WO2013121397A2 - Résine polyester moulable par injection et par intrusion, son procédé de fabrication et article moulé par injection et par intrusion - Google Patents

Résine polyester moulable par injection et par intrusion, son procédé de fabrication et article moulé par injection et par intrusion Download PDF

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Publication number
WO2013121397A2
WO2013121397A2 PCT/IB2013/051250 IB2013051250W WO2013121397A2 WO 2013121397 A2 WO2013121397 A2 WO 2013121397A2 IB 2013051250 W IB2013051250 W IB 2013051250W WO 2013121397 A2 WO2013121397 A2 WO 2013121397A2
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WO
WIPO (PCT)
Prior art keywords
injection flow
polymer
resin
molded article
present
Prior art date
Application number
PCT/IB2013/051250
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English (en)
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WO2013121397A3 (fr
Inventor
Nick BARTLETT
Sanjay Tammaji Kulkarni
Original Assignee
Smartflow Innovative Plastics Containers B.V.
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 Smartflow Innovative Plastics Containers B.V. filed Critical Smartflow Innovative Plastics Containers B.V.
Publication of WO2013121397A2 publication Critical patent/WO2013121397A2/fr
Publication of WO2013121397A3 publication Critical patent/WO2013121397A3/fr

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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
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes

Definitions

  • the present invention relates to poly (ethylene terephthalate) polyester resin composition and to a process for manufacturing the same.
  • the standard I. CM. molding process uses mechanically controlled moveable mold cores, located inside of a fully closed and clamped mold, to achieve an in mold compression and still does not overcome the fundamental inherent problem of process instability and lack of process control.
  • thermoplastic resin is injected into a fully closed and clamped mold using injection conditions of temperature and velocity that are appropriate to the particular resin type and product type.
  • the injection of the resin melt pressurizes the mold cavity, which contains a moveable mold part on the opposite side to the injection side of the cavity.
  • the mold cavity expands at a rate and to an extent that is dictated by the resin melt viscosity, as the material is then more free to follow its natural flow profile without externally imposed controls.
  • the pre-pressurized flexible mold part is able to return to close the mold back to its original dimensions with a resulting compression of the melt.
  • the injection flow molded articles consist of thin walled containers featuring good color, optical, mechanical, chemical and thermal properties and have low susceptibility to degradation, for both food and non-food applications, and which require the use of high melt strength and high melt flow polyester resin.
  • the injection flow molded articles offer significant economic benefits as well as quality improvements with a wide design window.
  • Injection molding in general is a well-established and widespread conversion process for the manufacture of various articles, particularly liquid containers and packaging items, having applications involving both food and non-food contact. It is being used very successfully since many decades.
  • Poly (ethylene terephthalate) (P.E.T.) on the other hand is a polymer having outstanding properties.
  • P.E.T. resins can be semi-rigid to rigid, and are very lightweight. They make good gas and fair moisture barriers, as well as good barriers to alcohol and other solvents, particularly after additional barrier treatment, like for instance metallization, sandwiching with polyvinyl alcohol etc .
  • P.E.T is an excellent material for food contact as it has extremely low levels of absorption and migration. Moreover they can be easily recycled and the base materials re-used.
  • P.E.T. resins are therefore used extensively in synthetic fibers; beverage, food and other liquid containers; thermoforming applications; and engineering resins often in combination with glass fiber reinforcement. Depending on their processing and thermal history, they may exist both as an amorphous and as a semi-crystalline polymer.
  • the amorphous polymer is transparent. Whereas the semi- crystalline material might appear transparent when it has crystal particles in sizes under about 500 nm or opaque and white when it has crystal particle with sizes up to a few microns .
  • melt extrusion of sheets subsequently followed by a thermoforming process is necessary, generating nevertheless up to 35 % of wastage which needs to be recycled. This unavoidably results in a considerable increase in overall investment and operating costs and has a negative impact on the environment.
  • If used in molding applications it exhibits a high melt viscosity and a high tendency to degrade thermally and hydrolytically at elevated temperatures. The latter invariably tend to cause deterioration of its mechanical, chemical and esthetic properties. For that reason it is not being used in common injection molding applications, particularly not for the manufacture of molded articles having wall thicknesses of less than 0,5 mm.
