WO2022266300A1 - Procédé de fabrication d'articles moulés - Google Patents

Procédé de fabrication d'articles moulés Download PDF

Info

Publication number
WO2022266300A1
WO2022266300A1 PCT/US2022/033754 US2022033754W WO2022266300A1 WO 2022266300 A1 WO2022266300 A1 WO 2022266300A1 US 2022033754 W US2022033754 W US 2022033754W WO 2022266300 A1 WO2022266300 A1 WO 2022266300A1
Authority
WO
WIPO (PCT)
Prior art keywords
mole
weight
polyester
acid
mpa
Prior art date
Application number
PCT/US2022/033754
Other languages
English (en)
Inventor
Robert Erik Young
Marc Alan Strand
Original Assignee
Eastman Chemical Company
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 Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO2022266300A1 publication Critical patent/WO2022266300A1/fr

Links

Classifications

    • 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
    • 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

Definitions

  • Thermoplastic polyester elastomers are typically considered inherently flexible materials with lower tensile strength and modulus values. In certain applications, it is useful to have materials with physical properties in between ⁇ rigid polyesters and elastomeric polyesters. It is also useful in certain applications and processing techniques such as powder coating to have improved color, processing and thermal stability properties. We have discovered that a range of rigid polyester and polyester elastomer compositions which incorporate thermal stabilizers create useful materials that have ⁇ improved initial color, improved thermal stability and physical properties.
  • a polyester composition comprising: a) at least one rigid polyester; b) at least one polyester ⁇ elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising extruding a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive in an extrusion zone to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising a) polymerizing at least one dicarboxylic acid and at least one diol in the presence of 1) at least one primary antioxidant; and 2) at least one secondary antioxidant to produce a rigid polyester having a Tg greater than 60°C; b) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 0°C, and c) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • polymers are synonymous with the term “comprising,” and is intended to mean that at least the named compound, element, particle, or method step, etc., is present in the composition or article or method, but does not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc., even if the other such compounds, material, particles, method steps, etc., have the same function as what is named, unless expressly excluded in the claims.
  • polyyester as used herein, is synonymous with the term “resin” and is intended to mean a polymer prepared by the polycondensation of one or more specific diacid components, diol components, and optionally polyol components.
  • the polyester composition exhibits a blister size of 6 or greater as determined by ASTM D714 after 500 hours of Salt Fog testing per ASTM B117. In another embodiment, the polyester composition exhibits a scribe rust value of 6 or greater as determined by ASTM D1654. In another embodiment of the invention, the polyester composition has an impact resistance of 160 ft-lbs or greater as measured by ASTM D2794 when applied to metal panels. Other ranges for impact resistance is 170 ft-lbs or greater, 180 ft-lbs or greater, 190 ft-lbs or greater, or 200 ft-lbs or greater as measured by ASTM D2794.
  • Rigid Polyesters can be any known in the art having a Glass Transition Temperature (Tg) of greater than 60°C.
  • Tg Glass Transition Temperature
  • Other rigid polyesters useful in this invention have a Tg of greater than 65°C, greater than 70°C, greater than 75°C, greater than 80°C, greater than 85°C, greater than 90°C, greater than 100°C, greater than 105°C, greater than 110°C, greater than 115°C, greater than 120°C, or greater than 125°C.
  • the Tg of the rigid polyesters or copolyesters useful in the invention can be, but is not limited to, at least one of the following ranges: 50 to 150°C; 50 to 145°C, 50 to 140°C, 50 to 135°C, 50 to 130°C, 50 to 125°C, 50 to 120°C, 55 to 150°C; 55 to 145°C, 55 to 140°C, 55 to 135°C, 55 to 130°C, 55 to 125°C, 55 to 120°C, 60 to 150°C; 60 to 145°C, 60 to 140°C, 60 to 135°C, 60 to 130°C, 60 to 125°C, 60 to 120°C, 65 to 150°C; 60 to 145°C, 60 to 140°C, 60 to 135°C, 60 to 130°C, 60 to 125°C, 60 to 120°C, 65 to 150°C; 60 to 145°C, 60 to 140°C, 60 to 135°C, 60 to 130°C, 60 to 125°C
  • copolyester is intended to include “polyesters” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and/or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and/or multifunctional hydroxyl compounds.
  • the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols.
  • diacid or “dicarboxylic acid” include multifunctional acids, such as branching agents.
  • the term “repeating unit,” as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through an ester group.
  • the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester.
  • polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, for example, as described in U.S. Patent No. 2,012,267, incorporated herein by reference in its entirety. More particularly, the reactions for preparing the copolyesters are usually carried out at temperatures of about 150° C to about 300° C in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, germanium or combinations thereof.
  • polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, germanium or combinations thereof.
  • the rigid polyester comprises dicarboxylic acid residues and diol residues; wherein the dicarboxylic residues are at least one selected from terepthalic acid and isothalic acid; and wherein the diol residues are at least one selected from ethylene glycol and diethylene glycol.
  • the rigid polyester comprises cyclohexanedimethanol residues, e.g. 1,4-cyclohexanedimethanol.
  • the rigid polyester useful in the invention can contain ethylene glycol residues.
  • Condensation polymers are also susceptible to hydrolytic degradation if not pre-dried or if they are held at elevated temperatures in moist air for a long period of time.
  • Condensation polymers are any polymers where monomers reacting during polycondensation to create a polymer and a by-product such as water or methanol is produced. The polymerization reaction is reversible; thus, condensation polymers are often pre-dried before processing.
  • the rigid polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the rigid polyester polymer as their corresponding residues.
  • the rigid polyester or copolyesters comprise compositions with a single diacid or combinations of diacids such as terephthalic acid or phthalic acid or other diacids with 8 to 20 carbon atoms, with combinations of modifying glycols such as cyclohexanedimethanol or ethylene glycol or other glycols with 2 to 20 carbon atoms.
  • the rigid polyester comprises at least one diol residue.
  • the rigid polyester comprises at least one dicarboxylic acid or an ester thereof and at least one diol, wherein the total of acid residues present is 100 mole% and wherein the total of diol residues is 100 mole%.
  • the rigid polyester comprises 1,4- cyclohexanedimethanol residues.
  • terephthalic acid, or an ester thereof such as, for example, dimethyl terephthalate, or a mixture of terephthalic acid and an ester thereof, makes up most or all of the dicarboxylic acid component used to form the rigid polyesters useful in the invention.
  • terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the rigid polyester at a concentration of at least 70 mole%, such as at least 80 mole%, at least 90 mole%, at least 95 mole%, at least 99 mole%, or 100 mole%.
  • the carboxylic acid component of the rigid polyesters useful in the invention can be further modified with up to 10 mole%, such as up to 5 mole% or up to 1 mole% of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids or their corresponding esters including, but not limited, to dimethyl adipate, dimethyl glutarate and dimethyl succinate.
  • aliphatic dicarboxylic acids containing 2-16 carbon atoms such as, for example, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids or their corresponding esters including, but not limited, to dimethyl adipate, dimethyl glutarate and dimethyl succinate.
  • the amount of one or more modifying glycols can range from any of these preceding endpoint values including, for example, from 0.01 to 15 mole% and from 0.1 to 10 mole%.
  • Modifying glycols useful in the rigid polyesters useful in the invention can contain 2 to 16 carbon atoms.
  • a modifying glycol can be residues of ethylene glycol.
  • ethylene glycol is excluded as a modifying diol.
  • the modifying glycol can be a glycol other than ethylene glycol and 1,4- cyclohexanedimethanol, for example.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the rigid polyester.
  • the rigid polyester(s) useful in the invention can thus be linear or branched.
  • branching monomers include, but are not limited to, multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, citric acid, tartaric acid, 3- hydroxyglutaric acid, pentaerythritol, sorbitol, 1,2,6-hexanetriol, glycerine tetra- maleaic anhydride, and trimesic acid, and the like or mixtures thereof.
  • multifunctional acids or multifunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane,
  • At least one of trimellitic acid, trimellitic anhydride, trimesic acid, pentaerythritol, glycerine, tetra-maleaic anhydride, and trimer acid can be used as the branching agent.
  • the branching monomer may be added to the rigid polyester reaction mixture or blended with the rigid polyester in the form of a concentrate as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176.
  • the rigid polyesters useful in the invention can comprise residues of 1,4-cyclohexanedimethanol in any amount, included but not limited to at least one of the following amounts: from 0.01 to 100 mole%; from 0.01 to 100 mole%; from 0.01 to 99.99 mole%; from 0.10 to 99 mole%; from 0.10 to 99 mole%; from 0.10 to 95 mole%; from 0.10 to 90 mole%; from 0.10 to 85 mole%; from 0.10 to 80 mole%; from 0.10 to 70 mole%; from 0.10 to 60 mole%; from 0.10 to 50 mole%; from 0.10 to 40 mole%; from 0.10 to 35 mole%; from 0.10 to 30 mole%; from 0.10 to 25 mole%; from 0.10 to 20 mole%; from 0.10 to 15 mole%; from 0.10 to 10 mole%; from 0.10 to 5 mole%; from 1 to 100 mole%; from 1 to 99 mole%; 1 to 95 mole%; from 1 to 90 mole%;
  • the rigid polyesters useful in the invention can be any of the traditional compositions described as polyethylene terephthalate (PET), acid-modified polyethylene terephthalate (PETA), glycol modified PET (PETG), glycol modified poly(cyclohexylene dimethylene terephthalate) (PCTG), poly(cyclohexylene dimethylene terephthalate) (PCT), acid modified poly(cyclohexylene dimethylene terephthalate) (PCTA), and any of the foregoing polymers modified with 2,2,4,4-tetramethylcyclobutane-1,3-diol.
  • the rigid polyester useful in the polyester compositions of the invention comprises residues of isosorbide.
  • the isosorbide polymer can also comprise residues of ethylene glycol and/or cyclohexanedimethanol.
  • the rigid polyester comprises residues of isosorbide and 1,4-cyclohexanedimethanol and optionally, ethylene glycol.
  • the rigid polyester comprises residues of isosorbide and ethylene glycol and optionally, 1,4-cycloehexanedimethanol.
  • terephthalic acid can be present in an amount of from 70 to 100 mole%.
  • Modifying dicarboxylic acids may be present in an amount of up to 30 mole%.
  • the modifying dicarboxylic acid can be isophthalic acid.
  • Aliphatic diacids can also be present in the terephthalic acid based polyesters of the invention.
  • the polyester compositions of the invention can include rigid copolyesters comprising residues of 70 to 100 mole% terephthalic acid, and optionally, 0.01 to 30 mole%, or 0.01 to 20 mole%, or 0.01 to 10 mole%, or 0.01 to 5 mole% of isophthalic acid, or esters there and/or mixtures thereof.
  • the polyester compositions of the invention can include rigid copolyesters comprising 1,4-cyclohexanedimethanol and, optionally, ethylene glycol.
  • the polymer compositions of the invention can include rigid copolyesters comprising from 50 mole% to 100 mole%, or from 60 mole% to 100 mole%, or from 65 mole% to 100 mole%, or from 70 mole% to 100 mole%, or from 75 mole% to 100 mole%, or from 80 mole% to 100 mole%, or from 90 mole% from to 100 mole%, or 95 mole% to 100 mole%, of residues of 1,4-cyclohexanedimethanol and, optionally, from 0 mole% to 50 mole%, or from 0 mole% to 40 mole%, or from 0 mole% to 35 mole%, or from 0 mole% to 30 mole%, or from 0 mole% to 25 mole%, or from 0 mole% to 20 mole%, or from 0 mole% to 10 mole%, or from 0 mole% to 5 mole%, of residues of ethylene glycol.
  • rigid copolyesters
  • the polyester compositions of the invention can include rigid copolyesters comprising residues of 99 to 100 mole% terephthalic acid and residues of 99 to 100 mole% 1,4-cyclohexanedimethanol.
  • the rigid polyester comprises residues of diethylene glycol.
  • the rigid polyester comprises residues of terephthalic acid, isophthalic acid and 1,4-cyclohexanedimethanol.
  • the rigid polyester comprises from 50 mole% to 99.99 mole% of residues of 1,4- cyclohexanedimethanol, 0.01 mole% to 50 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid.
  • the rigid polyester comprises from 80 mole% to 99.99 mole% of residues of 1,4-cyclohexanedimethanol and 0.01 mole% to 20 mole% of residues of ethylene glycol. In embodiments, the rigid polyester comprises from 90 mole% to 99.99 mole% of residues of 1,4-cyclohexanedimethanol and 0.01 mole% to 10 mole% of residues of ethylene glycol. In embodiments, the rigid polyester comprises from 95 mole% to 99.99 mole% of residues of 1,4- cyclohexanedimethanol and 0.01 mole% to 5 mole% of residues of ethylene glycol.
  • the rigid polyester comprises from 95 mole% to 99.99 mole% of residues of 1,4-cyclohexanedimethanol, 0.01 mole% to 10 mole% of residues of ethylene glycol, from 90 mole% to 100 mole% of residues of terephthalic acid, and 0.01 to 10 mole% of residues of isophthalic acid.
