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Patents for high Tg Polyesters

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Patent Literature to Develop High Temperature Polyesters

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Patents for high Tg Polyesters

  1. 1. IP Report on To improve Tg and heat resistance of PET Ester Industries Limited Khatima India February 18, 2012 This document is confidential and is proprietary to Ester industries Ltd. The contents of this report of this communication represent a technical opinion only.
  2. 2. S.No 1 PatentNo JP2006193575A PublicationData 7/27/2006 Assignee TEIJIN LTD Title Highheat resistance non-crystallinepolyester Abstract PROBLEMTO BE SOLVED: To provide ahighly heat-resistantandtransparent polyestersuitable foroptical uses andgeneral resinuses. SOLUTION:This polyesterisobtained,forexample,bypolymerizingdimethylterephthalate,9,9'- dihydroxymethylfluorene andethylene glycol asraw materials,isamorphous,and has a glass transitiontemperature of 100 to180°C. Novelty A polyesterisnon-crystalline andhasglasstransitiontemperature of 100-180°C, and isobtainedbyco-polymerizingdicarboxylicacid(A),aliphaticdihydroxy compound(B) and aliphaticdihydroxycompound(C) asmainmonomer.The mole compositionratioof residue of aliphaticdihydroxycompound(B) andresidue of aliphaticdihydroxycompound(C) inthe polyesterissatisfiespresetrelation. Use/Advantage The polyesterhasexcellentheatresistance,andfavorable transparencyandfilm workabilityanddoesnotcontaincrystal.The glasstransitiontemperature of the polyesterishigh. Formulation Preparationprocess: 9.709g (0.05mol)-dimethyl terephthalicacid 4.526g (0.02 mol) -9,9 '- dihydroxymethyl fluorene from Yurui (Shanghai) Chemical Co., Ltd. 6.207g (0.1 mol)-ethyleneglycol, 8 mg (0.1 mmol)- calciumacetate monohydrateand 7.2mg (0.025 mmol) - antimonytrioxide were chargedintoaflaskundera nitrogen atmosphere. The flaskwas heatedto180 ℃,dissolve the contentswere allowedto,will be carriedout transesterificationreached200 ℃,while heatingata rate of 10 ℃ per 15 minutes.Make sure that the endof the distillationof methanol and4ml of a theoretical amountof distillate,14mgof trimethyl phosphate asananti-coloring(1 x 10 -4 mol) wasadded,the flask90 0.5mmHg overa minute undervacuum. Heatedupto 270 ℃ overthe flaskfollowedby30 minutes,Iwenttoa highdegree of polymerization.Afterreaching270 ℃,the polymerizationterminates whenheld for 2 hours,removedthe polyestermeltinthe flask.The reducedviscosityof the resultingpolyester,Tg,as describedinTable 1 by protonNMR analysisand composition. Chemical formula
  3. 3. S.No 2 PatentNo JP2008308600A PublicationData 12/25/2008 Assignee TEIJIN FIBERS LTD Title The manufacturingmethodof the polyestercopolymercomposition excellentin heat resistance Abstract PROBLEMTO BE SOLVED:To provide amethodforproducinga copolyester compositionwhichinhibitsthe meltingpointloweringof polyesterscopolymerized withphosphorousflame retardants,cansuitablybe usedforusessuchas fibers, filmsandresins,andhasexcellentheatresistance. SOLUTION:This methodforproducingthe copolyester,havingthe firststep reactionforapplyinganesterificationreactionoratransesterificationreactionto produce the reactionproductand the secondstepreactionfor polycondensingthe reactionproduct,ischaracterizedbyadding(i) a specificcarboxyphosphinicacid- basedphosphoruscompoundinanamountof 0.1 to 10 mol% basedon an acid componentconstitutingthe obtainedpolyesteruntil the finishof the secondstep reactionandadding(ii) a laminarcompoundinanamountof 0.05 to 5 wt.