WO1991019767A1 - Compositions de polyesters thermoplastiques extrudables par soufflage - Google Patents

Compositions de polyesters thermoplastiques extrudables par soufflage Download PDF

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Publication number
WO1991019767A1
WO1991019767A1 PCT/US1991/003970 US9103970W WO9119767A1 WO 1991019767 A1 WO1991019767 A1 WO 1991019767A1 US 9103970 W US9103970 W US 9103970W WO 9119767 A1 WO9119767 A1 WO 9119767A1
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weight percent
pet
composition
component
melt
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PCT/US1991/003970
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English (en)
Inventor
King Lau Howe
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E.I. Du Pont De Nemours And Company
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Priority claimed from US07/539,753 external-priority patent/US5128404A/en
Priority claimed from US07/539,649 external-priority patent/US5091459A/en
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1991019767A1 publication Critical patent/WO1991019767A1/fr

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    • 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

  • compositions which in addition to the ethylene copolymers containing glycidyl groups use small amounts of catalytic cations which may be introduced in the form of a zinc ionomer.
  • catalytic cations which may be introduced in the form of a zinc ionomer.
  • these catalyzed compositions may form small lumps when the compositions are exposed to processing temperatures for an extended period of time. Such prolonged exposure is not unusual in commercial blow molding operations where a substantial proportion of the resin must be recycled as regrinds. The presence of these lumps results in molded objects having surface blemishes or surface irregularities.
  • polyester compositions particularly for PET-based compositions, which have sufficient melt strength and viscosity to permit extrusion blow molding of large and complex objects which at the same time exhibit uniform, smooth surfaces.
  • U.S. Patent 4,659,757 granted April 21, 1987 to Okamoto et al., discloses poly(ethylene terephthalate) (PET) molding compositions yielding impact resistant articles prepared by melt blending PET with 3 to 60 parts of a second polyester selected from the group consisting of (1) copolymers of ethylene glycol, terephthalic acid and aliphatic dicarboxylic acids containing at least 12 carbon atoms (2) copolymers of ethylene glycol, terephthalic acid and a pol (alkylene oxide) glycol, and (3) polyarylates.
  • PET poly(ethylene terephthalate)
  • compositions must also contain (i) a nucleating agent selected from the group of finely divided inorganic nucleating agents, a metal salt of an organic carboxylic acid and an ionomer, (ii) a polyolefin to which has been grafted an olefin having carboxyl or anhydride groups, (iii) an olefin copolymer containing units derived from glycidyl (meth)acrylate and optionlly units derived from vinyl acetate as a third monomer and (iv) an ester-based plasticizer.
  • the compositions must contain the second polyester and each of ingredients (i) , (ii) , (iii) and (iv) .
  • compositions which are blow moldable PET or poly(butylene terephthalate) , PBT, containing an epoxide group-containing copolymer and a source of catalytic metal cations which source could be a small amount of a zinc ionomer, for example.
  • the patents disclose olefin copolymers and acrylate copolymers containing epoxide groups, but prefers the olefin copolymers.
  • the examples of the reference demonstrate that sodium ionomers are ineffective in providing blow moldability when used at the same concentration at which zinc ionomers are effective.
  • (meth)acrylate A variety of optional ingredients may be added including plasticizers, poly(alkylene oxide) segments and crystallization promoters. As crystallization promoters one can use salts of hydrocarbon acids containing 7 to 54 carbon atoms or salts of ionomeric polymers.
  • Example 1 discloses a single poly(ethylene terephthalate) composition which contains 3.8 weight percent of a sodium ionomer of an ethylene/methacrylic acid copolymer added as a crystallization promoter.
  • Japanese Patent Publication 59-184251 published October 19, 1984 discloses that polyether ester block copolymers (100 parts) derived essentially from terephthalic acid, 1,4-butanediol and a pol (alkylene oxide) glycol when melt blended with 1-25 parts of an ionomer resin and 1-25 parts of an olefin copolymer containing epoxide groups form compositions having sufficiently high melt tension to permit extrusion blow molding.
  • the compositions are further characterized as exhibiting good elastic recovery and softness.
  • the present invention provides polyester compostions which are suitable for extrusion blow molding large objects having smooth surfaces.
  • the compositions are based on injection molding and extrusion grades of PET.
