KR20160012158A - Heat resistant polyethylene terephthalate and a process for the preparation of the same - Google Patents

Abstract

The present invention relates to a process for producing polyesters. The process for preparing the polyester essentially comprises the preparation of isosorbide oligomers and the preparation of isosorbide polymers from the isosorbide oligomers. The isosorbide oligomer or isosorbide polymer is then copolymerized with the polyester. The copolymerized isosorbide oligomer or isosorbide polymer may be carried out at any stage of the preparation of the polyester. The polyesters obtained according to the process of the present invention may be used in packaging applications such as packaging materials or containers. The material or container obtained from the polyester of the present invention can withstand temperatures of 60 to 90 占 폚 without undergoing any deformation and shrinkage. In addition, the material or container obtained from the polyester of the present invention is transparent or has a lower color b * value.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a heat-resistant polyethylene terephthalate,

The present invention relates to a heat-resistant polyester. The present invention also relates to heat-resistant polyesters and processes for their production.

BACKGROUND OF THE INVENTION Polyethylene terephthalate (PET) is a thermoplastic polymer widely used for packaging applications because of its characteristics such as acceptable processability and barrier properties, recyclability and compatibility with food applications. In addition, the packaging product made from PET is of light weight, non-breakable and aesthetic appeal.

Packing products made from PET and used to package foodstuffs such as fruit juices, food concentrates, sports drinks, ketchup, sauces and jams must be hot packable to achieve the desired shelf life of the product.

Extensive research is underway to improve the high-temperature filling ability of polyethylene terephthalate by adding isosorbide monomer. The polyethylene terephthalate modified with isosorbide exhibits a glass transition temperature of 82 to 180 캜 based on the amount of isosorbide used in the polyethylene terephthalate.

For example, US6818730 suggests a process for making isosorbide-containing polyesters.

US20120177854 suggests a process for preparing polyesters by using terephthalic acid, cyclohexanedimethanol and isosorbide.

US5959066 suggests a process for the preparation of polyesters. In the above method, a terephthaloyl residue; One or more other monomers optionally containing an aromatic diacid moiety; Monomers comprising ethylene glycol residues; Monomers comprising isosorbide moieties; One or more other monomers optionally comprising diol moieties; And optionally a diethylene glycol residue, are combined with a condensation catalyst to produce the polyester and heated.

US 6025061 suggests a method for making sheets. The process consists of preparing a polyester and producing a sheet from the polyester. The polyester is a terephthaloyl residue; Optionally one or more other aromatic disacyl moieties; Ethylene glycol residue; Isosorbide residues; And optionally one or more diol moieties, wherein said polyester has an intrinsic viscosity of at least about 0.35 dL / g.

US 6063464 suggests a process for making polyesters. The method comprising: providing a mixture comprising at least one monomer comprising a diacid moiety; Monomers comprising isosorbide moieties; And at least one monomer comprising another diol moiety is combined with a condensation catalyst and heated to a polymerization temperature to produce a polyester polymer having said discrete moiety, said isosorbide moiety and other diol moieties. The polyester obtained by the process proposed in US 6063464 has an intrinsic viscosity of at least about 0.15 dL / g.

The polyester containers obtained by using the polyesters obtained by these proposed methods have several drawbacks due to hygroscopicity and high reactivity of isosorbide. The isosorbide present in the container readily reacts with atmospheric moisture and readily undergoes oxidative degradation and discoloration. Because of these properties of isosorbide, the polyester container is not transparent and can not be used in many applications in the food industry because it does not provide the required barrier properties.

Additionally, the polyester containers can not withstand temperatures of 90 DEG C and tend to deform and shrink, and thus can not be used for high temperature filled packaging containers.

Accordingly, there is a need for a polyester that is capable of withstanding high temperatures without experiencing any deformation and shrinkage, as it has the physical and chemical properties permitted to package the application in light of the above drawbacks. In addition, there is a need for a process for making polyesters capable of withstanding high temperatures without suffering any deformation and shrinkage.

purpose:

Some objects of the invention that are adapted to provide one or more aspects are described below.

An object of the present invention is to provide a heat-resistant polyester.

It is still another object of the present invention to provide a heat-resistant polyester which can withstand high temperatures.

Still another object of the present invention is to provide a heat-resistant polyester having enhanced impact strength, tensile strength and elongation properties.

Still another object of the present invention is to provide heat-resistant polyesters having enhanced barrier properties.

It is a further object of the present invention to provide a heat-resistant polyester which is a transparent, colorless packaging material, packaging container or pre-form during processing.

It is a further object of the present invention to provide a heat-resistant polyester having improved melt flow properties and flow capabilities to enable the production of thin wall containers by an injection molding process.

It is a further object of the present invention to provide a process for producing heat-resistant polyesters.

It is still a further object of the present invention to provide a packaging material, packaging container or preform that is capable of withstanding high temperatures without experiencing any deformation and shrinkage.

Other objects and advantages of the present invention will become more apparent from the following description, which is not intended to limit the scope of the invention.

summary:

The invention relates to a process for preparing a polyester having at least one of the following properties: an intrinsic viscosity of greater than 0.7 dl / g at 25 ° C; Color L * in the range of 72 to 76%; A color b * in the range of -1.5 to -2.5; A diethylene content of less than 1.5%; A glass transition temperature ranging from 81 to 85 캜; An impact strength of 54 to 57 J / M; And a tensile strength of 500 to 600 Kgf / cm ² . The process for preparing the polyester essentially comprises the preparation of isosorbide oligomers and the preparation of isosorbide polymers from the isosorbide oligomers. The isosorbide oligomer or isosorbide polymer is then copolymerized with the polyester. The copolymerized isosorbide oligomer or isosorbide polymer can be carried out at any stage of producing the polyester. The isosorbide oligomer or isosorbide polymer improves the physical, mechanical and chemical properties of the polyester to which it is copolymerized.

