CN101395211A - Polytrimethylene terephthalate (PTT) derived from polyethylene terephthalate (PET) and containing PET residues - Google Patents

Abstract

A composition comprising a polytrimethylene terephthalate random copolymer (1) derived from the group consisting of polyethylene terephthalate and polyethylene terephthalate The polyethylene terephthalate component of the alcohol ester copolymer, and (2) comprising at least one residue derived from the polyethylene terephthalate component. Methods of making such copolymers and articles made from such copolymers.

Description

Polytrimethylene terephthalate (PTT) derived from polyethylene terephthalate (PET) and containing PET residues

Cross References to Related Applications

This application claims U.S. Provisional Application Nos. 60/820447 (filed July 26, 2006), No. 60/763093 (filed January 27, 2006), No. 60/777901 (filed March 1, 2006) The entire content of the above provisional application is hereby incorporated by reference.

Background of the invention

Polyethylene terephthalate (also known as "PET") is a polyester of terephthalic acid and ethylene glycol, and can be made from dimethyl terephthalate and ethylene glycol, or terephthalate It can be obtained by polycondensation of formic acid and ethylene glycol or ethylene oxide. PET is a thermoplastic material that can exist in both amorphous (transparent) and semi-crystalline (opaque and white) forms. In general, it is chemically resistant to mineral oils, solvents and acids, but not to alkalis. Semi-crystalline PET has good strength, ductility, rigidity and hardness. Amorphous PET has better ductility, but less rigidity and hardness. PET is used to make bottles for soft drinks, fibers for various uses and other household and consumer goods.

Unfortunately, despite recycling efforts, billions of pounds of PET end up in landfills or incinerated as solid waste worldwide each year. The large volumes of PET that are dumped into landfills create significant waste, while the incineration of PET destroys this material made from non-renewable hydrocarbon resources that should be used more efficiently.

Polytrimethylene terephthalate (also referred to herein as "PTT") is known as an engineering thermoplastic useful in injection molding applications, as described in US Patent No. 5,326,806. Generally, PTT is prepared by a multi-step reaction (esterification/polycondensation) of a molar excess of 1,3-propanediol with terephthalic acid at high Time for 1,3-propylene glycol terephthalate. Polymerization conditions are selected so as to produce a molten polyester having a target intrinsic viscosity of at least about 0.4 dl/g, preferably from about 0.4 to about 1.0 dl/g. Polypropylene terephthalate can also be prepared by reacting 1,3-propanediol with dimethyl terephthalate.

Unfortunately, traditional PTT production methods do not meet the long-standing requirement to reduce PET waste that is usually incinerated or buried in landfills. The preparation of PTT from monomers requires a large amount of energy. It is desirable to develop a new method for the preparation of PTT from non-monomeric sources. It would also be beneficial to develop modified PTT random copolymers prepared from PET rather than monomers and exhibit comparable properties to PTT derived from monomers.

For the above reasons, there is a need to develop improved processes for the preparation of poly(trimethylene terephthalate) by substituting PET for monomers.

For the above reasons, it is necessary to develop new materials derived from PET that have similar properties to the monomer-based polytrimethylene terephthalate.

Summary of the invention

The present invention relates to a composition comprising a random copolymer of polyethylene terephthalate (1) derived from the group consisting of polyethylene terephthalate and polyethylene terephthalate The polyethylene terephthalate component of the polyethylene formate copolymer, and (2) comprising at least one residue derived from the polyethylene terephthalate component.

In one embodiment, the invention relates to articles molded or extruded from such compositions.

In another embodiment, the present invention is directed to a method of preparing such compositions comprising the steps of:

(a) depolymerizing a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers by depolymerizing (i) polyethylene terephthalate The ethylene glycol diformate component and (ii) 1,3-propanediol are under a pressure of at least one atmosphere, in the presence of a catalyst component, and sufficient to depolymerize said polyethylene terephthalate component into Reaction under inert atmosphere conditions of a molten mixture comprising oligomers of polyethylene terephthalate, oligomers of polytrimethylene terephthalate, oligomers of mixed diols , 1,3-propanediol and ethylene glycol;

Wherein, in the process of step (a), the polyethylene terephthalate component and 1,3-propanediol are stirred and mixed in the liquid phase, and the 1,3-propanediol is refluxed and returned to the reactor;

(b) placing the molten mixture at subatmospheric pressure and raising the temperature of the molten mixture to a temperature sufficient to form a random copolymer of polytrimethylene terephthalate, the random copolymerization The material (1) is derived from a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers, and (2) comprises at least one derivative Residue from polyethylene terephthalate component.

