EP1644436A2 - Addition of uv absorbers to pet process for maximum yield - Google Patents

Addition of uv absorbers to pet process for maximum yield

Info

Publication number
EP1644436A2
EP1644436A2 EP04777167A EP04777167A EP1644436A2 EP 1644436 A2 EP1644436 A2 EP 1644436A2 EP 04777167 A EP04777167 A EP 04777167A EP 04777167 A EP04777167 A EP 04777167A EP 1644436 A2 EP1644436 A2 EP 1644436A2
Authority
EP
European Patent Office
Prior art keywords
group
chr
alkyl
hydrogen
reaction
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.)
Withdrawn
Application number
EP04777167A
Other languages
German (de)
English (en)
French (fr)
Inventor
Dale Milton Blakely
Frederick Leslie Colhoun
Max Allen Weaver
Jason Clay Pearson
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.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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
Priority claimed from US10/618,274 external-priority patent/US20050010017A1/en
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Publication of EP1644436A2 publication Critical patent/EP1644436A2/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to methods of efficiently inco ⁇ orating UN absorbers into polyester composition and to polyester compositions made by said methods.
  • the product of the polyester condensation reaction tends to be reversible and in order to increase the molecular weight of the polyesters, this reaction is often carried out in a multi-chamber polycondensation reaction system having several reaction chambers operating in series.
  • the diol and the dicarboxylic acid component are introduced in the first reactor at a relatively high pressure. After polymerizing at an elevated temperature the resulting polymer is then transferred to the second reaction chamber which is operated at a lower pressure than the first chamber. The polymer continues to grow in this second chamber with volatile compounds being removed. This process is repeated successively for each reactor, each of which are operated at lower and lower pressures.
  • the result of this step wise condensation is the formation of polyester with higher molecular weight and higher inherent viscosity.
  • UV absorbers are a particularly important additive, both for imparting stability to the polyesters and to protect those products packaged in PET containers from degradation induced by exposure to UV light.
  • U.S. Patent Number 4,617,374 discloses the use of certain UV- absorbing methine compounds that may be incorporated in a polyester or a polycarbonate during polycondensation. These compounds enhance ultraviolet or visible light absorption with a maximum absorbance within the range of from about 320 nm to about 380 nm. Functionally, these compounds contain an acid or ester group which condenses onto the polymer chain as a terminator.
  • the UV absorbers of the '374 patent have been found to be useful in the preparation of polyesters such as poly(ethylene terephthalate) and copolymers of poly(ethylene terephthalate) and poly(l,4-cyclohexylenedimethylene terephthalate). It has been observed, however, that some UV absorbers are somewhat- /• ⁇ ,. volatile causing the yield of these UV absorbers in the formed polyester to be somewhat less than 100% (values of 80% to 85% are typical). Moreover, these compounds may plug the equipment by condensing in the process lines. The loss of UV absorber results in added costs for the polyester formation because of the down time needed to clean process lines and because of the relatively high cost of these compounds. Accordingly, there is a need for improved methods of inco ⁇ orating UV absorbers into polyester compositions made by the melt phase polycondensation method, and/or improved polyester compositions containing UV absorbers.
  • a method comprises forming a reaction mixture substantially free of a titanium containing ester exchange catalyst compound and comprising combining a diol, a diacid component selected from the group consisting of dicarboxylic acids, dicarboxylic acid derivatives, and mixtures thereof, an antimony containing compound in an amount of less than 0.1% of the total weight of the reaction mixture, a phosphorus containing compound present in an amount of less than about 0.1% of the total weight of the reaction mixture, a metal containing compound selected from the group consisting of zinc containing compounds, manganese containing compounds, present in an amount from about 10 ppm to about 300 ppm, and a UV absorber with polyester reactive moieties.
  • the antimony containing compound, the phosphorus containing compound, and the metal- containing compound comprise the catalyst system used to promote the condensation polymerization that occurs in the method of the invention.
  • the reaction mixture is then polymerized in a polycondensation reaction system in the absence of the titanium ester exchange catalyst compound.
  • the polycondensation reaction system is characterized by having a first reaction chamber, a last reaction chamber, and optionally one or more intermediate reaction chambers between the first reaction chamber and the last reaction chamber.
  • the reaction system is operated in series such that the reaction mixture is progressively polymerized in the first reaction chamber, the one*or more intermediate reactions, and the last reaction chamber. Accordingly, as the reaction mixture proceeds through the series of reaction chambers, polymerization occurs and a polyester is formed; .
  • a method of inco ⁇ orating a UV absorber in a polyester composition comprises.
  • a titanium metal free polyester composition in another embodiment, comprises a diol residue, as diacid residue, a UN absorber residue, antimony atoms, phosphorus atoms, and metal atoms selected from the group consisting of zinc, manganese, and mixtures thereof.