% based on the obtainedcopolyester. Novelty Manufacture of polyestercopolymercompositioninvolvesesterifyingor transesterficationof terephthalicacidorits esterformingderivative and2-4C alkylene glycol,polycondenzingthe obtainedreactionproductandaddingcarboxy phosphinicacidtype phosphoruscompound(1) andlayeredcompoundbefore the completionof polycondenzationreaction.The additionalamountof carboxy phosphinicacidtype phosphoruscompoundis0.1-10 mol% withrespecttoacid componentof polyester.The additional amountof layeredcompoundis0.05-5 weight%withrespecttopolyestercopolymer. Use/Advantage The methodefficientlymanufacturespolyestercopolymercomposition having heat resistance and flame retardance. Formulation Transesterificationstep: 100 partsdimethyl terephthalate 60 parts of ethylene glycol 0.06 parts of manganese acetate dihydrate(0fordimethyl terephthalate 0.03mole percent) 0.004 parts cobaltacetate dihydrate andorganize acolorant(0.003 mole percent dimethyl terephthalate) Polycondensationstep: 0.026 part of trimethyl phosphate asastabilizer(0.036mole percentdimethyl terephthalate) 0.04 parts of antimonytrioxide and thenafter10 minutes(0.027 mole percent dimethyl terephthalate) wasadded, at the endof polycondensationlayeredcompound(silicates,mica,nanoclayetc) - 0.1 to 2 weight%
  4. 4. S.No 3 PatentNo JP2008291151A PublicationData 12/4/2008 Assignee SANYOCHEM INDLTD Title Heat resistantpolyesterresin Abstract PROBLEMTO BE SOLVED:To provide apolyesterresinof excellentheatresistance and impact resistance. SOLUTION:This heatresistantpolyesterresinisaheatresistantpolyester resin(III) constitutedof adiol component(I) anda dicarboxylicacidcomponent(II),and havinga contentof 5-99 mol.% of a bisphenol-Aethylene oxide adduct(A) inthe diol component(I).The bisphenol-Aethylene oxide adduct(A) isareactionmixture comprising0-1 mol.% of bisphenol-A ethylene oxideone-molaradduct(A1),92-100 mol.%of bisphenol-A ethylene oxide two-molaradduct(A2),and0-7 mol.% of bisphenol-A ethyleneoxide three-or-more-molaradduct(A3). Novelty A polyesterresincontains(inmol%) adiol component(5-99) anddicarboxylicacid component.The diol componentisa bisphenol-Aethylene oxide additionproduct. The bisphenol-A ethylene oxideadditionproductcontains1mol additionproduct of bisphenol-A ethylene oxide (0-1),2mol additionproductof bisphenol-A ethylene oxide(92-100) and 3 mol or more of additionproductof bisphenol-A ethylene oxide(0-7). Use/Advantage The polyesterresinhasexcellentheatresistance andimpactresistance. Formulation Preparationprocess: 332g of terephthalicacid(2.0mol) 211g ethylene glycol (3.4mol)and 190g (0.6mol) of Bisphenol-A andethyleneoxideadductwaschargedwith0.03g of titaniumtetra-isopropoxyesterificationcatalystandheatedto220 ℃. Promotedcondensationreactionwhile removingwater,wherethere are no condensationof waterdistillateunderatmosphericpressure,heatedto230 ℃,the systemwasgraduallyreducedpressure.Promote the reactionwhileremovingthe ethylene glycol,molecularweightwasfollowedbyGPC.The contentswere taken out at 18,000 numberaverage molecularweightpolyesterresinof the present invention(C-1) wasobtained.Ethyleneglycol wasremoved124g (2.0mol), respectively. Preparation of Bisphenol-Aandethyleneoxide adduct: In an autoclave made of glass,1100ml capacityinPreparationof bisphenolA228.0g (1.0mol) was chargedwith228.0g waterand,after nitrogensubstitution,90 ℃heatedup,dispersedinwater, bisphenol A.Here potassiumhydroxide(KOH) 3.0gto (0.054mol) was added.Performedagainreplaced withnitrogen,EO88.0g (2.0mol) 90 ℃, the reactionwasdrippinginthe range of reactionpressure 0.2MPa. Afterdroppingfourhoursfromthe start, 1.4g of phosphoricacid(0.014mol) was added, EO22.0g more (0.5mol) 90 ℃, the reactionwasdrippinginthe range of reactionpressure 0.2MPa.The reactionisterminatedafterdroppingfortwohours,fourwere transferredtothe reactionflask.Water was removedbyliquidseparationbyheatingto90 ℃.Furthermore,since itiscontaineddiethylene glycol and ethyleneglycol by-productinthe system, inordertoremove it,washedbystirringfor1 hourat 90 ℃ 300g addedwater.Wasthenfilteredandtreatedwithactivatedclaytoremove waterseparation. Vacuumdehydratedat130 ℃it,bisphenol A di (oxyethylene)ethersof the presentinvention(A-1) 265g (84 percentyield)wasobtained.