  • compositions of the present invention are semi-crystalline blow moldable compositions comprising melt blends consisting essentially of the following ingredients: a) 62-88 weight percent of at least one PET selected from the group consisting of branched PET having an inherent viscosity of at least about 0.60 dl/g and a mixture of the branched PET and a linear PET having an inherent viscosity of at least about 0.65 dl/g, the mixture containing up to 90 weight percent of the linear PET or at least one poly(butylene terephthalate) (PBT) having an inherent viscosity of at least about 0.8 dl/g, b) 10-30 weight percent of at least one ethylene copolymer, E/X/Y, wherein E is at least 50 weight percent of units derived from ethylene, X is 2-10 weight percent of units derived from glycidyl (meth)acrylate and Y is 0-40 weight percent of units derived from a C 1.-Cb,.
  • alkyl (meth)acrylate and c) 2-8 weight percent of at least one ionomer obtained by neutralizing with Na or K at least about 40 percent of the carboxyl groups in an ethylene copolymer which contains about 9-20 weight percent of units derived from (meth) acrylic acid and 0-35 weight percent of units derived from C -C fi alkyl (meth)acrylate.
  • component d) a second polyester other than PET
  • component d) may be added in the amount of 2-6 parts per 100 parts (pph) by weight of components a) , b) and c) , which second polyester assists in the processing of the compositions.
  • the second polyester is selected from the group consisting of (1) polyesters of C_-C. 0 o **' -diols and aromatic dicarboxylic acids, (2) polyarylates and (3) copolyetherester block copolymers.
  • the present invention relates to semi-crystalline blow moldable polyester compositions which possess high melt strengths and melt viscosities as well as yielding high quality smooth surface appearance on the blow molded parts.
  • compositions of the present invention are semi-crystalline blow moldable compositions comprising melt blends consisting essentially of the following ingredients: a) 62-88 weight percent of at least one PET selected from the group consisting of branched PET having an inherent viscosity of at least about 0.60 dl/g and a mixture of the branched PET with a linear PET having an inherent viscosity of at least about 0.65 dl/g, the mixture containing up to 90 weight percent of the linear PET or at least one PBT having an inherent viscosity of at least about 0.8 dl/g, b) 10-30 weight percent of at least one ethylene copolymer, E/X/Y, wherein E is at least 50 weight percent of units derived from ethylene, X is 2-10 weight percent of units derived from glycidyl (meth)acrylate and Y is 0-40 weight percent of units derived from a C -C 8 alkyl (meth)acrylate, and
  • weight percentages given for each of components a) , b) and c) are based on the total of these components only.
  • component d) a second polyester other than PET, may be added in the amount of 2-6 pph by weight of components a) , b) and c) , which second polyester assists in the processing of the compositions.
  • the second polyester is selected from the group consisting of (1) polyesters of C -C C ,1 ⁇ *-diols and aromatic dicarboxylic acids, (2) polyarylates and (3) copolyetherester block copolymers.
  • compositions of the present invention are semi-crystalline blow moldable compositions comprising melt blends consisting essentially of the following ingredients: a) 69-82 weight percent of at least one PET selected from the group consisting of branched PET having an inherent viscosity of at least about 0.60 dl/g and a mixture of the branched PET with a linear PET having an inherent viscosity of at least about 0.65 dl/g, the mixture containing up to 80 weight percent of the linear PET or at least one PBT having an inherent viscosity of at least about 0.8 dl/g, b) 15-25 weight percent of at least one ethylene copolymer, E/X/Y, wherein E is at least 57 weight percent of units derived from ethylene, X is 4-8 weight percent of units derived from glycidyl (meth)acrylate and Y is 10-35 weight percent of units derived from a C -C 8 alkyl (meth)acrylate, and
  • component d) a second polyester other than PET
  • component d) may be added in the amount of 3-5 parts per 100 parts by weight of components a) , b) and c) , which second polyester assists in the processing of certain compositions.
  • the second polyester is selected from the group consisting of (1) polyesters of C 3 ⁇ C 10 cK, -diols and aromatic dicarboxylic acids, (2) polyarylate ⁇ and (3) copolyetherester block copolymers.
  • Component a) is a polyester selected from the group consisting of branched pol (ethylene terephthalate) (PET) having an inherent viscosity of at least 0.60 dl/g, mixtures of the branched PET with up to 90 weight percent of linear PET having an inherent viscosity of at least about 0.65 dl/g and PBT having an inherent viscosity of 0,8 dl/g.
