[go: up one dir, main page]

WO2025112572A1 - Compositions ignifuges à ténacité élevée de copolyester - Google Patents

Compositions ignifuges à ténacité élevée de copolyester Download PDF

Info

Publication number
WO2025112572A1
WO2025112572A1 PCT/CN2024/106937 CN2024106937W WO2025112572A1 WO 2025112572 A1 WO2025112572 A1 WO 2025112572A1 CN 2024106937 W CN2024106937 W CN 2024106937W WO 2025112572 A1 WO2025112572 A1 WO 2025112572A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolyester
mole
copolyester composition
polyester
residues
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/106937
Other languages
English (en)
Inventor
Shuai ZHOU
Narong An
Brandon Robert WILLIAMSON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical China Co Ltd
Original Assignee
Eastman Chemical China Co Ltd
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 China Co Ltd filed Critical Eastman Chemical China Co Ltd
Publication of WO2025112572A1 publication Critical patent/WO2025112572A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to the use of a combination of certain additives in certain copolyesters to improve the flame-retardant properties of the copolyester composition and to also have high impact strength, and high flexural and/or tensile modulus. More specifically, the present invention relates to the use of a non-halogenated flame retardant in certain copolyesters to improve the flame-retardant properties while having high impact resistance, and high flexural and/or tensile modulus.
  • Flame retardant materials are added to some polymers to improve flame resistance, particularly to meet specific fire standards such as UL94 V-2.
  • specific fire standards such as UL94 V-2.
  • the addition of flame-retardant materials in amounts sufficient to meet the fire standards may have a deleterious effect on certain physical properties of the copolyester containing an effective amount of the flame retardant materials.
  • the addition of many flame-retardant materials will not be able to meet fire standards of UL94 V-0 or better regardless of the amount utilized, let alone maintaining the necessary physical properties of the polymer composition.
  • Copolyesters can be flame retarded in a variety of means but these methods have some drawbacks.
  • Certain halogen compounds such as Dechlorane decabromodiphenyl oxide or decabromodiphenyl ether can be effective flame retardants, but may be objectionable in the marketplace due to potential concerns of bio-accumulation.
  • Other halogen compounds may not have the same objections, but may cause embrittlement when used at sufficient quantities to flame retard copolyesters.
  • Liquid phosphorous compounds such as triphenyl phosphite or triphenyl phosphate can flame retard copolyesters but at effective use levels, they plasticize and soften the copolyester thus reducing heat resistance to distortion.
  • Solid flame retardants in the melamine and phosphorous classes can be used individually as well, but in the past, the concentrations needed to achieve flame retardancy have made the copolyester brittle or reduced tensile strength properties.
  • Plastics used in many applications such as electronics applications, housings for handheld and stationary appliances, and housings or shells for handheld and stationary power tools all have flammability requirements specified in various codes or standards. These applications also have durability or physical property requirements in addition to flammability requirements.
  • an improved copolyester composition comprising an effective amount of a combination of certain copolyesters, non-halogenated flame retardants, impact modifiers and optionally reinforcing materials, that is useful for making articles such as films, sheets, molded parts, or profiles which exhibit good flame resistance while providing high impact strength, flexural and/or tensile modulus and maintaining other required physical properties.
  • additional improvements were found using certain impact modifiers, e.g., acrylic silicone polymer impact modifier, and certain silane modified silicate mineral reinforcing materials.
  • a copolyester composition that comprises:
  • the inherent viscosity of the copolyester is from 0.725 to 1.2, or 0.8 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C, and
  • weight % is based on the weight of the copolyester, wherein the total mole %of the dicarboxylic acid component is 100 mole %and the total mole %of the glycol component is 100 mole %;
  • copolyester composition has a UL 94 V-0 rating or better at 1.5mm or less.
  • the copolyester composition has a notched Izod impact strength of 200 Joules/m or greater, measured according to ASTM D256, and a tensile elongation at break of 25%or greater, or 50%or greater, or 100%or greater, measured according to ASTM D638.
  • the polymeric impact modifier is an acrylic silicon impact modifier.
  • the acrylic silicon impact modifier contains less than 90 wt%, or less than 80 wt%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 10%, less than 5%, or less than 3%acrylic content.
  • the acrylic silicon impact modifier is a core shell impact modifier.
  • the silicone content is in the core of the core shell impact modifier.
  • the acrylic content is in both the core and shell of the core shell impact modifier.
  • the acrylic content is in the shell of the core shell impact modifier.
  • the impact modifier is classified as non-reactive. In certain embodiments, the impact modifier component contains no ethylene acrylate glycidyl methacrylate (EA-GMA) .
  • the diacid component comprises 75 to 99.5, or 90 to 99.5, or 95 to 99.5 mole %residues of terephthalic acid and 0.5 to 25, or 0.5 to 10, or 0.5 to 5 mole%residues of isophthalic acid.
  • the glycol component comprises from 78 to 95 mole %cyclohexanedimethanol residues and from 5 to 22 mole %of 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol residues. In certain embodiments, the glycol component comprises from 78 to 95 mole %cyclohexanedimethanol residues and from 9 to 15, or 10 to 22, or 10 to 20, or 17 to 22 mole %of 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol residues.
  • the inherent viscosity of the copolyester is from 0.725 to 0.95, 0.75 to 0.95, or 0.80 to 1.0, or 0.80 to 0.95 dL/g. In embodiments, the inherent viscosity of the copolyester is from 0.82 to 1.0 dL/g, or 0.82 to 0.95 dL/g, or 0.85 to 1.0 dL/g, or 0.85 to 0.95 dL/g, or 0.88 to 1.0 dL/g, or 0.88 to 0.95 dL/g.
  • the polyester component further comprises at least one second copolyester, said at least one second copolyester comprising:
  • the inherent viscosity of the copolyester is from 0.5 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C, and
  • weight % is based on the weight of the copolyester, wherein the total mole %of the dicarboxylic acid component is 100 mole %and the total mole %of the glycol component is 100 mole %.
  • the polyester component comprises a blend of the at least one copolyester and the at least one second copolyester, wherein the at least one second copolyester is present in an amount from 1 to 40 wt%, or 1 to 35 wt%, based on the weight of the polyester component.
  • the inherent viscosity of the polyester component containing the blend of the at least one copolyester and the at least one second copolyester is from 0.725 to 0.90, or 0.725 to 0.85, or 0.73 to 0.90, or 0.73 to 0.85, or 0.74 to 0.90, or 0.74 to 0.85, or 0.55 to 0.85 dL/g.
  • the glycol component of the at least one second copolyester comprises from 60 to 95 mole %cyclohexanedimethanol residues and from 5 to 40 mole %of 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol residues. In certain embodiments, the glycol component comprises from 70 to 95 mole %cyclohexanedimethanol residues and from 5 to 30, or 10 to 30, or 15 to 30, or 20 to 30, or 15 to 25 mole %of 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol residues.
  • the glycol component comprises from 60 to 75 mole %cyclohexanedimethanol residues and from 25 to 40, or 30 to 40 mole %of 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol residues.
  • the at least one second copolyester has a Tg or HDT higher than that of the at least one copolyester. In embodiments, the at least one second copolyester has a Tg of 100°C or higher, or 105°C or higher, 110°C or higher. In embodiments, the at least one second copolyester has a Tg of 100 to 140°C, or 105 to 140°C, or 110 to 140°C, or 100 to 130°C, or 105 to 130°C, or 110 to 130°C, or 100 to 125°C, or 105 to 125°C, or 110 to 125°C.
  • the flame-retardant additive comprises an aluminum phosphinate containing compound. In certain embodiments, the flame retardant additive is an aluminum diethyl phosphinate.
  • the reinforcing filler material can be discrete particles (e.g., spherical, spheroidal, fiber, fibril and/or irregularly shaped particles) that disperse in the polymer matrix.
  • the reinforcing filler material is a mineral filler.
  • the reinforcing filler material is a silane modified silicate material.
  • the silane modified silicate mineral has an average length greater than 10 microns, or 12 microns or greater, or 14 microns or greater, or 16 microns or greater, and an aspect (Length: Diameter, or L: D) ratio of greater than 8: 1, or 9: 1 or greater, or 9.5: 1 or greater.
  • the silane modified silicate mineral has an average length in a range from 12 to 40 microns, or 12 to 30 microns, or 14 to 22 microns, or 16 to 20 microns.
  • the silane modified silicate mineral is a calcium metasilicate, e.g., wollastonite (or CaSiO 3 ) .
  • the silane modified silicate mineral is aminosilane modified.
  • the flame-retardant additive is present in an amount from 8 to 20 wt%, or 8 to 18 wt%, or 8 to 15 wt%of the copolyester composition.
  • the copolyester composition comprises the impact modifier component in an amount from greater than 3 to 10 wt%, or 4 to 9 wt%, or 4 to 8 wt%, or greater than 5 to 10 wt%.
  • the copolyester composition can (optionally) comprise a reinforcing material component in an amount from 0 to 30wt%, or 5 to 30 wt%, or 8 to 28 wt%, or 10 to 28 wt%, or 15 to 28 wt%, or 18 to 27 wt%, or 20 to 25 wt%.
  • the copolyester composition further comprises:
  • the silicone compatibilizer is liquid at 25°C.
  • the liquid silicone compatibilizer is an alkyl, epoxy, amino, methacryloyloxy, phenyl or alkyl-phenyl silicone resin that is liquid at 25°C.
  • the liquid silicone resin comprises hydroxy and/or cyclophenylmethicone groups.
  • the copolyester composition further comprises:
  • the one or more antioxidants comprises at least one primary antioxidant and/or at least one primary antioxidant.
  • the copolyester composition further comprises:
  • the copolyester composition does not include a drip suppressant additive.
  • the copolyester composition comprises a drip suppressant additive in an amount from 0.05 to 0.4 wt%, or 0.05 to 0.25 wt%, or 0.1 to 0.2 wt%.
  • the drip suppressant can comprise a fluoropolymer.
  • the fluoropolymer can include, but is not limited to, polytetrafluoroethylene (PTFE) , e.g., Teflon TM polytetrafluoroethylene.