  • the rigid polyester comprises from 95 mole% to 100 mole% of residues of 1,4-cyclohexanedimethanol, 0.01 mole% to 5 mole% of residues of ethylene glycol, from 95 mole% to 100 mole% of residues of terephthalic acid, and 0.01 to 5 mole% of residues of isophthalic acid.
  • the rigid polyester consists essentially of residues of terephthalic acid or an ester thereof and 1,4-cyclohexanedimethanol. In embodiments, the rigid polyester comprising consist essentially of residues of terephthalic acid or an ester thereof, 1,4-cyclohexanedimethanol and ethylene glycol.
  • the rigid polyester comprises 0 mole% to 30 mole% or 0 mole% to 20 mole% or 0 mole% to 10 mole% or 0 mole% to 5 mole% or 0.01 mole% to 30 mole% or 0.01 mole% to 20 mole% or 0.01 mole% to 10 mole% or 0.01 mole% to 5 mole% isophthalic acid residues, based on a total of 100 mole% acid residues and a total of 100 mole% of diol residues.
  • the rigid polyester comprises from 20 mole% to less than 50 mole% of residues of 1,4- cyclohexanedimethanol, greater than 50 mole% to 80 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid. In embodiments, the rigid polyester comprises from 20 mole% to 40 mole% of residues of 1,4-cyclohexanedimethanol, 60 mole% to 80 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid.
  • the rigid polyester comprises from 25 mole% to 40 mole% of residues of 1,4-cyclohexanedimethanol, 60 mole% to 75 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid. In embodiments, the rigid polyester comprises from 25 mole% to 35 mole% of residues of 1,4-cyclohexanedimethanol, 65 mole% to 75 mole% of residues of ethylene glycol, and from 70 mole% to 100 mole% of residues of terephthalic acid.
  • the rigid polyester comprises 0 to 20 mole% of residues of 1,4-cyclohexanedimethanol and 80 to 100 of residues of ethylene glycol. In certain embodiments, the rigid polyester comprises residues of neopentyl glycol. In embodiments, the rigid polyester comprises 2,2,4,4- cyclobutanediol-1,3-cyclobutanediol residues. In embodiments, the rigid polyester comprises from 0.01 to 99 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 0.01 to 99 mole% 1,4-cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues.
  • the rigid polyester comprises from 20 to 40 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, from 20 to 40 mole% 1,4- cyclohexanedimethanol residues, 20 to 60 mole% of ethylene glycol residues. In embodiments, the rigid polyester comprises from 0.01 to 15 mole% 2,2,4,4- tetramethyl-1,3-cyclobutanediol residues. In embodiments, the rigid polyester comprises from 15 to 40 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 60 to 85 mole% 1,4-cyclohexanedimethanol residues.
  • the rigid polyester comprises from 20 to 40 mole% 2,2,4,4- tetramethyl-1,3-cyclobutanediol residues and from 60 to 80 mole% 1,4- cyclohexanedimethanol residues. In embodiments, the rigid polyester comprises from 20 to 30 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 70 to 80 mole% 1,4-cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues.
  • the rigid polyester comprises from 30 to 40 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and from 60 to 70 mole% 1,4-cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues.
  • the rigid polyester component comprises residues of 1,4-cyclohexanedicarboxylic acid or an ester thereof.
  • the rigid polyester component comprises residues of dimethyl-1,4- cyclohexanedicarboxylate.
  • the rigid polyester component comprises residues 1,4-cyclohexanedicarboxylic acid or an ester thereof in the amount of from 70 to 100 mole% or from 80 to 100 mole% or from 90 to 100 mole% or from 95 to 100 mole% or from 98 to 100 mole%, based on a total of 100 mole% acid residues and a total of 100 mole% diol residues.
  • the rigid copolyesters useful in the invention may comprise a diacid component comprising at least 70 mole% of residues of terephthalic acid, isophthalic acid, or mixtures thereof; and a diol component comprising (a) the residues of 2,2,4,4-tetramethyl-1,3- cyclobutanediol and residues of 1,4-cyclohexanedimethanol (TMCD Copolyesters).
  • TMCD Copolyesters 1,4-cyclohexanedimethanol
  • the rigid polyester can comprise from 0.01 to 99.99 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 99.99 to 0.01 mole% 1,4-cyclohexanedimethanol residues, or from 20 to 50 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 80 mole% 1,4- cyclohexanedimethanol residues, or from 20 to less than 50 mole% 2,2,4,4- tetramethyl-1,3-cyclobutanediol residues and greater than 50 to 80 mole% 1,4- cyclohexanedimethanol residues, or from 15 to 40 mole% 2,2,4,4-tetramethyl- 1,3-cyclobutanediol residues and 60 to 85 mole% 1,4-cyclohexanedimethanol residues, or from 20 to 40 mole% 2,2,4,4-tetramethyl-1,3-cyclo
  • the rigid polyester can comprise 20 to 40 mole% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole% 1,4- cyclohexanedimethanol residues and 70 to 100 mole% terephthalic acid residues, based on a total of 100 mole% acid residues and a total of 100 mole% diol residues.
  • the rigid polyester of the invention may can include copolyesters comprising diacids, wherein at least one diacid is selected from the group consisting of terephthalic acid and isophthalic acid, or esters there and/or mixtures thereof; and a diol component comprising: (a) from 20 to less than 50 mole% of 1,4-cyclohexanedimethanol and residues from greater than 50 to 80 mole% ethylene glycol residues; or from 20 to 40 mole% of 1,4- cyclohexanedimethanol residues and from 60 to 80 mole% ethylene glycol residues, or from 20 to 40 mole% of 1,4-cyclohexanedimethanol residues and from 60 to 80 mole% ethylene glycol residues, or from 25 to 40 mole% of 1,4- cyclohexanedimethanol residues and from 60 to 75 mole% ethylene glycol residues, or from 25 to 35 mole% of 1,4-cyclohexaned
  • the diol component can comprise from 10 mole% to 40 mole%, or from 15 mole% to 35 mole%, or from 20 mole% to 35 mole%, or from 20 mole% to 30 mole%, or from 20 mole% to 40 mole%, or from 20 mole% to 35 mole%, of residues of isosorbide; from 30 mole% to 70 mole%, or from 40 mole% to 70 mole%, or from 45 mole% to 65 mole%, or from 45 mole% to 60 mole%, or from 45 mole% to 55 mole%, or from 47 mole% to 65 mole%, or from 48 mole% from to 65 mole%, or 49 mole% to 65 mole%, or 50 mole% to 65 mole%, or from 47 mole% to 60 mole%, or from 48 mole% from to 60 mole%, or 49 mole% to 60 mole%, or 50 mole% to 60 mole%, of residues of 1,4-cyclohe
  • the diol component can comprise from 18 mole% to 35 mole%, or from 20 mole% to 35 mole%, of residues of isosorbide; from 40 mole% to 58 mole%, or from 45 mole% to 55 mole%, of residues of 1,4-cyclohexanedimethanol; and, from 15 mole% to 25 mole%, or from 20 mole% to 25 mole%, of residues of ethylene glycol.
  • the rigid polyester can comprise residues of a branching agent.
  • the polyester or the polyester component of said polyesterether comprises 0.01 to 5 mole% or 0.01 to 4 mole% or from 0.01 to 3 mole% or from 0.01 to 2 mole% or from 0.01 to about 1.5 mole% or from 0.01 to 1 mole% or from 0.1 to 5 mole% or 0.1 to 4 mole% or from 0.1 to 3 mole% or from 0.1 to 2 mole% or from 0.1 to about 1.5 mole% or from 0.1 to 1 mole or from 0.5 to 5 mole% or 0.5 to 4 mole% or from 0.5 to 3 mole% or from 0.5 to 2 mole% or from 0.5 to about 1.5 mole% or from 0.5 to 1 mole% or from 1 to 5 mole% or 1 to 4 mole% or from 1 to 3 mole% or from 1 to 2 mole% of at least one branching agent or at least one polyfunctional branching agent, based on a total of 100 mole% acid residues and a total of 100 mole% diol residues.
  • the polyfunctional branching agent has at least 3 carboxyl or hydroxyl groups.
  • the polyfunctional branching agent comprises residues of trimellitic acid, trimellitic anhydride, trimesic acid, trimethyol ethane, trimethyolpropane, pentaerythritol, glycerine, tetra-maleaic anhydride, and trimer acid.
  • the polyfunctional branching agent comprises residues of trimellitic anhydride, trimethyolpropane, pentaerythritol, glycerine, tetra-maleaic anhydride.
  • the rigid polyesters useful in the invention may exhibit at least one of the following inherent viscosities as determined in 60/40 (wt/wt) phenol/ tetrachloroethane at a concentration of 0.5 g/100 ml at 25oC per ASTM D4603: one of the following ranges: 0.35 to 1.5 dL/g; 0.35 to 1.2 dL/g; 0.35 to 1 dL/g; 0.50 to 1.5 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1 dL/g; 0.50 to 0.95 dL/g, 0.50 to 0.90 dL/g, 0.50 to 0.85 dL/g; 0.50 to .80 dL/g; 0.50 to 0.75 dL/g; 0.50 to less than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; 0.50 to less than 0.70 dL/g; 0.50 to less than 0.70 d
  • the rigid polyester of the invention can possess at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the rigid polyester of the invention can possess at least one of the Tg ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated. It is also contemplated that the rigid polyester of the invention can possess at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein unless otherwise stated.
  • the rigid polyester comprises at least one diacid residue selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid and at least one diol selected from the group consisting of ethylene glycol, diethylene glycol, cyclohexane dimethanol, 2,2,4,4 tetramethyl cyclobutane 1,3 diol, isosorbide, neopentyl glycol, and butane diol.
  • the amount of the rigid polyester in the polyester composition can range from about 1 to about 99% by weight based on the weight of the polyester composition.
  • the amount of rigid polyester in the polyester composition can range from about 10 to about 90 by weight, from about 20 to about 80 by weight, about 30 to about 70 by weight, from about 40 to about 60 by weight based on the weight of the polyester composition.
  • Polyester Elastomer The polyester elastomer used in the polyester composition of this invention can be any known in the art having a Tg of 50°C or less. In one embodiment, the polyester elastomer comprises at least one dicarboxylic acid; at least one dihydroxy alcohol; at least one polyol; and optionally a multi- functionalized acid, alcohol or anhydride branching agent; wherein the polyester elastomer has a Tg of 50°C or less.
  • the Tg of the polyester elastomer can be 45°C or less, or 40°C or less, or 35°C or less, 30°C or less, 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, -25°C or less, -30C or less, -35C or less, -40C or less, -50C or less, -55C or less, - 60C or less, -70C or less, and -80 or less.
  • the Tg of the polyester elastomer can also range from 50°C to -80°C, 45°C to -80°C, 40°C to -80°C, 35°C to - 80°C, 30°C to -80°C, 25°C to -80°C, 20°C to -80°C, 15°C to -80°C, 10°C to - 80°C, 5°C to -80°C, 0°C to -80°C, -5°C to -80°C, -10°C to -80°C, -15°C to - 80°C, -20°C to -80°C, -25°C to -80°C, -30°C to -80°C, -40°C to -80°C, -50°C to -80°C, -60°C to -80°C, 50°C to -75°C, 45°C to -75°C, 40°C to -75°C
  • the polyester elastomer can have a flexural modulus of less than 1000 Mpa, less than 950 Mpa, less than 900 Mpa, less than 850 Mpa, less than 800 Mpa, less than 750 Mpa, less than 700 Mpa, Less than 650 Mpa, Less than 600 Mpa, less than 550 Mpa, less than 500 Mpa, less than 450 Mpa, less than 400 Mpa, less than 350 Mpa, less than 300 Mpa, less than 250 Mpa, less than than 200 Mpa, less than 150 Mpa, less than 100 Mpa, less than 50 Mpa according to ASTM D790 at 25°C.
  • the polyester elastomer can have a flexural modulus ranging from 25 Mpa to 1000 Mpa, 50 Mpa to 1000 Mpa, 100 Mpa, to 1000 Mpa, 150 Mpa to 1000 Mpa, 200 Mpa to 1000 Mpa, 250 Mpa to 1000 Mpa, 300 Mpa to 1000 Mpa, 350 Mpa to 1000 Mpa, 400 Mpa to 1000 Mpa, 450 Mpa to 1000 Mpa, 500 Mpa to 1000 Mpa, 550 Mpa to 1000 Mpa, 600 Mpa to 1000 Mpa, 650 Mpa to 1000 Mpa, 700 Mpa to 1000 Mpa, 750 Mpa to 1000 Mpa, 800 Mpa to 1000 Mpa, 25 Mpa to 9000 Mpa, 50 Mpa to 900 Mpa, 100 Mpa, to 900 Mpa, 150 Mpa to 900 Mpa, 200 Mpa to 900 Mpa,
  • the polyester elastomer comprises residues of at least one dicarboxylic acid compound, its diester derivative, its anhydride, or a combination thereof.
  • the dicarboxylic acid compounds are capable of forming ester linkages with diol or polyol compounds.
  • the polyester elastomer comprises residues of alicyclic diacids such as, but are not limited to, hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 5- norbornene-2,3-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, 2,3- norbornanedicarboxylic acid anhydride, cyclohexane dicarboxylic acid (including the 1, 2-; 1,3-; and 1,4- isomers) (CHDA), dimethylcyclohexane (including the 1, 2-; 1,3-; and 1,4- isomers) (DMCD) and mixtures thereof.
  • HHPA hexahydrophthalic anhydride
  • tetrahydrophthalic anhydride tetrahydrophthalic anhydride
  • the polyester elastomer comprises residues of acyclic aliphatic diacids such as, but are not limited to adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, glutaric acid, sebacic acid, azelaic acid, and mixtures thereof.
  • acyclic aliphatic diacids such as, but are not limited to adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, glutaric acid, sebacic acid, azelaic acid, and mixtures thereof.
  • the polyester elastomer comprises residues of di-alcohol components such as, but are not limited to 2,2,4,4-tetraalkylcyclobutane-1,3-diol (such as 2,2,4,4- tetramethylcyclobutane-1,3-diol), 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2 cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2- ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-
  • the polyester elastomer comprises residues of at least one polyol.
  • the polyol includes, but is not limited to, polytetramethylene ether glycol (PTMG), polyethylene glycol, polypropylene glycol, or any other polyether polyols and mixtures thereof.
  • a polyol is an organic compound containing multiple hydroxyl groups. A molecule with more than two hydroxyl groups is a polyol, with three is a triol, one with with four is a tetrol and so on. By convention, polyols do not refer to compounds that contain other functional groups. Polyols typically have weight average molecular weights (Mw) of about 500 to 5000 with Mw’s of about around 1000 to 2000 prefered.
  • Mw weight average molecular weights
  • hydroxyl functionalities meaning the number of hydroxyl groups as polymer end groups, can range from about 1.9 to about 2.1 for thermoplastic materials and from about 2.1 and higher for crosslinked materials.