  • Linear PET is a well established commercial product which is normally made by esterification of terephthalic acid with ethylene glycol followed by polycondensation. PET having an inherent viscosity of about 0.65 dl/g may be made by polycondensation in the melt. PET having inherent viscosities of about
  • 1.0 dl/g are usually prepared by subsequent solid phase polycondensation of lower molecular weight PET first prepared by melt condensation.
  • Recycled PET bottle resin represents a source of relatively inexpensive linear PET which with proper recycling of PET bottles will be available in very substantial amounts.
  • the PET used for bottles normally contains a minor amount, about 2% by weight, of a second glycol such as diethylene glycol, the presence of which facilitates the manufacture of oriented PET bottles; and normally has an inherent viscosity of at least 0.65 dl/g and preferably has an inherent viscosity of about 0.7-0.72 dl/g.
  • the presence of the second glycol monomer does not adversely affect the use of recycled PET resin in the present invention.
  • Branched PET can be made by substantially the same processes as are used for linear PET with the exception that a minor amount of a tri- or higher functionality polyol or polyacid monomer is added to the polymerization.
  • Trifunctional acids are usually preferred and of these, trimellitic anhydride or tri-lower alkyl esters of trimellitic acid are especially preferred. From about 0.2-1.0 mole of trifunctional monomer per 100 moles of terephthalic acid can be used with 0.4 to 0.7 moles being preferred.
  • Branched PET containing preferred amounts of branching agent are useful for preparing compositions of this invention which can be used for forming very large articles by extrusion blow molding.
  • branching agent i.e., 0.4 to 0.7 moles of branching agent per 100 moles of terephthalic acid
  • Branched PET containing preferred amounts of branching agent are useful for preparing compositions of this invention which can be used for forming very large articles by extrusion blow molding.
  • branching agent i.e., 0.4 to 0.7 moles of branching agent per 100 moles of terephthalic acid
  • compositions prepared from mixtures containing 10-60 weight percent branched PET, preferably 20-50 weight percent, having the preferred concentration of branching agent with recycled PET bottle resin, which normally has an inherent viscosity of about 0.7 dl/g, are very economical and highly useful for extrusion blow molding.
  • Branched PET has a higher melt viscosity and greater melt strength than does linear PET having the same inherent viscosity. Because of these properties, branched PET having relatively low inherent viscosity is useful either alone or in admixture with linear PET in preparing the compositions of this invention. The use of branched PET alone or in blends with linear PET having a relatively low inherent viscosity yields compositions which are versatile in terms of the size and complexity of the articles which can be blow molded from them. For economic reasons, blends of branched PET with recycled PET bottle resin are of particular interest.
  • component a) may be pol (butylene terephthalate) (PBT) having an inherent viscosity of at least about 0.8 dl/g.
  • PBT is a well-known commercial product. It is normally made by transesterification of dimethyl terephthalate with excess 1,4-butanediol followed by polycondensation. It is also possible to start with terephthalic acid and butanediol. In order to obtain resins having inherent viscosities of at least about 0.8 dl/g it is necessary to use a continuous finisher when melt condensation is used exclusively. With batch finishing, melt condensation followed by solid phase condensation is generally required to obtain the desired inherent viscosities.
  • compositions prepared from PBT having inherent viscosities near the minimum value stated above are generally suitable for extrusion blow molding of articles requiring the use of parisons having a length of up to about 30.5 cm (one foot).
  • resins having inherents above about 0.8 dl/g are preferred.
  • Component b) is an ethylene copolymer, E/X/Y, where E is at least 50 weight percent of units derived from ethylene, X is 2-10 weight percent of units derived from glycidyl (meth)acrylate and Y is about 0-40 weight percent of units derived from C 1-C,6. alkyl (meth)acrylate.
  • component b may be a dipoly er of ethylene and glycidyl (meth)acrylate. More preferred are terpolymers containing up to 40 weight percent of units derived from meth(acrylate) lower alkyl esters of which n-butyl acrylate is preferred.
  • component b) is used in amounts of 10-30 weight percent, and more preferably 15-25 weight percent based on the total weight of components a) , b) , and c) . Since components b) and c) each contribute to the low moldability of the instant compositions by increasing melt viscosity, melt strength and die swell, the preferred amount of component b) used within the aforementioned ranges is partly dependent on the level of component c) . The epoxide content of component b) is another factor which affects the amount of component b) used. In general, the greater the epoxide content of component b) , the less of component b) will be required. Finally, consideration must be given to the proportion of branched PET used as well as its concentration of branching agent.
