Flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking and its preparation method and application

Abstract

The present disclosure provides a copolyester comprising structural units represented by [I], [II], [III], and [IV], wherein the number of structural units of [III] is 1 to 99% of the number of structural units of [I], and the number of structural units of [IV] is 0 to 99% of the number of structural units of [I]. The present disclosure also provides a preparation method and applications thereof. The introduced high-temperature self-crosslinking groups and ionic groups improve the melt viscosity and melt strength of the copolyester during combustion and effectively improve the copolyester's carbon-forming ability, resulting in the copolyester exhibiting excellent flame retardancy and anti-drip properties. The preparation process for the copolyester according to the present disclosure is mature, easy to operate, and amenable to control and industrialize production.

Description

[Technical Field]

[0001] This application claims priority to Chinese Patent Application No. 202010568973.0 filed on June 19, 2020, and Chinese Patent Application No. 202110655645.9 filed on June 11, 2021, the contents of which are incorporated by reference into this application.

[0002] The present invention relates to the field of polymer materials, and more particularly to a copolyester having high temperature self-crosslinking, flame retardancy and anti-drip properties, and its preparation method and application. [Background technology]

[0003] Semi-aromatic polyesters (abbreviated as "polyesters"), such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), are used in synthetic fibers, films, bottle materials, and engineering plastics due to their excellent thermal stability, mechanical properties, shape retention, corrosion resistance, and low gas permeability. However, polyesters are highly flammable polymers that not only emit large amounts of heat and dense smoke upon combustion, but also exhibit serious ignition and drip behavior. When a fire breaks out, the heat released by the burning polyester accelerates flame spread, the drips cause burns and secondary fires, and the dense smoke not only makes rescue and evacuation difficult but can also easily cause suffocation. All of these factors significantly limit the applications of polyesters in areas requiring flame retardancy, such as public transportation, protective clothing, automotive interiors, decorative textiles for hotels and department stores, and electronic devices.

[0004] Currently, the most common flame retardant method for polyester is melt blending or copolymerization with halogenated or phosphorus-based flame retardants. Halogenated flame retardants are gradually being phased out of the market because they emit toxic and corrosive gases such as hydrogen halides and dioxins during combustion, posing a risk to human safety. While phosphorus-based flame retardants are effective flame retardants for polyester, most commercially available phosphorus-containing flame retardants achieve their flame retardant effect by promoting "heat removal by dripping from the melt," which creates a contradiction between the flame retardant and anti-drip properties of polyester, and many phosphorus-containing flame retardants further worsen the smoke release behavior of polyester. Therefore, how to simultaneously achieve flame retardancy and anti-drip properties in polyester is a challenging problem currently plaguing both industry and academia and requires urgent resolution. Summary of the Invention [Problem to be solved by the invention]

[0005] Some research results currently disclosed mainly involve adding anti-drip agents such as polytetrafluoroethylene and its derivatives, glass fiber, silica, etc. to polyester. Although these additives can improve the flame retardancy and anti-drip effect of polyester to a certain extent, they also significantly damage the mechanical properties and spinnability of polyester, and cannot solve the problem of serious smoke emission during polyester combustion. Furthermore, during use, these additives precipitate from polyester and are released into the environment, resulting in the problem that the flame retardant effect does not last long, and long-term use can lead to potential environmental pollution and health problems. [Means for solving the problem]

[0006] The copolyester according to the first aspect of the present disclosure comprises structural units represented by the following [I], [II], [III], and [IV]: Structural Unit [I] [ka] (wherein R1 represents an arylene group). Structural Units [II] [ka] (wherein R2 represents an alkylene group). The structural unit [III] has a structure selected from the formulae [A] to [R], [ka] (In the formulae [A] to [R], R3 and R4 each represent a carbonyl group, an O atom, or [ka] wherein a is an integer of 2 to 12, R3 and R4 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom. The structural unit [IV] has a structure selected from the formulae [A1] to [F1], [ka] (In formulas [A1] to [F1], R5 and R6 each represent a carbonyl group, an O atom, or [ka] a is an integer of 2 to 12; R5 and R6 are the same or different; and R7 is C1 to C 12 R8 is a C1 to C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group (HN<), a nitrogen-containing methyl group (CH3N<) and a nitrogen-containing ethyl group (C2H5N<); M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs and Zn; and n is an integer of 1 to 3. The number of structural units of [III] is 1 to 99% of the number of structural units of [I], and the number of structural units of [IV] is 0 to 99% of the number of structural units of [I].

