Polymer materials and additives thereof

Abstract

The present invention provides a formulation for reducing the aldehyde content in a polymeric material, the formulation comprising a compound comprising at least three moieties (A) of formula: # imgabs0 # wherein each moiety (A) comprises an amine moiety (-NH2) ortho or meta bonded to an amide moiety (-CONH); wherein each R1 independently represents a substituent, m is an integer from 0 to 4; and wherein the three moieties (A) are bonded by their respective amide nitrogen atoms to respective carbon atoms of the host fragment, wherein the host fragment comprises only carbon atoms and hydrogen atoms and is saturated.

Description

Technical Field

[0001] The present invention relates to polymeric materials, in particular but not limited to polymeric materials such as polyesters, polyoxymethylene (POM), polyolefins, polyketones and polyurethanes, wherein aldehydes may be undesirably bound thereto, for example due to generation during the manufacture of the polymeric materials, during downstream melt processing of the polymeric materials and / or during use. The polymeric materials may also contain recycled materials that may be contaminated with aldehydes. This may particularly apply to recycled HDPE and / or PP. Background Art

[0002] Polyethylene terephthalate (PET) is used on a large scale to make food packaging such as bottles. Such bottles are widely used to package beverages such as carbonated soft drinks, beer or mineral water. The technology commonly used to make bottles from PET (i.e. converting PET from the raw material stage into a predetermined shape) generally involves a two-stage process. In the first stage, PET pellets are injection molded to make a preform. In the second stage, the preform is blow molded into the desired shape.

[0003] PET has a high softening point. Therefore, typical temperatures required for PET processing are in the range of 260°C to 285°C. It is a recognized problem in the industry that PET tends to degrade under the high temperature and shear conditions required for injection molding to make preforms and blow molding preforms to make bottles, resulting in the formation of acetaldehyde. The presence of acetaldehyde in the finished bottle material is undesirable, especially when the bottle is used for products consumed by humans, because the acetaldehyde can migrate from the walls of the package or bottle into its contents, thereby adversely affecting the flavor and aroma characteristics of the edible product. Although the formation of acetaldehyde in bottles made using virgin PET is an ongoing problem, the formation of acetaldehyde in bottles made using recycled PET (rPET) can be even higher due to the multiple thermal histories of PET.

[0004] Although the migration of acetaldehyde from PET bottles into flavored beverages is undesirable, trace amounts of acetaldehyde are usually tolerated because the taste and aroma of the beverage are usually not significantly affected. However, in carbonated beverages or non-carbonated beverages (such as mineral water), even the presence of trace amounts of acetaldehyde often imparts a most undesirable unpleasant taste and odor to the beverage.

[0005] It is known to add acetaldehyde scavengers to PET before or during melt processing to scavenge acetaldehyde that may be produced by PET degradation. However, there are various competing requirements related to the selection and use of acetaldehyde scavengers. For example, the weight of acetaldehyde scavenger incorporated into PET needs to be high enough to scavenge large amounts of acetaldehyde. However, higher levels of additives incorporated into PET may be detrimental to the optical properties of PET. For example, high levels of additives may adversely affect L* (i.e., reduce L*), a* or b*, each of which is undesirable, especially when PET is used in mineral water bottles, where aesthetics are particularly important. In addition, it is important that the acetaldehyde scavenger itself does not migrate significantly from PET, as this may undesirably enter the beverage contained in the bottle made from PET.

[0006] WO2017 / 033117A (Colormatrix) discloses a method for reducing the aldehyde content in a polymer material (e.g., polyethylene terephthalate). The document specifically exemplifies a series of acetaldehyde scavengers and evaluates the properties of the scavengers in Examples 6 to 13. However, even the scavenger (Example 6) that exhibits the lowest level of migration still exhibits a relatively high mobility, and the optical properties of the bottle containing the scavenger can be improved.

[0007] The present invention is based on the discovery of aldehyde scavengers which are improved over the scavengers described in WO2017 / 033117A.

[0008] Aldehydes, especially formaldehyde, may also be generated during the manufacture, processing and / or use of polyoxymethylene (POM) and other polymers. Aldehyde scavengers can be used to remove formaldehyde. Summary of the invention

[0009] The object of the present invention is to solve the problems associated with aldehydes, such as formaldehyde or acetaldehyde, generated in polymeric materials.

[0010] The object of the present invention is to provide an aldehyde scavenger which can be improved compared to the scavengers described in WO2017 / 033117A

[0011] According to a first aspect of the present invention, there is provided a formulation for reducing the aldehyde content, for example in a polymeric material, the formulation comprising a compound XX, the compound XX comprising at least three moieties (A) of the following formula:

[0012]

[0013] wherein each moiety (A) comprises an amine moiety (-NH2) bonded ortho or meta to an amide moiety (-CONH);

[0014] Each R 1independently represents a substituent, and m is an integer from 0 to 4; and

[0015] wherein the three moieties (A) are bonded via their respective amide nitrogen atoms to respective carbon atoms of the main fragment, wherein the main fragment comprises only carbon and hydrogen atoms and is saturated.

[0016] It has been found that compound XX has advantageous performance in providing high levels of aldehyde scavenging at acceptable addition rates in polymeric materials (e.g., polyesters) without significantly affecting optical properties (e.g., L*, a*, and / or b*), and advantageously exhibits relatively low levels of polymer migration. Compound XX is surprisingly superior to the compounds disclosed in WO2017 / 033117A.

[0017] One R 1 or each R 1 Can be selected from halogen atoms, or optional substituted alkyl, alkoxy, amido, amide groups, phenolic or carboxyl groups.Optional substituted alkyl can be substituted by one or more halogen atoms or by alkoxy, amido, amide groups, phenolic or carboxyl groups.Optional substituted alkyl is preferably unsubstituted.

[0018] One R 1 or each R 1 It can be an optionally substituted alkyl group, preferably an unsubstituted alkyl group, for example, an optionally substituted, preferably unsubstituted C 1-20 Alkyl groups, such as C 1-10 Alkyl. 1 can be arranged to improve the compatibility of compound XX in the polymeric material into which it can be incorporated, for example by R 1 Relevant functional groups are included to improve compatibility.

[0019] One or each m may be 0 or 1. Preferably, each m = 0. That is, except for the amine moiety and the amide moiety, each moiety (A) is unsubstituted.

[0020] Preferably, in compound XX, at least one moiety (A) comprises an amine moiety (-NH2) ortho-bonded to an amide moiety (-CONH). Preferably, in each moiety (A) of compound XX, the amine moiety is ortho-bonded to the amide moiety. Preferably, in this case, m=0.

[0021] Preferably, the main segment does not include any cyclic or aromatic moieties.Preferably, the main segment includes a linear or branched chain.

[0022] The main fragment may comprise 3 to 20 carbon atoms. Preferably, it comprises 5 to 15 carbon atoms, more preferably 7 to 12 carbon atoms, and in particular 8 to 10 carbon atoms. When the number of carbon atoms is n, the number of hydrogen atoms may be equal to 2n-1. Preferably, the main fragment comprises 5 to 39 hydrogen atoms. Preferably, it comprises 9 to 29 hydrogen atoms, more preferably 13 to 23 hydrogen atoms and in particular 15 to 19 hydrogen atoms.

[0023] In a preferred embodiment, the major fragment is C9H 17 part.

[0024] The main fragment may comprise a linear chain comprising 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. The linear chain may comprise branch points to which chains comprising 1 to 4 carbon atoms are attached.

[0025] The main fragment has the following general formula (B):

[0026]

[0027] wherein p, q and r are integers in the range of 1 to 10, preferably in the range of 1 to 5. Preferably, p is in the range of 2 to 4, q is in the range of 1 to 3 and r is in the range of 2 to 6.

[0028] Preferably, the sum of the integers p, q and r is at least 4, preferably at least 6, more preferably at least 7. The sum may be less than 20, preferably less than 15, more preferably less than 10.

[0029] In compound XX, the nitrogen atoms of the amide moiety (-CONH) are preferably spaced at least 2 carbon atoms apart, preferably at least 4 carbon atoms apart; and suitably not more than 10 carbon atoms apart, for example not more than 7 carbon atoms apart.

[0030] The compound XX may have the following formula:

[0031]

[0032] where p, q and r are as described above.

[0033] The compound XX is preferably:

[0034]

[0035] The formulation may comprise at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, especially at least 75 wt% of the carrier. The formulation may comprise less than 80 wt% of the carrier.

[0036] The formulation may include 50wt%-95wt% of a carrier, 5wt%-50wt% of the compound XX and 0-30wt% of other additives. The other additives may be selected from colorants, antioxidants, thickeners, process stabilizers, UV additives and reheat additives. In a preferred embodiment, the formulation comprises 0.5wt% to 10wt% of one or more colorants, such as at least one blue colorant. In another embodiment, the formulation includes 0.5wt% to 10wt% of one or more reheat additives, such as titanium nitride or tungsten oxide (especially the latter) as described in WO2016 / 063013, the contents of which are incorporated herein by reference in connection with titanium nitride and tungsten oxide. In a preferred embodiment, the formulation includes at least some colorants, such as a blue colorant.

[0037] The colorants described herein may be dyes or pigments.

[0038] Preferably, in the formulation, the sum of the weight percentages of the carrier and the compound XX is at least 80 wt%, at least 90 wt% or at least 95 wt%.

[0039] The formulation may be a solid masterbatch or a liquid formulation. When it is a solid masterbatch, it may contain 60 wt% to 95 wt% of a thermoplastic polymer. The thermoplastic polymer may be selected from polyesters, polyoxymethylene (POM), polyolefins, polyketones and polyurethanes. As described herein, the thermoplastic polymer preferably matches and / or contains the same functional groups as the functional groups in the polymer material to be treated to reduce the aldehyde content.

[0040] The formulation may comprise 10 wt% to 40 wt% of compound XX and 60 wt% to 90 wt% of a thermoplastic polymer.

[0041] The solid masterbatch may include up to 60 wt% of a colorant. The colorant may be a dye or a pigment. The solid masterbatch may include 0 to 10 wt%, preferably 0.5 wt% to 10 wt% of one or more colorants, such as one or several inorganic pigments.

[0042] When the formulation is a liquid formulation, the formulation may comprise 50 wt% to 90 wt% (e.g. 50 wt% to 80 wt%) of a liquid carrier and 10 wt% to 50 wt% (e.g. 20 wt% to 50 wt%) of compound XX. The liquid carrier may be a liquid at 25°C and atmospheric pressure. The carrier should ensure that it has good solubility in the polymer material to be added. It may include an oil (e.g. a vegetable oil or a mineral oil) or ethylene glycol. An organic liquid carrier that is compatible with the polymer material (particularly where the polymer material is a polyester) may be an oil-based carrier. An example of such a carrier is ColorMatrix Europe Ltd. (address: Unity Grove 9-11, Knowsley Business Park, Merseyside, L34 9GT) sold under the trade name Clearslip TM 2. Clearslip TM 3&Process Aid-1 Materials sold.

[0043] When the preparation is a solid preparation (ie, a masterbatch), a polymer resin can be used as a carrier. Such a carrier can be polyester, polyoxymethylene (POM), TPE, polyvinyl butyral (PVB), polyolefin or wax.

[0044] Certain compounds of formula XX are considered novel. Therefore, in a second aspect, there is provided a novel compound of formula XX comprising at least three moieties (A) of the following formula:

[0045]

[0046] wherein each moiety (A) comprises an amine moiety (-NH2) bonded ortho or meta to an amide moiety (-CONH);

[0047] Each R 1 independently represents a substituent, and m is an integer from 0 to 4; and

[0048] wherein the three moieties (A) are bonded via their respective amide nitrogen atoms to respective carbon atoms of the main fragment, wherein the main fragment comprises only carbon and hydrogen atoms and is saturated.

[0049] Preferably, the novel compound is:

[0050]

[0051] According to the third aspect of the present invention, there is provided a method for reducing the aldehyde content in a polymer material, the method comprising the step of contacting the polymer material or a monomer, oligomer or prepolymer involved in the preparation of the polymer material with the compound XX described in the first aspect and / or the second aspect.

[0052] The polymer material contacted in the method may be any polymer material which may incorporate an aldehyde which needs to be removed or otherwise reduced. The polymer material may comprise a polyester (particularly polyethylene terephthalate), a polyurethane, a polyoxymethylene (POM), a polyketone or a polyolefin. Preferably, it comprises a polyester (particularly polyethylene terephthalate). The polymer material may comprise virgin material or recycled material. The latter may be particularly relevant to HDPE and / or PP.

[0053] As used herein, "ppm" means "parts per million" by weight.

[0054] FlVillian et al., Journal of Polymer Science, Vol. 52, 55-60 (1994) have described a method for measuring acetaldehyde in industrial injection molded polyethylene terephthalate preforms.

[0055] The contacting step may be carried out when the polymer material is in a molten state. Alternatively, the compound may be suitably added to the solid polymer material at a temperature below the melting point of the polymer material so that the polymer material is not in a fluid and / or molten state. In a less preferred embodiment, compound XX may be added to a monomer, oligomer or prepolymer involved in the preparation of the polymer material. This may be particularly relevant to processes related to polyoxymethylene (POM), polyvinyl butyral (PVB), polyolefins and polyurethanes.

[0056] Advantageously, use of this method may improve the environment, reduce global emissions and sublimation, and improve oxidation induction times.

[0057] Prior to the contacting step, the polymeric material is preferably selected to be suitable when it is in a solid state as described above. The selected polymeric material is suitably present substantially in the absence of the monomers used to prepare the polymeric material. The selected polymeric material is preferably in a state separated from the reaction mixture from which it may have been formed. It is preferably an isolated polymeric material. The method may include the step of drying the polymeric material prior to the contacting step. The selected polymeric material is preferably in particulate form, such as pellets, microparticles or flakes.

[0058] The amount of compound XX contacted with the polymer material may be selected according to the desired performance level of the polymer material. In a preferred embodiment, the total ppm of compound XX contacted with the polymer material (based on the weight of the polymer) is suitably at least 100 ppm, preferably 200 ppm, more preferably at least 450 ppm. It may be less than 2000 ppm or less than 1000 ppm.

[0059] The compound XX may be part of a formulation according to the first aspect. In a preferred embodiment, the compound XX may be associated with, for example mixed with, an organic liquid carrier that is compatible with the polymer material. Typical carriers include hydrocarbons, hydrocarbon mixtures, alcohols, esters, polyethers, and mixtures of two or more thereof.

[0060] The organic liquid carrier which is compatible with the polymeric material (particularly where the polymeric material is a polyester) may be an oil-based carrier. Examples of such carriers are available from ColorMatrix Europe Ltd. (Address: 9-11 Unity Grove, Knowsley Business Park, Merseyside, L34 9GT) under the trade name Clearslip TM 2. Clearslip TM 3&Process Aid-1 Materials sold.

[0061] When the polymer material is a polyester, preferably, the polyester is preferably polyethylene terephthalate, which term is intended to include copolymerized terephthalate in the context of this specification. Copolymerized terephthalate may contain repeating units from at least 85 mol % of terephthalic acid and at least 85 mol % of ethylene glycol. In addition to terephthalic acid, dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexane dicarboxylic acid, cyclohexane diacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid may also be included. In addition to ethylene glycol, other diols that may be incorporated into the copolymerized ethylene terephthalate include diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-2,4-pentanediol, 2-methyl-1,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propylene glycol, 1,3-hexanediol, 1,4-bis(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane. In a preferred embodiment, the polyethylene terephthalate has a comonomer substitution of less than 10 mol%, more preferably less than 6 mol%, especially less than 2 mol%. Preferably, the copolymerized ethylene terephthalate does not include ethylene terephthalate copolymers; suitably, it essentially comprises a homopolymer prepared by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol to prepare bis(2-hydroxyethyl)terephthalate, followed by polycondensation in the presence of a catalyst in vacuum at elevated temperature.

[0062] As used herein, the term "IV" refers to the intrinsic viscosity of a polymeric material. It can be measured in a solution of 0.5 g of polymer dissolved in 100 ml of a mixture of phenol (60% by volume) and tetrachloroethane (40% by volume).

[0063] When the polymeric material is a polyester, the IV of the polyester when contacted with the compound XX is preferably greater than 0.5 dL / g, more preferably greater than 0.65 dL / g.

[0064] When the polymeric material is a polyester, the polyester may be particularly suitable for extrusion blow molding (EBM).Such adaptations are known to those skilled in the art and include increasing the amount of comonomer, changing IV and structure.

[0065] The polymer material is preferably part of and / or defines an article, such as a shaped article. The article may be selected from a preform, a container, a bottle, a cup, a tray, a thermoformed sheet, or other desired shape.

[0066] After contacting the polymer material with compound XX, the polymer material may comprise 50 ppm to 1000 ppm of compound XX, preferably 100 ppm to 700 ppm or 150 ppm to 600 ppm of compound XX, based on the amount of the polymer (eg polyester).

[0067] According to a fourth aspect of the present invention, there is provided a method for preparing an article (e.g. a shaped article) from a polymer material, the method comprising:

[0068] (a) selecting compound XX as described in the first aspect and / or the second aspect;

[0069] (b) contacting said polymeric material with said compound XX; and

[0070] (c) forming the polymeric material into an article, such as a shaped article.

[0071] Preferably, step (b) is carried out while the polymeric material is not in a fluid (eg molten) state. Thereafter, in step (c), the polymeric material is subjected to a suitable melt processing to define the article.

[0072] The article may be defined by any process known in the art. For example, the process may include injection molding, blow molding or thermoforming. For example, injection molding can be used to form a preform for blow molding bottles, food / beverage containers, trays or other desired shapes. In addition, the process may include the production of a sheet that can then be thermoformed to define an article, such as a container such as a cup or tray. Alternatively, the molten polymer material can be used in an extrusion blow molding operation to provide bottles, food containers, etc. The molten polymer material melt can similarly be fed into an extruder to produce films, sheets, profiles, pipes, etc.

[0073] Preferably, the article comprises a container or a preform for a container, preferably made from a polyester as described herein. More preferably, the shaped article comprises a preform, for example a preform for a bottle such as a beverage bottle.

[0074] The article may include one or more colorants, for example, at least one blue colorant. After the polymer material is contacted with compound XX, the polymer material may include 1 ppm to 1000 ppm of a colorant (e.g., a blue colorant), and preferably 5 ppm to 500 ppm of a colorant, the ppm being based on the amount of the polymer material (e.g., polyester). The colorant described herein may be a dye or a pigment.

[0075] The article may contain one or more reheat additives, such as titanium nitride or tungsten oxide (especially the latter) as described in WO2016 / 063013, the contents of which are incorporated herein by reference in relation to titanium nitride and tungsten oxide. After the polymer material is contacted with compound XX, the polymer material may contain 1 ppm to 1000 ppm of a reheat additive (such as titanium nitride or tungsten oxide), and preferably 5 ppm to 500 ppm of a reheat additive (such as titanium nitride or tungsten oxide), the above ppm being based on the amount of the polymer material (such as polyester).

[0076] Preferably, in the shaped article the sum of the weight % of polymeric material (eg amount of polyester) and the weight % of compound XX is at least 90 wt % or at least 95 wt % or at least 98 wt %.

[0077] According to a fifth aspect of the present invention, there is provided a polymeric material (e.g. polyester) having reduced levels of aldehydes (e.g. acetaldehyde), the polymeric material (e.g. polyester) incorporating compound XX according to the first aspect or the product of a reaction between compound XX and an aldehyde (e.g. acetaldehyde).

[0078] Suitably, the reaction product between compound XX and an aldehyde (eg acetaldehyde) comprises a fragment (N) as described below, derived from part (A) as described in the fragment of the first aspect:

[0079]

[0080] Where R 30 refers to the residue of an aldehyde, and when the aldehyde is acetaldehyde, R 30 Suitably methyl.

[0081] The product of the reaction preferably comprises the following moiety (O):

[0082]

[0083] According to the first aspect, the nitrogen atom adjacent to the carbonyl group is suitably bonded to the main fragment.

[0084] Any aspect of any invention described herein may be combined with any other aspect of any invention described herein mutatis mutandis. DETAILED DESCRIPTION

[0085] The specific embodiments of the present invention will now be described by way of example.

[0086] The following materials are described below:

[0087] JEFFAMINE (trademark) T-403 polyetheramine, its general structure is as follows:

[0088]

[0089] This material is a trifunctional primary amine having a molecular weight of approximately 440 Da when measured by GPC. The amine group is located on the second carbon atom from the end of the aliphatic polyether chain.

[0090] Tris(2-aminoethyl)amine was purchased from Sigma-Aldrich. It has a boiling point of 114°C and the structure is as follows:

[0091]

[0092] C93 PET - refers to the bottle grade PET widely used by Equipolymers.

[0093] Generally, an aldehyde scavenger is contacted and mixed with a polyester, particularly PET, and the combination (along with any other additives) is injection molded to produce a container preform. Preforms are well known. Suitably, they have a test tube-shaped body and a threaded neck adjacent an open end, with a cap flange associated with the neck. The preform is blow molded to form a container, such as a beverage container, which can be closed by a cap removably engaging the threaded neck.

[0094] The described aldehyde scavengers can be solid or liquid. When they are solid, they can be provided as a dispersion in a carrier, such as mineral oil or other carriers, which are compatible with the polyester to be mixed with the scavenger. When they are liquid, the liquid can be used directly or can be diluted by a carrier as described above. In some embodiments, the carrier of the acetaldehyde scavenger can be solid at 25°C.

[0095] Acetaldehyde scavengers may be prepared as described in Examples 1 to 3, preforms may be prepared as described in Example 4, and scavengers may be evaluated as described in subsequent Examples.

[0096] Example 1 - Based on Jeffamine TM Preparation of an acetaldehyde scavenger (referred to as "scavenger C1")

[0097] Jeffamine T-403 was reacted with isatoic anhydride to produce Scavenger C1 described in detail below, the amount of isatoic anhydride being selected to derivatize all of the primary amine functionalities of Jeffamine.

[0098]

[0099] The scavenger is the same as Example 7 in WO2017 / 033117.

[0100] Example 2 - Comparative acetaldehyde scavenger based on tris(2-aminoethyl)amine (referred to as "scavenger C2") preparation

[0101] Tris(2-aminoethyl)amine was reacted with isatoic anhydride, the amount of isatoic anhydride being selected to derivatize all primary amine functionalities of Jeffamine to produce scavenger C2 described in detail below.

[0102]

[0103] The scavenger is the same as Example 6 in WO2017 / 033117, and has a melting point of 146-148°C.

[0104] Example 3 - Acetaldehyde scavenger N,N-(2-(4-(2-aminobenzamido)butyl)pentane-1,5-diyl)bis ... Preparation of (2-aminobenzamide) (referred to as "scavenger EG3")

[0105] Scavenger EG3 has the following structure.

[0106]

[0107] The scavenger was prepared as follows:

[0108] 2H-Benzo[d][1,3]oxazine-2,4(1H)-dione (98.84 g, 3.5 eq., 605.9 mmol) was dissolved in dimethylformamide (500 ml) at room temperature. A solution of 4-(aminomethyl)octane-1,8-diamine (30.00 g, 1 Eq., 173.1 mmol) in dimethylformamide (250 ml) was added dropwise to the reaction mixture. The reaction mixture was stirred overnight at room temperature until LC-MS confirmed complete conversion. The dimethylformamide was removed under reduced pressure to give a dark brown oil. Water (1 liter) and ammonium hydroxide (25%, 50 ml) were added thereto and the product was extracted with dichloromethane. The dichloromethane was removed under reduced pressure and the product was recrystallized in a mixture of methanol and acetonitrile. The solid was collected by filtration and dried to give N,N-(2-(4-(2-aminobenzamido)butyl)pentane-1,5-diyl)bis(2-aminobenzamide) (51.0 g, 55.5% yield). The structure of the compound was confirmed by NMR and LC-MS, with a melting point of 160°C.

[0109] Example 4 - General steps for preparing a preform

[0110] C93 PET resin was dried using a Con-Air (trademark) dryer at 160°C for at least four hours before use.

[0111] The selected amount of scavenger was contacted with hot dry C93 PET in the presence of 1000 ppm (relative to C93 PET) of acetic acid ester of monoglyceride made from fully hydrogenated castor oil. The latter is a carrier. Although in practice a liquid formulation containing carrier and scavenger would be used, the separate addition of scavenger and carrier described facilitates the experimental procedure.

[0112] The mixture was added to the feed port of a Husky 160T injection molding machine according to the following parameters to produce a 34 g PET preform.

[0113] polymer EquipolymersC93 PET Drying conditions Motan dryer 160℃, 4 hours Machine Name Husky Mould 2 chambers, 33g preform Zone 5 temperature (℃) 285 Zone 4 temperature (℃) 285 Zone 3 temperature (℃) 285 Zone 2 temperature (℃) 285 Zone 1 temperature (℃) 285 Nozzle temperature (℃) 285 Mold temperature(℃) 285

[0114] Example 5 - General Procedure for Determining Acetaldehyde Content of Preform Samples

[0115] The acetaldehyde content of the samples was determined on preform samples that had been cryogenically ground to less than 1 mm. The acetaldehyde content was determined using a ThermoFisher 22 Scientific Trace 1310 gas chromatograph with a Triplus 500 headspace autosampler and FID detector. The reduction in acetaldehyde was calculated based on the percentage reduction in acetaldehyde content of the preform with additive compared to the preform without additive.

[0116] Example 6 - Optical property measurement steps

[0117] Samples were extracted from the sidewalls of the preforms and related controls were prepared and the optical properties (ie, L*, a*, and b*) were evaluated in transmission mode using a Minolta CM-3700d spectrophotometer equipped with a D65 / 10° illuminant.

[0118] Example 7 - Procedure for determining migration of acetaldehyde scavengers from PET

[0119] Bottles blown from preforms containing the selected acetaldehyde scavengers and related controls were filled with 20% ethanol / water (in accordance with EU-approved standard test conditions) and placed in an oven at 60°C for 10 days. At various times, the water was sampled using LC-MS to determine the level of acetaldehyde scavenger migration into the water, if any. Multiple bottles were evaluated for each scavenger tested and the average migration value was calculated.

[0120] Example 8 - Evaluation of acetaldehyde scavenging capabilities of selected materials

[0121] Using the general procedure described in Example 4, preforms were prepared using a series of compounds as described, and the compounds were evaluated for acetaldehyde scavenging ability as described in Example 5. The results are as follows. Please note that based on other experiments (not reported), the loading amount of each scavenger was selected based on the amount required to achieve an acetaldehyde reduction level comparable to that when using 500 ppm of anthranilamide, a commercially available acetaldehyde scavenger.

[0122] The following table provides the results related to the acetaldehyde scavenging ability of the acetaldehyde scavengers of Examples 1 to 3 and anthranilamide (composed of C93 PET) as a control:

[0123]

[0124] n / a means “not applicable”.

[0125] Example 9 - Evaluation of Optical Properties of Selected Materials

[0126] The preforms mentioned in Example 8 were evaluated as described in Example 6. The following table provides the results related to the optical properties (L*, a*, b*):

[0127]

[0128] Example 10 - Evaluation of Acetaldehyde Scavenger Migration

[0129] The preforms mentioned in Example 8 were evaluated as described in Example 7. The following table provides the results in terms of "parts per billion" (ppb) migration levels by weight:

[0130]

[0131] n / a means “not applicable”.

[0132] Example 11 - Calculation of comparative efficacy of acetaldehyde scavengers

[0133] Based on the above examples and results, and to illustrate the advantageous properties of scavenger EG3, the following calculations were performed:

[0134] (i) Amount of acetaldehyde scavenger to treat 1 kg of PET For this reason, it is desirable to achieve a high level of acetaldehyde reduction while using a relatively low amount.

[0135] (ii) Molecular weight (MW) of the scavenger.

[0136] (iii) The number of millimoles (mmol) of acetaldehyde scavenger used to achieve the specified scavenging level. A low value is preferred.

[0137] (iv) The number of millimoles (mmol) of nitrogen-containing active sites required to achieve a given level of scavenging.

[0138] (v) The ratio of the number of millimoles (mmol) of nitrogen-containing active centers to achieve a specified level of scavenging to the percentage (%) reduction in acetaldehyde. A lower value is preferred.

[0139] (vi) The ratio of mmol of nitrogen-containing active centers to ppb of acetaldehyde migration reduction to achieve a specified scavenging level. A higher value is preferred.

[0140]

[0141] discuss

[0142] From the above, it can be seen that according to (vi), scavenger EG3 has very low migration and has the best performance in its class (see (iii) and (v)), with higher L* and lower b* compared to other low migration scavengers.

[0143] The invention is not limited to the details of the foregoing embodiments. The invention extends to any novel feature or any novel combination of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel step or any novel combination of the steps of any method or process disclosed in this specification (including any accompanying claims, abstract and drawings).

Claims

1. A formulation for reducing the aldehyde content, for example in a polymeric material, comprising a compound XX comprising at least three moieties (A) of the following formula: wherein each moiety (A) comprises an amine moiety (-NH2) bonded ortho or meta to an amide moiety (-CONH); Each R 1 independently represents a substituent, and m is an integer from 0 to 4; and wherein the three moieties (A) are bonded via their respective amide nitrogen atoms to respective carbon atoms of the main fragment, wherein the main fragment comprises only carbon and hydrogen atoms and is saturated.

2. The preparation according to claim 1, wherein one R 1 or each R 1 is selected from a halogen atom, or an optionally substituted hydrocarbon group, alkoxy group, amine group, amide group, phenol group or carboxyl group.

3. The formulation according to claim 1 or 2, wherein each m=0.

4. A formulation according to any preceding claim, wherein In each portion (A) of compound XX, the amine portion is bonded ortho to the amide portion.

5. A formulation according to any preceding claim, wherein the main segment does not include any cyclic or aromatic moieties; and / or the main segment comprises a linear or branched chain.

6. A formulation according to any preceding claim, wherein the main fragment comprises from 3 to 20 carbon atoms; and / or comprises from 5 to 39 hydrogen atoms.

7. A formulation according to any preceding claim, wherein the main fragment has the following general formula (B): wherein p, q and r are integers in the range of 1 to 10, preferably in the range of 1 to 5.

8. A formulation according to claim 7, wherein p is in the range of 2 to 4, q is in the range of 1 to 3 and r is in the range of 2 to 6; and / or the sum of the integers p, q and r is at least 4, preferably at least 6; and the sum is less than 20, preferably less than 15.

9. The formulation according to claim 7 or 8, wherein the compound XX has the following formula:

10. A formulation according to any preceding claim, wherein the compound XX is:

11. The formulation according to any of the preceding claims, wherein the formulation comprises 50 wt% to 95 wt% of a carrier, 5 wt% to 50 wt% of the compound XX and 0 to 30 wt% of other additives.

12. A formulation according to any preceding claim, wherein the formulation comprises 0.5 to 10 wt% of one or more colourants, such as at least one blue colourant.

13. A formulation according to any preceding claim, wherein In the formulation, the sum of the weight percentages of the carrier and the compound XX is at least 80 wt%, at least 90 wt% or at least 95 wt%.

14. A formulation according to any preceding claim, wherein the formulation is a solid masterbatch comprising 60 wt% to 95 wt% of a thermoplastic polymer and 0 to 10 wt%, preferably 0.5 wt% to 10 wt% of one or more colorants; the thermoplastic polymer being selected from polyesters, polyoxymethylene (POM), polyolefins, polyketones, polyvinyl butyral (PVB) and polyurethanes.

15. The formulation according to any one of claims 1 to 13, wherein the formulation is a liquid formulation comprising 50 wt% to 90 wt% (e.g. 50 wt% to 80 wt%) of a liquid carrier and 10 wt% to 50 wt% (e.g. 20 wt% to 50 wt%) of compound XX.

16. A novel compound of formula XX comprising at least three moieties (A) of the following formula: wherein each moiety (A) comprises an amine moiety (-NH2) bonded ortho or meta to an amide moiety (-CONH); Each R 1 independently represents a substituent, and m is an integer from 0 to 4; and wherein the three moieties (A) are bonded via their respective amide nitrogen atoms to respective carbon atoms of the main fragment, wherein the main fragment comprises only carbon and hydrogen atoms and is saturated.

17. The compound according to claim 16, wherein the compound is:

18. A method for reducing the aldehyde content in a polymer material, said method comprising the step of contacting the polymer material or a monomer, oligomer or prepolymer involved in the preparation of said polymer material with a compound XX as claimed in any preceding claim.

19. A method according to claim 18, wherein the polymer material contacted in the method is any polymer material that may incorporate aldehydes that need to be removed or otherwise reduced; and / or the polymer material comprises polyester (especially polyethylene terephthalate), polyurethane, polyoxymethylene (POM), polyketone or polyolefin.

20. A method according to claim 18 or 19, wherein the polymeric material contacted in the method comprises polyester (especially polyethylene terephthalate).

21. The method according to any one of claims 18 to 20, wherein the total ppm of compound XX contacted with the polymeric material (based on the weight of the polymeric material) is at least 100 ppm, preferably 200 ppm, more preferably at least 450 ppm; and / or it is less than 2000 ppm or less than 1000 ppm.

22. The method according to any one of claims 18 to 21, wherein the compound XX is part of a formulation according to any one of claims 1 to 15.

23. A method according to any one of claims 18 to 22, wherein the polymeric material is part of and / or defines an article, such as a shaped article, optionally selected from a preform, a container, a bottle, a cup, a tray or a thermoformed sheet.

24. A method of making an article, such as a shaped article, from a polymeric material, the method comprising: (a) selecting a compound XX according to any one of claims 1 to 17; (b) contacting a polymer material with said compound XX; as well as (c) forming the polymeric material into an article, such as a shaped article.

25. The method of claim 24, wherein the article comprises a container or a preform for a container.

26. A polymeric material (eg polyester) having a reduced aldehyde (eg acetaldehyde) content, the polymeric material comprising compound XX or a reaction product of compound XX with an aldehyde (eg acetaldehyde) as claimed in any one of claims 1 to 17.

27. The polymer material according to claim 26, wherein the product of the reaction of compound XX with an aldehyde (e.g. acetaldehyde) comprises the following fragment (N), which is derived from the part (A) according to any one of claims 1 to 17: Where R 30 refers to the residue of an aldehyde, and when the aldehyde is acetaldehyde, R 30 Suitably it is methyl.

28. The polymer material of claim 26 or 27, wherein the product of the reaction comprises the following moiety (O):

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