In another embodiment, the present invention is directed to a method of preparing such compositions, wherein the method comprises:

Depolymerization of a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers by depolymerizing at a pressure of at least one atmosphere in a catalyst In the presence of the components, and under conditions sufficient to depolymerize the polyethylene terephthalate components into a first molten mixture, agitating the polyethylene terephthalate components and the ethylene glycol in a reactor an alcohol, the first molten mixture comprising oligomers selected from the group consisting of ethylene terephthalate moieties, ethylene glycol, and combinations thereof;

1,3-propanediol is added to a first molten mixture in a reactor in the presence of a catalyst component at a temperature in the range of 190°C to 240°C and under conditions sufficient to form a second molten mixture, the second molten mixture comprising a component selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers containing propylene terephthalate moieties, propylene glycol, ethylene glycol, and combinations thereof; and

(c) raising the temperature of the second molten mixture to a temperature of 240° C. to 260° C. under stirring and a pressure below one atmosphere, thereby forming a polytrimethylene terephthalate random copolymer , the random copolymer (1) is derived from a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers, and (2) comprising at least one residue derived from a polyethylene terephthalate component.

These and other features, properties and advantages of the present invention will be better understood with reference to the following description and appended claims.

Detailed description of the invention

The present invention is based on the remarkable discovery that it is now possible to prepare modified polytrimethylene terephthalate components from poly(ethylene terephthalate), such as used soft drink bottles . Unlike conventional polytrimethylene terephthalate (polytrimethylene terephthalate derived from monomers), this modified polytrimethylene terephthalate Components include polyethylene terephthalate residues, such as substances such as ethylene glycol and isophthalic acid. Advantageously, although the polytrimethylene terephthalate used is structurally different from the original, monomer-derived polytrimethylene terephthalate, the polytrimethylene terephthalate of the present application 1,3-trimethylene dicarboxylate exhibits similar properties to polytrimethylene terephthalate derived from monomers.

Except for the working examples and where otherwise stated, all numbers or expressions referring to quantities of ingredients, reaction conditions, etc. used in the specification and claims are to be understood as modified by "about" in all cases. Various numerical ranges are disclosed herein. Since numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges specified herein are approximations.

All molecular weights in this application refer to the number average molecular weight measured from polystyrene standards. The technical details include the following items: (i) equipment: Waters 2695 separation module; (ii) detector: Waters2487 dual absorption UV detector @273 and 295 nanometers and Waters410 refractometer (refractomer); (iii) mobile phase: 5 % HFIP95% chloroform; (iv) GPC column: Polymer LabsPL HFIP gel 250×4.6mm; (v) flow rate: 0.3ml/min; (vi) injection volume: 10μl; (vii) polystyrene standard sample: Polymer Lab's Easy PS-, 580-7,500,000Da.

The present invention relates to compositions comprising a random copolymer of polyethylene terephthalate (1) derived from the group consisting of polyethylene terephthalate and polyethylene terephthalate The polyethylene terephthalate component of the glycol ester copolymer, and (2) comprising at least one residue derived from the polyethylene terephthalate component.

The residues derived from the polyethylene terephthalate component present in the modified poly(trimethylene terephthalate) component may be selected from the group consisting of ethylene glycol groups, diethylene glycol groups, Isophthalic acid groups, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin-containing compounds, 1,3-cyclohexanedimethanol isomers, 1,4-cyclohexanedimethanol isomers 1,3-cyclohexanedimethanol cis isomer, 1,4-cyclohexanedimethanol cis isomer, 1,3-cyclohexanedimethanol trans isomer, 1,4 -Cyclohexanedimethanol trans isomer, alkali salt (alkali salt) (including calcium salt, magnesium salt, sodium salt and potassium salt), phosphorus-containing compounds and anions, sulfur-containing compounds and anions, naphthalene dicarboxylic acid ( naphthalane dicarboxylic acid), 1,3-propanediol groups, and combinations thereof.

