Phosphorus oligomers, polyester resins, and thermoplastic resin compositions comprising the same

Abstract

The present invention provides: a phosphorus (P) oligomer; a novel polyester resin comprising structural units from the phosphorus oligomer and having excellent flame retardancy and a high degree of polymerization; a thermoplastic resin composition comprising the polyester resin; and a molded article using the thermoplastic resin composition. By synthesizing an oligomer having a predetermined structure comprising phosphorus (P) in a new way instead of a phosphorus flame retardant in the form of a single compound that does not participate in an existing polymerization reaction, and by polymerizing a polyester in the same way, the present invention not only improves the flame retardancy of the resin itself, but also adjusts the degree of polymerization, thereby improving the physical stability of the final polyester resin.

Description

Technical Field

[0001] The present invention relates to a novel phosphorus (P) oligomer, a polyester resin having both excellent flame retardancy and high degree of polymerization by comprising structural units from the phosphorus oligomer, a thermoplastic resin composition comprising the polyester resin, and a molding article using the thermoplastic resin composition. Background Technology

[0002] Thermoplastic polyester resins exhibit excellent chemical resistance, mechanical strength, heat resistance, and electrical properties, and are therefore widely used in housings and connectors for electronic, electrical, and automotive components. Because these polyester resins are generally flammable, they are often used in conjunction with halogen-based flame retardants or antimony-based flame retardant additives in applications requiring flame retardancy. However, halogen-based or antimony-based flame retardant additives not only produce large amounts of toxic halogen gases in the event of a fire, but also present the problem of requiring excessive amounts of flame retardant to achieve the desired flame-retardant effect.

[0003] To address the aforementioned issues, a method has been proposed to impart flame retardancy to polyester resins using non-halogenated flame retardants such as organophosphonic acid metal salts, organophosphonic acid metal salts, and melamine phosphate. However, when using these compounds to impart flame retardancy, excessive amounts of low molecular weight flame retardants are used, leading to excessive degradation of the resin's physical properties and problems such as flame retardant leakage. In particular, when flame retardants that do not participate in the polymerization reaction are used, the degree of polymerization decreases, inevitably resulting in a deterioration of the final physical properties of the polyester resin.

[0004] [Existing technical documents]

[0005] (Patent Document 001) Korean Patent No. 10-2285778 Summary of the Invention

[0006] Technical issues

[0007] Embodiments of the present invention relate to a novel polyester resin with improved flame retardancy and degree of polymerization by synthesizing a phosphorus (P) oligomer and using the phosphorus oligomer for polyester polymerization.

[0008] Embodiments of the present invention also relate to a thermoplastic resin composition comprising the above-described polyester resin and a molding article using the thermoplastic resin composition.

[0009] Other objects and advantages of the present invention will be more clearly explained by the following detailed description and claims.

[0010] Technical solution

[0011] To achieve the above-mentioned technical objectives, the present invention provides a phosphorus (P) oligomer represented by the following chemical formula 1:

[0012] [Chemical Formula 1]

[0013]

[0014] In chemical formula 1,

[0015] A and A' are either the same as or different from each other, and are each independently selected from: C1 to C2. 40 Alkylene, C2 to C 40 alkenyl, C2 to C 40 Ethyne group, C3 to C 40 Cycloalkylene, heteroalkylene having 1 to 40 nuclear atoms, heteroalkylene having 3 to 40 nuclear atoms, C6 to C 60 Arenes and heteroaryl groups with 5 to 60 nuclear atoms,

[0016] The alkylene, alkenylene, ynylene, cycloalkylene, heteroalkylene, heterocycloalkylene, arylene, and heteroaryl groups of A and A' can each be independently substituted by one or more substituents selected from the following: deuterium (D), halogen, cyano, nitro, C1 to C2. 40 Alkyl, C6 to C 60 Aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when these substituents are numerous, they are either the same as or different from each other, where m is an integer in the range of 1 to 10.

[0017] n is an integer in the range of 2 to 50;

[0018] In some embodiments, the phosphorus oligomer represented by the above chemical formula 1 may have a weight-average molecular weight (Mw) in the range of 500 g / mol to 3,000 g / mol.

[0019] According to one embodiment, the polyester resin comprises: a structural unit (a1) derived from a dicarboxylic acid; a structural unit (a2) derived from a diol; and a structural unit (a3) ​​derived from a phosphorus oligomer represented by chemical formula 1.

[0020] In some embodiments, the structural unit (a3) ​​may be included in an amount of 0.5 parts by weight to 30 parts by weight relative to 100 parts by weight of the structural unit (a1) derived from dicarboxylic acid.

[0021] In some implementations, the phosphorus (P) atomic content can be in the range of 10 ppm to 10,000 ppm.

[0022] In some embodiments, the polyester resin may have a melt index (MI) in the range of 10 g / 10 min to 30 g / 10 min (relative to 235 °C), a weight-average molecular weight (Mw) in the range of 10,000 g / mol to 100,000 g / mol, and a melting point (T) in the range of 150 °C to 350 °C as measured by differential scanning calorimetry (DSC). m The intrinsic viscosity (IV) ranges from 0.7 cP to 1.5 cP (25°C).

[0023] In some embodiments, the polyester resin may be polybutylene terephthalate (PBT).

[0024] According to one embodiment, the thermoplastic resin composition may comprise the polyester resin.

[0025] According to one embodiment, the molding article comprises the polyester resin.

[0026] Beneficial effects

[0027] According to one or more embodiments of the present invention, since novel oligomers containing phosphorus (P) with predetermined structures can be synthesized instead of phosphorus flame retardants in the form of single compounds that do not participate in conventional polymerization reactions, and polyester polymerization is carried out using said oligomers, the flame retardancy of the resin itself can be improved by controlling the degree of polymerization and the physical stability of the final polyester resin can be further improved.

[0028] The effects of the invention are not limited to the examples described above, and many more effects are included in this specification. Detailed Implementation

[0029] The present invention will be described in detail below.

[0030] Unless otherwise defined, all terms used herein (including technical and scientific terms) are to be used in the sense that is commonly understood by one of ordinary skill in the art to which this invention pertains. Furthermore, unless specifically and explicitly defined, terms as defined in common dictionaries should not be interpreted ideally or excessively.

[0031] Throughout the specification, when a section “includes” a particular element, unless otherwise stated, it is an open-ended term that includes, but does not exclude, the possibility of further inclusion of other elements.

[0032] As used herein, "preferred" and "ideally" refer to embodiments of the invention that provide particular advantages in specific circumstances. However, other embodiments may also be preferred in the same or other circumstances. Furthermore, references to one or more preferred embodiments do not imply that other embodiments are not useful, nor are they intended to exclude other embodiments from the scope of the invention.

[0033] <Phosphorus oligomers>

[0034] One example of the present invention is an organophosphorus oligomer applied to the polymerization of polyester resins, and can be represented by the following chemical formula 1:

[0035] [Chemical Formula 1]

[0036]

[0037] In chemical formula 1,

[0038] There are no particular restrictions on A and A', as long as they are divalent hydrocarbon groups known in the art. For example, A and A' can be the same as or different from each other, and can each be independently selected from C1 to C2. 40 Alkylene, C2 to C 40 alkenyl, C2 to C 40 Ethyne group, C3 to C 40 Cycloalkylene, heteroalkylene having 1 to 40 nuclear atoms, heteroalkylene having 3 to 40 nuclear atoms, C6 to C 60 Arylenes and heteroarylenes having 5 to 60 nuclear atoms. Specifically, A and A' can be identical to each other and can be selected from, for example, C1 to C2. 10 Alkylene, C3 to C 12 Cycloalkylene, C6 to C 20 Arylenes and heteroarylenes with 5 to 60 nuclear atoms.

[0039] In this case, m can be an integer in the range of 1 to 10, and n can be an integer in the range of 2 to 50.

[0040] The alkylene, alkenylene, ynylene, cycloalkylene, heteroalkylene, heterocycloalkylene, arylene, and heteroaryl groups of A and A' can each be independently substituted by one or more substituents selected from: deuterium (D), halogen, cyano, nitro, C1 to C2. 40 Alkyl, C6 to C 60 Aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when these substituents are numerous, they can be the same as or different from each other.

[0041] The phosphorus (P) oligomer of Formula 1 according to the present invention can act as a phosphorus flame retardant for the preparation of conventional polyester resins. Specifically, it can prevent degradation of the polyester resin caused by heat applied to the transesterification and polycondensation reactions, as well as the heat of reaction generated during polymerization, and suppress yellowing caused by reverse or decomposition reactions, thereby making the polyester resin substantially transparent and colorless. Furthermore, in terms of preventing environmental pollution, the phosphorus (P) oligomer can replace conventional halogen-based flame retardants. Moreover, even using small amounts of the phosphorus flame retardant oligomer can impart sufficient flame retardancy and prevent the deterioration of the physical properties of conventional polyesters, such as viscosity, glass transition temperature, and processing properties.

[0042] In a specific instance of chemical formula 1, A and A' can each be independently selected from: C1 to C2. 10 Alkylene, C3 to C 12 Cycloalkylene and C6 to C6 20 Alpha-aryl

[0043] n can be an integer in the range of 2 to 45, and m can be an integer in the range of 1 to 5.

[0044] As a preferred example, the phosphorus oligomer represented by Formula 1 may be more specifically designated as any one of Formula 1A and Formula 1B below, depending on the type of substituents introduced into A and A'. However, the invention is not limited thereto.

[0045] [Chemical Formula 1A]

[0046]

[0047] [Chemical Formula 1B]

[0048]

[0049] In chemical formulas 1A to 1B,

[0050] Ring B can be a common hydrocarbon ring known in the art, and can be formed by condensation, fusion, bridging, or spirobonding with other adjacent rings. For example, ring B can be selected from monocyclic or polycyclic alicyclic rings, monocyclic or polycyclic heterocyclic alicyclic rings, monocyclic or polycyclic aromatic rings, and monocyclic or polycyclic heteroaromatic rings. Specifically, ring B can be an alicyclic ring having 3 to 10 carbon atoms, a heterocyclic alicyclic ring having 3 to 10 nuclear atoms, an aromatic ring having 6 to 20 carbon atoms, or a heteroaromatic ring having 5 to 20 nuclear atoms.

[0051] In this case, p and q can each be integers in the range of 1 to 10, and m and n can each be as defined in chemical formula 1.

[0052] In another preferred embodiment, according to m, the phosphorus oligomer of Formula 1 can be more specifically designated as Formula 1C below. However, the invention is not limited thereto.

[0053] [Chemical Formula 1C]

[0054]

[0055] In the above chemical formula,

[0056] A, A', and n can each be defined as in chemical formula 1.

[0057] In a specific instance of chemical formula 1C, A and A' can be identical to each other and can be selected from C1 to C2. 10 Alkylene, C3 to C 12 Cycloalkylene, C6 to C 20 Arylenes and heteroarylenes with 5 to 60 nuclear atoms.

[0058] The phosphorus oligomer represented by Formula 1C can be more specifically designated as any one of Formulas 1D to 1E below, depending on the type of substituents introduced into A and A'. However, the invention is not limited thereto.

[0059] [Chemical Formula 1D]

[0060]

[0061] [Chemical Formula 1E]

[0062]

[0063] In the above chemical formula,

[0064] Ring B can be selected from alicyclic rings having 3 to 10 carbon atoms and C6 to C6 rings. 20 Fang Huan,

[0065] p and q can each be an integer in the range of 1 to 6 independently.

[0066] n can be an integer in the range of 2 to 45.

[0067] The phosphorus oligomers of Formula 1 described above may be more specifically designated as the compounds exemplified below. However, the phosphorus oligomers of the present invention are not limited to those exemplified below.

[0068]

[0069] In the above chemical formula,

[0070] n can be as defined in Formula 1. For example, n can be an integer in the range of 2 to 45, specifically, in the range of 2 to 30, and more specifically, in the range of 3 to 25.

[0071] In a specific example, the phosphorus (P) oligomer represented by Formula 1 can have a weight-average molecular weight (Mw) in the range of 500 g / mol to 3,000 g / mol, specifically in the range of 500 g / mol to 2,000 g / mol.

[0072] As used herein, "alkyl" can refer to a monovalent substituent from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples of such alkyl groups may include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc.

[0073] As used herein, "alkenyl" can refer to a monovalent substituent from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples of such alkenyl groups may include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, etc.

[0074] As used herein, "alkynyl" can refer to a monovalent substituent from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples of such alkynyl groups may include, but are not limited to, ethynyl, 2-propynyl, etc.

[0075] As used herein, "aryl" can refer to a monovalent substituent from an aromatic hydrocarbon having 6 to 60 carbon atoms, having a single ring or two or more rings bonded together in its structure. Furthermore, it can also include forms in which two or more rings are side-attached (e.g., simply attached) or fused together. Examples of such aryl groups can include, but are not limited to, phenyl, naphthyl, phenanthryl, anthracene, etc.

[0076] As used herein, "heteroaryl" can refer to a monovalent substituent from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. In this case, one or more carbons, preferably one to three carbons, in the ring are substituted with heteroatoms such as N, O, S, or Se. Furthermore, forms in which two or more rings are side-connected or fused to each other can be included, and forms fused with an aryl group can also be included. Examples of such heteroaryls can include, but are not limited to: 6-membered monocyclic rings, including, for example, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings, including, for example, phenoxathienyl, dihydroindolyl, indolyl, purinyl, quinolinyl, benzothiazole, and carbazoleyl; 2-furanyl; N-imidazolyl; 2-isooxazolyl; 2-pyridinyl; 2-pyrimidinyl, etc.

[0077] As used herein, “cycloalkyl” can refer to a monovalent substituent from a monocyclic or polycyclic nonaromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl groups may include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, diamondyl, etc.

[0078] As used herein, "heterocyclic alkyl" can refer to a monovalent substituent from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein one or more carbons, preferably one to three carbons, in the ring are substituted with heteroatoms such as N, O, S, or Se. Examples of such heterocyclic alkyl groups may include, but are not limited to, morpholine, piperazine, etc.

[0079] <Polyester Resin>

[0080] One example of the present invention is a polyester resin that exhibits excellent flame retardancy by incorporating phosphorus (P) into the basic framework of the resin itself. In particular, it differs from conventional polyester resins that utilize phosphorus monomers in that it contains structural units (a3) ​​derived from phosphorus oligomers represented by the above-described chemical formula 1.

[0081] In a specific example, the polyester resin may comprise: a structural unit (a1) derived from a dicarboxylic acid; a structural unit (a2) derived from a diol; and a structural unit (a3) ​​represented by the following chemical formula 2.

[0082] [Chemical Formula 2]

[0083]

[0084] In chemical formula 2,

[0085] A can be selected from: C1 to C 40 Alkylene, C2 to C 40 alkenyl, C2 to C 40 Ethyne group, C3 to C 40 Cycloalkylene, heteroalkylene having 1 to 40 nuclear atoms, heteroalkylene having 3 to 40 nuclear atoms, C6 to C 60 Arenes and heteroaryl groups with 5 to 60 nuclear atoms,

[0086] The alkylene, alkenylene, ynylene, cycloalkylene, heteroalkylene, heterocycloalkylene, arylene, and heteroaryl groups of A can each be independently substituted by one or more substituents selected from the following: deuterium (D), halogen, cyano, nitro, C1 to C2. 40 Alkyl, C6 to C 60 Aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when these substituents are numerous, they can be the same as or different from each other.

[0087] m can be an integer in the range of 1 to 10.

[0088] n can be an integer in the range of 2 to 50.

[0089] In a specific instance of chemical formula 2, A can be selected from: C1 to C2. 10 Alkylene, C3 to C 12 Cycloalkylene, C6 to C 20 Arenes and heteroaryl groups with 5 to 60 nuclear atoms,

[0090] m can be an integer in the range of 1 to 6, and n can be an integer in the range of 2 to 45.

[0091] As a preferred example, the structural unit (a3) ​​represented by chemical formula 2 can be more specifically designated as either chemical formula 2A or chemical formula 2B below, depending on the type of substituent introduced into A. However, the invention is not limited thereto.

[0092] [Chemical Formula 2A]

[0093]

[0094] [Chemical Formula 2B]

[0095]

[0096] In chemical formulas 2A to 2B

[0097] Ring B can be selected from monocyclic or polycyclic alicyclic rings, heterocyclic alicyclic rings, aromatic rings, and heteroaromatic rings.

[0098] q can be an integer in the range of 1 to 10.

[0099] m and n can each be defined as in chemical formula 1.

[0100] In another preferred embodiment, the structural unit (a3) ​​represented by chemical formula 2 can be more specifically designated as chemical formula 2C below, depending on m. However, the invention is not limited thereto.

[0101] [Chemical formula 2C]

[0102]

[0103] In the above chemical formula,

[0104] A and n can each be defined as in chemical formula 2.

[0105] The structural unit (a3) ​​represented by the above chemical formula 2C can be more specifically designated as any one of the following chemical formulas 2D to 2E, depending on the type of substituent introduced into A. However, the present invention is not limited thereto.

[0106] [Chemical Formula 2D]

[0107]

[0108] [Chemical formula 2E]

[0109]

[0110] In the above chemical formula,

[0111] Ring B can be selected from alicyclic rings having 3 to 10 carbon atoms and C6 to C6 rings. 20 Fang Huan,

[0112] q can be an integer in the range of 1 to 6.

[0113] n can be an integer in the range of 2 to 45.

[0114] The structural unit (a1) constituting the polyester resin according to the invention is derived from carboxylic acid, and may be derived from conventional dicarboxylic acid monomers and their derivatives known in the art.

[0115] Non-limiting examples of applicable dicarboxylic acids may include: terephthalic acid, oxalic acid, malonic acid, azelaic acid, fumaric acid, pimelic acid, octanoic acid, isophthalic acid, dodecanedicarboxylic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, 1,2-norbornanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, sodium isophthalate-5-sulfonate, potassium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate, sodium terephthalate-2-sulfonate, or mixtures thereof. As needed, carboxylic acid ester derivatives may be used, and specific examples may include: esters of dicarboxylic acid compounds, namely, dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, dimethyl maleate, dimethyl dimeric acid, etc., but the present invention is not limited thereto.

[0116] In a specific instance, relative to the total mole percentage of the corresponding structural unit (a1), the structural unit (a1) from the dicarboxylic acid may contain at least one of terephthalic acid, isophthalic acid, dimethyl terephthalate, diethyl isophthalate and adipic acid in an amount ranging from 10 mol% to 70 mol% in particular.

[0117] The structural unit (a2) constituting the polyester resin according to the invention can be derived from diols, and can be derived from conventional diol monomers and their derivatives known in the art.

[0118] As a diol monomer, aliphatic diols having 2 to 10 carbon atoms may be used, and non-limiting examples may include: ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, 1,3-propanediol, diethylene glycol, triethylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, propylene glycol, 1,6-hexanediol, tetramethylcyclobutanediol, 1,4-cyclohexanediol, 1,10-decanediol, 1,12-dodecanediol, polyoxyethylene glycol, polyoxymethylene glycol, polyoxytetramethylene glycol, glycerol, or mixtures thereof.

[0119] In a specific example, relative to the total mole percentage of the corresponding structural unit (a2), the structural unit (a2) derived from the diol may comprise at least 10 mol% of ethylene glycol, propylene glycol, and butanediol. Specifically, it may be comprised in the range of 20 mol% to 70 mol%.

[0120] The polyester resin according to the present invention is not particularly limited in its structure, composition and / or composition, as long as it contains structural units (a1) from dicarboxylic acids, structural units (a2) from diols and structural units (a3) ​​represented by the above chemical formula 2.

[0121] As an example, the polyester resin may be a thermoplastic polyester or a copolyester resin, and specifically may be in the form of polyethylene terephthalate resin, polybutylene terephthalate resin, polypropylene terephthalate resin, or a combination thereof. Preferably, it may be polybutylene terephthalate (PBT) resin.

[0122] The polyester resin of the present invention can exhibit flame retardant and degree-of-polymerization improvement effects by including the structural unit (a3) ​​represented by Chemical Formula 2. In particular, by adjusting the content ratio of the structural unit (a1) from dicarboxylic acid, the structural unit (a2) from diol, and the structural unit (a3) ​​represented by Chemical Formula 2 to a predetermined ratio, the improvement of the flame retardancy and the increase of the degree of polymerization of the final polyester resin can be optimized.

[0123] In one specific example, the structural unit (a3) ​​represented by Formula 2 may be included in an amount ranging from 0.5 parts by weight to 30 parts by weight, specifically from 0.5 parts by weight to 20 parts by weight, relative to 100 parts by weight of the structural unit (a1) derived from the dicarboxylic acid. In this case, there is no particular limitation on the content ratio of the structural unit (a1) derived from the dicarboxylic acid to the structural unit (a2) derived from the diol, and it can be suitably adjusted within the range known in the art. For example, the amount of diol may be variablely added in an amount ranging from 1.1 to 1.7 equivalents relative to the amount of dicarboxylic acid to carry out polymerization.

[0124] When the content ratio between the various structural units constituting the polyester resin of the present invention falls within the above-mentioned range, the unreacted substances in the esterification and polycondensation reactions can be minimized, thereby increasing the yield of the polyester resin and significantly improving the flame retardancy and physical stability of the prepared polyester resin.

[0125] The polyester resin of the present invention, which comprises the above-mentioned structural units (a1) from dicarboxylic acids, structural units (a2) from diols, and structural units (a3) ​​represented by chemical formula 2, and has an optimized content ratio among them, exhibits excellent flame retardant effects due to the presence of phosphorus (P) atoms in the resin itself, even though it does not contain a separate flame retardant. Furthermore, due to the phosphorus oligomers participating in the polycondensation reaction, the degree of polymerization can be improved and the molecular weight can be increased, thereby improving the physical stability of the final resin.

[0126] In one specific example, the content of phosphorus (P) atoms contained in the polyester resin may be in the range of 10 ppm to 10,000 ppm.

[0127] In another specific example, the melt index (MI) of the polyester resin can range from 10 g / 10 min to 30 g / 10 min (relative to 235 °C), specifically from 12 g / 10 min to 25 g / 10 min. Furthermore, the weight-average molecular weight (Mw) can range from 10,000 g / mol to 100,000 g / mol, specifically from 30,000 g / mol to 100,000 g / mol, and more specifically from 40,000 g / mol to 80,000 g / mol. The melting point (T0) is measured by differential scanning calorimetry (DSC). m It can be in the range of 150°C to 350°C, more specifically, in the range of 200°C to 350°C.

[0128] In another specific example, the intrinsic viscosity (IV) of the polyester resin can be in the range of 0.7 cP to 1.5 cP (25°C), specifically in the range of 0.8 cP to 1.3 cP (25°C). Furthermore, the glass transition temperature (Tg) can be in the range of 50°C to 150°C, specifically in the range of 80°C to 130°C. The molecular weight distribution (PDI, Mw / Mn) can be in the range of 1 to 7, and specifically in the range of 1 to 4.

[0129] <Methods for preparing polyester resin>

[0130] The polyester resin according to one embodiment of the present invention can be prepared according to conventional preparation methods known in the art, and there are no particular limitations.

[0131] For example, it can be prepared by polymerizing monomers and / or oligomers capable of yielding structural units (a1), (a2), and (a3) ​​using known methods such as melt polymerization, solid polymerization, solution polymerization, and slurry polymerization. Furthermore, the above-described polymerization methods can be combined, and for example, it can be prepared by a two-step polymerization in which, for example, a prepolymer is prepared by melt polymerization, followed by solid polymerization.

[0132] One embodiment of the preparation method may include: preparing a polyester oligomer by esterifying a dicarboxylic acid with a diol; and mixing the polyester oligomer with a phosphorus (P) oligomer represented by chemical formula 2 and polycondensing the mixture.

[0133] Another embodiment of the preparation method may include: mixing and esterifying a dicarboxylic acid, a diol, and a phosphorus (P) oligomer represented by chemical formula 2, followed by polycondensation.

[0134] In the esterification and / or polymerization steps described above, conventional additives known in the art may be used. Examples of suitable additives may include at least one of catalysts for polymerization, heat stabilizers, chain extenders, light stabilizers, inorganic particles, and potassium hydroxide.

[0135] There are no particular limitations on the catalyst used for polymerization, and known catalysts used in polyester polymerization can be used. Specific examples may include: metal salt catalysts, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide; and organic compound catalysts, including nitrogen-containing heterocyclic compounds, such as N-methylimidazole. There are no particular limitations on the amount of catalyst used, and it can be appropriately adjusted within the range known in the art.

[0136] The heat stabilizer may be a conventional stabilizer known in the art and may include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, isopropylated triaryl phosphate, hydroquinone bis-diphenyl phosphate, or mixtures thereof.

[0137] In addition to the components described above, the present invention may further include any other additives commonly used in the preparation of polyester resins without impairing the effects of the invention. Examples of suitable additives include at least one selected from the following: defoamers, antioxidants, lubricants, hydrolytic stabilizers, mold release agents, pigments, antistatic agents, crosslinking agents, processing aids, anti-dripping agents, anti-abrasion agents, surfactants, particulate fillers, gloss improvers, viscosity modifiers, and coupling agents.

[0138] Furthermore, there are no particular limitations on the conditions for the ester reaction step and / or the polycondensation reaction step, and they can be appropriately adjusted within the range known in the art.

[0139] <Thermoplastic Resin Composition>

[0140] Another example of the present invention is a thermoplastic resin composition comprising the above-described polyester resin.

[0141] The polyester resin is not particularly limited in its components and / or composition, as long as it contains structural units (a1) derived from dicarboxylic acids, structural units (a2) derived from diols, and structural units (a3) ​​represented by the above chemical formula 2. As examples, thermoplastic polyesters and copolyester resins can be used, and specifically, polyethylene terephthalate resin, polybutylene terephthalate resin, polypropylene terephthalate resin, or combinations thereof can be used.

[0142] In addition to the polyester resins described above, the thermoplastic resin compositions according to the present invention may further comprise conventional resins known in the art. For example, they may comprise: polyolefin resins, such as polyethylene and polypropylene, cyclic olefin polymers; vinyl resins, such as polyvinyl chloride; (meth)acrylic resins, such as polyacrylate, polymethyl methacrylate, and polyphenylene ether resins; polyacetal resins; polyamide resins; imide resins, such as polyimide and polyetherimide; polystyrene resins, such as polystyrene, high-impact polystyrene, AS resin, and ABS resin; thermosetting resins, such as epoxy resins; cellulose resins; polyetheretherketone resins; fluoropolymers; polycarbonate resins, etc.

[0143] Furthermore, in this invention, additives suitable for the intended use or effect may be further included without impairing the effects of the invention. Examples of suitable additives may include, but are not limited to, one or more selected from: fillers, colorants, pigments, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, leveling agents, surfactants, lubricants, anti-friction agents, and chain extenders.

[0144] The thermoplastic resin composition according to the invention can be prepared according to conventional methods known in the art, for example, by melt kneading the mixture after properly mixing polyester resin, other resins or additives, etc., using a Banbury mixer, kneader, single-shaft or twin-shaft extruder, etc.

[0145] <Molded Products>

[0146] Another example of the present invention is a molding article comprising the above-described polyester resin.

[0147] The shape of the molded article can be appropriately modified according to its application, and can be, for example, a film shape, a sheet shape, a fiber shape, etc. However, the present invention is not particularly limited thereto. Specific examples of molded articles may include films, sheets, bottles, liquid crystal displays, holograms, filters, dielectric films, insulating materials for wires, insulating tapes, fiber-reinforced composite materials, other injection-molded articles, etc., but the present invention is not limited thereto.

[0148] Without impairing the effects of the invention, in addition to polyester resins, the molding articles according to the invention may further include conventional resins known in the art. For example, they may include polyolefin resins such as polyethylene and polypropylene, cyclic olefin polymers; vinyl resins such as polyvinyl chloride; (meth)acrylic resins such as polyacrylate, polymethyl methacrylate, and polyphenylene ether resins; polyacetal resins; polyamide resins; imide resins such as polyimide and polyetherimide; polystyrene resins such as polystyrene, high-impact polystyrene, AS resin, and ABS resin; thermosetting resins such as epoxy resins; cellulose resins; polyetheretherketone resins; fluoropolymers; polycarbonate resins, etc.

[0149] Furthermore, in this invention, without impairing the effects of the invention, conventional additives such as colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, and surfactants may be further included.

[0150] The molded articles according to the invention can be manufactured according to conventional methods known in the art, for example, by compression molding, foam molding, injection molding, extrusion molding, and stamping of a mixture comprising polyester resin and other resins or additives to obtain the molded articles. In this case, the mixture can be obtained by melt-kneading the mixture using a Banbury mixer, kneader, single-shaft or twin-shaft extruder, etc., after appropriately mixing the polyester resin, other resins or additives.

[0151] In a specific instance, the molded article can be a film.

[0152] The membrane can be manufactured using conventional methods known in the art, such as blow molding; extrusion molding such as melt extrusion; and solution casting. The manufactured membrane can be a single-layer membrane made of polyester resin, or a single-layer or multi-layer membrane containing different materials.

[0153] In another specific instance, the molded material can be fiber.

[0154] The fibers can be manufactured using conventional methods known in the art, such as melt spinning, solution spinning, etc. The manufactured fibers can be made from polyester resin or in the form of a mixture with a heterogeneous resin.

[0155] The polyester resin, thermoplastic resin composition, and molding article according to the present invention not only possess excellent flame retardancy due to the phosphorus (P) component contained in the resin itself, but also ensure the physical stability of the polyester resin by controlling the degree of polymerization. Therefore, they are effectively applicable to the manufacture of molding articles such as housings and connectors for electronic / electrical and automotive parts. However, they are not limited to the above-described uses and are applicable to all various technical fields and processes used with conventional polyester resins.

[0156] The present invention will be described in detail below by way of examples. However, the following examples are merely illustrative and the present invention is not limited to the examples described below.

[0157] [Synthetic Examples 1 to 5: Preparation of Phosphorus Oligomers]

[0158] [Synthesis example 1]

[0159] 200 g of 2-carboxyethylphenylphosphonic acid and 115 g of ethylene glycol were added to a reactor, and the temperature was raised to 150 °C. Then, 0.2 g of tetrabutyl titanate was added. A trap was installed to remove water produced after the reaction. After 12 hours, when the reaction was complete, the trap was removed, and the pressure was gradually reduced while maintaining the temperature at 100 °C. The remaining ethylene glycol was removed while maintaining a vacuum below 1 Torr, thereby preparing oligomer 1 represented by the following chemical formula 3a (yield: 85%, Mw: 1,500 g / mol).

[0160] [Chemical Formula 3a]

[0161]

[0162] [Synthesis example 2]

[0163] Except that 115 g of ethylene glycol was replaced with 150 g of 1,4-butanediol, oligomer 2 represented by the following chemical formula 3b was prepared in the same manner as in Synthesis Example 1 (yield: 81%, Mw: 1,180 g / mol).

[0164] [Chemical Formula 3b]

[0165]

[0166] [Synthesis example 3]

[0167] Except that 115g of ethylene glycol was replaced with 120g of hydroquinone, oligomer 3 represented by the following chemical formula 3c was prepared in the same manner as in Synthesis Example 1 (yield: 86%, Mw: 1,350g / mol).

[0168] [Chemical formula 3c]

[0169]

[0170] [Synthesis Example 4]

[0171] Except that 115 g of ethylene glycol was replaced with 125 g of cyclohexanediol, oligomer 4 represented by the following chemical formula 3d was prepared in the same manner as in Synthesis Example 1 (yield: 71%, Mw: 1,550 g / mol).

[0172] [Chemical formula 3d]

[0173]

[0174] [Synthesis example 5]

[0175] Except that 115 g of ethylene glycol was replaced with 120 g of cyclohexanediethanol, oligomer 5 represented by the following chemical formula 3e was prepared in the same manner as in Synthesis Example 1 (yield: 87%, Mw: 1,750 g / mol).

[0176] [Chemical formula 3e]

[0177]

[0178] [Examples 1 to 8: Preparation of polyester resin products]

[0179] [Example 1]

[0180] 1940 g of dimethyl terephthalate, 1,350 g of 1,4-butanediol, and 1.16 g of tetrabutyl titanate were added to a reactor. A transesterification reaction was carried out while methanol was refluxed and the temperature was gradually increased to 200 °C at atmospheric pressure and the temperature reached 140 °C. When 95% of the theoretical amount of methanol was discharged, 3 parts by weight of oligomer 1 prepared in Synthesis Example 1 were added relative to the total weight of dimethyl terephthalate. After the transesterification reaction was completed, the product was transferred to a polycondensation reactor, and 0.58 g of tetrabutyl titanate was added. The pressure was gradually reduced to maintain a vacuum below 0.3 Torr while the temperature was maintained at 250 °C to carry out the polycondensation reaction. When the desired degree of polymerization was reached, nitrogen was injected to release the vacuum. The polymer was then discharged and cooled to obtain final product 1. The physical properties of the final product are shown in Table 1 below.

[0181] [Example 2]

[0182] Except for changing the amount of oligomer 1 added from 3 parts by weight to 5 parts by weight, the final product 2 was obtained by polymerization in the same manner as in Example 1.

[0183] [Example 3]

[0184] Except that oligomer 2 was used instead of oligomer 1, the final product 3 was obtained by polymerization in the same manner as in Example 1.

[0185] [Example 4]

[0186] Except that oligomer 2 was used instead of oligomer 1 and the amount of oligomer 2 added was changed to 5 parts by weight, the final product 4 was obtained by polymerization in the same manner as in Example 1.

[0187] [Example 5]

[0188] Except that oligomer 3 was used instead of oligomer 1, the final product 5 was obtained by polymerization in the same manner as in Example 1.

[0189] [Example 6]

[0190] Except that oligomer 3 was used instead of oligomer 1 and the amount of oligomer 3 added was changed to 5 parts by weight, the final product 6 was obtained by polymerization in the same manner as in Example 1.

[0191] [Example 7]

[0192] Except that oligomer 4 was used instead of oligomer 1 and the amount of oligomer 4 added was changed to 5 parts by weight, the final product 7 was obtained by polymerization in the same manner as in Example 1.

[0193] [Example 8]

[0194] Except that oligomer 5 was used instead of oligomer 1 and the amount of oligomer 5 was changed to 5 parts by weight, the final product 8 was obtained by polymerization in the same manner as in Example 1.

[0195] [Comparative Example 1]

[0196] 1-1. Preparation of Phosphorus Monomers

[0197] 100 g of 2-carboxyethylphenylphosphonic acid, 200 g of bromoethanol, and 130 g of potassium carbonate were added to the reactor, and the temperature was raised to reflux. When the reaction was completed after 24 hours, the layers were separated using 500 ml of chloroform and 500 ml of water. After extracting the chloroform layer, magnesium sulfate was added to remove residual water and solvent, thereby preparing the monomer of Comparative Example 1 represented by the following chemical formula A (yield: 47%, n = 1).

[0198] [Chemical Formula A]

[0199]

[0200] 1-2. Manufacturing of Polyester Resin Products

[0201] Except that monomer A was used instead of oligomer 1, the final product of Comparative Example 1 was obtained by polymerization in the same manner as in Example 1.

[0202] [Comparative Example 2]

[0203] 2-1. Preparation of phosphorus oligomers

[0204] Except for replacing 2-carboxyethylphenylphosphinoic acid with 100g of methylphosphinoic acid, the oligomer represented by the following chemical formula B was prepared in the same manner as in Synthesis Example 1 (yield: 71%, Mw: 1,150g / mol).

[0205] [Chemical Formula B]

[0206]

[0207] 2-2. Preparation of phosphorus oligomers

[0208] Except that oligomer B was used instead of oligomer 1, the final product of Comparative Example 2 was obtained by polymerization in the same manner as in Example 1.

[0209] [Experimental Example: Evaluation of Physical Properties]

[0210] The physical properties of the final polyester resin products prepared in Examples 1 to 8 and Comparative Examples 1 to 2 are evaluated below, and the results are shown in Table 1.

[0211] Methods for evaluating physical properties

[0212] (1) Weight average molecular weight: Agilent 1200 series was used and measured by PC standard.

[0213] (2) Melt flow index (MI): Measured according to ASTM D1238 (235°C, 2.16 kg) test standard.

[0214] (3) Melting point (T) m The melting point (T0) was measured by raising the temperature from 15°C to 400°C using differential scanning calorimetry (METTLER TOLEDO DSC). m ).

[0215] (4) Flame retardancy rating: Flame retardancy is measured according to the UL94 V test method. In this case, a sample with a thickness of 0.8 mm is used.

[0216] (5) Intrinsic viscosity (IV): Measured according to ASTM D2196 test standard.

[0217] [Table 1]

[0218]

[0219] As shown in Table 1, it should be understood that the polyester resin products of Examples 1 to 8 exhibit excellent flame retardancy even with relatively small amounts of phosphorus (P) oligomers, and the polyester resin products of Examples 1 to 8 can prevent the deterioration of the physical properties of the final polyester resin, such as viscosity, melting temperature, processing properties and molecular weight, and ensure physical stability, because they are different from conventional phosphorus flame retardants, which can contribute to the polymerization reaction.

Claims

1. A phosphorus oligomer represented by the following chemical formula 1: [Chemical Formula 1] in, In chemical formula 1, A and A' are either the same as or different from each other, and are each independently selected from: C1 to C2. 40 Alkylene, C2 to C 40 alkenyl, C2 to C 40 Ethyne group, C3 to C 40 Cycloalkylene, heteroalkylene having 1 to 40 nuclear atoms, heteroalkylene having 3 to 40 nuclear atoms, C6 to C 60 Arenes and heteroaryl groups with 5 to 60 nuclear atoms, The alkylene, alkenylene, ynylene, cycloalkylene, heteroalkylene, heterocycloalkylene, arylene, and heteroaryl groups of A and A' can each be independently substituted by one or more substituents selected from: deuterium (D), halogen, cyano, nitro, C1 to C2. 40 Alkyl, C6 to C 60 Aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when the substituents are numerous, they may be the same as or different from each other. m is an integer in the range of 1 to 10. n is an integer in the range of 2 to 50.

2. The phosphorus oligomer according to claim 1, wherein, The phosphorus oligomer represented by Formula 1 is a phosphorus oligomer containing at least one of Formula 1A and Formula 1B: [Chemical Formula 1A] [Chemical Formula 1B] In the above chemical formula, Ring B is selected from monocyclic or polycyclic alicyclic rings, heterocyclic alicyclic rings, aromatic rings, and heteroaromatic rings. p and q are each integers in the range of 1 to 10. m and n are each defined as in chemical formula 1.

3. The phosphorus oligomer according to claim 1, wherein, A and A' are each independently selected from: C1 to C 10 Alkylene, C3 to C 12 Cycloalkylene, C6 to C 20 Arylenes and heteroarylenes having 5 to 60 nuclear atoms, and A and A' are the same.

4. The phosphorus oligomer according to claim 1, wherein, The phosphorus oligomer is a phosphorus oligomer comprising at least one of the compounds selected from the following chemical formulas: In the above chemical formula, n is as defined in claim 1.

5. The phosphorus oligomer according to claim 1, wherein, The phosphorus (P) oligomer has a weight-average molecular weight (Mw) in the range of 500 g / mol to 3,000 g / mol.

6. A polyester resin comprising: The structural unit a1 is derived from dicarboxylic acid; The structural unit a2 from diol; and Structural unit a3 derived from the phosphorus oligomer according to any one of claims 1 to 5.

7. The polyester resin according to claim 6, wherein, The structural unit a3 is represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, A is selected from: C1 to C 40 Alkylene, C2 to C 40 alkenyl, C2 to C 40 Ethyne group, C3 to C 40 Cycloalkylene, heteroalkylene having 1 to 40 nuclear atoms, heteroalkylene having 3 to 40 nuclear atoms, C6 to C 60 Arenes and heteroaryl groups with 5 to 60 nuclear atoms, The alkylene group, alkenyl group, alkyne group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, aryl group, and heteroaryl group of A may each be independently substituted by one or more substituents selected from the following: deuterium (D), halogen, cyano, nitro, C1 to C1. 40 Alkyl, C6 to C 60 Aryl groups and heteroaryl groups having 5 to 60 nuclear atoms, and when the substituents are numerous, they may be the same as or different from each other. m is an integer in the range of 1 to 10. n is an integer in the range of 2 to 50.

8. The polyester resin according to claim 7, wherein, The structural unit a3 represented by chemical formula 2 comprises at least one structural unit selected from chemical formula 2A and chemical formula 2B: [Chemical Formula 2A] [Chemical Formula 2B] In the above chemical formulas 2A and 2B, Ring B is selected from monocyclic or polycyclic alicyclic rings, heterocyclic alicyclic rings, aromatic rings, and heteroaromatic rings. q is an integer in the range of 1 to 10. m and n are each as defined in claim 7.

9. The polyester resin according to claim 6, wherein, The structural unit a3 is contained in an amount ranging from 0.5 parts by weight to 30 parts by weight relative to 100 parts by weight of the structural unit a1 derived from dicarboxylic acid.

10. The polyester resin according to claim 6, wherein, The phosphorus (P) atomic content ranges from 10 ppm to 10,000 ppm.

11. The polyester resin according to claim 6, wherein the polyester resin comprises: Melt index (MI) in the range of 10 g / 10 min to 30 g / 10 min relative to 235 °C. Weight-average molecular weight (Mw) in the range of 10,000 g / mol to 100,000 g / mol. Melting point (T0) in the range of 150°C to 350°C, measured by differential scanning calorimetry (DSC). m ),as well as Intrinsic viscosity (IV) in the range of 0.7 cP to 1.5 cP at 25°C.

12. The polyester resin according to claim 6, wherein, The polyester resin is polybutylene terephthalate (PBT).

13. A thermoplastic resin composition comprising the polyester resin according to claim 6.

14. A molding article comprising the polyester resin according to claim 6.

15. The molding article according to claim 14, wherein the molding article is a film or fiber.

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