CN101568568A - Process for producing polyester from post-consumer polyester - Google Patents

Abstract

The present invention relates to processes for manufacturing polyesters. The processes can be used for manufacturing polyesters from post-consumer polyesters. The processes include contacting a post-consumer polyester with at least one diol, at elevated temperature in presence of a catalyst, effecting a transesterification reaction. Biologically-derived diols can be used.

Description

Process for producing polyester from post-consumer polyester

field of invention

The present invention relates to a process for the manufacture of polyesters. The method is particularly useful for making polyesters from post-consumer polyesters that have properties and functions substantially similar to virgin polyesters.

Background of the invention

Polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate are used in numerous application markets, including fibers, films and engineered components. Due to the use of these polyesters which must be discarded, an enormous amount of waste is generated every year. Undoubtedly, discarding causes environmental problems. It is desirable to reuse these discarded post-consumer polyesters.

A conventional method of recycling polyester involves the isolation and purification of dimethyl terephthalate (DMT) or terephthalic acid (TPA) from the polyester and subsequent polycondensation of DMT or TPA with ethylene glycol. Recycling thus becomes energy intensive and thus an extremely expensive method.

New and/or improved methods of using waste polyester are desired.

Summary of the invention

One aspect of the invention is a method of making polyester from post-consumer polyester, the method comprising treating at least one diol with at least one diol (e.g. 1,3-propanediol) in contact with post-consumer polyester. In some preferred embodiments, the catalyst comprises tin or titanium.

In some preferred embodiments, the post-consumer polyester is post-industrial polyester.

Another aspect of the invention is a polyester prepared by a process comprising contacting a post-consumer polyester with at least one diol in the presence of a polymerization catalyst at a temperature ranging from about room temperature to about 300°C.

Detailed description of the invention

In the methods disclosed herein, common separation and purification steps used in conventional recovery methods are eliminated, thereby reducing the cost of polymer manufacture. In some embodiments, polymers produced by this route can provide properties and functionality similar to novel polyesters with an overall reduction in manufacturing cost and energy use, reduced emissions of greenhouse-causing gases, and thus a reduced environmental footprint.

Unless otherwise defined, 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 conflict, the definitions contained in this specification will control.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated.

When an amount, concentration or other value or parameter is given as a range, preferred range or a list of preferred upper and preferred lower values, it is to be understood as specifically disclosing any range upper or preferred value and any range lower or preferred value All ranges constituted by any pair of , whether or not the ranges are disclosed individually. Where a numerical range is given herein, that range is intended to include its endpoints, and all integers and fractions lying within the range, unless otherwise indicated. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

"Room temperature" means approximately ambient temperature; eg, about 20 to 25°C.

When the term "about" is used to describe a value or an endpoint of a range, the disclosure should be understood to include the specific value or endpoint referred to.

The quantifier "a" or "an" is used to describe an element or component of the invention. This is done merely 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 not intended to be limiting unless specifically stated otherwise.

In general, the present invention provides a method of making polyesters, especially from post-consumer polyesters, comprising making post-consumer The polyester is contacted with at least one diol.

In one embodiment, the polyester is produced from the post-consumer polyester by contacting the post-consumer polyester with at least one diol at an elevated temperature in the presence of a catalyst for transesterification. In a particular embodiment, the process provides polytrimethylene terephthalate from post-consumer polyesters comprising polyethylene terephthalate (PET) by transesterification of PET with 1,3-propanediol ester polymer. In some preferred embodiments, the 1,3-propanediol is biologically derived 1,3-propanediol.

In some embodiments, the post-consumer polyester comprises a polymer species selected from the group consisting of: polyethylene terephthalate (2GT or PET or PETE), polytrimethylene terephthalate (PTT), polyethylene terephthalate Butylene glycol dicarboxylate (PBT or 4GT), polypentylene terephthalate (5GT), polyhexamethylene terephthalate (6GT), polyheptylene terephthalate (7GT) , polyether esters, their mixtures, their blends, and their copolymers. Polyester polymer classes may include PEN, 3GN, and other naphthalene-containing copolymers.

