CN1791632A - Polyester masterbatch composition - Google Patents

Abstract

The present invention relates to masterbatches useful for modifying thermoplastic polyesters, in particular to masterbatches comprising dispersed polyol branching agent and/or chain coupling agents, such as for example dianhydrides. The invention also relates to a method for preparing the masterbatches, and to a method for modifying a polyester utilizing the masterbatches. Yet another aspect of the invention is the use of such a masterbatch composition for the modification of polyesters.

Description

Polyester Masterbatch Composition

technical field

The invention relates to a masterbatch for modifying thermoplastic polyester, especially a masterbatch containing dispersed polyol branching agent and/or chain coupling agent. The invention also relates to a method for preparing the masterbatch and a method for carrying out polyester modification with the masterbatch.

Thermoplastic polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are widely used in extrusion, injection and stretch blow molding to produce products such as fibers, containers and films and other products.

While polyesters are useful in other areas such as film inflation, tentering, thermoforming, and foam extrusion, their use in these areas is often limited by the need for narrow processing windows and specialized processing equipment. These limitations generally arise from deficiencies in polyester melt rheology. Specifically, typical polyesters 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 by introducing some degree of branching into the linear chain structure of the polymer, and/or by chain extension (chain extension) to increase the molecular weight of the polymer. One route to making branched or chain-extended polyesters involves the melt mixing of polyesters with branching and/or chain coupling agents, eg, polyfunctional carboxylic acids, anhydrides, or alcohols. During melt mixing, these reagents react with the molten polyester to chain extend and/or introduce branching into the linear chain structure of the polymer.

Depending on the type of branching/chain coupling agent used to modify the polyester, the overall effect of the melt mixing reaction may actually reduce the molecular weight of the polyester. This is usually the case when the only modifier type used is a polyol branching agent. In such circumstances, to achieve the desired increase in melt strength and melt viscosity, a chain coupling agent may be used in combination with the polyol, or the resulting branched polyester may be subjected to further processing, For example, the processing of solid phase condensation methods. In contrast, polyacid branching/chain coupling agents not only introduce branching during melt mixing, but often also lead to an increase in polymer molecular weight. Thus, the polybasic anhydride branching/chain coupling agent can be used as the sole branching/chain coupling agent without further processing of the modified polyester.

Regardless of the type of branching/chain coupling agent used, it is important to effectively modify polyesters that the degree of branching/chain coupling can be controlled during melt mixing processing and that the branching/chain coupling should be within Goes evenly in polyester.

Generally, melt compounding is performed in an extruder, and the branching/chain coupling agent can be added to the polyester prior to extrusion, or to the molten polyester during extrusion. The easiest way to add this modifier to polyester is by direct addition. However, this mode of incorporation, it was found, can lead to gel formation due to overly localized chain coupling, as well as non-uniform branching within the modified polyester. This also leads to unwanted discoloration. Furthermore, it is not uncommon to use less than 0.5 wt% branching/chain coupling agent relative to the polyester to be modified. Such low levels make it difficult to achieve a uniform distribution of the modifier in the polyester by direct addition.

Many of the above-mentioned problems associated with the addition of branching/chain coupling agents can be overcome by the use of polymer blends, concentrates or masterbatches as they are commonly called in the art. Although, the masterbatch contains a high level of branching/chain coupling agent, it actually acts as a source of dilution of the agent when added to the polyester. This dilution effect more evenly distributes the branching/chain coupling agent throughout the polyester and promotes more uniform branching/chain extension of the polyester.

In its simplest form, a masterbatch can be a physical blend of a carrier polymer and a branching/coupling agent, where both the (modifying) agent and the carrier polymer are usually in powder form. To avoid problems due to incompatibility, the carrier polymer is preferably the same, or of the same class, as the base polymer to be melt blended into the masterbatch. For example, if the base polymer is polyester, the carrier polymer is preferably also polyester. While effective, such physical blends do not have the tendency to break up into individual components and thus again result in uneven distribution of the branching/coupling agent.

Masterbatches are also readily formed by melt mixing carrier polymers with branch/chain coupling agents. However, this can cause problems when the carrier is polyester. Specifically, if the branching/chain coupling agent reacts with the polyester during melt mixing, the same or similar carrier polyester will generally also react with the agent during masterbatch preparation.

To overcome this problem, US 5,801,206 discloses a branching agent-containing masterbatch in which the carrier polymer is an inert polyolefin. Therefore, the method of preparing masterbatches of this type by melt processing does not cause a reaction between the branching agent and the carrier polymer. Although such masterbatches provide a means of incorporating the agent into polyesters, the resulting modified polyesters will always inherently contain polyolefin impurities. Such inclusions may be tolerated and may even be required in some cases, but it may also be detrimental and - depending on the actual amount added - may cloud the final product. For example, the quality of foamed polyester may be reduced by the presence of polyolefin impurities.

US 5,536,793 discloses a branching agent-containing masterbatch in which the carrier polymer is polyester, for example, PET. In this case, the reactivity of the branching agent towards the carrier polymer during melt processing is advantageously exploited. Specifically, by ensuring that sufficient branching agent is present during melt mixing, the end groups of the polyester chains are effectively blocked by the branching agent, which, in turn, is believed to prevent communication between the branching agent and the polyester. react further. By using an amount of branching agent in excess of that required to block all polyester chains, masterbatches containing unreacted branching agent can be made.

However, the masterbatch disclosed in US 5,536,793 is limited in composition. Sufficient branching agent to block the end groups of the polyester support must first be present during melt mixing to prevent crosslinking and gel formation. In practice, this will generally limit the masterbatch composition to contain no less than 5 wt% branching agent. Again, the disclosed blocking reactions rely on the reaction between polyester end groups and polyfunctional anhydride branching agents. Similar reactions with other modifiers such as polyfunctional alcohol branching agents are less likely to prevent reaction of the polyol with the carrier polyester during melt compounding. In particular, polyol compounds are known to readily react (transesterify) with the internal ester groups of PET chains during melt compounding. In such cases, most, if not all, of the polyol branching agent will react with the polyester carrier, making the material unsuitable for use as a masterbatch. Therefore, the composition of the masterbatch disclosed in US 5,536,793 is further limited to the case of using multifunctional anhydride branching agents.

Therefore, provided a kind of masterbatch can be provided, it comprises polyester as carrier material and a kind of branching and/or coupling agent, and wherein this masterbatch composition is in the amount and type of branching and/or coupling agent added It would be desirable to be less restricted.

Surprisingly, it has now been found that polyesters having a melt processing temperature of 250° C. or less can be melt blended with branching and/or coupling agents without a reaction between the branching agent and/or chain coupling agent and Significant reactions occur between polyesters. In this case, the polyesters can be melt blended with high and low concentrations of various branching and/or chain coupling agents to make masterbatches that are subsequently melt blended with other thermoplastic polyesters. Advantageously, agents such as polyfunctional anhydrides and polyols can be combined together in the masterbatch of the present invention.

One aspect of the present invention is a polyester masterbatch composition comprising, a branching and/or chain coupling agent dispersed within a polyester polymer matrix, wherein the polyester has a melt processing temperature equal to or less than 250°C .

The term "masterbatch" as used herein has its usual meaning as understood by those skilled in the art. In particular 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 chain coupling agent, in a concentration higher than that present in the final product required, and the composition is then diluted into a base polymer to produce a final product having the required amount of the agent.

As used herein, the term "melting temperature" of a branching or chain coupling agent is used to mean the temperature at which the agent begins to melt.

As used herein, the term "melt processing temperature" of a polyester is used to refer to the minimum temperature at which the polyester must be maintained in order to melt process it effectively.

As used herein, the term "branching agent" or "branching compound" is used to refer to a polyfunctional compound that can react with a polyester to introduce branching therein. It should be understood that in order to introduce branching, the branching agent will have to have at least 3 functional groups capable of reacting with the polyester.

As used herein, the term "branching and/or chain coupling agent" is used to refer to at least one chain branching agent or chain coupling agent. It covers both types of agents as well as combinations of agents.

Branching and/or chain coupling agents meeting the masterbatch requirements of the present invention are dispersed in the polymer matrix of the polyester. By "dispersed" is meant that the agent is present within the polymer matrix as separate substantially unreacted entities and thus has not yet reacted with the polymer matrix to become an integral part thereof.

In one embodiment of the present invention, the agent selected for the polyester masterbatch is preferably a branching agent, and the branching agent is preferably a polyol.

In another embodiment of the present invention, the agent selected for the polyester masterbatch is preferably a coupling agent, and the coupling agent is preferably a di(acid) anhydride. Those skilled in the art understand that dianhydrides can also function as branching agents. For convenience, agents that can function as both branching and coupling agents are also referred to herein as "branching/coupling agents."

In a preferred embodiment of the present invention, the agent selected for use in the polyester masterbatch is a branching agent used in conjunction with the coupling agent. In this case, the branching agent is preferably polyhydric alcohol, and the coupling agent is preferably dianhydride.

An important feature of the present invention is that the branching and/or chain coupling agent is dispersed in the polymer matrix of the polyester. Specifically, the branching and/or chain coupling agent is melt mixed with the polyester so as to become dispersed within the polymer matrix of the polyester. As discussed above, branching and/or chain coupling agents are known to react with polyesters during melt mixing. In this case, there are some limitations regarding the type and amount of branching and/or chain coupling agents that can be used to prepare the masterbatch. Surprisingly, it has now been found that polyesters having a melt processing temperature of 250° C. or less can be melt mixed with certain branching and/or chain coupling agents while simultaneously There was no significant reaction between the esters. Without intending to be bound by theory, it is believed that combinations of branching and/or chain coupling agents and polyesters that exhibit low reactivity with one another during melt mixing are those in which the melting temperature of the agent is higher than the polyester processing temperature. combinations, and/or combinations in which the solubility of the agent in molten polyester is poor.