  • the polyester elastomer may include at least one optional branching agent such as multi-functionalized acids, alcohols, anhydrides and combinations thereof.
  • the optional branching agent includes, but is not limited, to 1,1,1-trimethylol propane, 1,1,1- trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, neopentyl glycol, phenyl dianhydride, hexanediol, trimelletic anhydride (TMA) and combinations thereof.
  • TMA trimelletic anhydride
  • the diacid component of the polyester elastomer can include cyclohexane dicarboxylic acid (CHDA), and dimethylcyclohexane (DMCD), and combinations thereof, the diglycol component of the polyester includes cyclohexane dimethanol (CHDM), and the polyol includes polytetramethylene ether glycol (PTMG).
  • CHDA cyclohexane dicarboxylic acid
  • DMCD dimethylcyclohexane
  • the diglycol component of the polyester includes cyclohexane dimethanol (CHDM)
  • the polyol includes polytetramethylene ether glycol (PTMG).
  • the diacid component of the polyester elastomer includes cyclohexane dicarboxylic acid (CHDA), and dimethylcyclohexane (DMCD), and combinations thereof, the diglycol component of the polyester includes cyclohexane dimethanol (CHDM), the polyol includes polytetramethylene ether glycol (PTMG), and the branching agent includes trimelletic anhydride (TMA).
  • CHDA cyclohexane dicarboxylic acid
  • DMCD dimethylcyclohexane
  • the diglycol component of the polyester includes cyclohexane dimethanol (CHDM)
  • the polyol includes polytetramethylene ether glycol (PTMG)
  • the branching agent includes trimelletic anhydride (TMA).
  • the polyester elastomer in the inventive polyester composition can be a thermoplastic copolyester ether elastomer.
  • thermoplastic copolyester ether elastomers have high flexibility without plasticizers, very high clarity, excellent toughness and puncture resistance, outstanding low temperature strength and excellent flex crack & creep resistance.
  • the thermoplastic copolyester ether elastomer is poly(cyclohexylene dimethylene cyclohexanedicarboxylate) (PCCE), manufactured by the reaction of dimethylcyclohexane dicarboxylate with cyclohexane dimethanol and polytetramethylene glycol.
  • PCCE poly(cyclohexylene dimethylene cyclohexanedicarboxylate)
  • the invention thus relates to the use of polyester compositions that may comprise thermoplastic copolyester ethers that are elastomers, and especially elastomers that are high molecular weight semi-crystalline thermoplastic copolyester ethers manufactured by the reaction of dimethylcyclohexane dicarboxylate with cyclohexane dimethanol and polytetramethylene glycol.
  • the copolyester ethers useful according to the invention have high flexibility without plasticizers, very high clarity, excellent toughness and puncture resistance, outstanding low temperature strength, and excellent flex, crack, and creep resistance.
  • Copolyester ethers useful according to the invention include those disclosed in U.S. Pat.
  • copolyester ethers useful according to the invention are tough, flexible materials that can be extruded into clear sheets. They include copolyester ethers based on 1,4-cyclohexanedicarboxylic acid or an ester thereof, 1,4-cyclohexanedimethanol, and poly(oxytetramethylene) glycol, also known as polytetramethylene ether glycol.
  • copolyester ethers useful according to the invention include those available commercially from Eastman Chemical Company, Kingsport, TN, under the ECDEL brand.
  • the copolyester ethers may have an Inherent Viscosity (I.V.), for example, from about 0.8 to 1.5, and recurring units from (1) a dicarboxylic acid component comprising 1,4-cyclohexanedicarboxylic acid or an ester thereof typically having a trans isomer content of at least 70%, or at least 80%, or at least 85%; (2) a glycol component comprising, for example, (a) about 95 to about 65 mol % 1,4-cyclohexanedimethanol, and (b) about 5 to about 50 mol % poly(oxytetramethylene) glycol, or 10 to 40 mol%, or 15 to 35 mol%, having a molecular weight for example, from about 500 to about 1200, or from 900 to 1,100, in both cases being weight average molecular weight.
  • I.V. Inherent Viscosity
  • the copolyester ethers may have an I.V., for example, from about 0.85 to about 1.4, or from 0.9 to 1.3, or from 0.95 to 1.2.
  • the I.V. is determined by dissolving a sample of the polymer in a solvent, measuring the flow rate of the solution through a capillary and then calculating the I.V. based on flow.
  • ASTM D4603-18 Standard Test Method for Determining Inherent Viscosity of Poly(Ethylene Terephthalate) (PET) by Glass Capillary Viscometer, may be used to determine I.V.
  • Typical aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms that are useful in forming the copolyester ethers include those such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 1,2-propylene glycol, 1.4-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2- cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-isobutyl-1,3-propanediol, 2-methyl-1,3-propanediol
  • copolyester ethers include those such as adipic acid, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, dodecanedioic acid, succinic acid, succinic anhydride, glutaric acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, stilbene dicarboxylic acid, bibenzoic acid hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid, other aliphatic, cycloaliphatic or aromatic diacids or dianhydrides having 2 to 10 carbon atoms that are useful in forming the copolyester ethers include those such as adipic acid, maleic anhydride, maleic acid, fumaric acid, it
  • Aliphatic acids or anhydrides are preferred in addition to polytetramethylene ether glycol, other useful polyether polyols having 2-4 carbon atoms between ether units include polyethylene ether glycol, and polypropylene ether glycol, and combinations thereof.
  • polyol refers to “polymeric diols”.
  • Useful commercially available polyether polyols include Carbowax resins, Pluronics resins, and Niax resins.
  • Polyether polyols useful according to the invention include those that may be characterized generally as polylakylene oxides, and may have a molecular weight, for example, from about 300 to about 10,000 or 500 to 2000.
  • the copolyester ethers further may comprise, for example, up to about 1.5 mol %, based on the acid or glycol component, of a polybasic acid or polyhydric alcohol branching agent having at least three -COOH or -OH functional groups and from 3 to 60 carbon atoms. Esters of many such acids or polyols may also be used.
  • Suitable branching agents include 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, phenyl dianhydride, trimellitic acid or anhydride, trimesic acid, and trimer acid. It should be understood that the total acid reactants should be 100%, and the total glycol reactants should be 100 mol %. Although the acid reactant is said to comprise 1,4-cyclohexanedicarboxylic acid, if the branching agent is a polybasic acid or anhydride, it will be calculated as part of the 100 mol % acid.
  • the glycol reactant is said to comprise 1,4-cyclohexanedimethanol and poly(oxytetramethylene) glycol, if the branching agent is a polyol, it will be calculated as part of the 100 mol % glycol.
  • the trans and cis isomer contents of the final copolyester ethers may be controlled in order to give polymers that setup or crystallize rapidly. Cis- and trans- isomer contents are measured by conventional methods known to those skilled in the art. See, for example, U.S. Pat. No.4,349,469.
  • copolyester ethers useful according to the invention are copolyester ethers based on 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedimethanol, and polytetramethylene ether glycol or other polyalkylene oxide glycol.
  • the 1,4-cyclohexanedicarboxylic acid is present in an amount of at least 50 mol%, or at least 60 mol%, or at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol%, in each case based on the total amount of dicarboxylic acids present in the copolyester ether.
  • the 1,4- cyclohexanedimethanol is present in an amount of from about 60 mol% to about 98 mol%, or from 65 mol% to 95 mol%, or from 70 mol% to 90 mol%, or from 75 mol% to 85 mol%, in each case based on the total amount of glycol.
  • the polytetramethylene ether glycol is present in the copolyester ethers in an amount from about 2 to about 40 mol %, or from 5 mol% to 50 mol%, or from 7 mol% to 48 mol%, or from 10 mol% to 45 mol%, or from 15 to 40 mol%, or from 20 mol% to 35 mol%, in each case based on the total amount of glycol present.
  • the amount of 1,4-cyclohexanedicarboxylic acid is from about 100 mol% to about 98 mol%
  • the amount of 1,4- cyclohexanedimethanol is from about 80 mol% to about 95 mol%
  • the amount of polytetramethylene ether glycol is from about 5 mol% to about 20 mol%
  • trimellitic anhydride may be present in an amount from 0.1 to 0.5 mol% TMA .
  • the amount of 1,4-cyclohexanedicarboxylic acid is from 98 mol% to 100 mol%
  • the amount of 1,4-cyclohexanedimethanol is from 70 mol% to 95 mol%
  • the amount of polytetramethylene ether glycol is from 5 mol% to 30 mol%
  • trimellitic anhydride may be present in an amount from 0 to 0.5 mol%.
  • the amount of 1,4- cyclohexanedicarboxylic acid is from 99 mol% to 100 mol%
  • the amount of 1,4- cyclohexanedimethanol is from 70 mol% to 95 mol%
  • the amount of polytetramethylene ether glycol is from 5 mol% to 30 mol%
  • trimellitic ahydride may be present in an amount from 0 mol% to 1 mol%.
  • the copolyester ethers utilized in the polyester composition of this invention may include a phenolic antioxidant that is capable of reacting with the polymer intermediates. This causes the antioxidant to become chemically attached to the copolyester ether and be essentially nonextractable from the polymer.
  • Antioxidants useful in this invention may contain one or more of an acid, hydroxyl, or ester group capable of reacting with the reagents used to prepare the copolyester ether. It is preferred that the phenolic antioxidant be hindered and relatively non-volatile.
  • antioxidants examples include hydroquinone, arylamine antioxidants such as 4,4'-bis(.alpha.,.alpha.- dimethylbenzyl)diphenylamine, hindered phenol antioxidants such as 2,6-di- tert-butyl-4-methylphenol, butylated p-phenyl-phenol and 2-(.alpha.- methylcyclohexyl)-4,6-dimethylphenol; bis-phenols such as 2,2'-methylenebis- (6-tert-butyl-4-methylphenol), 4,4'bis(2,6-di-tert-butylphenol), 4,4'- methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butylene-bis(6-tert-butyl-3- methylphenol), methylenebis-(2,6di-tertbutylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), and 2,2'-thiobis(4-thi
  • the antioxidant is used in an amount of from about 0.1 to about 1.0, based on the weight of copolyester ether.
  • Copolyester ethers used in the polyester composition of this invention include those characterized by their good melt strength.
  • a polymer having melt strength is described as one capable of supporting itself on being extruded downward from a die in the melt. When a polymer with melt strength is extruded downward, the melt will hold together. When a polymer without melt strength is extruded downward, the melt rapidly drops and breaks. For purposes of comparison, the melt strength is measured at a temperature 20oC. above the melting peak.
  • the polyester elastomer comprises the residues of: a.
  • the polyester elastomer comprises: a. 99 to 100 mole percent, based on the total molar acid content of the polyester, of a diacid selected from the group consisting of cyclohexane dicarboxylic acid (CHDA), dimethylcyclohexane dicarboxylic acid (DMCD), and combinations thereof; b.
  • the invention comprises a polyester elastomer for low shear polymer melt processes comprising the residues of: a.
  • a diacid selected from the group consisting of a cyclohexane dicarboxylic acid, a dimethylcyclohexane dicarboxylic acid, and combinations thereof; b. 75 to 92 mole percent of 1,4- cyclohexane dimethanol and 4 to 25 mole percent of polytetramethylene ether glycol based on the total glycol content of the polyester; and c.
  • the polyester elastomer is Ecdel TM copolyester available commercially from Eastman Chemical Company, which are copolyesters based on a combination of cyclohexane dicarboxylic acid (CHDA) and cyclohexane dimethanol with polytetramethylene ether glycol having a molecular weight of 1000 (PTMG 1000).
  • CHDA cyclohexane dicarboxylic acid
  • PTMG 1000 polytetramethylene ether glycol having a molecular weight of 1000
  • TMA Trimelletic anhydride
  • TMA Trimelletic anhydride
  • the amount of the polyester elastomer in the polyester composition can range from about 1 to about 99% by weight based on the weight of the polyester composition. In other embodiments, the amount of polyester elastomer in the polyester composition can range from about 10 to about 90 by weight, from about 80 to about 20 by weight, about 70 to about 30 by weight, from about 60 to about 40 by weight based on the weight of the polyester portion of the composition.
  • the present invention involves the use of primary antioxidants, secondary antioxidants and chain extending additives to inhibit the thermal oxidative and hydrolytic degradation of polymers held at elevated temperatures for extended periods of time and improve polymer flow.
  • This combination has been shown to be effective in the polyester and copolyester classes of polymers.
  • the improved thermal oxidative and hydrolytic stability can be measured using gel-permeation chromatography and through visual color observations and spectrophotography. Viscosity improvements can be measured using parallel plate rheometry.
  • the polyester composition comprises at least one primary antioxidant of the hindered phenol type, at least one secondary antioxidant in the phosphite family and at least one chain extending agent with epoxide functionalities.
  • polymers undergo chain cleavage which results in the formation of free radical molecules and carboxylic acids which are highly reactive and will lead to autocatalytic degradation of the polymer.
  • the free radicals can also, in the presence of oxygen, react to create hydroxy, peroxy, peroxide, and mono and di-hydroxy terephthalates which are also very reactive and will lead to further polymer degradation.