In some embodiments, the diol is selected from the group consisting of C2-C20 alkanediols, polyalkylene glycols, alkoxyalkanediols, alkenoxyalkanediols, alkylene glycols, ethylene glycols, Alcohols, polyether diols, phenoxyalkanediols, alkylphenoxyalkanediols, phenylalkanediols, alkylphenylalkanediols and halogenated alkanediols. In a particular embodiment, the diol is selected from 1,3-propanediol, 1,3-n-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol (2,2-dimethyl-1 , 3-propanediol), 1,4-butanediol, triethylene glycol, and mixtures thereof.

In a preferred embodiment, the diol is 1,3-propanediol. In some preferred embodiments, the diol is biologically derived. In a preferred embodiment, the post-consumer polyester is derived from a beverage bottle, such as a soda or water bottle, comprising polyethylene terephthalate. In some preferred embodiments, the molar ratio of 1,3-propanediol to polyester is in the range of about 5:1 to about 1:1, and the catalyst used is an organotitanate. As used herein, "derived from beverage bottles" means that beverage bottles are processed, for example, by cutting or grinding, in order to use them in a method of making polyester, and that the thus processed bottles comprising post-consumer polyester are used in accordance with the methods of the present invention to make polyester.

In some embodiments where biologically derived diols are used, the methods disclosed herein preferably utilize less energy than is typically necessary to make polyesters from esterification of dibasic acids or diesters with diols using polycondensation catalysts. energy.

In some embodiments, the method comprises contacting post-consumer polyester with at least one diol in the presence of a catalyst at a temperature in the range of about 200°C to about 300°C, wherein the at least one diol is bio-derived 1,3-propanediol. In preferred embodiments, the catalyst comprises tin or titanium.

In some embodiments, the method comprises contacting a post-consumer polyester comprising polyethylene terephthalate with a diol at a temperature in the range of about 200°C to about 300°C in the presence of a polymerization catalyst, wherein the at least one diol is 1,3-propanediol, wherein the polyester is at least 80% by weight of 1,3-propanediol and PET is at most 20% by weight. For some applications, polyesters made according to the methods disclosed herein have an intrinsic viscosity in the range of about 0.2 to about 2.0.

Polyesters made according to the methods disclosed herein can be used in articles and finished products such as clothing fibers, carpet fibers, upholstery, molded products, monofilaments, and packaging products.

By "post-consumer polyester" is meant polyester that is produced after consumer use or industrial use of polyester. Therefore, if a "post-consumer polyester" is used in industrial applications rather than in household or other applications, it can be called "post-industrial polyester". Use post-consumer polyester as raw material.

聚醚酯弹性体聚合物。可用于本文所公开的方法的优选消费后聚酯包含由回收代码1标识的聚对苯二甲酸乙二醇酯。然而，消费后聚酯也可以采取与一种或多种其它聚合材料的共混物的形式。可用于本文所公开的方法的消费后聚酯中存在的聚酯原料可包含例如基于聚酯的热塑性弹性体。Exemplary post-consumer polyesters include polyethylene terephthalate (2GT or PET or PETE), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT or 4GT), Polypentylene terephthalate (5GT), polyhexylene terephthalate (6GT), polyheptylene terephthalate (7GT) and polyether esters such as

Polyetherester elastomeric polymer. Preferred post-consumer polyesters useful in the methods disclosed herein comprise polyethylene terephthalate, identified by recycling code 1. However, the post consumer polyester may also take the form of a blend with one or more other polymeric materials. The polyester raw material present in the post-consumer polyester useful in the methods disclosed herein may comprise, for example, a polyester-based thermoplastic elastomer.

For example, "waste polyester plastic" can be used. Suitable waste polyester plastics that can be used in the methods disclosed herein include recycled products containing polyester components such as bottles, cups, containers, packaging, carpet, textiles, fiber waste, films, engineering components, molded and extruded Products, laminates, coatings, adhesives, etc. Preferred post consumer polyesters are derived from beverage bottles, such as soda or water bottles.

As used herein, "polyester" includes polymers and oligomer species resulting from the condensation reaction (polymerization or oligomerization) of dihydroxy compounds with polyvalent acids. Suitable polybasic acids are dibasic acids. Preferred are organic dibasic acids having the formula HOOCACOOH, where A is an alkylene, arylene, alkenylene, or a combination of two or more thereof. Each A has from about 2 to about 30, preferably from about 3 to about 25, more preferably from about 4 to about 20, and most preferably from about 4 to 15 carbon atoms per group. Examples of suitable organic acids include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, 4,4'-diphenylene dicarboxylic acid, succinic acid, adipic acid, glutaric acid, biphenyl dicarboxylic acid, Formic acid, naphthalene dicarboxylic acid, bis(p-carbonylphenyl)methane, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-sulfonyl dicarboxylic acid Benzoic acid, p-(hydroxyethoxy)benzoic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, and their derivatives, such as those of these dicarboxylic acids Dimethyl, diethyl or dipropyl esters, and combinations of two or more thereof.

