JP2010514895A - Process for producing rubber elastic polyetheresters - Google Patents

Abstract

  A method is provided for producing rubber elastic polyetheresters from polyesters and polyols. The method can provide manufacturing costs, reduced energy usage and lower environmental impact than conventional methods, particularly when the method utilizes post-consumer polyester as a starting material.

Description

  The present invention relates to a process for producing a rubber elastic polyether ester. The method can use post-consumer polyester as a starting material, and such polyetheresters can have properties and functionality substantially similar to pure or virgin polyetheresters.

  Polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are used in a variety of application markets including fibers, films and engineering components. A tremendous amount of waste is generated every year from the use of these polyesters that must be discarded. Disposal clearly causes environmental problems. It would be desirable to reuse these discarded polyesters and post-consumption polyesters.

  Previous approaches to recycling polyester included separation and purification of either dimethyl terephthalate (DMT) or terephthalic acid (TPA) from the polyester and subsequent polycondensation of DMT or TPA with ethylene glycol. Thus, recycling is energy intensive and can result in prohibitively expensive methods.

  One embodiment of the present invention is a process for producing a polyetherester from a polyester, wherein the polyester is treated with at least one diol and at least one kind in the presence of a catalyst at a temperature in the range of about room temperature to about 300 ° C. A method comprising contacting with a polyol.

  Another aspect of the invention was prepared by a process comprising contacting a polyester with at least one diol and at least one polyol at a temperature in the range of about room temperature to about 300 ° C. in the presence of a catalyst. It is a polyether ester.

  In the process according to the invention, even when post-consumer polyester is used as starting material, the TPA or DMT separation and purification steps used in the conventional process are eliminated, reducing the cost of production. Polymers produced using these methods provide properties and functionality similar to virgin polyesters, and in a preferred embodiment, the overall cost of production and energy use and lower emissions of greenhouse gases, Thus providing a lower environmental impact. In a preferred embodiment, the diol and / or polyol used for the transesterification of the hard and soft segments in the polyetherester is derived from a bio-based source.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of dispute, the present specification, including definitions, will control.

  Unless otherwise specified, all percentages, parts and ratios are by weight. When an amount, concentration or other value or parameter is given as either a range, a preferred range or a list of preferred upper and preferred lower values, this is regardless of whether the range is disclosed separately. It should be understood that all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed. Where numerical ranges are listed herein, unless otherwise specified, the ranges are intended to include the endpoints and all integers and fractions within the range. It is not intended to limit the scope of the invention to the specific values recited when defining a range.

  As used herein, “comprises”, “comprising”, “includes”, “including”, “has”, “having” The term “)” or any variation thereof is intended to cover non-exclusive inclusions. For example, a process, method, article, or device that includes a list of elements is not necessarily limited to only those elements, and other elements not explicitly described in such processes, methods, articles, or devices are not unique. May also be included. Further, unless expressly specified otherwise, “or” means non-exclusive “or” and not exclusive “or”. For example, the condition A or B is satisfied by any one of the following. A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present) and both A and B are true (or present).

  The use of “a” or “an” is used to describe elements and components of the invention. This is done only for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  The materials, methods, and examples herein are illustrative only and are not intended to be limiting unless explicitly stated.

  In general, the process according to the invention comprises contacting the polyester with at least one diol and at least one polyol at an elevated temperature in the presence of a catalyst. The method can provide an overall reduction in manufacturing costs, energy use, and thus can provide a reduction in global warming gases and a lower environmental impact. In some embodiments, the polyester starting material comprises a polyester selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, mixtures thereof, blends thereof and copolymers thereof. In some embodiments, one polyol is used. In other embodiments, at least two polyols are used.

  In some embodiments, the present invention is a method for producing a polyetherester from a post-consumer polyester, comprising at least the post-consumer polyester in the presence of a catalyst at a temperature in the range of about room temperature to about 300 ° C. There is provided a method comprising contacting with one diol and at least one low polymer diol or polymeric diol (polyol) to cause a transesterification reaction. In a preferred embodiment, the reaction is performed in the presence of a catalyst comprising tin or titanium.

  In one embodiment, the method comprises a transesterification reaction of PET with 1,3-propanediol, preferably biologically derived 1,3-propanediol (biologically derived PDO) and PO3G, preferably biologically derived PO3G, for example Polyetheresters comprising polyethylene terephthalate-based hard segments and polytrimethylene ether glycol (PO3G) -based soft segments from post-consumer polyesters, including PET, including beverage bottles such as soda bottles or water bottles. In some preferred embodiments, the post-consumer polyester comprises a beverage bottle made from or derived from a polyester having a recycle code 1. In some preferred embodiments, the post-consumer polyester comprises a polymeric species selected from the group consisting of polyesters, polyetheresters, mixtures thereof, blends thereof, and copolymers thereof.

