about 950.
  • the Mn of the blended PO3G will preferably still be in the ranges mentioned above.
  • PO3G preferred for use herein is typically a polydisperse polymer having a polydispersity (i.e. Mw/Mn) of preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and still more preferably from about 1.5 to about 2.1.
  • the polydispersity can be adjusted by using blends of PO3G.
  • the soft segment can be represented as comprising units represented by the following structure:
  • the hard segment can be represented as comprising units having the following structure:
  • R′ represents a divalent radical remaining after removal of carboxyl functionalities from a dicarboxylic acid equivalent.
  • the dicarboxylic acid equivalents used to prepare the soft segment and the hard segment of the polyether ester of this invention will be the same.
  • the hard segment can also be prepared with less than 50 mole %, preferably up to about 25 mole %, more preferably up to about 15 mole %, and still more preferably up to about 5 mole %, of diols other than ethylene glycol, preferably having a molecular weight lower than about 400.
  • the other diols are preferably aliphatic diols and can be acyclic or cyclic.
  • diols with 3-15 carbon atoms such as trimethylene, tetramethylene, isobutylene, butylene, pentamethylene, 2,2-dimethyltrimethylene, 2-methyltrimethylene, hexamethylene and decamethylene glycols; dihydroxy cyclohexane; cyclohexane dimethanol; and hydroquinone bis(2-hydroxyethyl) ether. More preferred are aliphatic diols containing 3-8 carbon atoms, especially 1,3-propanediol (trimethylene glycol) and/or 1,4-butanediol (tetramethylene glycol). Two or more other diols can be used.
  • the dicarboxylic acid equivalent can be aromatic, aliphatic or cycloaliphatic.
  • aromatic dicarboxylic acid equivalents are dicarboxylic acid equivalents in which each carboxyl group is attached to a carbon atom in a benzene ring system such as those mentioned below.
  • Aliphatic dicarboxylic acid equivalents are dicarboxylic acid equivalents in which each carboxyl group is attached to a fully saturated carbon atom or to a carbon atom which is part of an olefinic double bond.
  • the equivalent is “cycloaliphatic.”
  • the dicarboxylic acid equivalent can contain any substituent groups or combinations thereof, so long as the substituent groups do not interfere with the polymerization reaction or adversely affect the properties of the polyether ester product.
  • dicarboxylic acid equivalents selected from the group consisting of dicarboxylic acids and diesters of dicarboxylic acids. More preferred are dimethyl esters of dicarboxylic acids.
  • aromatic dicarboxylic acids or diesters by themselves, or with small amounts of aliphatic or cycloaliphatic dicarboxylic acids or diesters.
  • dimethyl esters of aromatic dicarboxylic acids are especially preferred.
  • aromatic dicarboxylic acids useful in the present invention include terephthalic acid, isophthalic acid, bibenzoic acid, naphthalic acid, substituted dicarboxylic compounds with benzene nuclei such as bis(p-carboxyphenyl)methane, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4′-sulfonyl dibenzoic acid, and C1-C10 alkyl and other ring substitution derivatives such as halo, alkoxy or aryl derivatives.
  • benzene nuclei such as bis(p-carboxyphenyl)methane
  • 1,5-naphthalene dicarboxylic acid 1,5-naphthalene dicarboxylic acid
  • 2,6-naphthalene dicarboxylic acid 2,7-naphthalene dicarboxylic acid
  • Hydroxy acids such as p-(hydroxyethoxy)benzoic acid can also be used providing an aromatic dicarboxylic acid is also present.
  • Representative aliphatic and cycloaliphatic dicarboxylic acids useful in this invention are sebacic acid, 1,3- or 1,4-cyclohexane dicarboxylic acid, adipic acid, dodecanedioic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, fumaric acid, citraconic acid, allylmalonate acid, 4-cyclohexene-1,2-dicarboxylate acid, pimelic acid, suberic acid, 2,5-diethyladipic acid, 2-ethylsuberic acid, 2,2,3,3-tetramethyl succinic acid, cyclopentanenedicarboxylic acid, decahydro-1,5- (or 2,6-)naphthalene dicarboxylic acid, 4,4
  • dicarboxylic acid equivalents in the form of diesters, acid halides and anhydrides of the aforementioned aliphatic dicarboxylic acids are also useful to provide the polyether ester of the present invention.
  • Representative aromatic diesters include dimethyl terephthalate, bibenzoate, isophthalate, phthalate and naphthalate.
  • terephthalic, bibenzoic, isophthalic and naphthalic acid dimethyl terephthalate, bibenzoate, isophthalate, naphthalate and phthalate; and mixtures thereof.
  • Particularly preferred dicarboxylic acid equivalents are the equivalents of phenylene dicarboxylic acids especially those selected from the group consisting of terephthalic and isophthalic acid and their diesters, especially the dimethyl esters, dimethyl terephthalate and dimethyl isophthalate.
  • two or more dicarboxylic acids equivalents can be used.
  • terephthalic acid and/or dimethyl terephthalate can be used with small amounts of the other dicarboxylic acid equivalents.
  • At least about 70 mole % (more preferably at least about 80 mole %, still more preferably at least about 90 mole %, and still more preferably from about 95 to 100 mole %) of the dicarboxylic acid equivalent is terephthalic acid and/or dimethyl terephthalate.
  • compositions of the invention include a nucleating agent.
  • Preferred nucleating agents for use in the invention are alkali metal (Group IA) or alkaline earth metal (Group IIA) salts of, for example, sulfinates, phosphinates, phosphates, sulfates, sulfonates, phosphates, hydroxides, aliphatic carboxylates and aromatic carboxylates.
  • the salts comprise an alkali metal (lithium, sodium, potassium, rubidium or cesium) or alkaline earth metal (magnesium, calcium, strontium, or barium) cation and an anion preferably selected from the group consisting of carboxylate, sulfinate, phosphinate, sulfate, sulfonate, phosphate, hydroxide, aliphatic carboxylate and aromatic carboxylate.
  • Preferred metal cations are lithium, sodium, potassium and calcium.
  • Preferred anions are phosphate, sulfate, aliphatic carboxylates such as acetate and propionate, and aromatic carboxylates such as benzoate acid, terephthalate, isophthalate and phthalate.
  • Particularly preferred nucleating agents are trisodium phosphate and sodium acetate.
  • the polyether ester is preferably prepared by providing and reacting (a) a PO3G, (b) ethylene glycol and (c) a dicarboxylic acid equivalent.
  • a PO3G PO3G
  • ethylene glycol ethylene glycol
  • c dicarboxylic acid equivalent.
  • the other glycols, diols, etc., as described above are can also be provided and reacted.
  • the polyether ester of this invention is conveniently made starting with a conventional ester exchange reaction, esterification or transesterification depending on the starting dicarboxylic acid equivalent.
  • dimethyl terephthalate is heated with polytrimethylene ether glycol and an excess of ethylene glycol in the presence of a catalyst at 150-250° C., while distilling off the methanol formed by the ester exchange.
  • This reaction is typically performed at a pressure of about 1 atmosphere.
  • the reaction product is a mixture of the ester exchange reaction products of the dimethyl terephthalate and the polytrimethylene ether glycol and ethylene glycol, primarily bis(hydroxyethyl)terephthalate with varying amounts of (hydroxy-polytrimethylene ether) terephthalates, along with a small amount of the corresponding oligomers.
  • This precondensation product mixture then undergoes polymerization or polycondensation to a copolymer of an elastomeric polyether ester with a polytrimethylene ether glycol soft segment and a polyethylene terephthalate hard segment (condensation product of ethylene glycol and dimethyl terephthalate).
  • the polymerization involves additional ester exchange and distillation to remove the diol to increase molecular weight.
  • the polycondensation is typically performed under vacuum. Pressure is typically in the range of from about 0.01 to about 18 mm Hg (1.3 to 2400 Pa), preferably in the range of from about 0.05 to about 4 mm Hg (6.7 to 553 Pa), and more preferably from about 0.05 to about 2 mm Hg.
  • the polycondensation is typically carried out at a temperature in the range of from about 220° C. to about 290° C.
  • the precondensation (ester exchange) and polymerization steps may involve alternative processes than those described above.
  • polytrimethylene ether glycol can be reacted with polydimethylene ester (e.g., polyethylene terephthalate) in the presence of catalyst (such as those described for the ester exchange, preferably the titanium catalysts such as tetrabutyl titanate) until randomization occurs. Both processes result in block copolymers.
  • a catalyst can be (and preferably is) employed in the ester exchange.
  • Catalysts useful in the ester exchange process include organic and inorganic compounds of titanium, lanthanum, tin, antimony, zirconium, manganese, zinc, phosphorus and mixtures thereof.
  • Manganese acetate is a preferred transesterification catalyst and antimony trioxide is a preferred polycondensation catalyst.
  • Ester exchange polymerizations are generally conducted in the melt without added solvent, but inert solvents can be added to facilitate removal of volatile components, such as water and diols at low temperatures. This technique is useful during reaction of the polytrimethylene ether glycol or the diol with the dicarboxylic acid equivalent, especially when it involves direct esterification, i.e., the dicarboxylic acid equivalent is a diacid. Other special polymerization techniques can be useful for preparation of specific polymers.
  • Polymerization can also be accomplished in the solid phase by heating divided solid product from the reaction of polytrimethylene ether glycol, a dicarboxylic acid equivalent, and ethylene glycol in a vacuum or in a stream of inert gas to remove liberated diol.
  • This type of polycondensation is referred to herein as “solid phase polymerization” (or abbreviated “SPP”).
  • Batch or continuous methods can be used for the processes described above or for any stage of polyether ester preparation. Continuous polymerization, by ester exchange, is preferred.
  • a branching agent is typically used in a concentration of from about 0.00015 to about 0.005 equivalents per 100 grams of polymer.
  • the branching agent can be a polyol having 3-6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups, or a hydroxy acid having a total of 3-6 hydroxyl and carboxyl groups.
  • Representative polyol branching agents include glycerol, sorbitol, pentaerytritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylol propane, and 1,2,6-hexane triol.
  • Suitable polycarboxylic acid branching agents include hemimellitic, trimellitic, trimesic pyromellitic, 1,1,2,2-ethanetetracarboxylic, 1,1,2-ethanetricarboxylic, 1,3,5-pentanetricarboxylic, 1,2,3,4-cyclopentanetetracarboxylic and like acids. Although the acids can be used as is, it is preferred to use them in the form of their lower alkyl esters.
  • the nucleating agent can be introduced to the polyether ester in several ways. It can be added at any time during the synthesis of the polymer. That is, it can be added during the (trans)esterification and/or the polycondensation steps. It is also possible to mix the nucleating agent with the finished polyether ester while it is being processed in an extruder or other melt mixer. Preferably, the nucleating agent is added during the (trans)esterification stage. It may be added as a pure compound or as a masterbatch in the same or different polyether ester to which it is being added.
  • compositions of the present invention may include a plasticizer to improve their processability.
  • plasticizers include, for example, diesters of polyethylene glycol such as diethylene glycol di(2-ethylhexonate), triethylene glycol di(2-ethylhexonate), tetraethylene glycol diheptanoate, triethylene glycol di(2-ethylbutyrate), di-2ethylhexyl phthalate, and di-2-ethylhexyl adipate
  • the preferred amount of plasticizer in the composition is from about 0.1 to about 15%, and more preferably from about 1 to about 10%, by weight based on the total weight of the polymer.
  • compositions of the present invention may also include other well-known additives such as antioxidants, branching agents, heat and UV stabilizers, fillers, dyes, pigments and epoxides.
  • additives such as antioxidants, branching agents, heat and UV stabilizers, fillers, dyes, pigments and epoxides.
  • nucleated polyether esters of this invention are useful, for example, in making fibers, films and other shaped articles.
  • Yarns preferably comprise at least about 2, and more preferably at least about 25 filaments.
  • the yarns typically have a total denier of from about 1 to about 500, preferably at least about 20, more preferably at least about 50, and even more preferably from about 50 to about 100.
  • Filaments are preferably at least about 0.5 denier per filament (dpf), more preferably at least about 1 dpf, and up to about 20 or more dpf, more preferably up to about 10 dpf.
  • Typical filaments are about 3 to 10 dpf, and fine filaments are about 0.5 to about 2.5 dpf.
  • Spinning speeds can be at least about 200 meters/minute (m/min), more preferably at least about 1000 m/min, and ever more preferably at least about 500 m/min, and can be up to about 4000 m/min or higher.
  • the fibers can be drawn from about 1.5 ⁇ to about 6 ⁇ , preferably at least about 1.5 ⁇ , and preferably up to about 4 ⁇ .
  • Single step draw is the preferred drawing technique. In most cases it is preferred not to draw the fibers.
  • the fibers can be heat set, and preferably the temperature is at least about 140° C. and preferably up to about 160° C.
  • Finishes can be applied for spinning or subsequent processing, and include silicon oil, mineral oil, and other spin finishes used for polyesters and polyether ester elastomers, etc.
  • additives can be incorporated into the polyether ester or fiber by known techniques.
  • the additives include delusterants (e.g., TiO 2 , zinc sulfide and/or zinc oxide), colorants (e.g., dyes), stabilizers (e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.), fillers, flame retardants, pigments, antimicrobial agents, antistatic agents, optical brightners, extenders, processing aids, viscosity boosters, and other functional additives.
  • delusterants e.g., TiO 2 , zinc sulfide and/or zinc oxide
  • colorants e.g., dyes
  • stabilizers e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.
  • fillers flame retardants, pigments, antimicrobial agents, antistatic agents, optical brightners, extenders, processing aids, viscosity boosters, and other functional additives.
  • Particularly useful shaped articles are flexible films and sheets, particularly those having a thickness of from about 1 ⁇ m to about 500 ⁇ m.
  • the shaped article may, for example, comprise multilayers wherein at least one layer has a thickness of about 5 um or less.
  • the present invention provides flexible films comprising polytrimethylene ether ester elastomers having desirable mechanical properties such as tenacity, elasticity, toughness and flexibility, optionally without the use of plasticizers.
  • the films also possess very good breathability (high water vapor permeation rates).
  • Such films can be useful in making bags and packaging, e.g., for food, storage and transportation.
  • the films can be prepared from the polymers using methods known to those skilled in the art.
  • the flexible films can be cast films or oriented films Oriented films can be uniaxially oriented or biaxially oriented. Orientation can be effected by any process known in the art, such as, for example a tubular or flat film process. Orientation of films is disclosed, for example, in WO 01/48062.
  • the 1,3-propanediol utilized in the examples was prepared by biological methods described in US 2005/0069997A1, and had a purity of >99.8%
  • PO3G was prepared from 1,3-propanediol as described in US 20050020805A1.
  • Number-average molecular weights (Mn) were determined by end-group analysis using NMR spectroscopic methods.
  • Tm Melting point
  • Trc refcrystallization temperature
  • Tg glass transition temperature
  • ⁇ H the heat caused by the polymer crystallization
  • Crystallization behavior of polyether ester elastomers was investigated by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • IV inherent viscosity of the polymer sample was analyzed on a PolyVISC® automated viscometer (Cannon Instrument Co.) at a temperature of 30° C. in m-cresol with a 0.5% concentration.
  • This comparative example describes the synthesis of a polyether ester having 45 wt % polyethylene terephthalate and 5 wt % polybutylene terephthalate hard segments, and 50 wt % polytrimethylene ether terephthalate soft segment. No nucleating agent was utilized.
  • a 25 gallon autoclave was charged with 33.2 lbs of dimethyl terephthalate, 30 lbs of PO3G (Mn of 2250), 14 lbs of ethylene glycol, 2 lbs of 1,4-butanediol, 80 g of ETHANOX® 330 antioxidant (Albemarle), and 12 g of TYZOR® TPT catalyst (E.I. Du-Pont de Nemours and Company).
  • the reactant charge was designed to achieve a weight ratio of polyethylene terephthalate:polybutylene terephthalate:polytrimethylene ether glycol terephthalate of 45:5:50.
  • the temperature was then raised to 250° C. and held at that temperature at a pressure of 0.3 mm Hg for 3 hours.
  • the polymer obtained could not successfully be extruded into ribbons.
  • This example illustrates the preparation of a polyether ester with the same stoichiometry as that prepared in Comparative Example 1, but in this case including trisodium phosphate nucleating agent.
  • the temperature was then raised to 250° C. and held at that temperature at a pressure of 0.3 mm Hg for 2.5 hours.
  • the polymer was extruded into ribbons and converted into flakes.
  • This comparative example describes the synthesis of a polyether ester having 55 wt % polyethylene terephthalate hard segment and 45 wt % polytrimethylene ether terephthalate soft segment. No nucleating agent was utilized.
  • a 250 ml three-necked flask was charged with 42.1 g of dimethyl terephthalate, 29.3 g of PO3G (Mn of 1770), 20 g of ethylene glycol, 0.15 g of IRGANOX® 1098 antioxidant (Ciba Specialty Chemicals Inc.), and 25 mg of TYZOR® TPT catalyst.
  • the temperature was raised to 215° C. under nitrogen flush, and methanol generated was removed by distillation as a liquid condensate. The temperature was held at 210° C. for about 1.5 hours until no more methanol evolved indicating the end of transesterification reaction.
  • the temperature was then raised to 250° C. and held at that temperature at a pressure of 0.2 mm Hg for 2 hours.
  • the reaction was ended by removing the heat and vacuum.
  • This example illustrates the preparation of a polyether ester with the same stoichiometry as that prepared in Comparative Example 2 but including trisodium phosphate nucleating agent.
  • a 250 ml three-necked flask was charged with 42.1 g of dimethyl terephthalate, 29.3 g of PO3G (Mn of 1770), 20 g of ethylene glycol, 0.15 g of IRGANOX® 1098 antioxidant, 25 mg of TYZOR® TPT catalyst, and 0.36 g of trisodium phosphate (2100 ppm of sodium based on the final polymer) as nucleating agent.
  • the temperature was raised to 215° C. under nitrogen, and the methanol generated was removed as a liquid condensate by distillation. The temperature was held at 210° C. for about 1.5 hours until no more methanol evolved, indicating the end of transesterification reaction.
  • the temperature was raised to 250° C. and held at that temperature at a pressure of 0.2 mm Hg for 2 hours. Then the reaction was stopped by removal of the heat and vacuum, and the polymer was collected.
  • a polyether ester was prepared as described in Example 2 except that the amount of trisodium phosphate used was 0.26 g (corresponding to 1700 ppm of sodium based on the final polymer).
  • a polyether ester was prepared as described in Example 2 except the trisodium phosphate of Example 2 was replaced with 0.41 g of sodium acetate (corresponding to 1700 ppm of sodium based on the final polymer).
  • This example describes synthesis of a polyether ester having 50 wt % polyethylene terephthalate hard segments and 50 wt % polytrimethylene ether terephthalate soft segments in the presence of trisodium phosphate nucleating agent
  • a 25 gallon autoclave was charged with 36.5 lbs of dimethyl terephthalate, 30 lbs of PO3G (Mn of 1770), 16 lbs of ethylene glycol, 87 g of ETHANOX® 330 antioxidant, 12 g of TYZOR® TPT catalyst, 22 g trimethyl-trimellitate (1,2,4-benzene-tricarboxylic acid, methyl ester) and 150 g of sodium phosphate nucleating agent.
  • the temperature was raised to 215° C. under nitrogen, and the methanol generated was removed as a liquid condensate by distillation. The temperature was held at 210° C. for about 1.5 hours until no more methanol evolved, indicating the end of transesterification reaction.
  • the temperature was then raised to 250° C. and held at that temperature at a pressure of 0.3 mmHg for 2.5 hours.
  • the polymer was extruded into ribbons and converted into flakes.
  • Trc and decrease in t 1/2 suggest that the presence of nucleating agent in the elastomer effectively increases the crystallization rate.
  • Example 5 The mechanical properties of the polymer prepared in Example 5 were compared with those of HYTREL® 5556 polymer resin, a commercial thermoplastic elastomer available from E.I. duPont de Nemours and Company.
  • the data in Table 2 shows the excellent mechanical properties of the composition of the present invention.
  • the polymer of Example 5 has unique combination of properties: a lower glass transition temperature, higher melt temperature, and excellent mechanical properties.
  • This example demonstrates preparation of film from the nucleated polyether ester of Example 5.
  • the films were made using a 28 mm extruder (Werner & Pfleidener), equipped with Foremost #15 feeder, #3 casting drum, and #4 winder.
  • the hopper and throat of the extruder had a nitrogen blanket.
  • the polyether ester described in Example 5 was dried and fed through the hopper into the twin screw extruder.
  • the sample was heated to melt and fed into a film die.
  • the film was then cooled to 29° C. on a casting drum, which was equipped with a cooling water jacket. The cooled film was then wound onto a roll with a winder.
  • This example describes synthesis of a polyether ester having 28 wt % polyethylene terephthalate hard segment and 72 wt % polytrimethylene ether terephthalate soft segment in the presence of trisodium phosphate nucleating agent.
  • a 25 gallon autoclave was charged with 19.8 lbs of dimethyl terephthalate, 40 lbs of PO3G (Mn of 2270), 10.7 lbs of ethylene glycol, 79.6 g of ETHANOX® 330 antioxidant, 24 g of TYZOR® TPT catalyst, and 73.5 g of sodium phosphate nucleating agent.
  • the temperature was raised to 215° C. under nitrogen, and the methanol generated was removed as a liquid condensate by distillation. The temperature was held at 210° C. for about 1.5 hours until no more methanol evolved, indicating the end of transesterification reaction.
  • the temperature was then raised to 250° C. and held at that temperature at a pressure of 0.3 mm Hg for 2.5 hours.
  • the polymer was extruded into ribbons and converted into flakes.
  • the polymer had a Tm of 216.5° C., a Trc of 184° C., and an IV of 1.105 dL/g.
  • Example 7 The polymer of Example 7 was extruded through a sand filter spin pack and a three hole spinneret (0.3 mm diameter and 0.56 mm capillary depth holes, maintained at 257-259° C. The filamentary streams leaving the spinneret were quenched with air at 21° C., and converged to a bundle.
  • the spinning conditions for the yarns are described in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Nozzles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
US11/590,456 2004-02-26 2006-10-31 Polyether ester elastomer composition Abandoned US20080103217A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US11/590,456 US20080103217A1 (en) 2006-10-31 2006-10-31 Polyether ester elastomer composition
BRPI0716362 BRPI0716362A2 (pt) 2006-10-31 2007-10-31 "composiÇço de elastâmero de poliÉter Éster, elastÕmero de poliÉter Éster, fibra e filme flexivel"
KR1020097008179A KR20090082362A (ko) 2006-10-31 2007-10-31 폴리에테르 에스테르 탄성중합체 조성물
CN200780040870XA CN101535371B (zh) 2006-10-31 2007-10-31 聚醚-酯弹性体组合物
PCT/US2007/022988 WO2008054777A2 (en) 2006-10-31 2007-10-31 Polyether ester elastomer composition
DE112007002474T DE112007002474T5 (de) 2006-10-31 2007-10-31 Polyetherester-Elastomerzusammensetzung
CA002662834A CA2662834A1 (en) 2006-10-31 2007-10-31 Polyether ester elastomer composition
JP2009534707A JP2010508394A (ja) 2006-10-31 2007-10-31 ポリエーテルエステルエラストマー組成物
US12/899,117 US20110021697A1 (en) 2006-10-31 2010-10-06 Methods for preparing polyether ester elastomer composition
US14/672,015 US10507480B2 (en) 2004-02-26 2015-03-27 Method and apparatus for generating a mist