[0007] In one embodiment, the copolyester has an intrinsic viscosity [η] of 0.20 to 3.50 dL / g, a limiting oxygen index of 23.0 to 60.0%, and a vertical flammability level of V-2 to V-0.

[0008] In one embodiment, in the copolyester, the number of structural units [III] is 2 to 60% of the number of structural units [I], the number of structural units [IV] is 0.1 to 60% of the number of structural units [I], the intrinsic viscosity [η] is 0.30 to 3.20 dL / g, the limiting oxygen index is 24.0 to 55.0%, and the vertical flammability level is V-2 to V-0.

[0009] In a preparation method according to a second aspect of the present disclosure, polyester monomers of dibasic acid / dibasic acid ester and dihydric alcohol, and a catalyst are esterified by direct esterification or transesterification based on the blending ratio, and then the copolyester is prepared through a polycondensation reaction. Before the esterification reaction or after the esterification reaction and before the polycondensation, a monomer derived from the structural unit [III] that accounts for 1 to 99% of the molar amount of the dibasic acid or dibasic acid ester of the polyester monomer, and a monomer derived from the structural unit [IV] that accounts for 0 to 99% of the molar amount of the dibasic acid or dibasic acid ester of the polyester monomer, are added to the reaction system.

[0010] In one embodiment, in the above preparation method, preferably, a monomer derived from the structural unit [III] and a monomer derived from the structural unit [IV] are added in an amount of 2 to 60% relative to the number of moles of the dibasic acid or dibasic acid ester of the polyester monomer.

[0011] In one embodiment, the monomer derived from the structural unit [III] used in the above preparation method has at least one structure of the following general formula: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] wherein a is an integer of 2 to 12, Z1 and Z2 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom.

[0012] In one embodiment, the monomer derived from the structural unit [IV] used in the above preparation method has at least one structure of the following general formula: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] a is an integer of 2 to 12, Z1 and Z2 are the same or different, Z3 is a C2 to C8 alkylene group, and R7 is a C1 to C 12 R8 is a C1-C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group, a nitrogen-containing methyl group, and a nitrogen-containing ethyl group; M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, and Zn; and n is an integer of 1 to 3.

[0013] In one embodiment, the ester group of the monomer derived from the structural units [III] and [IV] is any one of a methyl ester group or an ethyl ester group obtained by esterifying a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentylene glycol ester group, a glycerol ester group, and a pentaerythritol ester group obtained by esterifying a polyhydric alcohol.

[0014] In applications of the copolyester according to the third aspect of the present disclosure, the copolyester is not only applied independently in the fields of fibers, nonwoven fabrics, engineering plastics, membrane materials, container materials, self-repairing materials, shape-memory materials, or 3D printer materials, but also used as a functional additive for modifying polymeric materials.