  In some embodiments, a method for producing a polyetherester from a post-consumer polyester biodegrades the post-consumer polyester at a temperature in the range of about 200 ° C. to about 300 ° C. in the presence of a catalyst comprising tin or titanium. Contacting with at least one diol that is a derived PDO and at least one polyol that is PO3G and / or PO4G within a molecular weight range of up to about 5000 Da, wherein the method comprises using a polycondensation catalyst with a diacid or Less energy is used than that required to produce the polyester from the esterification of the diester and diol.

  The polyester used in the process is also referred to herein as “polyester starting material”. Polyesters include, by way of example, thermoplastic resins commonly known as 2GT, 3GT, 4GT, 5GT, 6GT, 7GT, mixtures thereof, blends thereof and copolymers thereof. In some embodiments, the polyester starting material comprises a polyester selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, mixtures thereof, blends thereof, and copolymers thereof.

In one embodiment, the diol, monomer, C ₂ -C ₂₀ alkane diol dimers or trimers, alkoxy C ₂ -C ₂₀ alkanediol, alkenoxy C ₂ -C ₂₀ alkane diols, C ₂ ~ C ₂₀ alkene diol, phenoxy C ₂ -C ₂₀ alkane diols, alkyl phenoxy C ₂ -C ₂₀ alkanediol, a phenyl C ₂ -C ₂₀ alkane diols, alkyl phenyl C ₂ -C ₂₀ alkanediol, halo C ₂ -C ₂₀ alkane is selected from diols and the group consisting of chemical mixtures, polyols, monomeric, dimeric or C ₂ -C ₂₀ alkane diol trimers, polyalkylene diol, alkoxy alkane diols, alkenoxy alkanediol, alkene Diol, glycol, polyether glycol, phenoxyalkanedi Lumpur, alkylphenoxy sialic Kanji ol, phenyl alkane diols, alkyl phenyl alkane diols are selected from halo alkane diol and the group consisting of polyols resulting from their chemical mixture. Monomer, dimer or trimer ethylene glycol, 1,3-propanediol, n-butane-1,3-diol, 2-methyl-1,3-propanediol, neopentyl glycol (2,2 -Dimethyl-1,3-propanediol), 1,4-butanediol, triethylene glycol, isomers thereof and mixtures thereof are preferred. In one preferred embodiment, the 1,3-propanediol comprises biologically derived PDO. Biologically-derived PDO is a product name of E.I. I. Available from the DuPont de Nemours Company.

  Poly prepared by a process comprising contacting a post-consumer polyester with at least one diol and at least one polyol at a temperature in the range of about room temperature to about 300 ° C. in the presence of a catalyst comprising tin or titanium. Ether esters are also provided. In some embodiments, the catalyst is an organic titanate. In some embodiments, the polyetherester is a bio-derived PDO that is a post-consumer polyetherester comprising polyethylene terephthalate at a temperature in the range of about 200 ° C. to about 300 ° C. in the presence of a catalyst comprising tin or titanium. And contacting with one diol having a molecular weight up to about 5000 Da and at least one polyol which is poly (trimethylene glycol) (PO3G) and / or poly (tetramethylene glycol) and / or polypropylene glycol The polyester is at least 80% by weight poly (trimethylene terephthalate) and at most 20% by weight PET.

  Polyetheresters can be used to produce the final product. Examples include products selected from the group consisting of molded products, monofilaments and packaging materials, especially packaging materials for medical applications. In some embodiments, the polyetherester has an intrinsic viscosity in the range of about 0.2 to about 2.0.

Polyester starting materials Polyester starting materials include polyesters and polyester-based thermoplastic elastomers, and include post-consumer polyesters. Polyester means a high molecular species or low polymer species resulting from a condensation reaction (polymerization or oligomerization) of a dihydroxy compound and a polybasic acid. An example is an organic dibasic acid having the formula HOOCACOOH, where A is an alkylene group, an arylene group, an alkenylene group. It is possible to use a single kind of acid or a combination of two or more kinds of acids. Each A has about 2 to about 30, preferably about 3 to about 25, more preferably about 4 to about 20, and most preferably 4 to 15 carbon atoms per group. Examples of suitable acids are terephthalic acid, isophthalic acid, phthalic acid, 4,4'-diphenylenedicarboxylic acid, succinic acid, adipic acid, glutaric acid, dibenzoic acid, naphthalic acid, bis (p-carboxyphenyl) methane 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-sulfonyldibenzoic acid, p- (hydroxyethoxy) benzoic acid, succinic acid, glutaric acid, Adipic acid, sebacic acid, 1,12-dodecanedioic acid may be mentioned, but not limited thereto. Also suitable are derivatives of such acids, such as dimethyl esters, diethyl esters or dipropyl esters, and combinations of two or more thereof. The diacids or diesters can be aliphatic (including alicyclic) or aromatic or combinations thereof, preferably aromatic dicarboxylic acids and esters (preferably short chain alkyl esters, more preferably Methyl ester) as well as combinations thereof. Aliphatic diacids or aromatic diacids are preferred, and aromatic dicarboxylic acids and combinations thereof are more preferred. Preferably, the aliphatic diacid or aromatic diacid is an aromatic diacid selected from the group consisting of terephthalic acid and isophthalic acid. Of these, terephthalic acid and isophthalic acid and mixtures thereof are preferred, with terephthalic acid being most preferred.

