IP Report on

To improve Tg and heat resistance of PET

Ester Industries LimitedKhatima

IndiaFebruary 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.

S.No 1 Patent No JP2006193575A Publication Data 7/27/2006Assignee TEIJIN LTDTitle High heat resistance non-crystalline polyesterAbstract PROBLEM TO BE SOLVED: To provide a highly heat-resistant and transparent

polyester suitable for optical uses and general resin uses. SOLUTION: This polyester is obtained, for example, by polymerizing dimethyl terephthalate, 9,9'-dihydroxymethylfluorene and ethylene glycol as raw materials, is amorphous, and has a glass transition temperature of 100 to 180°C.

Novelty A polyester is non-crystalline and has glass transition temperature of 100-180°C, and is obtained by co-polymerizing dicarboxylic acid (A), aliphatic dihydroxy compound (B) and aliphatic dihydroxy compound (C) as main monomer. The mole composition ratio of residue of aliphatic dihydroxy compound (B) and residue of aliphatic dihydroxy compound (C) in the polyester is satisfies preset relation.

Use/Advantage The polyester has excellent heat resistance, and favorable transparency and film workability and does not contain crystal. The glass transition temperature of the polyester is high.

Formulation Preparation process:9.709g (0.05mol)-dimethyl terephthalic acid4.526g (0.02 mol) -9,9 '- dihydroxy methyl fluorene from Yurui (Shanghai) Chemical Co., Ltd.6.207g (0.1 mol)-ethylene glycol,8 mg (0.1 mmol)- calcium acetate monohydrate and7.2mg (0.025 mmol) - antimony trioxide were charged into a flask under a nitrogen atmosphere.The flask was heated to 180 ℃, dissolve the contents were allowed to, will be carried out transesterification reached 200 ℃, while heating at a rate of 10 ℃ per 15 minutes. Make sure that the end of the distillation of methanol and 4ml of a theoretical amount of distillate, 14mg of trimethyl phosphate as an anti-coloring (1 x 10 -4 mol) was added, the flask 90 0.5mmHg over a minute under vacuum. Heated up to 270 ℃ over the flask followed by 30 minutes, I went to a high degree of polymerization. After reaching 270 ℃, the polymerization terminates when held for 2 hours, removed the polyester melt in the flask. The reduced viscosity of the resulting polyester, Tg, as described in Table 1 by proton NMR analysis and composition.

Chemical formula

S.No 2 Patent No JP2008308600A Publication Data 12/25/2008Assignee TEIJIN FIBERS LTDTitle The manufacturing method of the polyester copolymer composition excellent in

heat resistanceAbstract PROBLEM TO BE SOLVED: To provide a method for producing a copolyester

composition which inhibits the melting point lowering of polyesters copolymerized with phosphorous flame retardants, can suitably be used for uses such as fibers, films and resins, and has excellent heat resistance.SOLUTION: This method for producing the copolyester, having the first step reaction for applying an esterification reaction or a transesterification reaction to produce the reaction product and the second step reaction for polycondensing the reaction product, is characterized by adding (i) a specific carboxyphosphinic acid-based phosphorus compound in an amount of 0.1 to 10 mol% based on an acid component constituting the obtained polyester until the finish of the second step reaction and adding (ii) a laminar compound in an amount of 0.05 to 5 wt.% based on the obtained copolyester.

Novelty Manufacture of polyester copolymer composition involves esterifying or transesterfication of terephthalic acid or its esterforming derivative and 2-4C alkylene glycol, polycondenzing the obtained reaction product and adding carboxy phosphinic acid type phosphorus compound (1) and layered compound before the completion of polycondenzation reaction. The additional amount of carboxy phosphinic acid type phosphorus compound is 0.1-10 mol% with respect to acid component of polyester. The additional amount of layered compound is 0.05-5 weight% with respect to polyester copolymer.

Use/Advantage The method efficiently manufactures polyester copolymer composition having heat resistance and flame retardance.

Formulation Transesterification step:100 parts dimethyl terephthalate60 parts of ethylene glycol0.06 parts of manganese acetate dihydrate (0 for dimethyl terephthalate 0.03 mole percent)0.004 parts cobalt acetate dihydrate and organize a colorant (0.003 mole percent dimethyl terephthalate)Polycondensation step:0.026 part of trimethyl phosphate as a stabilizer (0.036 mole percent dimethyl terephthalate)0.04 parts of antimony trioxide and then after 10 minutes (0.027 mole percent dimethyl terephthalate) was added,at the end of polycondensation layered compound (silicates, mica, nano clay etc) - 0.1 to 2 weight %

S.No 3 Patent No JP2008291151A Publication Data 12/4/2008Assignee SANYO CHEM IND LTDTitle Heat resistant polyester resinAbstract PROBLEM TO BE SOLVED: To provide a polyester resin of excellent heat resistance

and impact resistance.SOLUTION: This heat resistant polyester resin is a heat resistant polyester resin (III) constituted of a diol component (I) and a dicarboxylic acid component (II), and having a content of 5-99 mol.% of a bisphenol-A ethylene oxide adduct (A) in the diol component (I). The bisphenol-A ethylene oxide adduct (A) is a reaction mixture comprising 0-1 mol.% of bisphenol-A ethylene oxide one-molar adduct (A1), 92-100 mol.% of bisphenol-A ethylene oxide two-molar adduct (A2), and 0-7 mol.% of bisphenol-A ethylene oxide three-or-more-molar adduct (A3).

Novelty A polyester resin contains (in mol%) a diol component (5-99) and dicarboxylic acid component. The diol component is a bisphenol-A ethylene oxide addition product. The bisphenol-A ethylene oxide addition product contains 1 mol addition product of bisphenol-A ethylene oxide (0-1), 2 mol addition product of bisphenol-A ethylene oxide (92-100) and 3 mol or more of addition product of bisphenol-A ethylene oxide (0-7).

Use/Advantage The polyester resin has excellent heat resistance and impact resistance.Formulation Preparation process:

332g of terephthalic acid (2.0mol)211g ethylene glycol (3.4mol) and190g (0.6mol) of Bisphenol-A and ethyleneoxide adduct was charged with 0.03g of titanium tetra-isopropoxy esterification catalyst and heated to 220 ℃.Promoted condensation reaction while removing water, where there are no condensation of water distillate under atmospheric pressure, heated to 230 ℃, the system was gradually reduced pressure. Promote the reaction while removing the ethylene glycol, molecular weight was followed by GPC. The contents were taken out at 18,000 number average molecular weight polyester resin of the present invention (C-1) was obtained. Ethylene glycol was removed 124g (2.0mol), respectively.

Preparation of Bisphenol-A and ethyleneoxide adduct:

In an autoclave made of glass, 1100ml capacity in Preparation of bisphenol A228.0g (1.0mol) was charged with 228.0g water and, after nitrogen substitution, 90 heated up, dispersed in water, ℃bisphenol A. Here potassium hydroxide (KOH) 3.0g to (0.054mol) was added. Performed again replaced with nitrogen, EO88.0g (2.0mol) 90 , the reaction was dripping in the range of reaction pressure ℃0.2MPa. After dropping four hours from the start, 1.4g of phosphoric acid (0.014mol) was added, EO22.0g more (0.5mol) 90 , the reaction was dripping in the range of reaction pressure 0.2MPa. The ℃reaction is terminated after dropping for two hours, four were transferred to the reaction flask. Water was removed by liquid separation by heating to 90 . Furthermore, since it is contained diethylene ℃glycol and ethylene glycol by-product in the system, in order to remove it, washed by stirring for 1 hour at 90 300g added water. Was then filtered and treated with activated clay to remove water ℃

separation. Vacuum dehydrated at 130 it, bisphenol A di (oxyethylene) ethers of the present ℃invention (A-1) 265g (84 percent yield) was obtained.

S.No 4 Patent No US20080242783A1 Publication Data 10/2/2008Assignee GENERAL ELECTRIC COTitle POLYESTER COMPOSITIONS HAVING IMPROVED HEAT RESISTANCEAbstract A composition of matter comprising a polyester composition derived from: (i) 20 to

80 mole percent of a first diol derived from a disubstituted xylene glycol of the formula (I): wherein R 1 and R2 are independently selected from the group consisting of aliphatic radical, aromatic radical, cycloaliphatic, radical and halogen; and (ii) a second diol and (iii) a diacid is disclosed. Also disclosed are blends of these polyesters with polycarbonate and process to prepare these compositions and articles therefrom.

Novelty A polyester composition comprises 20-80 mol.% of first diol derived from disubstituted xylene glycol, diacid e.g. succinic acid, and second diol e.g. ethylene glycol.

Use/Advantage The composition has good balance of optical and mechanical properties, high heat resistance, processability, chemical resistance, and flame resistance.

Formulation Process:1) DMT Dimethyl Terephthalate2) BDO3) 20-80 mol.% of first diol derived from disubstituted xylene glycol (DmPXG) from GE4) EGXylene Glycol structure

S.No 5 Patent No JP2006089629A Publication Data 4/6/2006Assignee MITSUBISHI CHEMICALS CORPTitle Polyester resinAbstract PROBLEM TO BE SOLVED: To provide a polyester resin giving a bottle having high

heat resistance and excellent mechanical strength and transparency by stretch blow molding. SOLUTION: The polyester resin is composed of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid and a diol component consisting of two or more kinds of diols and containing polymethylene glycol as a main component. The resin has a glass transition temperature of 82-110°C and an intrinsic viscosity of 0.73-1.50 dL/g and satisfies either one or both of the properties A and B. (A) The peak value of the descending temperature crystallization temperature is ≥180°C or undetectable and (B) the injection-molded plate specimen having a thickness of 4 mm has a light absorbance of 0.06-0.30 at 1,000 nm wavelength, and a brightness index L of 70-90, a chromatic coordinate a of -3 to +3 and a chromatic coordinate b of -3 to +3 in the Hunter's color-difference formula in Lab color specification system.

Novelty Polyester resin contains aromatic dicarboxylic acid and polymethylene glycol, and has glass transition point of 82-110°C and intrinsic viscosity of 0.73-1.5 dl/g. The polyester resin has crystallization peak of 180°C or less during temperature fall, and/or injection molded board of polyester resin has light absorbency of 0.06-0.3 at 1000 nm wavelength, brightness index (L) of 70-90 and color coordinates (a,b) of -3 to 3.

Use/Advantage The polyester resin has excellent heat resistance, mechanical strength, transparency and moldability, and is manufactured with high productivity.

Formulation Preparation process95 mol% or more of terephthalic acid80 mol% or more of ethylene glycol,0.5 mol% or more of diol having cyclic structure or isosorbide, and3 mol% or less of diethylene glycol10-4-10-3 ppm of resin chosen from polyamide and/or polyolefin

Cyclc Sorbide structure

S.No 6 Patent No JP2004161967A Publication Data 6/10/2004Assignee NAKAMOTO PAKKUSU KKTitle PRODUCTION METHOD FOR HEAT-RESISTANT SHEET AND MOLDED PRODUCT OF

POLYETHYLENE TEREPHTHALATE-BASED POLYESTERAbstract PROBLEM TO BE SOLVED: To provide a production method for a heat-resistant

sheet and molded product of a polyethylene terephthalate-based polyester at a low cost, wherein the heat-resistant sheet is applicable to a container capable of filling contents by heating and resists to heating with a microwave oven, by having the properties of small drawdown and crystallization at a high speed. SOLUTION: The heat-resistant sheet and molded product are produced by using a block copolymer whose melt viscosity is increased to at least 10 times of that of a conventional linear-structured PET, by modifying the structure to that having branched long chains, enabling it to crystallize at a high speed, through reactive extrusion of the mixture consisting of (a) 100 pts.wt. PET-based polyester, (b) 0-100 pts.wt. other polyester or carboxy group-containing polyolefin, (c) 1-15 pts.wt. master batch of a mixture with 0-75/100-25 weight ratio of an at least trifunctional epoxy compound/a bifunctional epoxy compound as a bonding agent, and (d) 0.25-10 pts.wt. master batch of an organic acid metal salt composite as a binding catalyst, wherein heat-set is jointly used.

Novelty The transparent heat-resisting property sheet of PET group polyester is obtained by molding and thermoforming block copolymer having melt flow rate of 40 g/10 minutes or less. Copolymer is obtained by homogeneous reaction of PET group polyester, aromatic polyester, binder and catalyst masterbatches by carrying out degassing dehydration at 13.3×10 3 Pa or less and melting.

Use/Advantage The transparent heat-resisting property sheet of polyethylene terephthalate group polyester has excellent physical property, tensile strength and heat-resisting property, and is eco-friendly. The sheet is obtained using recovered PET bottle as prepolymer.

Formulation (a) 100 pts.wt. PET-based polyester,(b) 0-100 pts.wt. other polyester or carboxy group-containing polyolefin,(c) 1-15 pts.wt. master batch of a mixture with 0-75/100-25 weight ratio of an at least trifunctional epoxy compound/a bifunctional epoxy compound as a bonding agent, and(d) 0.25-10 pts.wt. master batch of an organic acid metal salt composite as a binding catalyst, wherein heat-set is jointly used.

S.No 7 Patent No JP2004067830A Publication Data 3/4/2004Assignee MITSUBISHI GAS CHEM CO INCTitle Polyester resin compositionAbstract PROBLEM TO BE SOLVED: To provide a polyester resin composition which has a

high glass transition temperature, a low crystallinity and an excellent heat resistance and transparency and inhibits coloration at molding. SOLUTION: The polyester resin composition is obtained by compounding 0.02-10 pts.wt. at least one chosen from a phenolic antioxidant, a sulfur antioxidant, a phosphorus antioxidant and an aromatic amine antioxidant with 100 pts.wt. polyester resin comprising a dicarboxylic acid unit and a diol unit. Here, 1-60 mol% of the diol unit has a cyclic acetal skeleton

Novelty polyester resin composition comprises polyester resin having dicarboxylic acid and diol structural units. The composition contains 0.02-10 weight parts (wt.pts) of phenolic antioxidant, sulfur group antioxidant, phosphorous group antioxidant and/or aromatic amine group antioxidant with respect to 100 wt.pts of the polyester resin. 1-60 mol% of the diol structural unit has cyclic acetal structure.

Use/Advantage The polyester resin composition has high glass transition temperature, low crystallinity, favorable color tone, heat resistance and transparency. The composition hardly colors during molding.

Formulation Formulation/Chemicals Used:1. DMT2. EG3. 0.02-10 weight parts (wt.pts) of phenolic antioxidant, sulfur group antioxidant, phosphorous group antioxidant and/or aromatic amine group antioxidant with respect to 100 wt.pts of the polyester resin4. 1-60 mol% of the diol structural unit has cyclic acetal structure.1) a phenolic antioxidant (B) (trade name: IRGANOX1222; IRGANOX1330; IRGANOX3114; IRGANOX1098 and IRGANOX1010)(2) a sulfur-based antioxidant (C)C-1: pentaerythrityl tetrakis (3 - lauryl thiodipropionate (trade name: SumilizerTP-D)(3) phosphorus-based antioxidant (D)D-1: Tris (2,4 - di-t-butylphenyl) phosphite (trade name: ADK STAB 2112)D-2: bis (2,6 - di-t-butyl-4 - methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36)(4) aromatic amine antioxidant (E)E-1: 4,4 '- dimethoxy diphenyl, 4,4' - bis (α, α-dimethylbenzyl) diphenylamine (product name: non-flex DCD)- rectification column packed tower type 1 ~ 4

cyclic acetal structure.

S.No 8 Patent No US6447859B2 Publication Data 9/10/2002Assignee MITSUBISHI GAS CHEM CO INCTitle Polyester resin and molded articleAbstract The polyester resin of the present invention is produced by polymerizing a

monomer mixture comprising a glycol component containing 5 to 60 mol % of a spiroglycol represented by Formula I: and 30 to 95 mol % of ethylene glycol, and a dicarboxylic acid component containing 80 to 100 mol % of terephthalic acid and/or an ester thereof. The polyester resin has (1) : an intrinsic viscosity of 0.4 to 1. 5 dL/g, (2) a melt viscosity of 700 to 5, 000 Pa·s, (3) a molecular weight distribution of 2.5 to 12.0; and (4) a glass transition temperature of 90° C. or higher and a cooling crystallization exotherm peak of 5 J/g or lower. The polyester resin of the present invention is excellent in heat resistance, transparency, mechanical properties, moldability and fabrication qualities and useful for producing shaped articles such as films, sheets, hollow containers and foamed products.

Novelty Water resin produced by polymerizing a monomer mixture comprising a glycol component containing 5 - 60 mol% of a spiroglycol and 30 - 95 mol% of ethylene glycol, and a dicarboxylic acid component containing 80 - 100 mol% of terephthalic acid and/or an ester.

Use/Advantage The polyester resin is excellent in heat resistance, transparency, mechanical properties, moldability and fabrication qualities.

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 glycol and80 - 100 mol% of terephthalic acidExample: 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 was heated to 200.degree. C. in nitrogen atmosphere in the presence of manganese acetate tetrahydrate in an amount of 0.03 mol based on 100 mol of DMT to conduct a transesterification reaction.After the amount of methanol distilled reached 90% or higher the stoichiometric amount, 0.01 mol of antimony (III) oxide and 0.06 mol of triphenyl phosphate (hereinafter referred to merely as "TPP"), each based on 100 mol of DMT, were added to the reaction mixture. The temperature was gradually raised and the pressure was gradually reduced to finally reach 280.degree.Spiroglycol structure:

S.No 9 Patent No EP1065230A2

Publication Data 1/3/2001

Assignee ARTEVA TECHNOLOGIESTitle Heat resistant, neutral colour, antimony-free polyesters and process for their

preparationAbstract Antimony-free polyesters based on aromatic di-acids and aliphatic diols are

obtained by (trans)esterification in presence of metal salt, inactivation of catalyst with phosphoric, phosphorous and/or phosphonic acid (or a derivative), addition of a cobalt compound and polycondensation in presence of a titanium compound without adding antimony. Thermally-stable, neutral-colored antimony-free polyesters (I) based on aromatic dicarboxylic acids (DCA) and aliphatic diols (DO), obtained by: (a) esterification of (DCA) with (DO) or transesterification of lower aliphatic esters of (DCA) with (DO) in presence of 20-120 ppm (based on metal) of a transesterification catalyst (TC) which is inactivated with a complexing agent after the reaction; followed by (b) polycondensation in presence of a titanium compound as catalyst. This involves adding a phosphoric, phosphorous and/or phosphonic acid (or a derivative) (PA) as complexing agent after reaction (a) at the rate of 100% of the equivalent amount to catalyst (TC) and 90-99% of the amount equivalent to the cobalt to be used, adding 20-80 ppm cobalt in the form of a Co compound and then performing stage (b) without adding antimony in presence of 1-10 ppm titanium in the form of a Ti compound.

Novelty Antimony-free polyesters based on aromatic di-acids and aliphatic diols are obtained by (trans)esterification in presence of metal salt, inactivation of catalyst with phosphoric, phosphorous and/or phosphonic acid (or a derivative), addition of a cobalt compound and polycondensation in presence of a titanium compound without adding antimony.

Use/Advantage Enables the reproducible production of thermally stable, neutral-colored polyesters containing no antimony.

Formulation 9.75 kg of dimethyl terephthalate,0.25 kg of dimethyl isophthalate,6 kg of ethylene glycol and3 g of manganese acetate.4H.sub.2 O (68 ppm of manganese based on the polyester), and the mixture is heated to 140.degree. C., while stirring and under nitrogen as an inert gas. The reaction temperature is increased to 230.degree. C. in the course of 4 hours and the methanol which has been split off and the excess ethylene glycol are distilled off.The molten reaction product in then transferred into a polycondensation vessel, 1.65 g (165 ppm) of Hsub3.3 PO.sub.3, as a complexing agent, and 1.27 g (127 ppm) of cobalt acetate (corresponding to 30 ppm of Co) are added and the mixture is stirred at 230.degree. C. for 10 to 15 minutes.Thereafter, 0.27 g (27 ppm) of potassium titanyloxalate (corresponding to 3.6 ppm of Ti) is added and the batch is stirred under nitrogen at 240.degree. C., ethylene glycol being distilled off under a slight vacuum.properties: L value is 64 and DEG content is 0.5

S.No 10 Patent No JP2097518A Publication Data 4/10/1990Assignee TEIJIN LTDTitle COPOLYESTER FOR HEAT-RESISTANT PACKAGING MATERIALAbstract PURPOSE: To improve heat resistance, gas barrier property, transparency and

mechanical strengths by using a specific compd. as a comonomer. CONSTITUTION: By copolymerizing an acid component contg. at least 80mole% terephthalic acid, a glycol component contg. at least 80mole% ethylene glycol, and 3-20mole% (based on said acid component) compd. of the formula (wherein R 1 and R2 are each H or 1-3C alkyl; R3 is H, or 1-10C alkyl, aralkyl or aryl), a copolyester for heat-resistant packaging material with a glass transition temperature of 83-90°C and an intrinsic viscosity (in a mixed solvent of phenol/ tetrachloroethane in a wt. ratio of 60/40, 35°C) of 0.4-1.0 is produced. COPYRIGHT: (C)1990,JPO&Japio

Novelty In a polyester consisting of an acid ingredient made up mainly of terephthalic acid and a glycol ingredient made up mainly of ethylene glycol, the improvement which comprises that the polyester contains 3-20 mol.% of a cpd. of formula (I) on the basis of total glycol ingredient as a copolymerisation ingredient and has a glass transition temp. of 83-90 deg. C. In (I) R1 and R2 are H or 1-3C alkyl and each R3-6 are H, 1-10C alkyl, alkylaryl or aryl.

Use/Advantage USE/ADVANTAGE Copolymer polyesters has good gas barrier properties, transparency and strength without distortion and strength loss during high temp. sterilisation with hot water for heat resistant wrapping materials such as for films and vessels. DWg.0/0

Formulation Formulation80mole% terephthalic acid80mole% ethylene glycol, and3-20 mole% (based on acid component) compd. of the formula (wherein R 1 and R2 are each H or 1-3C alkyl; R3 is H, or 1-10C alkyl, aralkyl or aryl)

S.No 11 Patent No JP7047592A Publication Data 2/21/1995Assignee KANEBO LTDTitle HEAT-RESISTANT POLYESTER BOTTLEAbstract PURPOSE: To manufacture a transparent bottle which can be filled at high

temperature by using a polyester polymer containing dicarboxylic acid composed of terephthalic acid or its derivative of ester forming properties as a main component and also a diol component containing a dihydroxy compound as a material. CONSTITUTION: A bottle is composed of a polyester polymer containing dicarboxylic acid composed of terephthalic acid or its derivative of ester forming properties and a diol component containing a dihydroxyl compound represented by a formula of 5-15mol%, and the glass transition temperature of the polymer is 80 C or over. In the formula, R 1 represents alkyl and R2-R5 represent hydrogen or alkyl. The polyester polymer to be used is prepared by performing ester exchange reaction for which calcium salt of organic acid is used as a catalyst and then polymerizing, and its natural viscosity is 0.70-0.90dl/g. As for a dihydroxyl compound, preferably 9,9-bis-(4-hydroxyethoxyphenyl)-fluorene is used. COPYRIGHT: (C)1995,JPO&Japio

Novelty Heat-resistant bottle made of polyester comprises a polyester copolymer having Tg of at least 80 deg. C. The polyester copolymer contains dicarboxylic acid comprising mainly terephthalic acid or its ester-forming deriv., and a diol component contg. 5-15 mol % dihydroxy cpd. of formula (I). R1 =2-4C alkyl gp.; R2 - R5 = H, or 1-4C alkyl gps. The polyester copolymer is formed by transesterification, using K salt of an organic acid as a catalyst and by polymerisation or is formed by direct polymerisation. The polyester copolymer has an intrinsic viscosity of 0.70 - 0.90 dl/g.

Use/Advantage ADVANTAGE The bottle has superior moulding, transparency, toughness, mechanical strength, heat resistance, and allows high-temp. filling. No heat treatment after moulding for providing heat resistance is required.

Formulation Formulation:1) terephthalic acid2) bis(hydroxy-alkoxy-phenyl)-fluorene (diol)-5-15mol%,3) EG

S.No 12 Patent No US20110213077A1 Publication date 9/1/2011Assignee SOLVAY ADVANCED POLYMERS LLCTitle Hydroquinone-containing polyesters having improved whitenessAbstract A polyester containing polymerized units of hydroquinone; 4,4’-biphenol; and

hydroxybenzoic acid; terephthalic acid and optionally isophthalic acid. A method of forming a polyester including first acylating a mixture of hydroquinone; 4,4′-biphenol; terephthalic acid and optionally isophthalic acid; and hydroxybenzoic acid; and then polycondensing the resulting acylated mixture. The polyester is suitable for uses such as lighting where high whiteness, high reflectivity and high heat resistance are desirable.

Novelty Polyester (A1) comprising structural 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 least 80 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 processing capability at moderate temperatures; exceptional properties; and superior heat resistance.

How to improve Heat resistance of PET

Polyester comprisesHydroquinone; 4,4'-biphenol; terephthalic acid and optionally isophthalic acid; and hydroxybenzoic acid;

Raw material details: 1) Hydroquinone-

Molar mass- 110.11g/mole2) 4 4’-biphenol –

Molar mass: 186.21 g/mole

S.No 12 Patent No JP2009179654A Publication date 8/13/2009Assignee NIPPON ESTER CO LTDTitle POLYESTER DIRECT BLOW MOLDED ARTICLEAbstract PROBLEM TO BE SOLVED: To provide a polyester direct blow molded article which can

be molded at a low processing temperature, can lower a production cost, and is excellent in moldability and heat resistance.SOLUTION: Provided is a polyester direct blow molded article characterized by molding a polyester resin which comprises a dicarboxylic acid component consisting mainly of terephthalic acid and a diol component containing 1,6-hexanediol in an amount of ≥50 mol%, has a melting point of 100 to 150°C, and contains a crystal-nucleating agent in an amount of 0.01 to 5.0 mass%, and in which a DSC curve exhibiting a temperature-falling crystallization determined by DSC satisfies an expression (1): b/a≥0.05 (mW/mg×°C).

Novelty A polyester direct blow molded product contains polyester resin which contains dicarboxylic acid component having terephthalic acid as main component and 50 mol% or more of 1,6-hexanediol as diol component. The polyester resin has melting point of 100-150° C. The polyester resin contains 0.01-5 mass% of crystal nucleating agent. The polyester direct blow molded product has temperature-fall crystallization (b/a) of 0.05 or less mW/mg.° C calculated using differential scanning calorimetry.

Use/Advantage Polyester direct blow molded product has excellent moldability and heat resistance and is manufactured economically with out variation in surpass shape stability.

How to improve Heat resistance of PET

Preparation of PETTerephthalic acid and1,6-hexanediolCrystal-nucleating agent (0.01 to 5.0 mass%)

Raw material details Crystal-nucleating agent: silicon oxides or talc particle size having 3.0 microns. It will be added in PTA and EG slurry

S.No 13 Patent No JP2010132832A Publication date 6/17/2010Assignee MITSUBISHI PLASTICS INCTitle FLAME-RETARDANT POLYESTER RESIN COMPOSITIONAbstract PROBLEM TO BE SOLVED: To provide a flame-retardant polyester resin composition

with flame retardancy, mechanical properties, and heat resistance.SOLUTION: This polyester resin composition includes a mixture of: a polyester resin (A) which contains 50-90 mol% of terephthalic acid as a polycarboxylic acid 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 resistance with a reduced amount of addition of an inorganic flame retardant relative to an amount conventionally examined.

Novelty A flame-retardant polyester-type resin composition contains a mixture of polyester-type resin and melamine (10-80 mass%). The resin has glass transition temperature of 40° C or less and crystal melting temperature of 140-90° C.

Use/Advantage The flame-retardant laminate comprising polyester-type resin composition has excellent flame retardance, mechanical characteristic and heat resistance.

How to improve Heat resistance of PET

By adding melamine to PET

New raw material details

Melamine:

Molar mass – 126.12

S.No 14 Patent No JP2007138160A Publication date 6/7/2007Assignee TOYOBOTitle METHOD FOR MANUFACTURING POLYESTER COMPOSITIONAbstract PROBLEM TO BE SOLVED: To provide a method for manufacturing a polyester

composition, which is suitably used as a material for a covering of a substrate or a molded product such as a blow molded product which is excellent in transparency, shows little variation thereof and inhibits production of aldehydes and variation thereof at molding, or a polyester composition capable of efficiently producing a blow molded product which is excellent in resistance to pressure and heat resistant dimensional stability, particularly a blow molded product excellent in various characteristics through high-speed molding.SOLUTION: In the method for manufacturing the polyester composition, at least two polyesters having different limiting viscosity numbers and substantially the same compositions are mixed, wherein the polyesters are separately obtained through solid-phase polymerization in a solid-phase polymerization apparatus. The difference in limiting viscosity 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 are subjected to solid-state polymerization separately by solid-state polymerization apparatus, are mixed to obtain a polyester composition. The difference in intrinsic viscosity 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 flow characteristics, excellent continuous formability is efficiently manufactured. The polyester composition provides compact with excellent transparency, mechanical characteristics such as pressure resistance, heat-resistant dimensional stability, and with suppressed aldehyde generation amount.

How to improve Heat resistance of PET

Manufacturing the polyester composition, at least two polyesters having different limiting viscosity numbers and substantially the same compositions are mixed,

S.No 15 Patent No JP2007177089A Publication date 7/12/2007Assignee MITSUI CHEMICALS INCTitle POLYETHYLENE TEREPHTHALATE RESIN COMPOSITION AND BLOW-MOLDED

CONTAINER MADE THEREFROMAbstract PROBLEM TO BE SOLVED: To provide a polyethylene terephthalate resin composition

capable of obtaining blow-molded containers with high heat resistance and transparency in high productivity, and to provide such 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 consisting maily of recurring units derived from dicarboxylic acid(s) comprising terephthalic acid and/or its ester-forming derivative and diol(s) comprising ethylene glycol and/or its ester-forming derivative, wherein the proportion of diethylene glycol units is 0.5-2.0 wt.%. The component (B) is an ethylene-based polymer composition comprising (a) polyethylene and/or (b) an ethylene-(meth)acrylic acid copolymer, being greater than 45 in Shore D hardness.

Novelty A polyethylene terephthalate resin composition contains polyethylene terephthalate (A), and ethylene-polymer composition (B) (0.1-10000 ppb). The component (A) contains repeating unit derived from dicarboxylic acid containing terephthalic acid and/or its ester-forming derivative, and diol containing ethylene glycol and/or its ester-forming derivative. The content of diethylene glycol unit in 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 blow molded container having excellent heat resistance and transparency, with favorable productivity.

How to improve Heat resistance of PET

Blending of PET with a polyethylene and/or an ethylene-(meth)acrylic acid copolymerFunction: Polyethylene and/or an ethylene-(meth)acrylic acid copolymer accelerating the crystallization rate of PET

S.No 16 Patent No JP2006070101A Publication date 3/16/2006Assignee MITSUBISHI CHEM CORP

Title POLYESTER RESIN, RESIN COMPOSITION, PREFORM FOR STRETCH BLOW MOLDING AND HOLLOW CONTAINER

Abstract PROBLEM TO BE SOLVED: To provide a polyester resin having high heat resistance, mechanical strength and transparency, excellent in bottle productivity and flavor preservability of drink of a bottle content, and suitable as a raw material 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 component consisting essentially of an aromatic dicarboxylic acid, and the unit (B) comprises two or more kinds of diols wherein at least one 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 molding at 280°C cylinder temperature.

Novelty A polyester resin contains unit (A) derived from dicarboxylic acid 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 drying resin to moisture content of 50 ppm or less and injection molding resin at cylinder temperature of 280°C is 30 ppm or less.

Use/Advantage The polyester resin composition formed using the polyester resin has excellent heat resistance and mechanical strength. The hollow container obtained using the composition has excellent flavor retainability of contents.

How to improve Heat resistance of PET

By using least one kind is a cyclic diol in the PET synthesis

S.No 17 Patent No JP2006089511A Publication date 4/6/2006Assignee DAIWA CAN CO LTDTitle POLYESTER RESIN AND MOLDED ARTICLE COMPOSED THEREOFAbstract PROBLEM TO BE SOLVED: To provide a 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 having an average particle diameter of <=50 nm in an amount of 1-10 pts. wt. based on 100 pts. wt. polyester resin, and the difference between the melting point and the recrystallization temperature in differential scanning calorimetry (DSC) is within 50[deg.]C. ; COPYRIGHT: (C)2006,JPO&NCIPI

Novelty A polyester resin is obtained using terephthalic acid and ethylene glycol. Silica powder (1-10 wt.pts) with average particle diameter of 50 nm or less is contained with respect to 100 wt.pts of polyester resin. The difference of melting point and recrystallization temperature of polyester resin is less than 50°C, as determined by differential scanning calorimeter.

Use/Advantage The polyester resin has outstanding crystallinity and heat resistance. The aggregation of silica particle in molded product formed using polyester resin is reduced.

How to improve Heat resistance of PET

Silica powder having an average particle diameter of <=50 nm in an amount of 1-10 pts. wt.