  • Component c) is an ionomer obtained by neutralizing with Na or K , provided by a basic sodium or potassium compound, at least about 40 percent of the carboxyl groups contained in an ethylene copolymer containing about 9-20 weight percent of units derived from (meth)acrylic acid.
  • these ionomers may contain up to about 35 weight percent of units derived from C.-C alkyl (meth)acrylate.
  • a preferred termono er is n-butyl acrylate.
  • Component c) is used in amounts of 2-8 weight percent, preferably 3-6 weight percent based on the total weight of components a) , b) , and c) .
  • component c) contributes to the blow moldability of the compositions of this invention
  • the preferred amount of component c) used depends at least in part on the amount of component b) present in a given composition.
  • component c) improves the stability of the molten composition during processing which in turn permits extrusion of smooth parisons and forming molded articles with smooth surfaces.
  • each of components b) and c) contributes to the blow moldability of the compositions of this invention.
  • increasing the concentration of either of the components within the ranges specified will raise the melt viscosity of a given blow molding composition.
  • compositions having melt viscosities at the above temperature of at least about 20,000 to 30,000 Pa sec at 1 sec " are usually suitable for forming articles requiring a parison greater than 61 cm in length.
  • the melt rheology of the compositions of the present invention makes them suitable for thermoforming applications. Reference to the Samples contained below will assist one in selecting amounts of components b) and c) which will yield a composition suitable for a given molding application.
  • compositions melting near 250°C or above generally exhibit melt viscosities which diminish rapidly with increasing tempertures in the range used for blow molding.
  • the ratio of the melt viscosity at 270°C to the melt viscosity at 280°C may approach 10 for some compositions. Because of this extreme sensitivity of the melt viscosity to temperature, minor fluctuations in temperature on the low side result in excessive torque within the extruder of the blow molding machine while conversely, temperatures on the high side cause the melt to be too fluid to form a stable parison.
  • Such compositions can only be blow molded satisfactorily in equipment where excellent temperature control is possible.
  • any polyester based on a diol other than ethylene glycol and/or based on a diacid other than terephthalic acid can be used to improve the processing of compositions which exhibit the problems just discussed.
  • Polyesters based on aromatic diacids are preferred because compositions modified with aliphatic polyesters may exhibit decreased hydrolytic stability.
  • Three classes of polyesters have been found to be particularly useful for the modification of temperature sensitive compositions. They are as follows:
  • the polyesters of class 1 are close relatives of PET and can be prepared substantially by the same condensation procedures used to make PET. i ⁇ jl ,W-diols are preferred.
  • Preferred dicarboxylic acids are the three isomeric phthalic acids, but substituted phthalic acids and acids such as 1,5-,2,6- and 1,4-naphthalene dicarboxylic acid are also useful.
  • the preferred polyester of class 1 is PBT.
  • the polyarylates of class 2 are aromatic polyesters derived from one or more dihydric phenols and one or more aromatic dicarboxylic acids.
  • the dihydric phenol is preferably a bisphenol as described in U.S. Patent 4,187,358 having the structure:
  • -X- is selected from the group consisting of nothing; i.e., a covalent bond, -0-, -S-, -SO -, -SO-, -CO-, an alkylene group containing 1 to 5 carbon atoms and an alkylidene group containing 2 to 7 carbon atoms
  • R. , R 2 , R_, R. , R. ,, R , , , and R may be the same or different, and each is selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an alkyl group containing 1 to 5 carbon atoms, and/or a functional derivative thereof.
  • 2,2'-Bis(4-hydroxyphenyl)propane is most preferred.
  • mononuclear dihydric phenols may be used in combination with the bi'sphenol ⁇ .
  • mononuclear dihydric phenols may be used in combination with the bi'sphenol ⁇ .
  • Representative are hydroquinone and resorcinol and substituted derivatives thereof containing one to four substituents selected from the group consisting of chlorine, bromine and lower alkyl.
  • a mixture of 90 to 0 mole percent of terephthalic acid and/or the functional derivatives thereof and 10 to 100 mole percent of isophthalic acid and/or its functional derivatives is used as the acid component to be reacted with the bisphenol to prepare the polyarylate.