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/590,456 US20080103217A1 (en) 2006-10-31 2006-10-31 Polyether ester elastomer composition

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/899,117 Continuation US20110021697A1 (en) 2006-10-31 2010-10-06 Methods for preparing polyether ester elastomer composition

Publications (1)

Publication Number Publication Date
US20080103217A1 true US20080103217A1 (en) 2008-05-01

Family

ID=39212219

Family Applications (3)

Application Number Title Priority Date Filing Date
US11/590,456 Abandoned US20080103217A1 (en) 2004-02-26 2006-10-31 Polyether ester elastomer composition
US12/899,117 Abandoned US20110021697A1 (en) 2006-10-31 2010-10-06 Methods for preparing polyether ester elastomer composition
US14/672,015 Expired - Lifetime US10507480B2 (en) 2004-02-26 2015-03-27 Method and apparatus for generating a mist

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/899,117 Abandoned US20110021697A1 (en) 2006-10-31 2010-10-06 Methods for preparing polyether ester elastomer composition
US14/672,015 Expired - Lifetime US10507480B2 (en) 2004-02-26 2015-03-27 Method and apparatus for generating a mist

Country Status (8)

Country Link
US (3) US20080103217A1 (enExample)
JP (1) JP2010508394A (enExample)
KR (1) KR20090082362A (enExample)
CN (1) CN101535371B (enExample)
BR (1) BRPI0716362A2 (enExample)
CA (1) CA2662834A1 (enExample)
DE (1) DE112007002474T5 (enExample)
WO (1) WO2008054777A2 (enExample)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010076981A3 (ko) * 2008-12-31 2010-09-10 에스케이케미칼주식회사 아이소소르바이드가 공중합된 폴리에스테르 수지의 제조방법
EP2886592A1 (en) * 2013-12-20 2015-06-24 Invista Technologies S.A R.L. Improved polyester-ether resin blends
EP2857430A4 (en) * 2012-06-01 2016-04-27 Sk Chemicals Co Ltd POLYMILIC ACID RESIN AND PACKAGING FILM THEREWITH
US20160222549A1 (en) * 2015-02-02 2016-08-04 Shinkong Synthetic Fibers Corporation Bicomponent conjugate fibers, complex yarns and fabrics having high crimping property
US20220169806A1 (en) * 2019-02-25 2022-06-02 Foshan King Wonder Hi-Tech Co., Ltd. Bio-based elastomer composition and film and laminate prepared therefrom
US11732126B2 (en) 2018-09-28 2023-08-22 Lotte Chemical Corporation Thermoplastic resin composition and molded product produced therefrom
EP4289900A1 (en) * 2022-06-08 2023-12-13 Ecovance Co. Ltd Biodegradable polyester resin composition, biodegradable polyester film including the same and biodegradable molded article including biodegradable polyester resin composition
US12180333B2 (en) 2018-03-28 2024-12-31 Mylar Specialty Films U.S. Limited Partnership Copolyesters derived from aliphatic glycols, aromatic dicarboxylic acids and poly(alkylene-oxides) and films made therefrom
WO2025117466A1 (en) * 2023-11-28 2025-06-05 Dupont Specialty Products Usa Llc Polyester comprising branched diols, methods of making, and adhesives comprising the polyester