[0015] In order to more clearly describe the technical solutions of the embodiments of the present invention, the following will briefly describe the drawings of some embodiments and comparative examples. Obviously, the drawings in the following description only relate to some embodiments of the present invention and are not intended to limit the present invention. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 shows the variable temperature dynamic rheology of the copolyester prepared in Example 4 and the pure PET prepared in Comparative Example 1. [Figure 2] FIG. 1 is a thermogravimetric curve diagram of a copolyester containing phenylacetylene self-crosslinking functional groups and sodium phosphinate ion groups prepared in Example 4, pure PET prepared in Comparative Example 1, a copolyester containing only phenylacetylene self-crosslinking functional groups prepared in Comparative Example 2, and a copolyester containing only sodium phosphinate ion groups prepared in Comparative Example 3. [Figure 3] 1 shows digital photographs of vertical burn tests of the copolyester prepared in Example 4 and the pure PET prepared in Comparative Example 1. [Figure 4]FIG. 1 is a curve showing the heat release rate in a cone calorimetry test of the copolyester prepared in Example 4 and the pure PET, the copolyester containing only high-temperature self-crosslinking functional groups, or the copolyester containing only ionic groups prepared in Comparative Examples 1 to 3. [Figure 5] FIG. 1 is a curve diagram showing the total smoke release (TSR) in a cone calorimetry test for the copolyester prepared in Example 4 and the pure PET, copolyester containing only high-temperature self-crosslinking functional groups, or copolyester containing only ionic groups prepared in Comparative Examples 1 to 3. DETAILED DESCRIPTION OF THE INVENTION

[0017] Unless otherwise defined, technical or scientific terms used in this disclosure have the common meaning that can be understood by one of ordinary skill in the art.

[0018] In this disclosure, the high-temperature self-crosslinking flame-retardant monomer refers to a monomer that can undergo chemical crosslinking reaction with itself or with polyester structural units.For example, the high-temperature self-crosslinking flame-retardant monomer is a monomer derived from structural unit [III], that is, after the high-temperature self-crosslinking flame-retardant monomer reacts, it generates structural unit [III] in the polymer.For example, it is a diphenylacetylene monomer having an unsaturated triple bond.

[0019] In the present disclosure, the ionic monomer refers to an ionic monomer composed of an organic anion and a metal cation. For example, the ionic monomer is a monomer derived from the structural unit [IV], i.e., after the ionic monomer reacts, it produces the structural unit [IV] in the polymer.

[0020] In the present disclosure, the term "dibasic acid esterified product" refers to an ester of a dibasic acid, such as a dibasic acid dimethyl ester or a dibasic acid diethyl ester.

[0021] The term "aryl group" refers to a cyclic aromatic hydrocarbon group having one to three aromatic rings, particularly a monocyclic or bicyclic group such as a phenyl or naphthyl group. A bicyclic or tricyclic aryl group must contain at least one fully aromatic carbon ring, but the other fused rings may be aromatic or non-aromatic and may optionally contain heteroatoms, the only restriction being that the point of attachment in the above situation must be at an aromatic carbon ring.

[0022] The term "arylene group" refers to a divalent aryl group, i.e., an aryl group as defined above, having two points of attachment to two other groups at any available points of attachment on the aryl ring, such as phenylene and naphthylene groups. Arylene groups may be substituted with any group suitable for substituting an aryl group as defined herein.

[0023] The term "alkyl group" or "alkylene group," as used herein, refers to branched and straight-chain saturated aliphatic hydrocarbons having the specified number of carbon atoms. For example, "C 1~8 An "alkyl group (or alkylene group)" is intended to include C1, C2, C3, C4, C5, C6, C7, and C8 alkyl groups (or alkylene groups). An alkyl group (or alkylene group) can be unsubstituted, or an alkyl group (or alkylene group) can be substituted, where at least one hydrogen therein is replaced with another chemical group.

[0024] Unexpectedly, the inventors have discovered that the structure of the flame-retardant and anti-drip copolyester according to the present disclosure not only contains a flame-retardant monomer (a monomer derived from structural unit [III]) that has high-temperature self-crosslinking properties and can effectively improve the melt viscosity and melt strength of the polyester during combustion, thereby suppressing dripping, but also contains an ionic monomer (a monomer derived from structural unit [IV]) that can form "physical crosslinks" through "ionic aggregates" to improve the melt viscosity of the polyester, thereby achieving a synergistic flame-retardant effect during combustion. Therefore, the copolyester has superior flame-retardant and anti-drip properties compared to copolyesters containing only self-crosslinking functional groups or copolyesters containing only ionic groups.