The polyesters obtained according to the process of the present invention can be used in packaging applications such as in the production of packaging materials or containers. The material or container obtained from the polyesters of the present invention can withstand temperatures of 60 to 90 占 폚 without undergoing any deformation and shrinkage. In addition, the material or container obtained from the polyester of the present invention is transparent or has a lower color b * value.

The present invention provides polyesters that can be used in packaging applications. The packaging container, packaging material or preform made from the polyester can withstand temperatures of 60 to 90 占 폚 without any deformation and shrinkage. The polyester of the present invention has an intrinsic viscosity of greater than 0.7 dl / g at 25 ° C, a color L * in the range of 72 to 76% A color b * in the range of -1.5 to -2.5; A diethylene content of less than 1.5%; A glass transition temperature ranging from 81 to 85 캜; An impact strength of 54 to 57 J / M; And a tensile strength of 500 to 600 Kgf / cm < ^{2 &} gt ;. The polyesters of the present invention comprise one or more polyesters, polymers of isosorbides and aromatic dicarboxylic acids or esters thereof, and one or more formulations.

The polyester present in the polyester product is obtained from the polymerization of one or more aromatic dicarboxylic acids or esters thereof and alkylene glycols. The aromatic dicarboxylic acids useful for obtaining the polyester include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, hexahydrophthalic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-methylenebis (benzoic acid), while the ester of an aromatic dicarboxylic acid which can be used to obtain the polyester is at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, dimethyl- A group composed of naphthalate, dimethyl-3,4'-diphenyl ether dicarboxylate, dimethylhexahydrophthalate, dimethyl-2,7-naphthalate, dimethyl phthalate and dimethyl-4,4'-methylenebis (benzoate) ≪ / RTI >

The alkylenediols are selected from the group consisting of ethylene glycol, propanediol, butanediol, cyclohexanedimethanol, hexanediol, and combinations thereof.

The aromatic dicarboxylic acid used to prepare the isosorbide polymer is at least one selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6 naphthalene dicarboxylic acid. The ester of an aromatic dicarboxylic acid used to prepare the isosorbide polymer is at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, and dimethyl-2,6-naphthalenedicarboxylate.

Examples of formulations useful for the purposes of the present invention are those which contain a branching agent in an amount from 10 ppm to 2000 ppm, a nucleating agent in an amount from 10 ppm to 2000 ppm and a liquid plasticizer in an amount from 0.5 to 2 wt%, one or more stabilizing agents and 0.1 to 5% Lt; RTI ID = 0.0 > of < / RTI > Other formulations useful for the purposes of the present invention include one or more end-capped oligomers in an amount of 1 to 20 wt%.

Branching agents useful for the purposes of the present invention include: 1.2.4-benzenetricarboxylic acid (trimellitic acid); Trimethyl-1,2,4-benzenetricarboxylate; 1,2,4-benzenetricarboxylic acid anhydride (trimellitic anhydride); 1,3,5-benzenetricarboxylic acid; 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid); 1,2,4,5-benzenetetracarboxylic acid dianhydride (pyromellitic anhydride); 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride; Citric acid; Tetrahydrofuran-2,3,4,5-tetracarboxylic acid; 1,3,5-cyclohexanetricarboxylic acid; Pentaerythritol, 2- (hydroxymethyl) -1,3-propanediol; 2,2-bis (hydroxymethyl) propionic acid; Sorbitol; Glycerol, and combinations thereof. Particularly, a branching agent such as pentaerythritol, trimellitic acid, trimellitic acid anhydride, pyromellitic acid, pyromellitic anhydride and sorbitol is used.

The nucleating agent improves the degree of crystallization and increases the heat distortion temperature of the polyester product. The nucleating agent may be an organic acid or an inorganic acid. Examples of inorganic acid nucleating agents useful for the purposes of the present invention are calcium silicate, nano silica powder, talc, microtalc, aclinc, kaolinite, montmorillonite, synthetic mica, calcium sulphide, boron nitride, barium sulphate, Aluminum, neodymium oxide, and metal salts of phenylphosphonate. The inorganic acid nucleating agent can be modified by an organic material to improve its dispersibility in the polyester product of the present invention.

Examples of organic coagulants include carboxylic acid metal salts such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, Sodium stearate, potassium stearate, lithium stearate, calcium stearate, potassium stearate, calcium stearate, sodium stearate, potassium stearate, potassium stearate, calcium stearate, Sodium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, potassium dibenzoate, sodium dodecylate, Benzoate, sodium? -Naphthalate Sodium cyclohexane carboxylate; Organic sulfonates such as sodium p-toluene sulfonate and sodium sulfoisophthalate; Carboxylic acid amides such as stearic acid amide, ethylene bis-lauric acid amide, palmitic acid amide, hydroxystearic acid amide, epsilon amide and tris (t-butyl amide) trimesate; Phosphate compounds, such as benzylidene sorbitol and its derivatives, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2- Di-t-butylphenyl) sodium.

