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WO2001021701A1 - Formulations ameliorees de polyester contenant un ou plusieurs imides halogenes, un ou plusieurs esters de pentaerythritol et une fibre de renforcement - Google Patents

Formulations ameliorees de polyester contenant un ou plusieurs imides halogenes, un ou plusieurs esters de pentaerythritol et une fibre de renforcement Download PDF

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Publication number
WO2001021701A1
WO2001021701A1 PCT/US2000/024377 US0024377W WO0121701A1 WO 2001021701 A1 WO2001021701 A1 WO 2001021701A1 US 0024377 W US0024377 W US 0024377W WO 0121701 A1 WO0121701 A1 WO 0121701A1
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WIPO (PCT)
Prior art keywords
composition
group
mole
pentaerythritol
acid
Prior art date
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Ceased
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PCT/US2000/024377
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English (en)
Inventor
Gerald Timothy Keep
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Eastman Chemical Co
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Eastman Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • HDT heat deflection temperatures
  • PCT is a high-melting polyester with a melting point of about 290°C and, consequently, is very challenging to formulate while retaining good molecular weight.
  • flammability characteristics are very important. Flame retardants are expensive and generally reduce the properties of the base resin.
  • United States Patent No. 4,548,956 by Schwarz et al discloses the use of a pentaerythritol with a foamed polystyrene system and hexabromocyclodecane.
  • United States Patent 5,041 ,470 by Gelorme et al discloses photocurable adhesives where pentaerythritol is used.
  • United States Patent 5,712,336 by Gareiss et al discloses polyester resins used in thermoplastic molding materials. The resins require decabromodiphenylethane. Pentraerythritol compounds are used as lubricants.
  • United States Patent 5,258,434 by Hanabusa discloses the use of a pentaerythritol a flame retardant (FR) in polybutylene terephthalate to improve mold release, heat resistance and mechanical properties.
  • FR flame retardant
  • United States Patent 4,506,050 by Hergenrother et al discloses the use of a pentaerythritol compound in PET as a plasticizer.
  • United States Patent 5,095,060 by Haaf discloses use of a pentaerythritol as a viscosity reducer in an FR blend of polyphenylene ether and polyetherimide siloxane.
  • This invention relates to a polymer composition comprised of:
  • (A) a polyester comprising: (1 ) terephthalic acid in the amount of 85 to 100 mole % based on the mole percentages of the dicarboxylic acid component equaling a total of 100 mole %. (2) a glycol component comprising from about 60 to 100 mole % of an alcohol selected from the group consisting of butylene glycol, ethylene glycol and 1 ,4- cyclohexanedimethanol;
  • a preferred embodiment of this invention comprises one or more antimony containing flame retardant synergists.
  • the polymer composition of this invention has improved flammability characteristics. It is the object of this invention to reduce the amount of flame retardant required to obtain the desired flammability characteristics.
  • Another preferred embodiment of this invention comprises a phosphorous compound in an amount in excess of that normally required for stabilizers.
  • This invention relates to an improvement in the flammability characteristics of a fiber reinforced polyester formulation as shown by UL- 94 flammability testing.
  • the polyester comprise 90 mole % or more of terephthalic acid based on the mole percentages of the dicarboxylic acid component of the polyester equaling a total of 100 mole %.
  • terephthalic acid suitable synthetic equivalents, such as dimethyl terephthalate, are included.
  • the polyester useful in this invention comprises 0 to 15 mole %, preferably 0 to 10 mole %, of dicarboxylic acids other than terephthalic acid, based on the mole percentages of the dicarboxylic acid component of the polyester equaling a total of 100 mole %.
  • the other dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids preferably having
  • 4 to 40 carbon atoms more preferably, 8 to 14 carbon atoms; aliphatic dicarboxylic acids having, preferably 4 to 40 carbon atoms, more preferably, 4 to 12 carbon atoms; or cycloaliphatic dicarboxylic acids having 4 to 40 carbon atoms, more preferably, 8 to 12 carbon atoms.
  • dicarboxylic acids useful in forming the copolyester of the invention include, but are not limited to, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, diphenyl-4, 4' -dicarboxylic acid, naphthalenedicarboxylate, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like.
  • isophthalic acid naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and naphthalenedicarboxyate are preferred, either singly or in combination.
  • cyclohexanedicarboxylic acid is used as a comonomer in the context of the invention, trans-, cis-, or cis/trans mixtures may be used.
  • Any of the naphthalenedicarboxylic acid isomers or mixtures of isomers may be used.
  • Some preferred naphthalenedicarboxylic acid isomers include 2,6-, 2,7- 1 ,4- and 1 ,5- isomers.
  • dicarboxylic acids includes the corresponding acid anhydrides, esters, and acid chlorides of these acids.