  5. 5. S.No 4 PatentNo US20080242783A1 PublicationData 10/2/2008 Assignee GENERAL ELECTRIC CO Title POLYESTER COMPOSITIONS HAVING IMPROVEDHEAT RESISTANCE Abstract A compositionof mattercomprisingapolyestercompositionderivedfrom:(i) 20to 80 mole percentof a firstdiol derivedfromadisubstitutedxylene glycolof the formula(I): whereinR1 and R2 are independentlyselectedfromthe group consistingof aliphaticradical,aromaticradical,cycloaliphatic,radical andhalogen; and (ii) aseconddiol and(iii) adiacidisdisclosed.Alsodisclosedare blendsof these polyesterswithpolycarbonateandprocesstoprepare these compositions and articlestherefrom. Novelty A polyestercompositioncomprises20-80 mol.% of firstdiol derivedfrom disubstitutedxyleneglycol,diacide.g.succinicacid,andseconddiol e.g.ethylene glycol. Use/Advantage The compositionhasgoodbalance of optical and mechanical properties,highheat resistance,processability,chemical resistance,andflame resistance. Formulation Process: 1) DMT Dimethyl Terephthalate 2) BDO 3) 20-80 mol.%of firstdiol derivedfromdisubstitutedxylene glycol (DmPXG) from GE 4) EG Xylene Glycol structure
  6. 6. S.No 5 PatentNo JP2006089629A PublicationData 4/6/2006 Assignee MITSUBISHI CHEMICALS CORP Title Polyesterresin Abstract PROBLEMTO BE SOLVED:To provide apolyesterresingivinga bottle havinghigh heat resistance and excellentmechanical strengthand transparency by stretch blow molding. SOLUTION: The polyesterresiniscomposedof adicarboxylicacid componentcomposedmainlyof anaromaticdicarboxylicacidanda diol componentconsistingof twoormore kindsof diolsandcontainingpolymethylene glycol as a maincomponent. The resin has a glass transition temperature of 82-110°C and an intrinsic viscosity of 0.73-1.50 dL/g and satisfieseitherone or bothof the propertiesA andB. (A) The peakvalue of the descendingtemperature crystallizationtemperature is≥180°C or undetectable and(B) the injection-molded plate specimenhavingathicknessof 4 mm has a lightabsorbance of 0.06-0.30 at 1,000 nmwavelength,andabrightnessindexLof 70-90, a chromaticcoordinate a of -3 to +3 and a chromaticcoordinate bof -3 to +3 in the Hunter'scolor-difference formulainLab color specificationsystem. Novelty Polyesterresincontainsaromaticdicarboxylicacidandpolymethylene glycol,and has glasstransitionpointof 82-110°C and intrinsicviscosityof 0.73-1.5 dl/g.The polyesterresinhascrystallizationpeakof 180°C or lessduringtemperature fall, and/orinjectionmoldedboardof polyesterresinhaslightabsorbencyof 0.06-0.3 at 1000 nm wavelength,brightnessindex (L) of 70-90 and colorcoordinates(a,b) of -3 to 3. Use/Advantage The polyesterresinhasexcellentheatresistance,mechanical strength, transparencyandmoldability,andismanufacturedwithhighproductivity. Formulation Preparationprocess 95 mol%or more of terephthalicacid 80 mol%or more of ethyleneglycol, 0.5 mol%or more of diol havingcyclicstructure or isosorbide,and 3 mol%or lessof diethyleneglycol 10-4-10-3 ppm of resinchosenfrompolyamide and/orpolyolefin Cyclc Sorbide structure
  7. 7. S.No 6 PatentNo JP2004161967A PublicationData 6/10/2004 Assignee NAKAMOTOPAKKUSUKK Title PRODUCTION METHOD FOR HEAT-RESISTANTSHEET ANDMOLDED PRODUCT OF POLYETHYLENE TEREPHTHALATE-BASEDPOLYESTER Abstract PROBLEMTO BE SOLVED:To provide aproductionmethodfora heat-resistant sheetandmoldedproductof a polyethyleneterephthalate-basedpolyesterata lowcost,whereinthe heat-resistantsheetisapplicabletoa container capable of fillingcontentsbyheatingandresiststoheatingwithamicrowave oven,byhaving the propertiesof small drawdownandcrystallizationata highspeed. SOLUTION: The heat-resistantsheetandmoldedproductare producedbyusingablock copolymerwhose meltviscosityisincreasedtoatleast10 timesof that of a conventional linear-structuredPET,bymodifyingthe structure tothat having branchedlongchains,enablingittocrystallize atahighspeed,throughreactive extrusionof the mixture consistingof (a) 100 pts.wt.PET-basedpolyester,(b) 0-100 pts.wt.otherpolyesterorcarboxygroup-containingpolyolefin,(c) 1-15 pts.wt. masterbatch of a mixture with0-75/100-25 weightratioof an at leasttrifunctional epoxycompound/abifunctional epoxycompoundasa bondingagent,and(d) 0.25- 10 pts.wt.masterbatch of an organic acidmetal saltcomposite asa binding catalyst,whereinheat-setisjointlyused. Novelty The transparentheat-resistingpropertysheetof PETgrouppolyesterisobtainedby moldingand thermoformingblockcopolymerhavingmeltflow rate of 40 g/10 minutesorless.Copolymerisobtainedbyhomogeneousreactionof PETgroup polyester,aromaticpolyester,binderandcatalystmasterbatchesbycarryingout degassingdehydrationat13.3×10 3 Paor lessandmelting. Use/Advantage The transparentheat-resistingpropertysheetof polyethyleneterephthalate group polyesterhasexcellentphysical property,tensilestrengthandheat-resisting property,andiseco-friendly.The sheetisobtainedusingrecoveredPETbottle as prepolymer. Formulation (a) 100 pts.wt.PET-basedpolyester, (b) 0-100 pts.wt.otherpolyesterorcarboxygroup-containingpolyolefin, (c) 1-15 pts.wt.masterbatchof a mixture with0-75/100-25 weightratioof an at leasttrifunctional epoxycompound/abifunctional epoxycompoundasa bonding agent,and (d) 0.25-10 pts.wt.masterbatchof an organicacid metal saltcomposite asa bindingcatalyst,whereinheat-setisjointlyused.