Examples of liquid plasticizers useful for the purposes of the present invention are N-isopropylbenzenesulfonamide, N-tert-butylbenzenesulfonamide, N-pentylbenzenesulfonamide, N-hexylbenzenesulfonamide, Nn-octylbenzenesulfonamide , N-methyl-N-butylbenzenesulfonamide, N-methyl-N-ethylbenzenesulfonamide, N-methyl-N-propylbenzenesulfonamide, N- N-ethyl-N-2 (2-ethylhexyl) benzenesulfonamide, N-ethyl p-butylbenzenesulfonamide, N-butyltoluenesulfonamide, Nt-octyltoluenesulfonamide, -Ethylhexyltoluenesulfonamide, N-ethyl-Nt-octyltoluenesulfonamide and tri-octyltrimellitate.

Examples of antioxidants include, but are not limited to, irganox 1010, irganox 1076, irgafos 126, and irgafos 168.

Examples of stabilizers include, but are not limited to, ortho-phosphoric acid, trimethylphosphate (TMP), triphenylphosphate (TPP) and triethylphosphonoacetate (TEPA). Preferably, ortho-phosphoric acid is used as the stabilizer.

Examples of endcapped oligomers include, but are not limited to, oligomers of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polytramethylene naphthalene and polybutylene naphthalate.

The polyester product of the present invention comprises a pigment; Flame retardant additives such as decabromodiphenyl ether and triaryl phosphate, such as triphenyl phosphate; Reinforcing agents, for example, glass fibers; Thermal stabilizers; Ultraviolet light stabilizer processing aids; Impact modifiers; Fluidity enhancing additive; Ionomers; Liquid crystal polymers; Fluoropolymers; Olefins comprising cyclic olefins; But are not limited to, polyamide and ethylene vinyl acetate copolymers.

The present invention also provides a method for producing a polyester. Initially, isosorbide and one or more antioxidants are mixed in water and heated to 60 to 90 占 폚, preferably 65 to 75 占 폚, to obtain an aqueous solution containing 60 to 95 wt% of isosorbide. Preferably, the isosorbide content in the aqueous solution ranges from 70 to 85%.

The diols used to prepare the isosorbide solution are monoethylene glycol; 1,3-propanediol; 1,4-butanediol; 1,6-hexanediol; 1,8-octanediol; 1,10-decanediol; 1,12-dodecanediol; 1,14-tetradecanediol; 1,16-hexadecanediol; Dimer diol; 1,4-cyclohexanedimethanol; Di (ethylene glycol); Tri (ethylene glycol); Poly (ethylene ether) glycols; Poly (butylene ether) glycol; (Cis, trans) 1,3-cyclohexanedimethanol; (Cis, trans) 1,4 cyclohexanedimethanol; 2-methyl-1,3-propanediol; 2,2-dimethyl-1,3-propanediol; 2-butyl-2-ethyl-1,3-propanediol; But are not limited to, trimethylpentanediol.

In one embodiment where a cycloaliphatic diol is used, for example, (cis, trans) 1,3-cyclohexanedimethanol and (cis, trans) 1,4 cyclohexanedimethanol, one or more additional cyclic or branched Diol is supplemented.

An aqueous solution of isosorbide is reacted with at least one aromatic dicarboxylic acid or ester thereof at 200-260 < 0 > C to obtain the esterified product trans-esterified product. The reaction is carried out in the presence of an acetate or other alkanoate salt of Co (II) and Sb (III), an oxide of Sb (III) and Ge (IV), and Ti (OR) ₄ , where R is 2 to 12 carbon atoms , ≪ / RTI > glycol solubilized oxides of these metal salts such as n-butylstannic acid may also be used.

Preferred catalysts for reacting isosorbide with one or more aromatic dicarboxylic acids or esters thereof include antimony trioxide, germanium dioxide, tetraisopropyl titanate. The esterified or trans-esterified product is spontaneously converted to an oligomerized product. The oligomerized product can be used to coat a normal polyester chip and then processed for solid state polymerization to increase the viscosity of the polyester to obtain improved Tg and mechanical properties.

The aromatic dicarboxylic acid reacted with isosorbide is terephthalic acid; Isophthalic acid; 2,6 naphthalene dicarboxylic acid, and combinations thereof. The ester of said aromatic dicarboxylic acid is selected from the group consisting of dimethyl terephthalate; Dimethyl isophthalate; Dimethyl-2,6-naphthalenedicarboxylate, and combinations thereof. The esterified or trans-esterified product depends on the acid used in the reaction. Thus, the esterified or trans-esterified product is D-glucitol; Dienhydro-2,2 '- (1,4-benzenedicarboxylate), 2,2' - (1,3-benzenedicarboxylate), diisosorbide- 6-naphthalene dicarboxylate, and combinations thereof.

The oligomerized product is applied to a polymerization reaction using one or more polymerization catalysts to obtain an isosorbide polymer having an intrinsic viscosity of 0.5 to 0.69 dl / g at 25 < 0 > C. The polymerization of the isosorbide oligomer is carried out at 220 to 300 ° C. The polymerization catalysts used for the polymerization of the isosorbide polymers are selected from the group consisting of antimony trioxide, germanium dioxide and cobalt acetate.

The isosorbide oligomer or isosorbide polymer is copolymerized with a polyester of an alkylene aryl dicarboxylate. The copolymerization of the isosorbide oligomer or of the isosorbide polymer with the polyester can be carried out at any stage. In one embodiment, the isosorbide oligomer or isosorbide polymer can be copolymerized with the polyester by adding an isosorbide oligomer or an isosorbide polymer prior to the polymerization of the alkylene aryl dicarboxylate. Alternatively or concurrently, the isosorbide oligomer or isosorbide polymer can be copolymerized with the polyester by adding an isosorbide oligomer or isosorbide polymer during or after the polymerization of the alkylene aryl dicarboxylate monomer .