  • the copolyester composition has a notched Izod impact strength of 200, 300, 400, 500, or 600 Joules/m or greater measured according to ASTM D256. In one embodiment, the copolyester composition exhibits 100%ductile behavior when tested according to ASTM D256.
  • the copolyester composition has a flexural modulus of 1800 MPa or greater, or 1900 MPa or greater, or 2000 MPa or greater, or 2100 MPa or greater, or 2500 MPa or greater, or 3000 MPa or greater, or 3500 MPa or greater, or 4000 MPa or greater, measured according to ASTM D790.
  • the copolyester composition has a tensile elongation at break of 25%or greater, or 50%or greater, or 75%or greater, or 100%or greater, or 120%or greater, or 140%or greater, measured according to ASTM D638. In embodiments, the copolyester composition has a tensile elongation at break of 25 to 150%, or 50 to 150%, or 75 to 150%, or 100 to 150%, or 120 to 150%, or 140 to 150%, measured according to ASTM D638.
  • an article that comprises a copolyester composition according to one or more of the embodiments, or a combination of any of the embodiments, described herein.
  • the article is in the form of a film, sheet, molded part, or profile.
  • the present invention provides a copolyester composition
  • a copolyester composition comprising a copolyester component, a flame retardant additive, an impact modifier component, and (optionally) a reinforcing material component in which the copolyester composition exhibits good flame retardancy, high impact strength, and high tensile and/or flexural modulus, as well as articles made therefrom, and methods of making the composition and articles.
  • the present invention involves the use of certain copolyesters, certain classes of flame-retardant additives, impact modifiers and (optional) reinforcing materials to improve both the flame retardant properties while providing relatively high impact and/or modulus properties.
  • the flame-retardant additive comprises a metal, e.g., aluminum phosphinate compound.
  • a flame retarded composition can be provided that possesses a flexural and/or tensile modulus of 1800 MPa or greater, or 2000 MPa or greater, or 2200 MPa or greater, or 2400 MPa or greater, or 2500 MPa or greater, or 3000 MPa or greater, or 3500 MPa or greater, or 4000 MPa or greater, or 4500 MPa or greater, measured according to ASTM D790.
  • the composition can also have a tensile elongation at break of 25%or greater, or 50%or greater, or 75%or greater, or 100%or greater, or 120%or greater, or 140%or greater, measured according to ASTM D638.
  • the composition can also have a notched Izod impact strength which is greater than about 200 Joules/m, or 300, or 400, or 500, or 600 Joules/m or greater, according to ASTM D256.
  • Flammability was determined using the Underwriters Laboratories test standard UL 94 vertical burning test. This test measures the ability of plastic part to extinguish the flame after ignition and its dripping behavior in response to a small open flame or radiant heat source under controlled laboratory conditions. This test uses a 13 mm wide by 126 mm long specimen which is held at one end in the vertical position and can be tested as a function of specimen thickness. A burner flame is applied to the free end of the specimen for two 10 second intervals separated by the time it takes for flaming combustion to cease after the first application. Duration of flame time, drip behavior, and whether the dripping sample ignites a piece of cotton under the sample are all recorded.
  • the combination of this data determines the UL 94 rating (most to least flammable: V-2, V-1, V-0, 5VB, and 5VA) .
  • a rating of V-0 or higher is preferred for select applications where plastics are in contact with power sources like batteries or have the potential for flame exposure.
  • UL 94 ratings are provided for a certain material at a certain sample thickness (for example, 0.8mm, 1.2mm, 1.5mm, 1.6mm, 3.0mm, or 3.2mm) .
  • thinner samples typically burn and/or drip more easily, resulting in lower ratings.
  • the UL 94 rating is V-0 or greater at a thickness of 3.2mm or lower, or 1.6mm or lower, or 1.5mm or lower, or 1.2mm or lower, or 1.0mm or lower, or 0.8mm or lower.
  • the copolyester composition has a UL 94 rating is V-0 or greater at a thickness of 1.5mm.
  • the metal phosphinate compound comprises a metal chosen from calcium, magnesium, aluminum, and/or zinc.
  • the metal phosphinate compound is an aluminum phosphinate.
  • the metal phosphinate is a metal dialkyl phosphinate.
  • the metal phosphinate is an aluminum dialkyl phosphinate.
  • the aluminum dialkyl phosphinate compound is aluminum diethyl phosphinate.
  • the metal phosphinate compound e.g., aluminum diethyl phosphinate
  • the metal phosphinate compound is present in an amount from 8 to 20 wt%, or 8 to 18 wt%, or 8 to 16 wt%, or 10 to 14 wt%of the copolyester composition.
  • the copolyester composition comprises a first metal phosphinate flame retardant and at least one additional second flame retardant that is different from the first metal phosphinate flame retardant.
  • the copolyester composition comprises two or more metal phosphinate flame retardants that are different from each other.
  • different flame retardant is meant chemically different and/or physically different.
  • a first aluminum diethyl phosphinate flame retardant having a first average particle size and a second aluminum diethyl phosphinate flame retardant having a second average particle size (that is different from the first average particle size) would be considered different flame retardants.
  • the particle size of the aluminum phosphinate compound can be described using the D (n) value. This value describes the particle diameter at (n) %of the cumulative distribution. For example, if D50 is 75 ⁇ m, then 50%of the particles are above 75 ⁇ m diameter and 50%of the particles are below 75 ⁇ m diameter. If D95 is 10 ⁇ m, then only 5%of the particles are above 10 ⁇ m diameter and 95%of the particles are below 10 ⁇ m diameter.
  • the particle size distribution can be measured using one of the many methods and instruments known in the art (especially sieving, laser diffraction) . Generally, incorporation of smaller particle size distributions of aluminum phosphinate have demonstrated increased toughness and lower notch sensitivity in these copolyester systems.
  • the aluminum phosphinate compound has a D50 value less than 100 ⁇ m, less than 75 ⁇ m, less than 50 ⁇ m, less than 30 ⁇ m, or less than 25 ⁇ m. In embodiments, the aluminum phosphinate compound has a D95 value less than 50 ⁇ m, less than 30 ⁇ m, less than 20 ⁇ m, or less than 10 ⁇ m. In embodiments, the aluminum phosphinate compound has a unimodal particle size distribution curve. In embodiments, the aluminum phosphinate compound exhibits a bimodal or multimodal particle size distribution curve, either as a result of blending multiple particle sizes or by selecting the manufacturing method to produce the bimodal or multimodal particle size distribution curve.
  • the aluminum phosphinate compound can be a commercially available product, such as OP 1240 or OP 935 (both from Clariant) .
  • the copolyester composition further comprises a small amount of a drip suppressant additive (as discussed herein) , but less than 1 wt%, or less than 0.5 wt%, or less than 0.25 wt%, or less than 0.1 wt%, or less than 0.05 wt%, or no flame-retardant synergist additive.
  • the copolyester composition does not include a drip suppressant additive.
  • a flame-retardant synergist can be used.
  • the flame-retardant synergist additive can include a phosphorus containing compound chosen from a phosphorus, nitrogen and/or sulfur containing compound; a phosphazene compound; an oligomeric phosphate ester; or combinations thereof.
  • Some examples of synergists can include a melamine polyphosphate (MPP) , liquid phosphorous compounds such as PhireGuard RDP and PhireGuard BDP, or other organophosphorus compounds, e.g., that contain phosphorus (V) with a double bond between P and N.
  • MPP melamine polyphosphate
  • V phosphorus
  • the impact modifier component comprises one or more polymeric impact modifiers.
  • Such compounds are generally in the form of elastomeric compounds or polymers which serve to absorb or dissipate the kinetic energy of an impact.
  • the impact modifier is in a dispersed phase with the copolyester being included in the continuous phase of the overall copolyester composition.
  • One example includes a core-shell polymer with a core comprised of a rubbery polymer, for example a core comprised of a silicone polymer or acrylic silicone copolymer and a shell comprised of an acrylic polymer or acrylic silicone copolymer.
  • the impact modifier component comprises an acrylic silicone polymer impact modifier.
  • the impact modifier component comprises an acrylic silicone polymer impact modifier and at least one additional impact modifier.
  • additional impact modifiers that can be included in the impact modifier component, in certain embodiments, include, various known graft copolymers, other core shell polymers, and block copolymers. These polymers may include at least one monomer selected from the group consisting of an alkene, an alkadiene, an arene, an acrylate, and an alcohol. (See, for example, EP 1,694,771B1) .
  • additional impact modifiers includes core-shell polymers with cores comprised of rubbery polymers and shells comprised of styrene copolymers (See, for example, US Patent No. 5,321,056, incorporated herein by reference. )
  • Other examples include core-shell and functional polyolefins such as those described in US 2014/0256848 A1, incorporated herein by reference. See also EP 2 139 948 B1.
  • the impact modifier component comprises an acrylic silicone impact modifier that is present in a dispersed phase in the composition.
  • the acrylic silicone impact modifier is a core-shell structure having a particle size (D50) in a range from 75 to 300 microns, 100 to 250 microns, or 100-200 microns.
  • the acrylic silicone impact modifier is a core-shell structure having an average particle size in a range from 650 to 1000 microns, or 700 to 950 microns, or 750 to 900 microns, or 800 to 900 microns.
  • the core-shell acrylic silicone impact modifier has a specific gravity in the range of 0.85 to 1.2 g/cm3, or 0.9 to 1.15 g/cm3, or 0.9 to 1.1 g/cm3. In embodiments, the core-shell acrylic silicone impact modifier has a bulk density in the range of 0.25 to 0.45 g/cm3, or 0.30 to 0.40 g/cm3. In embodiments, the acrylic silicone impact modifier contains less than 90 wt%, or less than 80 wt%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 20%, or less than 10%, less than 5%, or less than 3%acrylic content. In embodiments, the acrylic content is in the shell of the core-shell impact modifier. In embodiments, the acrylic content is in both the core and shell of the core shell impact modifier.