  Preferred polyesters are those resulting from esterification of dimethyl terephthalate, terephthalic acid or isophthalic acid and a diol. Polyesters also include copolyesters having either at least one type of acid component of the repeating unit and / or at least one type of diol component in the repeating unit.

  If a thermoplastic elastomer is present in the post-consumer polyester, the thermoplastic elastomer can be used as a starting material.

Post-consumer polyester Post-consumer polyester means polyester obtained after consumer use or industrial use of polyester. Post-consumer plastics often contain a polyester starting material suitable for the methods disclosed herein. Exemplary post-consumer polyesters include poly (ethylene terephthalate) (2GT or PET, or PETE), poly (trimethylene terephthalate) (PTT), poly (butylene terephthalate) (PBT or 4GT), poly (pentylene terephthalate). (5GT), poly (hexylene terephthalate) (6GT), and poly (heptylene terephthalate) (7GT) and polyether esters such as Hytrel® polymers, mixtures thereof, blends thereof and copolymers thereof Can be mentioned. Most post-consumer polyester or polyester plastic waste consists of poly (ethylene terephthalate) identified by recycle code 1.

  Examples of polyester plastic waste useful for this method are bottles, cups, containers, packaging materials, carpets, textiles, textile waste, films, engineering parts, molded articles, extrudates, laminates, paints, adhesives Recyclable products having a polyester component such as Preferred post-consumer polyesters include polyesters in the form of beverage bottles such as soda bottles and water bottles.

  Post-consumer polyesters that can be used in the present method also include waste containing thermoplastic elastomers (TPE) such as segmented copolyesters. Thermoplastic elastomers are a class of polymers that can be regenerated upon heating, that is, two other types of properties that are thermoplastics and elastomers that are rubber-like polymers. One form of TPE is a block that usually contains several blocks whose polymer properties are usually similar to those of thermoplastics and some blocks whose properties are usually similar to those of elastomers. A copolymer. Blocks whose properties resemble thermoplastics are often referred to as “hard” segments, while blocks whose properties resemble elastomers are often referred to as “soft” segments.

  Post-consumer polyester starting materials useful in the methods disclosed herein are US Pat. No. 6,562,457, US Pat. No. 6,599,625 and US Pat. No. 7,144,972. It can be prepared from additional aromatic dicarboxylic acids or diesters as disclosed in the specification.

  In a preferred embodiment, the post-consumer polyester comprises a polyester selected from PET, PBT, 3GT, mixtures thereof, blends thereof and copolymers thereof. The diol is selected from ethylene glycol, propylene glycol, butylene glycol, isomers thereof and combinations thereof. The polyol is selected from the group consisting of a polyol of ethylene glycol, a polyol of propylene glycol, a polyol of butylene glycol, a polyol of isomers thereof, and combinations thereof.

  In one embodiment, the post-consumer polyester waste comprises PET, the diol is bio-derived 1,3-propanediol, and the polyol is polytrimethylene glycol. In another embodiment, the post-consumer polyester is PET, the diol is bio-derived 1,3-propanediol, and the polyol is polytetramethylene glycol. In another embodiment, the post-consumer polyester is PBT, the diol is bio-derived 1,3-propanediol, and the polyol is polytrimethylene glycol. In another embodiment, the post-consumer polyester is PBT, the diol is bio-derived 1,3-propanediol, and the polyol is polytetramethylene glycol. In another embodiment, the post-consumer polyester is PET and PBT, the diol is bio-derived 1,3-propanediol, and the polyol is polytrimethylene glycol. In a preferred embodiment, the post-consumer polyester is PET and PBT, the diol is bio-derived 1,3-propanediol, and the polyol is polytetramethylene glycol.

Diol In this process, the polyester is contacted with one or more diols to cause a transesterification reaction. In some embodiments, at least one diol is used. In other embodiments, at least two diols are used.