  • Primary antioxidants are added to react with free radicals thus inhibiting further degradation or reacting with oxygen to create hydroxy, peroxy, and other oxygen containing radicals.
  • Secondary antioxidants also known as oxygen scavengers, react with the hydroxy, peroxy and oxygen radicals before they can cause further polymer degradation.
  • Condensation polymers are also susceptible to hydrolytic degradation if not pre-dried or if they are held at elevated temperatures in moist air for a long period of time. Condensation polymers are any polymer where monomers form together to create a polymer and a by-product such as water or methanol is produced. The polymerization reaction is reversible; thus, condensation polymers must be pre-dried before processing.
  • Primary Antioxidants Hindered phenols and hindered amines are the main types of primary antioxidants used in thermoplastics.
  • the weight effectiveness, the compatibility and the basicity must be considered in the choice of a hindered amine.
  • Several characteristics can be considered in the choice of a hindered phenolic antioxidant including the relative phenol content, which affects its reactivity, and the molecular weight sufficiently high to ensure that the antioxidant does not migrate easily out of the polymer.
  • the phenolic antioxidant can be sterically hindered and/or relatively non-volatile.
  • Suitable phenolic antioxidants include hydroquinone, arylamine antioxidants such as 4,4'-bis( ⁇ , ⁇ - dimethylbenzyl)diphenylamine, hindered phenol antioxidants such as 2,6-di- tert-butyl-4-methylphenol, butylated p-phenyl-phenol and 2-( ⁇ - methylcyclohexyl)-4,6-dimethylphenol; bis-phenols such as 2,2'-methylenebis- (6-tert-butyl-4-methylphenol), 4,4'bis(2,6-di-tert-butylphenol), 4,4'- methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butylene-bis(6-tert-butyl-3- methylphenol), methylenebis(2,6di-tertbutylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), and 2,2'-thiobis(4-methyl-6-tert-but
  • the primary antioxidant is selected from at least one hindered phenol, at least one secondary aryl amine, or a combination thereof.
  • the at least one hindered phenol useful in the polyestercompositions of the invention comprises one or more compounds selected from triethylene glycol bis[3-(3-t-butyl-5-methyl-4- hydroxyphenyl)propionate], 1,6-hexanediolbis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t- butylanilino)-1,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 2,2-thiodiethylene bis[3-(3,5-di-t-butyl-4- hydroxy
  • the phenolic antioxidants useful in the polyester compositions of the invention can be octadecyl-3-(3,5-di-tert.butyl-4- hydroxyphenyl)-propionate (CAS number 2082-79-3; pentaerythritol tetrakis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] (CAS# 6683-198, otherwise known as IrganoxTM 1010); N,N’-hexane-1,6-diyl-bis[3-(3,5-ditert-butyl-4- hydroxyphenyl]propionamide] (CAS# 23128-747-, IrganoxTM1098); benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecyl ester (IrganoxTM1076).
  • the Irganox phenolic brand of additives can be commercially obtained from BASF).
  • the hindered phenol comprises octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate.
  • at least one hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxy- 2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]- 1,3-propanediyl ester.
  • the phenolic antioxidant is present in the amount of from 0.01 to 5 weight%, or from 0.01 weight% to 4 weight%, or from 0.01 weight% to 3 weight%, or from 0.01 weight% to 2.0 weight%, or from 0.01 weight% to 1.0 weight%, or from 0.01 weight% to 0.90 weight%, or from 0.01 weight% to 0.80 weight%, or from 0.01 weight% to 0.75 weight%, or from 0.01 to 0.70 weight%, or from 0.01 to 0.60 weight%, or from 0.01 weight% to 0.50 weight% or from 0.10 weight% to 5 weight%, or from 0.10 weight% to 4 weight%, or from 0.10 weight% to 3 weight%, or from 0.10 weight% to 2.0 weight%, or from 0.10 weight% to 1.0 weight%, or from 0.10 weight% to 0.90 weight%, or from 0.10 weight% to 0.80 weight%, or from 0.10 weight% to 0.75 weight%, or from 0.10 weight% to 0.70 weight%, or from 0.10 weight% to 0.60 weight%, or from 0.10 weight% to
  • the primary antioxidant can be present (total loading) in the polyester compositions of the invention in the amount of from 0.01 weight% to 5 weight% or from 0.01 weight% to 4 weight% or from 0.01 weight to 3 weight% or from 0.01 to 2.0 weight% or from 0.01 to 1.5 or from 0.01 to 1 weight% or from 0.01 to 0.75 weight% or from 0.01 to 0.50 weight% or from or from 0.10 weight% to 5 weight% or from 0.10 weight% to 4 weight% or from 0.10 weight to 3 weight% or from 0.10 to 2.0 weight% or from 0.10 to 1.5 or from 0.10 to 1 weight% or from 0.10 to 0.75 weight% or from 0.10 to 0.60 weight% or from, based on the total weight of the polymer composition equaling 100 weight%.
  • the primary antioxidant can be present (total loading) in the polyester compositions of the invention in the amount of from 0.01 to 2.0 weight%, or from 0.10 to 2.0 weight%, from 0.01 to 1.0 weight%, or from 0.10 to 1.0 weight%, or from 0.10 to 1.5, or from 0.50 to 1.5, or from 0.75 to 1.25, or from 0.10 to 60 weight%, based on the total weight of the polyester composition equaling 100 weight%.
  • the primary antioxidant can be present (total loading) in the polyester compositions of the invention in the amount of from 0.01 to 1.0 weight%, 0.01 to 0.90 weight% or from 0.10 to 1.0 weight%, 0.10 to 0.90 weight% from 0.20 to 1.0 weight%, 0.20 to 0.90 weight% from 0.25 to 1.0 weight% or 0.25 to 0.90 weight%, based on the total weight of the polyester composition.
  • a “hindered amine” as used herein refers to a compound or polymer comprising a substituted piperidinyl group.
  • the substituted piperidinyl group may comprise 1, 2, 3, 4, 5, 6, 7, 8, or more substituents, such as, e.g., an alkyl, alkenyl, or alkoxy group.
  • the substituted piperidinyl group comprises 1 or 2 substituents (e.g., a C1-C20 alkyl or C1-C20 alkenyl group) at the 2- and/or 6-position of the piperidine ring.
  • the substituted piperidinyl group is a 2,2,6,6-tetraalkylpiperidinyl group (e.g., a 2,2,6,6-tetramethylpiperidinyl group).
  • the substituted piperidinyl group comprises hydrogen, an alkyl group or an alkoxy group at the 1-position of the piperidine ring.
  • a hindered amine light stabilizer comprises an amine group that acts through and/or participates in a regenerative free radical scavenging mechanism.
  • One or more (e.g., 1, 2, 3, 4, 5, or more) substituted piperidinyl group(s) may be present in a hindered amine light stabilizer.
  • the hindered amine light stabilizer is a polymer and comprises one or more (e.g., 1, 2, 3, 4, 5, or more) substituted piperidinyl group(s) per repeating unit of the hindered amine light stabilizer.
  • an acrylic composition of the present invention may comprise a hindered amine light stabilizer that comprises one or more (e.g., 1, 2, 3, 4, or more) 2,2,6,6- tetraalkylpiperidinyl group(s) in the hindered amine light stabilizer.
  • the hindered amine light stabilizer may be a polymeric or oligomeric hindered amine light stabilizer, and may comprise one or more (e.g., 1, 2, 3, 4, or more) 2,2,6,6-tetraalkylpiperidinyl group(s) per repeating unit of the hindered amine light stabilizer.
  • Example hindered amine light stabilizers include, but are not limited to, those under the tradename Tinuvin® commercially available from BASF, such as, e.g., Tinuvin® PA 123, Tinuvin® 371, Tinuvin® 111 and/or Tinuvin® 622; those under the tradename Chimassorb® commercially available from BASF, such as, e.g., Chimassorb® 2020; and/or those under the tradename Cyasorb® commercially available from Cytec Industries, Inc., such as, e.g., Cyasorb® UV-3529.
  • the polyester composition of this invention contains at least one secondary antioxidant.
  • the secondary antioxidant can be any that is known in the art. Molecular weight, reactivity and hydrolytic stability can be considered in the choice of secondary antioxidant.
  • secondary antioxidants are thiodipropionates, phosphites and metal salts.
  • Thiopropionates are mostly used in polyolefins and are of limited use in condensation polymers. Phosphites are the most typically used in thermoplastics.
  • a typical phosphite antioxidant structure is shown below: wherein R is selected from C1 to C20_ alkyl groups. Molecular weight, reactivity and hydrolytic stability must all be considered in the choice of secondary antioxidant.
  • the secondary antioxidant can also be selected from an organophosphate or thioester, or a combination thereof.
  • the secondary antioxidant comprises one or more compounds selected from tris(nonyl phenyl)phosphite [WestonTM399, available from Addivant, Connecticut), tetrakis(2,4-di-tert-butylphenyl) [1,1- biphenyl]-4,4 ⁇ -diylbisphosphonite, tris(2,4-di-tert-butylphenyl)phosphite (IrgafosTM168, available from BASF), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritoldiphosphite, and distearyl pentaerythritol diphosphite.
  • tris(nonyl phenyl)phosphite [WestonTM399, available from Addivant, Connecticut)
  • the polyester composition of the invention contains at least one phosphite comprising an aryl phosphite or an aryl monophosphite.
  • aryl monophosphite refers to a phosphite stabilizer which contains:(1) one phosphorus atom per molecule; and (2) at least one aryloxide (which may also be referred to as a phenoxide) radical which is bonded to the phosphorus.
  • the aryl monophosphite contains C1 to C20, or C1 to C10, or C2-C6 alkyl substituents on at least one of the aryloxide groups.
  • Example of C1 to C20 alkyl substituents include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and iso-butyl, tertiary butyl, pentyl, hexyl, octyl, nonyl, and decyl.
  • Preferred aryl groups include but are not limited to phenyl and naphthyl.
  • the phosphites useful in the invention comprise tertiary butyl substituted aryl phosphites.
  • the aryl monophosphite comprises at least one of triphenyl phosphite, phenyl dialkyl phosphites, alkyl diphenyl phosphites, tri(nonylphenyl)phosphite, tris-(2,4-di-t- butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, (believed to be IrgafosTM38, available from BASF), 2,2,2- nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite (believed to be IrgafosTM12, available from BASF.
  • the aryl monophosphite is selected from one or more of tris-(2,4-di-t- butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, and 2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)phosphite.
  • an aryl monophosphite useful in the invention is tris-(2,4- di-t-butylphenyl)phosphite.
  • suitable secondary antioxidant additives include, for example, organic phosphites such as, tris(nonyl phenyl)phosphite, tris(2,4- di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; or combinations comprising at least one of the foregoing antioxidants.
  • organic phosphites such as, tris(nonyl phenyl)phosphite, tris(2,4- di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; or combinations comprising at least one of the foregoing antioxidants.
  • the secondary antioxidant is present in the polyester composition in an amount from about 0.01 weight% to about 3.0 weight%, or from 0.01 weight% to 2 weight%, or from 0.01 weight% to 1 weight% or from 0.10 weight% to 5 weight%, or from 0.10 weight% to 4 weight%, or from 0.10 weight% to 3 weight%, or from 0.10 weight% to 2 weight%, or from 0.10 weight% to 1 weight%, or from 0.25 weight% to 1 weight%, or from 0.25 weight% to 0.75 weight%, based on the total weight of the polymer composition.
  • the secondary antioxidant is present in the polyester composition in an amount from about 0.01 weight% to about 2.5 weight%.
  • the secondary antioxidant is present in an amount from about 0.5 weight% to about 2.5 weight%. In yet another aspect, the secondary antioxidant is present in an amount from about 0.5 weight% to about 2.0 weight% In still another aspect, the secondary antioxidant is present in an amount from about 0.05 weight% to about 0.75 weight%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 weight% to about 0.75 weight%. In certain embodiments, the secondary antioxidant is present in an amount from about 0.1 weight% to about 1.0 weight%, or about 0.2 weight% to about 0.8 weight%, or 0.25 to 0.75 weight%. In one embodiment, the secondary antioxidant is present in an amount from about 0.35 weight% to about 0.65 weight%.
  • the weight ratio of primary antioxidant to secondary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1:5.
  • the weight ratio of primary antioxidant to secondary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4 or 1:5.
  • the weight ratio of primary to secondary antioxidant is 1:1 or 1:2 or 1:3 or 1:4 or 1:5.
  • the weight ratio of primary antioxidant to secondary antioxidant is 2:1 to 1:2, e.g., 2:1.
  • the weight ratio of primary antioxidant to secondary antioxidant is in the range from 1.1:1 to 4:1, or 1.2:1 to 4:1, or 1.5:1 to 4:1, or 1.6:1 to 4:1, or 1.8:1 to 4:1, or 2:1 to 4:1, or 1.1:1 to 3:1, or 1.2:1 to 3:1, or 1.5:1 to 3:1, or 1.6:1 to 3:1, or 1.8:1 to 3:1, or 2:1 to 3:1, 1.1:1 to 2.5:1, or 1.2:1 to 2.5:1, or 1.5:1 to 2.5:1, or 1.6:1 to 2.5:1, or 1.8:1 to 2.5:1, or 2:1 to 2.5:1.
  • the polyester compositions of the invention can comprise at least one chain extending agent.
  • Suitable chain extending agents include, but are not limited to, multifunctional (including, but not limited to, bifunctional) isocyanates, multifunctional epoxides, including for example, and phenoxy resins.
  • the chain extending agents have epoxide dependent groups.
  • the chain extending additive can be one or more styrene- acrylate copolymers with epoxide functionalities.
  • the chain extending additive can be one or more copolymers of glycidyl methacrylate with styrene.
  • Chain extending additives include compounds such as bisanhydrides, bisoxaolines, and bisepoxides which react with –OH or –COOH end groups caused by hydrolytic degradation.
  • Chain extending additives can also be added during melt processing to build molecular weight through ‘reactive extrusion’ or ‘reactive chain coupling’.
  • Another effective type of chain extending additive are styrene-acrylate copolymers with epoxide functionalities.