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008174620A (ja) * 2007-01-17 2008-07-31 Mitsubishi Chemicals Corp ポリエーテルエステルブロック共重合体組成物
KR20130046394A (ko) * 2010-02-28 2013-05-07 이 아이 듀폰 디 네모아 앤드 캄파니 고 용융 점도 폴리에스테르 또는 코폴리에스테르 조성물
JP5581999B2 (ja) * 2010-11-30 2014-09-03 東レ株式会社 ポリエステルの製造方法
EP2673317A1 (en) * 2011-02-09 2013-12-18 E.I. Du Pont De Nemours And Company Polyester compositions with improved properties
US10434526B2 (en) 2011-09-07 2019-10-08 3M Innovative Properties Company Mist generating apparatus
CN110229478B (zh) * 2013-12-20 2022-01-25 纳幕尔杜邦公司 聚(2,5-呋喃二甲酸1,3-丙二醇酯)(ptf)的成核结晶及其制品
KR20180035522A (ko) * 2016-09-29 2018-04-06 주식회사 엘지화학 폴리에테르에스테르 공중합체의 제조방법
US10512924B2 (en) * 2016-10-03 2019-12-24 FRF Inc. Portable misting system with combined air/water nozzle assembly
KR20180067396A (ko) * 2016-12-09 2018-06-20 주식회사 삼양사 무수당 알코올 유도체를 포함하는 열가소성 폴리에테르 에스테르 엘라스토머 및 이의 제조 방법
CN113429749A (zh) * 2021-06-29 2021-09-24 会通新材料(上海)有限公司 一种高透明低熔指热塑性聚酯弹性体及其制备方法
JP7561328B2 (ja) * 2022-11-02 2024-10-04 東洋紡エムシー株式会社 バイオマス資源由来ポリエステルエラストマー
KR20240171910A (ko) * 2023-05-31 2024-12-09 에스케이케미칼 주식회사 열가소성 폴리에스테르 엘라스토머 수지 및 이의 제조방법
CN119789914A (zh) * 2023-08-07 2025-04-08 英诺纳米喷射技术有限公司 用于产生气尖式干雾纳米射流喷雾的方法及系统
WO2025142232A1 (ja) * 2023-12-25 2025-07-03 東洋紡エムシー株式会社 バイオマス資源由来ポリエステルエラストマーを使用した難燃性樹脂組成物

Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3761450A (en) * 1969-09-11 1973-09-25 Hoechst Ag Salts of polycarboxylic acids as nucleating agents in polyesters
US4322335A (en) * 1979-09-21 1982-03-30 Imperial Chemical Industries Limited Fast crystallizing block copolyester composition
US4380621A (en) * 1979-12-12 1983-04-19 Imperial Chemical Industries Limited Fast crystallizing polyester compositions
US4983660A (en) * 1987-12-25 1991-01-08 Mitsubishi Rayon Company Ltd. Polyethylene terephthalate resin composition
US5015789A (en) * 1989-08-08 1991-05-14 Degussa Aktiengesellschaft Method of preparing 1,3-propanediol
US5264477A (en) * 1992-07-28 1993-11-23 Hoechst Celanese Corp. Liquid crystalline polyesters containing metal terephthalate nucleating agents
US5276201A (en) * 1991-11-27 1994-01-04 Degussa Aktiengesellschaft Process for the production of 3-hydroxyalkanals
US5284979A (en) * 1991-11-27 1994-02-08 Degussa Aktiengesellschaft Process for the prepartion of 3-hydroxyalkanals
US5334778A (en) * 1992-06-03 1994-08-02 Degussa Aktiengesellschaft Process for the production of 1,3-propanediol
US5364984A (en) * 1991-10-01 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol by the hydrogenation of hydroxypropionaldehyde
US5364987A (en) * 1992-07-10 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol
US5633362A (en) * 1995-05-12 1997-05-27 E. I. Du Pont De Nemours And Company Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase
US5686276A (en) * 1995-05-12 1997-11-11 E. I. Du Pont De Nemours And Company Bioconversion of a fermentable carbon source to 1,3-propanediol by a single microorganism
US5962745A (en) * 1997-02-14 1999-10-05 E. I. Du Pont De Nemours And Company Process for preparing 3-hydroxyalkanals
US6140543A (en) * 1997-01-30 2000-10-31 E. I. Du Pont De Nemours And Company Process for the production of 1,3-propanediol
US6232511B1 (en) * 1997-06-18 2001-05-15 E. I. Du Pont De Nemours And Company Process for the production of 1,3-propanediol by hydrogenating 3-hydroxypropionaldehyde
US6235948B1 (en) * 1998-08-18 2001-05-22 E. I. Du Pont De Nemours And Company Process for the purification of 1,3-propanediol
US6245844B1 (en) * 1998-09-18 2001-06-12 E. I. Du Pont De Nemours And Company Nucleating agent for polyesters
US6277289B1 (en) * 1999-07-01 2001-08-21 E. I. Du Pont De Nemours And Company Treatment of aqueous aldehyde waste streams
US6297408B1 (en) * 1998-09-04 2001-10-02 E. I. Du Pont De Nemours And Company Two-stage process for the production of 1,3-propanediol by catalytic hydrogenation of 3-hydroxypropanal
US6331264B1 (en) * 1999-03-31 2001-12-18 E. I. Du Pont De Nemours And Company Low emission polymer compositions
US6342646B1 (en) * 1999-07-30 2002-01-29 E. I. Du Pont De Nemours And Company Catalytic hydrogenation of 3-hydroxypropanal to 1,3-propanediol
US20020117081A1 (en) * 2000-11-16 2002-08-29 Visioli Donna Lynn Method to improve properties of poly (Trimethylene terephthalate) film
US6562457B1 (en) * 2001-10-31 2003-05-13 E. I. Du Pont De Nemours And Company Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment
US6599625B2 (en) * 2001-10-31 2003-07-29 E. I. Du Pont De Nemours And Company Polyether ester elastomer comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment
US20040030095A1 (en) * 2002-08-09 2004-02-12 Sunkara Hari B. Poly(trimethylene-ethylene ether) glycols
US6720459B2 (en) * 1999-12-17 2004-04-13 E. I. Du Pont Nemours And Company Continuous process for the preparation of polytrimethylene ether glycol
US20040225161A1 (en) * 2003-05-06 2004-11-11 Sunkara Hari Babu Hydrogenation of chemically derived 1,3-propanediol
US20040225162A1 (en) * 2003-05-06 2004-11-11 Sunkara Hari Babu Removal of color bodies from polytrimethylene ether glycol polymers
US20040260125A1 (en) * 2003-05-06 2004-12-23 Mayis Seapan Hydrogenation of biochemical derived 1,3 -propanediol
US20050020805A1 (en) * 2003-05-06 2005-01-27 Sunkara Hari Babu Polytrimethylene ether glycol and polytrimethylene ether ester with excellent quality
US20050028299A1 (en) * 2003-08-07 2005-02-10 Lg Electronics Inc. Method for sensing amount of clothes in washing machine
US20050069997A1 (en) * 2003-05-06 2005-03-31 Adkesson Dennis Michael Purification of biologically-produced 1,3-propanediol
US6977291B2 (en) * 1999-12-17 2005-12-20 E.I. Du Pont De Nemours And Company Production of polytrimethylene ether glycol and copolymers thereof
US20050282966A1 (en) * 2004-06-21 2005-12-22 Sunkara Hari B Polytrimethylene ether ester elastomer flexible films

