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WO2008105000A2 - Polyester à ramification contrôlée et procédé de production correspondant - Google Patents

Polyester à ramification contrôlée et procédé de production correspondant Download PDF

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Publication number
WO2008105000A2
WO2008105000A2 PCT/IN2008/000117 IN2008000117W WO2008105000A2 WO 2008105000 A2 WO2008105000 A2 WO 2008105000A2 IN 2008000117 W IN2008000117 W IN 2008000117W WO 2008105000 A2 WO2008105000 A2 WO 2008105000A2
Authority
WO
WIPO (PCT)
Prior art keywords
diol
polyester
branching
polymer
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IN2008/000117
Other languages
English (en)
Other versions
WO2008105000A3 (fr
Inventor
Vikas Madhusudan Nadkarni
Subbiah Venkatachalam
Pandurang Nagnath Honkhambe
Ashwin Kumar Jain
Raghunath Gharal Prashant
Amit Avinash Deshpande
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reliance Industries Ltd
Original Assignee
Reliance Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reliance Industries Ltd filed Critical Reliance Industries Ltd
Publication of WO2008105000A2 publication Critical patent/WO2008105000A2/fr
Anticipated expiration legal-status Critical
Publication of WO2008105000A3 publication Critical patent/WO2008105000A3/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation

Definitions

  • the present invention relates to polyester with controlled branching having composition comprising at least one carboxylic acid or anhydride or ester thereof, at least one diol or polyol and at least one branching agent; said branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol and at least one diol which is uniformly distributed in the polymer backbone.
  • the present invention also relates to a process of making the above polyester with controlled and uniformly distributed branching in the polymer backbone.
  • the present invention also relates to use of the above polyester in manufacturing post process curable fiber or filament, molded articles with high impact resistance and transparent films.
  • Thermoplastic polyesters are widely used in manufacturing of fibers or filaments or films or container by extrusion, molding (injection or stretch blow).
  • the polyester is known for deficiencies in melt rheology.
  • polyester has typically low melt viscosity, low melt strength and low melt elasticity.
  • Such limitations have left the polyester with narrow processing window and always required specialized equipments for processing.
  • melt viscosity and melt strength of polyester can be improved by introducing branching in the linear chain structure of the polyester and /or increasing molecular weight through chain extension.
  • branching agent such as poly- functional carboxylic acids or anhydrides or alcohols directly during the polymerization reaction or melt mixing process.
  • the overall effect of the reaction-melt mixing may in fact decrease the molecular weight of the polyester.
  • branching agent used to modify polyester
  • Most widely used branching agents are tri-functional monomer such as trimelletic anhydride, 1,3,5-Benzenetricarboxylic acid,l,l,l-Tris(hydroxymethyl)ethane, 1,1,1- Tris(hydroxymethyl)propane and tetra-functional monomer such as pentaerythritol for polyester.
  • branching agent used to effectively modify the polyester it is important that the degree of branching can be controlled during the reaction and that the branching occurs uniformly in the polyester.
  • polyester with controlled branching having composition comprising at least one carboxylic acid or anhydride or ester thereof, at least one diol or polyol and at least one branching agent; said branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol and at least
  • the branching agent prepared as per the above mentioned patent application is used between 0.1 -10 percentage by weight preferably between 0.2 to 3 percentages is used in this invention, for making branched condensation polymers.
  • the branching agent is added to a mixture of purified terephthalic acid and monoethylene glycol slurry in different molar ratios at temperature 260-265 °C under nitrogen atmosphere followed by polycondensation at
  • An object of the invention is to provide polyester with controlled branching having composition comprising at least one carboxylic acid or anhydride or ester thereof, at least one diol or polyol and at least one branching agent; said branching agent comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol and at least one diol which is uniformly distributed in the polymer backbone.
  • Another object of the invention is to provide polyester with controlled branching; said product is cost effective as there is no occurrence of gelling.
  • Another object of the invention is to provide polyester with controlled branching; said product is consistent in quality as the branching occurred uniformly in the polymer chain and controlled chain length.
  • Another object of the invention is to provide a process for making the above polyester with controlled branching; said process is cost-effective as there is no occurrence of gelling.
  • Another object of the invention is to provide a process for making the above polyester with controlled branching; said process gives product with controlled branching and uniformly distributed in the polymer backbone.
  • Another object of the invention is to provide the use of the above polyester in manufacturing post process curable fiber or filament, molded articles with high impact resistance, higher melt strength for blown film extrusion and extrusion blow molding and transparent films.
  • polyester with controlled branching having composition comprising at least one carboxylic acid or anhydride or ester thereof, at least one diol or polyol and at least one branching agent; said branching agent comprises at least one tri- functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol and at least one diol which is uniformly distributed in the polymer backbone.
