This document summarizes 7 patent documents related to improving the heat resistance of PET. The patents describe various methods for modifying the chemical structure and formulation of PET to increase its glass transition temperature (Tg) and heat deflection temperature. These include adding comonomers like 9,9'-dihydroxymethylfluorene or bisphenol A ethylene oxide adduct, using specific diols or dicarboxylic acids in the polymerization, and blending PET with other polymers or flame retardants. The goal is to develop PET compositions that can be used for applications requiring high heat resistance like bottles, films, fibers and resins.

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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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.