  • the impact modifier component comprises an acrylic silicone polymer impact modifier in an amount from about 3 to about 10 wt%, or 3 to 9 wt%, or 4 to 8 wt%, or 5 to 7 wt%, based on the total copolyester composition.
  • the copolyester composition contains less than 5 wt%, or less than 3 wt%, or less than 1 wt%of any other impact modifiers, based on the total weight of the copolyester composition.
  • the impact modifier component is an acrylic silicone polymer impact modifier and the copolyester composition contains no other impact modifiers.
  • the acrylic silicon impact modifier is a core shell impact modifier.
  • the silicone content is in the core of the core shell impact modifier.
  • the acrylic content is in both the core and shell of the core shell impact modifier.
  • the acrylic content is in the shell of the core shell impact modifier.
  • the impact modifier is classified as non-reactive.
  • the impact modifier component contains no ethylene acrylate glycidyl methacrylate (EA-GMA) .
  • the acrylic silicone impact modifier comprises a silicone/acrylic acid rubber with grafted maleic anhydride (MA) groups.
  • acrylic silicone polymer impact modifiers include: Kane MR-01, MR-02, MR-03 or MR-502, available from Kaneka Americas Holding, Inc., Metablen S-2100, S-2501 and S2200, available from Mitsubishi Chemical, BX IM 230, available from Baoxu Chemical, and TFL-205HC impact modifier, available from Eversun Polycarnate Sci&Tech Co., LTD.
  • additional impact modifiers include, but are not limited to, ethylene/propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and/or glycidyl methacrylate; styrene-based block copolymeric impact modifiers, and various acrylic core/shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition.
  • Kane M300 available from Kaneka Americas Holding, Inc.
  • Kane B564 available from Kaneka Americas Holding, Inc.
  • Kane ECO 1000 available from Kaneka Americas Holding, Inc.
  • Kane M722 available from Kaneka Americas Holding, Inc.
  • SOG-03 available from Fine-Blend Polymer (Shanghai) Co., LTD
  • TFL-205HC available from Guangdong Evergreen Chemical Co. LTD
  • MR-03 available from Kaneka Americas Holding, Inc.
  • 8900 available from Arkema.
  • the impact modifiers utilized as component (c) are generally present in an amount of about 3 to about 10 percent by weight. In other embodiments, they are present in amounts of about greater than 3 to 10 wt%, or 4 to 10 wt%, or 5 to 10 wt%, or greater than 5 to 10 wt%, or 6 to 10 wt%, or 3 to 9 wt%, or greater than 3 to 9 wt%, or 4 to 9 wt%, or 5 to 9 wt%, or greater than 5 to 9 wt%, or 6 to 9 wt%, or 3 to 8 wt%, or greater than 3 to 8 wt%, or 4 to 8 wt%, or 5 to 8 wt%, or greater than 5 to 8 wt%, or 6 to 8 wt%, or 3 to 7 wt%, or greater than 3 to 7 wt%, or 4 to 7 wt%, or 5 to 7 wt%, or greater than 5 to 7 wt%.
  • the flame retardant (FR) and impact modifier (IM) are present in the copolyester composition in a weight ratio of FR: IM greater than: 1: 1, or 1.1: 1, or 1.25: 1, or 1.4: 1, or 1.5: 1, or 1.75: 1, or 2: 1, or 2.25: 1, or 2.5: 1, or 2.75: 1, or 3: 1, or 3.25: 1, or 3.5: 1, or 3.75: 1, or 4: 1.
  • the weight ratio of FR: IM is in a range from 1.1 to 4.5: 1, or 1.4 to 4.5: 1, or 1.5 to 4.5: 1, or 2 to 4.5: 1, or 2.5 to 4.5: 1, or 3 to 4.5: 1, or 3.5 to 4.5: 1, or 1.1 to 4.25: 1, or 1.4 to 4.25: 1, or 1.5 to 4.25: 1, or 2 to 4.25: 1, or 2.5 to 4.25: 1, or 3 to 4.25: 1, or 3.5 to 4.25: 1, or 1.1 to 4: 1, or 1.4 to 4: 1, or 1.5 to 4: 1, or 2 to 4: 1, or 2.5 to 4: 1, or 3 to 4: 1, or 3.5 to 4: 1, or 1.1 to 3.5: 1, or 1.4 to 3.5: 1, or 1.5 to 3.5: 1, or 2 to 3.5: 1, or 3.5 to 4.5: 1, or 3 to 3.5: 1, or 1.1 to 3: 1, or 1.4 to 3: 1, or 1.5 to 3: 1, or 2 to 3: 1, or 2.5 to 3: 1, or 1.1 to 2.5: 1, or 1.4 to 3: 1,
  • the FR is an aluminum phosphinate, e.g., aluminum diethyl phosphinate
  • the IM is an acrylic silicone polymer, e.g., a core-shell acrylic silicone polymer.
  • such FR and IM are present in one or more of the ratios discussed above.
  • the silane modified silicate mineral has an average length greater than 10 microns, or 12 microns or greater, or 14 microns or greater, or 16 microns or greater, and an aspect (Length: Diameter, or L: D) ratio of greater than 8: 1, or 9: 1 or greater, or 9.5: 1 or greater.
  • the silane modified silicate mineral has an average length in a range from 12 to 40 microns, or 12 to 30 microns, or 14 to 22 microns, or 16 to 20 microns.
  • the silane modified silicate mineral is a calcium metasilicate, e.g., wollastonite (or CaSiO 3 ) .
  • the silane modified silicate mineral is aminosilane modified.
  • the copolyester composition comprises the reinforcing material component in an amount from greater than 0 to less than 30 wt%, or 6 to 28 wt%, or 8 to 26 wt%, or 10 to 25 wt%, or 15 to 25 wt%, or 18 to 25 wt%, or 20 to 25 wt%, based on the total weight of the copolyester composition.
  • the reinforcing material component consists essentially of, or consists of a silane modified silicate material.
  • silane modified silicate minerals include: WLA-18 and WLA-6 aminosilane modified wollastonite, available from Muheng Material Technology (Shanghai) Co., Ltd, and Wollastokup, available from Malvern Minerals Company.
  • Copolyesters useful in the present invention comprise residues of an aromatic diacid and residues of two or more glycols.
  • copolyester as used herein, 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.
  • glycol as used in this application includes, but is not limited to, diols, glycols, and/or multifunctional hydroxyl compounds.
  • the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid
  • the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone.
  • reduce, as used herein, means any organic structure incorporated into a polymer through a polycondensation and/or an esterification reaction from the corresponding monomer.
  • the term “repeating unit, ” as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group.
  • the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including 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.
  • terephthalic acid is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester.
  • modifying aromatic diacid means an aromatic dicarboxylic acid other than terephthalic acid.
  • modifying glycol means a glycol other than cyclohexanedimethanol (CHDM) or 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol (TMCD) .
  • terephthalic acid may be used as the starting material.
  • dimethyl terephthalate may be used as the starting material.
  • mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and/or as an intermediate material.
  • the copolyesters 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 copolyester polymer as their corresponding residues.
  • the copolyesters of the present invention therefore, can contain substantially equal molar proportions of acid residues (100 mole%) and diol (and/or multifunctional hydroxyl compounds) residues (100 mole%) such that the total moles of repeating units is equal to 100 mole%.
  • the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a copolyester containing 30 mole%isophthalic acid means the copolyester contains 30 mole%isophthalic acid residues out of a total of 100 mole%acid residues. Thus, there are 30 moles of isophthalic acid residues among every 100 moles of acid residues.
  • a copolyester containing 30 mole%1, 4-cyclohexanedimethanol means the copolyester contains 30 mole%1, 4-cyclohexanedimethanol residues out of a total of 100 mole%diol residues. Thus, there are 30 moles of 1, 4-cyclohexanedimethanol residues among every 100 moles of diol residues.
  • the polyester component comprises a copolyester that comprises 70 to 99.5 mole %of terephthalic acid (TPA) and 0.5 to 30 mole%of isophthalic acid (IPA) .
  • the copolyester can comprise 80 to 99.5 mole %TPA, or 90 to 99.5 mole %TPA or 95 to 99.5 mole %TPA or 100 mole %TPA.
  • the dicarboxylic acid component of the copolyester useful in the invention can comprise up to 30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or up to 1 mole %of one or more modifying aromatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole %modifying aromatic dicarboxylic acids.
  • modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 30 mole %, 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole %and from 0.01 to 1 mole.
  • modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical.
  • modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, 4, 4'-biphenyldicarboxylic acid, 1, 4-, 1, 5-, 2, 6-, 2, 7-naphthalenedicarboxylic acid, and trans-4, 4'-stilbenedicarboxylic acid, and esters thereof.
  • the carboxylic acid component of the copolyesters 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. Certain embodiments can also comprise 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole %of one or more modifying aliphatic dicarboxylic acids.
  • Yet another embodiment contains 0 mole %modifying aliphatic dicarboxylic acids.
  • the amount of one or more modifying aliphatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, from 0.01 to 10 mole %and from 0.1 to 10 mole %.
  • the total mole %of the dicarboxylic acid component is 100 mole %.
  • esters of terephthalic and isophthalic acids and the other modifying dicarboxylic acids or their corresponding esters and/or salts may be used instead of the dicarboxylic acids.
  • Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters.
  • the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.
  • the copolyesters useful in the copolyester compositions of the invention can comprise from 0 to 10 mole %, for example, from 0.01 to 5 mole %, from 0.01 to 1 mole %, from 0.05 to 5 mole %, from 0.05 to 1 mole %, or from 0.1 to 0.7 mole %, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof.
  • the branching monomer or agent may be added prior to and/or during and/or after the polymerization of the polyester.
  • the copolyester (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, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid and the like.
  • the branching monomer residues can comprise 0.1 to 0.7 mole %of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1, 2, 6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesic acid.
  • the branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Patent Numbers 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.
  • the CHDM can be 1, 4-cyclohexanedimethanol.
  • the 1, 4-cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example a cis/trans ratio of 60: 40 to 40: 60.
  • the trans-1, 4-cyclohexanedimethanol can be present in an amount of 60 to 80 mole %.
  • 1, 2-and/or 1-3-cyclohexanedimethanol may be used individually or in combination with each other and/or 1, 4-cyclohexanedimethanol.
  • the glycol component of the copolyester portion of the copolyester composition useful in the various embodiments can contain modifying glycols which are not CHDM or TMCD; in one embodiment, the copolyesters useful in the invention may contain less than 15 mole %, or 10 mole %or less, of one or more modifying glycols.