Family Cites Families (199)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US260125A (en) 1882-06-27 Curtain-holder
CA833980A (en) 1970-02-10 Gosling Rolf Method and apparatus for controlling a jet pump
US1004770A (en) * 1911-01-03 1911-10-03 John L Galloway Exhaust-nozzle for locomotives.
FR474904A (fr) 1913-07-12 1915-03-26 Anton Victor Lipinski Perfectionnements apportés à la pulvérisation des liquides et, notamment à celle des liquides peu fluides
US1289812A (en) * 1916-08-29 1918-12-31 William A Kinney Burner.
US1592448A (en) * 1925-09-08 1926-07-13 William E Patzer Spray nozzle
US2083801A (en) 1932-09-06 1937-06-15 Petroleum Rectifying Co California Method and apparatus for dehydrating petroleum
US2396290A (en) * 1945-03-01 1946-03-12 Schwarz Sigmund Sludge pump
US2971325A (en) 1948-05-17 1961-02-14 Aerojet General Co Jet propulsion device for operation submerged in water
US3073534A (en) * 1960-05-27 1963-01-15 Goodyear Aircraft Corp Nozzle for spraying a mixture of fibers and resin
US3259320A (en) 1960-12-19 1966-07-05 United Aircraft Corp Secondary injection thrust vector control system
NL283530A (enExample) 1961-08-19
FR1354965A (fr) 1963-01-29 1964-03-13 S E M I A C Soc De Materiel In Perfectionnements apportés aux atomiseurs de produits liquides, notamment pour l'agriculture
US3259310A (en) 1964-07-06 1966-07-05 Jean D Rochfort Ratio indicator
US3265027A (en) 1965-03-12 1966-08-09 Gen Electric Propulsor
US3326472A (en) * 1965-09-13 1967-06-20 Hydro Comb Corp Steam atomizing burner nozzle
US3304564A (en) * 1965-10-04 1967-02-21 Green Jack Apparatus for cleaning a body of liquid and maintaining its level
US3411301A (en) 1966-07-15 1968-11-19 Douglas R. Olsen Thermal hydrojet
US3469617A (en) 1967-03-20 1969-09-30 Parkson Ind Equipment Co Method for stripping of volatile substanes from fluids
US3402555A (en) 1967-04-19 1968-09-24 Jack N. Piper Steam-jet nozzle for propelling marine vessels
FR1535517A (fr) 1967-05-30 1968-08-09 Ejecteurs supersoniques perfectionnés
US3456871A (en) 1967-07-18 1969-07-22 Schutte & Koerting Co Method and apparatus for controlling a jet pump
US3493191A (en) 1967-09-05 1970-02-03 American Safety Equip Safety belt strap anchoring and retraction mechanism
FR2052002A5 (enExample) 1969-07-08 1971-04-09 Tunzini Sames
US3664768A (en) 1970-03-10 1972-05-23 William T Mays Fluid transformer
US3684188A (en) * 1970-08-20 1972-08-15 Comfort Inc Insulation applicator and method
FR2120393A5 (enExample) 1970-12-31 1972-08-18 Tunzini Sames
BE764407A (fr) 1971-03-17 1971-08-16 Four Industriel Belge Dispositif pour le dosage d'un melange de deux gaz.
US3873024A (en) * 1971-08-13 1975-03-25 Ransburg Corp Apparatus for spraying a plurality of different powders
US4014961A (en) 1973-04-24 1977-03-29 Vitaly Fedorovich Popov Ejector mixer for gases and/or liquids
ZA744265B (en) 1973-07-09 1975-07-30 Envirotech Corp Supersonic small bubble generation and method apparatus
US3823929A (en) 1973-09-13 1974-07-16 Berry Metal Co Nozzle for fuel and oxygen lance assembly
US3889623A (en) 1974-01-31 1975-06-17 Robert W Arnold Jet propulsion unit for boats
JPS5138392A (ja) * 1974-09-30 1976-03-31 Teijin Ltd Shinjuyohyomenkotakujushi no seizoho
US4101246A (en) 1974-11-26 1978-07-18 Kobe, Inc. Vortex jet pump
US3984504A (en) 1975-02-24 1976-10-05 Pick Heaters, Inc. Method and apparatus for preventing water hammer in high pressure steam injection water heaters
US4072470A (en) 1976-03-31 1978-02-07 Kao Soap Co., Ltd. Gas feeder for sulfonation apparatus
FR2376384A1 (en) 1976-12-30 1978-07-28 Cecil Snow cannon for making ski slopes - has adjustable nozzles for water and air to suit different ambient conditions
US4192465A (en) 1977-04-08 1980-03-11 Nathaniel Hughes Vortex generating device with external flow interrupting body
US4175706A (en) * 1977-07-18 1979-11-27 Scientific Energy Systems Corporation Spray nozzle
JPS5473452A (en) 1977-11-22 1979-06-12 Clevepak Corp Waste water aeration method and apparatus
US4221558A (en) 1978-02-21 1980-09-09 Selas Corporation Of America Burner for use with oil or gas
US4212168A (en) 1978-09-15 1980-07-15 Chicago Bridge & Iron Company Power producing dry-type cooling system
US4279663A (en) 1979-01-12 1981-07-21 American Can Company Reactor system and pump apparatus therein
US4201596A (en) 1979-01-12 1980-05-06 American Can Company Continuous process for cellulose saccharification
US4425433A (en) 1979-10-23 1984-01-10 Neves Alan M Alcohol manufacturing process
US4461648A (en) 1980-07-11 1984-07-24 Patrick Foody Method for increasing the accessibility of cellulose in lignocellulosic materials, particularly hardwoods agricultural residues and the like
US4314670A (en) * 1980-08-15 1982-02-09 Walsh William A Jun Variable gas atomization
JPS5945349A (ja) * 1982-09-09 1984-03-14 Teijin Ltd ポリエーテルエステル弾性糸
US4487553A (en) * 1983-01-03 1984-12-11 Fumio Nagata Jet pump
US4718870A (en) 1983-02-15 1988-01-12 Techmet Corporation Marine propulsion system
DE3316233A1 (de) 1983-05-04 1984-11-08 Leopold Dipl.-Ing.(FH) 5910 Kreuztal Schladofsky Vakuum-saugpumpe
JPS60223856A (ja) * 1984-04-20 1985-11-08 Kuraray Co Ltd 共重合ポリエステル樹脂組成物
US4659521A (en) 1985-03-29 1987-04-21 Phillips Petroleum Company Method for condensing a gas in a liquid medium
US4738614A (en) 1986-07-25 1988-04-19 Union Carbide Corporation Atomizer for post-mixed burner
US4781537A (en) 1987-03-11 1988-11-01 Helios Research Corp. Variable flow rate system for hydrokinetic amplifier
FR2613639A1 (fr) 1987-04-10 1988-10-14 Reclus Edouard Dispositif pour pulser et pulveriser, avec des gaz, des produits ou des melanges
GB8716626D0 (en) 1987-07-15 1987-08-19 Permutit Co Ltd Mixing liquids
US4809911A (en) 1987-08-20 1989-03-07 John Ryan High pressure mixing and spray nozzle apparatus and method
US4915300A (en) 1987-08-20 1990-04-10 John Ryan High pressure mixing and spray nozzle apparatus and method
US4836451A (en) 1987-09-10 1989-06-06 United Technologies Corporation Yaw and pitch convergent-divergent thrust vectoring nozzle
GB8724973D0 (en) 1987-10-24 1987-11-25 Bp Oil Ltd Fire fighting
DK158109C (da) 1988-02-04 1990-08-20 Dems Eng Omstillelig ejektor
US4915302A (en) 1988-03-30 1990-04-10 Kraus Robert A Device for making artificial snow
JPH02504600A (ja) 1988-04-25 1990-12-27 インゼネルヌイ、ツェントル、“トランズブク” 乳濁液を製造するための方法および装置
FR2637017B1 (fr) 1988-09-28 1990-11-30 Snecma Structure de tuyere pour propulseur combine turbo-stato-fusee
SU1653853A1 (ru) 1988-12-21 1991-06-07 Харьковский авиационный институт им.Н.Е.Жуковского Способ пневмораспыла жидкости и устройство дл его осуществлени
JP2665386B2 (ja) 1990-03-09 1997-10-22 三井造船株式会社 コアンダノズル
US5138937A (en) 1990-03-15 1992-08-18 General Mills, Inc. Continuously variable orifice exit nozzle for cereal gun puffing apparatus
GB2242370B (en) 1990-03-30 1993-11-03 Donovan Graham Ellam Pneumatic mixer
US5171090A (en) 1990-04-30 1992-12-15 Wiemers Reginald A Device and method for dispensing a substance in a liquid
IL95348A0 (en) 1990-08-12 1991-06-30 Efim Fuks Method of producing an increased hydrodynamic head of a fluid jet
US5338113A (en) 1990-09-06 1994-08-16 Transsonic Uberschall-Anlagen Gmbh Method and device for pressure jumps in two-phase mixtures
CA2050624C (en) * 1990-09-06 1996-06-04 Vladimir Vladimirowitsch Fissenko Method and device for acting upon fluids by means of a shock wave
US5061406A (en) 1990-09-25 1991-10-29 Union Carbide Industrial Gases Technology Corporation In-line gas/liquid dispersion
JP2713814B2 (ja) 1990-11-15 1998-02-16 三井造船株式会社 圧縮性流体用エジェクタ
DE4104686C2 (de) 1991-02-15 1994-06-01 Stephan & Soehne Verfahren und Vorrichtung zur Herstellung von Schmelzkäse
US5249514A (en) 1991-02-15 1993-10-05 A. Stephan Und Soehne Gmbh & Co. Apparatus for producing pumpable foodstuffs, in particular processed cheese
SE468341C (sv) 1991-03-20 1997-08-04 Kvaerner Pulping Tech Apparat för blandning av en suspension av ett cellulosahaltigt fibermaterial och ett fluidum
US5129583A (en) * 1991-03-21 1992-07-14 The Babcock & Wilcox Company Low pressure loss/reduced deposition atomizer
US5252298A (en) 1991-04-23 1993-10-12 Noell, Inc. Device for cleaning gases
AU665189B2 (en) 1991-05-20 1995-12-21 Marioff Corporation Oy Fire fighting equipment
DE69215334T2 (de) 1991-09-13 1997-06-19 Toshiba Kawasaki Kk Dampfinjektor
WO1993016791A2 (en) 1992-02-11 1993-09-02 April Dynamics Industries Ltd. A two-phase supersonic flow system
US5269461A (en) 1992-03-13 1993-12-14 Davis James F Aerosol nozzle system
RU2040322C1 (ru) 1992-05-15 1995-07-25 Белых Виктор Сергеевич Смеситель
JPH06144371A (ja) 1992-06-03 1994-05-24 I D C Kk 船舶用推進装置
WO1994008724A1 (en) 1992-10-13 1994-04-28 Alan Patrick Casey Gas/liquid mixing apparatus
JPH0680144B2 (ja) * 1992-12-02 1994-10-12 鐘淵化学工業株式会社 射出成形用ポリエステル共重合体組成物の製法
US5312041A (en) * 1992-12-22 1994-05-17 Cca, Inc. Dual fluid method and apparatus for extinguishing fires
ZA944999B (en) 1993-07-12 1995-02-21 Ivention Technologies Pty Ltd Fire extinguishing apparatus
DE4333439C1 (de) 1993-09-30 1995-02-02 Siemens Ag Vorrichtung zur Kühlmittelkühlung einer gekühlten Gasturbine einer Gas- und Dampfturbinenanlage
US5785258A (en) 1993-10-08 1998-07-28 Vortexx Group Incorporated Method and apparatus for conditioning fluid flow
DE4338585A1 (de) * 1993-11-11 1995-05-18 Graef Jordt Steffen Injektordüse
FR2717106B1 (fr) 1994-03-11 1996-05-31 Total Raffinage Distribution Procédé et dispositif de pulvérisation d'un liquide, notamment d'un liquide à haute viscosité, à l'aide d'au moins un gaz auxiliaire.
US5492276A (en) 1994-04-19 1996-02-20 Valkyrie Scientific Propritary, L.C. Method and means for merging liquid streams
US5495893A (en) 1994-05-10 1996-03-05 Ada Technologies, Inc. Apparatus and method to control deflagration of gases
US5484107A (en) * 1994-05-13 1996-01-16 The Babcock & Wilcox Company Three-fluid atomizer
US5598700A (en) 1994-06-30 1997-02-04 Dimotech Ltd. Underwater two phase ramjet engine
US5520331A (en) 1994-09-19 1996-05-28 The United States Of America As Represented By The Secretary Of The Navy Liquid atomizing nozzle
FI98892C (fi) 1994-11-15 1997-09-10 Turun Asennusteam Oy Polymeerien liuotusmenetelmä ja -laite
US5921472A (en) 1994-12-13 1999-07-13 Spraying Systems Co. Enhanced efficiency nozzle for use in fluidized catalytic cracking
US5738762A (en) 1995-03-08 1998-04-14 Ohsol; Ernest O. Separating oil and water from emulsions containing toxic light ends
US5779159A (en) * 1995-08-09 1998-07-14 Williams, Deceased; Leslie P. Additive fluid peripheral channeling fire fighting nozzle