  • the antimony, phosphorus, and metal atoms represent the residue of the catalyst system used to promote the condensation polymerization that forms the polyester composition.
  • an article made from the polyester is provided.
  • the method of this embodiment comprises forming a reaction mixture substantially free of a titanium containing ester exchange catalyst compound and comprising a diol, a diacid component selected from the group consisting of dicarboxylic acids, dicarboxylic acid derivatives, and mixtures thereof, an antimony containing compound in an amount of less than 0.1% of the total weight of the reaction mixture, a phosphorus containing compound present in an amount of less than about 0.1% of the total weight of the reaction mixture, a metal containing compound selected from the group consisting of zinc containing compounds, manganese containing compounds, present in an amount from about 10 ppm to about 300 ppm, and a UV absorber.
  • polyester compositions can be made from reaction mixtures substantially free of titanium containing ester exchange catalysts with high yields of UV absorbers. While the mechanism to explain this phenomena is not fully understood, it is believed that the presence of titanium containing ester exchange compounds have such high conversion activity that the catalyst may also contribute to reactions which degrade some UN absorbers, preventing the UN absorbers from absorbing, dissolving, or otherwise tying into the polyester polymer, or both.
  • the process is conducted using compounds containing 2 ppm or less of titanium metal, and more preferably 0.0 ppm of titanium metal containing compounds are used in the process of the invention.
  • the UV absorbers are characterized by having at least one 4-oxybenzylidene radical of Formula I present: wherein X is hydrogen or up to two moieties selected from the group consisting of hydroxy, C ⁇ -C 6 alkyl, Ci- alkoxy and halogen, and wherein the UV absorbing compound includes a polyester reactive group.
  • Preferred compounds useful in the practice of the invention which contain the moiety of Formula I include one or more of the compounds represented by Formulae II ⁇ V ⁇ below:
  • Suitable diacid components are selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, 1,4- cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, and the like; and esters of these dicarboxylic acids.
  • a functional acid derivative thereof such as the dimethyl, di ethyl, or dipropyl ester of the dicarboxylic acid.
  • the anhydrides of these acids also can be employed.
  • the metal containing component is zinc acetate or manganese acetate
  • the antimony containing component is antimony trioxide
  • the phosphorus containing component is phosphoric acid or an alkyl ester thereof.
  • the metal containing component is zinc acetate and is present in an amount from about 10 to about 200 ppm
  • the antimony trioxide is present in an amount from about 20 to about 500 ppm
  • phosphorous is present in an amount from about 5 to about 200 ppm.
  • the reaction mixture optionally includes one or more components selected from" the group consisting of an iron containing compound, a toner, a cobalt containing compound, and mixtures thereof.
  • the polycondensation system is operated in series such that a reaction product designatable as product P 1 from reaction chamber RC 1 is directly or indirectly transportable to reaction chamber RC 1+1 by a conduit designatable as conduit C 1 connecting reaction chamber RC 1 to reaction chamber RC 1+1 (i.e., the polymerization product from each reaction chamber is transported to the next reaction chamber in the series).
  • a reaction product designatable as product P 1 from reaction chamber RC 1 is directly or indirectly transportable to reaction chamber RC 1+1 by a conduit designatable as conduit C 1 connecting reaction chamber RC 1 to reaction chamber RC 1+1 (i.e., the polymerization product from each reaction chamber is transported to the next reaction chamber in the series).
  • indirectly transportable recognizes that the product from reaction chamber RC 1 can be physically disconnected from reaction chamber RC 1+1 but still provide feed stock to the reaction chamber, such as via tanker truck or rail car.
  • it is assumed herein that such reaction chambers and conduits are in fluid communication, but the scope of the invention includes both direct and
  • the reaction mixture is successively polymerized as it proceeds through the polycondensation system.
  • the UV absorber is added to reaction product P k"2 while reaction product P k"2 is transported between reaction chamber RC "2 and reaction chamber RC _1 (i.e., the UV absorber is added in the conduit connecting third from the last to the second from the last reaction chamber.)
  • the UV absorbers, the diol, and the diacid component are the same as set forth above with the same amounts as set forth above.
  • the UV absorber may be added neat or in a carrier such as the same or different diol used in RC 1 . By feeding the UV absorber; into the conduit, it is possible to increase the yield of the UV absorber in the polyester composition.
  • DMT dimethyl terephthalate
  • EG ethylene glycol
  • CHDM 1,4-cyclohexanedimethanol
  • 230 ppm antimony trioxide 230 ppm antimony trioxide
  • 70 ppm phosphoric acid are introduced into the first reaction chamber of a multi-chamber polycondensation reactor at a pressure of about 48 psi.
  • the DMT is fed into the first reaction chamber at a rate of 180 lb/min
  • the EG is fed into the first reaction chamber at a rate of about 130 lb/min EG
  • the CHDM is fed into the first reaction chamber at a rate of about 2.2 lb/min.
  • polyester having a low-color, low-migratory UN absorber is voluminous and cannot easily be enveloped. While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit' ⁇ and scope of the invention.