  • chain extending agents are added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, chain extending agents can be incorporated by compounding or by addition during conversion processes such as injection molding or extrusion.
  • the amount of chain extending agent used can vary depending on the specific monomer composition used and the physical properties desired but is generally about 0.01 percent by weight to about 10 percent by weight, 0.1 percent by weight to about 10 percent by weight, from about 0.01 to about 5 percent by weight, from about 0.1 to about 5 percent by weight, from about 0.01 percent by weight to about 3 percent by weight, from about 0.1 to about 3 percent by weight, from about 0.01 percent by weight to about 2 percent by weight, from about 0.1 to about 2 percent by weight, from about 0.01 percent by weight to about 1 percent by weight, from about 0.1 to about 1 percent by weight, from about 0.01 percent by weight to about 0.5 percent by weight, and from about 0.1 to about 0.5 based on the total weight of the polyester.
  • Chain extending additives can also be added during melt processing to build molecular weight through ‘reactive extrusion’ or ‘reactive chain coupling or any other process known in the art.
  • Chain extending agents useful in the invention can include, but are not limited to, copolymers of glycidyl methacrylate (GMA) with alkenes, copolymers of GMA with alkenes and acrylic esters, copolymers of GMA with alkenes and vinyl acetate, copolymers of GMA and styrene.
  • Suitable alkenes comprise ethylene, propylene, and mixtures of two or more of the foregoing.
  • Suitable acrylic esters comprise alkyl acrylate monomers, including, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations of the foregoing alkyl acrylate monomers.
  • the acrylic ester can be used in an amount of 15 weight% to 35 weight%, based on the total amount of monomer used in the copolymer, or in any other range described herein.
  • vinyl acetate can be used in an amount of 4 weight% to 10 weight% based on the total amount of monomer used in the copolymer.
  • the chain extending additive comprises acrylic esters comprising monomers selected from alkyl acrylate monomers, including, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations thereof.
  • the chain extending additive is a copolymer comprising at least one acrylic ester and styrene.
  • suitable chain extending agents comprise ethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-vinyl acetate copolymers, ethylene-glycidyl methacrylate-alkyl acrylate copolymers, ethylene-glycidyl methacrylate-methyl acrylate copolymers, ethylene-glycidyl methacrylate-ethyl acrylate copolymers, and ethylene-glycidyl methacrylate-butyl acrylate copolymers.
  • chain extending agents examples include but are not limited to Joncryl 4368, JoncrylTM4468 (copolymers of glycidyl methacrylate with styrene), JoncrylTM4368, JoncrylTM4470, JoncrylTM4370, JoncrylTM 4400, JoncrylTM4300, JoncrylTM4480, JoncrylTM4380, JoncrylTM4485, JoncrylTM4385, and mixtures thereof commercially available from BASF Corporation, New Jersey.
  • the chain extending agents can be styrene- acrylate copolymers with glycidyl groups.
  • the chain extending agent can be a copolymer of glycidyl methacrylate and styrene.
  • the polymeric chain extending agent can have an average of greater than or equal to 2 pendant epoxy groups per molecule, greater than or equal to 3 pendant epoxy groups per molecule; or an average of greater than or equal to 4 pendant epoxy groups per molecule; or an average of greater than or equal to 5 pendant epoxy groups per molecule; or an average of greater than or equal to 6 pendant epoxy groups per molecule; or an average of greater than or equal to 7 pendant epoxy groups per molecule; or more specifically, an average of greater than or equal to 8 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 11 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 15 pendant epoxy groups per molecule, or, more specifically, an average of greater than or equal to 17 pendant epoxy groups per molecule.
  • the chain extending agent can have from 2 to 20 pendant epoxy groups per molecule, or from 5 to 20 pendant epoxy groups per molecule, or from 2 to 15 pendant epoxy groups per molecule, or from 2 to 10 pendant epoxy groups per molecule, or from 2 to 8 pendant epoxy groups per molecule, or 3 to 20 pendant epoxy groups per molecule, or from 3 to 15 pendant epoxy groups per molecule, or from 5 to 15 pendant epoxy groups per molecule, or from 3 to 10 pendant epoxy groups per molecule, or from 5 to 10 pendant epoxy groups per molecule, or from 3 to 8 pendant groups per molecule, or from 3 to 7 pendant epoxy groups per molecule.
  • the chain extending agent can be present (total loading) in the polyester composition of the invention in the amount of from 0.01 weight% to 5 weight%, or from 0.01 weight% to 4 weight%, or from 0.01 weight% to 3 weight%, or from 0.01 weight% to 2, weight% or from 0.01 weight% to 1 weight%, or from 0.10 weight% to 5 weight%, or from 0.10 weight% to 4 weight%, or from 0.10 weight% to 3 weight%, or from 0.10 weight% to 2 weight%, or from 0.10 weight to 1.5 weight%, or from 0.10 weight% to 1 weight, or from 0.25 weight% to 5 weight%, or from 0.25 weight% to 4 weight%, or from 0.25 weight% to 3 weight%, or from 0.25 weight% to 2 weight%, or from 0.25 weight to 1.5 weight%, or from 0.25 weight% to 1 weight, or from 0.25 weight% to 0.75 weight%, or from 0.50 weight% to 5 weight%, or from 0.50 weight% to 4 weight%, or from 0.50 weight% to 3 weight
  • the chain extending agent can be present (total loading) in the polymer composition of the invention in the amount of from 0.25 weight% to 0.75 weight%, or from 0.30 weight% to 0.70 weight%, or from 0.4 weight% to 0.6 weight%. In certain aspects of the invention, the chain extending agent is present (total loading) in the polyester composition of the invention in the amount of from 0.01 weight% to 1.5 weight% or from 0.10 weight% to 1 weight% or from based on the total weight of the polyester composition. The initial amount of the chain extending agent used and order of addition will depend upon the specific chain extending agent chosen and the specific amounts of polyester employed.
  • the weight ratio of chain extending agent to primary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1:5. In certain aspects of the invention, the weight ratio of chain extending agent to primary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4 or 1:5. In certain aspects of the invention, the weight ratio of chain extending agent to primary antioxidant is 3:1 to 1:2, or 2.5-3:1. In certain aspects of the invention, the weight ratio of chain extending agent to primary antioxidant is 1:2 or 3:1. In certain aspects of the invention, the weight ratio of chain extending agent to secondary antioxidant present in the polyester compositions useful in the invention can be from 5:1 to 1:5.
  • the weight ratio of chain extending agent to secondary antioxidant can be 5:1 or 4:1 or 3:1 or 2:1 or 1:1 or 1:2 or 1:3 or 1:4 or 1:5. In certain aspects of the invention, the weight ratio of chain extending agent to secondary antioxidant is 3:1. In certain aspects of the invention, the weight ratio of chain extending agent to secondary antioxidant is 1:1 or 1.5:1 or 1.3:1. In another embodiment, the weight ratio of chain extending agent to secondary antioxidant is 1:1 to 3:1, or 1:1 to 2:1.
  • the polyester composition comprises: (1) at least one hindered phenolic antioxidant that comprises one or more compounds selected from pentaerythritol tetrakis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)- propionate, N,N’-hexane-1,6-diyl-bis[3-(3,5-ditert-butyl-4- hydroxyphenyl)propionamide, benzenepropanoic acid 3,5-bis(1,1- dimethylethyl)-4-hydroxyoctadecyl ester, and octadecyl-3-(3,5-di-tert.butyl-4- hydroxyphenyl)-propionate (CAS number 2082); (2) at least one phosphite that is chosen from tris-(2,4-di-
  • the polyester composition comprises at least one hindered phenolic antioxidant that is pentaerythritol tetrakis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate; at least one phosphite that is tris(2,4-di-tert- butylphenyl)phosphite; and at least one chain extending agent that is JoncrylTM4468 additive.
  • hindered phenolic antioxidant that is pentaerythritol tetrakis[3-(3,5-di-t- butyl-4-hydroxyphenyl)propionate
  • at least one phosphite that is tris(2,4-di-tert- butylphenyl)phosphite
  • at least one chain extending agent that is JoncrylTM4468 additive.
  • a primary antioxidant is incorporated in the hindered phenol family, i.e., Irganox tm 1010 commercially available from BASF Corporation, New Jersey, in the amounts of 0.01 to about 2.0 % by weight, a secondary antioxidant in the phosphite family, i.e, IrgafosTM168 commercially available from BASF Corporation, New Jersey, in the amounts of 0.01 to 2.0 % by weight, and a chain extending agent in the styrene-acrylate copolymer family, i.e., JoncrylTM4468 commercially available from BASF Corporation, New Jersey, in the amounts from .01 to 2.0 % by weight into a polyester or copolyester.
  • a primary antioxidant is incorporated in the hindered phenol family, i.e., Irganox tm 1010 commercially available from BASF Corporation, New Jersey, in the amounts of 0.01 to about 2.0 % by weight
  • a secondary antioxidant in the phosphite family
  • the polyester composition comprises (1) at least one phenolic antioxidant in the amount of from 0.01 weight% to 2.0 weight%, (2) at least one phosphite in the amount of from 0.10 weight% to 1.0 weight%, and (3) said chain extending agent in the amount of from 0.25 weight% to 2.0 weight percent, based on the total weight of the polyester composition.
  • the polyester composition comprises (1) at least one phenolic antioxidant in the amount of from 0.10 weight% to 1.5 weight%, or from 0.10 weight% to 1.0 weight%, or from 0.50 weight% to 1.5 weight%, or from 0.75 weight% to 1.25 weight%, (2) at least one phosphite in the amount of from 0.10 weight% to 1.0 weight%, or 0.10 weight% to 0.75 weight%, or from 0.25 weight% to 0.75 weight%, and (3) at least one chain extending agent in the amount of from 0.10 weight% to 1.0 weight%, or 0.25 weight% to 1.0 weight, or from 0.25 weight% to 0.75 weight% based on the weight of the polyester composition.
  • the polyester composition comprises (1) at least one phenolic antioxidant in the amount of from 0.75 weight% to 1.25 weight%, (2) at least one phosphite in the amount of 0.10 weight% to 1.0 weight%, or from 0.25 weight% to 0.75 weight%, and (3) at least one chain extending agent in the amount of 0.10 weight% to 1.0 weight%, or from 0.25 weight% to 0.75 weight% based on the weight of the polyester composition.
  • the polyester composition comprises a primary antioxidant in the hindered phenol family, preferably Irganox ® 1010 commercially available from BASF, in the amounts of 0.01 to about 2.0 % by weight, a secondary antioxidant in the phosphite family, preferably Irgafos ® 168 commercially available from BASF, in the amounts of 0.01 to 0.5 % by weight or Doverphos ® 9228 in the amounts of 0.01 to 0.5 %, and a chain extending agent in the styrene-acrylate copolymer family, preferably Joncryl ® 4468 commercially available from BASF, in the amounts from 0.01 to 2.0 % by weightwherein the % by weight is based on the weight of the polyester composition.
  • a primary antioxidant in the hindered phenol family preferably Irganox ® 1010 commercially available from BASF
  • a secondary antioxidant in the phosphite family preferably Irgafos ® 168 commercially available from BASF,
  • the present invention can employ a primary antioxidant of the hindered phenol type, a secondary antioxidant in the phosphite family and a chain extending agent with epoxide functionalities.
  • the weight percentages specified herein can also be combined with the ratios of additives to each other that are specified. They can also be combined with the particular classifications of additives that are described herein.
  • the weight ratios of one additive to another or weight percentages of additives are calculated based on the weight of the additive compared to the total weight of the polyester composition at the time of loading the additive into the composition (total loading) wherein all components equal 100 weight%.
  • the polyester composition comprises at least one rigid polyester, at least one polyester elastomer, from about 0.1 to about 2% by weight of at least one hindered phenol primary antioxidant, from about 0.01 to about 0.5 % by weight of at least one phosphite secondary antioxidant, and from about 0.01 to about 2.0% by weight of at least one styrene-acrylate cpolymer; wherein the weight percent is based on the total weight of the polyester composition.
  • the stabilizer compositions useful in the invention can improve or maintain color, reduce the loss of number average molecular weight, and/or inherent viscosity, and/or reduce the total number of carboxyl end groups, under the conditions as specified herein.
  • the improved thermal oxidative and hydrolytic stability can be measured by any method known in the art, for example, through using gel-permeation chromatography and through visual color observations, colorimeter, and/or spectrophotometry. Viscosity improvements can be measured by any method known in the art, for example, using parallel plate rheometry or inherent viscosity measures. Numbers of carboxyl end groups can be measured by titration.
  • polyester compositions useful in this invention may also contain at least one other additive selected from colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, other stabilizers (including but not limited to, UV stabilizers, thermal stabilizers, hydrolytic stabilizers), fillers, and impact modifiers.
  • additives selected from colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, other stabilizers (including but not limited to, UV stabilizers, thermal stabilizers, hydrolytic stabilizers), fillers, and impact modifiers.