US5779158A (en) 1996-04-16 1998-07-14 National Foam, Inc. Nozzle for use with fire-fighting foams
GB2313410B (en) 1996-05-25 2000-03-29 Ian Stephenson Improvements in or relating to pumps
RU2107554C1 (ru) 1996-07-08 1998-03-27 Научно-исследовательский институт низких температур при Московском государственном авиационном институте (техническом университете) Способ создания газокапельной струи, установка для его осуществления и сопло для создания газокапельной струи
JPH10141299A (ja) 1996-11-06 1998-05-26 Calsonic Corp 粉体噴出用エゼクタ
JP4380808B2 (ja) * 1996-11-08 2009-12-09 東レ・デュポン株式会社 ポリエステルエラストマ樹脂組成物
US5851139A (en) 1997-02-04 1998-12-22 Jet Edge Division Of Tc/American Monorail, Inc. Cutting head for a water jet cutting assembly
JP4066468B2 (ja) 1997-02-17 2008-03-26 株式会社Ｉｈｉ 空気オゾン混合器及びオゾンフォグ発生装置
US7140552B1 (en) 1998-04-06 2006-11-28 Williams Fire & Hazard Control, Inc. System for automatic self-proportioning of foam concentrate into fire fighting fluid variable flow conduit
GB9713822D0 (en) 1997-06-30 1997-09-03 Usf Ltd Ejector
US5860598A (en) 1997-08-14 1999-01-19 Cruz; Luis R Fog atomizer
FR2767492B1 (fr) 1997-08-25 1999-10-29 Prolitec Tete et appareil de nebulisation et dispositif de melange de maniere homogene de liquides non miscibles naturellement
GB9721297D0 (en) 1997-10-07 1997-12-10 Lurmark Ltd Spray nozzle
IL122396A0 (en) 1997-12-02 1998-06-15 Pekerman Oleg Method of heating and/or homogenizing of liquid products in a steam-liquid injector
US5863128A (en) 1997-12-04 1999-01-26 Mazzei; Angelo L. Mixer-injectors with twisting and straightening vanes
US6003789A (en) 1997-12-15 1999-12-21 Aec Oil Sands, L.P. Nozzle for atomizing liquid in two phase flow
RU2142580C1 (ru) 1998-02-13 1999-12-10 Фисенко Владимир Владимирович Способ струйной деаэрации и струйная установка для его реализации
RU2132752C1 (ru) 1998-04-13 1999-07-10 Научно-исследовательский институт низких температур при МАИ (Московском государственном авиационном институте - техническом университете) Устройство для создания газокапельной струи и клапан для подачи двухфазной рабочей среды
US6110356A (en) 1998-05-06 2000-08-29 Uop Llc Slurry circulation process and system for fluidized particle contacting
WO2000002653A1 (de) 1998-07-08 2000-01-20 Novafluid - Innovative Strömungs- & Wärmeübertragungs-Technologie Gmbh Verfahren und vorrichtung zur erhöhung des druckes beziehungsweise steigerung der enthalpie eines mit überschall strömenden fluids
AT407120B (de) 1998-08-14 2000-12-27 Novafluid Innovative Stroemung Anlage zum auftrennen eines strömenden dampf-flüssigkeit-gemisches
RU2152465C1 (ru) 1998-09-22 2000-07-10 Казаков Владимир Михайлович Кавитационная установка
ID29093A (id) 1998-10-16 2001-07-26 Lanisco Holdings Ltd Konversi mendalam yang menggabungkan demetalisasi dan konversi minyak mentah, residu atau minyak berat menjadi cairan ringan dengan senyawa-senyawa oksigenat murni atau tak murni
US6503461B1 (en) 1998-12-22 2003-01-07 Uop Llc Feed injector with internal connections
WO2000037143A1 (en) 1998-12-23 2000-06-29 Lockwood Hanford N Low pressure dual fluid atomizer
US6659635B2 (en) * 1999-01-26 2003-12-09 Kvaerner Pulping Ab Method for introducing a first fluid into a second fluid, preferably introduction of steam into flowing cellulose pulp
CN2356760Y (zh) 1999-03-18 2000-01-05 张树深 污垢清除机
US6200486B1 (en) 1999-04-02 2001-03-13 Dynaflow, Inc. Fluid jet cavitation method and system for efficient decontamination of liquids
US6883332B2 (en) * 1999-05-07 2005-04-26 Parker-Hannifin Corporation Fuel nozzle for turbine combustion engines having aerodynamic turning vanes
US6216961B1 (en) 1999-05-12 2001-04-17 Misty Mate Inc Fan propelled mister
WO2000071235A1 (en) 1999-05-20 2000-11-30 Stem Drive Limited Fluid mixing system
WO2001036105A1 (en) 1999-11-15 2001-05-25 Aura Tec Co., Ltd. Micro-bubble generating nozzle and application device therefor
FR2801648B1 (fr) 1999-11-30 2002-06-21 Commissariat Energie Atomique Injecteur a vapeur haute pression comportant un drain axial
US6456871B1 (en) 1999-12-01 2002-09-24 Cardiac Pacemakers, Inc. System and method of classifying tachyarrhythmia episodes as associated or disassociated
WO2001048062A1 (en) 1999-12-27 2001-07-05 E.I. Du Pont De Nemours And Company Oriented polymeric film comprising at least one copolyetherester
AU2001248366A1 (en) 2000-04-05 2001-10-23 Manfred Rummel Foam, spray or atomizer nozzle
SK283606B6 (sk) 2000-04-11 2003-10-07 Július Chrobák Spôsob zvýšenia dostreku kontinuálneho aerosólového lúča
US6623154B1 (en) * 2000-04-12 2003-09-23 Premier Wastewater International, Inc. Differential injector
US6796704B1 (en) 2000-06-06 2004-09-28 W. Gerald Lott Apparatus and method for mixing components with a venturi arrangement
EP1286885B1 (en) 2000-06-07 2007-08-08 Pursuit Dynamics PLC. Propulsion system
AUPQ802400A0 (en) 2000-06-07 2000-06-29 Burns, Alan Robert Propulsion system
JP2001354319A (ja) 2000-06-13 2001-12-25 Ogawa Jidosha:Kk エジェクタ
EP1163931A3 (en) 2000-06-14 2002-06-12 Williams Fire and Hazard Control, Inc. System for automatic self-proportioning of foam concentrate into fire fighting fluid variable flow conduit
US6308740B1 (en) 2000-08-15 2001-10-30 Lockheed Martin Corporation Method and system of pulsed or unsteady ejector
US6502979B1 (en) 2000-11-20 2003-01-07 Five Star Technologies, Inc. Device and method for creating hydrodynamic cavitation in fluids
TW583215B (en) * 2001-03-23 2004-04-11 Toyo Boseki Transparent flexible polyester
JP2004533317A (ja) * 2001-05-09 2004-11-04 ノーベル テクニカル ソリューションズ リミテッド 液状材料を微粒化する方法および装置
US20050001065A1 (en) 2001-08-01 2005-01-06 Kidde-Fenwal, Inc. Nozzle apparatus and method for atomizing fluids
JP3803270B2 (ja) 2001-08-10 2006-08-02 Ｓｍｃ株式会社 ミキシングバルブ
JP3801967B2 (ja) 2001-08-28 2006-07-26 株式会社いけうち ノズルおよび該ノズルによる導管内周面への流体噴射方法
WO2003030995A2 (en) 2001-10-11 2003-04-17 Life Mist, Llc Apparatus comprising a pneumoacoustic atomizer
US7029165B2 (en) * 2001-10-26 2006-04-18 Allen Thomas E Automatically adjusting annular jet mixer
US6802638B2 (en) * 2001-10-26 2004-10-12 Thomas E. Allen Automatically adjusting annular jet mixer
FI20020001A7 (fi) 2002-01-02 2003-07-03 Marioff Corp Oy Palonsammutusmenetelmä ja -laitteisto
GB2384027B (en) 2002-01-11 2006-04-12 Transvac Systems Ltd Ejector
US6969012B2 (en) * 2002-01-24 2005-11-29 Kangas Martti Y O Low pressure atomizer for difficult to disperse solutions
AU2003207347A1 (en) 2002-02-26 2003-09-09 Pursuit Dynamics Plc Jet pump
CN1298434C (zh) 2002-05-07 2007-02-07 喷洒系统公司 内混合式空气雾化喷射喷嘴组件
WO2004033920A1 (en) 2002-10-11 2004-04-22 Pursuit Dynamics Plc Jet pump
DE10249027A1 (de) 2002-10-21 2004-04-29 Gea Wiegand Gmbh Anlage zur Herstellung von Alkohol
JP2004184000A (ja) 2002-12-04 2004-07-02 Ichio Ota 温泉暖房器
GB0229604D0 (en) 2002-12-19 2003-01-22 Pursuit Dynamics Plc Improvements in or relating to pumping systems
EP1578536B1 (en) * 2002-12-30 2017-02-08 Novartis AG Prefilming atomizer
GB0306333D0 (en) 2003-03-20 2003-04-23 Advanced Gel Technology Ltd Restricting fluid passage and novel materials therefor
US6981997B2 (en) 2003-07-18 2006-01-03 Praxair Technology, Inc. Deaeration of water and other liquids
DE10335554A1 (de) 2003-08-02 2005-03-03 Stephan Machinery Gmbh & Co. Dampfinjektionsmodul zur Erwärmung pumpfähiger Produkte
DE10340380A1 (de) * 2003-08-25 2005-05-25 Ivo Edward Ruzek Durch Polypropylenglykol modifizierte Polyesterfasern
WO2005082546A1 (en) 2004-02-26 2005-09-09 Pursuit Dynamics Plc Method and apparatus for generating a mist
UA82780C2 (uk) 2004-05-31 2008-05-12 Телесто Сп. З О.О. Головка для створення водяного туману
CA2573712C (en) 2004-07-29 2013-04-09 Pursuit Dynamics Plc Jet pump
US20100129888A1 (en) 2004-07-29 2010-05-27 Jens Havn Thorup Liquefaction of starch-based biomass
US8419378B2 (en) * 2004-07-29 2013-04-16 Pursuit Dynamics Plc Jet pump
US20090072041A1 (en) 2004-08-17 2009-03-19 Tomohiko Hashiba Method of treating oil/water mixture
US20070298477A1 (en) 2004-08-31 2007-12-27 Biotech Progress, A.S. Method And Devices For The Continuous Processing Of Renewable Raw Materials
US7207712B2 (en) 2004-09-07 2007-04-24 Five Star Technologies, Inc. Device and method for creating hydrodynamic cavitation in fluids
US8017820B2 (en) 2004-09-30 2011-09-13 Iogen Energy Corporation Continuous flowing pre-treatment system with steam recovery
EP1843835A4 (en) 2005-01-03 2010-12-22 Western Oil Sands Inc NOZZLE REACTOR AND METHOD OF USE
PL204019B1 (pl) 2005-06-05 2009-12-31 Telesto Spo & Lstrok Ka Z Ogra Urządzenie do gaszenia pożarów i głowica gasząca
US20070000700A1 (en) 2005-06-30 2007-01-04 Switzer Bruce D Twist bit for drilling mortar and for optimizing dissipation of heat and dust created by the drilling
US20070095946A1 (en) 2005-09-26 2007-05-03 John Ryan Advanced Velocity Nozzle Fluid Technology
SE528449C2 (sv) 2005-09-28 2006-11-14 Kvaerner Pulping Tech Apparat för inblandning av ånga till ett flöde av cellulosamassa
GB0618196D0 (en) * 2006-09-15 2006-10-25 Pursuit Dynamics Plc An improved mist generating apparatus and method
GB0623469D0 (en) 2006-11-24 2007-01-03 Pursuit Dynamics Plc Method and apparatus for the removal of volatile elements from process fluids
CA2685537A1 (en) 2007-05-02 2008-11-13 Pursuit Dynamics Plc Liquefaction of starch-based biomass
CA2686454C (en) 2007-05-10 2016-08-02 Arisdyne Systems, Inc. Apparatus and method for increasing alcohol yield from grain
GB0710663D0 (en) * 2007-06-04 2007-07-11 Pursuit Dynamics Plc An improved mist generating apparatus and method
GB0803959D0 (en) 2008-03-03 2008-04-09 Pursuit Dynamics Plc An improved mist generating apparatus
EP2207601B1 (en) 2007-11-09 2017-02-15 Tyco Fire & Security GmbH An improved mist generating apparatus
US9050481B2 (en) 2007-11-09 2015-06-09 Tyco Fire & Security Gmbh Decontamination
EP2060544A1 (en) 2007-11-16 2009-05-20 APV Systems Ltd. Method and apparatus for preparing material for microbiologic fermentation
GB0810155D0 (en) 2008-06-04 2008-07-09 Pursuit Dynamics Plc An improved mist generating apparatus and method
US8246015B2 (en) 2008-07-03 2012-08-21 Hydro-Thermal Corporation Steam injection heater with stationary end seal assembly
US8484338B2 (en) 2008-10-02 2013-07-09 Actiance, Inc. Application detection architecture and techniques
GB0818362D0 (en) 2008-10-08 2008-11-12 Pursuit Dynamics Plc An improved process and system for breaking an emulsion
CA2741994A1 (en) 2008-10-30 2010-05-06 Pursuit Dynamics Plc A biomass treatment process and system
DE112012006288B4 (de) 2012-04-25 2020-09-03 Toyota Jidosha Kabushiki Kaisha Abdriftbeurteilungsvorrichtung