The residue may contain various combinations depending on factors such as polyethylene terephthalate and polyethylene terephthalate copolymer. For example, in one embodiment, the residue derived from the polyethylene terephthalate component comprises a mixture of ethylene glycol and diethylene glycol. The mixture may also contain additional substances such as isophthalic acid. The mixture may also contain 1,3-cyclohexanedimethanol cis isomers, 1,4-cyclohexanedimethanol cis isomers, 1,3-cyclohexanedimethanol trans isomers, 1,4-Cyclohexanedimethanol trans isomers and combinations thereof. In one embodiment, the residue derived from the polyethylene terephthalate component may be selected from 1,3-cyclohexanedimethanol cis isomer, 1,4-cyclohexanedimethanol cis isomers, 1,3-cyclohexanedimethanol trans isomers, 1,4-cyclohexanedimethanol trans isomers, and combinations thereof. In another embodiment, the residues derived from the polyethylene terephthalate component may be selected from the group consisting of ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, 1,3-cyclo Hexanedimethanol cis isomer, 1,3-cyclohexanedimethanol trans isomer, 1,4-cyclohexanedimethanol cis isomer, 1,4-cyclohexanedimethanol trans isomers and combinations thereof. In another embodiment, the residue derived from the polyethylene terephthalate component comprises a mixture of ethylene glycol, diethylene glycol, compounds containing antimony, germanium, tin, titanium, cobalt. As mentioned above, in such mixtures at least one residue derived from the polyethylene terephthalate component also contains isophthalic acid groups.

The molar amount of residues derived from the polyethylene terephthalate component may vary. In one embodiment, the residue derived from the polyethylene terephthalate component is selected from the group consisting of ethylene glycol groups, diethylene glycol groups and cyclohexanedimethanol groups in an amount of 0.1 mol % to 10 mol%, based on 100 mol% of diol in the composition (eg molding composition). In another embodiment, the residues derived from the polyethylene terephthalate component further comprise isophthalic acid groups in an amount of 0 to 10 mol%, in the form of polyethylene terephthalate 100 mol % of the acid functional groups in the ester copolymer is based on. The total amount of polyethylene terephthalate residues may vary. For example, sometimes the amount of the mixture can be 1.8 wt% to 2.5 wt%, or 0.5 wt% to 2 wt%, or 1 wt% to 4 wt%. Diethylene glycol groups may be present in an amount of 0.1 mol % to 10 mol %, based on 100 mol % of diol in the molding composition. The isophthalic acid groups are present in an amount of 0.1 mol % to 10 mol %, based on 100 mol % of acid in the molding composition.

In one embodiment, described further below, the polytrimethylene terephthalate random copolymer can be further derived from 1,3-propanediol obtained from biomass. The biomass may include, but is not limited to, sugars, such as those derived from starch or cellulose sources; grains, including, but not limited to, grains selected from corn, wheat, and combinations thereof. The biomass also includes other hydrocarbons that are biologically derived and suitable fermentation processes or chemical methods to produce 1,3-propanediol. Examples of such suitable biomass include, but are not limited to, glycerol, 3-hydroxypropionic acid.

The modified poly(trimethylene terephthalate) random copolymers of the present application can be prepared by a novel process in which PET is depolymerized and the resulting depolymerized PET melt mixture is subjected to polymerization Under the conditions of generating modified poly(trimethylene terephthalate) 1,3-trimethylene glycol ester random copolymer. For example, modified poly(trimethylene terephthalate) random copolymers can be prepared by methods including:

(a) depolymerizing a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers by depolymerizing (i) polyethylene terephthalate The ethylene glycol diformate component and (ii) 1,3-propanediol are under a pressure of at least one atmosphere, in the presence of a catalyst component, and sufficient to depolymerize said polyethylene terephthalate component into Reaction under inert atmosphere conditions of a molten mixture comprising oligomers of polyethylene terephthalate, oligomers of polytrimethylene terephthalate, oligomers of mixed diols , 1,3-propanediol and ethylene glycol; in the process of step (a), the polyethylene terephthalate component is stirred and mixed with 1,3-propanediol in the liquid phase, and 1,3 - reflux of propylene glycol to the reactor; and (b) subjecting the molten mixture to subatmospheric pressure and raising the temperature of the molten mixture until sufficient to form poly(trimethylene terephthalate) random copolymerization the temperature of the object, the random copolymer (1) is derived from a polyethylene terephthalate component selected from polyethylene terephthalate and polyethylene terephthalate copolymers, and (2) Contains at least one residue derived from a polyethylene terephthalate component.

The PET component for making the modified poly(trimethylene terephthalate) random copolymer generally comprises recycled (scrap) PET flakes, powder/crumb or pellets. Before use, PET is typically treated to remove impurities such as paper, adhesives, olefinic polymers, and other contaminants. Additionally, the PET component may contain PET flakes, chips or pellets that are not waste. In this way, PET, which would normally end up as solid waste, is now used efficiently and productively. In one embodiment, the PET component also includes other polyesters. These PET components may also include polyester copolymers. Examples of such materials include polyalkylene terephthalates, which may be selected from polyethylene terephthalate, polyethylene terephthalate, terephthalate esters and ring-containing Copolymers of comonomers of hexyldimethanol and ethylene glycol, copolymers of terephthalic acid and comonomers comprising cyclohexyldimethanol and ethylene glycol, polytrimethylene terephthalate, poly(trimethylene terephthalate) Xylylene terephthalate, polydianol terephthalate, polybutylene terephthalate, polynaphthalate, and combinations thereof.

The temperature employed in the method can vary. For example, polyethylene terephthalate components can be depolymerized at temperatures ranging from 180°C to 260°C. In another embodiment, the temperature of the molten mixture may be raised to a temperature range of 240°C to 270°C when the molten mixture is subjected to a pressure below one atmosphere.

As noted above, in some cases, the polytrimethylene terephthalate random copolymer can be further derived from 1,3-propanediol obtained from biomass.

The term "biomass" refers to living or dead biological material that can be directly or subsequently converted into useful chemicals, usually derived from non-renewable hydrocarbon resources. Biomass may include cellulosic materials, grains, starches derived from grains, fatty acids, vegetable oils, and derivatives of such biomass examples. Examples of useful chemicals include, but are not limited to, diols; diacids; monomers used to make diols or acids, such as succinic acid; monomers used to make polymers, and the like. Glycol-based biomass can be obtained from several sources. For example, the following method can be used to obtain biomass-based 1,4-butanediol. Agricultural biomass such as corn grain or grain-derived sugars can be converted to succinate by simple methods, such as fermentation in the presence of microorganisms. Such succinic acid is commercially available from several sources, such as "BioAmber ^(TM )" from Diversified Natural Products Inc. . The succinic acid can also be converted to 1,4-butanediol by methods described in several publications (eg, US Pat. No. 4,096,156), which patents are hereby incorporated by reference in their entirety. Biomass derived 1,4-butanediol can also be converted to tetrahydrofuran and further converted to polytetrahydrofuran, also known as polybutylene oxide glycol. Another method for converting succinic acid to 1,4-butanediol is described in Life Cycles Engineering Guidelines by Smith et al., as described in EPA Publication EPA/600/R-1/101 (2001). Biomass-based 1,3-propanediol is also available from commercial sources such as the aerobic fermentation method employed by DuPont, Tate and Lyle Bio Products.