  • the polymer compositions can contain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to 15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of the total weight of the polyester composition of common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • common additives such as colorants, dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and impact modifiers.
  • Examples of typical commercially available impact modifiers well known in the art and useful in this invention include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymer impact modifiers and various acrylic core/shell type impact modifiers.
  • UV additives can be incorporated into articles of manufacture through addition to the bulk, through application of a hard coat, or through coextrusion of a cap layer. Residues of such additives are also contemplated as part of the polymer composition. Reinforcing materials may be useful in the polyester compositions of this invention.
  • the reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
  • the reinforcing materials are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the polyester compositions of this invention can be blended with any other polymers known in the art.
  • the polyester compositions of the invention can comprise at least one polymer chosen from at least one of the following: poly(etherimides), polyphenylene oxides, poly(phenylene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester- carbonates), polycarbonates, polysulfones, polysulfone ethers, and poly(ether- ketones).
  • poly(etherimides) polyphenylene oxides
  • poly(phenylene oxide)/polystyrene blends polystyrene resins
  • polyphenylene sulfides polyphenylene sulfide/sulfones
  • poly(ester- carbonates) polycarbonates
  • polysulfones polysulfone ethers
  • poly(ether- ketones) poly(etherimides), polyphenylene oxides, poly(phenylene oxide)/polys
  • certain additional polymers other than the ones described in the polyester compositions of the invention can be present in an amount of 50 weight% or less, or 40 weight% or less, or 30 weight% or less, or 20 weight% or less, or 10 weight% or less, or 5 weight% or less; in another embodiment, 0.01 to 50 weight%, or 1 to 50 weight%, or 5 to 50 weight%, or 0.01 to 40 weight%, or 0.01 to 30 weight% or 0.01 to 20 weight%, or 0.01 to 10 weight% or 0.01 to 5 weight%.
  • the polyester compositions of the invention can comprise at least one other polymer.
  • the at least one other polymer is selected from liquid crystalline polyesters/amides/imides, polyesteramides, polyimides, polyetherimides, polyurethanes, polyureas, polybenzimidazole, polybenzoxazoles, polyimines, polycarbonates, other polyesters, other copolyesters, and polyamides.
  • the polyester composition does not include polycarbonate.
  • the polyester composition does not include bisphenol polycarbonate.
  • the polyester composition does not include polybutylene terephthalate.
  • the polyester composition does not include polyarylene ethers.
  • the polyester composition does not include cellulose esters.
  • the at least one other polymer is present in the composition in the amount of 50 weight% or less, or 40 weight% or less, or 30 weight% or less, or 20 weight% or less, or 10 weight% or less, or 5 weight% or less, based on the total weight of the polyester composition equaling 100 weight%. In embodiments, the at least one other polymer is present in the polyester composition in the amount of 0.01 to 50 weight%, or 1 to 50 weight%, or 5 to 50 weight%, or 0.01 to 40 weight%, or 0.01 to 30 weight% or 0.01 to 20 weight%, or 0.01 to 10 weight% or 0.01 to 5 weight%, based on the total weight of the polyester composition equaling 100 weight%.
  • the polyester compositions described herein do not contain carbon nanotubes.
  • An effective amount of the primary antioxidant, secondary antioxidant, and the chain extending additive can be determined by understanding fitness for use requirements, target properties and/or target criteria for various applications and/or thermoplastic processing conditions and/or when the chosen property is preserved during processing.
  • the polyester composition of this invention can be produced by any method known in the art. To make the polyester composition, blends of the primary antioxidant, secondary antioxidant, chain extending agent, rigid polyester and polyester elastomer can either be prepared directly during the polymerization process or compounded to produce pellets using typical plastics compounding and extrusion techniques.
  • a process to produce a polyester composition comprising contacting a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • the rigid polyester, the polyester elastomer, the primary antioxidant, the secondary antioxidant, and the chain extending additive additive can be melt compounded in either a twin screw compounding extruder, a single screw extruder, a Banbury TM type mixer or a Farrell Continuous Mixer TM to produce a homogenous blend.
  • the rigid polyester and the polyester elastomer melts at 240°C or below, 230°C or below, 220°C or below, 210°C or below, 200°C or below, 190°C or below or 180°C or below.
  • a process to produce a polyester composition comprising extruding a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive in an extrusion zone to produce a polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • the extrusion zone comprises at least one extruder.
  • a process to produce a polyester composition comprising 1) polymerizing at least one dicarboxylic acid and at least one diol; and b) at least one secondary antioxidant to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less; wherein the polymerizing in steps 1) and/or 2) is conducted in the presence of at least one primary antioxidant; and wherein the polymerizing in steps 1) and/or 2) is conducted in the presence of at least one secondary antioxidant.
  • a process to produce a polyester composition comprising 1) polymerizing at least one dicarboxylic acid and at least one diol in the presence of a) at least one primary antioxidant; and b) at least one secondary antioxidant to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to produce a polyester composition comprising 1) polymerizing at least one dicarboxylic acid and at least one diol to produce a rigid polyester having a Tg greater than 60°C; 2) polymerizing at least one dicarboxylic acid, at least one diol, and at least one polyol in the presence of a) at least one primary antioxidant; and b) at least one secondary antioxidant to produce a polyester elastomer having a Tg less than 0°C, and 3) contacting the rigid polyester with the polyester elastomer and at least one chain extending additive to produce the polyester composition; wherein the polyester composition has a enthalpy of melting of 3 cal/gm or less.
  • polyesters and copolyesters of the present invention are readily prepared by methods well known in the art, for example, as described in U.S. Patent No. 2,012,267, incorporated herein by reference in its entirety. More particularly, the reactions for preparing the polyesters are usually carried out at temperatures of about 150° C to about 300° C in the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof.
  • polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyl tin diacetate, zinc chloride, or combinations thereof.
  • the primary antioxidant can be in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one rigid polyester, the primary antioxidant, and optionally the secondary antioxidant.
  • the secondary antioxidant can be in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one rigid polyester, the secondary antioxidant, and optionally, the primary antioxidant.
  • the primary antioxidant can in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one polyester elastomer, the primary antioxidant, and optionally, the secondary antioxidant.
  • the secondary antioxidant is in the form of a masterbatch concentrate; wherein the masterbatch concentrate comprises at least one polyester elastomer, the secondary antioxidant, and optionally, the primary antioxidant.
  • the amount of primary antioxidant and/or secondary antioxidant in a masterbatch concentrate is that which is sufficient to supply the level of antioxidant as previously described in this disclosure.
  • the fully compounded or prepared pellets can be processed using convention polymer processing methods, or concentrates of the above additives can be prepared and diluted with neat polyesters and copolyesters, to make sheet, film, injection molded articles, and blow molded articles, using conventional thermoplastic processing methods.
  • the compounded pellets can be subsequently ground and reduced in size at cryogenic temperatures.
  • the invention further relates to articles of manufacture comprising any of the polyester compositions described above.
  • the polyester compositions of this invention can have usefulness in multiple applications.
  • the polyester of the present invention is suitable for use in low shear polymer melt processes such as rotational molding, powder slush molding, powder coating and 3D printing processes.
  • the article of manufacture can comprise at least one light emitting diode (LED) assembly housing, or reflector.
  • the article of manufacture comprises at least one 3D powder or material used to make a different article of manufacture.
  • the article of manufacture is a molded or extruded article.
  • the article of manufacture is a fiber or a filament.
  • the article of manufacture is a film or sheet
  • Lower shear melt viscosities are very useful for 3-D printing applications where fast polymer flow from the rapid heat up of the polymer from a laser or infrared heat source is helpful to ensuring a well-formed and fused article.
  • HSS High Speed Sintering
  • SLS Selective Laser Sintering
  • powdered polyester compositions are heated using an infrared (IR) heat lamp to create useful objects or in the SLS process, a CO2 laser is used to heat the powders.
  • IR infrared
  • CO2 laser is used to heat the powders.
  • the powders are often held at very high temperatures just below their melting point for up to 24 hours to minimize the heat output from the IR lamp.
  • LED light emitting diodes
  • LEDs require materials of construction that can also survive for long periods of time without degrading or losing their efficacy in these applications.
  • Compounded plastic materials are used as reflector materials in the construction of LEDs both to provide control over the direction of emitted light as well as to protect the actual diode from damage.
  • These compounded plastic materials can be thermoplastic or thermoset based on the needs of the LED in the application. For example, high power LEDs, with energy input requires >1.0 watts typically use thermoset materials due to the heat generated in use. Lower wattage LEDs can use thermoplastic materials that can be injection molded. These injection molded materials are cheaper to process and can include a range of conventional materials.
  • thermoplastic materials are dimensionally stable during the soldering process. This requires that material to be semi-crystalline with a crystalline melting point in excess of 280°C.
  • these molded thermoplastic parts reflect the LED light from the diode, they can provide high reflectivity during the lifetime of the application. Low color and high color stability, measured via color measurements as described herein, before and after aging, is often used as a proxy for reflectivity. In certain embodiments, these parts also have high mechanical properties because they protect the diode from damage and survive various processing steps without breaking. The properties of reflectivity and high mechanical strength can be improved by compounding various base resin with other additives.
  • PCT Due to the high demands of the thermoplastic materials in these applications, PCT is currently used in large amounts for the thermoplastic LED applications. PCT has a crystalline melting point of 285°C and is manufactured carefully to produce a material with very low color (high reflectivity). PCT can be compounded with titanium dioxide and glass fiber along with various stabilizers and additives to optimize the performance of this material in these applications.
  • US Patent Application 2007/0213458 discloses the use of PCT compounds in Light-Emitting Diode Assembly Housings.
  • thermoplastic resin undergoes thermal and shear induced degradation. Additionally, waste material that is not converted into usable parts should be recycled to reduce to overall cost of the material. For these reasons, the compounded thermoplastic material much be stable to processing without significant loss of the original performance. Additionally, the molded parts should maintain high reflectivity and high mechanical strength throughout the lifetime of the application, which in the case of LEDs, could be as long as 20+ years.
  • This invention describes an optimized combination of additives that improves the process robustness of the compounded PCT resins. Improvements in reflectivity are measured via color and color stability using the color measurement as described herein. Reprocessability is measured via inherent viscosity (IV) before and after an extrusion or processing step.
  • the invention further relates to articles of manufacture comprising any of the polyester compositions described above.
  • the methods of forming the polyester compositions into articles of manufacture, fibers, films, molded articles, containers, and sheeting are well known in the art.
  • the polyester compositions are useful in articles of manufacture including, but not limited to, fibers, filaments, films, sheets, containers, extruded, calendered, and/or molded articles including, but not limited to, injection molded articles, extruded articles, cast extrusion articles, profile extrusion articles, melt spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded articles.
  • polyester compositions useful in the invention may be used in various types of film and/or sheet, including but not limited to extruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s), compression molded film(s) and/or sheet(s), solution casted film(s) and/or sheet(s).
  • Methods of making film and/or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.