  • a process for making the above polyester with controlled branching comprises: a esterifying at least one carboxylic acid, anhydride or ester thereof and at least one diol or polyol at temperature in the range of 255 to 265° C under pressure in the range of 1.5 to 1.8 Kg/cm 2 , b adding at least one branching agent which comprises at least one tri-functional carboxylic acid or anhydride thereof, at least one mono alkyl alcohol and at least one diol at the end of the esterification reaction followed by agitating the reaction mixture for at least 10 min; and c polycondensing the reaction mixture at temperature in the range of 260 to 290° C under pressure in the range of 0.5 to lmm Hg and draining the polyester.
  • the dicarboxylic acid is selected from terephthalic acid, adipic acid, glutaric acid, naphthalene dicarboxylic acid, perylene dicarboxylic acid.
  • the diol or polyol is selected from ethylene glycol, butanediol, 1,3-propane diol, 1,6-hexane diol .
  • the mole ratio of hydroxyl group to carboxyl group is in the range of 1.2 to 2.
  • the reaction temperature also affects the reaction rate of poly-condensation. It is preferred to carry out the poly-condensation reaction at temperature in the range of 260-285 0 C.
  • the above process is either a batch process or a continuous process. In the batch process the branching agent is added towards the end of esterification reaction followed by agitation for at least 10 minutes while in the continuous process, the molten adduct is added by a transfer line injection followed by mixing for at least 10 minutes.
  • the tri-functional carboxylic acid or anhydride thereof used in the branching agent is selected from 1,3,5-Benzene-tri-carboxylic acid, 1,2,3-Benzene-tri-carboxylic acid or anhydride thereof, 1,2,4-Benzene-tri-carboxylic acid (Trimelletic acid) or anhydride thereof, 2,3,6-naphthalene tricarboxylic acid or anhydride thereof, perylene tri-carboxylic acid or anhydride thereof.
  • the mono alkyl alcohol used in the branching agent is a long chain alcohol having carbon chain length Of C 1 to C 25 or highly substituted branched aliphatic or aromatic alcohol.
  • the long chain mono alkyl alcohol is selected from butanol, hexanol, heptanol, octanol, nonanol or dodecanol.
  • Preferably highly substituted branched aliphatic or aromatic alcohol is selected from isobutanol, isooctyl alcohol, isododecyl alcohol, neopentyl alcohol or benzyl alcohol.
  • the diol used in the branching agent is selected from monoethylene glycol, 1,3-propane diol, butane diol or 1, 6 Hexane diol.
  • the ratio of trifunctional carboxylic acid or anhydride thereof, mono alkyl alcohol and diol is in the range of 1 :0.5:2 to 1 :1.5:7.
  • the branching agent is added in the range of 0.1 to 10 % by wt in the polyester, preferably between 0.4-2 % by weight of the polyester.
  • the above polyester is used in the manufacture of low pill fiber or filament.
  • the above polyester is used in the manufacture of molded articles with high impact resistance.
  • the above polyester is used in the manufacture of transparent films.
  • the present invention allows the change in the composition of matter of polyester in terms of extent and length of branching to suit the polyester for end application requiring specific attributes like post process curable fiber, filament film or molded articles with high impact or transparency.
  • Polyester of the invention has crystallization temperature in the range of 180-219° C and poly-dispersity in the range of 2.35 to 3.64. Die swell of the polymer increased with increase in the concentration of branching agent. This suggests the increased chain entanglement with increased branching and decrease in crystallization rate which is seen from the drop in crystallization temperature from DSC data.
  • the polyester has uniform branching in the polymer chain and controlling chain length of the alkyl group of the branching agent controls the branching length.
  • the product and process are cost-effective.
  • the process results in products with consistent quality.
  • the base chips can be either melt spun into fibers or melt cast into films, or processed to give molded articles which can be further polymerized in solid state, to give post process curable articles.
  • the process described in this invention gives a product with reduced gelling tendency compared to the products produced using conventional branching agents.
  • Example 1 1, 4- bis(2-hydroxy ethyl) 2-octyl tribenzoate
  • Trimelletic anhydride (424 g, 2.2 mol) and 1-octanol (287g, 2.2 mol) was heated at 200°C under nitrogen pressure of 25 psi with stirring. The reaction was carried out for 4 hours. The reaction mixture was cooled and further depressurized. To this reaction mixture, monoethylene glycol
  • PET polymer having IV of 0.6 dl/g prepared by melt-phase polymerization process.
  • Purified terephthalic acid (PTA) (6 kg) and monoethylene glycol (MEG) (8 Kg) were charged in 1:2 molar ratio.
  • antimony trioxide catalyst (2.8 gm ) were added to the above reaction mixture.
  • the esterification reaction was carried out at 256°C, under a pressure of 1.5-1.85kg/cm 2 .
  • the oligomer obtained was then subjected to polycondensation at temperature of 285°C under reduced pressure 1-5 mm Hg to obtain the polymer. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen.
  • the polymer was drained as strands by quenching in a water bath. The strands are then cut into chips in a pelletizer. The polyester was analysed by IV, GPC, DSC and Rheology and used as control polyester. The prepolymer chips are amorphous in nature. They were crystallized at 140 0 C to obtain the crystalline prepolymer.
  • Example 3 Polyester with 0.21 , 0.42 and 1.0 ( wt % ) of branching agent prepared according to Example 1;