  • Preparative methods for polyarylates are described in detail in U.S. Patent Nos. 3,884,990, 3,946,091, 4,052,481 and 4,485,230.
  • Preferred polyarylates for use in the compositions of this invention are derived from isophthalic acid optionally containing up to 30 weight percent terephthalic acid and 2,2"-bis(4-hydroxyphenyl)propane.
  • the copolyetherester block copolymers of class 3 consist essentially of 15-95 weight percent of short chain ester units which are derived from a low molecular weight diol and an aromatic dicarboxylic acid and 5-85 weight percent of long chain ester units which are derived from a poly(alkylene oxide) glycol having a number average molecular weight of 400-6000 and an aromatic dicarboxylic acid. These polymers are readily prepared by substantially the same procedures useful for preparing PET, with the exception of adding a poly(alkylene oxide) glycol to the reaction mass.
  • Polymers derived from terephthalic acid (optionally containing some isophthalic acid) , butanediol and a poly(alkylene oxide) glycol selected from the group consisting of poly(tetramethylene oxide) glycol, poly(1,2-propylene oxide) glycol and ethylene oxide-capped poly(1,2-propylene oxide) glycol are readily available as commercial products.
  • polyesters of class 3 are preferred with poly(butylene terephthalate) being especially preferred when molded articles having high flexural modulus are desired. It should be noted that the polyesters of class 3 which are known to be elastomers reduce the rigidity of the compositions of this invention and yield articles having outstanding impact resistance.
  • the second polyester should be used in amounts of 2-6 parts by weight, preferably 3-5 parts by weight, based on 100 parts of the sum of components a) , b) and c) .
  • the sum of the percentages of a) , b) and c) equals 100 weight percent and the amount of the second polyester, being an optional component, is in addition to the weight of the basic composition.
  • the compositions of the present invention may contain minor amounts of a variety of additives which are frequently used in plastics. Such additives include antioxidants, UV stabilizers, dyes, pigments, flame retardants, fibrillatable fluoropolymers and fillers.
  • reinforcing fillers such as chopped glass fibers and acicular calcium metasilicate permits the preparation of moldings which exhibit exceptional rigidity.
  • Reinforcing fillers may be used in amounts of up to about 40 parts by weight based on 100 parts of the total of components a) , b) and c) which three ingredients total 100%. In other words, up to about 40 parts by weight of filler can be used for 100 parts by weight of components a) , b) and c) .
  • the presence of reinforcing fillers generally raises the melt viscosity of the compositions of this invention.
  • the ingredients were blended on a Werner and Pfleiderer bilobal twin screw extruder having a diameter of 57 mm and a length to diameter ratio of 37.
  • the screw used was a general purpose screw with vacuum capability consisting of conveying elements to convey the feed material from the feed zone to a melting zone in which the material was compressed and melting begins.
  • a section of "kneading blocks” followed by “reverse elements” next provides high shear and pressure to further the melting and mixing process. The reverse elements serve also to provide a melt seal following which the melt is decompressed in the section under vacuum.
  • Zone 1 Zone 2 Zone 3 Zone 4 Zone 5-10 Die ⁇ h c) f b c) _ ⁇ a ⁇ a (°c) ,
  • the product was extruded at a rate of 90.8 kgs/hour through a six hole die. Temperature of the melt exiting the extruder die was measured as the melt temperature. Melt strands exiting the extruder were quenched in water and cut into pellets. The pelletized product was dried at 100-105°C in a circulating air drier equipped with dehumidifier.
  • Zone 1 Zone 2 Zone 3 Zone 4 Zone 5-10 Die
  • the screw recompresses the melt and passes it through kneading blocks and reverse elements which also serve as a vacuum seal for this side of the vacuum zone.
  • the melt is then further compressed and mixed as it passes through the end of the extruder and out the die.
  • Zone 1 Zone 2 Zone 3 Zone 4 Zone 5 Die f°c) f°c) _l__j £s) ( cj f*c)
  • Sample 7-1 had a melt viscosity, measured using a Kayeness viscometer at 270°C of 30045 Pa sec at 1 sec-1, and 968 Pa sec at 1000 sec-1.
  • Component b) 11.6 kg/hr.
  • Additive B 136 gm/hr.