Patent Citations (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3761450A (en) * 1969-09-11 1973-09-25 Hoechst Ag Salts of polycarboxylic acids as nucleating agents in polyesters
US4322335A (en) * 1979-09-21 1982-03-30 Imperial Chemical Industries Limited Fast crystallizing block copolyester composition
US4322335B1 (enExample) * 1979-09-21 1988-04-05
US4380621A (en) * 1979-12-12 1983-04-19 Imperial Chemical Industries Limited Fast crystallizing polyester compositions
US4983660A (en) * 1987-12-25 1991-01-08 Mitsubishi Rayon Company Ltd. Polyethylene terephthalate resin composition
US5015789A (en) * 1989-08-08 1991-05-14 Degussa Aktiengesellschaft Method of preparing 1,3-propanediol
US5364984A (en) * 1991-10-01 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol by the hydrogenation of hydroxypropionaldehyde
US5284979A (en) * 1991-11-27 1994-02-08 Degussa Aktiengesellschaft Process for the prepartion of 3-hydroxyalkanals
US5276201A (en) * 1991-11-27 1994-01-04 Degussa Aktiengesellschaft Process for the production of 3-hydroxyalkanals
US5334778A (en) * 1992-06-03 1994-08-02 Degussa Aktiengesellschaft Process for the production of 1,3-propanediol
US5364987A (en) * 1992-07-10 1994-11-15 Degussa Aktiengesellschaft Process for the preparation of 1,3-propanediol
US5264477A (en) * 1992-07-28 1993-11-23 Hoechst Celanese Corp. Liquid crystalline polyesters containing metal terephthalate nucleating agents
US5633362A (en) * 1995-05-12 1997-05-27 E. I. Du Pont De Nemours And Company Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase
US5686276A (en) * 1995-05-12 1997-11-11 E. I. Du Pont De Nemours And Company Bioconversion of a fermentable carbon source to 1,3-propanediol by a single microorganism
US5821092A (en) * 1995-05-12 1998-10-13 E. I. Du Pont De Nemours And Company Production of 1,3-propanediol from glycerol by recombinant bacteria expressing recombinant diol dehydratase
US6140543A (en) * 1997-01-30 2000-10-31 E. I. Du Pont De Nemours And Company Process for the production of 1,3-propanediol
US5962745A (en) * 1997-02-14 1999-10-05 E. I. Du Pont De Nemours And Company Process for preparing 3-hydroxyalkanals
US6232511B1 (en) * 1997-06-18 2001-05-15 E. I. Du Pont De Nemours And Company Process for the production of 1,3-propanediol by hydrogenating 3-hydroxypropionaldehyde
US6235948B1 (en) * 1998-08-18 2001-05-22 E. I. Du Pont De Nemours And Company Process for the purification of 1,3-propanediol
US6297408B1 (en) * 1998-09-04 2001-10-02 E. I. Du Pont De Nemours And Company Two-stage process for the production of 1,3-propanediol by catalytic hydrogenation of 3-hydroxypropanal
US6245844B1 (en) * 1998-09-18 2001-06-12 E. I. Du Pont De Nemours And Company Nucleating agent for polyesters
US6331264B1 (en) * 1999-03-31 2001-12-18 E. I. Du Pont De Nemours And Company Low emission polymer compositions
US6277289B1 (en) * 1999-07-01 2001-08-21 E. I. Du Pont De Nemours And Company Treatment of aqueous aldehyde waste streams
US6342646B1 (en) * 1999-07-30 2002-01-29 E. I. Du Pont De Nemours And Company Catalytic hydrogenation of 3-hydroxypropanal to 1,3-propanediol
US6977291B2 (en) * 1999-12-17 2005-12-20 E.I. Du Pont De Nemours And Company Production of polytrimethylene ether glycol and copolymers thereof
US6720459B2 (en) * 1999-12-17 2004-04-13 E. I. Du Pont Nemours And Company Continuous process for the preparation of polytrimethylene ether glycol
US20020117081A1 (en) * 2000-11-16 2002-08-29 Visioli Donna Lynn Method to improve properties of poly (Trimethylene terephthalate) film
US6562457B1 (en) * 2001-10-31 2003-05-13 E. I. Du Pont De Nemours And Company Polyether ester elastomer comprising polytrimethylene ether ester soft segment and tetramethylene ester hard segment
US6599625B2 (en) * 2001-10-31 2003-07-29 E. I. Du Pont De Nemours And Company Polyether ester elastomer comprising polytrimethylene ether ester soft segment and trimethylene ester hard segment
US20040030095A1 (en) * 2002-08-09 2004-02-12 Sunkara Hari B. Poly(trimethylene-ethylene ether) glycols
US20040225162A1 (en) * 2003-05-06 2004-11-11 Sunkara Hari Babu Removal of color bodies from polytrimethylene ether glycol polymers
US20040260125A1 (en) * 2003-05-06 2004-12-23 Mayis Seapan Hydrogenation of biochemical derived 1,3 -propanediol
US20050020805A1 (en) * 2003-05-06 2005-01-27 Sunkara Hari Babu Polytrimethylene ether glycol and polytrimethylene ether ester with excellent quality
US20050069997A1 (en) * 2003-05-06 2005-03-31 Adkesson Dennis Michael Purification of biologically-produced 1,3-propanediol
US20040225161A1 (en) * 2003-05-06 2004-11-11 Sunkara Hari Babu Hydrogenation of chemically derived 1,3-propanediol
US7038092B2 (en) * 2003-05-06 2006-05-02 E. I. Du Pont De Nemours And Company Purification of chemical 1,3-propanediol
US20050028299A1 (en) * 2003-08-07 2005-02-10 Lg Electronics Inc. Method for sensing amount of clothes in washing machine
US20050282966A1 (en) * 2004-06-21 2005-12-22 Sunkara Hari B Polytrimethylene ether ester elastomer flexible films