  • Modifying glycols useful in the copolyesters useful in embodiments refer to diols other than other than CHDM or TMCD and may contain 2 to 20, or 2 to 16, carbon atoms.
  • suitable modifying glycols include, but are not limited to, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol, isosorbide or mixtures thereof.
  • the modifying glycols are 1, 3-propanediol and/or 1, 4-butanediol.
  • the copolyester composition comprises at least one polyester, which comprises:
  • the inherent viscosity of the polyester is from 0.725 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.; and wherein the polyester has a Tg of from 100 to 200°C.
  • the polyester component comprises a blend of the at least one copolyester and the at least one second copolyester, wherein the at least one copolyester comprises:
  • the inherent viscosity of the copolyester is from 0.8 to 1.2, or 0.85 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.
  • the at least one second copolyester contained in the blend comprises:
  • the inherent viscosity of the polyester is from 0.35 to less than 0.80, or 0.35 to 0.75 dL/g as determined in 60/40 (wt/wt)
  • the dicarboxylic acid component comprises 100 mole %of terephthalic acid residues.
  • the copolyester composition comprising the polyester component, which comprises the blend of the at least one copolyester and at least one second copolyester, has an IV higher than the IV of the at least one second copolyester (as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C) .
  • the copolyester composition comprising the polyester component, which comprises the blend of the at least one copolyester and at least one second copolyester, has an HDT higher than the HDT of the at least one copolyester or higher than the HDT of a similar copolyester composition comprising only the at least one copolyester.
  • the polyester composition comprises at least one second polyester, which comprises:
  • the inherent viscosity of the polyester is from 0.35 to 0.85 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.; and wherein the polyester has a Tg of from 120 to 140°C.
  • the polyester composition comprises at least one second polyester, which comprises:
  • the inherent viscosity of the polyester is from 0.35 to 0.85 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.; and wherein the polyester has a Tg of from 100 to 140°C.
  • the polyester composition comprises at least one second polyester, which comprises:
  • the inherent viscosity of the polyester is from 0.1 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.; and wherein the polyester has a Tg of from 100 to 200°C.
  • any one of the polyesters or polyester compositions described herein can further comprise residues of at least one branching agent. In embodiments, any one of the polyesters or polyester compositions described herein can comprise at least one thermal stabilizer or reaction products thereof.
  • the polyesters can contain less than 15 mole %ethylene glycol residues, such as, for example, 0.01 to less than 15 mole %ethylene glycol residues.
  • the polyesters useful in the invention contain less than 10 mole %, or less than 5 mole %, or less than 4 mole %, or less than 2 mole %, or less than 1 mole %ethylene glycol residues, such as, for example, 0.01 to less than 10 mole %, or 0.01 to less than 5 mole %, or 0.01 to less than 4 mole %, or 0.01 to less than 2 mole %, or 0.01 to less than 1 mole %, ethylene glycol residues.
  • the polyesters useful in the invention contain no ethylene glycol residues
  • the glycol component for the polyesters can include but is not limited to at least one of the following combinations of ranges: 5 to less than 35 mole %2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and greater than 65 up to 95 mole %1, 4-cyclohexanedimethanol; 5 to less than 30 mole %2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and greater than 70 up to 95 mole %1, 4-cyclohexanedimethanol; 5 to less than 25 mole %2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and greater than 75 up to 95 mole %1, 4-cyclohexanedimethanol; 10 to 35 mole %2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and 65 to 90 mole %1, 4-cyclohexanedimethanol; 10 to 30 mole %2, 2, 4, 4-tetramethyl-1, 3-cyclobutanedi
  • the glycol component of the polyester component of the polyester composition can contain 25 mole %or less of one or more modifying glycols which are not 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol or 1, 4-cyclohexanedimethanol; in one embodiment, the polyesters useful in the invention may contain less than 15 mole %of one or more modifying glycols. In another embodiment, the polyesters can contain 10 mole %or less of one or more modifying glycols. In another embodiment, the polyesters can contain 5 mole %or less of one or more modifying glycols. In another embodiment, the polyesters can contain 3 mole %or less of one or more modifying glycols.
  • the polyesters can contain 0 mole %modifying glycols. Certain embodiments can also contain 0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %, or 10 or more mole %of one or more modifying glycols. Thus, if present, it is contemplated that 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 in the polyesters can refer to diols other than 2, 2, 4, 4, -tetramethyl-1, 3-cyclobutanediol and 1, 4- cyclohexanedimethanol and may contain 2 to 16 carbon atoms.
  • suitable modifying glycols in certain embodiments include, but are not limited to, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, p-xylene glycol or mixtures thereof.
  • the modifying glycol is ethylene glycol.
  • the modifying glycols are 1, 3-propanediol and/or 1, 4-butanediol.
  • ethylene glycol is excluded as a modifying diol.
  • 1, 3-propanediol and 1, 4-butanediol are excluded as modifying diols.
  • 2, 2-dimethyl-1, 3-propanediol is excluded as a modifying diol.
  • the mole %of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol in certain polyesters is greater than 50 mole %or greater than 55 mole %of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol or greater than 70 mole %of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol; wherein the total mole percentage of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and trans-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol is equal to a total of 100 mole %.
  • the mole %of the isomers of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol in certain polyesters is from 30 to 70 mole %of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol or from 30 to 70 mole %of trans-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, or from 40 to 60 mole %of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol or from 40 to 60 mole %of trans-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, wherein the total mole percentage of cis-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol and trans-2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol is equal to a total of 100 mole %.
  • the polyesters can be amorphous or semi-crystalline. In one aspect, certain polyesters can have a relatively low crystallinity. Certain polyesters can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.
  • the Tg of the polyesters can be at least one of the following ranges: 100 to 200°C.; 100 to 190°C.; 100 to 180°C.; 100 to 170°C.; 100 to 160°C.; 100 to 155°C.; 100 to 150°C.; 100 to 145°C.; 100 to 140 °C.; 100 to 138°C.; 100 to 135°C.; 100 to 130°C.; 100 to 125°C.; 100 to 120°C.; 100 to 115°C.; 100 to 110°C.; 105 to 200°C.; 105 to 190°C.; 105 to 180°C.; 105 to 170°C.; 105 to 160°C.; 105 to 155°C.; 105 to 150°C.; 105 to 145°C.; 105 to 140°C.; 105 to 138°C.; 105 to 135°C.; 105 to 130°C.; 105 to 125°C.;;
  • the glass transition temperature (Tg) of the polyesters can be determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C. /min.
  • the polyesters contained in the copolyester composition or polyester component 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 25°C (alternatively, the IV of the polyesters can be determined by GPC from a sample of the copolyester composition which, in addition to the polyester (s) , contains additives as described herein) : 0.725 to 1.2 dL/g; 0.725 to 1.1 dL/g; 0.725 to 1 dL/g; 0.725 to less than 1 dL/g; 0.725 to 0.98 dL/g; 0.725 to 0.95 dL
  • the polyester compositions 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 polyester compositions 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 polyester compositions 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 molar ratio of cis/trans 2, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol can vary from the pure form of each or mixtures thereof.
  • the molar percentages for cis and/or trans 2, 2, 4, 4, -tetramethyl-1, 3-cyclobutanediol are greater than 50 mole %cis and less than 50 mole %trans; or greater than 55 mole %cis and less than 45 mole %trans; or 30 to 70 mole %cis and 70 to 30%trans; or 40 to 60 mole %cis and 60 to 40 mole %trans; or 50 to 70 mole %trans and 50 to 30%cis or 50 to 70 mole %cis and 50 to 30%trans; or 60 to 70 mole %cis and 30 to 40 mole %trans; or greater than 70 mole cis and less than 30 mole %trans; wherein the total sum of the mole percentages for cis-and trans-2,
  • polyester component of the copolyester compositions can be made by processes known from the literature such as, for example, by processes in homogenous solution, by transesterification processes in the melt, and by two phase interfacial processes. Suitable methods include those disclosed in U.S. Published Application 2006/0287484, the contents of which is incorporated herein by reference.
  • the polyester can be prepared by a method that includes reacting one or more dicarboxylic acids (or derivative thereof) with one or more glycols under conditions to provide the polyester including, but are not limited to, the steps of reacting one or more dicarboxylic acids (or derivative thereof) with one or more glycols at a temperature of 100°C to 315°C at a pressure of 0.1 to 760 mm Hg for a time sufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methods of producing polyesters, the disclosure regarding such methods is hereby incorporated herein by reference.
  • the polyester composition can be a polymer blend, wherein the blend comprises: (a) 5 to 95 wt %of at least one of the polyesters or the blend of the at least one copolyester and at least one second copolyester as described herein; and (b) 5 to 95 wt %of at least one polymeric component.
  • polymeric components include, but are not limited to, nylon, polyesters different from those described herein, e.g., polyethylene or polybutylene terephthalate (PET or PBT) , polycyclohexylenedimethylene terephthalate (PCT) , polycyclohexylenedimethylene terephthalate, acid modified, e.g., isophthalic acid (PCTA) , polycyclohexylenedimethylene terephthalate, glycol modified, e.g., ethylene glycol (PCTG) , polycyclohexane dimethanol terephthalate, diol modified (other than with EG) , e.g., modified with 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol (PCTM) , or polyethylene terephthalate, glycol modified, e.g., cyclohexanedimethanol (PETG) , polyamides such as from DuPont; polys