  • the ingredients for Sample 9-1 were blended on a Werner and Pfleiderer bilobal twin screw extruder having a diameter of 57mm and a length to diameter ratio of 37.
  • the screw used was a general purpose screw with vacuum capability consisting of conveying elements to convey the feed material from the feed zone to a melting zone in which the material was compressed and melting begins.
  • a section of "kneading blocks” followed by “reverse elements” next provides high shear and pressure to further the melting and mixing process. The reverse elements serve also to provide a melt seal following which the melt is decompressed in the section under vacuum.
  • the product was extruded at a rate of 68 kgs/hour through a six hole die. Temperature of the melt exiting the extruder die was measured as the melt temperature. Melt strands exiting the extruder were quenched in water and cut into pellets. The . pelletized product was dried at 95°C in a circulating air drier equipped with dehumidifier.
  • the resulting dry blend was melt blended on a Werner and Pfleiderer twin-screw extruder having a diameter of 28mm and a length to diameter ratio of 27.5.
  • the screw used is a general purpose screw with vacuum capableitiy consisting of conveying elements to convey the feed materials from the feed zone to a melting zone in which the material is compressed and melting begins.
  • a section of "kneading blocks” followed by “reverse elements” next provides high shear and pressure to further the melting and mixing processes. The reverse elements serve also to provide a melt seal following which the melt is decompressed in the section under vacuum.
  • Sample 11-2 had a melt viscosity, measured using a Kayeness viscometer at 260°C of 23000 Pa sec at 1 sec-1, and 1200 Pa sec at 1000 sec-1.
  • the resins for each Sample in the Tables above were extruded at the designated screw speed through the die to produce a parison. Upon closing the molded, the part is blown with air at about 400 MPa. The blown part is cooled in the mold under pressure and ejected.
  • the mold geometry of the bottles are 22.5 cm high and 7.5 cm diameter; and the spoiler has dimensions of 136 cm long, 9 cm wide and 1.5 cm thick.
  • Blow molded automobile spoilers were also produced from the compositions of Table VIII.
  • the procedure and conditions used for blow molding the spoiler are as follows:
  • the dried resin product was blow molded using a Sterling blow molding machine equipped with a 819 cm diameter barrier type screw with a length to diameter ratio of 24:1 and an accumulator of the first-in-first-out design with a capacity of 6.8 kg.
  • the extruder barrel of the blow molding machine was heated and the temperature reulated at 260°C, 260°C. 255°C and 255°C for each of the four temperature zones, respectively.
  • the three zones of the accumulator were set at 263°C.
  • the extruder screw was operated at a rate of 30 RPM.
  • the automobile spoler mold was heated to 90°C.
  • the three zones of the accumulator were set at 257°C, 260°C, and 263°C and the die at 265°C.
  • the extruder screw was operated at a rate of 30 RPM.
  • the car spoiler mold was heated to 71°C:
  • the resins for each Sample in the Tables above were extruded at the designated screw speed through the die to produce a parison. Upon closing the molded, the part is blown with air at about 400 MPa. The blown part is cooled in the mold under pressure and ejected.
  • the mold geometry of the bottles are 22.5 cm high and 7.5 cm diameter; and the automobile spoilers have dimensions of 136 cm long, 9 cm wide and 1.5 cm thick.
  • melt viscosity A number of physical properties were measured for each composition. The notch Izod impact strength was determined according to ASTM D-256 measured at 23"C. Tensile properties (tensile yield strength and elongation) at room temperature were measured by ASTM Procedure"D-638. The flexural modulus was measured according to ASTM Procedure D-790. Samples were also tested for melt viscosity. The measurement of melt viscosity is described below:
  • the inherent viscosity of PBT was measured at 25°C according to ASTM Procedure D-2857, "Standard Method for Dilute Solution Viscosity of Polymers". Viscosity was measured using a solution containing 0.5 gm polymer per 100 ml of solution. The solvent used consisted of a mixture of 1 part trifluoroacetic acid and 3 parts methylene chloride by volume. The polyesters, ethylene copolymer, ionomers, and additives used in the Samples are defined in the following Tables (I through IV) .
  • PET Polyethylene terephthalate
  • IV inherent viscosity
  • C PET homopolymer whith an IV of 1.0 dl/g.
  • D Polybutylene terephthalate (PBT) homopolymer with a melt index of " 6.0 7.5 gm/10 min. by ASTM D1238 (240°C, 2160 gram weight) having an inherent viscosity of 0.93 dl/g.