  8. 8. S.No 7 PatentNo JP2004067830A PublicationData 3/4/2004 Assignee MITSUBISHI GAS CHEM CO INC Title Polyesterresincomposition Abstract PROBLEMTO BE SOLVED:To provide apolyesterresincompositionwhichhasa highglasstransitiontemperature,a lowcrystallinityand an excellentheat resistance and transparencyandinhibitscolorationatmolding. SOLUTION:The polyesterresincompositionisobtainedbycompounding0.02-10 pts.wt.at least one chosenfroma phenolicantioxidant,asulfurantioxidant,aphosphorus antioxidantand anaromaticamine antioxidantwith100pts.wt.polyesterresin comprisingadicarboxylicacidunitanda diol unit.Here,1-60 mol% of the diol unit has a cyclicacetal skeleton Novelty polyesterresincompositioncomprisespolyesterresinhavingdicarboxylicacidand diol structural units.The compositioncontains0.02-10weightparts(wt.pts) of phenolicantioxidant,sulfurgroupantioxidant,phosphorousgroupantioxidant and/oraromatic amine groupantioxidantwithrespectto100 wt.ptsof the polyesterresin.1-60 mol% of the diol structural unithascyclic acetal structure. Use/Advantage The polyesterresincompositionhashighglasstransitiontemperature,low crystallinity,favorable colortone,heatresistance andtransparency.The compositionhardlycolorsduringmolding. Formulation Formulation/ChemicalsUsed: 1. DMT 2. EG 3. 0.02-10 weightparts(wt.pts) of phenolicantioxidant,sulfurgroupantioxidant, phosphorousgroupantioxidantand/oraromaticamine groupantioxidantwith respectto 100 wt.ptsof the polyesterresin 4. 1-60 mol%of the diol structural unithas cyclic acetal structure. 1) a phenolicantioxidant(B) (trade name:IRGANOX1222; IRGANOX1330; IRGANOX3114; IRGANOX1098 and IRGANOX1010) (2) a sulfur-basedantioxidant(C) C-1: pentaerythrityl tetrakis(3- lauryl thiodipropionate(trade name:SumilizerTP- D) (3) phosphorus-basedantioxidant(D) D-1: Tris (2,4 - di-t-butylphenyl) phosphite (trade name:ADKSTAB2112) D-2: bis(2,6 - di-t-butyl-4- methylphenyl) pentaerythritol diphosphite(trade name: ADKSTAB PEP-36) (4) aromaticamine antioxidant(E) E-1: 4,4 '- dimethoxydiphenyl,4,4'- bis (α,α-dimethylbenzyl) diphenylamine (productname:non-flexDCD) - rectificationcolumnpackedtowertype 1~ 4 cyclicacetal structure.
  9. 9. S.No 8 PatentNo US6447859B2 PublicationData 9/10/2002 Assignee MITSUBISHI GAS CHEM CO INC Title Polyesterresinandmoldedarticle Abstract The polyesterresinof the presentinventionisproducedbypolymerizinga monomermixture comprisingaglycol componentcontaining5to 60 mol % of a spiroglycol representedbyFormulaI: and 30 to 95 mol % of ethylene glycol,anda dicarboxylicacidcomponentcontaining80to 100 mol % of terephthalicacid and/oran esterthereof.The polyesterresinhas(1) :an intrinsicviscosityof 0.4to 1. 5 dL/g, (2) a meltviscosityof 700 to 5, 000 Pa·s,(3) a molecularweight distributionof 2.5to 12.0; and (4) a glass transitiontemperature of 90° C. or higherand a coolingcrystallizationexothermpeakof 5 J/gor lower.The polyesterresinof the presentinventionisexcellentinheatresistance, transparency,mechanical properties,moldabilityandfabricationqualitiesand useful forproducingshapedarticlessuchasfilms,sheets,hollowcontainersand foamedproducts. Novelty Water resinproducedbypolymerizingamonomermixture comprisingaglycol componentcontaining5- 60 mol% of a spiroglycol and 30 - 95 mol% of ethylene glycol,anda dicarboxylicacidcomponentcontaining80- 100 mol% of terephthalic acid and/oran ester. Use/Advantage The polyesterresinisexcellentinheatresistance,transparency,mechanical properties,moldabilityand fabricationqualities. Formulation Formulation: 5 - 60 mol%of a spiroglycol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10- tetraoxaspiro[5.5]undecane ) 30 - 95 mol%of ethylene glycoland 80 - 100 mol%of terephthalicacid Example:A mixture of 13,313 g (69 mol) of DMT, 7,191 g (116 mol) of EG and 2,294 g (7.5 mol) of SPG washeatedto200.degree.C. innitrogenatmosphere inthe presence of manganese acetate tetrahydrate inanamountof 0.03 mol basedon 100 mol of DMT to conduct a transesterification reaction. Afterthe amountof methanol distilledreached90% or higherthe stoichiometric amount,0.01 mol of antimony(III) oxide and0.06 mol of triphenyl phosphate (hereinafterreferredtomerelyas"TPP"),eachbasedon100 mol of DMT, were addedto the reactionmixture.The temperature wasgraduallyraisedandthe pressure wasgraduallyreducedtofinallyreach280.degree. Spiroglycol structure:
  10. 10. S.No 9 PatentNo EP1065230A2 PublicationData 1/3/2001 Assignee ARTEVA TECHNOLOGIES Title Heat resistant,neutral colour,antimony-free polyesters andprocessfortheir preparation Abstract Antimony-freepolyestersbasedonaromaticdi-acidsandaliphaticdiolsare obtainedby(trans)esterificationinpresence of metal salt, inactivationof catalyst withphosphoric,phosphorousand/orphosphonicacid(ora derivative),additionof a cobalt compoundandpolycondensationinpresence of atitaniumcompound withoutaddingantimony.Thermally-stable,neutral-coloredantimony-free polyesters(I) basedonaromaticdicarboxylicacids(DCA) andaliphaticdiols(DO), obtainedby:(a) esterificationof (DCA) with(DO) ortransesterificationof lower aliphaticestersof (DCA) with(DO) inpresenceof 20-120 ppm(basedonmetal) of a transesterificationcatalyst(TC) whichisinactivatedwithacomplexingagentafter the reaction;followedby(b) polycondensationinpresence of atitanium compoundas catalyst.Thisinvolvesaddingaphosphoric,phosphorousand/or phosphonicacid(ora derivative)(PA) ascomplexingagentafterreaction(a) atthe rate of 100% of the equivalentamounttocatalyst(TC) and 90-99% of the amount equivalenttothe cobaltto be used,adding20-80 ppmcobalt inthe form of a Co compoundandthenperformingstage (b) withoutaddingantimonyinpresence of 1-10 ppm titaniuminthe formof a Ti compound. Novelty Antimony-freepolyestersbasedonaromaticdi-acidsandaliphaticdiolsare obtainedby(trans)esterificationinpresence of metal salt,inactivationof catalyst withphosphoric,phosphorousand/orphosphonicacid(ora derivative),additionof a cobalt compoundandpolycondensationinpresence of atitaniumcompound withoutaddingantimony. Use/Advantage Enablesthe reproducibleproductionof thermallystable, neutral-colored polyesterscontainingnoantimony. Formulation 9.75 kg of dimethyl terephthalate, 0.25 kg of dimethyl isophthalate, 6 kg of ethylene glycoland 3 g of manganese acetate.4H.sub.2O(68 ppm of manganese basedonthe polyester),andthe mixture isheatedto140.degree.C.,whilestirringandunder nitrogenasan inertgas. The reactiontemperature isincreasedto230.degree.C.in the course of 4 hoursand the methanol whichhasbeensplitoff andthe excess ethylene glycol are distilledoff. The moltenreactionproductinthentransferredintoapolycondensationvessel, 1.65 g (165 ppm) of Hsub3.3 PO.sub.3,as a complexingagent,and1.27 g (127 ppm) of cobalt acetate (correspondingto30 ppmof Co) are addedandthe mixture isstirredat 230.degree.C. for10 to 15 minutes. Thereafter,0.27 g (27 ppm) of potassiumtitanyloxalate (correspondingto3.6 ppm of Ti) isaddedand the batch isstirredundernitrogenat240.degree.C.,ethylene glycol beingdistilledoff underaslightvacuum. properties:Lvalue is64 andDEG contentis0.5
  11. 11. S.No 10 PatentNo JP2097518A PublicationData 4/10/1990 Assignee TEIJIN LTD Title COPOLYESTER FORHEAT-RESISTANTPACKAGINGMATERIAL Abstract PURPOSE:To improve heatresistance,gas barrierproperty,transparencyand mechanical strengthsbyusingaspecificcompd.asa comonomer. CONSTITUTION:Bycopolymerizinganacidcomponentcontg.at least80mole% terephthalicacid,a glycol componentcontg.atleast80mole% ethylene glycol,and 3-20mole%(basedonsaidacid component) compd.of the formula(whereinR1 and R2 are each H or 1-3C alkyl;R3 isH, or 1-10C alkyl,aralkyl oraryl),a copolyesterforheat-resistantpackagingmaterialwithaglasstransition temperature of 83-90°C and an intrinsicviscosity(inamixedsolventof phenol/ tetrachloroethaneinawt. ratioof 60/40, 35°C) of 0.4-1.0 isproduced.COPYRIGHT: (C)1990,JPO&Japio Novelty In a polyesterconsistingof anacidingredientmade upmainlyof terephthalicacid and a glycol ingredientmade upmainlyof ethyleneglycol,the improvementwhich comprisesthatthe polyestercontains3-20mol.% of a cpd. of formula(I) on the basisof total glycol ingredientasacopolymerisationingredientandhasa glass transitiontemp.of 83-90 deg.C.In (I) R1 and R2 are H or 1-3C alkyl andeach R3-6 are H, 1-10C alkyl,alkylaryloraryl. Use/Advantage USE/ADVANTAGECopolymerpolyestershasgoodgas barrierproperties, transparencyandstrengthwithoutdistortionandstrengthlossduringhightemp. sterilisationwithhotwaterforheatresistantwrappingmaterialssuchasforfilms and vessels.DWg.0/0 Formulation Formulation 80mole%terephthalicacid 80mole%ethyleneglycol,and 3-20 mole%(basedonacidcomponent) compd.of the formula(whereinR1 and R2 are each H or 1-3C alkyl;R3 is H, or 1-10C alkyl,aralkyl oraryl)