  • the mole percentages of the acids of the polyester referred to herein equal a total of 100 mole %.
  • the mole percentages of the glycols referred to herein equal a total of 100 mole %.
  • the preferred halogenated flame retardant of the invention is a halogenated organic compound containing at least one imide group and having a melting point greater than 240°C.
  • imide-group containing compounds include N.N'-arylenediphthalimides wherein the arylene group includes phenylene, diphenylene, naphthylene and sulfone bridged bisphenyls, tetrabrominated phthalimides,
  • Preferred imide group containing compounds are those corresponding to the following formula:
  • n and m may be 1 or 0, X may be halogen, particularly chlorine or bromine, or hydrogen, and
  • N,N'-alkylenebis(tetrahalophthalimides) suitable in the present invention and a process for their production are described in U.S. Pat. No. 4,087,441 , incorporated herein by reference.
  • the preferred N,N'- alkylenebis(tetrahalophthalimides) are represented by the formula:
  • R represents a Ci-C ⁇ alkyl group, preferably a C -C ⁇ alkyl group, and most preferably an ethyl group, and Hal which may be the same or different, represents a halogen atom, preferably Br or Cl, and most preferably Br.
  • N,N'- alkylenebis(tetrahalophthalimide) is particularly preferred.
  • N,N'-ethylenebis(tetrabromophthalimide) (R is an ethyl group and Hal is a Br atom).
  • the sum of all flame retardants used in this invention is 5-30%, preferably 10-20%, by weight of the total composition.
  • One or more flame retardants may be used within the context of this invention.
  • pentaerythritol ester known by one skilled in the art is included within the context of this invention.
  • Mixed pentaerythritol esters are also useful within the context of this invention.
  • suitable pentaerythritol esters include, but are not limited to, are pentaerythritol monohexylester, pentaerythritol monooctylester, pentaerythritol monononylester, pentaerythritol monodecylester, pentaerythritol monododecylester, pentaerythritol monomyristylester, pentaerythritol monohexadecylester, pentaerythritol monostearylester, pentaerythritol monooleylester, pentaerythritol monoisostearyl- and -isopalmitiacid ester; the corresponding
  • Aromatic esters of pentaerythritol and benzoate esters of pentaerythritol are preferred. Benzoate esters of pentaerythritol are more preferred. The (tetra)benzoate ester of penaerythritol is even more preferred. The pentaerythritol esters can be easily prepared and many representatives of these compounds are commercially available, f i.
  • Reolube LP 3600 a pentaerythritol tetrapelargonate
  • Reolube LPE 504 a pentaerythritol tetraoctylester
  • Reolube LPE 602 a pentaerythritol tetraheptylester
  • Ketjenlube 12 a pentaerythritol tetradecyl/dodecylester having a statistical C10/C12-distribution
  • Henkel AG under the tradename Edenor Ke 230 (a pentaerythritol tetraisopalmitic acid ester) and pentaerythritol tetraisostearic acid ester.
  • Pentaerythritol esters be present in the invention in the amount of 0 to 10 weight %, preferably 1 to
  • melt stability of the composition of the invention can be further improved by addition of certain amounts of a phosphorous-based compound.
  • phosphorous-based compounds include, but are not limited to, one or more phosphites or phosphonites wherein at least one of the P-O bonds is attached to an aryl radical. Such compounds may be represented by the formulas
  • R ⁇ R 2 and R 3 is an aryl radical of 6 to 30 carbon atoms and any other(s) of R ⁇ , R 2 and R3 are H or alkyl of 1 to 30 carbon atoms, or
  • R 4 , R5 and Re is an aryl radical of 6 to 30 carbon atoms.
  • phosphorous-based compounds which may be used include, but are not limited to, Ultranox® 633 phosphite, (General Electric Chemicals), lrgafos®168 phosphite (Ciba-Geigy Corporation), Ethanox® 398 phosphonite (Ethyl Corporation) and Sandostab® P-EPQ phosphonite (Sandoz Chemicals).
  • the phosphorous based compounds may be present in amounts equal to or greater than 0.5 % of the total polymer composition. This amount is in excess of the normal amount used as a stabilizer, suggesting that the excess phosphorous compound may be catalysing the action
  • additives such as other stabilizers, other flame retardants (FR), flame retardant synergists, tougheners, epoxy compounds, branching agents, mold release agents, nucleating agents, reinforcing agents such as reinforcing fibers, fillers, antioxidants and colorants such as carbon black, might also be desirable in such formulations. These may be added either during or after polymerization to form a copolyester composition, depending on the chemical structure of the additive.
  • 0.1 to 5.0 weight %, preferably less than 2.0 weight %, of one or more branching agents is included within the context of this invention, including but not limited to, trimellitic acid, trimellitic anhydride, pyromellitic anhydride, multifunctional epoxy compounds and multi-functional phenoxy compounds, and the like. If the branching agent is a phenoxy compound, 2.0 to 5.0 weight % is preferred.
  • reinforcing agents are glass fibers, carbon fibers, mica, clay, talc, wollastonite, and calcium carbonate.