  • PBT Polybutylene terephthalate
  • A Sodium ionomer derived from ethylene/15% methacrylic acid copolymer (MAA) in which 59% of the acid groups have been converted to the corresponding sodium salt.
  • B Sodium ionomer derived from ethylene/10% MMA copolymer in which 75% of the acid groups have been converted to the corresponding sodium salt.
  • Sample 6-1 which is a control Sample contains no component c) , the ionomer. Bottles could only be obtained at the very beginning of blow molding (when the screw was only partially filled) on this sample due to the poor processibility, as shown by the fact that the screw speed dropped to zero.
  • Sample 6-2 which contains component c) shows a higher melt viscosity at both 1 sec-1 and 1000 sec-1 than Sample 6-1 but was significantly more processible than Sample 6-1 as shown by the screw speed. Parisons were extruded continuously and blown without difficulty for Sample 6-2.
  • Sample 6-3 which contains a second polyester, component d, in addition to the ingredients used in Sample 6-2, shows good processibility as evidenced by the high screw speed despite its increased melt viscosity at shear rates of 1 sec-1 and 1000 sec-1 as compared to Sample 6-2.
  • the bottles obtained for Sample 6-3 were smooth inside and outside.
  • Sample 7-1 through 7-4 in Table VII show PET compositions of the present invention containing linear PET and branched PET.
  • Sample 7-1 gives bottles with smoother surface than Sample 7-3 which contained no component d and higher levels of ionomer component c) .
  • control samples 7-2 and 7-4 which contain no branched PET to Samples 7-1 and 7-3 which contain branched PET. It can be seen that the control samples show lower processibility in the blow molding screw speed.
  • Sample 8-1 in Table VIII demonstrates the use of branched and linear PET in a composition of the present invention.
  • the melt viscosities at both 1 sec-1 and 1000 sec-1 are excellent and the blow molded automobile spoiler obtained showed very smooth surfaces and excellent melt strength.
  • Samples 9-1 and 9-2 in Table IX illustrate the compositions of the present invention blow molded into automobile spoilers and bottles, respectively.
  • the extruded parison had the smooth glossy surfaces and the high melt strength needed for blow molding of large parts with good surface quality.
  • Samples 5-1 and 5-2 refer to the same blow molding composition but they are distinguished from one another by forming to different parts.
  • Samples 10-1 through 10-10 in Table X illustrate the compositions of the present invention when component c) contains sodium and/or zinc.
  • Comparison of Sample 10-3 to 10-4 illustrates that in the presence of 5% sodium ionomer, component c) , the addition of 0.5 % of a zinc ionomer further enhances melt viscosity at 1 sec —l, however, at the same time, melt viscosity at 1000 sec —l is unchanged, indicating that processibility of the compositon is not adversely affected with the improvement in melt strength.
  • the zinc ionomer while not essential in the present composition had a minor beneficial effect.
  • Tough bottles smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt Tough bottles, smooth surfaces, strong melt
  • Samples 11-1 through 11-7 in Table VII compare compositions containing zinc and sodium ionomer.
  • Sample 11-1 which is a control Sample, contains no component c) .
  • the melt viscosity is lower than Sample 11-2 which contains component c) .
  • Samples 11-1 through 11-4 show an increase m melt viscosity at both 1 sec -1 and 1000 sec-1 as the level of sodium ionomer increases.
  • Samples 11-2, 11-5 and 11-6 illustrate the increase in melt viscosity at both 1 sec " and 1000
  • melt extrudate of Sample 11-7 is lumpy in contrast to the smooth extrudate of Sample 11-2.
  • Table XI shows that component c) , A, is superior to Additive C in providing not only high melt strength but substantially improved surface in the extruded parisons.

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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)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

Compositions de polyesters extrudables par soufflage semi-cristallins formées par mélange en fusion d'un polyester, d'un copolymère d'éthylène contenant des groupes époxydes, d'un ionomère obtenu par neutralisation à l'aide de Na+ ou K+ et facultativement d'un second polyester.