[0025] The co-action of the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer not only improves the melt viscosity and melt strength of the copolyester of the present disclosure through chemical and physical crosslinking at high temperatures, but also significantly improves its ability to form carbon during combustion, thereby exhibiting excellent flame retardancy and anti-drip properties.

[0026] The present disclosure includes the following embodiments.

[0027] 1. It is composed of the following structural units I, II, III and IV: [ka] [I] (wherein R1 represents an arylene group). [ka] [II] (wherein R2 represents an alkylene group). [ka] [III] (wherein R3 and R4 are each a carbonyl group, an O atom, or [ka] wherein a is an integer of 2 to 12, R3 and R4 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom. [ka] [IV] (wherein R5 and R6 are each a carbonyl group, an O atom, or [ka] a is an integer of 2 to 12; R5 and R6 are the same or different; and R7 is C1 to C 12 R8 is a C1-C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group, a nitrogen-containing methyl group, and a nitrogen-containing ethyl group; M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, and Zn; and n is an integer of 1 to 3. A flame-retardant and drip-resistant copolyester based on high-temperature self-crosslinking, characterized in that the number of structural units of [III] is 1 to 99% of the number of structural units of [I], and the number of structural units of [IV] is 0 to 99% of the number of structural units of [I].

[0028] 2. The flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 1, characterized in that the intrinsic viscosity [η] is 0.20-3.50 dL / g, the limiting oxygen index is 23.0-60.0%, and the vertical burning level is V-2 to V-0.

[0029] 3. The flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 1, wherein the number of structural units [III] is 2 to 60% of the number of structural units [I], the number of structural units [IV] is 0.1 to 60% of the number of structural units [I], the intrinsic viscosity [η] is 0.30 to 3.20 dL / g, the limiting oxygen index is 24.0 to 55.0%, and the vertical burning level is V-2 to V-0.

[0030] 4. A method for preparing the flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking as described in embodiment 1, by esterifying polyester monomers of dibasic acid / dibasic acid ester and dihydric alcohol, catalyst according to a conventional blending ratio by a conventional direct esterification method or ester exchange method, and then carrying out a polycondensation reaction, characterized in that before the esterification reaction or after the esterification reaction and before the polycondensation, a high-temperature self-crosslinking flame-retardant monomer is added to the reaction system in an amount of 1-99% and an ionic monomer is added in an amount of 0-99% based on the mole number of the dibasic acid or dibasic acid ester of the polyester monomer.

[0031] 5. A method for preparing the flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 4, characterized in that 2-60% of the high-temperature self-crosslinking flame-retardant monomer and 0.1-60% of the ionic monomer are added based on the mole number of the dibasic acid or dibasic acid ester of the polyester monomer.

[0032] 6. The method for preparing a flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking, as described in embodiment 4 or 5, wherein the high-temperature self-crosslinking flame-retardant monomer used is at least one of the structures of the following general formula: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] wherein a is an integer of 2 to 12, Z1 and Z2 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom.

[0033] 7. The method for preparing a flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 4 or 5, wherein the ionic monomer used is at least one of the structures of the following general formula: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] a is an integer of 2 to 12, Z1 and Z2 are the same or different, Z3 is a C2 to C8 alkylene group, and R7 is a C1 to C 12 R8 is a C1-C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group, a nitrogen-containing methyl group, and a nitrogen-containing ethyl group; M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, and Zn; and n is an integer of 1 to 3.

[0034] 8. The method for preparing a flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 6, wherein the ester group of the high-temperature self-crosslinking flame-retardant monomer used is either a methyl ester group or an ethyl ester group obtained by esterifying a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentylene glycol ester group, a glycerol ester group, or a pentaerythritol ester group obtained by esterifying a polyhydric alcohol.