  • the blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.
  • the polycarbonate is not present in the polyester composition.
  • the polyester compositions useful in the invention also contemplate the exclusion of polycarbonate as well as the inclusion of polycarbonate.
  • the polyester component comprises a blend of the at least one copolyester and at least one second polyester that is different from the at least one copolyester.
  • the at least one second polyester is chosen from PCT, PCTA, PCTG, PCTM, PETG, or combinations thereof.
  • the polyester component comprises a blend of from 25 to 99 wt%of said at least one copolyester and 1 to 75 wt%of said at least one second polyester; or a blend of from 50 to 99 wt%of said at least one copolyester and 1 to 50 wt%of said at least one second polyester; or a blend of from 75 to 99 wt%of said at least one copolyester and 1 to 25 wt%of said at least one second polyester; based on the weight of the polyester component.
  • copolyester composition may further comprise one or more additional additives chosen from colorants, dyes, mold release agents, additional flame retardants, plasticizers, processing aids, rheology modifiers, nucleating agents, additional antioxidants, light stabilizers, fillers, and additional reinforcing materials.
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the component described herein) from 0.01 to 25%by weight of the overall composition common additives such as colorants, dyes, mold release agents, additional flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers and/or reaction products thereof, fillers, and additional impact modifiers.
  • UV additives can be incorporated into the articles (e.g., ophthalmic product (s) ) through addition to the bulk or in the hard coat.
  • 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 copolymeric impact modifiers, epoxide-functionalized impact modifiers, and various acrylic core/shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition. In one embodiment, the composition comprises an epoxide-functionalized impact modifier.
  • the polyester composition can comprise one or more UV stabilizers.
  • the one or more UV stabilizers are present in an amount from 0.1 to 5 wt%, or 0.1 to 3 wt%, or 0.1 to 2 wt%, or 0.2 to 5 wt%, or 0.2 to 3 wt%, or 0.2 to 2 wt%, or 0.4 to 5 wt%, or 0.4 to 3 wt%, or 0.4 to 2 wt%, based on the weight of the polyester composition.
  • the one or more UV stabilizers can be chosen from triazines, oxalanilides, cyanoacrylates, benzotriazoles, naphthalenes, benzophenones, and benzoxazine-4-ones, or combinations thereof.
  • the one or more UV stabilizers is chosen from a triazine UV absorber, an oxalanilide UV absorber, or a combination of these UV absorbers.
  • the one or more UV stabilizers is a combination of a triazine UV absorber and an oxalanilide UV absorber.
  • the triazine UV absorber and an oxalanilide UV absorber are each present in an amount from 0.1 to 2 wt%, or 0.1 to 1 wt%, or 0.2 to 2 wt%, or 0.2 to 1 wt%, or 0.4 to 2 wt%, or 0.4 to 1 wt%, or 0.4 to 0.8 wt%, based on the weight of the polyester composition.
  • suitable UV absorbers include Tiangang UV-630 triazine UV absorber, available from Beijing Tiangang Auxiliary, and Hostavin VSU P, or VSU P-S1000 oxalanilide UV absorber, available from Clariant.
  • the polyester compositions and the polymer blend compositions may contain fillers or additional reinforcing additives, such as glass (or other) fibers, in an amount from 1 to 45 wt%, or 1 to 40 wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 5 to 45 wt%, or 5 to 40 wt%, or 5 to 35 wt%, or 5 to 30 wt%, or 10 to 45 wt%, or 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 15 to 45 wt%, or 15 to 40 wt%, or 15 to 35 wt%, or 15 to 30 wt%, or 20 to 45 wt%, or 20 to 40 wt%, or 20 to 35 wt%, or 20 to 30 wt%, based on the total composition.
  • fillers or additional reinforcing additives such as glass (or other) fibers
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the components described herein and the fillers/reinforcing additives) from 0.01 to 25%, or 0.01 to 20%, or 0.01 to 15%, or 0.01 to 10%by weight of the overall composition other common additives, such as those discussed above.
  • the polyester compositions and the polymer blend compositions may contain colorants, such as pigments, e.g., carbon black or TiO 2 , in an amount from 1 to 40 wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 1 to 25wt%, or 5 to 40 wt%, or 5 to 35 wt%, or 5 to 30 wt%, or 5 to 25 wt%, or 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 10 to 25 wt%, or 15 to 40 wt%, or 15 to 35 wt%, or 15 to 30 wt%, or 15 to 25 wt%, or 20 to 40 wt%, or 20 to 35 wt%, or 20 to 30 wt%, or 20 to 25 wt%, based on the total composition.
  • colorants such as pigments, e.g., carbon black or TiO 2 , in an amount from 1 to 40
  • the polyester compositions and the polymer blend compositions may contain colorants, such as TiO 2 , in an amount from 0.1 to 15 wt%, or 0.1 to 10 wt%, or 0.1 to 8 wt%, or 0.1 to 6 wt%, or 0.5 to 15 wt%, or 0.5 to 10 wt%, or 0.5 to 8 wt%, or 0.5 to 6 wt%, or 1 to 15 wt%, or 1 to 10 wt%, or 1 to 8 wt%, or 1 to 6 wt%, or 2 to 15 wt%, or 2 to 10 wt%, or 2 to 8 wt%, or 2 to 6 wt%, or 5 to 15 wt%, or 5 to 10 wt%, or 8 to 15 wt%, or 10 to 15 wt%, based on the total composition.
  • colorants such as TiO 2
  • the polyester compositions and the polymer blend compositions may also contain (in addition to the components described herein and the colorants) from 0.01 to 25%, or 0.01 to 20%, or 0.01 to 15%, or 0.01 to 10%by weight of the overall composition other common additives, such as those discussed above.
  • the copolyester compositions of the present invention comprise a polyester composition comprising any of the copolyesters or blends described above, the flame retardant additive, the impact modifier component, and the (optional) reinforcing mineral component.
  • the copolyester composition further comprises:
  • the silicone compatibilizer is liquid at 25°C.
  • the liquid silicone compatibilizer is an alkyl, phenyl or alkyl-phenyl silicone resin that is liquid at 25°C.
  • the liquid silicone resin comprises hydroxy and/or cyclophenylmethicone groups.
  • the silicone resin e.g., a phenyl silicone resin
  • the phenyl silicone resin is an alkyl phenyl silicone resin, e.g., a methyl phenyl silicone resin or an octyl phenyl silicone resin.
  • the liquid methyl phenyl silicone resin has a phenyl/methyl molar ratio from 0.1/1.0 to 2.0/1.0, or 0.1/1.0 to 1.8/1.0, or 0.1/1.0 to 1.6/1.0, or 0.1/1.0 to 1.4/1.0, or 0.1/1.0 to 1.2/1.0, or 0.1/1.0 to 1.1/1.0, or 0.1/1.0 to 1.0/1.0, or 0.1/1.0 to 0.8/1.0, or 0.1/1.0 to 0.6/1.0, or 0.1/1.0 to 0.4/1.0, or 0.1/1.0 to 0.2/1.0, or 0.2/1.0 to 2.0/1.0, or 0.2/1.0 to 1.8/1.0, or 0.2/1.0 to 1.6/1.0, or 0.2/1.0 to 1.4/1.0, or 0.2/1.0 to 1.2/1.0,
  • the liquid silicone resin has a solids content of 90%or greater, or 95%or greater. Solids content can be determined by weight loss after heating to 120°C for 2 hours to drive off liquids.
  • the liquid silicone resin has a molecular weight (Mw) in a range from 1000 to 50000, or 1000 to 40000, or 1000 to 30000, or 1000 to 20000, or 1000 to 10000, or 1000 to 5000, or 2000 to 50000, or 2000 to 40000, or 2000 to 30000, or 2000 to 20000, or 2000 to 10000, or 2000 to 5000, 4000 to 50000, or 4000 to 40000, or 4000 to 30000, or 4000 to 20000, or 4000 to 10000, or 8000 to 50000, or 8000 to 40000, or 8000 to 30000, or 8000 to 20000, or 8000 to 15000, or 10000 to 50000, or 10000 to 40000, or 10000 to 30000, or 10000 to 20000, 20000 to 50000, or 20000 to 40000, or 10000 to 30000
  • silicone compatibilizers include: DOWSIL TM 40-001 and DOWSIL TM 4-7081, available from Dow Chemical Company.
  • the copolyester composition further comprises:
  • the copolyester compositions may contain one or more antioxidants in an amount from 0.01 to 2 wt%, or 0.01 to 1.5 wt%, or 0.01 to 1 wt%, or 0.01 to 0.75 wt%, or 0.01 to 0.5 wt%, or 0.01 to 0.4 wt%, or 0.01 to 0.3 wt%, based on the total composition.
  • the one or more antioxidants comprises at least one primary antioxidant and/or at least one secondary antioxidant. In certain embodiments, the one or more antioxidants comprises at least one primary antioxidant and at least one secondary antioxidant.
  • the at least one primary antioxidant and at least one secondary antioxidant can each be present in an amount from 0.01 to 1 wt%, or 0.01 to 0.9 wt%, or 0.01 to 0.8 wt%, or 0.01 to 0.7 wt%, or 0.1 to 1 wt%, or 0.1 to 0.9 wt%, or 0.1 to 0.8 wt%, or 0.1 to 0.7 wt%, or 0.1 to 0.6 wt%, or 0.1 to 0.5 wt%, or 0.2 to 1 wt%, or 0.2 to 0.9 wt%, or 0.2 to 0.8 wt%, or 0.2 to 0.7 wt%, or 0.2 to 0.6 wt%, or 0.2 to 0.5 wt%, or 0.3 to 1 wt%, or 0.3 to 0.9 wt%, or 0.3 to 0.8 wt%, or 0.3 to 0.7 wt%, or 0.3 to 0.6 wt%, or 0.1 to 0.5 w
  • the copolyester composition further comprises:
  • the drip suppressant can comprise a fluoropolymer.
  • the fluoropolymer can include, but is not limited to, polytetrafluoroethylene (PTFE) , e.g., Teflon TM polytetrafluoroethylene.
  • PTFE polytetrafluoroethylene
  • Commercial examples include FA5601 PTFE, available from Daikin Fluorochemicals (China) Co., Ltd. UN105, available from Union Chemical (Dongguan) CO., Ltd. FS-200, available from Han Nanotech CO., Ltd. Blendex 6530, available from Galata Chemicals.
  • Thermal stabilizers are compounds that stabilize polyesters during polyester manufacture and/or post polymerization, including, but not limited to, phosphorous compounds, including, but not limited to, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof.
  • the esters can be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers, aryl, and substituted aryl.
  • the number of ester groups present in the particular phosphorous compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the thermal stabilizer used.
  • the term “thermal stabilizer” is intended to include the reaction product (s) thereof.
  • reaction product refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive. In embodiments, these can be present in the polyester compositions.
  • additional reinforcing materials may be useful in the polyester compositions.
  • the additional reinforcing materials may include, but are not limited to, carbon filaments, additional silicates, mica, clay, talc, titanium dioxide, additional Wollastonite materials, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.
  • the additional reinforcing materials are glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.
  • the invention relates to copolyester compositions comprising a copolyester produced by a process comprising:
  • step (II) heating the initial copolyester of step (I) at a temperature of 240 to 320°C for 1 to 4 hours;
  • Suitable catalysts for use in this process include, but are not limited to, organo-zinc or tin compounds.
  • organo-zinc or tin compounds include, but are not limited to, organo-zinc or tin compounds.