PCT/US1991/003970 1990-06-18 1991-06-11 Compositions de polyesters thermoplastiques extrudables par soufflage WO1991019767A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/539,753 US5128404A (en) 1990-06-18 1990-06-18 Thermoplastic blow moldable polybutylene terephthalate compositions
US07/539,649 US5091459A (en) 1990-06-18 1990-06-18 Thermoplastic blow moldable polyethylene terephthalate compositions
US539,753 1990-06-18
US539,649 1990-06-18

Publications (1)

Publication Number Publication Date
WO1991019767A1 true WO1991019767A1 (fr) 1991-12-26

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018561A1 (fr) * 1991-04-12 1992-10-29 E.I. Du Pont De Nemours And Company Procede de production d'une couche plastique amorphe et article en mousse ainsi produit
EP0511475A1 (fr) * 1991-03-08 1992-11-04 Nippon Petrochemicals Company, Limited Composition de résine de polyester
WO1993008234A1 (fr) * 1991-10-24 1993-04-29 E.I. Du Pont De Nemours And Company Compositions thermoplastiques a base de terephtalate de polybutylene destines aux revetements de cables
EP0666285A1 (fr) * 1994-02-02 1995-08-09 European Economic Community E.E.C. Matériau d'emballage de PET
WO1996034057A1 (fr) * 1995-04-26 1996-10-31 Alliedsignal Inc. Compositions de moulage a base de polyester
US5824412A (en) * 1991-10-24 1998-10-20 E. I. Du Pont De Nemours And Company Thermoplastic polybutylene terephthalate compositions for wire coating applications
EP1208970A1 (fr) * 2000-11-28 2002-05-29 Apex Research Ltd., Inc. Récipient multicouche thermoplastique
EP1260346A2 (fr) 2001-05-25 2002-11-27 Toyo Seikan Kaisha Limited Procédé d'extrusion de compositions de polymères

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673139A (en) * 1970-04-06 1972-06-27 Sandoz Ltd Process for the production of injection moulded and extrusion moulded polyester products
JPS59184251A (ja) * 1983-04-04 1984-10-19 Toray Ind Inc 樹脂組成物
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions
US4914152A (en) * 1986-11-20 1990-04-03 Kanegafuchi Kagaku Kogyo Kabushiki Polyester resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3673139A (en) * 1970-04-06 1972-06-27 Sandoz Ltd Process for the production of injection moulded and extrusion moulded polyester products
JPS59184251A (ja) * 1983-04-04 1984-10-19 Toray Ind Inc 樹脂組成物
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions
US4914152A (en) * 1986-11-20 1990-04-03 Kanegafuchi Kagaku Kogyo Kabushiki Polyester resin composition

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511475A1 (fr) * 1991-03-08 1992-11-04 Nippon Petrochemicals Company, Limited Composition de résine de polyester
WO1992018561A1 (fr) * 1991-04-12 1992-10-29 E.I. Du Pont De Nemours And Company Procede de production d'une couche plastique amorphe et article en mousse ainsi produit
WO1993008234A1 (fr) * 1991-10-24 1993-04-29 E.I. Du Pont De Nemours And Company Compositions thermoplastiques a base de terephtalate de polybutylene destines aux revetements de cables
US5824412A (en) * 1991-10-24 1998-10-20 E. I. Du Pont De Nemours And Company Thermoplastic polybutylene terephthalate compositions for wire coating applications
EP0666285A1 (fr) * 1994-02-02 1995-08-09 European Economic Community E.E.C. Matériau d'emballage de PET
WO1996034057A1 (fr) * 1995-04-26 1996-10-31 Alliedsignal Inc. Compositions de moulage a base de polyester
US5723520A (en) * 1995-04-26 1998-03-03 Alliedsignal Inc. Polyester molding compositions and articles exhibiting good impact, heat and solvent resistance
AU714545B2 (en) * 1995-04-26 2000-01-06 Honeywell International, Inc. Polyester molding compositions
EP1208970A1 (fr) * 2000-11-28 2002-05-29 Apex Research Ltd., Inc. Récipient multicouche thermoplastique
US6773735B1 (en) 2000-11-28 2004-08-10 Associated Packaging Enterprises, Inc. Multi-layered thermoplastic container
EP1260346A2 (fr) 2001-05-25 2002-11-27 Toyo Seikan Kaisha Limited Procédé d'extrusion de compositions de polymères
EP1260346A3 (fr) * 2001-05-25 2003-11-19 Toyo Seikan Kaisha Limited Procédé d'extrusion de compositions de polymères

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