[0035] 9. The method for preparing a flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 7, wherein the ester group of the ionic monomer used is any one of methyl ester or ethyl ester groups obtained by esterifying a monohydric alcohol, or ethylene glycol ester, propylene glycol ester, butanediol ester, pentylene glycol ester, glycerol ester, or pentaerythritol ester groups obtained by esterifying a polyhydric alcohol.

[0036] 10. The application of the flame-retardant and anti-drip copolyester based on high-temperature self-crosslinking according to embodiment 1, which is a single application in the fields of fibers, nonwoven fabrics, engineering plastics, membrane materials, container materials, self-repairing materials, shape-memory materials or 3D printer materials, or is used as a functional additive for modifying polymeric materials.

[0037] The copolyester according to the present disclosure comprises structural units represented by the following [I], [II], [III] and [IV]: Structural Unit [I] [ka] (wherein R1 represents an arylene group). Structural Units [II] [ka] (wherein R2 represents an alkylene group). The structural unit [III] has a structure selected from the formulae [A] to [R], [ka] (In the formulae [A] to [R], R3 and R4 each represent a carbonyl group, an O atom, or [ka] wherein a is an integer of 2 to 12, R3 and R4 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom. The structural unit [IV] has a structure selected from the formulae [A1] to [F1], [ka] (In formulas [A1] to [F1], R5 and R6 each represent a carbonyl group, an O atom, or [ka] a is an integer of 2 to 12; R5 and R6 are the same or different; and R7 is C1 to C 12 R8 is a C1 to C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group (HN<), a nitrogen-containing methyl group (CH3N<) and a nitrogen-containing ethyl group (C2H5N<); M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs and Zn; and n is an integer of 1 to 3.

[0038] The number of structural units of [III] is 1 to 99% of the number of structural units of [I], and the number of structural units of [IV] is 0 to 99% of the number of structural units of [I].

[0039] In a preferred embodiment, in the copolyester, the number of structural units [III] is 2 to 60% of the number of structural units [I], and the number of structural units [IV] is 0.1 to 60% of the number of structural units [I].

[0040] In one embodiment, the copolyester has an intrinsic viscosity [η] of 0.20 to 3.50 dL / g, a limiting oxygen index of 23.0 to 60.0%, and a vertical flame level of V-2 to V-0. Preferably, the copolyester has an intrinsic viscosity [η] of 0.30 to 3.20 dL / g, a limiting oxygen index of 24.0 to 55.0%, and a vertical flame level of V-2 to V-0.

[0041] In one embodiment, the monomer containing the R arylene group is selected from terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dipropyl terephthalate, dipropyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl ester, 2,7-naphthalenedicarboxylic acid dimethyl ester, 1,4-naphthalenedicarboxylic acid dimethyl ester, and the like.

[0042] In one embodiment, the R2 alkylene group-containing monomer is selected from ethylene glycol, propylene glycol (e.g., 1,3-propanediol), butanediol (e.g., 1,4-butanediol), pentanediol (e.g., neopentyl glycol), hexanediol, glycerin, pentaerythritol, and the like.

[0043] In one embodiment, the monomer derived from the structural unit [III] is selected from at least one of the following: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] wherein a is an integer of 2 to 12, Z1 and Z2 are the same or different, X1 and X2 are any of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, X1 and X2 are the same or different, and Y1 is an O atom or a S atom.

[0044] In one embodiment, the monomer derived from structural unit [IV] is selected from at least one of the following: [ka] (wherein Z1 and Z2 each represent a carboxyl group, an ester group, a hydroxyl group, or [ka] a is an integer of 2 to 12, Z1 and Z2 are the same or different, Z3 is a C2 to C8 alkylene group, and R7 is a C1 to C 12 R8 is a C1-C8 alkylene or arylene group; Y2 is an O atom or a S atom; Y3 is any one of an O atom, a S atom, a secondary amino group, a nitrogen-containing methyl group, and a nitrogen-containing ethyl group; M is any one of a metal atom Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, and Zn; and n is an integer of 1 to 3.