Examples of alkylene aryl dicarboxylates include ethylene terephthalate; Ethylene isophthalate; Ethylene-2,6-naphthalate; Ethylene-3,4'-diphenyl ether dicarboxylate; Ethylene hexahydrophthalate; Ethylene-2,7-naphthalate; But are not limited to, ethylene phthalate and ethylene-4,4'-methylene bis (benzoate).

The alkylene aryl dicarboxylate is selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 3,4'-diphenylester dicarboxylic acid, hexahydrophthalic acid, 2,7-naphthalenedicarboxylic acid, phthalic acid, Is obtained by an esterification reaction of an aromatic dicarboxylic acid such as methylene bis (benzoic acid) with at least one diol selected from the group consisting of ethylene glycol, propanediol, butanediol, cyclohexanedimethanol, hexanediol, and combinations thereof. One or more stabilizers and, optionally, one or more endcapped oligomers are added to the alkylene aryl dicarboxylate. Subsequently, the alkylene aryl dicarboxylate is subsequently polymerized to prepare a polyester.

Alternatively, the alkylene aryl dicarboxylate may be an ester of an aromatic dicarboxylic acid, such as dimethyl terephthalate, dimethyl isophthalate, dimethyl-2,6-naphthalate, dimethyl-3,4'-diphenyl ether dicarboxylate Propyleneglycol, butylene glycol, neopentyl glycol, MP diol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, Hexanediol, isosorbide. ≪ / RTI > One or more stabilizers and optionally one or more end-capped oligomers are added to the alkylene aryl dicarboxylate. Subsequently, the alkylene aryl dicarboxylate is subsequently polymerized to prepare a polyester.

In one embodiment, the isosorbide oligomer or isosorbide polymer may be copolymerized with the polyester by adding an isosorbide oligomer or isosorbide polymer prior to esterification or ester interchange. Alternatively or concurrently, the isosorbide oligomer or isosorbide polymer may be copolymerized with the polyester by adding an isosorbide oligomer or isosorbide polymer during or after the esterification or ester interchange reaction.

Polymerization of alkylene aryl dicarboxylate is carried out by methods known to those skilled in the art, including process steps such as polycondensation and solid state polymerization to obtain polyesters copolymerized with isosorbide polymers. The polyester produced in the polymerization reaction is crystallized in any conventional crystallizer and subsequently processed in batch or continuous solid state polymerization (SSP) to obtain the desired intrinsic viscosity (IV). The batch SSP can be cleaned with nitrogen to promote the reaction. In a continuous SSP, the circulating nitrogen gas is used as a carrier of by-products.

The polymerization reaction is carried out using at least one agent selected from the group consisting of branching agents, nucleating agents and liquid plasticizers.

The additive may also be added before or after the polymerization reaction to impart properties desired to the resulting polyester. The additive comprises a pigment; Flame retardant additives such as decabromodiphenyl ether and triaryl phosphate, such as triphenyl phosphate; Reinforcing agents, for example, glass fibers; Thermal stabilizers; But are not limited to, ultraviolet light stabilizer processing aids, impact modifiers, flow enhancing additives, ionomers, liquid crystal polymers, fluoropolymers, olefins including cyclic olefins, polyamides and ethylene vinyl acetate copolymers.

Examples of formulations useful for the purposes of the present invention are described herein before.

The polyester is extruded and cut in water to obtain a polyester chip. The chip is dried at 270-290 占 폚, blow-molded and cooled to obtain a material, container or pre-form having a hot fillability in the range of 70-90 占 폚. In particular, the material, container or preform has a hot fillability in the range of 70 to 85 ° C.

The present invention also provides a packaging product comprising the polyester product of the present invention. The packaging product may be a preform or a packaging material or a packaging container.

The isosorbide polymers prepared according to the present invention have improved heat resistance, superior color (L *> 55%, a * of -1.0 and b * of -1.0) and transparency (haze value of less than 5 NTU) The flow properties are imparted to the polyester to which it is added. The polyester produced in accordance with the present invention can be used for applications in various beverages, sports drinks, sauces, jams, etc., which can be filled at a temperature of from 60 to 90 캜, using the normal ISBM, IBM, IM, EBM method ). ≪ / RTI >

The polyesters of the present invention are used to make transparent and hazy flexible and rigid packaging containers, films, sheets, fabrics and yarns. The polyesters of the present invention are also used to prepare hot fill and cold fill containers by using one or more casting processes selected from the group consisting of a heat-set blow mold process and a cooling fixed blow mold process.

The invention is further described in the following Examples, which are intended to illustrate the invention but not to limit the scope thereof

How to analyze quality parameters

A. Intrinsic Viscosity

The intrinsic viscosity or IV is a measure of the molecular mass of the polymer and is measured by a dilute solution viscosity meter. All IV were measured in a 3: 2 mixture of phenol-1,2-dichlorobenzene solution at 25 ° C. About 8 to 10 chips were dissolved to prepare a solution having a concentration of about 0.5%. IV is obtained from a measurement of the relative humidity nr for a homopolymer concentration by using the Bill Meyer equation shown below (FW Billmeyer, J. of Polymer Sci. 1949 IV, 83) It is valid for 0.5-0.65 g / dL.