  • Monoethylene glycol MEG (6 kg) and purified terephthalic acid (PTA) (8 kg) (1:2 molar ratio) was esterified in the presence of Sb 2 O 3 (2. 8 g) as a catalyst at 26O 0 C under nitrogen pressure of 1.5 - 1.85 kg / cm 2 .
  • the branching agent prepared according to the example 1 was added at the ratios given in Table 1 at the end of esterification at 260 0 C and the resultant reaction mixture was further agitated for 30 minutes.
  • the esterified mixture was polycondensed at 285 0 C under reduced pressure of 1-5 mm Hg. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen. The polymer was drained as strands by quenching in a water bath. The strands are then cut into chips in a pelletizer.
  • the polymer is characterized by IV, DSC and GPC methods. The presence of branching in copolyester was confirmed by GPC, DSC and Rheology.
  • the prepolymer chips are amorphous in nature. They were crystallized at 140 0 C to obtain the crystalline prepolymer.
  • the crystallized prepolymers were polymerized to high molecular weight polymer by solid state polymerization at 200°C. Samples were taken at different time intervals and IV values were measured. The results are given in Table.2.
  • Example 4 The crystallized polymer prepared in Example 4, was solid state polymerized at 160 & 180 0 C and IV build-up was measured at different time intervals. The IV build up did not take place and it was remaining at 0.588 even after 8hrs at 160 or at 180 0 C indicating solid state polymerization did not take place at the 160 or 180 °C
  • Example 7 & 8 Polyester with 2.1 wt %, 3.2 wt % branching agent Monoethylene glycol MEG (6 kg) and purified terephthalic acid (PTA) (8 kg) (1 :2 molar ratio) was esterified in the presence of Sb 2 O 3 (2. 8 g) as a catalyst at 26O 0 C under nitrogen pressure of 1.5 - 1.85 kg / cm 2 .
  • the branching agent prepared according to the example 1 was added at ratios given in Table 3 at the end of esterification at 260 0 C and the resultant reaction mixture was further agitated for 30 minutes. Table 3. Wt % of branching agents used for different examples
  • the esterif ⁇ ed mixture was polycondensed at 285 0 C under reduced pressure of 1-5 mm Hg. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen. The polymer was drained as strands by quenching in a water bath. The strands are then cut into chips in a pelletizer. The polymer is characterized by IV, DSC and GPC methods. The presence of branching in copolyester was confirmed by GPC, DSC and Rheology.
  • the prepolymer chips are amorphous in nature. They were crystallized at 140 0 C to obtain the crystalline prepolymer. The crystallized chips were polymerized further by SSP at 190, 200, and 210 0 C. The samples were taken at different time intervals to check molecular weight buid-up. Intrisic viscosity (IV) could not be measured. The polymer got gelled. The gel content measured at different times (for the polymer prepared by Example 4) are given in Table 4
  • Example 9 Polyester containing 0.15 % ( by wt ) penta erithritol as branching agent Monoethylene glycol (MEG) (5.25 kg) and purified terephthalic acid (PTA) (7 kg) (1 :2 molar ratio) was esterified in the presence of Sb 2 O 3 (2. 45 g) as a catalyst at 26O 0 C under nitrogen pressure of 1.5 - 1.85 kg / cm 2 .
  • the branching agent penta erithritol (10.5 gm) was added as a solution in MEG (100ml) at the end of esterification at 260 0 C and the resultant reaction mixture was further agitated for 30 minutes.
  • the esterified mixture was polycondensed at 285 0 C under reduced pressure of 1-5 mm Hg. After a certain rise in torque, vacuum was broken and the reactor was pressurized with nitrogen. The polymer was drained as strands by quenching in a water bath. The strands are then cut into chips in a pelletizer.
  • the polymer is characterized by IV, DSC and GPC methods. The presence of branching in copolyester was confirmed by GPC, DSC and Rheology.
  • the prepolymer chips are amorphous in nature. They were crystallized at 140 0 C to obtain the crystalline prepolymer. The crystallized chips were polymerized further by SSP at 200°C. The samples were taken at different time intervals to check molecular weight buid-up. Intrinsic Viscosity (IV) data for the polymer is given in Table 2.
  • FIG. 2 illustrates the build up of IV (7) for the polymer chips with time (6) during the SSP at 200°C. 8 indicates the build up of IV (7) for the polymer chips of Example 5 when polymerized in solid state at 200 °C at different time interval.
  • the IV buid up data for the corresponding chips without any branching agent (Example 2) is indicated by 10 and with conventional branching agent pentaerithritol ( Example 9) is indicated by 9 in the figure 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de production de polyester thermoplastique à ramification contrôlée ou à structures linéaires comprenant des agents de ramification dans son squelette, lequel procédé consiste à préparer un produit de condensation d'au moins un acide carboxylique trifonctionnel ou d'un anhydride de celui-ci avec au moins un monoalkylalcool à une température de 255 à 265°C et sous une pression de 1,5 à 1,8 kg/cm2, puis à le faire réagir avec des diols tels que le monoéthylène glycol, le 1,3 propane diol, le 1,6 hexane diol ou le 1,4 butane diol pour former un adduit. Le polymère est ensuite polymérisé par polymérisation à l'état solide dans une atmosphère d'azote à une température de 190 à 210°C de façon qu'on obtienne des copeaux de poids moléculaire élevé, lesquels copeaux sont ensuite extrudés et filés en fusion en filament ou fibre ou extrudés en films et articles durcissables post-traitement. Le polyester formé permet d'obtenir une plus grande vitesse de polymérisation à l'état solide et une vitesse réduite de cristallisation des polymères.
PCT/IN2008/000117 2007-03-01 2008-02-29 Polyester à ramification contrôlée et procédé de production correspondant Ceased WO2008105000A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN396/MUM/2007 2007-03-01
IN396MU2007 2007-03-01