[0045] In one embodiment, the monomer derived from the structural unit [III] is 4-(phenylethynyl)phthalic acid, dimethyl 5-(phenylethynyl)-1,3-isophthalate, dimethyl 5-benzimidazole-1,3-isophthalate, dimethyl 5-benzamido-1,3-isophthalate, dimethyl 5-benzamido-1,3-isophthalate, dimethyl 5-benzimidophenylacetylene-1,3-dibenzoic acid, (E)-5-(benzylideneamino)benzene-1,3-diol, dimethyl (E)-5-(benzylideneamino)benzene-1,3-isophthalate, dimethyl 5-(2,5-dioxa-1,2-diol), Dimethyl 3-phenyl-2,5-dihydro-1H-pyrrol-1-yl)isophthalate, (1-(3,5-bis(2-hydroxyethoxy)phenyl)-3-phenyl-1H-pyrrole-2,5-dione, 5-benzamido-1,3-isophthalic acid, N-(3,5-bis(2-hydroxyethoxy)phenyl)benzamide, 3,5-dihydroxy-N-phenylbenzamide, dimethyl 5-(3-cyanophenoxy)isophthalate, 3,5-bis(2-hydroxyethoxy)-N-phenylbenzamide, 5-((diphenylphosphine) Dimethyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, N-(3-cyanophenyl)-3,5-bis(2-hydroxyethoxy)benzamide, Dimethyl 5-benzimido-1,3-isophthalate, Dimethyl 5-(4-cyanophenoxy)isophthalate, 4-(3,5-bis(2-hydroxyethoxy)phenoxy)benzonitrile, 5-(benzenesulfonyl)isophthalic acid, N-(3,5-dihydroxyphenyl)benzenesulfonamide , dimethyl 5-(N-phenylsulfamoyl)isophthalate, dimethyl 5-benzimido-1,3-isophthalate, methyl 4-(N-(4-(methoxycarbonyl)phenyl)sulfamoyl)benzoate, methyl 2-cyano-4((4-methoxycarbonyl)phenyl)sulfonamido)benzoate, 4,4'-azobenzenedicarboxylic acid, N-(2-methyl-5-carbomethoxyphenyl)-4-carbomethoxybenzimide, dimethyl 4,4'-((1,3-phenylene-5-cyano)dioxy)dibenzoate, dimethyl 4,4'-((1,The methyl 3-cyano-5-((4-(methoxycarbonyl)phenyl)carbamoyl)benzoate is selected from at least one of dimethyl 3-phenylene-2-cyanodioxybenzoate, methyl 3-cyano-5-((4-(methoxycarbonyl)phenyl)carbamoyl)benzoate, methyl 2,2'-(1,4-phenylene)bis(1H-benzimidazole-5-carboxylate), 4-((4-cyanophenyl)ethynyl)phthalic acid, dimethyl (E)-5-((4-cyanobenzylidene)amino)benzene-1,3-isophthalate, and the like.

[0046] In one embodiment, the monomer derived from the structural unit [IV] is potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, potassium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, sodium isophthalic acid-5-sulfonate, sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, , sodium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, potassium isophthalic acid-5-sulfonate, magnesium (3-(2-hydroxyethoxy)-3-oxopropyl(phenyl)phosphinate, sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 3 ,5-Di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonic acid potassium salt, 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinic acid potassium salt, (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinic acid potassium salt, 3,5-bis(methoxycarbonyl)phenyl)phosphonic acid potassium salt, 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonic acid potassium salt sodium anthraxaphosphinate, sodium 3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, sodium 3,5-dihydroxybenzenesulfonate, potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, and the like.

[0047] The high-temperature self-crosslinking flame-retardant monomers used in the above methods may be prepared by referring to the methods disclosed in documents such as Journal of Materials Chemistry, 2012, 22, 19849-19857, Polymer Chemistry, 2016, 7, 2698-2708, and Chemical Engineering Journal, 2019, 374, 694-705. The ionic monomers used in the above methods may be prepared by referring to the methods disclosed in documents such as Polymer Chemistry, 2014, 5, 1982-1991, and Polymer, 2015, 60, 50-61.