  • the use of this type of catalyst is well known in the art.
  • Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide.
  • Other catalysts may include, but are not limited to, those based on titanium, zinc, manganese, lithium, germanium, and cobalt.
  • Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 based on the catalyst metal and based on the weight of the final polymer.
  • the process can be carried out in either a batch or continuous process.
  • step (I) can be carried out until 50%by weight or more of the glycol has been reacted.
  • Step (I) may be carried out under pressure, ranging from atmospheric pressure to 100 psig.
  • reaction product as used in connection with any of the catalysts useful in the invention refers to any product of a polycondensation or esterification reaction with the catalyst and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.
  • step (II) and step (III) can be conducted at the same time. These steps can be carried out by methods known in the art such as by placing the reaction mixture under a pressure ranging from 0.002 psig to below atmospheric pressure, or by blowing hot nitrogen gas over the mixture.
  • the at least one copolyester can be prepared by blending (e.g., melt blending) at least two different polyesters.
  • the at least one copolyester is a melt blend polyester prepared by a process that includes melt blending at least two different starting polyesters to provide a final copolyester that includes the monomeric residues contained in starting polyesters.
  • a PCTA copolyester containing residues of TPA, IPA and CHDM is melt blended with a copolyester containing residues of TPA, CHDM, and TMCD to provide a final copolyester having residues of TPA, IPA, CHDM, and TMCD.
  • the melt blended copolyester has residues in (net) amounts according to any of the embodiments for the at least one copolyester (as described herein) .
  • the melt blended copolyester is subjected to solid stating to increase the inherent viscosity (IV) of the copolyester.
  • the solid stated copolyester has an IV according to any of the embodiments for the copolyester (as described herein) .
  • a method for providing the at least one copolyester comprising:
  • Polyester A that comprises:
  • the inherent viscosity is 0.55 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C; and wherein the polyester has a Tg of at least 95°C;
  • Polyester B comprises:
  • the blended polyester composition comprises:
  • the total net mole %of the dicarboxylic acid component is 100 mole %, and the total net mole %of the glycol component is 100 mole %; and wherein the inherent viscosity is 0.80 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°C.
  • Polyester A comprises:
  • Polyester B comprises:
  • Polyester B is included in an amount to provide a weight ratio of Polyester A: B in a range from 90: 10 to 50: 50, or 90: 10 to 60: 40, or 90: 10 to 65: 35, or 85: 15 to 50: 50, or 85: 15 to 60: 40, or 85: 15 to 65: 35, or 80: 20 to 50: 50, or 80: 20 to 60: 40, or 80: 20 to 65: 35, or 80: 20 to 70: 30.
  • the at least one copolyester is a melt blended copolyester having an IV of 0.60 to 0.95 dL/g, or 0.70 to 0.90 dL/g.
  • the melt blended copolyester is solid stated to increase the IV.
  • the solid stated copolyester has an IV from 0.80 to 1.0 dL/g, or 0.85 to 1.0 dL/g, or 0.87 to 0.97 dL/g, or 0.90 to 0.95 dL/g.
  • the at least one copolyester prepared by blending can be further blended with the at least one second copolyester to provide the polyester component of the copolyester composition, as described herein.
  • the flame retardant, impact modifier and silicate mineral can be incorporated into the copolyester in a concentrate form by any conventional method for ultimate formation into an article.
  • the flame retardant and impact modifier can be incorporated into the polymeric composition by being blended and fed into an extruder.
  • the reinforcing material e.g., the silicate mineral
  • the extruder e.g., via a side feeder port.
  • the flame retardant can be incorporated in a plastics compounding line such as a twin-screw compounding line to form a copolyester composition concentrate.
  • the pellets are then fed into the throat of the extruder and melted from 430°F to 520°F (221°C to 271°C) to produce a viscous thermoplastic material.
  • the flame retardant is added as a single powder with a loss-in-weight feeder or added singly in a loss-in-weight feeder.
  • the rotation of the two screws disperses the flame retardant into the copolyester.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands are fed through a water trough to cool the pellets.
  • the strands Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the flame retardants can be incorporated into a plastics compounding line such as a two-rotor continuous compounding mixer (such as a Farrell Continuous Mixer) to form a copolyester composition concentrate.
  • a plastics compounding line such as a two-rotor continuous compounding mixer (such as a Farrell Continuous Mixer) to form a copolyester composition concentrate.
  • copolyester pellets are dried for 4 to 6 hours at 150°F to 190°F (65.6°C to 87.8°C) to reduce moisture.
  • the copolyester pellets and the flame retardant are fed into the throat of the continuous mixer and melted into a homogenous mixture at 430°F to 520°F (221°C to 271°C) .
  • the output rate of the mixer is controlled by varying the area of a discharge orifice.
  • the melt can be sliced off into ‘loaves’ and fed to a two-roll mill or the throat of a single screw extruder.
  • the melt covers one of the rolls to form a sheet of the concentrate which is cut into strips which are fed to the throat of a single screw extruder.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands are fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the mixture is extruded through a die to produce multiple strands.
  • the strands can be fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the flame retardant can be incorporated in a high-intensity mixer such a batch type mixer to form a copolyester composition concentrate.
  • the copolyester pellets can be dried for 4 to 6 hours at 150°F to 190°F (65.6°C to 87.8°C) to reduce moisture.
  • the copolyester pellets and the flame retardants are charged into a high-intensity mixer and a ram lowered to compress the pellet/flame retardants mixture into the mixing chamber. Two rotating mixer blades melt the pellets and disperse the flame retardant into the melt. When the desired temperature is reached, a door is opened in the bottom of the mixer and the mixture is dropped onto a two-roll mill.
  • a ribbon from the two-roll mill can then be fed to a single screw extruder.
  • the mixture is then extruded through a die to produce multiple strands.
  • the strands can be fed through a water trough to cool the pellets. Upon exiting the water trough, the strands are dried and fed into a dicer to cut the strands into pellets.
  • the mixture can be extruded through a circular flat plate die with multiple openings into water.
  • the flat plate die has a rotating cutter that slices the strands as they extrude from the die to produce pellets.
  • the continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge to separate the pellets from the water.
  • the present invention includes plastic articles comprising the copolyester compositions.
  • the plastic articles may be made by processes comprising, but not limited to, extrusion of the copolyester composition to produce a continuous flat sheet or profile or injection molding to create discrete articles or calendering to produce a continuous film or sheet or additive manufacturing of a powder or filament to produce a three-dimensional shape.
  • Films and/or sheets useful in the present invention can be of any thickness which would be apparent to one of ordinary skill in the art.
  • the films (s) of the invention have a thickness of less than 30 mils or less than 20 mils or less than 10 mils or less than 5 mils.
  • the sheets of the invention have a thickness of greater than 30 mils.
  • the sheets of the invention have a thickness of from 30 mils to 100 mils or from 30 mils to 200 mils or from 30 mils to 500 mils.
  • the invention further relates to the films and/or sheets comprising the polyester compositions of the invention.
  • the methods of forming the polyesters into films and/or sheets are well known in the art.
  • films and/or sheets of the invention include, but are not limited to, extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, injection molded films or sheets, and solution casted films and/or sheets.
  • Methods of making film and/or sheet include but are not limited to extrusion, calendering, extrusion molding, compression molding, and solution casting. These films or sheets may be made or subjected to further processing such as orientation (uniaxial or biaxial) , heat setting, surface treatment, etc.
  • the invention comprises a flat sheet or profile.
  • the sheet or profile is prepared by extruding the copolyester composition to produce a flat sheet or profile.
  • pellets of the copolyester composition are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours and are then fed to either a single screw extruder, a twin-screw extruder, or a conical twin screw extruder.
  • the copolyester composition pellets are conveyed and compressed by the screw (s) down the extruder barrel to melt the pellets and discharge the melt from the end of the extruder.
  • the melt is fed through a screening device to remove debris and/or a melt pump to reduce pressure variations caused by the extruder.
  • the melt is then fed through a die to create a continuous flat sheet or into a profile die to create a continuous shape.
  • the melt is extruded onto a series of metal rolls, typically three, to cool the melt and impart a finish onto the sheet.
  • the flat sheet is then conveyed in a continuous sheet for a distance or period of time sufficient to cool the sheet.
  • the sheet is then trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form of desired dimensions.
  • a flat sheet can also be formed into a shaped article through mechanical means to form a desired shaped article and then cooled either by spraying with water, by conveying through a water trough or by blowing air on the shaped article. The article then sawed or sheared to the desired length.
  • the die In the case of a profile die, the die is designed to produce the desired shape of the profile. After exiting the die, the profile is then cooled either by spraying with water, by conveying through a water trough or by blowing air on the profile. The profile is then sawed or sheared to the desired length.
  • the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • Another embodiment of the invention comprises mixing neat copolyester pellets with a concentrate of flame retardant and then extruding the copolyester composition.
  • the flame-retardant concentrate can be compounded as a pellet.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours before extrusion.