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Publication Number Publication Date
WO2008105000A2 true WO2008105000A2 (fr) 2008-09-04
WO2008105000A3 WO2008105000A3 (fr) 2009-12-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2924060A4 (fr) * 2012-11-21 2016-07-06 Lotte Fine Chemical Co Ltd Procédé de préparation d'un copolymère polyester biodégradable
EP2593494A4 (fr) * 2010-07-14 2016-12-21 Basf Se Composition de résine polyester et son procédé de fabrication

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9458354B2 (en) 2010-10-06 2016-10-04 Resinate Technologies, Inc. Polyurethane dispersions and methods of making and using same
WO2012170978A2 (fr) 2011-06-10 2012-12-13 Felice Kristopher M Revêtements transparents, revêtements acryliques

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5262476A (en) * 1992-03-10 1993-11-16 The Dow Chemical Company Polycarbonate/polyester blends modified with poly(phenylene ether)
US6337046B1 (en) * 1997-12-22 2002-01-08 Eastman Chemical Company Process for producing containers from polymer/platelet particle compositions
US20020004578A1 (en) * 2000-04-14 2002-01-10 Shelby Marcus David Polyester compositions containing polar chain terminatos
US20060293416A1 (en) * 2003-05-19 2006-12-28 Gary Peeters Polyester masterbatch composition
US20050154147A1 (en) * 2003-12-22 2005-07-14 Germroth Ted C. Polyester compositions
US20060036012A1 (en) * 2004-08-10 2006-02-16 Hayes Richard A Process for producing a wollastonite containing polyester and products and articles produced therefrom
US20060182984A1 (en) * 2005-02-17 2006-08-17 Abele Wolfgang P Protected polycarbonate films having thermal and UV radiation stability, and method of making

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2593494A4 (fr) * 2010-07-14 2016-12-21 Basf Se Composition de résine polyester et son procédé de fabrication
EP2924060A4 (fr) * 2012-11-21 2016-07-06 Lotte Fine Chemical Co Ltd Procédé de préparation d'un copolymère polyester biodégradable
US9464165B2 (en) 2012-11-21 2016-10-11 Lotte Fine Chemical Co., Ltd. Method for preparing biodegradable polyester copolymer

Also Published As

Publication number Publication date
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