[0048] In one embodiment, the ester group of the high-temperature self-crosslinking flame-retardant monomer and the ionic monomer is either a methyl ester group or an ethyl ester group obtained by esterifying a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentylene glycol ester group, a glycerol ester group, or a pentaerythritol ester group obtained by esterifying a polyhydric alcohol.

[0049] The process steps and conditions of the conventional direct esterification or transesterification method used in the present invention are specifically as follows:

[0050] Direct esterification: Based on the blending ratios, dibasic acid, dihydric alcohol, catalyst, high-temperature self-crosslinking flame-retardant monomer, and ionic monomer are added to a reactor, pressurized and heated to 190-240°C, and the esterification reaction is carried out for 2-5 hours. After esterification is complete, polycondensation is carried out under low vacuum at 240-250°C for 0.5-2 hours, followed by polycondensation under high vacuum at 250-280°C for 1-4 hours. The copolyester melt is extruded using an inert gas (preferably nitrogen gas) and water-cooled to obtain the desired copolyester. The high-temperature self-crosslinking flame-retardant monomer and ionic monomer can be added to the reactor before esterification or after esterification and before polycondensation.

[0051] Transesterification: Based on the blending ratio, a dibasic acid ester, a dihydric alcohol, a catalyst, a high-temperature self-crosslinking flame-retardant monomer, and an ionic monomer are added to a reactor, and the transesterification reaction is carried out at normal pressure at 180-220°C for 3-6 hours. After the transesterification reaction is complete, polycondensation is carried out under low vacuum at 240-250°C for 0.5-2 hours, and then under high vacuum at 250-280°C for 1-4 hours. The copolyester melt is extruded using an inert gas (preferably nitrogen gas) and water-cooled to obtain the desired copolyester. The high-temperature self-crosslinking flame-retardant monomer and ionic monomer can be added to the reactor before the transesterification reaction or before polycondensation after the transesterification reaction.

[0052] The catalyst used in the above preparation method is at least one of catalysts such as germanium-based catalysts, titanium-based catalysts, antimony-based catalysts, aluminum-based catalysts, and tin-based catalysts, such as germanium dioxide, antimony acetate, antimony trioxide, ethylene glycol antimony, titanium oxide, potassium titanium oxalate, potassium hexafluorotitanate, titanate esters, titanium alkoxides, titanium complexes, tin oxide, aluminum hydroxide, aluminum acetate, silica, zinc acetate, manganese acetate, and magnesium acetate.

[0053] The application of the flame-retardant and anti-drip copolyester based on the above-mentioned high-temperature self-crosslinking of the present invention may be a standalone application in the fields of fibers, nonwoven fabrics, engineering plastics, membrane materials, container materials, self-repairing materials, shape-memory materials or 3D printer materials, or may be used as a functional additive for modifying polymer materials.

[0054] Compared to the prior art, the present invention has one or more of the following advantages.

[0055] 1. Because the structural units of the flame-retardant and anti-drip copolyester of the present invention contain structures capable of undergoing high-temperature self-crosslinking reactions, these self-crosslinking structures do not stably crosslink during polymerization or processing, but can rapidly crosslink at higher temperatures or during combustion (Figure 1). The crosslinking reaction significantly improves the melt viscosity / strength of the polyester during combustion, thereby suppressing dripping. On the other hand, the aromatic fused ring structure formed by the crosslinking further evolves to form a stable and dense carbon layer, which provides thermal insulation and oxygen protection and inhibits the volatilization of flammable substances, thereby imparting excellent flame retardancy to the copolyester.

[0056] 2. The flame-retardant and anti-drip copolyester of the present invention has a structure that not only contains a flame-retardant monomer that has high-temperature self-crosslinking properties and effectively improves the melt viscosity and melt strength of the polyester during combustion, thereby suppressing dripping, but also contains an ionic monomer that can form a "physical crosslink" through "ionic aggregates" to improve the melt viscosity of the polyester, thereby achieving a synergistic flame-retardant effect during combustion. Compared with copolyesters containing only self-crosslinking functional groups or copolyesters containing only ionic groups, this copolyester has better flame-retardant and anti-drip properties.