  • the polymer compositions and/or polymer blend compositions can be useful in forming fibers, films, light diffusing articles, light diffusing sheets, light reflecting articles, light reflecting sheets, light emitting diodes, 3D powders or other materials, 3D articles containing powders or other materials.
  • the extruded sheet can be further modified using typical fabrication techniques such as thermoforming, cold bending, hot bending, adhesive bonding, cutting, drilling, laser cutting, etc. to create shapes useful for application as light reflectors and/or light diffusers.
  • the light reflector article comprising the polymer compositions of the invention can comprise at least one inorganic light reflecting additive, for example, titanium dioxide, barium sulfate, calcium carbonate or mixtures thereof.
  • Other end-use applications that can employ the polyester compositions of the invention include but are not limited to: (1) membrane backing. It can be a film or a woven or nonwoven (wetlaid or melt blown/melt spun) mat.
  • spun-laid nonwoven webs using processes well known in the art such as meltblowing and spun bond processes, wherein the continuous PCT fiber is spun from a pellet and laid into a nonwoven fabric in a single processing step; dry-laid or wet-laid nonwoven webs using processes well known in the art such as carding or air-laid processes, wherein PCT fiber is first spun in one process, chopped into staple fiber and laid into nonwoven fabric in a secondary step, using dry-laying technologies;
  • Such nonwoven webs can be useful for air and liquid filtration media, particularly those filtration applications which are routinely exposed to high temperatures (80- 200 C) or corrosive chemicals.
  • Wet laid webs is a common method for producing filtration media.
  • Machine clothing comprising monofilament, multifilament fibers, films or sheet, with improved thermal stability over existing PCT, PCT copolymers and additive formulations, to enable use in high temperature manufacturing environments, including for example belts used in the dryer section of paper and tissue making processes.
  • Dry-laid media can include high temperature and/or chemically resistant bag house filters and variation thereof used to capture pollutants, such as those in in coal burning power plants, and various manufacturing processes. Certain embodiments would include using the polyester compositions of the invention in film application. Film substrates with enhanced stability to high temperature processes and use conditions.
  • High temperature processes may include variations of lead free soldering processes on films requiring good registration, flexibility, and/or optical clarity, as standalone or part of a multilayer system that may include inks, coatings, and/or other functionality.
  • the abbreviation "wt” means "weight”.
  • the inherent viscosity of the polymers, for example, the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.
  • a process of making a polyester coated article comprising coating an article with a polyester composition to produce the polyester coated article; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less.
  • a process to coat a surface comprising : a. providing the polyester composition in powdered form to produce a powdered polyester composition; b. spreading the powdered solid polyester composition onto a surface; c. heating the powdered polyester composition to form a molten polyester coating; and d. cooling the molten polyester coating to form a solid polyester coating.
  • a process to coat a metal article comprising: a. providing the polyester composition in powdered form to produce a powdered polyester composition; b. Spreading the powdered solid polyester composition onto a metal surface; c. Heating the powdered polyester composition on the metal surface to form a molten polyester coating; and d.
  • a process of manufacturing a molded article comprising: 1. placing a polyester composition in a mold having mold surfaces; wherein the polyester composition comprises a) at least one rigid polyester; b) at least one polyester elastomer; c) at least one primary antioxidant; d) at least one secondary antioxidant; and e) at least one chain extending additive; wherein the composition has a enthalpy of melting of 3 cal/gm or less; 2. heating the polyester composition until it becomes molten; 3. dispersing the molten polyester composition to cover the mold surfaces; 4.
  • pellets were then injection molded into 4” x 4” x .125” plaques and 0.125” tensile and flexural bars on a BOY 22 injection molding machine. Barrel temperature was set at 240 °C, mold at 70°C, injection pressure was set at 80 bar, cooling was set for 25 seconds, and ejection force was set at 125 bar. Samples for powder coating were prepared by cryogenically grinding pellets of each formulation in an attrition mill with liquid nitrogen until a particle size of approximately 100 to 150 microns was achieved. This powdered material was then spray coated using an electrostatic coating applicator to cold rolled steel panels. The panels were then heated above the melting point of each formulation to form a film on each panel.
  • the hot stage microscope method is a method developed to monitor the visual changes in a material with a microscope as the material is subjected to increased temperatures.
  • the system was designed around an existing stereo microscope, the Nikon SMZ1000.
  • a Point Grey Research Flea3 color camera was used to capture images from the microscope’s objective.
  • the camera has a 1/1.8 inch CCD sensor with 1928x1448 pixel resolution with a 3.69 ⁇ m pixel size.
  • a 1” CCD C-mount adapter from SPOT Imaging Solutions was used to combine the camera with the microscope.
  • a Linkam DSC 600 hot stage system was used for controlling heating and cooling cycles during experiments. Additionally, a fiber optic halogen lamp system was used for sample illumination.
  • Sample dimension The standard ASTM D 2240 type specimen shall be a minimum of 6.0 mm thick
  • Relative Humidity The samples were conditioned in the PCL (Lab 118) at a temperature of 73 ⁇ 2 o F and relative humidity of 50 ⁇ 5 % for 40 hours according to ASTM D- 618 "Standard Practice for Conditioning Plastics for Testing”. Instrumentation: he Rex Durometer Model OS-I Stand Type D was used.
  • ASTM D256 Notched IZOD & ASTM D4812 Unnotched IZOD Notched & Unnotched IZOD Test The test specimen is cut from either a molded flex or tensile bar, and loaded into the cantilever beam for impact.
  • the sample consisted of a flex or tensile bar cut to a standard 2.50 +/- 0.08 in x .500 +/- 0.008 in, with a width between 0.118 – 0.500 in (typically 0.125 in), and if notched IZOD is requested “notched” to a depth of 10.16 +/- 0.05 mm in the center of the bar. This was verified using a calibrated Mitutoyo micrometer.
  • the notch angle is 22.5 o +/- 0.5 o on either side of the vertex, and the radius of the notch is cut to 0.25R +/- 0.05.
  • Relative Humidity The samples were conditioned in the PCL Lab 136 at a temperature of 73 ⁇ 2 o F and relative humidity of 50 ⁇ 5 % for 40 hours according to ASTM D- 618 "Standard Practice for Conditioning Plastics for Testing”. Instrumentation: Testing Machines Incorporated (TMI) Cantilever beam IZOD impact instrument, using custom software to acquire data. At least five specimens were tested for each sample to obtain both the “break type” average as well as a total average. Definitions Non-break – A break that presents with greater than 10% of the specimen width remaining at the break. Partial – A break that presents with less than 10% of the specimen width remaining at the break, and able to support itself above a 90 o axis.
  • Sample dimension The standard ASTM D 790 type specimen shall be 3.175 mm (1/8 in.) thick, 12.7 mm (0.5 in.) wide, and 130 mm (5 in.) long Relative Humidity: The samples were conditioned at a temperature of 73 ⁇ 2 o F and relative humidity of 50 ⁇ 5 % for 40 hours according to ASTM D-618 "Standard Practice for Conditioning Plastics for Testing”. Instrumentation: The Instron frame used Bluehill 3 and TestMaster 2 Software. Five specimens were tested for each sample to obtain an average value. The samples were tested at a span length of 2 inches with a speed of 0.05 inches/minute. Each sample was flexed to 5.5% strain. Glass Transition Temperature Data Glass transition temperatures were measured using ASTM D3418- 15.
  • sample 1 was combined with liquid nitrogen in a stainless steel beaker and the chilled material was fed into the grinder under the same conditions as the first test.
  • the material was easier to pulverize but was still too coarse for electrostatic spray.
  • the ring sieve was swapped to one with 0.75mm openings and the process was repeated.
  • the pulverized material was passed through an 80 mesh (180 ⁇ m) screen and the fine powder was used to spray test panels. This process was repeated for the remainder of the thermoplastic samples.
  • Electrostatic Application and Bake The powder was sprayed on bare cold rolled steel (QD-46) and Bonderite 1000 pre-treated cold rolled steel (R-46-I) test panels using a Nordson Encore electrostatic spray gun. The powder applied readily to the substrate.
  • compositions 4, 7, and 9 did not appear to fully melt at 230°C and were reintroduced to the oven for 10 minutes at 250°C.
  • Adhesion was evaluated per the ASTM 3359 crosshatch adhesion and tape pull test. Impact resistance was measured using a Gardner impact tester using ASTM D2794.
  • Salt Fog The coated metal panels were scribed with an “X” were exposed in a Q-Fog salt fog spray tester at 35 C and tested per ASTM B117 and removed periodically and visually inspected for appearance, blister size and blister frequency per ASTM D714, face rust per ASTM D610 and scribe rust per ASTM D1654.
  • Tensile Properties Samples were injection molded to a thickness of 3 mm into large tensile bars (Type I) and tested per ASTM D638. ⁇ Color, Light Transmission and Haze Samples of each composition were injection molded into 4” x 4” x 3mm plaques and measured for light transmission and haze per ASTM D 1003 and color difference per ASTM D2244.
  • blends of rigid and flexible copolyesters incorporating an antioxidant package can be suitable for applications requiring polymers in a powdered form that are processed at high temperatures and low shear.
  • Critical attributes for a powder coated article can include good adhesion to a substrate, good impact resistance, good corrosion resistance, low temperature processing, good thermal stability, and good low shear flow properties. Good adhesion is important in many cases and applications so the coating will not flake or chip off the substrate. This can also be related to good impact and corrosion resistance because if interfacial adhesion is compromised, corrosive liquids could infiltrate under the coating and cause corrosion and cause low impact strength and brittle failures during impact by not conforming and deforming.
  • Low temperature processing is important for saving energy during processing and decreasing cycle times.
  • Good thermal stability is important as materials could be at elevated temperatures close to their melting point for multiple hours or at highly elevated temperatures to allow them to flow and coalesce from a powder to “liquid” state to form a continuous film. This can be accomplished by incorporating a robust antioxidant system to prevent thermal oxidative degradation and decrease of molecular weight.
  • the present invention solves many of these problems and can be illustrated by the following examples. Table 2 contains data which supports the below observations. An antioxidant system is incorporated into examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 11. The importance of this will be shown in the other tests. Good melt or flow at is illustrated in examples 1, 2, 3, 6, 7, 9, 10, 11 as they melt and flow at 240 C or less in the hot stage melt test.
  • example 1 having good corrosion resistance which indicates some degree of adhesion, but the lack of thermal stability caused the material to not adhere to the metal panel and fracture due to polymer degradation.
  • examples 2, 3, 6, 10 and 11 which contain an antioxidant package, have the combination good low shear melt flow, good corrosion resistance, and good impact resistance.
  • Good corrosion resistance and good impact resistance indicate good interfacial adhesion.
  • the rigid portion of the composition is agnostic of polymer structure and chemistry; as long as the final attributes of good low shear melt flow, good corrosion resistance and good impact resistance are achieved, the composition can be characterized by a heat of fusion of 3 cal/gm or less. This is unexpected and inventive.
  • Polyester Compositions 1 Tritan® TX2000 amorphous polyester obtained from Eastman Chemical Company. 2 Tritan® TX1000 amorphous polyester obtained from Eastman Chemical Company. 3 Polyester 1 polydimethylcyclohexanedicarboxylatecyclohexanedimethanol obtained from __. 4 PETG (GN071) – polyethylene terephthalate glycol copolyester GN071 obtained from Eastman Chemical Company. 5 PET (EN076) – Eastar EN076 polyethylene terephthalate copolyester obtained from Eastman Chemical Company 6 PCT (13319) – polycyclohexylenedimethylene terephthalate obtained from __________________.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un article moulé, le procédé consistant à : a) placer une composition de polyester dans un moule présentant des surfaces de moule ; la composition de polyester comprenant : 1) au moins un polyester rigide ; 2) au moins un élastomère de polyester ; 3) au moins un antioxydant primaire ; 4) au moins un antioxydant secondaire ; et 5) au moins un additif d'extension de chaîne ; ladite composition ayant une enthalpie de fusion inférieure ou égale à 3 cal/gm ; b) chauffer la composition de polyester jusqu'à ce qu'elle fonde ; c) disperser la composition de polyester fondu pour recouvrir les surfaces du moule ; d) solidifier le polyester fondu pour former un article moulé solide ; et e) retirer l'article moulé du moule.
PCT/US2022/033754 2021-06-17 2022-06-16 Procédé de fabrication d'articles moulés WO2022266300A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202163202607P 2021-06-17 2021-06-17
US63/202,607 2021-06-17