  • the melting temperature of P.E.T. resins lies in the range of about 250°C to about 260°C as taught by A.K. van der Vegt, L.E.Govaert in "Polymeren, van keten tot kunststof", ISBN 90-407-2388-5, and the glass transition temperature at about 75°C.
  • the P.E.T. polymer itself is usually produced in a reactor by forming a pre-polymer first by an esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct, and in which monomers and pre-polymers are formed in the presence of a catalyst. This esterification reaction is then immediately followed by polymerization reaction of the monomers and pre-polymers through polycondensation, with again water as the by product. This polymerization reaction through polycondensation is typically carried out at a temperature range of about 270°C to about 305°C, and under reduced pressure of less than 10 mbar. In case additives, stabilizers, rheology modifiers, lubricating agents, nucleating agents etc. are incorporated, they are usually compounded in only after solid state polymerization of the mass.
  • This known compounding process however has severe shortcomings in that it consists of an additional process step which is not only expensive, time and energy consuming and needs additional equipment, but also exposes the polymer to further degradation by oxygen, temperature and moisture. It also often results in the formation of gel particles in the final polymer which, in turn, tend to affect adversely the color, clarity and mechanical properties of the final product.
  • the polyester resin formed has an intrinsic viscosity (I.V.) range of : 0,40 to 0,70 dl/g for textile fiber grade;
  • the standard grades used for making preforms, bottles and sheets typically have a melt flow index (M.F.I.) of 25 g/min at 270°C with a 3,2 kg load.
  • M.F.I. melt flow index
  • a process for the preparation of injection flow moldable polyester resin compositions essentially consisting of a poly (ethylene terephthalate-isophthalate) co-polymer, wherein said process comprises the following steps: a. charging a reactor with a diol-dicarboxylic acid pair, along with co-monomer to obtain a reaction mixture; b. subjecting said reaction mixture to an esterification reaction yielding a pre-polymer; c. adding to the pre-polymer at least one resin modifying additive and forming a pre-polymer - additive mixture; d.
  • melt flow index MFI
  • I.V. intrinsic viscosity
  • iol-dicarboxylic acid pair is understood a reactive pair of chemical compounds, consisting of a diol and a dicarboxylic acid, typically mono ethylene glycol and therephtalic acid, which react together in an esterifaction reaction to form the structural unit with molecular formula ⁇ 3 ⁇ 4 ⁇ 4 from which the main polymer chain is essentially built in a consecutive polymerization reaction based on a polycondensation process.
  • ' 'co-monomer' is understood a reactive chemical compound, either diol or dicarboxylic acid, capable of forming a monomer that is incorporated into the polymer chain by an esterification reaction followed by polymerization through polycondensation, but forms repeat units that are different from those the main chain is essentially constituted of.
  • pre-polymer' is understood a monomer, oligomer, polyester or co-polyester, or a blend of any of those, having low molecular weight and hence low intrinsic viscosity.
  • a P.E.T. polyester resin suitable for injection flow molding applications, particularly for the manufacture of molded articles having a local wall thickness not exceeding 300 ⁇ .
  • an injection flow molded article in the form of a thin walled container capable of being filled at up to 95°C.
  • an injection flow molded article in the form of a transparent ovenable tray capable of withstanding up to 210°C for an extended period of time.
  • a process for making injection flow moldable polyester resin wherein the various additives are introduced in the reaction mixture during the monomer, oligomer or pre-polymer formation, when the viscosity of the reaction mixture is still very low.
  • a process for the preparation of injection flow moldable polyester resin essentially consisting of a poly (ethylene terephthalate-isophthalate) co-polymer, wherein said process comprises the following steps: a. charging a reactor with a diol-dicarboxylic acid pair, along with co-monomer to obtain a reaction mixture; b. subjecting the reaction mixture to esterification yielding a pre-polymer; c.
  • a pre-polymer additive mixture d. subjecting the pre-polymer additive mixture to a polycondensation polymerization reaction at a temperature in the range of about 255 to about 265°C, under vacuum and increased rate of agitation, to obtain a final polyester resin having a Melt flow Index (MFI) of about 130 g/10 min.to about 140 g/10 min. at 270°C with a load of 3.2 kg, and an intrinsic viscosity (I.V.) of about 0,50 dl/g to about 0,80 dl/g.
  • MFI Melt flow Index