B. Color

Color parameters are Hunter Lab Colorplex Model Number 45/0, Serial Number. CX 0969. < / RTI > Amorphous chips were used in a transparent state without grinding or crystallization. In general, the measured change can also be seen. The color of the transparent amorphous chip was categorized using CIE 3 stimulus L *, a * and b * values. L * represents the degree of whiteness of the sample, and a high value represents a high degree of whiteness. L * = 100 means completely white; L * = 0 is completely black, a * indicates green-red contrast (- indicates green, and + indicates red); The b * value represents the blue-yellow contrast (the - value represents blue and the + represents yellow).

The color measurement of the SSP chip was performed without grinding. The L * value after SSP is higher than that due to the bleaching caused by crystallization on the late summer of the polymer.

C. Hayes

The haze of the brown bottle was measured on a panel of about 3 cm diameter and 0.238 mm thickness cut from a flat portion of a 1.5 L bottle made from 32 g of pre-form, using Haze Gard Plus (BYK Gardner) Respectively. The haze is the percentage of transmitted light scattered by more than 2.5 degrees (ASTM D-1003-97) after sample penetration. The value is reported as percent haze normalized to sample thickness (% / mm, or sample thickness% haze per mm).

In the case of experiments performed in a smaller scale, the test plates were prepared by injection molding (in cold mold) and the haze was visually evaluated.

D. Diethylene glycol (PEG) content:

To determine the DEG content, PET was trans-esterified from methanol in an autoclave at 220 < 0 > C. During this time, the PET is depolymerized and DEG is liberated as a diol. The liquid formed was analyzed by gas chromatography (GC) to determine the DEG content of the polymer after appropriate calibration.

E. COOH terminal group

The PET was dissolved in a mixture of o-cresol and chloroform under reflux conditions. After cooling to room temperature, the COOH terminal group was determined using potentiometric titration with an ethanolic KOH solution under a nitrogen atmosphere. The results are expressed as COOH mVal / PET kg (COOH milliequivalents per kg of PET).

F. DSC analysis

The thermal properties of all copolymer samples were monitored at a heating and cooling rate of 10 [deg.] C per minute using Perkin-Elmer DSC-7. Nitrogen rinsing was used to block oxidative degradation. The results are expressed in terms of glass transition temperature (Tg), crystallization exothermic peak temperature and crystallization heat (ΔH) as well as peak endothermic reaction temperature and fusion heat for all materials.

The present invention will now be described through the following non-limiting examples.

Example 1: Preparation of isosorbide polymers

Step 1A: Preparation of isosorbide solution

80 kg of isosorbide and 20 kg of water along with a mixture of 0.5 kg of Irganox 1010, irganox 1076 and 1 kg of Irgafos-168 were added to an additional formulation vessel equipped with a stirrer, heating coil and ventilation tube through a head condenser, . The mixture was heated mildly at 60 占 폚 for 20 minutes to obtain 100 kg of an aqueous solution containing 80% of isosorbide.

Step IB: Preparation of isosorbide oligomer

To a 200 liter volumetric reactor equipped with a stirrer, a nitrogen sweep, a vacuum connector, a device for collecting distillate, and means for heating and stirring, 75 kg of the above prepared isosorbide aqueous solution, isophthalic acid (IPA) 60.1 kg and 140 mg of n-butylstanoic acid. The molar ratio of isosorbide: IPA was 1.16: 1. The reactor was flushed with nitrogen and the contents of the reactor were heated with stirring. The temperature was raised to 240 캜 and maintained there for about 20 minutes to remove water formed as a by-product of the condensation reaction. After about 30 minutes at about 250 < 0 > C, a clear solution was obtained. The clear solution was heated at 250 [deg.] C for an additional 1.5 hours until no further water emerged, yielding 105 kg of isosorbide oligomer.

Step 1C: Preparation of 100 mol% polyisosorbide isophthalate masterbatch

The isosorbide oligomer was prepared by adding 200 ppm of antimony trioxide as antimony and 50 ppm of cobalt acetate as cobalt at 260 DEG C and polymerizing in an autoclave under vacuum to obtain 100 kg of amorphous polyisosorbide isophthalate .

 Example 2: Preparation of modified polyethylene terephthalate by PTA process

In a 250 liter reactor equipped with a stirrer, a condenser, a pressurized and a vacuum system, 82 kg of terephthalic acid (PTA) and 36.0 kg of monoethylene glycol (1: 1.16 PTA: MEG molar ratio) were pasted and fed to the reactor . 4.65 g of polyisosorbide isophthalate, 24 gm (200 ppm as Sb) antimony trioxide catalyst, 4.32 gm (30 ppm as Ge) Ge02 catalyst, 25 gm (60 ppm as Co) cobalt acetate powder, 12 g (120 ppm) of pentaerythritol, 6 g (60 ppm) of sodium acetate and 0.25 wt% of n-butylbenzene sulfonamide (nBBSA) were also added to the reactor to give a mixture. The mixture was heated to 250 DEG C to obtain a reaction mass containing ethylene terephthalate monomer. 18 gm (50 ppm as P) of orthophosphoric acid was added to the reaction mass containing ethylene terephthalate monomer. The reaction mass containing ethylene terephthalate monomer was transferred to a polycondensation reactor through a 10 micron filter, where the polycondensation reaction was carried out at 270-285 ° C with a peak temperature of 288 ° C. The polycondensation reaction is monitored on the basis of the reactor agitator power consumption and the reaction is terminated to yield an amorphous polyethylene terephthalate having an IV of about 0.621 dl / g copolymerized with polyisosorbide isophthalate, And cut in water to collect the amorphous chips. These amorphous chips were pre-precipitated prior to application to solid state polymerization (SSP) to dry and increase I.V. to 0.838 dl / g.