Useful Exemplary diols, C ₂ -C ₂₀ alkanediol, alkoxy C ₂ -C ₂₀ alkanediol, alkenoxy C ₂ -C ₂₀ alkane diols, C ₂ -C ₂₀ alkene diols for the present method, phenoxy C ₂ -C ₂₀ alkane diols, alkyl phenoxy C ₂ -C ₂₀ alkanediol, a phenyl C ₂ -C ₂₀ alkane diols, alkyl phenyl C ₂ -C ₂₀ alkane diols and halo C ₂ -C ₂₀ alkane diols. Preferred diols include linear or branched C ₂ -C ₂₀ alkane diols such as ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol, dipropylene glycol, tripropylene glycol or tetrapropylene glycol and dibutylene glycol, Tributylene glycol or tetrabutylene glycol, 1,2-propanediol, isopropylene glycol, 1-methylpropylene glycol, 1,3-propanediol, n-butane-1,3-diol, 2-methyl-1,3- Propanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2 Ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,4-butanediol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,2-, 1,3- And 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3,3,4, 4,5,5-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol and 3,3,4,4 5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol. Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbitol are also preferred. 1,3-propanediol (PDO) is a highly preferred diol.

  1,3-propanediol means a reactant comprising at least one of 1,3-propanediol, 1,3-propanediol dimer and 1,3-propanediol trimer, and mixtures thereof including. 1,3-propanediol can be obtained by any of various chemical routes or by biochemical transformation routes known to those skilled in the art. Preferably, the PDO has a purity greater than about 99% as determined by gas chromatographic analysis.

  Although any combination of PDO and dimers or trimers of PDO can be used, it is preferred that the reactants contain about 90% by weight or more of PDO. More preferably, the PDO reactant contains 99 wt% or more of PDO.

  Biologically derived 1,3-propanediol (bioderived PDO) is particularly preferred.

  A biochemical pathway to PDO has been described that utilizes raw materials produced from biological and renewable resources such as corn raw materials. Such PDO is referred to herein as “biologically-derived PDO” or “bio-derived PDO”. For example, strains that can convert glycerol to 1,3-propanediol have been found, for example, in the species Crabsiella, Citrobacter, Clostridium and Lactobacillus. This technique is disclosed in several patents including US Pat. No. 5,633,362, US Pat. No. 5,686,276 and US Pat. No. 5,821,092. . In US Pat. No. 5,821,092, Nagarajan et al. Disclose a method for the biological production of 1,3-propanediol from glycerol, particularly using recombinant organisms. This method introduces E. coli transformed with a heterologous pdudiol dehydratase gene that has specificity for 1,2-propanediol. The converted E. coli grows in the presence of glycerol as a carbon source, and 1,3-propanediol is separated from the growth medium. Since both fungi and yeast can convert glucose (eg, corn sugar) or other carbohydrates to glycerol, the method of the present invention is useful in the production of polyesters, polyethers and other polymers. -Provided a quick, inexpensive and environmentally reliable source of propanediol monomer.

When 1,3-propanediol is used, the 1,3-propanediol can be added in small amounts in addition to the reactant 1,3-propanediol or its dimer and trimer without compromising the efficacy of the process. Preferably, it may also contain no more than about 30% by weight, more preferably no more than about 10% by weight comonomer diol, based on the total weight of the diol. Examples of preferred comonomer diols include ethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol; and 2,2-diethyl-1,3- Propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4 - C ₆ -C ₁₂ diols such as cyclohexane diol and 1,4-cyclohexanedimethanol. A more preferred comonomer diol is ethylene glycol.

  In one embodiment, the method comprises subjecting a post-consumer polyester plastic to 1,3-propanediol (a PDO such as a biological PDO) in the presence of a catalyst in a nitrogen atmosphere at a temperature in the range of about 200 ° C. to about 300 ° C. ) And polyols can be used to convert such plastics. An organic titanate such as Tyzor® TPT can be used as a catalyst for the process.

  In another embodiment, the method comprises the conversion of PET-based post-consumer polyester (waste) to 1,3-propane in the presence of a catalyst in a nitrogen atmosphere at a temperature in the range of about 200 ° C to about 300 ° C. These polyesters can be used to convert by reacting with diols (PDO or biologically derived PDO) and polyols. An organic titanate such as Tyzor® TPT is used as a catalyst for the process. The resulting polymer is a copolyester containing ethoxy repeat units and butoxy repeat units.

Low polymer diol or high molecular diol ("polyol")
“Polyol” means a low polymer diol or a high molecular diol. Low polymer diol generally means a species or combination of comonomer diols having more than 3 of the same monomeric diol and no more than about 20 repeating units. A polymeric diol generally means a chemical species having more than 20 repeating units of the same monomeric diol or a combination in the main chain of a comonomer diol.