Landscapes

  • 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)
  • Compositions Of Macromolecular Compounds (AREA)
EP04777167A 2003-07-11 2004-06-28 Addition of uv absorbers to pet process for maximum yield Withdrawn EP1644436A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/618,274 US20050010017A1 (en) 2003-07-11 2003-07-11 Addition of UV inhibitors to pet process for maximum yield
US10/855,723 US20050008885A1 (en) 2003-07-11 2004-05-27 Addition of UV absorbers to PET process for maximum yield
PCT/US2004/020645 WO2005007735A2 (en) 2003-07-11 2004-06-28 Addition of uv absorbers to pet process for maximum yield

Publications (1)

Publication Number Publication Date
EP1644436A2 true EP1644436A2 (en) 2006-04-12

Family

ID=34083690

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04777167A Withdrawn EP1644436A2 (en) 2003-07-11 2004-06-28 Addition of uv absorbers to pet process for maximum yield

Country Status (7)

Country Link
EP (1) EP1644436A2 (pt)
JP (1) JP2007521378A (pt)
KR (1) KR20060056318A (pt)
BR (1) BRPI0412403A (pt)
CA (1) CA2530484A1 (pt)
MX (1) MXPA06000426A (pt)
WO (1) WO2005007735A2 (pt)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7541407B2 (en) * 2004-05-27 2009-06-02 Eastman Chemical Company Process for adding methine UV light absorbers to PET prepared by direct esterification
US20060287477A1 (en) 2005-06-17 2006-12-21 Crawford Emmett D Greenhouses comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4- cyclohexanedimethanol
US7955674B2 (en) 2005-03-02 2011-06-07 Eastman Chemical Company Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7462684B2 (en) 2005-03-02 2008-12-09 Eastman Chemical Company Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US7959836B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US7959998B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7704605B2 (en) 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
JP5543714B2 (ja) 2005-10-28 2014-07-09 イーストマン ケミカル カンパニー 高いガラス転移温度を有するシクロブタンジオールを含むポリエステル組成物及びそれから製造される物品
US8586701B2 (en) 2005-10-28 2013-11-19 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US8193302B2 (en) 2005-10-28 2012-06-05 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7737246B2 (en) 2005-12-15 2010-06-15 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US9169388B2 (en) 2006-03-28 2015-10-27 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
WO2008051320A1 (en) * 2006-10-27 2008-05-02 Eastman Chemical Company Polyester compositions which comprise tetramethylcyclobutanediol, cyclohexanedimethanol and ethylene glycol, and manufacturing processes therefor
EP2225084B1 (en) 2007-11-21 2013-05-29 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8501287B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US8895654B2 (en) 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
US20130217830A1 (en) 2012-02-16 2013-08-22 Eastman Chemical Company Clear Semi-Crystalline Articles with Improved Heat Resistance

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US5032631A (en) * 1988-11-10 1991-07-16 Hoechst Celanese Corporation UV-light stabilized polyester molding compositions
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US6806304B2 (en) * 2001-09-27 2004-10-19 Cytec Technology Corp. Process for improving the shelf life of a hindered phenol antioxidant
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Also Published As

Publication number Publication date
BRPI0412403A (pt) 2006-09-05
JP2007521378A (ja) 2007-08-02
KR20060056318A (ko) 2006-05-24
MXPA06000426A (es) 2006-03-17
WO2005007735A2 (en) 2005-01-27
WO2005007735A8 (en) 2005-05-26
CA2530484A1 (en) 2005-01-27
WO2005007735A3 (en) 2005-04-14

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