  • a particularly preferred reinforcing agent is glass fiber. It is preferable that the glass fibers be present in the polyester composition at from 0 1 to 45%, preferably 1 0 to 40%, by weight based on the total weight of said polyester composition
  • Glass fibers suitable for use in the polyester compositions of the invention may be in the form of glass filaments, threads, fibers, or whiskers, etc., and may vary in length from about 1/8 inch to about 2 inches.
  • copolyester composition of the invention may be blended and/or mixed by any suitable technology known in the art
  • Compounding temperatures must be at least the melting point of the polyester.
  • the polyester can be mixed dry in any suitable blender or tumbler with the other components and the mixture melt- extruded.
  • the extrudate can be chopped. If desired the reinforcing material can be omitted initially and added after the first melt extrusion, and the resulting mixture can then be melt extruded.
  • the copolyester of this invention may be melt processed and extruded, injection molded or compression molded into a variety of shapes and forms including fibers, molded parts, bottles, pellets, containers, sheeting, film and the like.
  • the product is especially suitable as an injection molding material for producing molded articles.
  • I.V Inherent viscosity or "I.V.” - refers to inherent viscosity expressed in dL/g measured as described herein;
  • Good melt stability is characterized by a loss of less than about 15% of the original Mn and Mw, after exposure for 10 minutes, the original molecular weights being defined as that at zero time. Blends with less than this degree of melt stability may still be useful, but are correspondingly inferior;
  • the fiber reinforced PCT blends of this work were prepared by extrusion compounding using a twin screw extruder at temperatures of 305°C.
  • the resulting pellets were injection molded into tensile and flexural bars for use in mechanical and flammability property testing.
  • Melt stability was determined on these blends by drying a small sample of the compounded pellets. Adequate drying can be obtained by drying in a vacuum oven overnight at 80°C, or by drying for 4 hours at 125°C in a hot air circulating oven.
  • the dried pellets were then loaded into a Tinius Olsen melt indexer or capillary rheometer and held for 10 minutes at 305°C melt temperature, then analyzed by gel permeation chromatography.
  • the melt stability of these blends was shown by the retention of number average molecular weight (Mn) and weight average molecular weight (Mw) after 10 minutes at 305°C.
  • Blends A-l in Table 1 are described as follows:
  • Blend A is described as follows: 30.0% GF2 16.0% FR1 2.0% FRS2 4.0% PL B
  • Blend B is described as follows:
  • Blend A Same as Blend A except that ST5 is added at 0.1 %
  • Blend D is described as follows:
  • Blend E Same as Blend A except that ST6 is increased to 1.0% Blend E is described as follows:
  • Blend D Same as Blend D except that ST5 is added at 0.1 % ⁇
  • Blend F is described as follows:
  • Blend D Same as Blend D except that ST5 is added at 0.25%
  • Blend G is described as follows:
  • Blend H is described as follows: Same as Blend G except that ST5 is added at 0.1 %
  • Blend I is described as follows:
  • Blend G Same as Blend G except that ST5 is added at 0.25% TABLE 1
  • Table 1 illustrates the fact that many properties such as viscosity and molecular weight/branching are at a minimum with intermediate levels of phosphite. Also that flammability improves with phosphite present.
  • Blends J-N in Table 2 are described as follows: Blend J is described as follows:
  • Blend K is described as follows:
  • Blend L is described as follows:
  • Blend M is described as follows:
  • Blend K Same as Blend K except that ST7 is replaced by ST 5.
  • Blend N is described as follows:
  • Blends P-S in Table 3 are described as follows: Blend P is described as follows:
  • Blend R Same as Blend R except that PL J is added at 3.0%
  • Blends T-AA in Tables 4a and 4b are described as follows:
  • Blend T is described as follows: 30.0% GF2 12.0% FR1
  • PCT in an amount sufficient for the composition to total 100 weight%
  • Blend U is described as follows: Same as Blend T except that additives are adjusted as follows:
  • Blend T Same as Blend T except that additives are adjusted as follows: 2.5% RIM 1 3.5% RIM 2
  • Blend W is described as follows:
  • Blend T Same as Blend T except that additives are adjusted as follows: 2.5% RIM 1 3.5% RIM 2 1.0% RIM 3
  • Blend T Same as Blend T except that additives are adjusted as follows: 3.5% RIM 1 2.5% RIM 2 1.0% RIM 3 0.5% ST5
  • Blend Y is described as follows: Same as Blend T except that additives are adjusted as follows:
  • Blend Z is described as follows:
  • Tables 4a and 4b illustrates the fact that a) PL A has the least effect on physical properties of the above 3 variables b) Increasing ST5 from 0.5 to 1.0 % increases branching, as a catalyst would, rather than decreasing it as a stabilizer might be expected to do. c) All three variables improved FR performance, with PL A stronger than ST5 but weaker than the FR1 change.
  • Blends BB-CC in Table 5 are described as follows:
  • Table 5 illustrates the fact that phosphite (ST5) increase from 0 to 0.25 in FR1/ST8 system improves properties while reducing branching.
  • Blends DD-EE in Table 6 are described as follows:
  • Blend DD is described as follows: 30.0% GF2 14.0% FR2