  In some embodiments of the methods disclosed herein, the polyester is contacted with at least one diol and at least one polyol in the presence of a catalyst at an elevated temperature to produce a rubber elastic polyether ester. . In general, the diol in the reaction mixture contributes to transesterification due to the hard segment of the resulting rubber elastic polyetherester, and the polyol contributes to transesterification due to the soft segment of the resulting rubber elastic polyetherester.

  Diols including the diols listed above can be converted to polyols in a polycondensation reaction in the presence of a polycondensation catalyst. One or more diols can be used to produce such polyols having comonomer diol-based repeat units. US Pat. No. 6,905,765 describes a condensation catalyst that can be used to produce a polyol. Condensation catalysts include homogeneous catalysts such as Lewis acids, Bronsted acids, superacids and mixtures thereof. Examples include inorganic acids, organic sulfonic acids, heteropolyacids and their metal salts. Sulfonic acid, fluorosulfonic acid, phosphorous acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoro-ethanesulfonic acid, 1, 1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, trifluoromethanesulfonic acid Scandium and zirconium trifluoromethanesulfonate are preferred. It is also possible to use heterogeneous catalysts such as zeolite, fluorinated alumina, acid-treated silica, acid-treated silica alumina, heteropolyacids and zirconia, titania, alumina and / or heteropolyacids supported on silica. The aforementioned homogeneous catalyst is preferred, and sulfuric acid is most preferred.

Diols capable of producing such polyols include monomeric, dimeric, trimer or low polymer C ₂ -C ₂₀ alkane diols, alkoxy C ₂ -C ₂₀ alkane diols, alkeneoxy C ₂ -C ₂₀ alkanes. diols, C ₂ -C ₂₀ alkane diol, phenoxy C ₂ -C ₂₀ alkane diols, alkyl phenoxy C ₂ -C ₂₀ alkanediol, a phenyl C ₂ -C ₂₀ alkane diols, alkyl phenyl C ₂ -C ₂₀ alkane diols and halo C ₂ -C ₂₀ alkane diols.

The additional diol capable of producing such polyols, monomeric straight-chain and branched-chain, dimer, C ₂ -C ₂₀ alkanediol trimeric or oligomeric, such as ethylene glycol, diethylene glycol, triethylene Glycol or tetraethylene glycol, dipropylene glycol, tripropylene glycol or tetrapropylene glycol and dibutylene glycol, tributylene glycol or tetrabutylene glycol, 1,2-propanediol, isopropylene glycol, 1-methylpropylene glycol, 1,3 -Propanediol, n-butane-1,3-diol, 2-methyl-1,3-propanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 2-methyl-1,3 Propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,4-butanediol, triethylene glycol, 1,5-pentane Diol, 1,6-hexanediol, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol, 3,3,4,4,5,5-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5- Octafluoro-1,6-hexanediol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12- Dodecanj Lumpur and diols or polyols and diol chain and polyols than was produced by the reaction products of alkylene oxides, as well as polyethylene glycol 400 to 4000.

  Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbitol are also useful.

  Preferred diols for making such polyols include monomeric, dimeric, trimer or low polymer ethylene glycol, propylene glycol and butylene glycol and isomer forms thereof. A preferred diol is 1,3-propanediol (PDO). A more preferable diol is bio-derived 1,3-propanediol (bio-derived PDO). Preferred polyols are PDO polyols and biological PDO polyols that are low polymers or polymers. Such a polyol is separately called polytrimethylene ether glycol (PO3G).

Table by _{(OCH 2 CH 2 CH 2)} X-O-CO-R 4 -CO- - In a preferred embodiment, when using PO3G to form the soft segment of the resulting polyetherester, soft segments, structural It can be expressed as including the unit.
In the formula, R ⁴ represents a divalent group remaining after removal of the carboxyl functional group from the dicarboxylic acid equivalent. A wide range of molecular weights of PO3G can be used. PO3G preferably has a number average molecular weight (Mn) of at least about 1000, more preferably at least about 1,500, and most preferably at least about 2,000. Mn is preferably less than about 5000, more preferably less than about 4,000, and most preferably less than about 3,500. Thus, x in the above formula is at least about 17, more preferably at least about 25, most preferably at least about 34 and less than about 86, more preferably less than about 67, and most preferably less than about 60. PO3G useful for the present invention is disclosed in US 2002 / 0007043A1 and US 2002 / 0010374A1 and PCT publications WO 01/44348 and International It is described in the publication 01/44150 pamphlet.