  12. 12. S.No 11 PatentNo JP7047592A PublicationData 2/21/1995 Assignee KANEBOLTD Title HEAT-RESISTANT POLYESTER BOTTLE Abstract PURPOSE:To manufacture atransparentbottle whichcanbe filledathigh temperature byusingapolyesterpolymercontainingdicarboxylicacidcomposed of terephthalicacidorits derivativeof esterformingpropertiesasa main componentandalsoa diol component containingadihydroxycompoundasa material. CONSTITUTION:A bottle iscomposedof a polyesterpolymercontaining dicarboxylicacidcomposedof terephthalicacidorits derivativeof esterforming propertiesandadiol componentcontainingadihydroxyl compoundrepresented by a formulaof 5-15mol%,and the glasstransitiontemperature of the polymeris 80 C or over.Inthe formula,R 1 representsalkyl andR2-R5representhydrogenor alkyl.The polyesterpolymertobe usedispreparedbyperformingesterexchange reactionforwhichcalciumsaltof organicacid isusedas a catalystand then polymerizing,anditsnatural viscosityis0.70-0.90dl/g.Asfora dihydroxyl compound,preferably9,9-bis-(4-hydroxyethoxyphenyl)-fluorene isused. COPYRIGHT: (C)1995,JPO&Japio Novelty Heat-resistantbottlemade of polyestercomprisesapolyestercopolymerhavingTg of at least80 deg.C.The polyestercopolymercontainsdicarboxylicacidcomprising mainlyterephthalicacidoritsester-formingderiv.,andadiol componentcontg.5- 15 mol % dihydroxycpd.of formula(I).R1=2-4C alkyl gp.;R2 - R5 = H, or 1-4C alkyl gps.The polyestercopolymerisformedbytransesterification,usingKsaltof an organicacid as a catalyst andby polymerisationorisformedbydirect polymerisation.The polyestercopolymerhasanintrinsicviscosityof 0.70 - 0.90 dl/g. Use/Advantage ADVANTAGEThe bottle hassuperiormoulding,transparency,toughness, mechanical strength,heatresistance,andallowshigh-temp.filling.Noheat treatmentaftermouldingforprovidingheatresistance isrequired. Formulation Formulation: 1) terephthalicacid 2) bis(hydroxy-alkoxy-phenyl)-fluorene (diol)-5-15mol%, 3) EG
  13. 13. S.No 12 Patent No US20110213077A1 Publicationdate 9/1/2011 Assignee SOLVAY ADVANCED POLYMERS LLC Title Hydroquinone-containingpolyesters havingimproved whiteness Abstract A polyester containingpolymerized units of hydroquinone; 4,4’-biphenol;and hydroxybenzoic acid;terephthalic acid and optionally isophthalic acid.Amethod of forming a polyester includingfirstacylatinga mixtureof hydroquinone; 4,4′- biphenol;terephthalic acid and optionally isophthalicacid;and hydroxybenzoic acid; and then polycondensingthe resultingacylated mixture.The polyester is suitablefor uses such as lightingwhere high whiteness, high reflectivity and high heat resistance are desirable. Novelty Polyester (A1) comprisingstructural units derived from hydroquinone(I), 4,4'-biphenol (II),terephthalic acid (III),p-hydroxybenzoic acid (V) and, optionally isophthalic acid (IV), is new. (V) is present at 40-80 mole%. (III) and (IV) are present at 10-30 mole%, and (I) and (II) are present at 10-30 mole%, where mole% is based on the total number of moles of (I)-(V) present in (A1). The molar ratio of: (I) to (II) is 0.1-1.5; and (IV) to (III) is 0-0.1,where at least80 mole% of all of the structural units of (A1) are (I)-(V). Use/Advantage (A1) and (B1) exhibit: superior mechanical properties e.g. high temperature performance, and low color and processingcapability atmoderate temperatures; exceptional properties; and superior heat resistance. How to improve Heat resistance of PET Polyester comprises Hydroquinone; 4,4'-biphenol; terephthalic acid and optionally isophthalicacid;and hydroxybenzoic acid; Raw material details: 1) Hydroquinone- Molar mass- 110.11g/mole 2) 4 4’-biphenol – Molar mass:186.21 g/mole
  14. 14. S.No 12 Patent No JP2009179654A Publicationdate 8/13/2009 Assignee NIPPON ESTER CO LTD Title POLYESTER DIRECT BLOW MOLDED ARTICLE Abstract PROBLEM TO BE SOLVED: To providea polyester directblow molded articlewhich can be molded at a low processingtemperature, can lower a production cost,and is excellent in moldability and heat resistance. SOLUTION: Provided is a polyester direct blow molded articlecharacterized by molding a polyester resin which comprises a dicarboxylic acid component consistingmainly of terephthalic acid and a diol component containing1,6-hexanediol in an amountof ≥50 mol%, has a melting pointof 100 to 150°C, and contains a crystal- nucleatingagent in an amount of 0.01 to 5.0 mass%,and in which a DSC curve exhibitinga temperature-fallingcrystallization determined by DSC satisfies an expression (1): b/a≥0.05 (mW/mg×°C). Novelty A polyester directblow molded product contains polyester resin which contains dicarboxylicacid component havingterephthalic acid as main component and 50 mol% or more of 1,6-hexanediol as diol component. The polyester resin has meltingpoint of 100-150°C. The polyester resin contains 0.01-5 mass%of crystal nucleatingagent. The polyester directblow molded product has temperature-fall crystallization (b/a) of 0.05 or less mW/mg.° C calculated usingdifferential scanningcalorimetry. Use/Advantage Polyester directblow molded product has excellent moldability and heatresistance and is manufactured economically with out variation in surpassshapestability. How to improve Heat resistance of PET Preparation of PET Terephthalic acid and 1,6-hexanediol Crystal-nucleating agent (0.01 to 5.0 mass%) Raw material details Crystal-nucleatingagent: siliconoxidesor talc particle size having3.0microns.It will be addedinPTA and EG slurry