  • the pellets are dried after being blended in a low-intensity mixer such as a ribbon blender, a tumbler, or conical screw blender.
  • the pellets are then fed to an extruder including, but not limited to, a single screw extruder, a twin-screw extruder, or a conical twin screw extruder.
  • a flat sheet can also be formed into a shape through mechanical means to form a desired shape and then cooled either by spraying with water, through a water trough or by blowing air on the shaped article. It can then be sawed or sheared to the desired length.
  • the film may be produced and wound into a roll.
  • the die is designed to produce the desired shape of the article. After exiting the die, the profile can then be cooled either by spraying with water, through a water trough or by blowing air on the profile. It can then be sawed or sheared to the desired length.
  • the fiber In the case of a fiber, the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • Another embodiment can include mixing neat copolyester pellets with a flame retardant and/or impact modifier concentrate and then extruding them with either short or long strand glass fiber reinforcement or extruding them into a continuous glass fiber composite film, sheet or tape.
  • the flame retardant can be compounded as a single pellet.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours before extrusions.
  • the pellets can be dried separately or together after being blended in a low-intensity mixer such as a ribbon blender, a tumbler, or conical screw blender.
  • the pellets are then fed to either a single screw extruder, a twin-screw extruder, or a conical twin screw extruder.
  • the pellets are conveyed and compressed by the screw (s) down the extruder barrel to melt the pellets and discharge the melt from the end of the extruder.
  • the melt can be fed through a screening device to remove debris and/or a melt pump to reduce pressure variations caused by the extruder.
  • the melt can then be fed through a die to create a continuous flat sheet or into a profile die to create a continuous shape.
  • the melt is extruded onto a series of metal rolls, typically three, to cool the melt and impart a finish onto the sheet.
  • the flat sheet is then conveyed in a continuous sheet to cool the sheet. It can then be trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form.
  • a flat sheet can also be formed into a shape through mechanical means to form a desired shape and then cooled either by spraying with water, through a water trough or by blowing air on the profile. It can then be cut, e.g., sawed, or sheared to the desired length or a film may be produced and wound into a roll.
  • the die In the case of a profile die, the die is designed to produce the desired shape of the article. After exiting the die, it can then be cooled either by spraying with water, through a water trough or by blowing air on the profile. It can then be cut or sheared to the desired length.
  • the fiber can be pulled out of the extrusion die spinnerets to the desired fiber diameter and crystallized for physical property enhancement.
  • Another embodiment can comprise extruding fully compounded pellets of the copolyester composition, comprising the copolyester, flame retardant (s) , impact modifier (s) , and (optional) silicate mineral (s) to produce an injection molded article.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours to dry the pellets which are then fed to an injection molding machine.
  • a gate is opened at the end of the extruder and the melted plastic is pumped by the screw into a heated mold to form an article of the desired shape.
  • a coolant is pumped through the mold to cool it and the melted plastic. Once the plastic has solidified, the mold is opened and the article is removed from the mold.
  • Another embodiment can comprise mixing neat copolyester pellets with a concentrate of the flame retardant and/or the impact modifier and/or silicate mineral, optionally with or without short or long strand glass fiber, to form the copolyester composition and then molding the copolyester composition to produce an injection molded article.
  • the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours and are then fed to an injection molding machine. Once the pellets reach the desired temperature, a gate is opened at the end of the extruder and the melted plastic is pumped by the screw into a heated mold to form an article of the desired shape. Once the mold is filled, a coolant is pumped through the mold to cool it and the melted plastic. Once the plastic has solidified, the mold is opened and the article is removed from the mold.
  • Another embodiment can comprise mixing neat copolyester pellets with a concentrate of flame retardant (s) , the impact modifier (s) and/or the silicate mineral (s) to form the copolyester composition and then calendering the copolyester composition to produce a film product.
  • Calendering is a well-known process of forming a film or sheet through successive co-rotating parallel rollers.
  • the pellets may not need to be pre-dried if the processing temperatures are low enough (e.g., 350°F to 400°F; 177°C to 204°C) . In such a case, degradation and hydrolysis of the polyester may not occur in a significant amount.
  • the copolyester and flame retardant/impact modifier/silicate mineral composition may be melted by using a high intensity mixer or extruder, including but not limited to, Buss Ko-kneader, a planetary gear extruder, Farrell continuous mixer, a twin-screw extruder, or a type mixer.
  • the melt is then conveyed to the calender.
  • a calender typically consists essentially of a system of three or more large diameter heated rollers which convert high viscosity plastic into a film or sheet.
  • the flat sheet or film is conveyed in a continuous web to cool the sheet. It can then be trimmed to the desired width and then either rolled up into a roll or sheared or sawed into sheet form.
  • the copolyester composition may be prepared by mixing or blending a concentrate of flame retardants and/or the impact modifiers and/or silicate minerals and copolyester
  • the copolyester composition may alternatively be prepared by blending the flame retardants, impact modifiers and silicate minerals directly with the copolyester, using any of the mixing or blending processed previously described for making the copolyester composition by blending the flame retardant/impact modifier concentrate and the copolyester. Flame retardants, impact modifiers and silicate minerals may be mixed or blended with the copolyester simultaneously or sequentially.
  • articles comprising any of the copolyester compositions can articles or components of articles configured for use or otherwise useful in any application where flame retardant properties are beneficial, for example in one or more of the following applications: medical device housings or components, housings for electronic devices or peripherals, personal electronic device components, television or monitor housings or components, power tool housings or components, power adapter housings or components, home automation device components, gaming device housings or components, building and construction materials and components, furnishing and home decoration components, wiring and connector housings or components, and automotive structural or decorative components.
  • J is Joules
  • J/m is Joules per meter
  • MPa is megapascal
  • FR flame retardant
  • DS drip suppressant
  • IM impact modifier
  • ST stabilizer
  • FOT flame out time
  • weight % is weight percent
  • TPA is terephthalic acid
  • TMCD 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol and 1
  • 4-CHDM is 1, 4-cyclohexanedimethanol.
  • PCTM is a glycol modified polyethylene cyclohexane dimethanol terephthalate. The materials used in testing are listed in Table 1.
  • Copolyester compositions were prepared by compounding a combination of materials via an extrusion process using a 26mm twin screw extruder (Coperion ZSK 26 Mc18) and a 3.5mm -2 hole die. All pelletized polymers and additives were mixed prior to feeding through a primary pellet feeder, except the OP 1240 and other powdered additives were blended and fed through a separate powder feeder. When used, the silicone oil was premixed with the OP1240. Processing conditions were shown in Table 2.
  • Extruded strands were pelletized via a water bath/cutter or underwater pelletizer system, achieving an appropriate pellet size/shape for further processing.
  • copolyester compositions were molded into parts for testing via an injection molding process using a FANUC100 injection molding machine. Barrel temperatures ranged from 265-275°C with water-cooled mold temperatures ranging from 35-45°C. Test bars were molded at thicknesses of 1.5 mm (for UL 94 testing) and 3.2 mm (for notched Izod and tensile testing) .
  • Examples 1 to 3 were prepared as described above.
  • the UL 94 Vertical Burn and Notched Izod impact were measured for each example.
  • UL 94 Vertical Burn testing results included FOT (seconds for 5 test bars) , UL94 classification and phenomena.
  • the compositions and test results are listed below in Table 3.
  • the notched Impact strength of EXP-6 was dramatically increased compared with that of EXP-4 and EXP-5.
  • the notched Impact strength of EXP-6 was about more than 3 times than that of EXP-4 and EXP-5.
  • Examples 7 to 9 were prepared as described above.
  • the UL 94 Vertical Burn and Notched Izod were measured for each example similar to Table 3.
  • the compositions and test results are listed below in Table 5.
  • Examples 10 to 17 were prepared as described above, except different resin pellets were melt blended during the compounding process for Examples 11 to 13 and 15 to 17.
  • the UL 94 Vertical Burn and Notched Izod were measured for each example similar to Table 3.
  • the compositions and test results are listed below in Tables 6 and 7.
  • Examples 18 to 23 were prepared as described above.
  • the UL 94 Vertical Burn and Notched Izod were measured for each example similar to Table 3.
  • the compositions and test results are listed below in Table 8.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de copolyester comprenant un agent ignifuge à base de phosphinate métallique, un modificateur d'impact polymère et/ou un matériau de charge de renforcement qui présente des propriétés ignifuges améliorées tout en fournissant une résistance aux chocs, un allongement à la rupture et un module de traction et/ou de flexion élevés, des procédés de préparation de la composition de copolyester et des articles fabriqués à partir de la composition de copolyester.
PCT/CN2024/106937 2023-11-29 2024-07-23 Compositions ignifuges à ténacité élevée de copolyester Pending WO2025112572A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNPCT/CN2023/134929 2023-11-29
PCT/CN2023/134929 WO2025111838A1 (fr) 2023-11-29 2023-11-29 Compositions de copolyester ignifuges à module élevé