Publications (1)

Publication Number Publication Date
WO2022266300A1 true WO2022266300A1 (fr) 2022-12-22

Family

ID=84525852

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/033754 WO2022266300A1 (fr) 2021-06-17 2022-06-16 Procédé de fabrication d'articles moulés

Country Status (1)

Country Link
WO (1) WO2022266300A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118373962A (zh) * 2024-06-24 2024-07-23 华大化学集团有限公司 一种热塑性聚氨酯弹性体及制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050124779A1 (en) * 2003-12-04 2005-06-09 Shelby Marcus D. Shaped articles from cycloaliphatic polyester compositions
US20160137834A1 (en) * 2013-06-11 2016-05-19 Sk Chemicals Co., Ltd. Polymer resin composition having excellent chemical resistance
US20190144661A1 (en) * 2016-04-25 2019-05-16 Kao Corporation Polyester resin molding composition for damping materials
US20200157342A1 (en) * 2017-07-20 2020-05-21 Eastman Chemical Company Polymer compositions having improved properties of thermal stability, color, and/or flow
WO2020231778A1 (fr) * 2019-05-10 2020-11-19 Eastman Chemical Company Articles moulés recyclables à partir de mélanges de copolyesters et de pet recyclé
US20210155750A1 (en) * 2019-11-21 2021-05-27 Eastman Chemical Company Copolyesters for use in low shear melt applications

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050124779A1 (en) * 2003-12-04 2005-06-09 Shelby Marcus D. Shaped articles from cycloaliphatic polyester compositions
US20160137834A1 (en) * 2013-06-11 2016-05-19 Sk Chemicals Co., Ltd. Polymer resin composition having excellent chemical resistance
US20190144661A1 (en) * 2016-04-25 2019-05-16 Kao Corporation Polyester resin molding composition for damping materials
US20200157342A1 (en) * 2017-07-20 2020-05-21 Eastman Chemical Company Polymer compositions having improved properties of thermal stability, color, and/or flow
WO2020231778A1 (fr) * 2019-05-10 2020-11-19 Eastman Chemical Company Articles moulés recyclables à partir de mélanges de copolyesters et de pet recyclé
US20210155750A1 (en) * 2019-11-21 2021-05-27 Eastman Chemical Company Copolyesters for use in low shear melt applications

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118373962A (zh) * 2024-06-24 2024-07-23 华大化学集团有限公司 一种热塑性聚氨酯弹性体及制备方法

Similar Documents

Publication Publication Date Title
US11492484B2 (en) Polymer compositions having improved properties of thermal stability, color, and/or flow
JP5858979B2 (ja) ポリエステルエラストマーのための難燃性組合せ物、及びそれからなる難燃性成形押し出し物又は成形物
JP2008163334A (ja) ポリエステル系樹脂組成物及びプラスチック成形品
WO2022266292A1 (fr) Procédé de fabrication d'articles comprenant des compositions d'élastomère de polyester/polyester
JP2010018697A (ja) 熱可塑性エラストマ樹脂組成物およびその成形体
WO2022266300A1 (fr) Procédé de fabrication d'articles moulés
WO2022266297A1 (fr) Articles comprenant des compositions de polyester/élastomère polyester
WO2022266289A1 (fr) Procédé de fabrication de compositions de polyester/élastomère polyester
EP4355806A1 (fr) Compositions de polyester/élastomère polyester
WO2022266299A1 (fr) Procédé de fabrication de compositions élastomères de polyester/polyester
US20240352276A1 (en) Process of making articles comprising polyester/polyester elastomer compositions
US11629224B2 (en) Polymer compositions comprising crystalline polymers and a stabilizer composition
US20220049069A1 (en) Polymer compositions with improved weathering resistance
JP6042271B2 (ja) 反射材用ポリエステル樹脂組成物および反射板
JP2018168212A (ja) 熱可塑性エラストマー組成物
JP2014133810A (ja) 複合成形体用ポリエステルブロック共重合体樹脂組成物および複合成形体
JPH10287791A (ja) 帯電防止性アクリル系樹脂組成物およびその成形品
WO2024158786A1 (fr) Compositions de copolyester ignifuges
JP2012126832A (ja) 薄肉成形用ポリエステルブロック共重合体樹脂組成物及び成形体
JPH07304959A (ja) 難燃性ポリマ組成物および成形物品
JP2000053848A (ja) 熱可塑性ポリエステル樹脂組成物
JPH0853612A (ja) 難燃性芳香族ポリエステル樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22825801

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22825801

Country of ref document: EP

Kind code of ref document: A1