Aliphatic or aromatic dibasic acids or diesters may be aliphatic (including cycloaliphatic) or aromatic, or combinations thereof, and are preferably selected from aromatic dicarboxylic acids and esters (preferably short chain alkyl esters, and more preferably methyl esters), and combinations thereof. Preferred are aliphatic or aromatic dibasic acids, and most preferred are aromatic dicarboxylic acids and combinations thereof. Preferably, the aliphatic or aromatic dibasic acid is an aromatic dibasic acid selected from terephthalic acid, isophthalic acid, wherein terephthalic acid and isophthalic acid and mixtures thereof are preferred, wherein terephthalic acid Formic acid is most preferred.

Post consumer polyester feedstock useful in the methods disclosed herein can be made from additional aromatic dicarboxylic acids or diesters as described in US6562457, US6599625 and US7144972.

As noted above, post-consumer polyesters useful in the methods disclosed herein include waste materials that also contain thermoplastic elastomers (TPEs), such as segmented copolyesters. Thermoplastic elastomers are a class of polymers that combine the properties of the other two classes of polymers, ie, thermoplastics that reform upon heating, and rubber-like polymer elastomers. One form of TPE is a block copolymer, usually comprising some blocks with polymeric properties generally similar to those of thermoplastics and some blocks with properties generally similar to those of elastomers. Those blocks that behave like thermoplastics are often referred to as "hard" segments, while those that behave like elastomers are often referred to as "soft" segments.

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

In the process of the present invention, post-consumer polyester is treated with one or more diols to effect transesterification. Suitable diols include C2-C20 alkanediol, alkoxy C2-C20 alkanediol, alkenoxy C2-C20 alkanediol, C2-C20 alkylene glycol, phenoxy C2- C20 alkanediol, alkylphenoxy C2-C20 alkanediol, phenyl C2-C20 alkanediol, alkylphenyl C2-C20 alkanediol, and halogenated C2-C20 alkanediol alcohol. Preferred diols include straight or branched C2-C20 alkanediols such as ethylene glycol, diethylene glycol, di, tri or tetraethylene glycol, di, tri or tetrapropylene glycol and di, tri or tetra Butanediol, 1,2-propanediol, isopropylene glycol, 1-methylpropanediol, 1,3-propanediol, 1,3-n-butanediol, 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 base)-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. Also preferred are cycloaliphatic diols, such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbide. An especially preferred diol is 1,3-propanediol (PDO). Even more particularly preferred is biologically derived ("bioderived") 1,3-propanediol.

By 1,3-propanediol (PDO) is meant a reactant comprising at least one of 1,3-propanediol, 1,3-propanediol dimer and 1,3-propanediol trimer or a mixture thereof. The 1,3-propanediol reactant used in the methods of the invention can be obtained by any of a variety of chemical routes or by biochemical transformation routes.优选的途径描述于US5015789、US5276201、US5284979、US5334778、US5364984、US5364987、US5633362、US5686276、US5821092、US5962745、US6140543、US6232511、US6235948、US6277289、US6284930、US6297408、US6331264、US6342646、US2004/0225161A1、US2004/0260125A1、US2005 /0069997A1. Preferably, PDO used as a reactant or as a component of a reactant will have a purity of greater than about 99% by weight, as determined by gas chromatographic analysis.

Although any of PDO and dimers or trimers of PDO may be used as the diol in the process, it is preferred that the reactants contain about 90% by weight or more of PDO. More preferably, the reactants will contain 99% by weight or more of PDO.