Publications (1)

Publication Number Publication Date
WO2025112572A1 true WO2025112572A1 (fr) 2025-06-05

Family

ID=95896169

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/CN2023/134929 Pending WO2025111838A1 (fr) 2023-11-29 2023-11-29 Compositions de copolyester ignifuges à module élevé
PCT/CN2024/106937 Pending WO2025112572A1 (fr) 2023-11-29 2024-07-23 Compositions ignifuges à ténacité élevée de copolyester

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/134929 Pending WO2025111838A1 (fr) 2023-11-29 2023-11-29 Compositions de copolyester ignifuges à module élevé

Country Status (1)

Country Link
WO (2) WO2025111838A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998017725A1 (fr) * 1996-10-21 1998-04-30 Eastman Chemical Company Melanges polyester a base de 1,4-cyclohexanedimethanol
US5759647A (en) * 1993-04-28 1998-06-02 Nippon Petrochemicals Co., Ltd. Tubular article method for injection molding thereof
CN103003359A (zh) * 2010-06-29 2013-03-27 沙伯基础创新塑料知识产权有限公司 阻燃聚酯组合物、其制备方法、及其制品
CN107001601A (zh) * 2014-12-12 2017-08-01 伊士曼化工公司 阻燃共聚聚酯组合物
WO2023178548A1 (fr) * 2022-03-23 2023-09-28 Eastman Chemical (China) Co., Ltd. Compositions de copolyester ignifuges
WO2023206073A1 (fr) * 2022-04-26 2023-11-02 Eastman Chemical (China) Co., Ltd. Compositions de copolyester ignifuges

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6169149B1 (en) * 1998-12-04 2001-01-02 General Electric Company Emulsion polymerized silicone-acrylate rubber impact modifiers thermoplastic blends, and methods for making
US20050085589A1 (en) * 2003-10-20 2005-04-21 General Electric Company Modified weatherable polyester molding composition
US8604105B2 (en) * 2010-09-03 2013-12-10 Eastman Chemical Company Flame retardant copolyester compositions
CN104845239A (zh) * 2014-12-17 2015-08-19 王妮娜 增韧改性ptt/petg复合材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5759647A (en) * 1993-04-28 1998-06-02 Nippon Petrochemicals Co., Ltd. Tubular article method for injection molding thereof
WO1998017725A1 (fr) * 1996-10-21 1998-04-30 Eastman Chemical Company Melanges polyester a base de 1,4-cyclohexanedimethanol
CN103003359A (zh) * 2010-06-29 2013-03-27 沙伯基础创新塑料知识产权有限公司 阻燃聚酯组合物、其制备方法、及其制品
CN107001601A (zh) * 2014-12-12 2017-08-01 伊士曼化工公司 阻燃共聚聚酯组合物
WO2023178548A1 (fr) * 2022-03-23 2023-09-28 Eastman Chemical (China) Co., Ltd. Compositions de copolyester ignifuges
WO2023206073A1 (fr) * 2022-04-26 2023-11-02 Eastman Chemical (China) Co., Ltd. Compositions de copolyester ignifuges

Also Published As

Publication number Publication date
WO2025111838A1 (fr) 2025-06-05

Similar Documents

Publication Publication Date Title
US20190194448A1 (en) Flame retardant copolyester compositions
CN103228730B (zh) 阻燃共聚聚酯组合物
US20250206944A1 (en) Flame retardant copolyester compositions
EP4103644B1 (fr) Compositions de copolyester ignifuges
EP4103647A1 (fr) Compositions de copolyester ignifuges non halogénées
US20250277110A1 (en) Flame retardant copolyester compositions
WO2025112572A1 (fr) Compositions ignifuges à ténacité élevée de copolyester
EP4655351A1 (fr) Compositions de copolyester ignifuges
EP4380995B1 (fr) Compositions de copolyester ignifuges
JP2001207041A (ja) 熱可塑性樹脂組成物
WO2025116949A2 (fr) Compositions de copolyester de cyclobutanediol ayant une résistance à la peinture, une résistance chimique et une résistance aux intempéries améliorées
WO2025212724A1 (fr) Copolyesters ignifuges
JPS59217754A (ja) 熱可塑性ポリエステル系樹脂組成物

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: 24895675

Country of ref document: EP

Kind code of ref document: A1