  In some embodiments, depending on how much additional polyol or diol is used in the reaction, up to 60% by weight of the soft segment can include a polymeric ether glycol other than PO3G. High selected from the group consisting of polyethylene ether glycol (PEG), polypropylene ether glycol (PPG), polytetramethylene ether glycol (PO4G), polyhexamethylene ether glycol and a copolymer of tetrahydrofuran and 3-alkyltetrahydrofuran (THF / 3MeTHF). Molecular ether glycols are preferred. Other polymeric ether glycols preferably have a number average molecular weight of at least about 1000, more preferably at least about 1,500 and preferably up to about 5,000, more preferably up to about 3,500. A particularly important copolymer is a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran (THF / 3MeTHF). The polyethylene ether glycol used to form the soft segment is preferably up to 55 wt%, more preferably up to 50 wt%, most preferably up to 15 wt% PO3G.

  For example, substituted glycols such as tetrahydrofuran-based polyols are included, and methyl-substituted tetrahydrofuran-based polyols are included.

  In another embodiment, the polyetherester polymer or copolymer is a plastic based on PET by reacting waste with a mixture of 1,3-propanediol and polytrimethylene glycol in the molecular weight range of about 500 to about 5000. Manufactured by polycondensation of waste. By controlling the ratio of 1,3-propanediol and PO3G polymer / oligomer, it is also possible to control the soft segment content of the resulting polyetherester.

Catalyst The method disclosed herein comprises contacting a post-consumer polyester with at least one diol, such as a bio-derived or other 1,3-propanediol, in the presence of a catalyst comprising tin and / or titanium. including. Any tin-containing compound that can be used as an esterification catalyst can be used. In general, the catalyst can be an inorganic tin compound or an organic tin compound. Examples of suitable tin compounds include n-butyl stannous acid, octyl stannous acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, diphenyltin oxide, tri-n-butyltin acetate, tri-n chloride -Butyltin, fluorinated tri-n-butyltin, triethyltin chloride, triethyltin bromide, triethyltin acetate, trimethyltin hydroxide, triphenyltin chloride, triphenyltin bromide, triphenyltin acetate, or their A combination of two or more types can be mentioned. Tin oxide catalysts are preferred. Suitable tin compounds are generally commercially available. For example, n-butyl stannous acid can be obtained from Witco Chemical Corp. (Greenwich, Conn.).

A preferred titanium compound is an organic titanium compound, in particular titanium tetrahydrocarbyl oxide, also called tetraalkyl titanate. Examples of suitable titanium tetrahydrocarbyl oxide compounds include the general formula Ti (OR) ₄ wherein each R represents from 1 to about 30, preferably from 2 to about 18, and most preferably from 2 to 12 carbon atoms per group. Individually selected from the alkyl or aryl groups it contains, and each R can be the same or different. Most preferred is titanium tetrahydrocarbyl oxide where the hydrocarboxyl group contains from 2 to about 12 carbon atoms per group and is a linear or branched alkyl group. This is because such titanium tetrahydrocarbyl oxide is relatively inexpensive, more readily available, and effective in forming a solution. Suitable titanium tetrahydrocarbyl oxides include titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrahexoxide, titanium tetra-2-ethylhexoxide, titanium tetraoctoxide. And combinations of two or more thereof, but are not limited thereto. Titanium tetrahydrocarbyl oxide can be produced, for example, by mixing titanium tetrachloride with an alcohol in the presence of a base such as ammonia to produce titanium tetracarbyl oxide or tetraalkyl titanate. The alcohol can be ethanol, n-propanol, isopropanol, n-butanol or isobutanol. The titanium tetrahydrocarbyl oxide thus produced is recovered by first removing the byproduct ammonium chloride by any means known to those skilled in the art, such as filtration, and then distilling the titanium tetrahydrocarbyl oxide from the reaction mixture. Is possible. The method can be performed at a temperature in the range of about 0 to about 150 ° C. Titanates with longer alkyl groups can also be prepared by transesterification of alcohols with more than 4 carbon atoms per molecule and titanium tetrahydrocarbyl oxides having C ₄ or less R groups.

  Examples of commercially available organic titanium compounds include E.I. I. TYZOR® TPT and TYZOR® TBT (tetraisopropyl titanate and tetra-n-butyl titanate, respectively) available from du Pont de Nemours and Company (Wilmington, Del., USA) It is done.

  When using both tin and titanium, the weight ratio of tin compound to titanium compound can be any ratio as long as it can catalyze the esterification of acid and 1,3-propanediol. is there. The ratio can generally be about 0.01: 1 to about 100: 1, preferably about 0.1: 1 to about 10: 1.

  The catalyst can be prepared by any method known to those skilled in the art. For example, by combining a tin compound or a titanium compound with an acid, 1,3-propanediol or both, the tin compound or the titanium compound is acid or 1 in situ in the esterification medium or in the esterification medium. , 3-propanediol can be combined separately to produce a catalyst.