A more preferred PDO is biologically derived PDO. Biologically derived PDO is PDO synthesized via biochemical pathways. The biochemical pathway of PDO has been described using feedstocks produced from biological and renewable resources such as corn feedstocks. For example, bacterial strains capable of converting glycerol to 1,3-propanediol are found in, for example, the species Klebsiella, Citrobacter, Clostridium and Lactobacillus middle. This technique is disclosed in several patents, including US5633362, US5686276 and US5821092, all of which are incorporated herein by reference. In US5821092 to Nagarajan et al, inter alia a method for the bioproduction of 1,3-propanediol from glycerol using recombinant organisms is disclosed. The method introduces E. coli transformed with a heterologous pdu diol dehydratase gene specific for 1,2-propanediol. Transformed E. coli were grown in the presence of glycerol as a carbon source, and 1,3-propanediol was isolated from the growth medium. Since both bacteria and yeast are capable of converting glucose (such as corn sugar) or other carbohydrates into glycerol, the method of the present invention provides a fast, cheap and environmentally friendly method for the production of polyesters, polyethers and other polymers. , 3-propanediol monomer source.

When 1,3-propanediol is the diol used in the process of the present invention, it may also contain small amounts, preferably no more than about 30%, more preferably no more than about 10%, by weight of starting materials, or other than reactant 1 , comonomer diols other than 3-propanediol, or dimers or trimers thereof, without reducing the efficacy of the process. Examples of preferred comonomer diols include ethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and C6-C12 diols such as 2,2 -Diethyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol alcohol, 1,12-dodecanediol, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. A more preferred comonomer diol is ethylene glycol.

TPT钛酸四异丙酯可用作该方法的催化剂。所得共聚物包含相对较高部分(例如超过50％)的聚对苯二甲酸丙二醇酯聚合物和较小部分基于2GT的重复单元。在一些实施方案中，聚对苯二甲酸丙二醇酯的量为70％或更高，甚至95％或更高。In a preferred embodiment, the process of the present invention is carried out by reacting such plastics with 1,3-propanediol at a temperature in the range of about 200°C to about 300°C under a nitrogen atmosphere in the presence of a catalyst to convert post-consumer polyester plastics. Organic titanates such as

Tetraisopropyl titanate TPT can be used as a catalyst for this method. The resulting copolymer comprises a relatively high fraction (eg, over 50%) of polytrimethylene terephthalate polymer and a smaller fraction of 2GT-based repeat units. In some embodiments, the amount of polytrimethylene terephthalate is 70% or higher, even 95% or higher.

TPT钛酸四异丙酯可用作催化剂。所得聚合物是包含乙氧基和丁氧基重复单元的共聚酯。如本文所用，术语“至少一种二醇”是指在一些实施方案中使用至少两种不同的二醇。In another preferred embodiment, the method of the present invention reacts such polyesters with 1,3- Propylene glycol is reacted to convert PET-based post-consumer polyester (waste). Organic titanates such as

TPT tetraisopropyl titanate can be used as a catalyst. The resulting polymer is a copolyester comprising ethoxy and butoxy repeat units. As used herein, the term "at least one diol" means that in some embodiments at least two different diols are used.

Catalysts are used to carry out the process of the invention. In a preferred embodiment, the catalyst comprises tin and/or titanium. Any tin-containing compound capable of acting as an esterification catalyst can be used. Generally, the catalyst can be an inorganic tin compound or an organic tin compound. Examples of suitable tin compounds include, but are not limited to, n-butylstannoic acid, octylstannoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, diphenyltin oxide, tri-n-butyltin acetate, tri-n-butyl Trimethyltin chloride, tri-n-butyltin fluoride, triethyltin chloride, triethyltin bromide, triethyltin acetate, trimethyltin hydroxide, triphenyltin chloride, triphenyl Tin bromide, tin triphenylacetate, or a combination of two or more of them. Tin oxide catalysts are preferred. These tin compounds are generally commercially available. For example, n-butylstannoic acid is available from Witco Chemical Corp., Greenwich, Conn.

Preferred titanium compounds are organotitanium compounds. Titanium dioxide can also be used. Tetraalkoxy titanates, also referred to herein as tetraalkyl titanates, are currently the most preferred organotitanium compounds because of their availability and effectiveness. Examples of suitable tetraalkoxy titanate compounds include those represented by the general formula Ti(OR)4, wherein each R is independently selected from the group consisting of 1 to about 30, preferably 2 to about 18, and An alkyl or aryl group of 2 to 12 carbon atoms is most preferred and each R may be the same or different. Tetraalkoxy titanates in which the hydrocarboxyl groups contain from 2 to about 12 carbon atoms per linear or branched alkyl group are most preferred because they are relatively inexpensive, more readily available, and efficiently form solutions. Suitable tetraalkoxytitanates include, but are not limited to, tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrahexyloxytitanium, tetra-2-ethyl Hexyloxytitanium, tetraoctyloxytitanium, and combinations of two or more thereof.