  • I.V. intrinsic viscosity
  • P.E.T. resins are commonly prepared by using either a iol-dicarboxylic acid' pair, a , diol-dicarboxylic ester pair' or a iol-P . E . . ' pair as polyester forming materials.
  • the esterification step b) is typically carried out at a temperature in the range of about 200 to about 300°C. It is during this esterification reaction or immediately after that according to one important aspect of the present invention useful additives are added to the reaction mixture.
  • catalysts are normally used which are not different from those know by people skilled in the art, for instance at least one catalyst selected from the group consisting of antimony, germanium, titanium, tin, or aluminum compounds .
  • This polymerization reaction, step d) , of the reaction mixture through polycondensation is typically carried out at a temperature range of about 290 to about 300°C.
  • the temperature at which the polycondensation reaction is carried out is significantly reduced and adjusted in the range of about 255°C to about 265°C, under vacuum, and with increased rate of agitation.
  • I.V. intrinsic viscosity
  • This also has the advantage that lower cycle times and better productivity can be obtained in consecutive injection flow molding processes.
  • melt flow index lies in the range of 25 g/10 min. at 270°C with a 3,2 kg load
  • M.F.I the melt flow index of the polyester resin made according to the invention lies at about 135 g/10 min. under the same conditions. This indicates that there is over a 500 % increase of flow compared with that of a conventional P.E.T. resin of corresponding intrinsic viscosity (I .V. ) .
  • One of the important benefits of the present invention is that useful materials in the form of additives are added at the melt polymerization stage c) which largely prevents the formation of gels in the final polymer or the need for addition of those additives in a subsequent compounding operation. At the same time avoiding additional costs, investments and adverse environmental effects.
  • the P.E.T. resin according to the present invention can be supplied in crystallized form, so that it can be dried at about 160°C to about 180°C without hydrolytic degradation taking place.
  • thermoforming line The investment and operating costs of a sheet extrusion line, and expensive thermoforming line, can be saved because they are no longer needed.
  • the dicarboxylic acid of the diol-dicarboxylic acid pair of step a) is at least one selected from the group consisting of terephthalic acid and isophthalic acid, and the diol is mono- ethylene glycol.
  • terephthalic acid In accordance with another embodiment of the present invention about 4 wt% to about 20 wt% of terephthalic acid is replaced by isophthalic acid.
  • the co- monomer in step a) is at least one dicarboxylic acid selected from the group consisting of malonic-, succinic-, glutaric- and adipic acid, and is present in a concentration in the range of about 0,5 wt% to about 2,0 wt% in respect of the mass of the reaction mixture.
  • the co-monomer in step a) is at least one diol selected from the group consisting of di-ethylene glycol (DEG) , poly-ethylene glycol having a molecular weight up to 4000, neo-pentylglycol (N.P.G.) 1,3- and 1 , 4 -cyclohexane dimethanol (1,3 C.H.D.M. and 1,4 C.H.D.M.), 1, 4-butanediol, and is present in a concentration up to 20 wt% in respect to the mass of the reaction mixture.
  • DEG di-ethylene glycol
  • N.P.G. neo-pentylglycol
  • 4 -cyclohexane dimethanol 1,3 C.H.D.M. and 1,4 C.H.D.M.
  • 4-butanediol 1, 4-butanediol
  • the resin modifying additive in step c) is at least one stabilizer selected from the group consisting of phosphoric acid, aliphatic phosphoric acid compounds and phosphites, and is incorporated in a concentration of up to 6000 ppm.
  • the resin modifying additive in step c) is at least one internal lubricating agent selected from the group consisting of fatty acid esters, synthetic waxes and micronized waxes, particularly alkanes with 50 to 100 carbon atoms, silicone fluids, and is incorporated in a concentration of up to 1 wt%.
  • the resin modifying additive in step c) is at least one nucleating agent selected from the group consisting of: A. solids, particularly silicon dioxide, talc, clay particles ;
  • alkali and alkaline metal earth salts of aromatic carboxylic acids particularly sodium benzoate, sodium salicylate ;
  • C. salts of aliphatic acids particularly sodium acetate, and that has a range size of about 20 nm to about 10 ⁇ . It is added in a concentration ranging from about 0,1 wt% to about 1,0 wt%.
  • these nano-sized nucleating agents can be very well dispersed the P.E.T. matrix and then act synergistically with the co-monomers mentioned above, in particular gluconic, succinic, malonic and adipic acid, which can interfere locally with the large scale crystallization of P.E.T. They obviously allow the production of very large numbers of small sized spherulites that do not interfere with the light transmittance and also do not interfere with the mechanical and other desirable properties of the resin or the injection flow molded article.
  • co-monomers mentioned above are melt mixed with the P.E.T raw materials and the nano-sized nucleating agents mentioned above in the esterification phase of the manufacturing process, i.e during formation of pre-polymer, and before polymerization through polycondensation.
  • the resin modifying additive in step c) is at least one flow promoter selected from the group consisting of finely dispersed silica, micronized graphite particles, metallic and non-metallic stearates, particularly calcium stearate, zinc stearate, butyl stearate, and is suspended or dissolved in at least one diol before being added to the mixture in a concentration of up to 5 wt%.
  • an injection flow molded article consisting of a parison, a container, a film, a tube, or a tray .
  • an injection flow molded article that has at least a local wall thickness of less than 300 ⁇ .
  • an injection flow molded article formed is provided having a thin wall and capable of being hot filled at about 95°C without dimensional deterioration.
  • an injection flow molded article consisting in a transparent ovenable tray that can withstand up to 210°C.
  • thin wall containers are provided produced in multi-cavity molds with typical wall thicknesses of 300 ⁇ by injection flow molding of high flow P.E.T. grades having a Melt Flow Index (I.M.F.) of 90 g/10 min., (at 270 °C, under 2.16 kg load).
  • I.M.F. Melt Flow Index
  • Injection flow molded containers with a wall thicknesses of 200 ⁇ are provided using a P.E.T. grade with a Melt Flow Index (I.M.F.) of 120 g/10 min., (at 270 °C, under 2.16 kg load).
  • I.M.F. Melt Flow Index
  • injection flow molded containers are provided that are heat sealed with lids made from a high flow P.E.T grade of different formulation in such a way as to allow the lid to be subsequently removed by peeling the seal area manually.
  • said sealable lid is designed with clips that allow the lid to be clipped back onto the container, after opening, to act as a re-closable lid.
  • injection flow molded high heat resistant crystallized containers resistant up to 220 °C, are provided that are suitable for chilled and frozen ready meals.
  • injection flow molded high heat resistant crystallized transparent thin wall ovenable containers are provided, resistant up to 220 °C, and in which transparency is achieved by designing the crystal wall structure so that the crystal size is kept smaller than the wavelength of visible light so as not to scatter the light.
  • transparent high oxygen barrier injection flow molded containers are provided that suitable for packaging shelf stable processed foods, in which the foods are aseptically processed either by pasteurizing or sterilizing using Ohmic heating and filled under clean, ultra clean or aseptic conditions, and that have an oxygen barrier with a maximum oxygen ingress of 1 ppm oxygen per year.
  • transparent high oxygen barrier injection flow molded containers are provided that are coated with an aqueous 0.1 ⁇ Si02 coating in the mold, and in which the coating prevents bacterial growth on the container surface, not requiring chemical sterilization of the containers anymore immediately prior to the entrance of the filling machine.
  • both transparent and opaque high oxygen barrier injection flow molded containers are provided that are suitable for hot filling and pasteurizing high acid shelf stable foods at 100 °C.
  • both transparent and opaque high oxygen barrier injection flow molded P.E.T. containers are provided that are suitable for hot filling and sterilizing low acid shelf stable foods at 121 °C.
  • reusable washable injection flow molded beer glasses are provided that can subsequently pass the washing cycle of 90 °C for 2 minutes as typically used for cleaning beer glasses.
  • said glasses are coated in the with a 0.1 ⁇ Si02 coating and rendered scratch resistant for the lifetime of the glasses.
  • single use injection flow molded beer containers which contain the C02 level in the beer over a 4 month shelf life and which have a fully peel off lid allowing the consumer to drink directly from the wide mouth container.
  • high stretch ratio thin wall P.E.T. injection flow molded preforms are provided which are suitable for manufacturing of ultra-light weight 0.5 liter carbonated soft drink bottles which include a step design for manufacturing a champagne base containing a thin walled gate.
  • high barrier, creep resistant injection flow molded aerosol containers are provided which exhibit increased heat resistant to pass the 50 °C standard pressure test.
  • transparent and opaque injection flow molded squeezable tubes are provided by using a high flow soft P.E.T.grade.
  • the present invention is in no way limited to the form of embodiment described by way of an example, however, such an invention of a process for making injection flow moldable polyester resin, the resin composition produced herewith, and the molded articles made from it by injection flow molding techniques can be realized in various ways or forms without leaving the scope of the invention.

Abstract

L'invention concerne une composition de résine en PET utilisée pour le moulage par injection et par intrusion d'articles moulés, et son procédé de fabrication.
PCT/IB2013/051250 2012-02-17 2013-02-15 Résine polyester moulable par injection et par intrusion, son procédé de fabrication et article moulé par injection et par intrusion WO2013121397A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1202734.8 2012-02-17
GB1202734.8A GB2499583A (en) 2012-02-17 2012-02-17 Poly(ethylene terephthalate-isophthalate) copolymer

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WO2013121397A2 true WO2013121397A2 (fr) 2013-08-22
WO2013121397A3 WO2013121397A3 (fr) 2013-11-21

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PCT/IB2013/051250 WO2013121397A2 (fr) 2012-02-17 2013-02-15 Résine polyester moulable par injection et par intrusion, son procédé de fabrication et article moulé par injection et par intrusion

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WO (1) WO2013121397A2 (fr)

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP1433804A1 (fr) * 2002-12-03 2004-06-30 Nan Ya Plastics Corp. Composition des copolyesters pour produire des grandes bouteilles
US20070066792A1 (en) * 2005-09-16 2007-03-22 Colhoun Frederick L Late addition to effect compositional modifications in condensation polymers
WO2007047322A1 (fr) * 2005-10-20 2007-04-26 Eastman Chemical Company Polymere pet presentant des proprietes ameliorees
WO2011010179A1 (fr) * 2009-07-22 2011-01-27 Momexx B.V. Procédé et équipement de moulage de matière plastique par extrusion

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JP2001098058A (ja) * 1999-07-26 2001-04-10 Kanebo Ltd 共重合ポリエステル樹脂およびそれからなるプリフォーム
JP4326241B2 (ja) * 2003-03-13 2009-09-02 大和製罐株式会社 ポリエステル樹脂およびそれからなる成形体
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EP1433804A1 (fr) * 2002-12-03 2004-06-30 Nan Ya Plastics Corp. Composition des copolyesters pour produire des grandes bouteilles
US20070066792A1 (en) * 2005-09-16 2007-03-22 Colhoun Frederick L Late addition to effect compositional modifications in condensation polymers
WO2007047322A1 (fr) * 2005-10-20 2007-04-26 Eastman Chemical Company Polymere pet presentant des proprietes ameliorees
WO2011010179A1 (fr) * 2009-07-22 2011-01-27 Momexx B.V. Procédé et équipement de moulage de matière plastique par extrusion

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GB2499583A (en) 2013-08-28
WO2013121397A3 (fr) 2013-11-21
GB201202734D0 (en) 2012-04-04

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