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010076981A3 (ko) * 2008-12-31 2010-09-10 에스케이케미칼주식회사 아이소소르바이드가 공중합된 폴리에스테르 수지의 제조방법
EP2857430A4 (en) * 2012-06-01 2016-04-27 Sk Chemicals Co Ltd POLYMILIC ACID RESIN AND PACKAGING FILM THEREWITH
EP2886592A1 (en) * 2013-12-20 2015-06-24 Invista Technologies S.A R.L. Improved polyester-ether resin blends
US20160222549A1 (en) * 2015-02-02 2016-08-04 Shinkong Synthetic Fibers Corporation Bicomponent conjugate fibers, complex yarns and fabrics having high crimping property
US12180333B2 (en) 2018-03-28 2024-12-31 Mylar Specialty Films U.S. Limited Partnership Copolyesters derived from aliphatic glycols, aromatic dicarboxylic acids and poly(alkylene-oxides) and films made therefrom
US11732126B2 (en) 2018-09-28 2023-08-22 Lotte Chemical Corporation Thermoplastic resin composition and molded product produced therefrom
US20220169806A1 (en) * 2019-02-25 2022-06-02 Foshan King Wonder Hi-Tech Co., Ltd. Bio-based elastomer composition and film and laminate prepared therefrom
US11884785B2 (en) * 2019-02-25 2024-01-30 Foshan King Wonder Hi-Tech Co., Ltd. Bio-based elastomer composition and film and laminate prepared therefrom
EP4289900A1 (en) * 2022-06-08 2023-12-13 Ecovance Co. Ltd Biodegradable polyester resin composition, biodegradable polyester film including the same and biodegradable molded article including biodegradable polyester resin composition
WO2025117466A1 (en) * 2023-11-28 2025-06-05 Dupont Specialty Products Usa Llc Polyester comprising branched diols, methods of making, and adhesives comprising the polyester