TPT钛酸四异丙酯和

TBT钛酸四正丁酯，得自E.I.du Pont de Nemours and Company，Wilmington，Del.，U.S.A.。Suitable tetraalkoxy titanates can be produced, for example, by mixing titanium tetrachloride and an alcohol in the presence of a base such as ammonia to form tetraalkoxy titanates or tetraalkyl titanates. The alcohol may be ethanol, n-propanol, isopropanol, n-butanol or isobutanol. The tetraalkoxytitanate so produced may be recovered by first removing the by-product ammonium chloride by any means known to those skilled in the art, such as filtration followed by distillation of the tetraalkoxytitanate from the reaction mixture. The process can be carried out at a temperature in the range of about 0 to about 150°C. Titanates with longer alkyl groups can also be produced by transesterification of those with R groups up to C4 with alcohols having more than 4 carbon atoms per molecule. Examples of commercially available organotitanium compounds include, but are not limited to

TPT tetraisopropyl titanate and

TBT tetra-n-butyl titanate available from EI du Pont de Nemours and Company, Wilmington, Del., USA.

If a catalyst comprising both tin and titanium is used, the weight ratio of tin compound to titanium compound can be any ratio as long as the ratio can catalyze the esterification reaction of the acid with 1,3-propanediol. Generally, the ratio may be from about 0.01:1 to about 100:1, and preferably from about 0.1:1 to about 10:1.

Catalysts can be produced by any method known to those skilled in the art. For example, the catalyst can be produced by combining a tin compound or a titanium compound with an acid or 1,3-propanediol, respectively, in an esterification reaction medium. The catalyst can also be produced in situ in the esterification reaction medium by combining tin or titanium compounds with acid, 1,3-propanediol, or both. Preferably, it is produced by combining tin or titanium compounds prior to contacting with the esterification reaction medium. In other words, the premixed catalyst preferably comprises, consists essentially of, or consists of, the tin compound and the titanium compound produced prior to contacting the esterification reaction medium. More preferably, the tin and titanium catalysts are mixed in an organic solvent prior to use in the process. Any solvent that can substantially dissolve or disperse the catalyst and does not interfere with the polymerization reaction can be used. For convenience, the organic solvent may be 1,3-propanediol. Preferably, tin is present in an amount between about 2 and 400 ppm and titanium is present in an amount between about 2 and 400 ppm, each substantially based on the weight of reactants in the esterification reaction medium.

The process of the present invention also permits control of the ratio of acid repeat units to alkoxy repeat units by controlling the initial molar ratio of alkanediol to polyester in the post consumer polyester. In a preferred embodiment, the molar ratio of alkane diol to polyester in post consumer polyester is in the range of about 100:1 to about 1:1. A more preferred molar ratio of alkane diol to polyester in post consumer polyester is in the range of 5:1 to about 1:1.

The transesterification reaction of the process may take place at a preferred temperature range of about 200°C to about 300°C. In one embodiment, the temperature can be maintained at one point throughout the reaction. In another embodiment, the temperature is maintained at more than one temperature point for different or the same period of time one or more than one time.

Conventional additives can be incorporated into the polyester product of this process by addition during the esterification reaction. Suitable additives include matting agents (such as TiO2, zinc sulfide or zinc oxide), colorants (such as dyes), stabilizers (such as antioxidants, anti-UV agents, heat stabilizers, etc.), fillers, flame retardants, pigments , antimicrobial agents, antistatic agents, fluorescent whitening agents, fillers, processing aids, tackifiers, and other functional additives.

The polyesters made by the process of the invention are generally useful in any application in which polyesters are obtained from the esterification of dibasic acids or diesters with diols. For example, polyester can be used to make fibers for all fiber applications such as clothing, fabrics, carpets, ropes, tire components, woven materials, nonwoven materials, packaging materials, engineering applications such as molded parts, extruded parts, Laminated parts, thermal insulation, electrical insulation, automotive parts, exterior and interior, bottles, beverage bottles and other containers. Polyesters can also be used to make films, including injection molded articles, injection stretch blow molded articles, and other shaped articles. For example, polyesters can be used to make continuous fibers (e.g., those used in textile end uses such as fabrics for clothing, and in carpet fibers, including bulked continuous filament (BCF) fibers) and staple fibers ( Such as those used in textile end uses, including fabrics used in clothing, carpet fibers, upholstery fibers, and automotive fiber end uses.)