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  • 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

Cette invention se rapporte à une composition polymère composée (A) d'un polyester contenant (1) de l'acide téréphtalique en quantité représentant 85 à 100 % en moles par rapport aux pourcentages molaires du composant d'acide dicarboxylique équivalent à 100 % en moles, et (2) un composant glycol comportant approximativement 60 à 100 % en moles d'un alcool sélectionné dans le groupe constitué par le butylène-glycol, l'éthylène-glycol et le 1,4-cyclohexanediméthanol; (B) d'un ou de plusieurs agents ignifugeants halogénés; (C) d'un ou de plusieurs esters de pentaérythritol et (D) d'une fibre de renforcement.
PCT/US2000/024377 1999-09-23 2000-09-05 Formulations ameliorees de polyester contenant un ou plusieurs imides halogenes, un ou plusieurs esters de pentaerythritol et une fibre de renforcement Ceased WO2001021701A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15572699P 1999-09-23 1999-09-23
US60/155,726 1999-09-23
US45095399A 1999-11-30 1999-11-30
US09/450,953 1999-11-30

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WO2001021701A1 true WO2001021701A1 (fr) 2001-03-29

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110945046A (zh) * 2017-07-05 2020-03-31 巴斯夫欧洲公司 Tpu管

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604078A1 (fr) * 1992-12-22 1994-06-29 General Electric Company Compositions de polyester renforcées par du verre, à teinte améliorée
EP0736571A1 (fr) * 1995-04-03 1996-10-09 Basf Aktiengesellschaft Masses de moulage thermoplastiques ignifugés
EP0796743A1 (fr) * 1996-03-20 1997-09-24 General Electric Company Composition ignifuge pour marquage par laser

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0604078A1 (fr) * 1992-12-22 1994-06-29 General Electric Company Compositions de polyester renforcées par du verre, à teinte améliorée
EP0736571A1 (fr) * 1995-04-03 1996-10-09 Basf Aktiengesellschaft Masses de moulage thermoplastiques ignifugés
EP0796743A1 (fr) * 1996-03-20 1997-09-24 General Electric Company Composition ignifuge pour marquage par laser

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110945046A (zh) * 2017-07-05 2020-03-31 巴斯夫欧洲公司 Tpu管

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