Particularly when the branching agent is a polyol, an important feature of the invention is that the polyol is melt mixed with the polyester so that it becomes dispersed within the polymer matrix of the polyester. As discussed above, polyol compounds are known to react with polyesters during melt mixing. In this case, it is not possible to disperse the polyol within the polymer matrix, since the polyol can react with the polyester to become an integral part of it. Surprisingly, it has now been found that certain combinations of polyesters with melting temperatures below 250°C and polyol branching agents can be melt mixed without significant reaction between the polyester and polyol.

As will be seen from the discussion just now, the lack of reactivity between the branching and/or chain coupling agent and the polyester is important. However, it will be appreciated that this does not exclude the possibility that the agent has at least some reactivity towards the polyester. In particular, as long as there is no significant reaction between the agent and the polyester during melt mixing, it is possible to prepare a useful masterbatch in which the branching and/or chain coupling agent is dispersed within the polymer matrix of the polyester.

Preferably, no more than 50wt%, more preferably no more than about 20wt%, further preferably no more than about 10wt%, most preferably no more than about 5wt% polyester and branching and/or chain coupling agent in melt mixing to prepare the masterbatch A reaction occurred during this period.

The term "reaction of the polyester with a branching and/or chain coupling agent" means that the polyester chain end groups and/or internal portions within the polyester chain are reacted with the branching and/or chain coupling agent.

The extent of reactions that can occur between branching and/or chain coupling agents and polyesters during masterbatch preparation can often 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 branching agents such as pentaerythritol with the polyester will be evident from the increase in the polyester MFI, whereas a significant reaction of branching/chain coupling agents such as pyromellitic dianhydride (PMDA) will be evident from the decrease in the polyester MFI see clearly. These can be detected by measuring the intrinsic viscosity of the carrier polymer.

The composition of the masterbatch can also be analyzed using techniques such as NMR and IR spectroscopy, where end group determination can be very useful. Alternatively, depending on the choice of branching and/or chain coupling agent and polyester, the masterbatch can be extracted with an appropriate solvent to selectively isolate unreacted agent. Subsequently, mass balance calculations are used to determine the extent of the reaction.

Branching and/or reactions between chain coupling agents and polyesters will generally result in chain scission or chain coupling of polyester chains, which in turn will be reflected in polyester melt viscosity and/or polyester intrinsic viscosity (IV ) of the lower and higher. For example, the reaction of polyols with polyesters will generally result in scission of the polyester chains, which in turn will be reflected in a decrease in the melt viscosity of the polyester and/or the intrinsic viscosity (IV) of the polyester.

The viscosity of the polyester during melt mixing is readily assessed by measuring the force required to drive the mixing elements of the melt mixing apparatus. The force required to actuate the mixing elements will generally decrease with decreasing melt viscosity and increase with increasing melt viscosity. In the case of an extruder, this force is conveniently determined by measuring the drive torque of the extruder motor. The increase or decrease of polyester IV can be conveniently determined using techniques well known in the art.

A particular advantage afforded by the masterbatch of the present invention is that it can be prepared using both high and low concentrations of a wide variety of branching and/or chain coupling agents without appreciably altering the rheological properties of the carrier polyester. This advantage is particularly evident with polyol branching agents, or with low levels (about 1 to about 5 wt %) of branching/chain coupling agents such as pyromellitic dianhydride.

It will be readily apparent to those skilled in the art that the addition of certain additives to molten polymers can result in a melt of the polymer/additive mixture simply through the presence of the additive in the melt rather than through any reaction of the additive with the polymer. increase or decrease in viscosity. Therefore, such an increase or decrease in the melt viscosity of the polymer/additive mixture should not be viewed as an increase or decrease in the polymer melt viscosity itself.

Preferably, when the polyester is melt-mixed with branching and/or chain coupling agents, the polyester melt viscosity and/or polyester intrinsic viscosity decrease or increase by no more than 30%, more preferably by no more than 15%, more preferably Not more than 5%. In particularly preferred embodiments, the melt viscosity and/or intrinsic viscosity of the polyester remains substantially unchanged when the polyester is melt mixed with the branching and/or chain coupling agent.

Since there is no significant reaction between the branching and/or chain coupling agent and the polyester during melt compounding, the resulting masterbatch can be easily extruded and generally has sufficient physical and mechanical properties to function as a masterbatch. In particular, the molecular weight of the polyester does not decrease or increase during masterbatch preparation to the point that extrusion becomes infeasible or difficult.

As discussed above, the relative melting temperature of the branching and/or chain coupling agent and the polyester, and/or the solubility of the agent in the molten polyester, is believed to affect the reactivity of the agent to the polyester Important parameters. Depending on the particular combination of the agent and polyester, either of these two parameters can affect reactivity, or alternatively, both parameters can affect reactivity together.

Preferably, the melting temperature of the branching and/or chain coupling agent is at least 10°C higher than the melt processing temperature of the polyester, more preferably at least 20°C higher, even more preferably at least 40°C higher.

Preferably, the branching and/or chain coupling agent is present as a separate phase in the molten polyester during melt mixing. In particular, preferably at least 50 wt%, more preferably at least 65 wt%, most preferably at least 85 wt% of the branching and/or chain coupling agent is present as a separate phase in the molten polyester during melt mixing. In one 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.

In the preceding paragraph, by "molten polyester during melt mixing" is meant molten polyester at the melting temperature of the polyester.

The masterbatch of the present invention provides a means of uniformly dispersing branching and/or chain coupling agents throughout the base polyester. To ensure that branching and/or chain growth occurs uniformly in the base polyester during melt compounding, it is important that the masterbatch melts rapidly so that the agent is rapidly dispersed throughout the molten base polyester. It is believed that the agent is more effectively dispersed throughout the base polyester when the masterbatch carrier polyester is processed at a lower temperature than the base polyester.

A common base polyester that can be modified with the masterbatch of the present invention is PET. Polyesters suitable for use as the carrier polyester in the masterbatch of the present invention have a processing temperature equal to or less than 250°C, which is advantageously lower than that of PET (typically about 260°C). The use of polyesters with such low melt processing temperatures also provides a means of increasing the melting temperature differential between the carrier polyester and branching and/or chain coupling agents having a melting temperature greater than or approximately 250°C, the effect of which is believed to be Can reduce the reactivity of the agent to the carrier polyester during masterbatch preparation.

Preferably, low melt processing temperature polyesters suitable for use in masterbatches will have a melt processing temperature of between 150°C and 250°C, more preferably from about 170°C to about 240°C, most preferably from about 180°C to about 230°C.

In considering low melt processing temperature polyesters suitable for use in the present invention, those skilled in the art understand that there are a number of factors that affect the melt properties of the polyester. Factors believed to contribute to providing low melt processing temperature polyesters include irregularities in chain structure, non-linear linkage of monomer units, lack of interchain attraction, bulky side chains, flexibility of internal bonding structures, and repeating units The number of odd carbon atoms in . Many of these factors actually inhibit the polyester's ability to crystallize, so polyesters with low percent crystallization often also have low melt processing temperatures.

Crystallinity, for example, can be determined using a variety of techniques known to those skilled in the art. For example, Differential Scanning Calorimetry (DSC) measures the heat of fusion at the melting temperature, a value proportional to the degree of crystallinity. The density of polyesters is also linked to the degree of crystallinity: the lower the density, the higher the degree of crystallinity. Both methods require a calibration test. Absolute methods to detect crystallinity, eg wide angle X-ray scattering. In the case of a low density polyester as the low melting processing temperature polyester, it preferably has a crystallinity of less than about 15%, more preferably less than about 5%. It is particularly preferred that such low-crystalline polyesters have substantially no crystallinity and are therefore amorphous.

Another important parameter of low melting processing temperature polyesters is their glass transition temperature: suitable polyesters exhibit a glass transition temperature about 70 °C below the melting temperature of the branching or chain coupling agent, more preferably about 110 °C. °C, most preferably about 150 °C.

Those skilled in the art will appreciate that the degree of crystallinity of a given polyester will depend to a very large extent on the molecular structure of the polyester. In particular, the crystallinity of polyesters can be altered by simply changing the number and/or type and/or distribution of monomer units making up the polyester chain. For example, if about 8 mol% of ethylene glycol repeating units are exchanged in PET for 1,4-cyclohexanedimethanol repeating units, or about 15 mol% of diethylene glycol repeating units, the resulting modified polyester may be amorphous And has a low melting temperature. Similarly, if about 15 mole percent of the terephthalic acid repeat units are exchanged for isophthalic acid repeat units in PET, the resulting modified polyester can also be amorphous and have a low melt processing temperature. The two concepts can also be combined in one polyester or by melt blending of at least two different polyesters. Therefore, a particular modifying acid or diol can significantly affect the melt processability of polyesters.

The terms "modifying acid" and "modifying diol" as used herein are intended to define compounds which generate a portion of the acid and diol repeating units of the polyester respectively and which modify the polyester to reduce its crystallinity Or make 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, sebacic acid, suberic acid, acid, 1,12-dodecanedioic acid, etc. In fact, it is often preferred to use a derivative of a certain functional acid, for example, the dimethyl, diethyl or dipropyl ester of the dicarboxylic acid. Anhydrides or halides of these acids may also be used, if practical. Isophthalic acid is preferred.

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, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3 - cyclohexanedimethanol, Z,8-bis(hydroxymethyl)-tricyclo-[5.2.1.0]-decane, where Z represents 3, 4 or 5; 1,4-bis(2-hydroxyethoxy base) benzene and glycols containing one or more oxygen atoms in the chain, for example, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like. Generally, these diols contain 2 to 18, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be used in their cis or trans configuration or as mixtures of the two forms. 1,4-Cyclohexanedimethanol or diethylene glycol are preferred modifying diols.

Other suitable low melt processing polyesters are based on the addition polymerization of lactones, eg, poly-ε-caprolactone.