Example

聚合物 Example 1 - Preparation of Polytrimethylene Terephthalate from PET

polymer

TPT钛酸四异丙酯(36mg)作为催化剂。In a 250mL three-necked flask, 60g PET-3934 (obtained from EIdu Pontde Nemours & Co., Wilmington, DE) and 38g biologically derived PDO (obtained from EIdu Pont de Nemours & Co., Wilmington, DE) were charged into a 250mL three-necked flask, and the PDO and The molar ratio of PET polymer was 1.6:1. Add to the polymerization reaction mixture

TPT tetraisopropyl titanate (36 mg) was used as catalyst.

The reaction mixture was placed under a nitrogen atmosphere and the temperature was gradually increased to 230°C. The temperature was maintained at 230°C for about 1 hour. The temperature was further raised to 250° C. and kept at 250° C. for 1.5 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 209°C and an intrinsic viscosity (IV) of 0.85 dL/g. The IV of a polymer is the intrinsic viscosity of the polymer and is defined as the limiting value of the reduced or intrinsic viscosity of the polymer in infinitely diluted solution. As detected by NMR, the weight ratio of polypropylene terephthalate to PET was 85:15.

聚合物 Example 2 - Preparation of Polytrimethylene Terephthalate from PET

polymer

A 250 mL three-neck flask was charged with 60 g of PET-3934 and 71 g of bio-derived PDO to give a molar ratio of PDO to PET polymer of about 3:1. Add to the polymerization reaction mixture TPT tetraisopropyl titanate (36 mg) was used as catalyst. The reaction mixture was placed under a nitrogen atmosphere and the temperature was gradually increased to 220°C. The temperature was maintained at 230°C for about 1 hour. The temperature was further raised to 250° C. and kept at 250° C. for 1.5 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 220.5°C and an IV of 0.81 dL/g. As detected by NMR, the weight ratio of polypropylene terephthalate to PET was 93:7.

Example 3 - Prepared from PBT Copolymer

TPT钛酸四异丙酯(36mg)作为催化剂。使反应混合物处于氮气环境下，将温度逐渐升高至220℃。将温度保持在220℃约1小时。A 250 mL three-necked flask was charged with 65 g of PBT (obtained from EI du Pont de Nemours & Co., Wilmington, DE) and 76 g of bio-derived PDO (making the molar ratio of PDO to PBT polymer approximately 3:1). Add to the polymerization reaction mixture

TPT tetraisopropyl titanate (36 mg) was used as catalyst. The reaction mixture was placed under a nitrogen atmosphere and the temperature was gradually increased to 220°C. The temperature was maintained at 220°C for about 1 hour.

The temperature was further raised to 250°C and kept at 250°C for 1 hour 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 195°C and an IV of 0.88 dL/g. As detected by NMR, the weight ratio of polypropylene terephthalate to PBT was 72:28.

聚合物 Example 4 - Manufacture of Polytrimethylene Terephthalate from PET

polymer

TPT钛酸四异丙酯(17g)作为催化剂。使反应混合物处于氮气环境下，将温度逐渐升高至230℃。将温度保持在230℃约1小时。进一步将温度升高至250℃，并且在0.2mm(2.66X10-5MPa)的真空下在250℃保持4小时。在反应结束时，将聚合物粒化。A 25 gallon autoclave was charged with 100 lbs of PET-3934 and 80 lbs of bio-derived PDO for a molar ratio of PDO to PET polymer of approximately 2:1. Add to the polymerization reaction mixture

TPT tetraisopropyl titanate (17 g) was used as catalyst. The reaction mixture was placed under a nitrogen atmosphere and the temperature was gradually increased to 230°C. The temperature was maintained at 230°C for about 1 hour. The temperature was further raised to 250° C. and maintained at 250° C. for 4 hours under a vacuum of 0.2 mm (2.66×10 −5 MPa). At the end of the reaction, the polymer was pelletized.

The resulting polymer had a melting point of 214.8°C and an IV of 0.76 dL/g. As detected by NMR, the weight ratio of polypropylene terephthalate to PET is 90:10.