  Preferably, the catalyst is produced prior to contacting with the esterification medium. Therefore, it is preferable to prepare a premix catalyst comprising a tin compound and a titanium compound, consisting essentially of a tin compound and a titanium compound, or contacting a premix catalyst comprising a tin compound and a titanium compound with an esterification medium. More preferably, the tin catalyst and / or titanium catalyst is mixed in an organic solvent prior to addition to the reaction. Any solvent that can substantially dissolve or disperse the catalyst and does not interfere with the polymerization can be used. For convenience, the organic solvent can be 1,3-propanediol.

  Preferably, the amount of tin used as a catalyst is between about 2 and 400 ppm and the amount of titanium used as a catalyst is between about 2 and 400 ppm. The amount of each element is based on the weight of the reactants in the esterification medium.

  The method controls the ratio of acid repeat units to alkoxy repeat units and soft segments to hard segments in the rubber elastic polyetherester produced by the method by controlling the initial molar ratio of diol, polyol and polyester. Allows control. In a preferred embodiment, the molar ratio is (diol + polyol) to polyester (or the amount of polyester in the post-consumer polyester when other components such as waste are present); from about 100: 1 to about 1: 1. Within range. In a more preferred embodiment, the molar ratio of diol to polyol is from about 100: 1 to about 1: 100. The preferred molar ratio of (diol + polyol) to polyester is in the range of 5: 1 to about 1: 1.

  The transesterification can occur within a preferred temperature range of about 200 ° C to about 300 ° C. If necessary, the temperature can be maintained at a single point throughout the reaction. Alternatively, the temperature can be maintained at the same or different times at more than one point, and the temperature can be changed once or more than once.

  When preparing polyetherester elastomers, it is sometimes desirable to introduce known branching agents to increase melt strength. Such agents are introduced into the reaction mixture prior to transesterification. In such cases, the branching agent is typically used at a concentration of 0.00015 to 0.005 equivalents per 100 grams of polymer. The branching agent can be a polyol having 3-6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups, or a hydroxy acid having a total of 3-6 hydroxyl groups and carboxyl groups It is. Exemplary polyol branching agents include glycerol, sorbitol, pentaerythritol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane, trimethylolpropane and 1,2,6-hexanetriol. Suitable polycarboxylic acid branching agents include hemimellitic acid, trimellitic acid, trimesic acid, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5- Pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid and similar acids. Although the acid can be used as is, it is preferred to use the acid in the form of a lower alkyl ester of the acid.

It is possible to introduce conventional additives into the polyester product by adding them during esterification. Additives include matting agents (eg TiO ₂ , zinc sulfide or zinc oxide), colorants (eg dyes), stabilizers (eg antioxidants, UV stabilizers, heat stabilizers etc.), fillers Flame retardants, pigments, antibacterial agents, antistatic agents, optical brighteners, extenders, processing aids, thickeners and other functional additives.

  The polyesters produced by the methods disclosed herein can be used in all applications where the polyesters are obtained from esterification of diacids or diesters with diols. For example, polyesters produced by this method can be used for fibers, molded articles, extruded parts, laminated parts, in all textile applications such as clothing, textiles, carpets, cords, tire parts, woven materials, non-woven materials, packaging materials, etc. It can be used for engineering applications such as heat insulating materials, insulating materials, automobile parts, external building parts, internal building parts, bottles and containers.

Example 1
Recyclable rubber elastic polyetherester polymer from PET into a 250 ml three-necked flask (for a PDO: PET polymer molar ratio of about 3: 1) (EI du Pont de Nemours & Co. (Wilmington) ), Obtained from 30 g PET-3934 (obtained from EI du Pont de Nemours & Co. (obtained from Wilmington, Del.)) And 31 g bio PDO (obtained from EI du Pont de Nemours). & Co. (obtained from Wilmington, Del.) 38.4 g of poly (trimethylene glycol) with a molecular weight of 1700 Da (for an estimated polyol soft segment content of about 60% in the final polymer) was charged. Tyzor® TPT (36 mg) was added to the polymerization mixture as a catalyst. The temperature of the reaction mixture in the flask was gradually raised to 240 ° C. while the reaction mixture was placed in a nitrogen environment. The temperature was held at 240 ° C. for about 1 hour. The temperature was further raised to 250 ° C. and held at 250 ° C. for 2 hours under a vacuum of 0.2 mm (2.66 × 10 ⁻⁵ MPa). At the end of the reaction, the flask was cooled and the polymer was collected.

  The resulting polymer had a melting point of 190.4 ° C. and an IV of 0.92 dL / g. The PET content by NMR analysis was 1.5% by weight.