Polyester masterbatch compositions are preferred wherein the polyester suitable for the masterbatch is glycol-modified polyethylene terephthalate (PET-G), poly-ε-caprolactone, or contains greater than about Copolyester with 15% isophthalic acid units.

Polyesters suitable for use in the masterbatches of the present invention generally have an intrinsic viscosity (IV) of from about 0.4 dL/g to about 1.5 dL/g, but those having from about 0.6 dL/g to about 1.0 dL/g are preferred. Intrinsic viscosity can be measured at 25°C in a 60/40 (wt/wt) phenol/tetrachloroethane solution at a concentration of 0.5 g/100 mL.

In a particular embodiment, the polyester used in the masterbatch is characterized by a melt viscosity of less than 2000 Pa.s at a shear rate equal to 100 s ^-1 at a temperature lower than the melting temperature of the branching agent and/or chain coupling agent temperature measurement.

Below the melting temperature of the branching agent and/or chain coupling agent is meant a temperature of at least 10°C, preferably at least 20°C, below said temperature.

The inventive masterbatches may contain branching agents. Preferred branching agents include, but are not limited to, polyols and polyfunctional anhydrides.

Polyol branching agents suitable for masterbatches have a functionality of 3 or higher, meaning that they have at least 3 hydroxyl groups per molecule. For example, glycerol has a functionality of 3, while pentaerythritol has a functionality of 4. Examples of suitable polyol branching agents or precursors thereof include, but are not limited to, trimethylolethane, pentaerythritol, sorbitol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, and dimer Pentaerythritol, tripentaerythritol, etc. One or more polyol branching agents may be used in combination.

Preferred polyol branching agents or derivatives thereof include pentaerythritol, dipentaerythritol, tripentaerythritol and trimethylolethane.

As indicated above, the polyol branching agent may be provided in the form of a precursor thereof or a derivative thereof. By "precursor thereof" or "derivative thereof", it is meant a compound which can be converted into the polyol during the preparation of the masterbatch by melt mixing.

Where the masterbatch of the present invention comprises a polyol branching agent, the polyol is preferably present in an amount of from about 0.3 to about 30 wt%, more preferably from about 0.3 to about 20 wt%, most preferably from about 1 to about 10 wt%, relative to Polyester carrier polymer.

Polyfunctional anhydrides suitable for use in the masterbatch have a functionality of 3 or higher, it being understood that the polyfunctional anhydride has at least three acid group residues per molecule. For example, trimellitic anhydride has a functionality of 3, while pyromellitic dianhydride has a functionality of 4.

Examples of polyfunctional anhydrides that can be used in the masterbatch of the present invention include aromatic anhydrides, cycloaliphatic anhydrides, halogenated anhydrides, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, diphenyl Sulfonetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bis(3,4 -Dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, bisphenol-A bisether dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2 , 2',3,3'-biphenyltetracarboxylic acid, hydroquinone diether dianhydride, 3,4,9,10-tetra(formic) dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid Dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-succinic dianhydride, bicyclo(2,2)-oct-7-ene-2,3,5,6 -Tetracarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 3,3',4,4'- Biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride (ODPA) and ethylenediaminetetraacetic dianhydride (EDTAh). Anhydrides containing polymers or copolymers can also be used as the anhydride component. 2 or more polyfunctional acid anhydrides may be used in combination.

Preferred polyfunctional anhydrides include pyromellitic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and tetrahydrofuran-2,3 , 4,5-Tetracarboxylic dianhydride. The most preferred polyfunctional anhydride is pyromellitic dianhydride.

As noted above, the polyfunctional anhydrides may contain acid groups or residues of acid groups. By "acid group residue" is meant the residue of a carboxylic acid which has been condensed with a second carboxylic acid to form an anhydride. In this case, the resulting anhydride will contain 2 acid group residues.

Where the masterbatch of the present invention contains a branching agent other than a polyol branching agent, the branching agent is preferably present in an amount of from about 1 to about 60 wt%, more preferably from about 5 to about 40 wt%, most preferably from about 5 to About 30% by weight relative to the polyester carrier polymer.

The masterbatches of the present invention may contain chain coupling agents. Chain coupling agents useful in the present invention include, but are not limited to, polyfunctional anhydrides, epoxy compounds, oxazoline derivatives, oxazolinone derivatives, lactams, and related species. Examples of further chain coupling agents can be found in Inata and Matsumura, J.Appl Pol.Sci., 303325 (1988) and Lootjens et al., J.Appl Pol.Sci.65 1813 (1997) and Brown in Reaction Extrusion In Plastic, ed. Xanthos, Hanger, New York 1992p.75.

When masterbatches are subsequently used, those containing anhydride or lactam units are preferably reacted with the alcohol functionality of the base polyester. Those containing oxazoline, oxazolone, epoxide, carbodiimide units preferably react with the acid functionality of the base polyester when the masterbatch is subsequently used.

Preferred chain coupling agents which may be used alone or in combination include the following compounds:

(1) Polyepoxides such as bisphenol-A-diglycidyl ether, bis(3,4-epoxycyclohexylmethyl)adipate; N,N-diglycidylbenzamide (and related diepoxides); N,N-diglycidylaniline and its derivatives; N,N-diglycidylhydantoin, uracil, barbituric acid or isocyanuric acid derivatives; N , N-diglycidyl imide; N, N-diglycidyl imidazolinone; epoxy novolac; phenyl glycidyl ether; diethylene glycol diglycidyl ether; Epikote 815 ( Diglycidyl ether of bisphenol A-epichlorohydrin oligomer).

(2) Polyoxazoline/polyoxazolone such as 2,2-bis(2-oxazoline); 1,3-phenylene bis(2-oxazolone-2), 1,2-bis( 2-oxazolinyl-2)ethane; 2-phenyl-1,3-oxazoline; 2,2'-bis(5,6-dihydro-4H-1,3-oxazoline); N,N'-hexamethylenebis(carbamoyl-2-oxazolinebis[5(4H)-oxazolone]; bis(4H-3,1-benzoxazin-4-one); 2,2'-bis(H-3,1-benzoxazin-4-one);

(3) Polyisocyanates, for example, 4,4'-methylene bis(phenyl isocyanate) (MDI); toluene diisocyanate, isocyanate chain-ended polyurethanes; isocyanate chain-ended polymers;

(4) Anhydride

Examples of polyfunctional anhydrides are those defined above for branching agents.

(5) Polylactams such as N,N'-terephthaloylbis(caprolactam) and N,N'-terephthaloylbis-(laurolactam). The use of these and similar compounds for chain extension of PET is disclosed in US 4,857,603 by Akkapeddi and Gervasi.

(6) Phosphorous (III) coupling agents such as triphenylphosphite (Jaques et al. "Polymers" 38 5367 (1997)) and other compounds such as those disclosed in US 5326830 by Aharoni. In the case where the masterbatch of the present invention contains a chain coupling agent, the chain coupling agent is preferably present in an amount of about 1 to about 60 wt%, more preferably about 5 to about 40 wt%, more preferably about 5 to about 30 wt%, relatively for polyester carriers.

In another embodiment of the invention, the masterbatch composition may additionally contain phosphite, hypophosphite or phosphonate compounds.

Phosphonates are generally preferred.

Preferably, the phosphonate has the general formula II

in

R ₁₀₃ is H/C ₁ -C ₂₀ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl or naphthyl,

R ₁₄ is hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl or naphthyl; or

M ^r+ /r,

M ^r+ is an r-valent metal cation or ammonium ion,

n is 0, 1, 2, 3, 4, 5 or 6, and

r is 1, 2, 3 or 4;

Q is hydrogen, -XC(O)-OR ₁₀₇ , or the group

R ₁₀₁ is isopropyl, tert-butyl, cyclohexyl or cyclohexyl substituted with 1 to 3 C ₁ to C ₄ alkyl groups,

R ₁₀₂ is hydrogen, C ₁ -C ₄ alkyl, cyclohexyl or cyclohexyl substituted with 1 - 3 C ₁ -C ₄ alkyl groups,

R ₁₀₅ is hydrogen, C ₁ -C ₁₈ alkyl, OH, halogen or C ₃ -C ₇ cycloalkyl;

R ₁₀₆ is hydrogen, methyl, trimethylsilyl, benzyl, phenyl, sulfonyl or C ₁ ~C ₁₈ alkyl;

R ₁₀₇ is hydrogen, C ₁ -C ₁₀ alkyl or C ₃ -C ₇ cycloalkyl; and

X is phenylene, C ₁ -C ₄ alkyl group-substituted phenylene or cyclohexylene.

Other suitable phosphonates are listed below.

Sterically hindered hydroxyphenylalkyl phosphates or half esters, such as those known from US 4 778 840, are preferred.

Halogen is fluorine, chlorine, bromine or iodine.

Alkyl substituents containing up to 18 carbon atoms are suitable groups, for example methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl, octadecyl, also the corresponding branched Isomers; C ₂ -C ₄ alkyl and isooctyl are preferred.

C ₁ to C ₄ alkyl-substituted phenyl or naphthyl, preferably containing 1 to 3, more preferably 1 or 2 alkyl groups, for example o-, m-, p-methylphenyl, 2 , 3-dimethylphenyl, 2,4-dimethylphenyl, 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-methyl Naphthyl, 2-methyl-naphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

C ₁ to C ₄ alkyl substituted cyclohexyl, preferably containing 1 to 3, more preferably 1 or 2 branched or unbranched alkyl groups, such as cyclopentyl, methylcyclopentyl, dimethyl Cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl or tert-butylcyclohexyl.

The mono-, di-, tri- or tetravalent metal cations are preferably alkali metal, alkaline earth metal, heavy metal or aluminum cations, e.g. Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Ba ⁺⁺ , Zn ⁺⁺ , Al ⁺⁺⁺ or Ti ⁺⁺⁺⁺ . Ca ⁺⁺ is particularly preferred.

Preferred compounds of general formula 1 are those containing at least one tert-butyl group as R ₁ or R ₂ . Very particularly preferred compounds are those for which _R1 and _R2 are simultaneously tert-butyl.

n is preferably 1 or 2, especially 1.

For example, phosphonates have the general formula IIa

in

R ₁₀₁ is hydrogen, isopropyl, tert-butyl, cyclohexyl or cyclohexyl substituted with 1 to 3 C ₁ to C ₄ alkyl groups,

R ₁₀₂ is hydrogen, C ₁ -C ₄ alkyl, cyclohexyl or cyclohexyl substituted with 1 - 3 C ₁ -C ₄ alkyl groups,

R ₁₀₃ is C ₁ -C ₂₀ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl or naphthyl;

R ₁₀₄ is hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl or naphthyl; or

M ^r+ /r,

M ^r+ is an r-valent metal cation, r is 1, 2, 3 or 4; and

n is 0, 1, 2, 3, 4, 5 or 6.

Preferably, the phosphonate has the general formula III, IV, V, VI or VII

wherein R ₁₀₁ are each independently of each other hydrogen or M ^r+ /r.

Certain compounds of general formula II, IIa, III, IV, V, VI, VII or VIII are commercially available or may be prepared following standard methods, for example as described in US 4 778 840.

The phosphonate has the general formula XX

in

R ₂₀₁ is hydrogen, C ₁ to C ₂₀ alkyl, phenyl or C ₁ to C ₄ alkyl substituted phenyl; biphenyl, naphthyl, -CH ₂ -OC ₁ -C ₂₀ alkyl or -CH ₂ -SC ₁ -C ₂₀ alkyl,

R ₂₀₂ is hydrogen, C ₁ to C ₂₀ alkyl, phenyl or C ₁ to C ₄ alkyl substituted phenyl; biphenyl, naphthyl, -CH ₂ -OC ₁ -C ₂₀ alkyl or -CH ₂ -SC ₁ -C ₂₀ alkyl, or R ₁ and R ₂ together are a group of general formula XXI

wherein R ₂₀₃ , R ₂₀₄ and R ₂₀₅ are independently C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₄ alkyl-substituted phenyl.

A specific phosphite is, for example, compound 101

Typical phosphites useful in the present invention are, for example, listed below.

For example, triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecane base) phosphite, di(octadecyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri(tert-butyl-phenyl)pentaerythritol diphosphite, tris(deca Octyl)sorbitol triphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxo Phosphocin, 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-methyl-dibenzo[d,g]-1,3,2-dioxane Phosphine, 2,2′,2″-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)phosphite, 5- Butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba Specialty Chemicals), Tris(nonylphenyl)phosphite,

The masterbatches of the present invention are prepared by melt mixing polyesters with branching and/or chain coupling agents. Melt mixing can be carried out by methods well known in the art. Preferably, melt mixing is accomplished by continuous extrusion equipment such as twin-screw extruders, single-screw extruders, other multi-screw extruders, eg, Buss kneaders and Farell mixers. Preferably, melt mixing is carried out under conditions that maintain the polyester at its melt processing temperature.

In preparing the masterbatch, one or more polyesters and one or more branching and/or chain coupling agents may be used.

Therefore, another aspect of the present invention provides a method for preparing a polyester masterbatch, comprising melt mixing polyester with branching and/or chain coupling agent so that the branching and/or chain coupling agent is dispersed in the polymerization of polyester within a material matrix where the polyester has a melt processing temperature equal to or less than 250°C.

A specific embodiment of the invention is a method for melt processing a base polyester comprising:

(1) forming a molten mixture comprising

(i) a major amount of a first resin composition comprising a base polyester and 0 to about 1 wt% chain coupling agent and/or branching agent, and

(ii) a minor amount of the above-described polyester masterbatch composition comprising at least about 50 wt% polyester resin and greater than about 2 wt% chain coupling agent and/or branching agent,

wherein the relative amounts of (i) and (ii) correspond to - said molten mixture contains from about 0.1 wt% to about 1 wt% of said chain coupling agent and/or branching agent;

(2) melt processing the resulting molten mixture under conditions of time and temperature sufficient to modify the base polyester; and

(3) The molten mixture is directly made into film, sheet, injection molded product, fiber or non-woven fabric.

Suitable melt processing conditions are described above.

As used herein, the term "directly made" is understood to mean that the molten mixture of base polymer and masterbatch is not first converted into powder or pellets for remelting into the desired article in subsequent manufacturing, but is directly melt processed make this product.

The definitions and preferences given above for the composition also apply to the process of making the polyester masterbatch.

The method of making a masterbatch can be done in one or more processing steps.

Alternatively, all components of the masterbatch can be premixed and metered into the extruder, or metered separately.

Another option is to extrude a portion of the masterbatch first and then add the rest of the masterbatch to the process. For example, the carrier polyester is metered into the extruder at the outset, while the active ingredient is metered in in the higher extrusion zone.

The masterbatch can be supplemented by solid-state polycondensation to increase the molecular weight of the carrier polyester. This is useful for adjusting the molecular weight of the polyester in the masterbatch to that of the base polyester to be modified.

The masterbatch of the present invention can be used to modify the base polyester by melt mixing the base polyester with the masterbatch. A single masterbatch or a combination of several masterbatches can be used. Using this method, the polyester introduces branching within the polyester chain structure, or increases the chain length, by reacting with a branching agent. Typically, the base polyester will have a higher melt processing temperature than the masterbatch carrier polyester. Therefore, at such higher temperatures, the branching and/or chain coupling agents will have a greater tendency to react with the base polyester, extending chains and/or introducing branch points.

If desired, the modified polyester can be subjected to further treatment, for example, solid state condensation methods, to increase its molecular weight. Alternatively, where a chain coupling agent has not been used, the modified polyester can then be melt blended with a chain coupling agent to increase the molecular weight, preferably the base polyester is melted with a masterbatch containing the chain coupling agent mix.

High melt strength polyesters can be prepared by melt blending the base polyester with polyol branching agents and polyfunctional anhydrides. In a preferred embodiment of the invention, the base polyester is modified using a combination of masterbatches prepared according to the invention comprising polyol branching agents and multifunctional anhydrides, respectively.

In another preferred embodiment of the present invention, the masterbatch comprises a polyol branching agent in combination with a multifunctional anhydride. By combining these two agents in a masterbatch, the need for 2 separate masterbatches can be avoided. It is believed that by selecting the carrier polyester, polyol and anhydride in accordance with the present invention, the masterbatch can be prepared without significant reaction between the carrier polyester, polyol and anhydride. Accordingly, such a masterbatch advantageously comprises a polyol branching agent and a polyfunctional anhydride dispersed within the polymer matrix of the polyester.

Other chain coupling agents may also be combined with the polyol branching agent in the masterbatches of the present invention.

In the case of preparing a masterbatch comprising a combination of branching and/or chain coupling agents, the branching and/or chain coupling agents may react with each other to some extent during melt mixing. In this case, the reaction product formed can also itself be a branching and/or chain coupling agent and thus a modifier suitable for acting as branching and/or chain coupling agent according to the invention.

Another aspect of the present invention provides a method of modifying a polyester comprising melt mixing the polyester with the polyester masterbatch described above at a temperature above 250°C.

The polyesters that can be modified by the method of the present invention are preferably thermoplastic polyesters, including all heterochain macromolecular compounds having repeating units of carboxylate groups in the polymer backbone. Also suitable as polyesters are polymers containing esters in side chains or grafts, copolymers comprising monomers with carboxylate groups (in the main chain or as side groups or grafts), and ( Polyester derivatives retaining carboxylate groups on the main chain or side groups or grafts). The polyesters may also contain acids, anhydrides and alcohols (for example, acrylic and methacrylic acid containing polymers) in the backbone or as side chains. Preferred polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate 1, 3-propanediol ester (PTT), copolymer of PET, copolymer of PBT, copolymer of PEN, liquid crystal polyester (LCP) and polyester of carbonic acid (polycarbonate) and blends of one or more thereof .

Copolymers of PET include variants containing other comonomers. For example, ethylene glycol can be exchanged for other diols, such as cyclohexanedimethanol, to produce PET copolymers. 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 can be blended with other polyesters.

Liquid-crystalline polyesters include polyhydroxybenzoic acid (HBA), poly-2-hydroxy-6-naphthoic acid, and polynaphthalenediol terephthalate (PNT), which is a combination of 2,6-dihydroxynaphthalene and terephthalic acid of copolymers. Copolymers of liquid crystal polyesters with other polyesters are also suitable.

Polymers containing pendant or grafted esters, acids or alcohols include: polymethyl methacrylate (or other methyl methacrylate or acrylate); polymethacrylic acid; polyacrylic acid; polyhydroxyethyl methacrylate , starch, cellulose, etc.

Copolymers or graft copolymers containing acid, ester or alcohol groups include ethylene-co-ethyl acetate, ethylene-co-vinyl alcohol, ethylene-co-acrylic acid, maleic anhydride grafted polyethylene, polypropylene, etc. .

In the case where the masterbatch of the present invention comprises a polyol branching agent and a multifunctional acid anhydride, preferably, the molar ratio of the polyfunctional anhydride to the polyol branching agent or its precursor is between 0.5:1 and (10×C):1 , where C is the number of moles of hydroxyl groups per molecule of polyol branching agent. Particularly preferably, the molar ratio of the polyfunctional anhydride to the polyol, or its precursor, is in the range of 2:1˜(2×C):1.

To clearly show how the molar ratio is calculated, the following example is given:

Example calculation: masterbatch comprising pyromellitic dianhydride (PMDA) and pentaerythritol.

PMDA = tetrafunctional anhydride

Pentaerythritol = tetrafunctional alcohol

The polyol used in this example has a functionality equal to 4, therefore C=4.

The molar ratio of PMDA to pentaerythritol is therefore in the range of 0.2:1˜40 (10×4):1, wherein the preferred molar ratio of PMDA to pentaerythritol is in the range of 2:1˜8 (2×4):1. Thus, a masterbatch containing 2.5 wt% pentaerythritol will contain preferably between about 8 wt% and about 32 wt% PMDA (ie, in a molar ratio between 2:1 and 8:1).

In the case where the masterbatch of the present invention contains only one of the polyfunctional anhydrides or polyol branching agents, but the masterbatch is used to modify the base polyester using both polyols and anhydrides, the combination of the polyol branching agent and the polyfunctional The molar ratio between the anhydrides is preferably also specified as before.

The masterbatch of the present invention may contain other additives such as fillers, pigments, stabilizers, blowing agents, nucleating agents, and the like. See US 6,469,078 for these and other suitable additional additives.

The masterbatch may also contain additives such as heat stabilizers, light stabilizers, processing stabilizers, metal deactivators, nucleating agents, and optical brighteners. Examples are given below.

1. Antioxidant

1.1. Alkylated monohydric phenols, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4- Ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol , 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-bis(octadecyl)-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethylphenol, nonylphenols linear or branched in the side chain, for example, 2,6-dinonyl-4-methylphenol, 2,4 -Dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecan-1'-yl)phenol , 2,4-Dimethyl-6-(1'-methyltridecyl-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthio-6-methylphenol, 2,4 -Dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2 , 6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4 -Hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, eg α-tocopherol, β-tocopherol, γ-tocopherol, iδ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, eg, 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-di-sec-pentylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidene bisphenols, for example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4- ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6 -cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2 , 2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-isobutylphenol), 2,2'- Methylbis[6-(α-methylbenzyl)-4-nonylphenol 1,2,2'-methylenebis(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis( 5-tert-butyl-4-hydroxy-2-methylphenol) butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1 , 1,3-tris(5-tert-butyl-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)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl- 4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl -4-hydroxyphenyl) propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5 , 5-Tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example, 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4- Hydroxy-3,5-dimethylbenzyl thioglycolate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl thioglycolate, tris(3,5-di-tert-butyl -4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl -4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonate, for example, bis(octadecyl)-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, bis(decyl) Octyl)-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, bis(dodecyl)mercaptoethyl-2,2-bis(3,5 -Di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5- Di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, for example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,4- Bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 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-hydroxyanilino)-1,3,5-triazine, 2-octyl Mercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 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-hydroxybenzyl) 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-phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tri (3,5-Dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzyl phosphonates, for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl Phosphonate, bis(octadecyl) 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, bis(octadecyl)-5-tert-butyl-4-hydroxy-3-methyl Benzyl phosphonate, calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid.

1.12. Acylaminophenols, for example, 4-hydroxy-N-lauroanilide, 4-hydroxy-N-stearanilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)octylcarbamate ester.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, n-octanol, isooctyl alcohol, octadecane Alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, triethylene glycol (Hydroxyethyl) isocyanurate, N, N'-bis(hydroxyethyl) oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, Esters of trimethylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, n-octanol, isooctyl alcohol, decanol, Octanol, 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) oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanedi alcohol, trimethylolpropane, 4-hydroxymethyl-1-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]-deca An ester of an alkane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, stearyl alcohol, 1,6- Hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)iso Cyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, Esters formed from 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16.3, Esters of 5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, for example, with methanol, ethanol, octanol, stearyl alcohol, 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)oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-methylol -1-phospha-2,6,7-trioxabicyclo[2.2.2]octane esters.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, for example, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) ) hexamethylene diamide, N, N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide, N,N'-bis(3,5-di tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl ] Oxamide (Naugard(R) XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic (amine) antioxidants, for example, N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1, 4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methyl Heptyl)-p-phenylenediamine, N,N'-dicyclohexyl-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'-phenyl-p-phenylenediamine, N-( 1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfonyl)diphenylamine, N , N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N -Phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example, p, p'-di-tert-butyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecane Acylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis(2-methylphenyl)amino) Ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-Phenyl-1-naphthylamine, mixtures of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, mixtures of mono- and dialkylated nonyldiphenylamines, Mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl/isohexyldiphenylamines, mono- and dialkylated t-butyl 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine mixtures, mono- and dialkylated tert-octylphenoxy Mixture of thiazine, N-allylphenoxythiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2, 2,6,6-tetramethylpiperidin-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2 , 6,6-tetramethylpyridin-4-one, 2,2,6,6-tetramethylpyridin-4-ol.

2. UV absorbers and light stabilizers,

2.1.2-(2'-hydroxyphenyl)benzotriazole, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-bis tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2-'-hydroxy-5'- (1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzo Triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl Base-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl -2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-( 3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2 -(2-Ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxyl-5′-( 2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxyl-5'-(2-methoxycarbonylethyl)phenyl) Benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl -5'-[2-(2-Ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxyl-5 '-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxyl-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2 , 2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol];2-[3'-tert-butyl -5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300 transesterification product; [R-CH ₂ CH ₂ -COO- CH ₂ CH ₂ -] ₂ , where R=3'-tert-butyl-4'-hydroxyl-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxyl-3'- (α,α-Dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole; 2-[2′-Hydroxy-3′- (1,1,3,3-Tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2.2-Hydroxybenzophenones, for example, 4-hydroxy, 4-methoxy, 4-octyloxy-4-decyloxy-4-dodecanyloxy, 4-benzyloxy, 4,2 Derivatives of ',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy.

2.3. Esters of substituted and unsubstituted benzoic acids, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl meta Hydroquinone esters, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol esters, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl- 4-Hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate of hexadecyl, 3,5-di-tert-butyl-4-hydroxybenzoic acid of octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoate of 2-methyl-4,6-di-tert-butylphenyl.

2.4. Acrylates, for example, ethyl α-cyano-β,β-diphenylacrylate, α-cyano-β,β-isooctyl diphenylacrylate, methyl α-carbonylmethoxycinnamate , α-cyano-β-methyl-p-methoxycinnamate methyl ester, α-cyano-β-methyl-p-methoxycinnamate butyl ester, α-carbonylmethoxy-p-methoxy Methyl cinnamate and N-(β-carbonylmethoxy-β-cyanoethenyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g. methyl or ethyl base esters, 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example, 2-hydroxy-4-methylphenylundecylketoxime, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

2.6. Sterically hindered amines, for example, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4- Piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6 -Tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl -4-Hydroxybenzylmalonate, condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N,N'- Bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine Linear or cyclic condensates, tris(2,2,6,6-tetramethyl-4-piperidinyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl- 4-piperidinyl)-1,2,3,4-butane tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethyl piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1 , 2,2,6,6-pentamethylpiperidinyl)-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-octyloxy-2,2, 6,6-tetramethylpiperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidinyl)succinate, N,N'-bis( 2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and the linear or Cyclic condensate, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine and 1,2 -Condensate of bis(3-aminopropylamino)-ethane, 2-chloro-4,6-bis-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidine Base)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensation product, 2-chloro-4,6-bis-(4-n-butylamino-1 , condensate of 2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl- 3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6 -pentyl-4-piperidinyl)pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-octadecyloxy-2,2,6,6-tetramethylpiper A mixture of pyridine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 , Condensate of 3,5-triazine, condensate of condensate of 1,2-bis(2-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine , and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS rule number [136504-96-6]); 1,6-hexanediamine and 2,4,6-trichloro -Condensates of 1,3,5-triazine and N,N-dibutylamine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS rule number [192268-64- 7]); N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-penta Methyl-4-piperidinyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaze Hetero-4-oxo-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4 -The reaction product of oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)- 2-(4-methoxyphenyl)ethylene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexaethylene Methyldiamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-2-oxy Base-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, maleic anhydride-α-olefin and 2,2,6,6-tetramethyl-4- The reaction product of aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example, 4,4'-dioctyloxy-N,N'-oxanilide, 2,2'-diethoxy-N,N'-oxanilide, 2,2 '-Dioctyloxy-5,5'-di-tert-butyl-N,N'-oxalanilide, 2,2'-bis(dodecyloxy)-5,5'-di-tert-butyl -N,N'-oxalidianilide, 2-ethoxy-2'-ethyl-N,N'-oxalidianilide, N,N'-bis(3-dimethylaminopropyl) oxalic acid Amide, 2-ethoxy-5-tert-butyl-2'-ethyl-N, N'-oxalanilide and its combination with 2-ethoxy-2'-ethyl-5,4'-di Mixtures of tert-butyl oxanilides, mixtures of o- and p-methoxy-disubstituted N,N'-oxanilides and o- and p-ethoxy-disubstituted N,N' - Mixtures of oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazine, 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-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl) )-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl))-4,6-bis(4- Methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 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-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5 -triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3, 5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3 , 5-triazine, 2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl phenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2 , 4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-tri Oxazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-( 3-butoxy-2-hydroxypropyl)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-benzene Base-1,3,5-triazine, 2-{2-hydroxy-4-[3(2-ethylhexyl-1-oxyl)-2-hydroxypropoxy]-phenyl}-4,6 - bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example, N, N'-diphenyl oxamide, N-salicylaldehyde-N'-salicylic hydrazide, N, N'-bis(salicyloyl) hydrazine, N, N'- Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionoyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalohydrazide, N, N'-oxalyl dianilide, isophthaloyl dihydrazide, sebacyl bisphenyl hydrazide, N,N'-diacetyladipyl dihydrazide, N,N'-bis(water Salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N- -Di(tetradecyl)hydroxylamine, N,N-di(hexadecyl)hydroxylamine, N,N-di(octadecyl)hydroxylamine, N-hexadecyl-N-octadecylamine Alkylhydroxylamines, N-heptadecyl-N-octadecylhydroxylamines, N,N-dialkylhydroxylamines derived from hydrogenated tallowamine.

5. Nitrones, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α- Undecyl nitrone, N-tridecyl-α-tridecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone Alkyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecyl nitrone, nitrone derived from N,N-dialkylhydroxylamine ketone.

6. Thio-synergists, for example, dilauryl thiodipropionate or dioctadecyl thiodipropionate.

7. Peroxide scavengers, for example, esters of β-thiodipropionic acid, for example, lauryl, octadecyl, cinnamyl or tridecyl esters, mercaptobenzimidazole, or 2-mercaptobenzo Zinc salt of imidazole, zinc salt of dibutyl dithiocarbamate, dioctadecyl disulfide, tetrakis(β-dodecylmercaptan) propionate of pentaerythritol.

8. Polyamide stabilizers, for example copper salts in combination with iodide and/or phosphorous compounds, and divalent manganese salts.

9. Alkaline co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and alkaline earth metal salts, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol, zinc pyrocatechol.

10. Nucleating agents, for example, inorganic substances, for example, talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and Salts thereof, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example, ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol, 1,3:2,4-bis(paramethyldibenzylidene)sorbitol and 1,3: 2,4-Di(benzylidene)sorbitol.

11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, glass bubbles, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and Powders or fibers of other natural products, synthetic fibers.

12. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

13. Benzofuranones and indolinones, for example, disclosed in US Patent 4,325,863, US Patent 4,338,244, US Patent 5,175,312, US Patent 5,216,052, US Patent 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316622, DE - in A-4316876, EP-A-0589839 or EP-A-0591102, or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzo Furan-2-one, 5,7-di-tert-butyl-3-[4-(2-stearyloxy)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-ethoxybenzene Base) benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3 , 5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5, 7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

In the process of the invention, the base polyester is modified by melt mixing with the masterbatch of the invention. Condensation or transesterification catalysts may also be added to the melt mixing process to increase the rate of reaction of the polyol branching agent, and, if present, the chain coupling agent, with the base polyester.

In particular embodiments, the masterbatch composition further comprises 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.

Other additives that can be incorporated into the masterbatch during melt compounding to modify the polyester include monofunctional additives that act as blocking agents to control the degree of chain growth and/or branching, as described by Edelman et al. in U.S. Patent 4 , 1611,579, for the production of controlled branched polyesters by a combination of condensation/solid-state polycondensation. Examples of suitable monofunctional additives include acids (eg, benzoic acid) or anhydrides or esters thereof (eg, benzoic anhydride, acetic anhydride). Monofunctional alcohols can also be used. Additives (eg, carbonates) may be added to facilitate foaming of the modified polyester, if a foamed product is desired. Gas can also be injected into the molten polyester during melt mixing to achieve physical rather than chemical foaming.

In the process of the invention, the base polyester is modified by melt mixing it with the masterbatch of the invention. Melt mixing can be achieved using continuous extrusion equipment, eg, twin-screw extruders, single-screw extruders, other multi-screw extruders, and Farrell mixers, respectively. Static mixing equipment consists of a number of tubes with fixed obstacles arranged in such a way as to facilitate splitting and recombining of the streams for thorough mixing of the masterbatch and any additives or agents used in the polyester.

The molecular structure of the modified polyesters formed according to the invention may exhibit a certain degree of branching. As discussed above, it may also be desirable to increase the molecular weight of the modified polyester in order to increase polymer melt strength and melt viscosity. This can be achieved separately using a variety of methods, for example, the modified polyester can be subjected to a solid state condensation treatment, or chain coupling agents can be used in the modification process itself.

Modified polyesters exhibiting improved melt strength can be advantageously used in the field of blown films, where (obtained) higher melt viscosity, viscoelasticity and melt strength allow the adoption of higher expansion ratios, larger double Axial orientation and faster production rates while maintaining cell stability.

Increased melt strength is readily detectable by an increase in polyester strand diameter at the extruder die compared to unmodified polyester (ie, die swell). Some other equipment/parameters to characterize melt strength are: Goettfert Rheotens, uniaxial elongational viscosity and dynamic rheology.

The improved melt rheology of such modified polyesters advantageously allows for reduced processing steps and improved material properties. The improvement in melt rheology allows the modified polyester to be processed without prior drying and facilitates blow molding of the polyester. In particular, improved melt rheology facilitates stretch blow molding, facilitates the forming of polyesters, improves polyester adhesion to polar fillers such as those used in glass-reinforced polyesters, and allows polyesters to be very easily Geothermal forming.

The application of the masterbatch composition of the present invention can bring benefits to several plastic applications, such as:

●Beverage or cosmetic bottle

●Food or non-food film packaging

Sheets (e.g. thermoformable) for packaging (trays), construction or automotive sectors

●Injection products

●Belt or strap

●Profile or pipe

●Cylinder

●Bottle basket

●Textiles and nonwovens

The benefits brought by the masterbatch composition of the present invention are based on the following effects, for example:

● Higher productivity due to adjustment of melt rheology of polyester (easier processing)

The technology of extrusion blow molding or extrusion blown film is made possible by the modification of polyester

●Increase molecular weight and/or melt strength without incurring discoloration or gelation

●Enhance long-term thermal stability by increasing initial molecular weight

● Increased mechanical properties (eg, better tensile strength, higher elongation at break, higher bottle burst strength)

Improved impact properties (e.g. impact strength at ambient or -40°C temperature, which is important, for example, to achieve better frozen food drop test results on trays)

●Improve gas permeation resistance (eg, O ₂ , CO ₂ ) by increasing molecular weight and modifying polymer chain structure

●Excellent thermal dimensional stability by increasing molecular weight and modifying polymer chain structure

●Processing of polyester without pre-drying

●Compensate for molecular weight loss (I.V. loss) during processing

● Upgrading of low-value PET grades during processing

● Recycling of downgrade PET (post-consumer or production waste)

●Pultrusion of PET-fiber

●C-PET (crystallizable) processing performance matching

●Replacement with modified polyesters, e.g. polycarbonate

The masterbatch of the present invention can be preferably used in the following fields. Modification of bottle grade (IV ~ 0.80) or recycled PET to produce polyester suitable for thermoforming. Modification of recycled PET to produce polyester suitable for extrusion blow molding. Modification of bottle or recycled PET to produce polyester suitable for foaming.

Therefore, another aspect of the present invention is the use of the polyester masterbatch composition as described above for polyester modification.

The present invention will be further described below with reference to the following non-limiting examples.

example

Preparation of masterbatch:

A) Masterbatches containing pentaerythritol or pyromellitic dianhydride

The masterbatch is prepared by Japan Steel (JSW) TEX 30 twin-screw extruder. The carrier polyester used was PETG (Eastar 6763). Before preparing the masterbatch, the PETG was dried at 75°C in a dehumidifier for 2.5 days. The polyol branching agent used was pentaerythritol, while pyromellitic dianhydride was used as coupling/branching agent. Pentaerythritol and pyromellitic dianhydride were dried in separate vacuum ovens at 150° C. for 3 days before preparing the masterbatch.

PETG is melt mixed with metered amounts of pentaerythritol or pyromellitic dianhydride and extruded into pellet form, which is cooled under dry nitrogen and subsequently pelletized. The barrel temperature of the extruder was set at 170 (feed section), 180, 180, 180, 180, 180, 180, 180, 180, 180°C, while the 10mm diameter rod die was set at 180°C. The prepared masterbatches contained 5wt% and 20wt% of pentaerythritol and pyromellitic dianhydride, respectively. See Table 1 for test data.

B) Master batch containing pentaerythritol and pyromellitic dianhydride and catalyst

The masterbatch is prepared by Japan Steel (JSW) TEX 30 twin-screw extruder. The carrier polyester used was PETG (Eastar 6763). Before preparing the masterbatch, PETG was dried in a nitrogen-forced air oven at 85 °C for 50 h. The polyol branching agent used was pentaerythritol, while pyromellitic dianhydride was used as coupling/branching agent. In the masterbatch this also includes a transesterification catalyst (antimony trioxide). Before preparing the masterbatch, the pentaerythritol, pyromellitic dianhydride and antimony trioxide were dried overnight in a vacuum oven at 120°C. To facilitate incorporation of the agents into PETG during the melt mixing step, the agents were blended with a small amount of PET powder (BK2180, melt processing temperature about 270°C).

PETG was melt mixed with metered amounts of the above mentioned agents and extruded into pellet form which was cooled under dry nitrogen and subsequently pelletized. The barrel temperature of the extruder was set at 170 (feed section), 180, 180, 180, 180, 180, 180, 180, 180, 180°C, while the 10mm diameter rod die was set at 180°C. The prepared masterbatch contained 2.72 wt% pyromellitic dianhydride, 0.33 wt% pentaerythritol and 0.04 wt% antimony trioxide. See Table 2 for test data.

In the table below, CE-#=Comparative Example, and EX-#+Example#

Table 1: Preparation of master batches EX-1 and EX-2 sample number PDMAWt% Pentaerythritol Wt% PETGWt% Motor, A Melt temperature (℃) (JSW) Melt pressure (kg/cm2) Falling time from the die (s) Die temperature (℃) Note CE-1 0 0 100 19 232 2 16.7 232 transparent product EX-1 20 0 80 18 - - - - Deep Turbidity Products EX-2 0 5 95 18 - - - - Deep Turbidity Products

Table 2: Preparation of masterbatch EX-3 sample number PDMAWt% Pentaerythritol Wt% SbO ₃ wt% BK2180Wt% PETGWt% Motor, A Melt temperature (℃) (JSW) Melt pressure (kg/cm2) Falling time from the die (s) Die temperature (℃) Note CE-2 0 0 0 0 100 19 232 2 16.7 232 transparent product EX-3 2.72 0.33 0.04 6.00 90.91 17 222 0 18.8 213 Deep Turbidity Products

Modification of basic polyester by using the masterbatch prepared in Ex-1～Ex-3

The base polyester (BK3180, bottle grade PET, melt processing temperature about 270°C and IV = 0.82 dL/g) was modified using the masterbatches prepared in Ex-1 and Ex-2. The base polyester was dried overnight in a desiccator at 130°C before modification. PETG masterbatches, EX-1 and Ex-2, were dried at 85°C for 48h under nitrogen.

A blend of the base polyester with metered quantities of masterbatches Ex-1 and Ex-2 was melt mixed to provide a concentration of the agents in the base polyester equal to 0.25 wt % pyromellitic dianhydride, wherein pyromellitic acid di The molar ratio of anhydride to pentaerythritol was equal to 8:1 (ie, 0.0194 wt% pentaerythritol). The temperature curve of the extruder is: 260°C, 280°C (by 10), and the die used is a 10mm Brabender standard die. The extrudate exhibited significant die swell, indicating that a considerable degree of chain branching/coupling had occurred. See Table 3 for test data.

The base polyester (Shinpet 5015W, bottle grade PET, melt processing temperature about 270 °C and IV = 0.75 dL/g) was modified using the masterbatch prepared in Ex-3. The base polyester was dried overnight in a desiccator at 130°C before modification. PETG masterbatch, Ex-3, was dried under nitrogen at 85°C for 48h.

A blend of the base polyester with a metered amount of Master Batch Ex-3 was melt mixed to provide a concentration of the agents in the base polyester equal to 0.27 wt % pyromellitic dianhydride, 0.03 wt % pentaerythritol and 0.004 wt % trioxide Antimony concentration. The temperature profile of the extruder is: 260°C, 280°C (by10), and the die used is a 10mm Brabender standard die. The extrudate exhibited significant die swell, indicating that a considerable degree of chain branching/coupling had occurred. See Table 4 for test data.

Table 3: Modification of basic polyester using masterbatches Ex-1 and Ex-2 sample number EX-1Wt% EX-2Wt% BK3180Wt% Modifier wt% Motor, A Melt temperature (℃) (JSW) Melt pressure (kg/cm2) Falling time from the die (s) Die temperature (℃) Note CE-3 0 0 100 PDMA=0 Penta=0 10 280 2 4 282 transparent product EX-4 1.25 0.39 98.36 PDMA=0.25 Penta=0.0194 twenty two - - -Dark cloudy product Dark cloudy product - Clear product, indicating die expansion

Table 4: Modification of basic polyester using masterbatch Ex-3 sample number EX-3Wt% Shinpet5015WWt% Modifier wt% Motor, A Melt temperature (℃) (JSW) Melt pressure (kg/cm2) Falling time from the die (s) Die temperature (℃) Note CE-4 0 100 PDMA=0 Penta=0 10 280 2 4 282 transparent product EX-5 10 90 PDMA=0.27 Penta=0.03 12 284 0 8 284 Clear product, indicating die expansion

NMR (nuclear magnetic resonance) spectroscopic analysis of masterbatches prepared in Ex-1 and Ex-2

Sample preparation:

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 excess trichloroacetyl isocyanate (10 μL, 6.3 mg, 3.36 mmol ). ¹ H NMR spectra were recorded at room temperature on a Bruker DRX 500 operating at 500 MHz.

¹ H NMR (CDCl ₃ , ppm, δ): 8.05 (M, 99H, ArH), 8.50 (m, 0.30H, NH Alcohol), 8.65 (s.0.08H, NH Alcohol), 10.36 (s, 1H, NH Acid).

A sample of master batch Ex-1 (pyrimellitic dianhydride) (30 mg) was dissolved in CDCl ₃ (0.5 mL), and after dissolution, the mixture was filtered and transferred to an NMR tube, and excess trichloroacetyl isocyanate (10 μL , 6.3mg, 3.36mmol). ¹ H NMR spectra were recorded at room temperature on a Bruker DRX 500 operating at 500 MHz.

¹ H NMR (CDCl ₃ , ppm, δ): 8.05 (m, 71H, ArH), 8.50 (m, 0.10H, NH Alcohol), 10.36 (s, 1H, NHAcid).

A sample of masterbatch Ex-2 (pentaerythritol) (30 mg) was dissolved in _CDCl3 (0.5 mL), and after dissolution, the mixture was filtered and transferred to an NMR tube, and excess trichloroacetyl isocyanate (10 μL, 6.3 mg, 3.36 mmol). ¹ H NMR spectra were recorded at room temperature on a Bruker DRX 500 operating at 500 MHz.

¹ H NMR (CDCl ₃ , ppm, δ): 8.05 (m, 85H, ArH), 8.55 (m, 0.30H, NH Alcohol), 10.36 (s, 1H, NH Acid).

result:

The addition of trichloroacetyl isocyanate (TAI) to PETG in chloroform produced several additional peaks in the ¹ H NMR spectrum, which appeared at δ 10.36, 8.65 and 8.50 ppm. The signal at δ 10.36 ppm was assigned to the adduct generated by the reaction between TAI and PETG acid end groups. The other 2 signals are at δ8.65.

C) Preparation of masterbatch containing polyol or PMDA

The example below shows that both low melting point (trimethylolpropane, melting point 60°C) and high melting point polyols (pentaerythritol, melting point 255°C) can be used to produce PETG masterbatch when low processing temperature (170°C) is used .

The masterbatch was prepared on a Brabender single screw extruder (19 mm diameter screw, compression ratio ~3:1 and equipped with a slot mixing head), L/D = 25:1, 3 heating zones and a 6 mm rod die . The low temperature profile has 3 heating zones at 160°C, 170°C, 170°C and the die is at 170°C. The high temperature profile has 3 heating zones at 260°C, 270°C, 270°C and the die is at 270°C. A nitrogen blanket was maintained over the feed throat.

Moisture content was measured with an Arizona Instruments Computrac 3000 Moisture Analyzer on samples added at 80°C.

The carrier polyester used was PETG (Eastar 6763). Before masterbatch preparation, the PETG pellets were dried in a vacuum oven at 75°C for 48h (the moisture content after drying was 55ppm H ₂ O, and the melt flow index was 18.35g/10min at 270°C). The PETG powder was dried in a vacuum oven at 75°C for 3h (the moisture content after drying was 215ppm H ₂ O, and the melt flow index was 1.13g/10min at 200°C). Before masterbatch preparation, PMDA and pentaerythritol were dried in a vacuum oven at 100°C for 15 h. Trimethylolpropane was used directly as supplied.

PETG is mixed with a weighed amount of polyol or PMDA and extruded into strand form, which is cooled under dry nitrogen and subsequently pelletized. The extruder barrel temperature was set at the levels shown in Tables 5-10. The test data are shown in Table 5-10.

Table 5. Preparation of masterbatches using pentaerythritol (Penta) at 170°C example ^* C rpm torque pressure psi Throughput g/kg fall time MFIg/10min additive% Additives used Comparative example EX6EX7 170170170 101010 131512131130 939192 369.6299.9314 147.56181.02209.85 1.31.21.35 00.31 No Penta Penta

Table 6. Attempts to prepare masterbatches using pentaerythritol (Penta) at 270°C example ^* C rpm torque pressure psi Throughput g/kg fall time MFIg/10min additive% Additives used Comparative example CECE 270270270 101010 000 000 248302.8304.8 14.419.534.16 3.6324.5243.89 00.31 No Penta Penta

Table 7. Preparation of masterbatches using trimethylolpropane (TMP) at 170°C example ^* C rpm torque pressure psi Throughput g/kg fall time MFIg/10min additive% Additives used Comparative example EX8EX9 170170170 101010 131516181029 936343 369.6431287 147.56148.25181.25 1.31.881.77 00.31 no TMPTMP

Table 8. Trial Masterbatch Formulation Using Trimethylolpropane (TMP) at 270°C example ^* C rpm torque pressure psi Throughput g/kg fall time MFIg/10min additive% Additives used Comparative example CE 270270 1030 00 00 248147.2 14.410.2 3.6367.2 01 no TMP

Table 9. Preparation of masterbatches using PMDA at 170°C example ^* C Rpm torque pressure psi Throughput g/kg fall time MFIg/10min additive% Additives used Comparative example EX10EX11EX12 170170170170 10121215 1315136914121576 93788394 369.6389.4361.7395.1 147.56159.37171173.11 1.31.221.271.65 00.3110 No PMDAPMDAPMDA

Table 10. Trial masterbatch formulated with PMDA at 270°C example ^* C Rpm torque pressure psi Throughput g/kg fall time MFIg/10mim additive% Additives used CECE CECE 270270270270 10101010 0000 0036 248255191.3155.9 14.4115.7219.0322.81 3.632.762.211.81 00.30% 0.30% 1.00% No PMDAPMDAPMDA

D) Formulation of masterbatches containing different carrier polyesters and additives

Intrinsic viscosity (I.V.):

1 g of polymer was dissolved in a mixture of phenol/dichlorobenzene (1/1). The viscosity of the solution was measured in an Ubbelohde viscometer at 30°C and extrapolated to give the intrinsic viscosity.

color:

Color (b-value of yellowness index) was determined according to ASTM D1925 using a Hunter Lab Scan instrument.

Melt Flow Rate (MFR):

MFR was measured using Goettfert MP-P, according to ISO1133 at 260°C, with a load of 2.16 kg, after polyester pre-drying.

Material:

All carrier polyesters are dried before use (>12h at 60°C under vacuum)

Carrier Polyester A:

Polyesters of the following composition:

81.8mol% terephthalic acid

18.2mol% isophthalic acid

96.9% ethylene glycol

3.1% diethylene glycol

Commercially available product, produced by Nan Ya Plastics (USA) Company

The polyester has a melt viscosity of 1315 Pa.s, measured in a Goettfert capillary rheometer "Rheograph 2001" at a shear rate of 100 s ⁻¹ and 190° C.; 10 mm capillary length, 1 mm capillary diameter.

Carrier Polyester B:

Polyesters of the following composition:

70.1mol% terephthalic acid

29.9mol% isophthalic acid

92.9% ethylene glycol

7.1% diethylene glycol

Commercially available product, produced by Nan Ya Plastics (USA) Company

The polyester has a melt viscosity of 1035 Pa.s, measured in a Goettfert capillary rheometer "Rheograph 2001" at a shear rate of 100 s ⁻¹ and 200° C.; 10 mm capillary length, 1 mm capillary diameter.

Carrier Polyester C:

Poly-ε-caprolactone from Fluka

The polyester exhibited a melt viscosity of 858 Pa.s at a shear rate of 100 s ⁻¹ and 160° C. (measured in a Goettfert capillary rheometer “Rheograph 2001”; 10 mm capillary length, 1 mm capillary diameter).

Chain coupling agent:

PMDA 1, produced by Beyo (China), (powder) (melting temperature: 284°C)

PMDA 2, produced by Beyo (China), (coarse grain) (melting temperature: 287°C)

Alinco®, DSM (= dodecahydro-1,1'-carbonyl-bis-azapin-2-one, CAS RN19494-73-6)

Branching agent:

Pentaerythritol, Perstorp (Finland) (melting temperature: 262°C) (=Penta)

Other additives:

Irgamod 195a phosphonate, commercial product, Ciba Specialty Chemicals, export

Irganox 1222a phosphonate, commercial product, Ciba Specialty Chemicals, export

IRGAFOS 12a phosphite, commercial product, Ciba Speciality Chemicals, export

IRGAFOS 168a phosphite, commercial product, exported by Ciba Specialty Chemicals

IRGANOX HP136 a lactone, commercial product, exported by Ciba Specialty Chemicals

Compound 101: synthesized using standard procedures

Compound 102: Diisooctyl hypophosphorous acid available from Fluka

Basic polyester (to be modified with masterbatch):

The base polyester used is dried before use (at 80°C, under vacuum, >12h)

PET D: Polyclear T94 Supplier KoSa Gersthofen

PET E: Polyclear RT48 Supplier KoSa Gersthofen

PET F: Polyclear RT21 Supplier KoSa Gersthofen

PET G1: ICI LaserPlus Supplier ICI

PBT X: Crastin SK605 NC010 Supplier DuPont

Example MB1～MB23

Prepare masterbatch according to procedure A

General Procedure A:

In a twin-screw extruder (ZSK 25, produced by Werner & Pfleiderer), the screws rotate in the same direction to extrude the following formulations, with the highest extrusion temperature _Tmax =180°C (heating zone 1～6), throughput 5kg/h, 100rpm and pellet in a water bath.

General Procedure A was used for the following compositions: instance number polyester carrier chain coupling agent branching agent additive Composition A 100%A - - - Composition B 95%A - - 5% Irgamod 195 MB1 95%A - 5% Penta - MB2 90%A 10%PMDA1 - - MB3 89%A 10% PMDA 1 1%Penta - MB4 88%A 10%PMDA1 2%Penta - MB5 88%A 10%PMDA1 1%Penta 1% Irgamod 195 MB6 89%B 10%PMDA1 1%Penta - MB7 88%B 10%PMDA1 1%Penta 1% Irgamod 195 MB8 88%B 10%PMDA1 - 2% Irgamod 195 MB9 75%B 25% PMDA1 - - MB10 72.5%B 25% PMDA1 2.5% Penta - MB11 70%B 25% PMDA1 2.5% Penta 2.5% Irgamod 195 MB12 70%B 25% PMDA1 - 5% Irgamod 195 MB13 89%C 10%PMDA1 1%Penta - MB14 88%A 10%PMDA1 1%Penta 1% Irgafos 168 MB15 88%A 10%PMDA1 1%Penta 1% Irgafos 12

instance number Polyester carrier chain coupling agent branching agent Additives 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%IrgafosHP136 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

Example MB24～MB27

Prepare masterbatch according to procedure B

General procedure B:

In a Buss co-kneader (MDK140) with a separate transverse screw for extrusion to the die, the formulations listed below were passed through Amount of 400kg/h, 140rpm (kneading blade) conditions are extruded, and pelletized in a water bath.

General Procedure B was used for the following compositions: instance number polyester carrier chain coupling agent branching agent additive Composition C 100% B - - - MB24 89%B 10%PMDA1 1%Penta - MB25 88%B 10%PMDA1 1%Penta 1% Irgamod 195 MB26 88%B 10%PMDA1 - 2% Irgamod 195 MB27 76%B 20% PMDA 2 2%Penta 2% Irgamod 195

E) Modification of base polymer with masterbatch

General procedure

In a twin-screw extruder (ZSK 25, produced by Werner & Pfleiderer), the screws rotate in the same direction to extrude the following formulations, with the highest extrusion temperature _Tmax = 280°C (heating zone 1-6), throughput 6kg/h, 100rpm and pellet in a water bath.

The general procedure was used for the following comparative examples:

instance number Basic polyester Additives MFRg/10min I.V.dl/g color B ^* -value Composition D 100%E - 62 0.55 0.92 Composition E 100%E 0.2% PMDA 10.02% Penta 0.02% Irgamod 195 25 0,66 9.2 Composition F 100%F - 18 0.57 - Composition G 100%G1 - 14 0.75 - Composition H 100%D - 16 0.76 -

This general procedure was used in Examples C1-C25 below. instance number polyester masterbatch Equivalent to additive composition MFRg/10min IVdl/g color B ^* -value Ex C1 100%E 2% MB15 0.2% PMDA 10.02% Penta 0.02% Irgamod 195 twenty one 0.69 -1.3

The performance of the masterbatch MB15 is much better (in terms of MFR reduction, I.V. improvement and color) compared to the direct addition of the active ingredient (as was the case in the tests in comparative composition E).

instance number Basic polyester masterbatch MFRG/10min I.V.dl/g Ex C2 100%D 1% MB2 6.3 0.84 Ex C3 100%D 3% MB2+0.6% MB1 2.1 0.91 Ex C4 100%D 1% MB3 8.7 0.86 Ex C5 100%D 1% MB3+0.5% Comp B 4.3 0.94 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.B1 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

F) Preparation of extrusion-blown film

General procedure:

In a twin-screw extruder (Haake TW100, counter-rotating conical screws), the formulation below was extruded into a film blown die at _Tmax temperature = 280 °C, throughput 1.8 kg/h and 60 rpm .

This general procedure was used for Comparative Examples M and N, and for Examples D1 and D2 according to the invention.

instance number Basic polyester Additives film thickness Note Composition M 100%D - ^*** Composition N 100%D 0.3% PMDA 10.03% Penta 25.3μm yellow film many gels

^*** : Extrusion of blown film is not feasible because the melt strength is too low instance number base polyester additive film thickness Note Ex D1 100%D 3% MB3 17.5μm no discoloration no gel Ex D2 100%D 3% MB5 10.9μm no discoloration no gel

Claims (20)

CLAIMS 1. A polyester masterbatch composition comprising, a branching and/or chain coupling agent dispersed within a polyester polymer matrix, wherein the polyester has a melt processing temperature equal to or less than 250°C. 2. The polyester masterbatch composition of claim 1, wherein the agent is a chain branching agent. 3. The polyester masterbatch composition of claim 2, wherein the chain branching agent is a polyol. 4. The polyester masterbatch composition of claim 1, wherein the agent is a chain coupling agent. 5. The polyester masterbatch composition of claim 4, wherein the chain coupling agent is a dianhydride. 6. The polyester masterbatch composition of claim 1, wherein the agents are chain branching agents and chain coupling agents. 7. The polyester masterbatch composition of claim 6, wherein the chain branching agent is a polyol and the chain coupling agent is a dianhydride. 8. The polyester masterbatch composition of claim 1, wherein the melt viscosity of the polyester and/or the intrinsic viscosity of the polyester, when melt-mixed with branching and/or chain coupling agents, reduce or increase by no more than 30%. 9. The polyester masterbatch composition of claim 1, wherein the melting temperature of the branching and/or chain coupling agent is at least 10°C higher than the melt processing temperature of the polyester. 10. The polyester masterbatch composition of claim 1, wherein the melt processing temperature of the polyester suitable for the masterbatch is between 150°C and 250°C. 11. The polyester masterbatch composition of claim 1, wherein the polyester suitable for the masterbatch has a crystallinity of less than 15%. 12. The polyester masterbatch composition of claim 1, wherein the polyester suitable for the masterbatch is glycol-modified polyethylene terephthalate (PETG), poly-ε-caprolactone, or containing Copolyesters with greater than 15% isophthalic acid units. 13. The polyester masterbatch composition of claim 1, wherein the branching agent is a polyol present in an amount of 0.3 to 30 wt%, based on the weight of the polyester masterbatch polymer. 14. The polyester masterbatch composition of claim 1, wherein the chain coupling agent is present in an amount of 1 to 60 wt%, based on the weight of the polyester masterbatch polymer. 15. The polyester masterbatch composition of claim 1 additionally comprising a phosphite, hypophosphite or phosphonate compound. 16. The polyester masterbatch composition of claim 15, wherein the phosphonate has the general formula III, IV, V, VI or VII wherein R ₁₀₁ are each independently of each other hydrogen or M ^r+ /r. 17. The polyester masterbatch composition of claim 1 further comprising a condensation or transesterification catalyst. 18. A method of preparing a polyester masterbatch, comprising melt mixing polyester with a branching and/or chain coupling agent so as to disperse the branching and/or chain coupling agent within a polymer matrix of the polyester, wherein the Polyesters have a melt processing temperature equal to or less than 250°C. 19. A method of modifying a polyester comprising melt mixing the polyester with the polyester masterbatch of claim 1 at a temperature greater than 250°C. 20. Use of the polyester masterbatch composition of claim 1 for polyester modification.