Also Published As

Publication number Publication date
CA2662834A1 (en) 2008-05-08
CN101535371B (zh) 2012-08-29
US10507480B2 (en) 2019-12-17
WO2008054777A2 (en) 2008-05-08
BRPI0716362A2 (pt) 2013-09-17
KR20090082362A (ko) 2009-07-30
US20110021697A1 (en) 2011-01-27
JP2010508394A (ja) 2010-03-18
US20150202639A1 (en) 2015-07-23
WO2008054777A3 (en) 2008-06-19
CN101535371A (zh) 2009-09-16
DE112007002474T5 (de) 2009-09-17

Similar Documents

Publication Publication Date Title
US20110021697A1 (en) Methods for preparing polyether ester elastomer composition
US9273206B2 (en) Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD
US7531593B2 (en) Thermoplastic elastomer blend composition
US20130079440A1 (en) Copolyester blends with enhanced tear strength
CN102652148B (zh) 共聚醚酯弹性体
US20080255300A1 (en) Polytrimethylene ether ester elastomer flexible films
US8273850B2 (en) Polyester compositions from biologically-derived materials
US20100151165A1 (en) Polyester compositions from biologically-derived materials
JP7159213B2 (ja) ポリエステルコポリマー
US20110213055A1 (en) Copolyesters with enhanced tear strength
CN101415776A (zh) 聚乳酸组合物
JP3727144B2 (ja) 結晶化抑制型ポリエステル
KR20210052697A (ko) 무수당 알코올 유도체와 폴리에스테르 폴리올을 포함하는 열가소성 폴리에스테르 에스테르 엘라스토머 및 이의 제조 방법
JP2012184347A (ja) 共重合ポリエステルアミド、ポリエステルアミド繊維
US20110229674A1 (en) Polymerization of aliphatic-aromatic copolyetheresters
WO2011062600A1 (en) Polycondensation with a kneader reactor
JPH0245646B2 (enExample)
JPH04285631A (ja) 熱可塑性ポリエステルエラストマー
JP2005187732A (ja) ポリエステルエラストマ樹脂組成物
KR20120105462A (ko) 폴리에스테르의 물리적 특성을 개선시키기 위한 방법
JPS6335172B2 (enExample)

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SUNKARA, HARI BABU;REEL/FRAME:018929/0730

Effective date: 20070117

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION