Phosphorus-based oligomer, polyester resin containing the same, and thermoplastic resin composition

Abstract

The present invention provides a novel polyester resin that contains a phosphorus (P)-based oligomer or a structural unit derived therefrom and has excellent flame retardancy and a high degree of polymerization, a thermoplastic resin composition containing the polyester resin, and a molded article using the same.

Description

Technical Field

[0001] The present invention relates to a novel phosphorus (P)-based oligomer, a polyester resin containing a structural unit derived therefrom, having excellent flame retardancy and a high degree of polymerization at the same time, a thermoplastic resin composition containing the polyester resin, and a molded article using the same.

Background Art

[0002] Thermoplastic polyester resins are widely used in housings, connectors, etc. of electronic and electrical and automotive parts because they are excellent in chemical resistance, mechanical strength, heat resistance, and electrical properties. Generally, since polyester resins have a flammable property, in order to be applied to fields where flame retardancy is required, they are used by adding a halogen-based flame retardant or an antimony-based flame retardant auxiliary. However, halogen-based flame retardants or antimony-based flame retardant auxiliaries have problems in that they not only generate a large amount of halogen harmful gases during a fire, but also an excessive amount of flame retardant needs to be used in order to exhibit the desired flame retardant effect.

[0003] In order to solve the above-described problems, methods have been proposed for imparting flame retardancy to polyester resins using non-halogen flame retardants such as organic phosphinate metal salt flame retardants, organophosphinic acid metal salt flame retardants, and melamine polyphosphate. However, when imparting flame retardancy using the above-described compounds, an excessive amount of low molecular weight flame retardant needs to be used, so there are problems such as excessive deterioration of the physical properties of the resin and bleeding out of the flame retardant. In particular, when using a flame retardant that does not participate in the polymerization reaction, there is a problem that the degree of polymerization decreases and inevitably the physical properties of the finally obtained polyester resin deteriorate.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been devised to solve the above-described problems, and its technical problem is to provide a novel polyester resin in which both flame retardancy and degree of polymerization are improved by newly synthesizing a phosphorus (P)-containing oligomer and performing polyester polymerization using the same.

[0006] Another technical problem of the present invention is to provide a thermoplastic resin composition containing the above-described polyester resin and a molded article using the same.

[0007] Other further objects and advantages of the present invention can become clearer from the following detailed description and claims.

Means for Solving the Problems

[0008] To achieve the above-described technical problems, the present invention provides a phosphorus (P)-based oligomer represented by the following Chemical Formula 1.

[0009]

Chem.

[0010] In the above Chemical Formula 1, A and A' are the same as or different from each other, and each independently is selected from the group consisting of an alkylene group having 1 to 40 carbon atoms, an alkenylene group having 2 to 40 carbon atoms, an alkynylene group having 2 to 40 carbon atoms, a cycloalkylene group having 3 to 40 carbon atoms, a heteroalkylene group having 1 to 40 nuclear atoms, a heterocycloalkylene group having 3 to 40 nuclear atoms, an arylene group having 6 to 60 carbon atoms, and a heteroarylene group having 5 to 60 nuclear atoms, The alkylene group, alkenylene group, alkynylene group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, arylene group, and heteroarylene group of A and A' above are each independently deuterium (D), halogen, cyano group, nitro group, C1-C 40 alkyl group of 60 , aryl group of C6-C , and one or more substituents selected from the group consisting of heteroaryl groups having 5 to 60 nuclear atoms can be replaced. When there are a plurality of the above substituents, these may be the same as or different from each other. m is an integer from 1 to 10.

[0011] In one embodiment of the present invention, the phosphorus (P)-based oligomer represented by the above chemical formula 1 can have a weight average molecular weight (Mw) of 500 to 3,000 g / mol.

[0012] The present invention also provides a polyester resin containing a structural unit (a1) derived from a dicarboxylic acid, a structural unit (a2) derived from a diol, and a structural unit (a3) derived from the above phosphorus-based oligomer.

[0013] In one embodiment of the present invention, the above structural unit (a3) is contained in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the structural unit (a1) derived from the above dicarboxylic acid.

[0014] In one embodiment of the present invention, the phosphorus (P) atom content of the above polyester resin can be 10 to 10,000 ppm.

[0015] In one embodiment of the present invention, the above polyester resin has a melt index (MI) of 10 to 30 g / 10 min (based on 235°C), a weight average molecular weight (Mw) of 10,000 to 100,000 g / mol, and a melting point (T m ) measured by a differential scanning calorimeter (DSC) of 150 to 350°C, and an intrinsic viscosity (IV) of 0.7 to 1.5 cP (25°C).

[0016] In one embodiment of the present invention, the polyester resin can be polybutylene terephthalate (PBT).

[0017] The present invention also provides a thermoplastic resin composition containing the above polyester resin.

[0018] Furthermore, the present invention provides a molded article containing the above polyester resin.

Advantages of the Invention

[0019] According to one embodiment of the present invention, instead of a phosphorus-based flame retardant in the form of a single compound that does not participate in the conventional polymerization reaction, an oligomer having a predetermined structure containing phosphorus (P) is newly synthesized, and polyester polymerization is carried out using this, thereby improving the flame retardant properties of the resin itself and adjusting the degree of polymerization to finally improve the physical properties of the obtained polyester resin.

[0020] The effects of the present invention are not limited to the contents exemplified above, and more various effects are included in this specification.

Modes for Carrying Out the Invention

[0021] Hereinafter, the present invention will be described in detail.

[0022] All terms (including technical and scientific terms) used in this specification have the same meaning as generally understood by those having ordinary knowledge in the technical field to which the present invention pertains, unless otherwise defined. Also, terms defined in commonly used dictionaries are not to be construed in an ideal or overly formal sense unless explicitly defined in this specification.

[0023] In this specification, the expression that a certain part "includes" a certain component should be understood as an open-ended term that does not exclude other components and may further include other components, unless otherwise specified.

[0024] Also, as used herein, "preferred" and "suitable" refer to embodiments of the present invention that can provide certain advantages under certain circumstances. It should be noted that there may be other suitable embodiments under the same or other circumstances. Also, the mention of one or more suitable embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present invention.

[0025] <Phosphorus-based oligomer> An example of the present invention is an organophosphorous oligomer applied to the polymerization of polyester resins, which can be represented by the following Chemical Formula 1.

[0026]

Chemical formula

[0027] In the above Chemical Formula 1, As A and A', there are no particular limitations as long as they are divalent hydrocarbon groups well-known in the art. As an example, A and A' may be the same as or different from each other, and each independently may be selected from the group consisting of an alkylene group having 1 to C 40 carbon atoms, an alkenylene group having 2 to C 40 carbon atoms, an alkynylene group having 2 to C 40 carbon atoms, a cycloalkylene group having 3 to C 40 carbon atoms, a heteroalkylene group having 1 to 40 nuclear atoms, a heterocycloalkylene group having 3 to 40 nuclear atoms, an arylene group having 6 to C 60 carbon atoms, and a heteroarylene group having 5 to 60 nuclear atoms. Specifically, A and A' can be the same as each other. For example, they can be selected from the group consisting of an alkylene group having 1 to C 10 carbon atoms, a cycloalkylene group having 3 to C 12 carbon atoms, an arylene group having 6 to C 20 carbon atoms, and a heteroarylene group having 5 to 60 nuclear atoms.

[0028] m is an integer from 1 to 10, and n is an integer from 2 to 50.

[0029] The alkylene group, alkenylene group, alkynylene group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, arylene group, and heteroarylene group of A and A' above are each independently deuterium (D), halogen, cyano group, nitro group, C1-C 40 alkyl group of, C6-C 60 aryl group of, and one or more substituents selected from the group consisting of heteroaryl groups having 5 to 60 nuclear atoms can be replaced. When there are a plurality of the above substituents, they may be the same as or different from each other.

[0030] The phosphorus (P)-based oligomer represented by Chemical Formula 1 according to the present invention serves as a phosphorus-based flame retardant used in the production of conventional polyester resins, that is, heat added to the transesterification reaction and polycondensation reaction, and reaction heat generated as the polymerization reaction proceeds. It can prevent the deterioration of the polyester resin, suppress the occurrence of yellowing due to reverse reaction or decomposition reaction, and make the color of the polyester resin approach transparent and colorless. At the same time, from the viewpoint of preventing environmental pollution, it can be used as an alternative to conventional halogen-based flame retardants. In addition, even if a small amount of the phosphorus-based flame-retardant oligomer is used, sufficient flame retardancy can be imparted, and a decrease in physical properties such as the viscosity, glass transition temperature, and processability of existing polyesters can be prevented.

[0031] In specific examples of the above Chemical Formula 1, A and A' are each independently selected from the group consisting of an alkylene group of C1-C 10 cycloalkylene of C3-C 12 and an arylene group of C6-C 20 and n is an integer from 2 to 45, and m is an integer from 1 to 5. n is an integer from 2 to 45, and m is an integer from 1 to 5.

[0032] In a preferred specific example, the phosphorus-based oligomer represented by Chemical Formula 1 above is more specifically embodied in either one of Chemical Formula 1A and Chemical Formula 1B below, depending on the type of substituent introduced into A and A', but is not limited thereto.

[0033] [Chemistry]

[0034] [Chemistry]

[0035] In the above Chemical Formula 1A and Chemical Formula 1B, Ring B can be a hydrocarbon ring well-known in the art, and these can be in the form of condensation, fusion, cross-linking, or spiro-bonding with other adjacent rings. As an example, Ring B can be selected from the group consisting of monocyclic or polycyclic alicyclic rings, monocyclic or polycyclic heteroalicyclic 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 heteroalicyclic 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.

[0036] p and q are each an integer from 1 to 10, m and n are as defined in Chemical Formula 1, respectively.

[0037] In another preferred specific example, the phosphorus-based oligomer of the above Chemical Formula 1 is more specifically defined by the following Chemical Formula 1C depending on m, but is not limited thereto.

[0038] [Chemistry]

[0039] In the above formula, A, A', and n are as defined in Chemical Formula 1, respectively.

[0040] In one specific example of the above Chemical Formula 1C, A and A' are identical to each other, and the alkylene group of C1 to C 10 and the cycloalkylene group of C3 to C 12 and the C6 to C 20It may be selected from the group consisting of an arylene group and a heteroarylene group having 5 to 60 nuclear atoms.

[0041] The phosphorus-based oligomer represented by the above Chemical Formula 1C is more specifically defined as any one of the following Chemical Formulas 1D to 1E depending on the types of substituents introduced into A and A’, but is not limited thereto.

[0042]

Chemical formula

[0043]

Chemical formula

[0044] In the above formula, Circle B is selected from the group consisting of an alicyclic ring having 3 to 10 carbon atoms and an aromatic ring having 6 to 20 carbon atoms, p and q are each independently an integer from 1 to 6, n is an integer from 2 to 45.

[0045] The phosphorus-based oligomer of the above Chemical Formula 1 is more specifically exemplified by the compounds shown below. However, the phosphorus-based oligomer of the present invention is not limited by these examples.

[0046]

Chemical formula

[0047] In the above formula, n is as defined in Chemical Formula 1. As an example, n is an integer from 2 to 45, specifically from 2 to 30, and more specifically can be from 3 to 25.

[0048] In one specific example, the phosphorus (P)-based oligomer represented by the above Chemical Formula 1 has a weight average molecular weight (Mw) of 500 to 3,000 g / mol, and specifically can be 500 to 2,000 g / mol.

[0049] In the present invention, "alkyl" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

[0050] In the present invention, "alkenyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

[0051] In the present invention, "alkynyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

[0052] In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms, which is a single ring or a combination of two or more rings. Further, two or more rings can include a form in which they are merely pendant or condensed to each other. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

[0053] In the present invention, "heteroaryl" means a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. At this time, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Further, two or more rings can include a form simply pendant to each other or condensed, and further can include a form condensed with an aryl group. Examples of such heteroaryl include, but are not limited to, monocyclic 6-membered rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, etc.

[0054] In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, etc.

[0055] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S, or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, etc.

[0056] <Polyester resin> An example of the present invention relates to a polyester resin containing phosphorus (P) in the basic skeleton of the resin itself and having excellent flame retardancy. In particular, it is differentiated from polyester resins to which conventional phosphorus-based monomers are applied in that it contains a structural unit (a3) derived from the phosphorus-based oligomer represented by Chemical Formula 1 above.

[0057] In one specific example, the polyester resin contains 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.

[0058]

Chemical formula

[0059] In the above Chemical Formula 2, A is selected from the group consisting of an alkylene group having 1 to C 40 an alkenylene group having 2 to C 40 an alkynylene group having 2 to C 40 a cycloalkylene group having 3 to C 40 a heteroalkylene group having 1 to 40 nuclear atoms, a heterocycloalkylene group having 3 to 40 nuclear atoms, an arylene group having 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms, The alkylene group, alkenylene group, alkynylene group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, arylene group, and heteroarylene group of A described above can each be independently replaced with one or more substituents selected from the group consisting of deuterium (D), halogen, cyano group, nitro group, an alkyl group having 1 to C 40 an aryl group having 6 to C 60 and a heteroarylene group having 5 to 60 nuclear atoms. When there are a plurality of the above substituents, they may be the same as or different from each other. m is an integer from 1 to 10, n is an integer from 2 to 50.

[0060] In one specific example of the above Chemical Formula 2, A is C1 to C10 an alkylene group, C3-C 12 a cycloalkylene group, C6-C 20 an arylene group, and a heteroarylene group having 5 to 60 nuclear atoms, selected from the group consisting of m is an integer from 1 to 6, and n is an integer from 2 to 45.

[0061] In a preferred embodiment, the structural unit (a3) represented by Chemical Formula 2 above is more specifically represented by any one of the following Chemical Formulas 2A and 2B, depending on the type of substituent introduced into A, but is not limited thereto.

[0062]

Chemical formula

[0063]

Chemical formula

[0064] In the above Chemical Formulas 2A and 2B, ring B is selected from the group consisting of a monocyclic or polycyclic alicyclic ring, a monocyclic or polycyclic heteroalicyclic ring, a monocyclic or polycyclic aromatic ring, and a monocyclic or polycyclic heteroaromatic ring, q is an integer from 1 to 10, m and n are as defined in Chemical Formula 1, respectively.

[0065] In another preferred embodiment, the structural unit (a3) represented by Chemical Formula 2 above is more specifically represented by the following Chemical Formula 2C depending on m, but is not limited thereto.

[0066]

Chemical formula

[0067] In the above formula, A and n are as defined in Claim 2, respectively.

[0068] The structural unit (a3) represented by the above chemical formula 2C is more specifically defined as any one of the following chemical formulas 2D to 2E depending on the type of substituent introduced into A, but is not limited thereto.

[0069]

Chem.

[0070]

Chem.

[0071] In the above formula, ring B is selected from the group consisting of an alicyclic ring having 3 to 10 carbon atoms and an aromatic ring having 6 to 20 carbon atoms, q is an integer from 1 to 6, n is an integer from 2 to 45.

[0072] The structural unit (a1) constituting the polyester resin according to the present invention is derived from a carboxylic acid and can be derived from dicarboxylic acid monomers and their derivatives well known in the art.

[0073] Examples of the dicarboxylic acids that can be used include, but are not limited to, terephthalic acid, oxalic acid, malonic acid, azelaic acid, fumaric acid, pimelic acid, suberic acid, isophthalic acid, dodecane dicarboxylic acid, naphthalene dicarboxylic acid, biphenyldicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 2,6-naphthalene dicarboxylic acid, 1,2-norbornane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, or mixtures thereof.Depending on requirements, carboxylic acid ester derivatives can be used. Specifically, for example, esterified products of dicarboxylic acid compounds, namely, dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, dimethyl maleate, dimethyl dimer acid, etc. can be mentioned, but are not limited thereto.

[0074] In one specific example, the structural unit (a1) derived from the above dicarboxylic acid contains at least 10 mol% or more of at least one of terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, and adipic acid with respect to the total mol% of the structural unit (a1), and specifically, it can be contained in the range of 20 to 70 mol%.

[0075] The structural unit (a2) constituting the polyester resin according to the present invention is derived from a diol and can be derived from diol-based monomers and their derivatives well-known in the art.

[0076] As the above diol-based monomer, aliphatic diols having 2 to 10 carbon atoms can be used. For example, ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, propanediol, 1,6-hexanediol, tetramethylcyclobutanediol, 1,4-cyclohexanedimethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyoxyethylene glycol, polyoxymethylene glycol, polyoxytetramethylene glycol, glycerol, or a mixture thereof, etc. can be mentioned, but are not limited thereto.

[0077] In one specific example, the structural unit (a2) derived from the diol contains at least 10 mol% of at least one of ethylene glycol, propylene glycol, and butylene glycol, based on the total mol% of the structural unit (a2), and specifically, it can be contained in the range of 20 to 70 mol%.

[0078] The polyester resin according to the present invention is not particularly limited in its structure, components, and / or composition as long as it contains the structural unit (a1) derived from the dicarboxylic acid, the structural unit (a2) derived from the diol, and the structural unit (a3) represented by Chemical Formula 2 described above.

[0079] As an example, the polyester resin can be a thermoplastic polyester and a copolymerized polyester resin, and specifically, it can be a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polypropylene terephthalate resin, or a combination thereof. Preferably, it can be a polybutylene terephthalate (PBT) resin.

[0080] The polyester resin of the present invention includes the structural unit (a3) represented by Chemical Formula 2 and can exhibit the effects of flame retardancy and improvement in the degree of polymerization. In particular, by adjusting the contents of the structural unit (a1) derived from the dicarboxylic acid, the structural unit (a2) derived from the diol, and the structural unit (a3) represented by Chemical Formula 2 in a predetermined ratio, the effects of improving the flame retardancy and the degree of polymerization of the finally obtained polyester resin can be optimized.

[0081] In one specific example, the structural unit (a3) represented by Chemical Formula 2 can be contained in the range of 0.5 to 30 parts by weight, specifically 0.5 to 20 parts by weight, based on 100 parts by weight of the structural unit (a1) derived from the dicarboxylic acid. Here, the content ratio of the structural unit (a1) derived from the dicarboxylic acid and the structural unit (a2) derived from the diol is not particularly limited and can be appropriately adjusted within the range well known in the art. For example, the polymerization can be carried out by variously varying the content of the diol in the range of 1.1 to 1.7 equivalents compared to the dicarboxylic acid and then charging it.

[0082] When the content ratio of each constituent unit constituting the polyester resin of the present invention is within the above-described range, unreacted substances in the esterification reaction and polycondensation reaction are suppressed as much as possible, the yield of the polyester resin increases, and the flame retardancy and physical properties of the produced polyester resin are significantly improved.

[0083] The polyester resin of the present invention containing the structural unit (a1) derived from the above-described dicarboxylic acid, the structural unit (a2) derived from diol, and the structural unit (a3) represented by Chemical Formula 2, and having the content ratios thereof optimized, exhibits an excellent flame retardant effect by the phosphorus (P) atoms contained in the resin itself even without containing a separate flame retardant. Further, the phosphorus-based oligomer involved in the polycondensation reaction improves the degree of polymerization and increases the molecular weight, thereby ensuring the effect of improving the physical properties of the finally obtained resin.

[0084] In one specific example, the content of phosphorus (P) atoms contained in the polyester resin can be 10 to 10,000 ppm.

[0085] In another specific example, the polyester resin has a melt index (MI) of 10 to 30 g / 10 min (based on 235 °C), specifically, it can be 12 to 25 g / 10 min. Further, the weight average molecular weight (Mw) is 10,000 to 100,000 g / mol, specifically, 30,000 to 100,000 g / mol, and more specifically, 40,000 to 80,000 g / mol. Furthermore, the melting point (T m ) measured by a differential scanning calorimeter (DSC) is 150 to 350 °C, and more specifically, it can be 200 to 350 °C.

[0086] In another specific example, the above polyester resin has an intrinsic viscosity (IV) of 0.7 to 1.5 cP (25 °C), and specifically, it can be 0.8 to 1.3 cP (25 °C). Further, the glass transition temperature (Tg) is 50 to 150 °C, and specifically, it can be 80 to 130 °C. Furthermore, the molecular weight distribution (PDI, Mw / Mn) can be 1 to 7, specifically 1 to 4.

[0087] <Method for producing polyester resin> The polyester resin according to an embodiment of the present invention can be produced by a conventional method well-known in the art and is not particularly limited.

[0088] As an example, it can be produced by polymerizing monomers and / or oligomers capable of deriving constitutional unit (a1), constitutional unit (a2), and constitutional unit (a3) by a well-known method such as melt polymerization, solid-phase polymerization, solution polymerization, and slurry polymerization. Further, the above-described polymerization methods can be used in combination. For example, it can be produced by a two-step polymerization in which a prepolymer is produced by melt polymerization and then further subjected to solid-phase polymerization.

[0089] In one embodiment of the above production method, it can include a step of esterifying a dicarboxylic acid and a diol to produce a polyester oligomer; and a step of mixing the polyester oligomer and the phosphorus (P)-based oligomer represented by the above Chemical Formula 2 and subjecting them to polycondensation.

[0090] In another embodiment, it can include a step of mixing a dicarboxylic acid, a diol, and the phosphorus (P)-based oligomer represented by the above Chemical Formula 2, esterifying them, and then performing polycondensation.

[0091] In the steps of the above-described esterification reaction and / or polymerization reaction, additives well-known in the art can be used. The additives that can be used can be, for example, at least one or more of a polymerization catalyst, a heat stabilizer, a chain extender, a light stabilizer, inorganic particles, and potassium hydroxide.

[0092] The polymerization catalyst is not particularly limited, and well-known catalysts used for the polymerization of polyesters can be used. Specific examples 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 such as nitrogen-containing heterocyclic compounds like N-methylimidazole. The amount of the catalyst used is not particularly limited and can be appropriately adjusted within the range well-known in the art.

[0093] Also, as the heat stabilizer, stabilizers well-known in the art can be used. For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, isopropylated triaryl phosphate, hydroquinone bis-(diphenylphosphate), or a mixture thereof can be mentioned.

[0094] In addition to the components described above, in the present invention, any additives commonly applied to the production of polyester resins can be further included within the range that does not inhibit the effects of the invention. Examples of usable additives include at least one or more of an antifoaming agent, an antioxidant, a lubricant, a hydrolysis stabilizer, a mold release agent, a pigment, an antistatic agent, a crosslinking agent, a processing aid, a dripping inhibitor, an abrasion-resistant agent, a surfactant, a fine particle filler, a gloss improver, a viscosity regulator, and a coupling agent, which can be appropriately introduced.

[0095] Regarding the conditions of the esterification reaction and / or polycondensation reaction steps, there are no particular limitations, and they can be appropriately adjusted within the well-known range.

[0096] <Thermoplastic resin composition> Another example of the present invention relates to a thermoplastic resin composition containing the polyester resin described above.

[0097] The polyester resin is not particularly limited in terms of components and / or composition as long as it contains a structural unit (a1) derived from the dicarboxylic acid, a structural unit (a2) derived from the diol, and a structural unit (a3) represented by the above chemical formula. As an example, thermoplastic polyester and copolymerized polyester resins can be used. Specifically, polyethylene terephthalate resin, polybutylene terephthalate resin, polypropylene terephthalate resin, or a mixture of one or more of these can be used. 2 As long as it contains a structural unit (a3) represented by the above chemical formula, it is not particularly limited in terms of components and / or composition. As an example, thermoplastic polyester and copolymerized polyester resins can be used. Specifically, polyethylene terephthalate resin, polybutylene terephthalate resin, polypropylene terephthalate resin, or a mixture of one or more of these can be used.

[0098] In addition to the above-described polyester resin, the thermoplastic resin composition according to the present invention can further contain resins well-known in the art. As an example, polyolefin resins such as polyethylene and polypropylene, cycloolefin polymers, vinyl resins such as polyvinyl chloride, (meth)acrylic resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins such as polyimide and polyetherimide, polystyrene resins such as polystyrene, impact-resistant polystyrene, AS resin, and ABS resin, thermosetting resins such as epoxy resins, cellulose resins, polyether ether ketone resins, fluorine resins, and polycarbonate resins can be mentioned.

[0099] Also, in the present invention, within a range that does not inhibit the effects of the invention, additives suitable for the intended use and effects can be further contained. Examples of usable additives include, but are not limited to, one or more selected from the group consisting of fillers, colorants, pigments, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, leveling agents, ultraviolet absorbers, surfactants, lubricants, lubricants, and chain extenders.

[0100] The thermoplastic resin composition according to the present invention can be produced by conventional methods well-known in the art. For example, after appropriately blending a polyester resin, other resins, additives, etc., melt-kneading is performed using a Banbury mixer, a kneader, a single-screw or twin-screw extruder, etc., to obtain it.

[0101] <Molded article> Another example of the present invention relates to a molded article comprising the above-described polyester resin.

[0102] The shape of the above molded article can be appropriately changed according to the use. Examples include, but are not limited to, film shape, plate shape, fiber shape, etc. Specific examples of the molded article include, but are not limited to, films, sheets, bottles, liquid crystal displays, holograms, filters, dielectric films, insulating materials for electric wires, insulating tapes, fiber-reinforced composites, and other injection molded articles.

[0103] The molded article according to the present invention can further contain, in addition to the polyester resin, resins well-known in the art within a range not inhibiting the effects of the invention. Examples include polyolefin resins such as polyethylene and polypropylene, cycloolefin polymers, vinyl resins such as polyvinyl chloride, (meth)acrylic resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate, 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, polyether ether ketone resins, fluorine resins, and polycarbonate resins.

[0104] Further, in the present invention, within a range not inhibiting the effects of the invention, ordinary additives such as colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, etc. can be further contained.

[0105] The molded article according to the present invention can be manufactured by conventional methods well-known in the art. For example, a mixture containing a polyester resin, other resins, additives, etc. can be obtained by performing press molding, foam molding, injection molding, extrusion molding, punching molding, etc. At this time, the mixture is obtained by appropriately blending a polyester resin, other resins, additives, etc., and then melt-kneading using a Banbury mixer, kneader, single-screw or twin-screw extruder, etc.

[0106] In one specific example, the molded article can be a film.

[0107] The film can be manufactured by conventional methods well-known in the art, such as extrusion molding methods such as inflation molding and melt extrusion molding, and solution casting method. The manufactured film can be a single-layer film made of a polyester resin, or a single-layer or multilayer film made of different materials.

[0108] In another specific example, the molded article can be a fiber.

[0109] The fiber can be manufactured by conventional methods well-known in the art, such as melt spinning method and solution spinning method. The manufactured fiber can be made of a polyester resin or be miscible with different resins.

[0110] The polyester resin, thermoplastic resin composition, and molded article according to the present invention described above have excellent flame retardancy due to the phosphorus (P) component contained in the resin itself, and can ensure the physical properties of the polyester resin by adjusting the degree of polymerization. Therefore, it is useful for the manufacture of molded articles such as housings and connectors for electronic and electrical and automotive parts. It is applicable not only to the above-mentioned uses but also to all technical fields and processes to which conventional polyester resins are applied.

Examples

[0111] Hereinafter, a detailed description will be given based on embodiments of the present invention. However, the embodiments described below are merely illustrative of the present invention, and the present invention is not limited by these embodiments.

[0112] [Synthesis Examples 1 - 5: Production of Phosphorus - based Oligomers] [Synthesis Example 1] 200 g of 2 - carboxyethylphenylphosphinic acid and 115 g of ethylene glycol were charged into a reactor. After heating to 150°C, 0.2 g of tetrabutyl titanate was added. A trap was provided to remove the water generated after the reaction. After 12 hours, when the reaction was completed, the trap was removed, and while maintaining the temperature at 100°C, the pressure was gradually reduced to maintain the vacuum degree at 1 torr or less, and the remaining ethylene glycol was removed to produce Oligomer 1 represented by the following Chemical Formula 3a (yield: 85%, Mw: 1,500 g / mol).

[0113] [Chemical Formula]

[0114] [Synthesis Example 2] Oligomer 2 represented by the following Chemical Formula 3b (yield: 81%, Mw: 1,180 g / mol) was produced in the same manner as in Synthesis Example 1 except that 115 g of ethylene glycol was changed to 150 g of 1,4 - butanediol.

[0115] [Chemical Formula]

[0116] [Synthesis Example 3] Oligomer 3 represented by the following Chemical Formula 3c (yield: 86%, Mw: 1,350 g / mol) was produced in the same manner as in Synthesis Example 1 except that 115 g of ethylene glycol was changed to 120 g of hydroquinone.

[0117] [Chemical Formula]

[0118] [Synthesis Example 4] An oligomer 4 represented by the following Chemical Formula 3d (yield: 71%, Mw: 1,550 g / mol) was produced in the same manner as in Synthesis Example 1 above, except that 115 g of ethylene glycol was changed to 125 g of cyclohexanediol.

[0119] [Chemical Formula]

[0120] [Synthesis Example 5] An oligomer 5 represented by the following Chemical Formula 3e (yield: 87%, Mw: 1,750 g / mol) was produced in the same manner as in Synthesis Example 1 above, except that 115 g of ethylene glycol was changed to 120 g of cyclohexanedimethanol.

[0121] [Chemical Formula]

[0122] [Examples 1 - 8: Production of Polyester Resin Products] [Example 1] 1,940 g of dimethyl terephthalate, 1,350 g of 1,4 - butanediol, and 1.16 g of tetrabutyl titanate were charged into a reactor. When the temperature reached 140°C at normal pressure, the temperature was gradually raised to 200°C while refluxing methanol to carry out a transesterification reaction. When 95% of the theoretical amount of methanol had distilled off, 3 parts by weight of the oligomer 1 produced in Synthesis Example 1 above was added based on the total weight of dimethyl terephthalate. After completion of the transesterification reaction, the product was transferred to a polycondensation reactor, 0.58 g of tetrabutyl titanate was added, and the reaction temperature was maintained at 250°C while gradually reducing the pressure to maintain the vacuum degree at 0.3 torr or less to carry out a polycondensation reaction. When the desired degree of polymerization was reached, nitrogen was injected to release the vacuum, and the polymer was discharged and cooled to obtain the final product 1. The physical property values of the produced final product are shown in Table 1 below.

[0123] [Example 2] The final product 2 was obtained by polymerization in the same manner as in Example 1 above, except that the addition amount of oligomer 1 was changed from 3 parts by weight to 5 parts by weight.

[0124] [Example 3] The final product 3 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 2 was used instead of oligomer 1.

[0125] [Example 4] The final product 4 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 2 was used instead of oligomer 1 and the addition amount of oligomer 2 was changed to 5 parts by weight.

[0126] [Example 5] The final product 5 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 3 was used instead of oligomer 1.

[0127] [Example 6] The final product 6 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 3 was used instead of oligomer 1 and the addition amount of oligomer 3 was changed to 5 parts by weight.

[0128] [Example 7] The final product 7 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 4 was used instead of oligomer 1 and the addition amount of oligomer 4 was changed to 5 parts by weight.

[0129] [Example 8] The final product 8 was obtained by polymerization in the same manner as in Example 1 above, except that oligomer 5 was used instead of oligomer 1 and the addition amount of oligomer 5 was changed to 5 parts by weight.

[0130] [Comparative Example 1] 1-1. Production of Phosphorus-Based Monomer 100 g of 2-carboxyethylphenylphosphinic acid, 200 g of bromoethanol, and 130 g of potassium carbonate were charged into a reactor. After heating up, the mixture was refluxed. After 24 hours, when the reaction was completed, 500 ml of chloroform and 500 ml of water were used to separate the layers. After extracting the chloroform layer, magnesium sulfate was added to remove the residue, and the solvent was removed to produce the monomer of Comparative Example 1 represented by the following Chemical Formula A (yield: 47%, n = 1).

[0131] [Chemical Formula]

[0132] 1-2. Production of Polyester Resin Products Polymerization was carried out in the same manner as in Example 1 above except that monomer A was used instead of oligomer 1 to obtain the final product of Comparative Example 1.

[0133] [Comparative Example 2] 2-1. Production of Phosphorus-based Oligomer An oligomer represented by the following Chemical Formula B (yield 71%, Mw: 1,150 g / mol) was produced in the same manner as in Synthesis Example 1 above except that 2-carboxyethylphenylphosphinic acid was changed to 100 g of methylphosphinic acid.

[0134] [Chemical Formula]

[0135] 2-2. Products made of polyester resin Production of Polymerization was carried out in the same manner as in Example 1 above except that oligomer B was used instead of oligomer 1 to obtain the final product of Comparative Example 2.

[0136] [Experimental Example: Physical Property Evaluation] Regarding the final products of the polyester resins produced in Examples 1 to 8 and Comparative Examples 1 to 2, the physical properties were evaluated as follows, and the results are shown in Table 1 below.

[0137] [Physical Property Evaluation Method] (1) Weight-average molecular weight: Measured by calibration with a PC standard using an Agilent 1200 series.

[0138] (2) Melt index (MI): Measured in accordance with the test standard of ASTM D1238 (conditions of 235°C and 2.16 kg).

[0139] (3) Melting point (Tm): Measured by differential scanning calorimetry (METTLER TOLEDO DSC) while heating from 150°C to 400°C to measure the melting point (Tm).

[0140] (4) Flame retardant grade: Flame retardancy was measured by the test method of UL94 V. At this time, a test piece with a thickness of 0.8 mm was used.

[0141] (5) Intrinsic viscosity (IV): Measured in accordance with the test standard of ASTM D2196.

[0142]

Table 1

[0143] As shown in Table 1 above, the products of the polyester resins of Examples 1 to 8 can exhibit excellent flame retardancy even when using a relatively small amount of phosphorus (P)-based oligomer, and different from conventional phosphorus-based flame retardants, by contributing to the polymerization reaction, it can be seen that it is possible to prevent a decrease in physical properties such as the viscosity, melting temperature, processability, and molecular weight of the finally obtained polyester resin and ensure stability.

Claims

1. A phosphorus (P)-based oligomer represented by the following Chemical Formula 1. 【Chemical 1】 (In the above Chemical Formula 1, A and A' are the same as or different from each other, and each independently is C 1 to C 40 alkylene group, C 2 to C 40 alkenylene group, C 2 to C 40 alkynylene group, C 3 to C 40 cycloalkylene group, heteroalkylene group having 1 to 40 nuclear atoms, hetero-cycloalkylene group having 3 to 40 nuclear atoms, C 6 to C 60 arylene group, and heteroarylene group having 5 to 60 nuclear atoms, and is selected from the group consisting of The alkylene group, alkenylene group, alkynylene group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, arylene group, and heteroarylene group of A and A' above can each independently be replaced by one or more substituents selected from the group consisting of deuterium (D), halogen, cyano group, nitro group, C 1 -C 40 alkyl groups of, C 6 -C 60 aryl groups of, and heteroaryl groups having 5 to 60 nuclear atoms, and when there are a plurality of these substituents, they may be the same as or different from each other. m is an integer from 1 to 10, n is an integer from 2 to 50.)

2. The phosphorus-based oligomer represented by the above Chemical Formula 1 is any one selected from the group consisting of the following Chemical Formula 1A and Chemical Formula 1B. The phosphorus-based oligomer according to Claim 1. 【Chemical Formula 2】 【Chemical 3】 (In the above Chemical Formula 1A and Chemical Formula 1B, Circle B is selected from the group consisting of a C3-C40 cycloalkylene group, a heterocycloalkylene group having 3 to 40 nuclear atoms, a C6-C60 arylene group, and a heteroarylene group having 5 to 60 nuclear atoms, p and q are each an integer from 1 to 10, m and n are each as defined in Chemical Formula 1.)

3. A and A' are each independently selected from the group consisting of an alkylene group of C 1 to C 10 , a cycloalkylene group of C 3 to C 12 , an arylene group of C 6 to C 20 , and a heteroarylene group having 5 to 60 nuclear atoms The A and A' above are identical to each other. The phosphorus-based oligomer according to Claim 1.

4. The phosphorus-based oligomer contains one or more selected from the group of compounds represented by the following chemical formula. The phosphorus-based oligomer according to Claim 1. 【Chemical Formula 4】 (In the above chemical formula, n is as defined in Claim 1.)

5. The phosphorus (P)-based oligomer has a weight average molecular weight (Mw) of 500 to 3,000 g / mol. The phosphorus-based oligomer according to Claim 1.

6. A structural unit (a1) derived from a dicarboxylic acid; A structural unit (a2) derived from a diol; and A structural unit (a3) derived from the phosphorus-based oligomer according to Claim 1 or 5; and contains, The diol is a polyester resin different from the phosphorus-based oligomer.

7. The above structural unit (a3) is the one represented by the following Chemical Formula 2. The polyester resin according to Claim 6. 【Chemical Formula 5】 (In the above Chemical Formula 2, A and A' are the same as or different from each other and are each independently selected from the group consisting of C 1 to C 40 alkylene groups, C 2 to C 40 alkenylene groups, C 2 to C 40 alkynylene groups, C 3 to C 40 cycloalkylene groups, heteroalkylene groups having 1 to 40 nuclear atoms, heterocycloalkylene groups having 3 to 40 nuclear atoms, C 6 to C 60 arylene groups, and heteroarylene groups having 5 to 60 nuclear atoms The alkylene group, alkenylene group, alkynylene group, cycloalkylene group, heteroalkylene group, heterocycloalkylene group, arylene group, and heteroarylene group of A and A' above can each independently be replaced with one or more substituents selected from the group consisting of deuterium (D), halogen, cyano group, nitro group, C 1 ~C 40 alkyl groups of, C 6 ~C 60 aryl groups of, and heteroaryl groups having 5 to 60 nuclear atoms, and when there are a plurality of these substituents, they may be the same as or different from each other. m is an integer from 1 to 10, n is an integer from 2 to 50.)

8. The structural unit (a3) represented by the above Chemical Formula 2 contains at least one structural unit selected from the group consisting of the following Chemical Formula 2A and Chemical Formula 2B. The polyester resin according to Claim 7. 【Chemical Formula 6】 【Chemical Formula 7】 (In the above Chemical Formula 2A and Chemical Formula 2B, Circle B is selected from the group consisting of a C3-C40 cycloalkylene group, a heterocycloalkylene group having 3 to 40 nuclear atoms, a C6-C60 arylene group, and a heteroarylene group having 5 to 60 nuclear atoms, p and q are integers from 1 to 10, m and n are each as defined in Claim 7.) Claim 9: In Chemical Formula 2 above, A and A' are each independently selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a heteroarylene group having 5 to 60 nuclear atoms. The polyester resin according to claim 7, wherein the above A and A' are identical to each other. Claim 10: The polyester resin according to claim 6, wherein the above phosphorus-based oligomer contains one or more selected from the group of compounds represented by the following chemical formula. [Chemical Formula 8] (In the above chemical formula, n is an integer of 2 to 50.) Claim 11 The polyester resin according to claim 6, wherein the above structural unit (a3) is contained in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the structural unit (a1) derived from the above dicarboxylic acid. Claim 12 The polyester resin according to claim 6, wherein the content of phosphorus (P) atoms is 10 to 10,000 ppm. Claim 13 The melt index (Melt Index: MI) is 10 to 30 g / 10 min (based on 235 °C), The weight average molecular weight (Mw) is 10,000 to 100,000 g / mol, The melting point (T m ) measured by differential scanning calorimetry (DSC) is 150 to 350 °C, and The intrinsic viscosity (IV) is 0.7 to 1.5 mPa·s (cP) (25 °C), The polyester resin according to claim 6. Claim 14 The polyester resin according to claim 6, wherein the above polyester resin contains a structural unit derived from terephthalic acid as the above structural unit (a1) and a structural unit derived from 1,4-butanediol as the above structural unit (a2). Claim 15 A thermoplastic resin composition containing the polyester resin according to claim 6. Claim 16 A molded article containing the polyester resin according to claim 6. Claim 17 The molded article according to claim 16, which is a film or fiber.

Images