  15. 15. S.No 13 Patent No JP2010132832A Publicationdate 6/17/2010 Assignee MITSUBISHI PLASTICS INC Title FLAME-RETARDANT POLYESTER RESIN COMPOSITION Abstract PROBLEM TO BE SOLVED: To providea flame-retardantpolyester resin composition with flame retardancy,mechanical properties, and heat resistance. SOLUTION: This polyester resin composition includes a mixtureof: a polyester resin (A) which contains 50-90 mol% of terephthalic acid as a polycarboxylicacid component and 70-100 mol% of the total of 1,4-butane diol,ethylene glycol,and diethylene glycol as a polyhydric alcohol component; and melamine (B), wherein the resin composition does not spoil original characteristics of the polyester resin (A), and attains excellent flame retardancy,mechanical properties,and heat resistancewith a reduced amount of addition of an inorganic flameretardantrelativeto an amount conventionally examined. Novelty A flame-retardantpolyester-type resin composition contains a mixtureof polyester- type resin and melamine (10-80 mass%). The resin has glass transition temperature of 40° C or less and crystal meltingtemperature of 140-90° C. Use/Advantage The flame-retardant laminatecomprisingpolyester-typeresin composition has excellent flame retardance, mechanical characteristic and heatresistance. How to improve Heat resistance of PET By addingmelamine to PET Newraw material details Melamine: Molar mass – 126.12
  16. 16. S.No 14 Patent No JP2007138160A Publicationdate 6/7/2007 Assignee TOYOBO Title METHOD FOR MANUFACTURING POLYESTER COMPOSITION Abstract PROBLEM TO BE SOLVED: To providea method for manufacturinga polyester composition,which is suitably used as a material for a coveringof a substrateor a molded product such as a blow molded product which is excellent in transparency, shows littlevariation thereof and inhibits production of aldehydes and variation thereof atmolding, or a polyester composition capableof efficiently producinga blow molded product which is excellent in resistance to pressure and heat resistant dimensional stability,particularly a blowmolded product excellent in various characteristicsthrough high-speed molding. SOLUTION: In the method for manufacturingthe polyester composition,atleasttwo polyesters havingdifferent limitingviscosity numbers and substantially thesame compositions aremixed, wherein the polyesters are separately obtained through solid- phasepolymerization in a solid-phasepolymerization apparatus.Thedifference in limitingviscosity numbers of the polyesters is 0.03-0.30 dL/g, the average weight (W) of chips of each polyester is within the range of 3-50 mg, and the ratio of the average weights of the chips of the polyesters is 1.00-1.20. Novelty Polyesters of 2 or more types which differ in intrinsic viscosity and which aresubjected to solid-statepolymerization separately by solid-statepolymerization apparatus,are mixed to obtain a polyester composition.The difference in intrinsicviscosity of the polyesters is 0.03-0.3 deciliter/g.The average weight of the chip of each of polyester is 50 mg. The ratio of average weight of chip of the polyester is 1-1.2.The composition of the polyesters is same. Use/Advantage The polyester composition of improved fluid flowcharacteristics,excellentcontinuous formability is efficiently manufactured.The polyester composition provides compact with excellent transparency,mechanical characteristicssuch as pressureresistance, heat-resistantdimensional stability,and with suppressed aldehydegeneration amount. How to improve Heat resistance of PET Manufacturingthe polyester composition,at leasttwo polyesters havingdifferent limitingviscosity numbers and substantially the same compositions aremixed,
  17. 17. S.No 15 Patent No JP2007177089A Publicationdate 7/12/2007 Assignee MITSUI CHEMICALS INC Title POLYETHYLENE TEREPHTHALATE RESIN COMPOSITION AND BLOW-MOLDED CONTAINER MADE THEREFROM Abstract PROBLEM TO BE SOLVED: To providea polyethylene terephthalate resin composition capableof obtainingblow-molded containers with high heat resistance and transparency in high productivity, and to providesuch a blow-molded container using the above resin composition. SOLUTION: The polyethylene terephthalate resin composition comprises the components (A) and (B) described below, wherein the component (B) is contained at 0.1-10,000 ppb in the composition.The component (A) is a polyethylene terephthalate component consistingmaily of recurringunits derived from dicarboxylic acid(s) comprisingterephthalic acid and/or its ester-formingderivativeand diol(s) comprising ethylene glycol and/or its ester-formingderivative,wherein the proportion of diethylene glycol units is 0.5-2.0 wt.