Example 2
Resiliently recycled rubber elastic polyetherester polymer from a mixture of PET and PBT In a 250 ml three-necked flask (due to a 3: 1 PDO: (PET + PBT) polymer molar ratio) 16 g PET 3934, (E.I. Du Pont de Nemours & Co. (obtained from Wilmington, Del.) 16 g PBT, 35 g bio-PDO and MW500 Da 32 g poly (trimethylene glycol) (50 wt% estimated polyol soft segment in the final polymer) For content). Tyzor® TPT (36 mg) was added to the polymerization mixture as a catalyst. The temperature of the reaction mixture in the flask was gradually raised to 230 ° C. while being placed in a nitrogen environment. The temperature was held at 230 ° C. for 1 hour. The temperature was further raised to 250 ° C. and held at 250 ° C. for 2 hours under a vacuum of 0.2 mm (2.66 × 10 ⁻⁵ MPa). At the end of the reaction, the flask was cooled and the polymer was collected.

  The resulting polymer had a melting point of 120 ° C. and an IV of 0.6 dL / g. According to NMR analysis, the PET content was 8.6% by weight and the PBT content was 4.9% by weight.

Claims (21)

  A process for producing a polyetherester from a polyester comprising contacting the polyester with at least one diol and at least one polyol in the presence of a catalyst at a temperature in the range of about room temperature to about 300 ° C.   The method of claim 1, wherein the polyester is a post-consumer polyester.   The method of claim 2, wherein the post-consumer polyester comprises a beverage bottle made from the polyester.   The method of claim 3, wherein the beverage bottle is made from polyester having a recycle code 1.   The post-consumer polyester is poly (ethylene terephthalate), poly (trimethylene terephthalate), poly (butylene terephthalate), poly (pentylene terephthalate), poly (hexylene terephthalate), poly (heptylene terephthalate), polyether ester The method of claim 2, comprising one or more polymer species selected from the group consisting of: a mixture thereof; a blend thereof; a blend thereof; and a copolymer thereof. The diol, monomer, C ₂ -C ₂₀ alkane diol dimers or trimers, alkoxy C ₂ -C ₂₀ alkanediol, alkenoxy C ₂ -C ₂₀ alkane diols, C ₂ -C ₂₀ alkene diol , phenoxy C ₂ -C ₂₀ alkane diols, alkyl phenoxy C ₂ -C ₂₀ alkanediol, a phenyl C ₂ -C ₂₀ alkane diols, alkyl phenyl C ₂ -C ₂₀ alkanediol, halo C ₂ -C ₂₀ alkane diols and their It is selected from the group consisting of chemical mixture, wherein the polyol is a monomer, C ₂ -C ₂₀ alkane diol dimers or trimers, polyalkylene diol, alkoxy alkane diols, alkenoxy alkanediols, alkenediols, glycol , Polyether glycol, phenoxyalkanediol, al Le phenoxide sialic Kanji ol, phenyl alkane diols, alkyl phenyl alkane diol is selected from the group consisting of polyols resulting from halo alkanediols and mixtures thereof The method of claim 1.   The diol is monomer, dimer or trimer ethylene glycol, 1,3-propanediol, n-butane-1,3-diol, 2-methyl-1,3-propanediol, neopentyl glycol 7. The method of claim 6, selected from the group consisting of (2,2-dimethyl-1,3-propanediol), 1,4-butanediol, triethylene glycol, isomers thereof and mixtures thereof.   The method according to claim 7, wherein the 1,3-propanediol is derived from a living organism.   A member of the group wherein the polyol comprises ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol and mixtures thereof; The process according to claim 1, selected from polyols resulting from the polymerization of   The method of claim 1, wherein the catalyst comprises tin or titanium.   The method of claim 10, wherein the catalyst is an organic titanate.   A polyether ester prepared by a process comprising contacting a polyester with at least one diol and at least one polyol at a temperature in the range of about room temperature to about 300 ° C. in the presence of a catalyst.   The polyetherester according to claim 12, wherein the polyester is a post-consumer polyester.   The polyetherester of claim 12, wherein the post-consumer polyester comprises a beverage bottle made from polyester.   13. The polyetherester of claim 12, wherein the beverage bottle is made from a polyester having a recycle code 1.   The polyetherester of claim 12, wherein the catalyst comprises tin or titanium.   The at least one diol comprises a biologically derived 1,3-propanediol, and the at least one polyol is selected from poly (trimethylene glycol), poly (tetramethylene glycol) and polypropylene glycol, the polyol from room temperature The polyetherester of claim 12, having a molecular weight of up to about 5000 Da at a temperature in the range of about 300 ° C.   The polyetherester according to claim 12, wherein the diol is a biologically-derived 1,3-propanediol.   13. A final product made from the polyetherester of claim 12, selected from the group consisting of monofilaments, molded articles and packaging materials.   The polyetherester of claim 12, having an intrinsic viscosity in the range of about 0.2 to about 2.0.   The polyetherester of claim 12, having a melting temperature in the range of 800C to 2400C.