AU2004239029A1 - Polyester masterbatch composition - Google Patents

Description

WO 2004/101666 PCT/EP2004/050744 Polyester Masterbatch Composition The present invention relates to masterbatches useful for modifying thermoplastic polyesters, in particular to masterbatches comprising dispersed polyol branching agents and/or chain coupling agents. The invention also relates to a method for preparing the masterbatches, and 5 to a method for modifying a polyester utilizing the masterbatches. Thermoplastic polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) are widely used in the fields of extrusion, injection molding and stretch blow molding to produce products such as fibers, containers and films. 10 While polyesters may be used in other fields such as film blowing, tentering, thermoforming and foam extrusion, their use in these fields is often limited by the need for a narrow processing window and spezialised processing equipment. Such limitations generally stem from deficiencies in the melt rheology of the polyesters. In particular, polyesters typically 15 have low melt viscosity, low melt strength and low melt elasticity. It is known that the melt strength and melt viscosity of polyesters can be improved through the introduction of a degree of branching in the linear chain structure of the polymer, and/or by increasing the polymers molecular weight through chain extension. One approach used to 20 prepare branched or chain extended polyesters has involved melt mixing polyesters with branching and/or chain coupling agents such as polyfunctional carboxylic acids, anhydrides or alcohols. During melt mixing, the agents react with the molten polyester to chain extend and/or introduce branching in the linear chain structure of the polymer. 25 Depending upon the type of branching/chain coupling agent(s) used to modify the polyester, the overall effect of the melt mixing reaction may in fact decrease the molecular weight of the polyester. This will often be the case where the only type of agent used is a polyol branching agent. Under these circumstances, in order to achieve the desired increase in melt strength and melt viscosity, a chain coupling agent can be used in combination with the polyol, or the 30 resulting branched polyester can be subjected to a further processing step such as a solid state condensation process. In contrast, polyanhydride branching/chain coupling agents can introduce branching, but also generally cause an increase in the molecular weight of the polymer during melt mixing. Accordingly, polyanhydride branching/chain coupling agents can WO 2004/101666 PCT/EP2004/050744 -2 be used as a sole branching/chain coupling agent without subjecting the modified polyester to further processing. Regardless of the type of branching/chain coupling agent used, to effectively modify the 5 polyester it is important that the degree of branching/chain coupling can be controlled during the melt mixing process, and that branching/chain coupling occurs uniformly in the polyester. Generally melt mixing is performed in an extruder, and the branching/chain coupling agent can be added to the polyester either before extrusion, or to the molten polyester during 10 extrusion. The most simplistic way in which the agent can be added to the polyester is by direct addition. However, this mode of addition has been found to lead to gel formation through excessive localized chain coupling, and non-uniform branching within the modified polyester. This also leads to detrimental discoloration. Furthermore, it is not uncommon to use amounts of less than 0.5 weight percent of the branching/chain coupling agent, relative 15 to the polyester to be modified. At these low levels, it is difficult to provide a uniform distribution of the agent in the polyester by direct addition. Many of the aforementioned problems associated with the addition of branching/chain coupling agents can be overcome through use of a polymer blend, concentrate, or 20 masterbatch as it is commonly referred to in the art. The masterbatch comprises high levels of the branching/chain coupling agent, but when added to the polyester it in effect acts as a diluted source of the agent. This diluent effect enables the branching/chain coupling agent to be distributed more evenly throughout the polyester and promotes a more uniformly branched/chain extended polyester. 25 In its simplest form, the masterbatch may be a physical blend of a carrier polymer and the branching/chain coupling agent, with both the agent and the carrier polymer often being in a powdered form. To avoid problems associated with incompatibility, the carrier polymer is preferably the same as, or of the same general class as, the base polymer to which the 30 masterbatch is to be melt mixed with. For example, if the base polymer is a polyester, the carrier polymer is preferably also a polyester. Although effective, such physical blends do have a tendency to separate out into the individual components and again give rise to non uniform distribution of the branching/chain coupling agent.

WO 2004/101666 PCT/EP2004/050744 -3 A masterbatch can also be readily formed by melt mixing a carrier polymer with the branching/chain coupling agent. However, when the carrier polyester this may lead to problems. In particular, given that the branching/chain coupling agents react with a polyester during melt mixing, the same or similar carrier polyester will also generally react with the 5 agents during preparation of the masterbatch. As a means of circumventing this problem, US 5,801,206 discloses a masterbatch comprising branching agents where the carrier polymer is an inert polyolefin. Preparation of a masterbatch of this type by melt processing does therefore not result in the reaction of the 10 branching agents with the carrier polymer. Although these masterbatches provide a means to add the agents to a polyester, the resulting modified polyester will inherently always be contaminated with polyolefin. This contamination may be tolerable, and possibly desired, in some instances, however it can also be detrimental and - depending on the actual addition level - might lead to hazy end products. For example, the quality of foamed polyester can be 15 reduced by the presence of polyolefin contamination. US 5,536,793 discloses a masterbatch comprising branching agents where the carrier polymer is a polyester such as PET. In this case, the reactivity of the branching agent toward the carrier polymer during melt processing is used advantageously. In particular, by ensuring 20 sufficient branching agent is present during melt mixing, the end groups of the polyester chains are in effect capped by the branching agent, which in turn is believed to prevent further reaction of the branching agent with the polyester. By using higher amounts of branching agent than is required to cap all of the polyester chains, a masterbatch comprising unreacted branching agent can be prepared. 25 However, masterbatches disclosed in US 5,536,793 are limited in terms of composition. Sufficient branching agent to cap the end groups of the polyester carrier must initially be present during melt mixing to prevent crosslinking and gel formation. In practice, this typically limits the masterbatch composition to comprising no less than 5 weight percent of the 30 branching agent. Furthermore, the capping reaction disclosed is based on the reaction of the polyester end groups with a polyfunctional anhydride branching agent. A similar reaction using other agents such as a polyfunctional alcohol branching agent is unlikely to prevent reaction of the polyol with the carrier polyester during melt blending. In particular, polyol compounds are known to readily react with internal ester groups of a PET chain during a WO 2004/101666 PCT/EP2004/050744 -4 melt blending process (transesterification). Under these circumstances, most, if not all, of the polyol branching agent would react with the polyester carrier to thereby render the material unsuitable for use as a masterbatch. Accordingly, the composition of the masterbatch disclosed in US 5,536,793 is further limited to the use of a polyfunctional anhydride 5 branching agents. It would therefore be desirable to provide a masterbatch that comprised a polyester as a carrier material and a branching and/or a coupling agent, wherein the composition of the masterbatch was less restricted in terms of the amount and type of the 10 branching and/or coupling agent incorporated. Surprisingly, it has been found that polyesters having a melt processing temperature of 2500C or less can be melt mixed with branching and/or chain coupling agents without significant reaction occurring between the branching and/or chain coupling agent and the 15 polyester, Under these circumstances, a polyester can be melt mixed with a wide array of branching and/or chain coupling agents at both high and low concentrations to prepare masterbatches useful for subsequent melt mixing with other thermoplastic polyesters. Advantageously, agents such as polyfunctional acid anhydrides and polyols can be combined together within the masterbatch of the present invention. 20 One aspect of the present invention is a polyester masterbatch composition comprising a branching and/or a chain coupling agent dispersed within a polymeric matrix of polyester, wherein the polyester has a melt processing temperature of 2500C or less. 25 As used herein, the term "masterbatch" has the common meaning as would be understood by one skilled in the art. With particular reference to the present invention, a masterbatch is a composition comprising a polyester as a carrier polymer and an agent, such as a branching and/or a chain coupling agent, where the concentration of the agent is higher than desired in a final product, and which composition is subsequently let down in a base polymer to 30 produce the final product having the desired amount of agent. As used herein, the term "melting temperature" of a branching or chain coupling agent is used to denote a temperature at which the agent begins to melt.

WO 2004/101666 PCT/EP2004/050744 -5 As used herein, the term "melt processing temperature" of a polyester is used to denote the lowest temperature that the polyester can be maintained at to enable it to be effectively melt processed. 5 As used herein, the term "branching agent" or "branching compound" is used to denote a polyfunctional compound which can react with a polyester to introduce branching therein. It will be appreciated that in order to introduce branching, the branching agent will necessarily have at least three functional groups that are capable of reacting with the polyester. 10 As used herein, the phrase "a branching and/or a chain coupling agent" is used to mean at least one chain branching agent or chain coupling agent. It embraces both types of agent and multiple agents in combination. The branching and/or chain coupling agent in accordance with the masterbatch of the 15 present invention is dispersed within a polymeric matrix of polyester. By "dispersed" is meant that the agent is present as a separate largely unreacted entity within the polymeric matrix, and has therefore not reacted with the polymeric matrix to become an integral part thereof. In one embodiment of the present invention, the agent(s) selected for the polyester 20 masterbatch is preferably a branching agent, and the branching agent is preferably a polyol. In another embodiment of the present invention, the agent(s) selected for the polyester masterbatch is preferably a coupling agent, and the coupling agent is preferably a dianhydride. It will be appreciated by those skilled in the art that a dianhydride can also 25 function as a branching agent. For convenience, an agent which can function as both a branching and a coupling agent may herein also be referred to as a "branching/coupling agent". In a preferred embodiment of the present invention, the agents selected for the polyester 30 masterbatch are a branching agent in conjunction with a coupling agent. In this case, the branching agent is preferably a polyol and the coupling agent is preferably a dianhydride. It is an important feature of the present invention that the branching and/or chain coupling agent is dispersed in a polymeric matrix of polyester. In particular, that the branching and/or WO 2004/101666 PCT/EP2004/050744 -6 chain coupling agent is melt mixed with the polyester to become dispersed within the polymeric matrix of the polyester. As discussed above, branching and/or chain coupling agents are renowned for reacting with polyesters during melt mixing. Under these circumstances, there are limitations as to the type and amount of branching and/or chain 5 coupling agents that can be used in the preparation of the masterbatches. Surprisingly, it has been found that polyesters having a melt processing temperature of 2500C or less can be melt mixed with particular branching and/or chain coupling agents without significant reaction occurring between the branching and/or chain coupling agent and the polyester. Without wishing to be limited by theory, combinations of branching and/or chain coupling agents and 10 polyesters that demonstrate low reactivity toward each other during melt mixing are believed to be those where the agent has a higher melting temperature than the melt processing temperature of the polyester, and/or where the agent has a poor solubility in the molten polyester. 15 In particular when the branching agent is a polyol, it is an important feature of the present invention that the polyol is melt mixed with the polyester to become dispersed within the polymeric matrix of the polyester. As discussed above, polyol compounds are renowned for reacting with polyesters during melt mixing. Under these circumstances, it is not possible to disperse polyol within the polymeric matrix as the polyol reacts with the polyester to become 20 an integral part thereof. Surprisingly, it has been found that particular combinations of polyesters, with melt processing temperatures below 250* C, and polyol branching agents can be melt mixed without significant reaction between the polyester and the polyol occurring. 25 As will be appreciated from the discussion directly above, the lack of reactivity between the branching and/or chain coupling agent and the polyester is important. However, it is to be understood that this does not exclude the possibility of there being at least some reactivity of the agent toward the polyester. In particular, provided that there is no significant reaction between the agent and the polyester during melt mixing, it will be possible to prepare a 30 useful masterbatch with branching and/or chain coupling agent dispersed within a polymeric matrix of polyester. Preferably, no more than about 50 weight percent, more preferably no more than about 20 weight percent, still more preferably no more than about 10 weight percent, most preferably WO 2004/101666 PCT/EP2004/050744 -7 no more than about 5 weight percent of the polyester reacts with the branching and/or chain coupling agent during preparation of the masterbatch by melt mixing. In a particularly preferred embodiment of the present invention, substantially none of the polyester reacts with the branching and/or chain coupling agent during preparation of the masterbatch by melt 5 mixing. By the phrase "the polyester reacts with the branching and/or chain coupling agent" is meant that polyester chain end groups and/or internal moieties within the polyester chain react with the branching and/or chain coupling agent. 10 The degree of reaction that may occur between the branching and/or chain coupling agent and the polyester during preparation of the masterbatch can typically be assessed by a number of convenient and simple techniques. The simplest technique is to measure the melt flow index (MFI) of the masterbatch. Significant reaction of a branching agent such as 15 pentaerythritol with the polyester will be evidenced by an increase in the polyesters MFI, whereas significant reaction of a branching/chain coupling agent such as pyromellitic dianhydride (PMDA) will be evidenced by a decrease in the polyesters MFI. The same can be detected by measuring the Intrinsic Viscosity of the carrier polyester. 20 The composition of the masterbatch may also be analyzed using techniques such as NMR and IR spectroscopy, where end group determination can be usefully applied. Alternatively, depending upon the choice of branching and/or chain coupling agent and polyester, the masterbatch could be extracted using an appropriate solvent to selectively isolate unreacted agent. Mass balance calculations could then be used to establish the degree of reactivity. 25 Reaction of the branching and/or chain coupling agent with the polyester will typically cause chain scission or chain coupling of the polyester chains, this in turn will be reflected in a reduction or increase, respectively, in the polyesters melt viscosity and/or the polyesters intrinsic viscosity (IV). For example reaction of the polyol with the polyester will typically 30 cause chain scission of the polyester chains, this in turn will be reflected in a reduction of the polyesters melt viscosity and/or the polyesters intrinsic viscosity (IV). The viscosity of the polyester melt during melt mixing can be readily assessed by measuring the force required to drive the mixing elements of the melt mixing device. In the case where WO 2004/101666 PCT/EP2004/050744 -8 the viscosity of the melt is reduced, the force required to drive the mixing elements will also generally be reduced, and where the viscosity of the melt is increased, the force required will also generally be increased. Where an extruder is used, this force can conveniently be determined by measuring the motor drive torque of the extruder. A reduction or increase in 5 the IV of the polyester can be conveniently measured using techniques well known in the art. A particular advantage provided by the masterbatch of the present invention is that it can be prepared using a diverse range of branching and/or chain coupling agents at both high and low concentrations without significant change in the rheological properties of the carrier 10 polyester occurring. This advantage is particularly evident where a polyol branching agent is employed, or where low levels (from about 1 to about 5 weight percent) of a branching/chain coupling agent such as pyromelletic dianhydride are employed. It will be appreciated by those skilled in the art the addition of some additives to a molten 15 polymer may cause the melt viscosity of the polymer/additive mixture to increase or decrease simply through an additive being present in the melt, and not through any reaction of the additives with the polymer. Accordingly, such an increase or decrease in melt viscosity of the polymer/additive mixture should not be considered as an increase or decrease in the polymers melt viscosity per se. 20 Preferably, the polyesters melt viscosity and/or the polyesters intrinsic viscosity is reduced or increased by no more than 30 %, more preferably no more than 15 %, more preferably no more than 5 % when it is melt mixed with the branching and/or chain coupling agent. In a particularly preferred embodiment, the melt viscosity and/or the intrinsic viscosity of the 25 polyester remains substantially unchanged when it is melt mixed with the branching and/or chain coupling agent. By virtue of there being no significant reaction between the branching and/or chain coupling agent and the polyester during melt mixing, the resulting masterbatch can be readily 30 extruded and generally will have adequate physical and mechanical properties to function as a masterbatch. In particular, the molecular weight of the polyester is not reduced or increased during preparation of the masterbatch to a point where extrusion becomes impractical and/or difficult.

WO 2004/101666 PCT/EP2004/050744 -9 As discussed above, the relative melt temperatures of the branching and/or chain coupling agent and the polyester, and/or the solubility of the agent in the molten polyester are believed to be important parameters that influence the reactivity of the agent toward the polyester. Depending upon the particular combination of agent and polyester, any one of 5 these parameters may influence the reactivity, or alternatively both parameters may collectively influence the reactivity. Preferably, the branching and/or chain coupling agent has a melt temperature which is at least 10*C higher, more preferably at least 20 0 C higher, still more preferably at least 40*C 10 higher than the melt processing temperature of the polyester. Preferably, branching and/or chain coupling agent is present as a separate phase in the molten polyester during melt mixing. In particular, it is preferred that at least 50 weight percent, more preferably at least 65 weight percent, most preferably at least 85 weight 15 percent of the branching and/or chain coupling agent is present as a separate phase in the molten polyester during melt mixing. In a particularly preferred embodiment, substantially all of the branching and/or chain coupling agent is present as a separate phase in the molten polyester during melt mixing. 20 In the immediately preceding paragraph, reference to the "molten polyester during melt mixing" is intended to be a reference to the molten polyester at the melt processing temperature of that polyester. The masterbatch of the present invention provides a means of distributing the branching 25 and/or chain coupling agent uniformly in a base polyester. In order to ensure branching and/or chain extension occurs uniformly in the base polyester during melt mixing, it is important that the masterbatch rapidly melts to thereby rapidly disperse the agent throughout the molten base polyester. It is believed that the agent can be more efficiently dispersed throughout the base polyester when the melt processing temperature of the masterbatch 30 carrier polyester is lower than that of the base polyester. A common base polyester that may be modified using a masterbatch in accordance with the present invention is PET. Suitable polyesters for use as the carrier polyester in the masterbatch of the present invention have a melt processing temperature of 250*C or less, WO 2004/101666 PCT/EP2004/050744 -10 which is advantageously lower than that of PET (typically about 260"C). Utilizing such low melt processing temperature polyesters also provides a means of increasing the melt temperature difference between the carrier polyester and branching and/or chain coupling agents having melt temperatures greater or around 250*C, the effect of which is believed to 5 reduce reactivity of the agent toward the carrier polyester during preparation of the masterbatch. Preferably, a low melt processing temperature polyester suitable for use in the masterbatch will have a melt processing temperature ranging from 150*C to 250*C, more preferably from 10 about 170 0 C to about 240"C, most preferably from about 1800C to about 230 0 C. In considering suitable low melt processing polyesters for use in accordance with the present invention, those skilled in the art will appreciate that there are numerous factors which influence the melting properties of polyesters. Factors that are believed to contribute to 15 providing a low melting polyester include chain structure irregularity, non-linear connection of monomeric units, lack of interchain attraction, bulky side chains, flexibility in the internal bond structure and an odd number of carbon atoms in the repeat units. Many of these factors in effect inhibit the ability of the polyester to develop crystallinity, and therefore polyesters having a low percentage of crystallinity often also have a low melt processing temperature. 20 The degree of crystallinity can, for example, be measured by various techniques, known by those skilled in the art. For instance differential scanning calorimetry (DSC) detects the heat of fusion at the melt temperature, which is directly proportional to the degree of crystallinity. The density of the polyester is also linked to the degree of crystallinity: as lower the density 25 as higher is the degree of crystallinity. Both methods need calibration tests. An absolute method of detecting the degree of crystallinity is, for example, wide angle X-ray scattering. Where a low crystalline polyester is used as a low melt processing temperature polyester, it preferably has a crystallinity of less than about 15 %, more preferably of less than about 5 %. It is particularly preferred that such a low crystalline polyester has substantially no 30 crystallinity and is amorphous. Another important parameter of low melt processing polyesters is their glass transition temperature: Suitable polyesters show a glass transition temperature of about 700C, more WO 2004/101666 PCT/EP2004/050744 - 11 preferably about 1 10*C and most preferably about 150"C below the melting temperature of the branching agent or chain coupling agent. Those skilled in the art will appreciate that the degree of crystallinity of a given polyester will 5 very much depend upon the molecular structure of the polyester. In particular, the degree of crystallinity of a polyester can be altered by simply changing the amount and/or type and/or distribution of monomer units that make up the polyester chain. For example, if about 8 mole percent of the ethylene glycol repeat units in PET are replaced with 1,4-cyclohexanedi methanol repeat units, or about 15 mole percent by di-ethylene glycol repeat units, the 10 resulting modified polyester can be amorphous and has a low melt processing temperature. Similarly, if about 15 mole percent of the terephthalic acid repeat units in PET are replaced with isophthalic acid repeat units, the resulting modified polyester can also be amorphous and have a low melt processing temperature. Such concepts can also be combined into one polyester or by melt mixing at least 2 different polyesters. Accordingly, the choice of a 15 particular modifying acid or diol can significantly affect the melt processing properties of the polyester. As used herein, the terms "modifying acid" and "modifying diol" are meant to define compounds, which can form part of the acid and diol repeat units of a polyester, respectively, 20 and which can modify a polyester to reduce its crystallinity or render the polyester amorphous. Examples of modifying acid components may include, but are not limited to, isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, 25 sebacic acid, suberic acid, 1,12-dodecanedioic acid, and the like. In practice, it is often preferable to use a functional acid derivative thereof such as the dimethyl, diethyl, or dipropyl ester of the dicarboxylic acid. The anhydrides or acid halides of these acids also may be employed where practical. Preferred is isophthalic acid. 30 Examples of modifying diol components may include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, Z,8-bis(hydroxymethyl)-tricyclo-[5.2.1.01-decane wherein Z represents 3, 4, or 5; 1,4-Bis(2-hydroxyethoxy)benzene and diols containing one or more WO 2004/101666 PCT/EP2004/050744 - 12 oxygen atoms in the chain, e.g. diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like. In general, these diols contain 2 to 18, preferably 2 to 8 carbon atoms. Cycloalphatic diols can be employed in their cis or trans configuration or as mixtures of both forms. 1,4-cyclohexanedimethanol or di-ethylene glycol are the preferred 5 modifying diols. Other suitable low melt processing polyesters are based on polyaddition of lactones, for example poly-e-caprolacton. 10 Preferred is a polyester masterbatch composition wherein the polyester suitable for use in the masterbatch is glycol modified poly(ethylene terephthalate) (PET-G), poly-e-caprolactone, or a copolyester containing greater than about 15% isophthalic units. Polyesters suitable for use in the masterbatch of the present invention generally have an 15 intrinsic viscosity (IV) of about 0.4 dL/g to about 1.5 dL/g, but those having values of about 0.6 dUg to about 1.0 dUg are preferred. Intrinsic viscosity can be determined in a 60/40 (wt/wt) phenol/tetrachloroethane solution at a concentration of 0.5 grams per 100ml at 25 0 C. 20 In a specific embodiment the polyester for use in the masterbatch, is characterized by a melt viscosity of less than 2000 Pa sec at a shear rate of 100 s-1 measured at a temperature below the melting temperature(s) of the branching agent and/or chain coupling agent Below the melting temperature of the branching agent and/or chain coupling agent means at 25 least 10* C and preferably at least 20* C below said temperature. The masterbatch in accordance with the present invention may comprise a branching agent. Preferred branching agents include, but are not limited to, polyols and polyfunctional acid anhydrides. 30 Suitable polyol branching agents for use in the masterbatch have a functionality of three or more, which will be understood to mean that they have at least three hydroxy groups per molecule. For example, glycerol has a functionality of three and pentaerythritol has a functionality of four. Examples of suitable polyol branching agents, or precursors thereto, include, but are not limited to, trimethylolethane, pentaerythritol sorbitol, 1,1,4,4- WO 2004/101666 PCT/EP2004/050744 -13 tetrakis(hydroxymethyl)cyclohexane, and dipentaerythritol, tripentaerythritol etc. One or more polyol branching agent may be used in combination. Preferred polyol branching agents, or derivatives thereof, include pentaerythritol, 5 dipentaerythritol, tripentaerythritol, and trimethylolethane. As indicated above, the polyol branching agent may be provided in the form of a precursor thereto, or derivative thereof. By "precursor thereto" or "derivative thereof" it is meant a compound that is converted to the polyol during preparation of the masterbatch by melt 10 processing. Where the masterbatch in accordance with the present invention comprises a polyol branching agent, the polyol is preferably present in an amount from about 0.3 to about 30 weight percent, more preferably from about 0.3 to about 20 weight percent, most 15 preferably from about 1 to about 10 weight percent, relative to the polyester carrier polymer. Suitable polyfunctional acid anhydrides for use in the masterbatch have a functionality of three or more, which will be understood to mean that the polyfunctional acid anhydrides have at least three acid groups or acid group residues per molecule. For example, trimellitic acid 20 anhydride has a functionality of three and pyromellitic acid dianhydride has a functionality of four. Examples of polyfunctional and anhydrides that can be used in the masterbatch of the present invention include aromatic acid anhydrides, cyclic aliphatic anhydrides, halogenated 25 acid anhydrides, pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cydohexene-1,2-dicarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bisphenol-A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane 30 dianhydride, 2,3,6,7-napthalenetetracarboxylic acid dianhydride, bis(3,4 dicarboxyphenyl)sulfone dianhydride, 1,2,5,6-napthalenetetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid, hydroquinone bisether dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-succinic acid dianhydride, bicyclo(2,2)oct-7- WO 2004/101666 PCT/EP2004/050744 -14 ene-2,3,5,6-tetracarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 3,3',4,4' biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA), and ethylenediamine tetraacetic acid dianhydride (EDTAh). It is also possible to use acid 5 anhydride containing polymers or copolymers as the anhydride component. Two or more polyfunctional acid anhydrides may be used in combination. Preferred polyfunctional acid anhydrides, include pyromellitic dianhydride, 1,2,3,4 cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid 10 dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride. Most preferably the polyfunctional acid anhydride is pyromellitic dianhydride. As indicated above, the polyfunctional acid anhydride may contain acid groups or acid group residues. By "acid group residue" is meant a residue of a carboxylic acid that has condensed 15 with a second carboxylic acid to form an anhydride. In this case, the anhydride formed would contain two acid group residues. Where the masterbatch in accordance with the present invention comprises a branching agent other than a polyol branching agent, the branching agent is preferably present in an 20 amount from about 1 to about 60 weight percent, more preferably from about 5 to about 40 weight percent, most preferably from about 5 to about 30 weight percent, relative to the polyester carrier polymer. The masterbatch in accordance with the present invention may comprise a chain coupling 25 agent. Chain coupling agents that may be used with the present invention include, but are not limited to, polyfunctional acid anhydrides, epoxy compounds, oxazoline derivatives, oxazolinone derivatives, lactams and related species. For examples of additional chain coupling agents we refer to Inata and Matsumura, J. App. Pol. Sci., 303325 (1988) and Lootjens et al J. App. Pol. Sci 65 1813 (1997) and Brown in "Reactive Extrusion" Ed Xanthos, 30 Hanger, New York 1992 p75. Those containing anhydride or lactam units are preferred for reaction with alcohol functionality of a base polyester when the masterbatch is subsequently used. Those WO 2004/101666 PCT/EP2004/050744 - 15 containing oxazoline, oxazolinone, epoxide, carbodiimide units are preferred for reaction with acid functionality of a base polyester when the masterbatch is subsequently used. Preferred chain coupling agents which may be used alone or in combination include the 5 following: (1) Polyepoxides such as bisphenole-A-diglycidylether, ebis(3,4-epoxycycohexylmethyl) adipate; N,N-diglycidyl bemzamide (and related diepoxies); N,N-diglycidyl aniline and derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid or isocyanuric acid derivatives; 10 N,N-diglycidyl diimides; N,N-diglycidyl imidazolones; epoxy novolaks; phenyl glycidyl ether; diethyleneglycol diglycidyl ether; Epikote 815 (diglycidyl ether of bisphenol A-epichlorohydrin oligomer). (2) Polyoxazolines/Polyoxazolones such as 2,2-bis(2-oxazoline); 1,3-phenylene bis 15 (2-oxazoline-2), 1,2-bis(2-oxazolinyl-2)ethane; 2-phenyl-1,3-oxazoline; 2,2'-bis(5,6-dihydro 4H-1,3-oxazoline); NN'-hexamethylenebis (carbamoyl-2-oxazoline; bis[5(4H)-oxazolone); bis(4H-3,1 benzoxazin-4-one); 2,2'-bis(H-3,1 -benzozin-4-one); (3) Polyisocyanates such as 4,4'-methylenebis(phenyl isocyanate) (MDI); toluene 20 diisocyanate, isocyanate terminated polyurethanes; isocyanate terminated polymers; (4) Anhydrides Examples of polyfunctional acid anhydrides are as previously defined for the branching 25 agents. (5) Polyacyllactams such as N,N'-terephthaloylbis(carpolactam) and N,N'-terephthaloylbis (laurolactam). The use of these and similar compounds for PET chain extension has been disclosed by Akkapeddi and Gervasi in US 4857603. 30 (6) Phosphorous (111) coupling agents such as triphenyl phosphite (Jaques et al Polymer 38 5367 (1997)) and other compounds such as those disclosed by Aharoni in US5326830. Where the masterbatch in accordance with the present invention comprises a chain coupling agent, the chain coupling agent is preferably present in an amount of from about I to about WO 2004/101666 PCT/EP2004/050744 -16 60 weight percent, more preferably from about 5 to about 40 weight percent, more preferably from about 5 to about 30 weight percent, relative to the polyester carrier. In a further embodiment of the invention the masterbatch composition may comprise 5 additionally a phosphite, a phospinate or a phosphonate compound. Phosphonates are in general preferred. Preferably the phosphonate is of formula 11 0 10 Q -(CH 2 ) P OR,o, n I

OR

1 03 (11) , wherein

R

1 m is H, C-C2oalkyl, unsubstituted or C-C 4 alkyl-substituted phenyl or naphthyl,

R

1 04 is hydrogen, C-C2alkyl, unsubstituted or C-C 4 alkyl-substituted phenyl or naphthyl; or Mr+/ Mr is an r-valent metal cation or the ammonium ion, 15 n is 0, 1, 2, 3,4, 5 or 6, and r is 1, 2, 3 or 4; Q is hydrogen, -X-C(O)-OR 1 0 7 , or a radical

R

1 05

R

105

OR

106 ,

R

1 0 2

R

1 01 is isopropyl, tert-butyl, cyclohexyl, or cyclohexyl which is substituted by 1-3 C-C 4 alkyl 20 groups,

R

1 o2 is hydrogen, C-C 4 alkyl, cyclohexyl, or cyclohexyl which is substituted by 1-3 C 1

-C

4 alkyl groups,

R

1 05 is H, C-C 1 aalkyl, OH, halogen or C 3

-C

7 cycloalkyl;

R

1 06 is H, methyl, trimethylsilyl, benzyl, phenyl, sulfonyl or C-C 1 5 alkyl; WO 2004/101666 PCT/EP2004/050744 - 17

R

10 7 is H, Cl-C 1 oalkyl or C 3

-C

7 cycloalkyl; and X is phenylene, C 1

-C

4 aIkyl group-substituted phenylene or cyclohexylene. Other suitable phosphonates are listed below. 5

H

2 H

\H

3 H C-C-OH /\\ % CH S2 / H , P /l \C ' C-N~ 2/\

CH

3 0 OCH3 p C-C-OH CICH 2

-CH

2 OCH2CH2CI H2 H2 C2HO

OC

2 H 2 2 IiC 0 OC-C- IC-O-P-0-CH \ || / Fl/I N-C-O-P-0-C-N

H

2

C

H .- / H O H- N HOC 2C -C 0H /OH O H HC- ]

/CCH

2 HC--C-CH / O H2 .' H H3C--P--O-C \\ , C-N - 2, H H 2 / OCH 3 2,

CH

3 0O -bC O CH, HC-O-\-O-CH H- O C\

H

3 C H/ OH n O HOH - HO HO~tC-t H WO 2004/101666 PCT/EP2004/050744 - 18 0 01 0 N - H + fPKO H/CH2OH ONCH Na 2 OCH3 NCO OH CH 3 0 HOK OH H2O3 1 P C ||

H

2 O Sterically hindered hydroxyphenylalkylphosphonic acid esters or half-esters, such as those 5 known from US 4 778 840, are preferred. Halogen is fluoro, chloro, bromo or iodo. Alkyl substituents containing up to 18 carbon atoms are suitably radicals such as methyl, 10 ethyl, propyl, butyl, pentyl, hexyl and octyl, stearyl and also corresponding branched isomers;

C

2

-C

4 aIkyl and isooctyl are preferred.

C

1

-C

4 Alkyl-substituted phenyl or naphthyl which preferably contain I to 3, more preferably 1 or 2, alkyl groups is e.g. o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 15 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6 ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methyl naphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

C

1

-C

4 Alkyl-substituted cyclohexyl which preferably contains 1 to 3, more preferably I or 2, 20 branched or unbranched alkyl group radicals, is e.g. cyclopentyl, methyl cyclopentyl, dime thylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl or tert butylcyclohexyl. A mono-, di-, tri- or tetra-valent metal cation is preferably an alkali metal, alkaline earth metal, 25 heavy metal or aluminium cation, for example Na , K+, Mg , Ca , Ba , Zn , Al , or Ti 4 "* . Ca is particularly preferred.

WO 2004/101666 PCT/EP2004/050744 -19 Preferred compounds of formula I are those containing at least one tert-butyl group as R 1 or

R

2 . Very particularly preferred compounds are those, wherein R 1 and R 2 are at the same time tert-butyl. 5 n is preferably 1 or 2 and, in particular 1. For example the phosphonate is of formula Ila 0 HO /(CH 2 )n OR 1 04 (Ila), R12 OR 1 03 10 wherein

R

1 01 is H, isopropyl, tert-butyl, cyclohexyl, or cyclohexyl which is substituted by 1-3 CI-C 4 alkyl groups,

R

1 02 is hydrogen, C-C 4 alkyl, cyclohexyl, or cyclohexyl which is substituted by 1-3 C-C 4 alkyl groups, 15 R 1 03 is C-C2alkyl, unsubstituted or C-C 4 alkyl-substituted phenyl or naphthyl,

R

1 04 is hydrogen, C-Coalkyl, unsubstituted or C 1

-C

4 alkyl-substituted phenyl or naphthyl; or Mr / r; Mr is an r-valent metal cation, r is 1, 2, 3 or 4; and n is 1, 2, 3, 4,5 or 6. 20 Preferably the phosphonate is of formula 111, IV, V, VI or VII HGC

CH

3

H

3 C 0 HO C P-OCH 2

CH

3 _ H2 I

H

3 C OCH2CH3

H

3 C CH 3 WO 2004/101666 PCT/EP2004/050744 -20

H

3 C CH 3 CH 3 H 3C O HO C- P- C- 2+ OR 10 - H 2

H

3 C OCH 2

CH

3 / P-OR 101 H C CH 3 O (IV) 2

OR,

0 , OR 101 --- OR-OR, (VI)' 5 wherein the R 1 01 are each independently of one another hydrogen or M+ / r. Some of the compounds of formulae 11, Ila, III, IV, V, VI, VII and VIII are commercially available or can be prepared by standard processes, as for example described in US 4 778 840. 10 The phosphinates are of the formula XX R201 //0 P (XX) R2o2 OH 15 wherein R20 1 is hydrogen, C-C2alkyl, phenyl or C-C 4 alkyl substituted phenyl; biphenyl, naphthyl, -CH 2 -O-C-C20alkyl or -CH 2 -S-C-C20alkyl, WO 2004/101666 PCT/EP2004/050744 -21

R

2 02 is C 1

-C

2 0 alkyl, phenyl or C 1

-C

4 alkyl substituted phenyl; biphenyl, naphthyl,

-CH

2

-O-C

1 -C20alkyl or -CH 2

-S-C

1 -C2oalkyl, or R 1 and R 2 together are a radical of the formula XXI 5 R;CH-O-CH-0-CH-R (XXI)

R

2 04 wherein

R

2 03, R 2 04 and R 2 05 independently of each other are C 1 -C2oalkyl, phenyl or C 1

-C

4 alkyl substituted phenyl. 10 0 H A specific phosphinate is for example compound 101 Typical phosphites useful in the instant invention are for example listed below. 15 For example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4 methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di 20 tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butyl phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, 6-isooctyloxy-2,4,8,10 tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10 tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2',2" 25 nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2 ethylhexyl(3,3',5,5'-tetra-tert-butyl- 1, 1'-biphenyl-2,2'-diyl)phosph ite, 5-butyl-5-ethyl-2-(2,4,6 tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

WO 2004/101666 PCT/EP2004/050744 - 22 Especially preferred are the following phosphites: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos" 168, Ciba Specialty Chemicals), tris(nonyl 5 phenyl) phosphite,

(CH

3

)

3 C C(CH A) (CHC C(CHA o -~ 0 (A) H 3 C-CH /P-F P-0-CH 2

CH

2 N (B) 0 0 CCH(CH3A3

(CH(C

3 C C(CHHCC - 0 P- - C H PH(C-HO)C- -N (B (CH3CH3 C(CHCC) 10 /0 0\

(CH

3

)

3 C - -P 3 C(CH) / C( C(CH( 3 (CHC 0 0 H3 3 C / O-'P P-O CH 3 () (CHal (CHC 0-' 0 - 3 (E)

C(CH

3

)

3

(CH

3

)

3

C

WO 2004/101666 PCT/EP2004/050744 -23

CH

3 I

H

3

C-C-CH

3 0 0 (F) H 3 7 C.;-O-P P-0-CH 3 3 |--P-OCH2 CH3 (G). C CJC

CH

3

CH

3 2 The masterbatch of the present invention is prepared by melt mixing a polyester with a branching and/or chain coupling agent. Melt mixing can be performed using methods well 5 known in the art. Preferably, melt mixing is achieved by continuous extrusion equipment such as twin screw extruders, single screw extruders, other multiple screw extruders, such as Buss kneaders and Farell mixers. Preferably, melt mixing is performed so as to maintain the polyester at its melt processing temperature. 10 In preparing the masterbatch, one or more polyesters and one or more branching and/or chain coupling agents may be used. Consequently in another aspect, the present invention provides a method of preparing a polyester masterbatch comprising melt mixing a polyester with a branching and/or chain 15 coupling agent such that the branching and/or chain coupling agent is dispersed within the polymeric matrix of the polyester, wherein the polyester has a melt processing temperature of 250 0 C or less. A specific embodiment of the invention is a process for melt processing a base polyester 20 comprising: (1) formation of a molten mixture comprising (i) a major amount of a first resin composition comprising base polyester and from 0 up to about 1 weight % of the chain coupling agent and/or branching agent, and (ii) a minor amount of the above described polyester master batch composition 25 comprising at least about 50 weight % polyester resin and greater than about 2 weight % of a chain coupling agent and/or branching agent, wherein the relative amounts of (i) and (ii) are such that said molten mixture comprises from about 0.1 wt% to about 1 wt% of said chain coupling agent and/or branching agent; WO 2004/101666 PCT/EP2004/050744 -24 (2) melt processing of the resultant molten mixture under conditions of time and temperature sufficient to modify the base polyester; and (3) direct fabrication of the molten mixture into a film, sheet, injection molded article, fiber or non-woven. 5 Suitable melt processing conditions are described above. The term "direct fabrication" as used herein should be understood to mean that the molten mixture of base polymer and masterbatch is not first converted to powder or pellets for subsequent remelting in a later fabrication of desired articles, but is instead immediately melt 10 fabricated into such article. The definitions and preferences given above for the composition also apply for the process of manufacturing a polyester master batch. 15 The process of preparing the masterbatch can be performed in one or more processing steps. Moreover, all the ingredients of the masterbatch can be mixed before and metered into an extruder, or metered separately. 20 Another option is the extrusion of one part of the masterbatch, and adding the other parts of the masterbatch later in the process. For example, the carrier polyester is metered into the extruder right from the beginning, and the active ingredients are metered in higher extrusion zones. 25 The masterbatch can be supplemented to a solid-state polycondensation for increasing the molecular weight of the carrier polyester. This is useful for adjusting the molecular weight of the polyester within the masterbatch to the molecular weight of the base polyester to be modified. 30 The masterbatches of the present invention may be used to modify a base polyester by melt mixing the base polyester with the masterbatch. A single masterbatch or a combination of masterbatches may be used. By this method, the polyester is modified through reaction with the branching agent to introduce branching within, or chain extend, the polyester chain WO 2004/101666 PCT/EP2004/050744 -25 structure. Typically, the base polyester will have a higher melt processing temperature than the masterbatch carrier polyester. Accordingly, at these higher temperatures the branching and/or chain coupling agent will have a greater tendency to react with the base polyester to chain extend it, and/or introduce branching points. 5 If desired, the modified polyester can be subjected to further processing, such as a solid state condensation process, to increase its molecular weight. Alternatively, where a chain coupling agent has not been used, the modified polyester may be subsequently melt mixed with a chain coupling agent to increase its molecular weight. Preferably, the base polyester is 10 melt mixed with a masterbatch comprising a chain coupling agent. High melt strength polyesters may be obtained by melt mixing a base polyester with a polyol branching agent and a polyfunctional acid anhydride. In one preferred embodiment of the present invention a base polyester is modified using a combination of masterbatches 15 prepared in accordance with the present invention comprising a polyol branching agent and a polyfunctional acid anhydride, respectively. In another preferred embodiment of the invention, the masterbatch comprises a combination of a polyol branching agent and a polyfunctional acid anhydride. By combining these two 20 agents in the masterbatch, the need for two separate masterbatches is conveniently avoided. It is believed that by selecting the carrier polyester, the polyol and the anhydride in accordance with the present invention, the masterbatch may be prepared without significant reaction between the carrier polyester, the polyol and the anhydride occurring. Accordingly, such a masterbatch advantageously comprises both a polyol branching agent and a 25 polyfunctional acid anhydride dispersed within a polymeric matrix of polyester. Other chain coupling agents may also be combined with a polyol branching agent in a masterbatch according to the present invention. 30 Where a masterbatch comprising a combination of branching and/or chain coupling agents is prepared, it may be that the branching and/or chain coupling agents react with each other to some extent during melt mixing. In this case, the resulting reaction product(s) may also be a branching and/or chain coupling agent(s) in its own right and therefore be a suitable agent(s) to act as a branching and/or chain coupling agent in accordance with the present invention.

WO 2004/101666 PCT/EP2004/050744 -26 In a further aspect, the present invention provides a method for modifying a polyester comprising melt mixing the polyester at a temperature above 2500 C together with a polyester masterbatch as described above. 5 Polyesters that can be modified by the method of the present invention are preferably thermoplastic polyesters and include all heterochain macromolecular compounds that possess repeat carboxylate ester groups in the backbone of the polymer. Also suitable for use as polyesters are polymers which contain esters on side chains or grafts, copolymers 10 which incorporate monomers having carboxylate ester groups (in the backbone or as side groups or grafts) and derivatives of polyesters which retain the carboxylate ester groups (in the backbone or side groups or grafts). The polyesters may also contain acids, anhydrides and alcohols in the backbone or as side chains (eg acrylic and methacrylic containing polymers). Preferred polyesters include poly(ethylene terephthalate) (PET), poly(butylene 15 terephthalate) (PBT), poly(ethylene naphthalate) (PEN), poly(tri-methylene terephthalate) (PTT), copolymers of PET, copolymers of PBT, copolymers of PEN, liquid crystalline polyesters (LCP) and polyesters of carbonic acid (polycarbonates) and blends of one or more thereof. 20 Copolymers of PET include variants containing other comonomers. For example, the ethane diol may be replaced with other diols such as cyclohexane dimethanol to form a PET copolymer. Copolymers of PBT include variants containing other comonomers. Copolymers of PEN include variants containing other comonomers. Copolymers of PEN/PET are also useful in the present invention. These copolymers may be blended with other polyesters. 25 Liquid crystalline polyesters include poly(hydroxybenzoic acid) (HBA), poly(2-hydroxy-6 naphthoic acid) and poly(naphthalene terephthalate) (PNT) which is a copolymer of 2,6 dihydroxynaphthalene and terephthalic acid. Copolymers of liquid crystal polyesters with other polyesters are also suitable. 30 Side chain or graft ester, acid or alcohol containing polymers include: poly(methyl methacrylate) (or other methacrylates or acrylates); poly(methacrylic acid); poly(acrylic acid); poly(hydroxyethyl methacrylate), starch, cellulose etc.

WO 2004/101666 PCT/EP2004/050744 - 27 Copolymers or graft copolymers containing acid, ester or alcohol groups include ethylene co-vinyl acetate, ethylene co-vinyl alcohol, ethylene co-acrylic acid, maleic anhydride grafted polyethylene, polypropylene etc. 5 Where the masterbatch of the present invention comprises a polyol branching agent and a polyfunctional acid anhydride, it is preferred that the molar ratio of the polyfunctional acid anhydride to the polyol branching agent, or precursor thereto, is in the range of 0.5:1 to (10 x C):1, where C is the number of moles of hydroxy groups per mole of polyol branching agent. It is particularly preferred that the molar ratio of polyfunctional acid anhydride to 10 polyol, or precursor thereto, is in the range of from 2:1 to (2 x C):1. In order to clearly demonstrate the calculation of the molar ratio the following example is provided: 15 Example Calculation: Masterbatch composition comprising pyromellitic dianhydride (PMDA) and pentaerythritol. PMDA = tetra functional anhydride Pentaerythritol = tetra functional alcohol The polyol, pentaerythritol, used in this example has a functionality of 4, therefore C=4. 20 The mole ratio of PMDA to pentaerythritol is therefore in the range of from 0.2:1 to 40 (10 x 4):1, with the preferred mole ratio of PMDA to pentaerythritol being in the range of from 2:1 to 8 (2 x 4):1. Accordingly, a masterbatch comprising 2.5 weight percent of pentaerythritol would comprise PMDA preferably in an amount ranging from about 8 weight percent to about 25 32 weight percent (ie in a mole ratio ranging from 2:1 to 8:1). Where the masterbatch of the present invention only comprises one of a polyfunctional acid anhydride or a polyol branching agent, but the masterbatch is used to modify a base polyester where both a polyol and an anhydride are used, the molar ratio of polyol branching 30 agent and polyfunctional acid anhydride is also preferably as previously defined. The masterbatch in accordance with the present invention may comprise other additives such as fillers, pigments, stabilizers, blowing agents, nucleating agents etc. For examples of these and other suitable additional additives see US 6,469,078.

WO 2004/101666 PCT/EP2004/050744 - 28 The masterbatch may also comprise additives, such as heat stabilizers, light stabilizers, processing stabilizers, metal deactivators, nucleating agents and optical brighteners. Examples are given below. 5 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di 10 methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu tyl-4-isobutylphenol, 2,6-dicydopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl phenol, 2,6-dioctadecyl-4-methyl phenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1' 15 methylheptadec-1'-yI)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures there of. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4 20 nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl hydroqu inone, 2,6-diphenyl-4-octade cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu 25 tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxypheny stearate, bis(3,5-di-tert-butyl-4-hy droxyphenyl) adipate. 1.4. Tocopherols, for example a-tocopherol, B-tocopherol, y-tocopherol, 6-tocopherol and mixtures thereof (vitamin E). 30 1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2 methylphenol), 4,4'-thiobis(3,6-d i-sec-amyl phenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

WO 2004/101666 PCT/EP2004/050744 - 29 1.6. Al kvlidenebisphenols, for example 2,2Z-methylenebis(6-tert-butyl-4-methy phenol), 2.2' methylenebis(6-tert-butyl-4-ethy phenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl ) phenol], 2,2'-methyleneb is(4-methyl-6-cyclohexyl phenol), 2,2'-methylenebis(6-nonyl-4 5 methylphenol), 2,2'-methylene bis(4,6-di-tert-buty phenol), 2,2'-ethyl idenebis(4,6-di-tert-butyl phenol), 2,2'-ethylideneb is(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben zyl)-4-nonylphenol], 2,2'-methylenebis[6-(otca-d imethylbenzyl)-4-nonyl phenol], 4,4'-methy lenebis(2,6-di-tert-butylphenol), 4,4'-methyle nebis(6-tert-butyl-2-methyl phenol), 1,1 -bis(5-tert butyl-.4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4 10 methylphenol, 1,1 ,3-tris(5-tert-burtyl-4-hydroxy-2-methylphenyl)butane, 1,1 -bis(5-tert-butyl-4 hydroxy-2-methylphenyl )-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicydopenta diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha late, 1,1 -bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe 15 nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecyl merc-aptobutane, 1, 1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane. 1.7. 0-, N- and S-benzvt compound , for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy 20 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyi)amine, bis(4 tert-butyl-3-hydroxy-2,6-dimethylbenzyl )dithioterephthalate, bis(3,5-d i-tert-butyl-4-hydroxy benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate. 1.8. Hydroxvbenzvlated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy 25 droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di dodecylmercaptoethyl-2,2-bis(3,5-d i-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1I,3,3-te tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate. 1.9. Aromatic hydroxybengyl compounds, for example I ,3,5-tris(3,5-di-tert-butyl-4-hydroxy 30 benzyl)-2,4,6-trimethyl benzene, I ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2, 3,5,6-tetrame thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. 1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy anilino)- 1,3, 5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- I 3,5-tri- WO 2004/101666 PCT/EP2004/050744 - 30 azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyben zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy 5 phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso cyanurate. 1.11. Benzvlphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyphospho nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy 10 droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. 15 1.13. Esters of B-(3.5-di-tert-butyl-4-hydroxvphenl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9 nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy 20 droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of f-(5-tert-butyl-4-hydroxy-3-methylphenvl)propionic acid with mono- or poly hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi 25 ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl olpropane, 4-hydroxymethyl-I-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] 30 undecane. 1.15. Esters of p-(3,5-dicyclohexyl-4-hydroxyphenyi)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri- WO 2004/101666 PCT/EP2004/050744 -31 ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane. 5 1.16. Esters of 3,5-di-tert-butyl-4-hydroxVphenvl acetic acid with mono- or polyhydric alco hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy 10 droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.17. Amides of p-(3,5-di-tert-butyl-4-hydroxypheny)propionic acid e.g. N,N'-bis(3,5-di-tert butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy 15 drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethy]oxamide (Nau gard"XL-1, supplied by Uniroyal). 1.18. Ascorbic acid (vitamin C) 20 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu tyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3 methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy dohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phe 25 nyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N' phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-I-naphthylamine, N-phenyl-2-naph thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl 30 aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4 octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra methyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)aminolethane, 1,2-bis(phenyl amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethyl butyl)phenyl]amine, tert-octylated N- WO 2004/101666 PCT/EP2004/050744 - 32 phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro 5 3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert butylltert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetra methylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethypiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. 10 2. UV absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)benzo triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe 15 nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2' hydroxy-4'-octyloxypheny)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(ac,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5' 20 (2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2 methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy 25 phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1,1,3,3 tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH 2 CH -COO-CH 2

CH

2 -] , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri 30 azol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl] benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(o,-dimethylbenzyl)phenyl]ben zotriazole.

WO 2004/101666 PCT/EP2004/050744 - 33 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl 5 salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate. 10 2.4. Acrylates, for example ethyl a-cyano-pP-diphenylacrylate, isooctyl a-cyano-@,P-diphe nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinna mate, butyl ax-cyano- -methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycin namate and N-( -carbomethoxy- -cyanovinyl)-2-methylindoline. 15 2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethyl butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe 20 nylundecylketoxime, nickel complexes of I -phenyl-4-lauroyl-5-hydroxypyrazole, with or with out additional ligands. 2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 25 bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperi dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl) 2,2,6,6-tetramethy-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetra 30 methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrame thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)succi- WO 2004/101666 PCT/EP2004/050744 -34 nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n butylamino-2,2,6,6-tetramethypiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) 5 1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetrame thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr rolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6 10 dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-tri chloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6 15 pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1 -oxa-3,8-di aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa 3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4 piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetrame thyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 20 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4 piperidyl)]siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy 25 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 30 2.8. 2-(2-Hydroxvphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl) 1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4 methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- WO 2004/101666 PCT/EP2004/050744 - 35 1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2 [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2 hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4 (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) 5 1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hy droxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hy droxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl 1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4 10 dimethylphenyl)-1,3,5-triazine. 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyoyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl 15 dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropiony dihydrazide. 4. HydroxVlamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, NN 20 dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N -hexadecyl-N-octadecylhydrox ylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 5. Nitrones, for example N -benzyl-alpha-pheny nitrone, N-ethyl-al pha-methylnitrone, N-octyl 25 alpha-heptylnitrone, N-lauryl-al pha-undecyl nitrone, N-tetradecyl-alpha-tridecylnitrone, N hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecynitrone, N-heptadecyl-alpha-hepta decylnitrone, N-octadecyl-alpha-hexadecynitrone, nitrone derived from N,N-dialkylhydroxyl amine derived from hydrogenated tallow amine. 30 6. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate. 7. Peroxide scavengers, for example esters of P-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- WO 2004/101666 PCT/EP2004/050744 - 36 benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(p dodecylmercapto)propionate. 8. Polyamide stabilisers, for example copper salts in combination with iodides and/or phos 5 phorus compounds and salts of divalent manganese. 9. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, 10 zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 10. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, 15 alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzyli dene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol. 20 11. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers. 25 12. Other additives, for example plasti cisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents. 13. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; 30 U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy) phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl] benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7- WO 2004/101666 PCT/EP2004/050744 - 37 di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzo furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphe nyl)-5,7-di-tert-butylbenzofuran-2-one. 5 In a method of the present invention, a base polyester is modified by melt mixing the polyester with the masterbatch of the present invention. Condensation or transesterification catalysts may also be added to the melt mixing process in order to enhance the reaction rate of the polyol branching agent, and if present chain coupling agent, with the base polyester. 10 In a specific embodiment the masterbatch composition also includes a condensation or transesterification catalyst. Typical transesterification or condensation catalysts include, but are not limited to, Lewis acids such as antimony trioxide, titanium oxide and dibutyltin dilaurate. 15 Other additives which may be incorporated with the masterbatch during melt mixing to modify the polyester include monofunctional additives to act as blockers so as to control the degree of chain extension and/or branching, as described by Edelman et al. in US 4,1611,579, for the production of controlled branched polyesters by a combination of condensation/solid 20 state polycondensation. Examples of suitable monofunctional additives include acids (eg. benzoic acid) or anhydrides or esters thereof (eg. benzoic acid anhydride, acetic anhydride). Monofunctional alcohols may also be used. Additives (eg. carbonates) may be incorporated to enhance foaming of the modified polyester where foamed products are required. Gases may also be injected into the molten 25 polyester during melt mixing in order to achieve physical rather than chemical foaming. In a method of the present invention a base polyester is modified by melt mixing it with the masterbatch of the present invention. Melt mixing may conveniently be achieved by continuous extrusion equipment such as twin screw extruders, single screw extruders, other 30 multiple screw extruders and Farell mixers. Semi-continuous or batch polymer processing equipment may also be used to achieve melt mixing. Suitable equipment includes injection moulders, Banbury mixers and batch mixers. Static mixing equipment may include pipes containing fixed obstacles arranged in such a way as to favour the subdivision and WO 2004/101666 PCT/EP2004/050744 - 38 recombination of the flow to thoroughly mix the masterbatch, and any other additives or agents used, with the polyester. The molecular structure of a modified polyester formed by the method of the present 5 invention may exhibit a degree of branching. As discussed above, it may also be necessary to increase the molecular weight of the modified polyester to effect an increase in the polymers melt strength and melt viscosity. This can conveniently be achieved in a number of ways, for example the modified polyester may be subjected to a solid state condensation process, or a chain coupling agent may be used in the modification process itself. 10 Modified polyesters that exhibit improved melt strength may be advantageously used in blown film applications where higher melt viscosity, viscoelasticity and strength in the melt allow higher blow up ratios, greater biaxial orientation and faster through-puts while maintaining bubble stability. 15 The increased melt strength can be easily detected by an increase of the diameter of the polyester strand at the die of the extruder (i.e. die swell), compared to unmodified polyester. Further apparatus/parameters for characterizing the melt strength are: Goettfert Rheotens, uniaxial elongational viscosity and dynamic rheology. 20 The improved melt rheology of such modified polyester advantageously allows the reduction in processing steps and improvement in material properties. The improvements in melt rheology can allow the modified polyesters to be processed without prior drying, and facilitate the blow molding of polyesters. In particular, the improvements in the melt rheology facilitate 25 stretch blow molding, facilitate the foaming of polyesters, enhance adhesion of the polyester to polar fillers such as those used in glass reinforced polyesters, and permit polyesters to be thermoformed with greater ease. The use of the masterbatch composition according to the invention is beneficial within 30 several plastic applications, for instance: e Beverage or cosmetic articles bottles " Film packaging for food or non-food e Sheets (e.g. thermoformable) for packaging (trays), construction or automotive applications WO 2004/101666 PCT/EP2004/050744 - 39 e Injection molded articles e Belts or strappings " Profiles or pipes e Drums 5 - Bottle crates e Textiles and non-wovens The benefits caused by the instant masterbatch compositions are for example based on following effects: 10 e Higher productivity according to adjusted melt rheology of the polyester (simpler processing) e Reaching technical feasibility of performing extrusion blow molding or extrusion blowing films with modified polyesters e Increasing molecular weight or/and melt strength without discoloration or gel 15 formation e Increasing long-term thermal stability by initially higher molecular weight e Increasing mechanical properties (e.g. better tensile strength, higher elongation at break, higher burst pressure of bottles) * Improved impact properties (e.g. impact strength at ambient and temperature of 20 40 0 C, which is for example important for achieving better drop test result of frozen food articles in a tray) e Enhanced gas barrier (e.g. 0 2, CO 2 ) by higher molecular weight and modified polymer chain structure * Superior thermal dimensional stability by higher molecular weight and modified 25 polymer chain structure e processing polyester without pre-drying * compensating loss of molecular weight (1.V. loss) during melt processing e up-grading lower value PET grades during processing a recycling of degraded PET (post consumer or production waste) 30 * pultrusion of PET-fibers e matching processing properties of C-PET (crystallizable) e replacing e.g. polycarbonate by modified polyesters WO 2004/101666 PCT/EP2004/050744 - 40 The masterbatches of the present invention may be preferably used in the following applications. Modification of bottle grade (IV - 0.80) or recycle PET to produce a polyester suitable for thermoforming. Modification of recycle PET to produce a polyester suitable for reforming into bottles. Modification of bottle or recycle PET to produce a polyester suitable 5 for extrusion blow molding. Modification of bottle or recycle PET to produce a polyester suitable for foaming. Consequently a further aspect of the invention is the use of a polyester masterbatch composition as described above for the modification of polyesters. 10 The present invention is further described with reference to the following non-limiting examples. EXAMPLES 15 Preparation of Masterbatches: A) Masterbatches comprising pentaerythritol or pyromellitic dianhydride 20 Masterbatches were prepared using a Japanese Steel Works (JSW) TEX 30 twin screw extruded. The carrier polyester used was PETG (Eastar 6763). Prior to preparing the masterbatches, the PETG was dried in a dehumidifier dryer at 75*C for 2.5 days. The polyol branching agent used was pentaerythritol, and pyromellitic dianhydride was used as a coupling/branching agent. Prior to preparing the masterbatches the pentaerythritol and 25 pyromellitic dianhydride were dried in separate vacuum ovens at 150 0 C for 3 days. The PETG was melt mixed with a metered amount of the pentaerythritol or pyromellitic dianhydride and extruded in the form of a strand which was cooled under dry nitrogen then pelletized. The temperature of the barrels of the extruder were set at 170 (feed section), 180, 30 180, 180, 180, 180, 180, 180, 180, 180*C, with a 10mm diameter rod die set at 180 0 C. The resulting masterbatches contained 5 weight percent, and 20 weight percent of pentaerythritol and pyromellitic dianhydride, respectively. For experimental data see Table 1.

WO 2004/101666 PCT/EP2004/050744 -41 B) Masterbatch comprising pentaerthritol and pyromellitic dianhydride and a catalyst A masterbatch was prepared using a Japanese Steel Works (JSW) TEX 30 twin screw extruded. The carrier polyester used was PETG (Eastar 6763). Prior to preparing the 5 masterbatch, the PETG was dried for 50 hours at 85"C in a nitrogen forced oven. The polyol branching agent used was pentaerythritol, and pyromellitic dianhydride was used as a branching/chain coupling agent. A transesterification catalyst (antimony trioxide) was also included in the masterbatch. Prior to preparing the masterbatch, the pentaerythritol, pyromellitic dianhydride and the antimony trioxide were dried in a vaccum over overnight at 10 120*C. To assist in the introduction of the agents to the PETG during the melt mixing step, the agents were blended with a small amount of PET powder (BK2180, melt processing temperature of about 270"C). The PETG was melt mixed with a metered amount of aforementioned agents and extruded in 15 the form of a strand which was cooled under dry nitrogen then pelletized. The temperature of the barrels of the extruder were set at 170 (feed section), 180, 180, 180, 180, 180, 180, 180, 180, 1800C, with a 10mm diameter rod die set at 1800C. The resulting masterbatch contained 2.72 weight percent of pyromellitic dianhydride, 0.33 weight percent of pentaerythritol and 0.04 weight percent of antimony trioxide. For experimental data see 20 Table 2.

WO 2004/101666 PCTIEP20011050744 - 42 (D E CC C) a- LZ m 2.90U 60 9 =U3) E -V CA 0 7 0 cL~E E~ co. C 2 0 C (D(0( 50 E D C C 0-I' C~ N 0 E E 4) L. 0 m L. 00 II 0)c x C) aU ) CO 0) -> C- 0 x CDx 0 EU (U E m 0 0, 0.C CC co 0 02 a Cj)L a CON 00 .2 ,2 CD (MU 4 a)w (f) L LA 0 WO 2004/101666 PCT/EP2004/050744 -43 Modification of a base polyester using the masterbatches prepared in EX-1 to EX-3 A base polyester (BK3180, a bottle grade PET having a melt processing temperature of about 270 0 C and an IV = 0.82dL/g) was modified using masterbatches prepared in EX-1 and 5 Ex-2. Prior to modifying the base polyester, it was dried overnight in a dehumidifier drier at 130"C. The PETG masterbatches, Ex-1 and Ex-2, were dried for 48 hours at 85 0 C under nitrogen. The base polyester was melt mixed with a metered amount of a blend of masterbatches Ex-1 10 and Ex-2 to afford a concentration of the agents in the base polyester of 0.25 weight percent pyromellitic dianhydride, with an 8:1 molar ratio of pyromellitic dianhydride to pentaerythritol (i.e. 0.0194 weight percent of pentaerythritol). The temperature profile of the extruder was: 260*C, 280*C (by 10), the die used was a 10mm Brabender strand die. The extrudate exhibited a significant amount of die swell, indicating than an appreciable amount of chain 15 branching/coupling has occurred. For experimental data see Table 3. A base polyester (Shinpet 5015W, a bottle grade PET having a melt processing temperature of about 270 0 C and an IV = 0.75dL/g) was modified using the masterbatch prepared in Ex-3. Prior to modifying the base polyester, it was dried overnight at 130*C under nitrogen. The 20 PETG masterbatch, EX-3 was dried for 48 hours at 85 0 C under nitrogen. The base polyester was melt mixed with a metered amount of masterbatch Ex-3 to afford a concentration of the agents in the base polyester of 0.27 weight percent pyromellitic dianhydride, 0.03 weight percent pentaerythritol and 0.004 weight percent of antimony 25 trioxide. The temperature profile of the extruder was: 260*C, 280*C (by 10), the die used was a 10mm Brabender strand die. The extrudate exhibited a significant amount of die swell, indicating that an appreciable amount of chain branch/coupling has occurred. For example experimental data see Table 4.

WO 2004/101666 PCT/EP2004/050744 - 44 C CM E _3": o m -0m 0 oO~ u Q~ o be 0 00 0 a- in in (o 0 ac -O 0 ov ___ 0 2 " 0a E) co U)1 1-5 P c (D~j C) cc co a ) C.) E a) 0)0 w 0 -oo C U)) X U)U)Oco W wjC .0 g. c c 0 (L) C). C 0 .u 002- 0 eq 04 E INE <:~ 0006 0 0) 0D 0 (D. CLCLO..O. <) m4 C<~ _: C',0 0 0) 4 o)C 0 < 0.- r_ 0(0 0 w o o0 c U) .0 e 0) .0 c m m V m m CLO 00 0) LA .2 m UJ> 0 __ .0 2 C140 2i C CU U 0 <C (f) C-) C w 0 1W WO 2004/101666 PCT/EP2004/050744 -45 Analysis of the masterbatches prepared in Ex-1 and Ex-2 by NMR spectroscopy Sample Preparation: 5 A sample of PETG (30 mg, Eastar 6763), as a control, was dissolved in CDCl 3 (0.5 mL), after dissolution the mixture was transferred to an NMR tube and an excess of trichloroacetyl isocyanate (10 pL, 6.3 mg, 3.36 mmol) was added. The 'H NMR spectrum was recorded at room temperature on a Bruker DRX 500 operating at 500 MHz. 1 H NMR (CDCl 3 , ppm, ): 8.05 (M, 99H, ArH), 8.50 (m, 0.30H, NH Alcohol), 8.65 (s. 0.08H, NH Alcohol), 10.36 (s, 1H, 10 NH Acid). A sample of masterbatch EX-1 (pyromellitic dianhydride) (30 mg) ws dissolved in CDCl 3 (0.5 mL), after dissolution the mixture was filtered and transferred to an NMR tube and an excess of trichloroacetyl isocyanate (10 paL, 6.3 mg, 3.36 mmol) was added. The 'H NMR 15 spectrum was recorded at room temperature on a Bruker DRX 500 operating at 500 MHz. 'H NMR (CDCl 3 , ppm, 8): 8.05 (m, 71H, ArH), 8.50 (m, 0.10H, NH Alcohol), 10.36 (s, 1H, NH Acid). A sample of masterbatch EX-2 (pentaerythritol) (30 mg) was dissolved in CDC1 3 (0.5 mL), 20 after dissolution the mixture was transferred to an NMR tube and an excess of trichloroacetyl isocyanate (10 pL, 6.3 mg, 3.36 mmol) was added. The 'H NMR spectrum was recorded at room temperature on a Bruker DRX 500 operating a 500 MHz. 1 H NMR (CDC 3 , ppm, 5): 8.05 (m, 85H, ArH), 8.55 (m, 0.30H, NH Alcohol), 10.36 (s, 1H, NH Acid). 25 Results: Addition of trichloroacetyl isocyanate (TAI) to a chloroform solution of PETG gives rise to a number of additional peaks in the 1 H NMR spectrum which occur at 8 10.36, 8.65 and 8.50 ppm. The signal at 8 10.36 ppm has been assigned to the adduct resulting from the 30 reaction between TAI and the acid end groups of PETG. The other two signals at 8 8.65.

WO 2004/101666 PCT/EP2004/050744 -46 C) Preparation of masterbatches comprising polyols or PMDA The following examples show that both low melting (trimethylolpropane mp 600C) and high melting polyols (pentaerythritol mp 255 *C) may used to form PETG masterbatches when a low processing temperature (170 *C) is used. 5 Masterbatches were prepared using a Brabender single screw extruder (19mm diameter screw with compression ratio-3:1 and fitted with slotted mixing head) with, L/D=25:1, three heated zones and a 6mm rod die. The low temperature profile had the three heated zones at 160 *C, 170 *C, 1700C and die at 170 *C. The high temperature profile had the three 10 heated zones at 260 *C, 270 *C, 270"C and die at 270 "C. A nitrogen blanket was maintained over the feed throat. Moisture levels were determined with a Arizona Instruments Computrac 3000 Moisture Analyzer on samples heated at 80*C. 15 The carrier polyester used was PETG (Eastar 6763). Prior to preparing the masterbatches, the PETG pellets were dried in a vacuum oven at 75 *C for 48 hrs (moisture level after drying was 55 ppm H 2 0, melt flow index at 270 *C was 18.35 g/10min). PETG powder was dried in vaccum oven at 75C for 3 hrs (moisture level after drying was 215ppm H 2 0, melt flow index 20 at 200C was 1.13 g/10min). Prior to preparing the masterbatches the PMDA and pentaerythritol were dried in a vacuum oven at 100*C for 15 hours. Trimethylolpropane was used as received. The PETG was mixed with a weighed amount of the polyol or PMDA and extruded in the 25 form of a strand, which was cooled under dry nitrogen then pelletized. The temperature of the barrel of the extruder was set at as indicated in the Table 5-10. For experimental data see Tables 5-10.

WO 2004/101666 PCT/EP2004/050744 -47 Table 5. Formation of masterbatch at 170*C with pentaeryithritol (Penta) Example *C rpm torq pressure throughput Drop Time MFI Additive Additive psi g/kg g/10min % Used control 170 10 1315 93 369.6 147.56 1.3 0 none EX6 170 10 1213 91 299.9 181.02 1.2 0.3 Penta EX7 170 10 113092 314 209.85 1.35 1 Penta Table 6. Attempted formation of masterbatch at 270*C with pentaeryithritol (Penta) Example *C rpm torq pressure throughput Drop Time MFI Additive Additive psi g/kg g/10min % Used control 270 10 0 0 248 14.41 3.63 0 none CE 270 10 0 0 302.8 9.53 24.52 0.3 Penta CE 270 10 0 0 304.8 4.16 43.89 1 Penta 5 Table 7. Formation of masterbatch at 170*C with trimethylolpropane (TMP) Drop Example *C rpm torq pressure throughput Time MFI Additive Additive psi g/kg g/10min % Used control 170 10 1315 93 369.6 147.56 1.3 0 none EX8 170 10 161863 431 148.25 1.88 0.3 TMP EX9 170 10 102943 287 181.25 1.77 1 TMP Table 8. Attempted formation of masterbatch at 270*C with trimethylolpropane (TMP) Drop Example *C rpm torq pressure throughput Time MFI Additive Additive psi g/kg g/10min % Used control 270 10 0 0 248 14.41 3.63 0 none CE 270 30 0 0 147.2 0.2 67.2 1 TMP WO 2004/101666 PCT/EP2004/050744 -48 Table 9. Formation of masterbatch at 1700C with PMDA Drop Example *C Rpm Torq pressure throughput Time MFI Additive Additive psi g/kg g/10min % Used control 170 10 1315 93 369.6 147.56 1.3 0 none EX10 170 12 1369 78 389.4 159.37 1.22 0.3 PMDA EX11 170 12 1412 83 361.7 171 1.27 1 PMDA EX12 170 15 157694 395.1 173.11 1.65 10 PMDA Table 10. Attempted formation of masterbatch at 270*C with PMDA Drop Example *C Rpm Torq PressureThroughputTime MFI Additive Additive psi g/kg g/10min % Used CE 270 10 0 0 248 14.41 3.63 0 none CE 270 10 0 0 255 15.72 2.76 0.30% PMDA CE 270 10 0 3 191.3 19.03 2.21 0.30% PMDA CE 270 10 0 6 155.9 22.81 1.81 1.00% PMDA 5 D) Preparation of masterbatches comprising different carrier polyester and additives. Intrinsic Viscosity (I.V.): 1g polymer is dissolved in 100g of a mixture of phenol/di-chlorobenzene (1/1). The viscosity 10 of this solution is measured at 30*C in an Ubelode-viscosimeter and extrapolated to give the intrinsic viscosity. Color: Color (b value of the Yellowness Index) is measured according to ASTM D1925 using a 15 Hunter Lab Scan instrument. Melt Flow Rate (MFR): MFR is determined with a Goettfert MP-P according to ISO 1133 at 260*C with 2.16kg weight after pre-drying the polyester. 20 WO 2004/101666 PCT/EP2004/050744 - 49 Materials: All carrier polyesters are dried prior to use (>12h at 60*C in vacuum) Carrier polyester A: 5 Polyester with following composition: 81.8 mol% p-terephthalic acid 18.2 mol% isophthalic acid 96.9% ethylene glycol 3.1% diethylene glycol 10 Commercial product of NanYa Plastics America Inc. The polyester has a melt viscosity of 1315 Pa sec at a shear rate of 100 sec~' at 190*C, measured within Goettfert capillary rheometer "Rheograph 2001"; 10mm capillary length, 1mm capillary diameter. 15 Carrier polyester B: Polyester with following composition: 70.1 mol% p-terephthalic acid 29.9 mol% isophthalic acid 20 92.9% ethylene glycol 7.1% diethylene glycol Commercial Product of NanYa Plastics America Inc. The polyester shows a melt viscosity of 1035 Pa sec at a shear rate of 100 sec' at 200*C, 25 measured within Goettfert capillary rheometer "Rheograph 2001"; 10mm capillary length, 1mm capillary diameter. Carrier polyester C: Poly-F-caprolactone ex Fluka 30 The polyester shows a melt viscosity of 858 Pa sec at a shear rate 100/sec at 160"C (measured within Goettfert capillary rheometer "Rheograph 2001"; 10mm capillary length, 1mm capillary diameter) WO 2004/101666 PCT/EP2004/050744 - 50 Chain coupling agents: PMDA 1 ex Beyo (China) (powder) (melt temperature: 2840C) PMDA 2 ex Beyo (China) (coarse) (melt temperature: 287*C) Allinco@ ex DSM (=dodecahydro-1,1'-carbonyl-bis-azepin-2-one, CAS RN 19494-73-6) 5 Branching agent: Pentaerythrol ex Perstorp (Finland) (melt temperature: 262"C) (=Penta) 10 Further Additives: Irgamod 195 a phosphonate, commercial product of Ciba Specialty Chemicals, Irganox 1222 a phosphonate, commercial product of Ciba Specialty Chemicals, IRGAFOS 12 a phosphite, commercial product of Ciba Specialty Chemicals, IRGAFOS 168 a phosphite, commercial product of Ciba Specialty Chemicals 15 IRGANOX HP136 a lactone, commercial product of Ciba Specialty Chemicals Compound 101: synthesized by standard procedure 0 0 P Compound 102: Di-isooctylphosphinic acid, purchased ex Fluka o CH \ / 8 17 20 HO CH17 Base Polyester (to be modified by masterbatches): All base polyesters are dried prior to use (>12h at 80*C in vacuum) PET D: Polyclear T94 supplied by KoSa Gersthofen 25 PET E: Polyclear RT48 supplied by KoSa Gersthofen PET F: Polyclear RT21 supplied by KoSa Gersthofen PET G1: ICI LaserPlus supplied by ICI WO 2004/101666 PCT/EP2004/050744 - 51 PBT X: Crastin SK605 NC010 supplied by DuPont Examples MB1 to MB23 Producing masterbatch according to procedure A 5 General procedure A: In a twin screw extruder (ZSK 25 from Werner & Pfleiderer) with screws rotating in the same direction, the below mentioned formulations are extruded at a temperature of Tmax = 180*C 10 (heating zone 1 - 6), a throughput of 5 kg/h, 100 rev/min and pelletized in a water bath. The general procedure A is applied to following compositions: Ex.No. Polyester Carrier Chain coupling agent Branching agent Additive Comp A 100%A Comp B 95% A - 5% Irgamod 195 MB1 95% A 5% Penta MB2 90% A 10% PMDA 1 MB3 89% A 10% PMDA 1 1% Penta MB4 88% A 10% PMDA 1 2% Penta MB5 88% A 10% PMDA 1 1% Penta 1% Irgamod 195 MB6 89% B 10% PMDA 1 1% Penta MB7 88% B 10% PMDA 1 1% Penta 1% Irgamod 195 MB8 88% B 10% PMDA 1 - 2% Irgamod 195 MB9 75% B 25% PMDA 1 - MB10 72.5% B 25% PMDA 1 2.5% Penta MB1 1 70% B 25% PMDA 1 2.5% Penta 2.5% Irgamod 195 MB12 70% B 25% PMDA 1 - 5% Irgamod 195 MB13 89% C 10% PMDA 1 1% Penta MB14 88% A 10% PMDA 1 1% Penta 1% Irgafos 168 MB15 88% A 10% PMDA 1 1% Penta 1% Irgafos 12 WO 2004/101666 PCT/EP2004/050744 -52 Ex.No. Polyester Carrier Chain coupling agent Branching agent Additive MB16 90% A 10% Allinco - MB17 89% A 10% Allinco - 1% Irgamod 195 MB18 89% A 10% Allinco 1% Penta MB19 88% A 10% Allinco 1% Penta 1% Irgamod 195 MB20 89% A 10% PMDA 1 1% Penta 1% Irgafos HP136 MB21 89% A 10% PMDA 1 1% Penta 1% compound 101 MB22 89% A 10% PMDA 1 1% Penta 1% compound 102 MB23 89.4% A 10% PMDA 1 0.5% Penta 0.1% Sb 2

O

3 Examples MB24 to MB27 Producing masterbatch according to procedure B 5 General procedure B: In a Buss co-kneader (MDK 140), with a separate transversal screw for extrusion into the die, the below mentioned formulations are extruded at body temperature of 210 0 C, kneader axe and die temperature of both 180*C , a throughput of 400 kg/h, 140 rev/min (kneader axe) and 10 pelletized in a water bath. The general procedure B is applied to following compositions: Ex.No. Polyester Carrier Chain coupling agent Branching agent Additive CompC 100%B MB24 89% B 10% PMDA 1 1% Penta MB25 88% B 10% PMDA 1 1% Penta 1% Irgamod 195 MB26 88% B 10% PMDA I - 2% Irgamod 195 MB27 76% B 20% PMDA 2 2% Penta 2% Irgamod 195 15 WO 2004/101666 PCTIEP2004/050744 - 53 E) Modification of base polymer using the masterbatches: General procedure In a twin screw extruder (ZSK 25 from Werner & Pfleiderer) with screws rotating in the same direction, the below mentioned formulations were extruded at a temperature of Tmax = 5 2800C (heating zone 1 - 6), a throughput of 6 kg/h and 100 rev/min and pelletized in a water bath. The general procedure is applied to the following comparative examples. Ex. Base Additives MFR I.V. Color No. Polyester g/10min dl/g B*-value Comp D 100% E - 62 0.55 0.92 Comp E 100% E 0.2% PMDA 1 25 0,66 9.2 0.02% Penta 0.02% Irgamod 195 Comp F 100% F - 18 0.57 Comp G 100% G1 - 14 0.75 Comp H 100% D - 16 0.76 10 The general procedure is applied to the following examples C1 -C25. Ex. Polyester Master- Equivalent to MFR I.V. Color batch additive composition No. g/10min dl/g B*-value Ex C1 100% E 2% MB15 0.2% PMDA 1 21 0.69 -1.3 0.02% Penta 0.02% Irgamod 195 The performance of the masterbatch MB15 is much better (with regard to decrease of MFR, 15 increase of l.V. and color) compared to the addition of the active ingredients directly (as tested in the comparative example Comp E).

WO 2004/101666 PCT/EP2004/050744 -54 Ex. No. Base Polyester Masterbatch MFR I.V. G/10min dl/g Ex C2 100% D 1% MB2 6.3 0.84 Ex C3 100% D 3% MB2 2.1 0.91 0.6% MB1 Ex C4 100% D 1% MB3 8.7 0.86 Ex C5 100% D 1% MB3 4.3 0.94 0.5% Comp B Ex C6 100% D 1% MB4 9.4 0.82 Ex C7 100% D 1% MB5 8.3 0.86 Ex C8 100% E 3% MB6 11 0.74 Ex C9 100% E 3% MB7 14 0.72 Ex C10 100% E 3% MB8 9.0 0.75 Ex C11 100% G1 1% MB9 7.4 0.80 Ex C12 100% G1 1% MB10 9.0 0.78 Ex C13 100% G1 1% MB11 8.6 0.81 Ex C14 100% G1 1% MB12 11 0.80 Ex C15 100% E 3% MB13 10 0.73 Ex C16 100% E 3% MB14 11 0.75 Ex C17 100% E 3% MB15 9.8 0.75 Ex C18 100% D 3% MB16 15 0.76 Ex C19 100% D 3% MB17 14 0.81 Ex C20 100% D 3% MB18 14 0.82 Ex C21 100% D 3% MB19 13 0.83 Ex C22 100% E 2% MB20 14 0.70 Ex C23 100% E 2% MB21 15 0.71 Ex C24 100% E 2% MB22 15 0.72 Ex C25 100% E 2% MB23 16 0.70 WO 2004/101666 PCT/EP2004/050744 - 55 F) Producing extrusion-blown films General procedure: In a twin screw extruder (Haake TW100, counter-rotating conical screws), the below 5 mentioned formulations are extruded at a temperature of Tmax = 280*C, a throughput of 1.8 kg/h and 60 rev/min into a film blowing die. The general procedure is applied to comparative examples M and N and to the examples D1 and D2 according to the invention. 10 Ex. No. Base Polyester Additives Film thickness Remarks Comp M 100% D Comp N 100% D 0.3% PMDA 1 25.3 pm Yellow film 0.03% Penta Many gels *: extrusion blowing a film was not feasible due to too low melt strength Ex. No. Base Polyester Additives Film thickness Remarks Ex D1 100% D 3% MB3 17.5 pm No discoloration No gels Ex D2 100% D 3% MBS 10.9 pm No discoloration No gels 15

Claims (20)

1. A polyester masterbatch composition comprising a branching and/or a chain coupling agent dispersed within a polymeric matrix of polyester, 5 wherein the polyester has a melt processing temperature of 250*C or less.

2. A polyester masterbatch composition according to claim 1 wherein the agent is a chain branching agent. 10

3. A polyester masterbatch composition according to claim 2 wherein the chain branching agent is a polyol.

4. A polyester masterbatch composition according to claim 1 wherein the agent is a chain coupling agent. 15

5. A polyester masterbatch composition according to claim 4 wherein the chain coupling agent is a dianhydride.

6. A polyester masterbatch composition according to claim 1 wherein the agents are a chain 20 branching agent and a chain coupling agent.

7. A polyester masterbatch composition according to claim 6 wherein the chain branching agent is a polyol and the chain coupling agent is a dianhydride. 25

8. A polyester masterbatch composition according to claim 1 wherein the polyester's melt viscosity and/or the polyesters intrinsic viscosity is reduced or increased by no more than 30 % when it is melt mixed with the branching and/or chain coupling agent.

9. A polyester masterbatch composition according to claim 1 wherein the branching and/or 30 chain coupling agent has a melt temperature which is at least 10 0 C higher than the melt processing temperature of the polyester.

10. A polyester masterbatch composition according to claim 1 wherein the polyester suitable for use in the masterbatch has a melt processing temperature ranging from 150*C to 250*C. WO 2004/101666 PCT/EP2004/050744 -57

11. A polyester masterbatch composition according to claim 1 wherein the polyester suitable for use in the masterbatch has a crystallinity of less than 15 %. 5

12. A polyester masterbatch composition according to claim 1 wherein the polyester suitable for use in the masterbatch is glycol modified poly(ethylene terephthalate) (PETG), poly-c caprolactone, or a copolyester containing greater than about 15% isophthalic units.

13. A polyester masterbatch composition according to claim 1 wherein the branching agent is 10 a polyol, which is present in an amount of from 0.3 to 30 weight percent based on the weight of the polyester masterbatch polymer.

14. A polyester masterbatch composition according to claim 1 wherein the chain coupling agent is present in an amount of from 1 to 60 weight percent based on the weight of the 15 polyester masterbatch polymer.

15. A polyester masterbatch composition according to claim 1, which additionally comprises a phosphite, a phospinate or a phosphonate compound. 20

16. A polyester masterbatch composition according to claim 15 wherein the phosphonate is of formula Ill, IV, V, VI or VII H3O OH 3 H 3 00 HO C P-OCH 2 CH 3 -_ H2 H 3 C OCH 2 CH 3 CH 3 H 3 0 H (111) WO 2004/101666 PCT/EP2004/050744 -58 H 3 C CH 3 HC a /I 2+ OR 1 0 1 HO C-P-O Ca - H 2 H 3 C OCH 2 CH 3 P--- 0R, H 3 C CH 3 (IV) 2 OR OR 0 , \ OR11 VI, P (VII), 5 wherein the R 1 1 are each independently of one another hydrogen or M" / r.

17. A polyester masterbatch composition according to claim 1, which also includes a condensation or transesterification catalyst. 10

18. A method of preparing a polyester masterbatch comprising melt mixing a polyester with a branching and/or chain coupling agent such that the branching and/or chain coupling agent is dispersed within the polymeric matrix of the polyester, wherein the polyester has a melt processing temperature of 250 0 C or less. 15

19. A method for modifying a polyester comprising melt mixing the polyester at a temperature above 2500 C together with a polyester masterbatch according to claim 1.

20. Use of a polyester masterbatch composition according to claim I for the modification of 20 polyesters.