%. The component (B) is an ethylene-based polymer composition comprising(a) polyethyleneand/or (b) an ethylene-(meth)acrylic acid copolymer,being greater than 45 in Shore D hardness. Novelty A polyethylene terephthalate resin composition contains polyethyleneterephthalate (A), and ethylene-polymer composition (B) (0.1-10000 ppb). The component (A) contains repeatingunit derived from dicarboxylicacid containingterephthalic acid and/or its ester-forming derivative, and diol containingethylene glycol and/or its ester- forming derivative.The content of diethylene glycol unitin polyethylene terephthalate (A) is 0.5-2 wt.%. The composition (B) contains polyethylene(a) and/or ethylene- (meth)acrylic acid copolymer and has Shore D hardness of 45 or more. Use/Advantage The polyethylene terephthalate resin composition provides blowmolded container havingexcellent heat resistanceand transparency,with favorableproductivity. How to improve Heat resistance of PET Blendingof PET with a polyethylene and/or an ethylene-(meth)acrylic acid copolymer Function: Polyethylene and/or an ethylene-(meth)acrylic acid copolymer accelerating the crystallization rate of PET
  18. 18. S.No 16 Patent No JP2006070101A Publicationdate 3/16/2006 Assignee MITSUBISHI CHEM CORP Title POLYESTER RESIN, RESIN COMPOSITION, PREFORM FOR STRETCH BLOW MOLDING AND HOLLOW CONTAINER Abstract PROBLEM TO BE SOLVED: To providea polyester resin having high heat resistance, mechanical strength and transparency,excellentin bottle productivity and flavor preservability of drink of a bottle content, and suitableas a rawmaterial for the bottle. SOLUTION: The polyester resin comprises a unit(A) derived from a dicarboxylic acid component and a unit (B) derived from a diol component. The unit (A) is composed of the dicarboxylic acid componentconsistingessentially of an aromatic dicarboxylicacid, and the unit(B) comprises two or more kinds of diols wherein at leastone kind is a cyclic diol.The polyester resin has 82-110°C glass transition temperature, and 0.73-1.5 dl/g intrinsic viscosity,and provides a preform having≤30 ppm aldehyde content when the resin is dried so as to have ≤50 ppm water content, and subjected to injection moldingat280°C cylinder temperature. Novelty A polyester resin contains unit(A) derived from dicarboxylicacid component and unit derived from diol component. The polyester resin has glass transition temperature of 82-110°C and intrinsic viscosity of 0.73-1.5 dl/g. The acetaldehyde content in preform obtained by dryingresin to moisture content of 50 ppm or less and injection molding resin atcylinder temperature of 280°C is 30 ppm or less. Use/Advantage The polyester resin composition formed usingthe polyester resin has excellentheat resistanceand mechanical strength.The hollowcontainer obtained usingthe composition has excellentflavor retainability of contents. How to improve Heat resistance of PET By usingleastone kind is a cyclicdiol in thePET synthesis S.No 17 Patent No JP2006089511A Publicationdate 4/6/2006 Assignee DAIWA CAN CO LTD Title POLYESTER RESIN AND MOLDED ARTICLE COMPOSED THEREOF Abstract PROBLEM TO BE SOLVED: To providea polyester resin excellent in crystallinity and heat resistance. ; SOLUTION: The polyester resin has terephthalic acid and ethylene glycol as the main components and contains a silica powder havingan average particlediameter of <=50 nm in an amount of 1-10 pts. wt. based on 100 pts. wt. polyester resin,and the difference between the melting pointand the recrystallization temperature in differential scanningcalorimetry (DSC) is within 50[deg.]C. ; COPYRIGHT: (C)2006,JPO&NCIPI Novelty A polyester resin is obtained usingterephthalic acid and ethylene glycol.Silica powder (1-10 wt.pts) with average particlediameter of 50 nm or less is contained with respect to 100 wt.pts of polyester resin.The difference of melting pointand recrystallization temperature of polyester resin is less than 50°C, as determined by differential scanning calorimeter. Use/Advantage The polyester resin has outstandingcrystallinity and heatresistance.The aggregation of silica particlein molded product formed usingpolyester resin is reduced. How to improve Heat resistance of PET Silicapowder havingan average particlediameter of <=50 nm in an amount of 1-10 pts. wt.

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