聚合物 Example 5 - Manufacture of Polytrimethylene Terephthalate from PET

polymer

TPT钛酸四异丙酯(18g)作为催化剂。使反应混合物处于氮气环境下，将温度逐渐升高至230℃。将温度保持在230℃约1小时。进一步将温度升高至250℃，并且在0.2mm(2.66X10-5MPa)的真空下在250℃保持4.5小时。在反应结束时，将聚合物粒化。A 25 gallon autoclave was charged with 100 lbs of PET-3934 and 118 lbs of bio-derived PDO for a molar ratio of PDO to PET polymer of about 3:1. Add to the polymerization reaction mixture

TPT tetraisopropyl titanate (18 g) was used as catalyst. The reaction mixture was placed under a nitrogen atmosphere and the temperature was gradually increased to 230°C. The temperature was maintained at 230°C for about 1 hour. The temperature was further raised to 250° C. and maintained at 250° C. for 4.5 hours under a vacuum of 0.2 mm (2.66×10 −5 MPa). At the end of the reaction, the polymer was pelletized.

The resulting polymer had a melting point of 219°C and an IV of 0.82 dL/g. As detected by NMR, the weight ratio of polypropylene terephthalate to PET is 95:5.

Claims (21)

1. method that is used for being made by post-consumer polyester polyester, described method are included under the temperature of about room temperature to about 300 ℃ of scopes, in the presence of polymerizing catalyst, described post-consumer polyester are contacted with at least a glycol.

2. the process of claim 1 wherein that described catalyzer is selected from tin catalyst, antimony catalyst, germanium catalyst and titanium catalyst.

3. the process of claim 1 wherein that described catalyzer is selected from tin catalyst and titanium catalyst.

4. the process of claim 1 wherein that described post-consumer polyester is derived from the polyester article of being made by the polyester with recovery code 1.

5. the process of claim 1 wherein that described post-consumer polyester comprises is selected from following type of polymer: poly-to ethylene glycol dibenzoate, poly-to propylene glycol dibenzoate, poly-to dibenzoic acid butanediol ester, poly-to dibenzoic acid pentadiol ester, poly-to dibenzoic acid hexylene glycol ester, poly-to dibenzoic acid heptanediol ester, polyether ester, their mixture, their blend and their multipolymer.

6. the process of claim 1 wherein that described at least a glycol is selected from C2-C20 alkanediol, polyalkylene glycol, alkoxyl group alkane glycol, alkenyloxy alkanediol, aklylene glycol, glycols, polyether glycol, phenoxy group alkanediol, alkyl phenoxy alkanediol, phenyl alkanediol, alkyl phenyl alkanediol and halogenated alkane glycol.

7. the method for claim 6, wherein said at least a glycol is selected from 1, ammediol, 1, the positive butyleneglycol of 3-, 2-methyl isophthalic acid, ammediol, neopentyl glycol (2), 1,4-butyleneglycol, triglycol and their mixture.

8. the process of claim 1 wherein describedly 1, ammediol is biologically-derived.

9. the process of claim 1 wherein that described polyester comprises polyethylene terephthalate.

10. the process of claim 1 wherein the mol ratio of polyester in described at least a glycol and the described post-consumer polyester at about 100: 1 to about 1: 1 scope.

11. the method for claim 10, the mol ratio of wherein said glycol and described polyester at about 5: 1 to about 1: 1 scope.

12. the method for claim 10, wherein said catalyzer is an organic titanate.

13. method that is used for making polyester by post-consumer polyester, described method is included under about 160 ℃ of temperature to about 300 ℃ of scopes, in the presence of the catalyzer that comprises tin or titanium, described post-consumer polyester is contacted with at least a glycol, and wherein said at least a glycol is biologically-derived glycol.

14. polyester by the preparation of the method for claim 1.

15. by the polyester of the method for claim 14 preparation, wherein said polyester is at least 80 weight %

Poly-to propylene glycol dibenzoate, and PET is maximum 20 weight %.

16. the finished product of making by the polyester of claim 14.

17. comprise the fiber of the polyester of claim 14.

18. comprise the moulded product of the polyester of claim 14.

19. comprise the wrapped product of the polyester of claim 14.

20. the polyester of claim 14, described polyester have about 0.2 to about 2.0 limiting viscosity.

21. the process of claim 1 wherein that described catalyzer is a titanium dioxide.