However, the preparation of the modified poly(trimethylene terephthalate) random copolymer of the present application is not limited to the method of depolymerizing these polyethylene terephthalate components with 1,3-propanediol. In one embodiment, such modified poly(trimethylene terephthalate) random copolymers may be prepared by a process comprising: (a) depolymerizing a poly(ethylene terephthalate) selected from The polyethylene terephthalate component of the glycol ester and polyethylene terephthalate copolymer: under a pressure of at least one atmosphere, in the presence of a catalyst component, and sufficient to convert the polyethylene terephthalate Under the condition that the ethylene glycol phthalate component is depolymerized into a first molten mixture, the polyethylene terephthalate component and ethylene glycol are stirred in a reactor, and the first molten mixture contains a mixture selected from the group consisting of Oligomers of ethylene glycol phthalate moieties, ethylene glycol, and combinations thereof; (b) in the presence of catalyst components, at temperatures ranging from 190°C to 240°C, and sufficient to form a second 1,3-propanediol is added to a first molten mixture in a reactor under conditions of the molten mixture, the second molten mixture comprising a component selected from the group consisting of oligomers containing ethylene terephthalate moieties, oligomers, oligomers of mixed glycols, propylene glycol, ethylene glycol, and combinations thereof containing a trimethylene terephthalate moiety; and (c) mixing the first The temperature of the two molten mixtures is raised to a temperature of 240° C. to 260° C., thereby forming a polytrimethylene terephthalate random copolymer (1) derived from a poly(trimethylene terephthalate) selected from a polyethylene terephthalate component of a copolymer of ethylene glycol ester and polyethylene terephthalate, and (2) comprising at least one component derived from polyethylene terephthalate residues.

The temperature employed in the process can vary. For example, the temperature range at which depolymerization of the polyethylene terephthalate component can occur can be from 190°C to 250°C. Both of these temperatures can be used under an inert atmosphere.

Alternatively, the method of depolymerizing the PET component with ethylene glycol may include an embodiment in which the polytrimethylene terephthalate random copolymer is further derived from a 1,3-propanediol, The alcohol is derived from biomass by a process involving multiple transformations, such as conversion of biomass to starch, to sugar, to 1,3-propanediol. Such biomass can be grains such as corn, wheat and combinations thereof.

The method for preparing the modified polytrimethylene terephthalate random copolymer can be carried out in the presence of a catalyst. The catalyst may be selected from antimony compounds, tin compounds, titanium compounds and combinations thereof, as well as many other metal catalysts and combinations of metal catalysts already disclosed in the literature. The amount of catalyst will vary according to specific practical needs. Suitable catalyst amounts range from 1 to 5000 ppm, or more.

In use, such modified poly(trimethylene terephthalate) random copolymers can be used to make articles having a number of useful properties.

The modified poly(trimethylene terephthalate) random copolymer of the present application can be molded into useful articles by various methods and different processes to provide useful shaped products, such as injection molding, extrusion, rotational molding , foam molding, calender molding and blow molding and thermoforming, compression molding, melt spinning and melt blown products. Non-limiting examples of various articles made from the thermoplastic compositions of the present invention include: fibers, such as fabrics; injection molded articles, such as connectors; blow molded articles, such as fluid containers. In one embodiment, such polyesters can be blended with other conventional polymers.

Thus, the present invention includes molded or extruded articles of random copolymers of polytrimethylene terephthalate (1) derived from the group consisting of polyethylene terephthalate and The polyethylene terephthalate component of the polyethylene terephthalate copolymer, and (2) comprising at least one residue derived from the polyethylene terephthalate component, according to For use, the residue may be any of the residues described above. Residues derived from polyethylene terephthalate copolymer components, for example, may be selected from ethylene glycol groups, diethylene glycol groups, isophthalic acid groups, 1,3-cyclohexanedi Methanol cis isomers, 1,3-cyclohexanedimethanol trans isomers, 1,4-cyclohexanedimethanol cis isomers, 1,4-cyclohexanedimethanol trans isomers bodies and their combinations.

The modified poly(trimethylene terephthalate) imparts useful properties to the article. These properties are variable and depend on factors such as desired performance, equipment used, process parameters, etc. In another embodiment, the intrinsic viscosity varies from 1 to 1.3 dL/g. In another embodiment, the intrinsic viscosity varies from 0.95 to 1.05 dL/g. All intrinsic viscosities in this application refer to intrinsic viscosities measured in a solution of 60 wt% phenol and 40 wt% 1,1,2,2-tetrachloroethane at 25°C.

The modified poly(trimethylene terephthalate) random copolymer has a melting point of at least 200°C or at least 210°C. In another embodiment, the melting point varies from 220 to 230°C. In another embodiment, the melting point varies from 210 to 225°C. The crystallization temperature of this modified polytrimethylene terephthalate random copolymer is at least 120°C. In another embodiment, the crystallization temperature varies from 140 to 150°C.

The tensile strength (@break) of this modified polytrimethylene terephthalate random copolymer is at least 30 MPa. In another embodiment, the tensile strength ranges from 30 MPa to 100 MPa. In another embodiment, the tensile strength ranges from 51 MPa to 565 MPa. The tensile elongation (@yield) of this modified polytrimethylene terephthalate random copolymer is at least 2%.

In another embodiment, the tensile elongation (break) varies from 2% to 10%. In another embodiment, the tensile elongation (@break) varies from 10 to 300%. The notched Izod impact strength of the modified polytrimethylene terephthalate random copolymer is at least 10 J/m. In another embodiment, the notched Izod impact strength varies from 20 J/m to 60 J/m. In another embodiment, the notched Izod impact strength varies from 20 J/m to 40 J/m.

Other examples include blends of PTT derived from PET and PET copolymers with other functional ingredients including fillers, alloys with other polymers such as polycarbonate, impact modifiers, flame retardants Agents, stabilizers, nucleating agents, and combinations thereof.

The present invention provides unprecedented advantages. For example, the present invention provides an efficient method for the efficient preparation of modified PTT random copolymers from polyethylene terephthalate instead of monomers. In addition, the modified PTT random copolymers of the present application exhibit useful performance properties. In addition, articles can be prepared from the modified PTT random copolymers of the present application, thereby reducing the amount of polyethylene terephthalate that is typically incinerated or dumped into landfills.

For example, methods to prepare PET-derived randomly modified PTT copolymers can also reduce CO2 emissions and carbonaceous waste. Since the PET-derived randomly modified PTT copolymer prepared by the method of the present invention is prepared from PET instead of monomer, the method can reduce carbon dioxide emission and carbon-containing waste. Furthermore, the effect of carbon dioxide on the modified PTT copolymer was further improved when using bio-derived 1,3-propanediol.

The invention is further described by the following illustrative examples. All parts and percentages herein are by weight unless otherwise indicated.

Example 1

Green colored recycled PET pellets (green colored recycled PET) were obtained from North American supplier ST. Jude. These post-consumer recycled PET pellets have an intrinsic viscosity (iv) specification of 0.68 to 0.78 and a melting point specification of 245 to 255°C. 1,3-Propanediol (PDO) was obtained from Shell Chemicals with a purity specification of >99.9 wt%. Catalyst TPT was an industrial grade Tyzor from Dupont.

70.0 grams of recycled PET pellets and 84.04 grams of 1,3-propanediol (molar ratio 1:3) were mixed in a 500 ml reactor. The temperature of the oil bath (for the kettle) was gradually increased from 180°C to 255°C. The stirring speed was set at 20 rpm. At this stage, 0.08 ml of TPT catalyst was also added to the reaction mixture. The reactants reached 214°C (the boiling point of 1,3-propanediol), and the PDO was refluxed at this temperature for 2 hours. This is called the glycolytic stage of PET.

For the polymerization stage, the reflux condenser was removed and the autoclave was evacuated. Excess glycol and other volatile fractions are collected in a "Dean and Stark" condenser. The stirring speed was increased to 220 rpm. Use a vacuum pump to depressurize at a rate of 40 torr/min until the pressure reaches 0.15 torr. The increase in polymer molecular weight was monitored by increasing the torque of the overhead stirrer, after reaching the maximum torque value of the stirrer, the stirring rate was reduced to allow the reaction to proceed. This polymerisation phase is complete after reaching three consecutive maximum torque values at 220, 120, 60 rpm. Approximately 10 grams of polyester were collected from the reactor for further testing and analysis. The polyester samples were subjected to the following tests: intrinsic viscosity (IV), nuclear magnetic (NMR) analysis and differential calorimetry scanning (DSC) analysis. NMR analysis of the resin indicated that the composition of the material consisted of 98.3 mol% polytrimethylene terephthalate and 1.63 mol% PET residues. The material has an intrinsic viscosity of 0.736 dL/g. The melting point and crystallization temperature were measured by DSC (heating rate 20°C/min), and were 222°C and 144°C, respectively. The heats of fusion and crystallization for these transitions are 36 and -37 J/g, respectively.

Although the invention has been described in detail with reference to some preferred aspects thereof, other modifications are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the versions contained herein.

Claims (27)

1. composition, it comprises poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from described polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).

2. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from the ethylene glycol group, diethylene glycol group, isophthalic acid group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, 1, the 3-cyclohexane dimethanol, 1, the 4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexanedimethanol trans-isomer(ide), P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids, 1, ammediol group, and combination.

3. the described composition of claim 1, wherein at least a residue derived from the polyethylene terephthalate component comprises the mixture of ethylene glycol and glycol ether.

4. the described composition of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises m-phthalic acid.

5. the described composition of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.

6. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.

7. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group, isophthalic acid group, 1,3-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexane dimethanol, 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.

8. the described composition of claim 1, wherein at least a residue derived from the polyethylene terephthalate component comprises the mixture of following material: ethylene glycol, glycol ether and cobalt compound, antimony containing compounds, sn-containing compound, germanium-containing compound and combination thereof.

9. the described composition of claim 8, wherein at least a residue derived from the polyethylene terephthalate component further comprises isophthalic acid group.

10. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group and cyclohexanedimethanol group, and the amount of this residue is 0.1 to 10mol%, is as the criterion in the glycol of 100mol% in the composition.

11. the described composition of claim 10, wherein the residue derived from the polyethylene terephthalate component further comprises isophthalic acid group, its content is 0 to 10mol%, with this poly terephthalic acid 1, and the acid functional group of the 100mol% meter that is as the criterion in the ammediol ester copolymer.

A 12. composition molding according to claim 1 or extrude the goods of making.

A 13. composition molding according to claim 7 or extrude the goods of making.

14. the described composition of claim 1, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.

15. the described composition of claim 14, wherein biomass are cereals.

16. the described composition of claim 15, wherein cereal is selected from corn, wheat and combination thereof.

17. one kind prepares the described method for compositions of claim 1, it comprises:

(a) be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: with (i) polyethylene terephthalate component and (ii) 1, ammediol is under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component depolymerized under the inert atmosphere conditions of molten mixture and react, this molten mixture comprises the oligopolymer of poly terephthalic acid ethylene glycol, poly terephthalic acid 1, the oligopolymer of ammediol ester, the oligopolymer of blended glycol, 1, ammediol and ethylene glycol;

Wherein, in step (a) process, described polyethylene terephthalate component and 1, ammediol mixes in liquid phase, with 1, ammediol backflow Returning reactor;

(b) molten mixture is placed be lower than under the atmospheric environment, and the temperature of this molten mixture that raises, until being enough to form poly terephthalic acid 1, the temperature of ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from described polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).

18. the described method of claim 16, wherein the polyethylene terephthalate component is 180 ℃ to 260 ℃ temperature range generation depolymerization.

19. the described method of claim 16, wherein the temperature of molten mixture is elevated to 240 ℃ to 270 ℃ temperature.

20. the described method of claim 16, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.

21. the described method of claim 20, wherein biomass are cereals.

22. the described method of claim 21, wherein cereal is selected from corn, wheat and combination thereof.

23. one kind prepares the described method for compositions of claim 1, it comprises:

Be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component is depolymerized under the condition of first molten mixture, in reactor, stir polyethylene terephthalate component and ethylene glycol, this first molten mixture contains oligopolymer, the ethylene glycol that is selected from the ethylene glycol terephthalate part, and combination;

In the presence of catalyst component, in 190 ℃ to 240 ℃ temperature range, and be enough to form under the condition of second molten mixture, in first molten mixture of reactor, add 1, ammediol, this second molten mixture comprises and is selected from following component: contain the ethylene glycol terephthalate part oligopolymer, contain oligopolymer, blended oligomers of glycols, propylene glycol, the ethylene glycol of propylene glycol ester terephthalate's part and combination thereof; With

(c) be lower than under the atmospheric condition in stirring and pressure, the temperature of second molten mixture is elevated to 240 ℃ to 260 ℃ temperature, thereby form poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).

24. the described method of claim 23, wherein depolymerization takes place in the polyethylene terephthalate component under inert atmosphere in 190 ℃ to 250 ℃ temperature ranges.

25. the described method of claim 24, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.

26. the described method of claim 24, wherein biomass are cereals.

27. the described method of claim 26, wherein cereal is selected from corn, wheat and combination thereof.