Example 3: Preparation of polyethyleneterephthalate by DMT process

35.4 kg of ethylene glycol (EG) and 95.9 kg of dimethyl terephthalate (DMT) were charged to the reactor and heated with stirring. 4.65 kg of polyisosorbide isophthalate was charged to the reactor. Initially, the heating rate was adjusted to maintain the temperature in the reactor at 140 占 폚. After reaching 140 캜, 84.7 gm (200 ppm as Mn) of manganese acetate catalyst solution, 25 gm (60 ppm as Co) of cobalt acetate powder, 12 g (120 ppm) of pentaerythritol and 6 g Of sodium acetate is added to the reactor to initiate the trans-esterification reaction, during which the methanol is distilled off by a column packed through a condenser. The temperature of the top column is kept at 75 캜 to avoid loss of ethylene glycol. The temperature of the reaction mass was increased progressively and slowly from 140 ° C to 230 ° C in 150 minutes. After the end of the trans-esterification reaction, 17 gm (50 ppm as P) of phosphoric acid was added as a stabilizer to the trans-esterified reaction mass and the reaction mass was filtered through a 10 micron filter into a polycondensation reactor.

The polycondensation reactor was progressively evacuated to a pressure of 0.5 mbar and heated to 280 < 0 > C. The polycondensation reaction was monitored on the basis of reactor stirrer power consumption and the reaction was terminated to yield amorphous polyethylene terephthalate with I.V of 0.618 dl / g copolymerized with polyisosorbide isophthalate. The polyethylene terephthalate was extruded into an amorphous chip. Subsequently, the amorphous PET chips were crystallized in batch solid state polymerization at a temperature of 140 ° C and top graded to final IV of 0.84 dl / g.

Example 4: Preparation of polyethylene terephthalate through consumer recycle (PCR) process

39 kg of terephthalic acid (PTA) and 17 kg of monoethylene glycol (PTA: MEG molar ratio of 1: 1.16) were pasted and fed to the esterification reactor in a 250 liter reactor equipped with a stirrer, a condenser, a pressurized and a vacuum system . 50 kg of hot-washed cleaned polyethylene terephthalate bottle flakes (Recycle after User-PCR) equivalent to 50 wt%; 4.65 kg of polyisosorbide isophthalate, 24 gm (200 ppm as Sb) of antimony trioxide catalyst, 4.32 g (30 ppm as Ge) of Ge02 catalyst, 25 gm (60 ppm as Co) of cobalt acetate powder, 12 g (120 ppm) of pentaerythritol, and 6 g (60 ppm) of sodium acetate were added to the esterification reactor to give a reaction mass. The reaction mass was heated to 240 to 250 DEG C to obtain a reaction mass containing ethylene terephthalate. 18 gm (50 ppm as P) of orthophosphoric acid was added to the reaction mass containing ethylene terephthalate and transferred to the polycondensation reactor via a 10 micron filter. The polycondensation reaction was carried out at 270-285 캜 with a peak temperature of 288 캜 to obtain amorphous polyethylene terephthalate having I.V of 0.623 dl / g copolymerized with polyisosorbide isophthalate. The amorphous polyethylene terephthalate was extruded as a strand, cut in water and collected as an amorphous chip. These amorphous chips were pre-crystallized prior to application to solid state polymerization (SSP) to dry and increase I.V to 0.836 dl / g.

Examples 5A-5C: Preparation of modified polyethylene terephthalate by addition of endcapped low IV polyesters

The modified co-polyesters of Examples 5A, 5B and 5C were prepared in the same manner as in Examples 2, 3 and 4, respectively, by using the raw materials mentioned in Table 2 below, There was a difference in the use of the added PBN / PTN endcapped oligomers.

Example 6A-6C: Preparation of polyethylene terephthalate

The modified co-polyesters of Examples 6A, 6B and 6C were prepared in the same manner as in Examples 2, 3 and 4 except that the kinds of raw materials were changed as shown in Table 3 below.

Example 7: Preparation of pre-formers / bottles by two-stage ISBM

Using the co-polyester chips from Examples 5 and 6, a long preform of 38 g * 130 mm was produced on a four gauge injection molding machine with a total gross tonnage of 130 g. Before that, the resin was dried at 170 DEG C for 5 hours. The molding temperature was 280-285 占 폚. The pre-form was conditioned for 24 hours before initiating blowing into the bottle on a blowing machine with a single care ring.

The pre-form was heated to 112 ° C.

The blowing cycle time was 4.13 seconds.

The preliminary blow pressure was 8 bar. The blow pressure was 30 bar.

The bottles thus prepared can be charged at 82 +/- 2 DEG C without any modification.

Example 8: Preparation of thin wall container by IM

A container was prepared using the resin from Example 5 for the IM machine. Prior to this, the chips were dried at 160 DEG C for 7 hours. The mold was cooled with cooling water at 6 캜. The melt fluidity was satisfactory. A container with a wall thickness of 350 mu was prepared. The container can be filled at a temperature of 82 DEG C with good color and transparency.

Example 9: Preparation of a 20 liter container by two-stage ISBM

A 20 liter water container was prepared using the co-polyester from Example 2. The chips were dried at a temperature of 170 DEG C for 6 hours. The preforms were prepared on a single care ring injection molding machine. The extruder temperature was 275-285 占 폚.

The pre-form was then heated at 120 ° C on a single care-ringing machine and then blown at 30 bar pressure. The prepared 20 liter vessel can be washed at 72 占 폚.

BRIEF DESCRIPTION OF THE DRAWINGS The various aspects and various advantages of the present application and its advantageous details are set forth in the description that follows, by way of non-limiting embodiments. The description of well known components and processing techniques has been omitted in order not to unnecessarily obscure aspects of the present disclosure. The embodiments used herein are intended to facilitate an understanding of the manner in which the embodiments of the invention may be practiced and to enable one of ordinary skill in the art to further implement the embodiments herein. Accordingly, the above embodiments should not be construed as limiting the scope of the embodiments of the present invention.

The previous description of particular embodiments fully discloses the general nature of embodiments in which the particular embodiment can be readily modified and / or adapted without departing from the general concept for various applications by applying current knowledge, And variations are to be understood and are intended to be within the meaning and range of equivalents of the described aspects. It is to be understood that the phraseology or terminology used herein is for the purpose of description and should not be regarded as limiting. Thus, although aspects of the present disclosure are described in terms of preferred embodiments, those skilled in the art will recognize that embodiments of the invention may be practiced with modifications within the spirit and scope of the embodiments described herein.

The use of the phrases "at least" or "at least one" refers to the use of one or more elements or components or amounts as may be used in the described embodiments to achieve one or more of the desired objects or results.

Any discussion of documents, practices, materials, devices, products, etc. included in the disclosure is provided solely for the purpose of describing the subject matter. It should not be taken as acknowledging that any or all of the above subject matter forms part of a prior art basis or that it is a common general knowledge of the art relating to the foregoing by virtue of being present before the priority date of the present application.

It is emphasized herein that certain features of the subject matter are emphasized herein, but it is appreciated that various modifications can be made and many changes can be made in the preferred embodiments without departing from the principles of the invention. These and other modifications in the context of the present disclosure or in the preferred embodiments shall be apparent to those skilled in the art from the description herein and that it should be explicitly understood that the foregoing description is only for purposes of illustration and not limitation.

Claims (17)

An intrinsic viscosity of greater than 0.7 dl / g at 25 ° C, a color L * in the range of 72 to 76%; A color b * in the range of -1.5 to -2.5; A diethylene content of less than 1.5%; A glass transition temperature ranging from 81 to 85 캜; An impact strength of 54 to 57 J / M; And a tensile strength of 500 to 600 Kgf / cm < ² >, the method comprising:
The method comprises:
a. Dissolving isosorbide and one or more antioxidants in water and optionally in one or more of the diols to obtain an aqueous solution;
b. Reacting said isosorbide aqueous solution with at least one aromatic dicarboxylic acid or ester thereof to obtain an oligomerized product via esterification or ester interchange;
c. Polymerizing said isosorbide oligomer using at least one polymerization catalyst to obtain an isosorbide polymer; And
d. By adding said oligomerized product or said isosorbide polymer in at least one step selected from the group consisting of before, during and after the polymerization of one or more alkylene aryldicarboxylate monomers, said isosorbide polymer Is copolymerized with the polyester to obtain a polyester. 2. The process of claim 1, wherein said dissolving process step is carried out at a temperature in the range of from 30 to 90 < 0 >C; Wherein said antioxidant is selected from the group consisting of irganox 1010, irganox 1076, irgafos 168; Wherein the diol is selected from the group consisting of monoethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, Cyclohexanedimethanol, di (ethylene glycol), tri (ethylene glycol), poly (ethylene ether) glycol, poly (butyl 1,3-cyclohexanedimethanol, (cis, trans) 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 2,2-dimethyl- , 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, trimethylpentanediol; Wherein the concentration of isosorbide in the aqueous solution is in the range of 60 to 95 wt%. The method of claim 1, wherein the reaction wherein the method steps are Co (II) and Sb (III) acetate or alkanoate salts, Sb (III), Ge ( IV), Ti (OR) 4 ( wherein, in which R is 2 In the presence of a catalyst selected from the group consisting of an oxide of n-butylstannanoic acid, antimony trioxide, germanium dioxide, tetraisopropyl titanate, an alkyl of from 1 to 12 carbon atoms, Lt; / RTI > Wherein the aromatic dicarboxylic acid is at least one compound selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; The ester of said compound in step (b) is at least one compound selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate and dimethyl-2,6-naphthalenedicarboxylate; Wherein the esterified or trans-esterified product is selected from the group consisting of D-glucitol, 1,4: 3,6-dianhydro-, 2,2 '- (1,4-benzenedicarboxylate) (1,3-benzenedicarboxylate), and diisosorbide-2,6-naphthalenedicarboxylate. 2. The process of claim 1 wherein said process step (c) is carried out at a temperature in the range of from 220 to 300 < 0 >C; Wherein the polymerization catalyst is at least one compound selected from the group consisting of antimony trioxide, germanium dioxide, and cobalt acetate. 2. The process of claim 1, wherein the isosorbide polymer exhibits an intrinsic viscosity of 0.50 to 0.69 dl / g at 25 < 0 > C. The composition of claim 1, wherein the alkylene aryl dicarboxylate monomer is selected from the group consisting of ethylene terephthalate, ethylene isophthalate, ethylene-2,6-naphthalate, ethylene-3,4'-diphenyl ether dicarboxylate, ethylene hexahydrophthalate , Ethylene-2,7-naphthalate, ethylene phthalate, and ethylene-4,4'-methylenebis (benzoate); Wherein the alkylene aryl dicarboxylate monomer is selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, hexahydrophthalic acid, 2,7-naphthalene dicarboxylic acid, phthalic acid, '' - methylenebis (benzoic acid) or an esterification reaction of ethylene glycol with at least one aromatic dicarboxylic acid selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, dimethyl-2,6-naphthalate, dimethyl- At least one ester selected from the group consisting of diphenyl ether dicarboxylate, dimethyl hexahydrophthalate, dimethyl-2,7-naphthalate, dimethyl phthalate and dimethyl-4,4'-methylenebis (benzoate) Diols selected from the group consisting of propanediol, butanediol, cyclohexanedimethanol, hexanediol, and combinations thereof. Following the trans-esterification reaction, one or more stabilizers selected from the group consisting of orthophosphoric acid, trimethylphosphate (TMP), triphenylphosphate (TPP), triethylphosphonoacetate (TEPA) and optionally polyethylene terephthalate, polybutyl Is obtained by the addition of at least one terminally-capped oligomer selected from the group consisting of rheneterephthalate, polytrimethylene terephthalate, polytrimethylene naphthalate and polybutylene naphthalate. The method of claim 1, comprising adding the oligomerized product or isosorbide polymer in at least one step selected from the group consisting of before, during, and after the esterification or ester interchange reaction. The method of claim 1, wherein the polymerization of the alkylene aryl dicarboxylate monomer is carried out using at least one agent selected from the group consisting of a branching agent, a nucleating agent, a liquid plasticizer and an additive. 9. The method of claim 8, wherein the branching agent is at least one compound selected from the group consisting of pentaerythritol, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride and sorbitol. The method of claim 8, wherein the nucleating agent is selected from the group consisting of carboxylic acid metal salts such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium Sodium stearate, potassium stearate, lithium stearate, potassium stearate, potassium stearate, sodium stearate, sodium stearate, sodium stearate, sodium stearate, potassium stearate, , Calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluoylate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate , Lithium dibenzoate, sodium beta n- De-rate and sodium cyclohexane carboxylate; Organic sulfonates such as sodium p-toluene sulfonate and sodium sulfoisophthalate; Carboxylic acid amides such as stearic acid amide, ethylene bis-lauric acid amide, palmitic acid amide, hydroxystearic acid amide, epsilon amide and tris (t-butyl amide) trimesate; Phosphate compounds, such as benzylidene sorbitol and its derivatives, sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2- Di-t-butylphenyl) sodium. The process according to claim 8, wherein the liquid plasticizer is selected from the group consisting of N-isopropylbenzenesulfonamide, N-tert-butylbenzenesulfonamide, N-pentylbenzenesulfonamide, N-hexylbenzenesulfonamide, Methyl-N-ethylbenzenesulfonamide, N-methyl-N-propylbenzenesulfonamide, N-ethyl-N-propylbenzenesulfonamide, N- N-ethyl-N-2-ethyl (N-ethyl-N-ethyl) Hexyltoluenesulfonamide, N-ethyl-Nt-octyltoluenesulfonamide and tri-octyltrimellitate. The composition of claim 8, wherein the additive is selected from the group consisting of pigments, flame retardant additives, reinforcing agents, heat stabilizers, ultraviolet light stabilizers, processing aids, impact modifiers, flow enhancing additives, ionomers, liquid crystal polymers, fluoropolymers, , Polyamides, and ethylene vinyl acetate copolymers. The process of claim 1, wherein said polymerization of one or more alkylene aryl dicarboxylates comprises a polycondensation reaction and a solid state polymerization; The polyester extruding the polyester and cutting it in water to obtain a polyester chip, and drying the polyester chip to obtain a dried chip; The material or the container is further processed by blow molding at 270 to 290 占 폚 and cooling the mold to obtain a preform, material or container, wherein the preform, , Preferably from 70 to 85 < 0 > C. A polyester product obtained by the process according to claim 1,
a. One or more polyesters obtained from one or more aromatic dicarboxylic acids or esters thereof and ethylene glycol;
b. Polymers of isosorbide in an amount of from 1 to 20 wt% and one or more aromatic dicarboxylic acids or esters thereof; And
c. A liquid plasticizer in an amount of 0.5 to 2 wt%; At least one nucleating agent in an amount from 10 ppm to 2000 ppm; At least one branching agent in an amount from 10 ppm to 2000 ppm; One or more antioxidants in an amount ranging from 0.1 to 5 wt%; At least one stabilizer; One or more additives selected from the group consisting of one or more additives and optionally one or more end-capped oligomers in an amount of 1 to 20 wt%
At this time,
An intrinsic viscosity of greater than 0.7 dl / g at 25 ° C;
Color L * in the range of 72 to 76%;
A color b * in the range of -1.5 to -2.5;
A diethylene content of less than 1.5%;
A glass transition temperature in the range of 81 to 85 캜;
An impact strength of 54 to 57 J / M; And
A tensile strength of 500 to 600 Kgf / cm < ² >. A polyester product of a packaging material, a packaging container or a preform, said polyester product having an intrinsic viscosity of greater than 0.7 dl / g at 25 ° C; Color L * in the range of 72 to 76%; A color b * in the range of -1.5 to -2.5; A diethylene content of less than 1.5%; A glass transition temperature ranging from 81 to 85 캜; An impact strength of 54 to 57 J / M; And a tensile strength of 500 to 600 Kgf / cm < ² >, wherein the packaging material, the packaging container or the preform is heated to a temperature of from 70 to 90 DEG C, Wherein the polyester product exhibits a hot-fill capacity. 15. The polyester of claim 14, used to make transparent and turbid flexible and rigid packaging containers, films, sheets, fabrics and yarns. 15. The polyester of claim 14, wherein the polyester is used to produce hot fill and cool fill containers by using at least one molding process selected from the group consisting of a heat-set blow molding process and a cooling fixed blow molding process.