[0057] 3. The flame-retardant and anti-drip copolyester of the present invention also has a high carbon-forming ability. During combustion, the copolyester forms a stable and dense carbon layer, which can effectively inhibit the volatilization of organic smoke. As a result, the copolyester exhibits a high smoke-suppressing effect, which is not available in most flame-retardant polyesters.

[0058] 4. The flame-retardant and anti-drip copolyester of the present invention has high antistatic properties and affinity for cationic dyes because the structure of the copolyester contains ionic groups.

[0059] 5. The flame-retardant and anti-drip copolyester of the present invention has a structure containing conjugated aromatic groups, which can form π-π stacking interactions. Using the π-π stacking as a dynamic crosslinking point, the copolyester can not only be endowed with certain self-healing and shape-memory properties, but also improve the mechanical strength of the copolyester and the adhesive strength between melts, making it suitable for use as an intelligent polymer material and a 3D printer material.

[0060] 6. The flame-retardant and anti-drip copolyester of the present invention does not contain any additives that affect fiber production, and therefore has excellent spinnability. It can be used directly as a copolyester for fibers, and can also be used as a polymer compatibilizer for immiscible polymer blends, which can improve the mechanical properties of the material and impart flame-retardant and anti-drip properties to the material.

[0061] 7. The flame-retardant and anti-drip copolyester of the present invention does not contain any halogen-based elements in its structure, making it an environmentally friendly green polymer material.

[0062] 8. The preparation method of the copolyester of the present invention is basically identical to the conventional polyester synthesis method, so the process is mature, the equipment is highly portable, and it is easy to operate, control, and industrialize the production.

[0063] Hereinafter, examples are provided to further explain the present invention, but the embodiments of the present invention are not limited thereto. It should be noted that the following examples cannot be understood as limiting the scope of protection of the present invention, and any non-essential improvements and adjustments made to the present invention by those skilled in the art based on the present disclosure still fall within the scope of protection of the present invention.

[0064] Measurement method

[0065] Measurement method of complex viscosity of copolyester: Using a TA DHR-2 rotational rheometer, the size of the copolyester sample is a sheet with a diameter of 25 mm and a thickness of 1 mm, and the shear rate of the measurement is 1 rads. -1 The temperature rise rate was 5℃ min -1 The higher the complex viscosity of a copolyester at high temperatures, the higher its melt viscosity and melt strength during combustion, which means that the anti-drip ability is correspondingly stronger.

[0066] The thermogravimetric analysis of the copolyester was carried out using a NETZSCH TG 209 F1 thermogravimetric analyzer (TGA) to measure the thermal stability of the copolyester in a nitrogen atmosphere and an air atmosphere, with a heating rate of 10 K / min and a measurement temperature range of 40 to 700°C.

[0067] The intrinsic viscosity [η] of each copolyester was measured at 25°C using an Ubbelohde viscometer after preparing a 5 g / L solution in phenol / 1,1,2,2-tetrafluoroethylene (1:1, v:v) solvent.

[0068] The limiting oxygen index of the copolyester is 3 The limiting oxygen index (LOI) is measured on an HC-2 oxygen index meter in accordance with the ASTM D2863-97 standard, using a standard oxygen index measuring spline. The limiting oxygen index (LOI) characterizes the self-extinguishing ability of a material; the higher the LOI value, the more flame-retardant the material is. Generally, a material is considered self-extinguishing if its LOI is greater than 26%.

[0069] The vertical flame test was carried out on a 125 x 12.7 x 3.2 mm copolyester sheet. 3 The test is conducted using a CZF-2 type vertical combustion apparatus in accordance with the UL-94 standard (UL-94). The test levels are classified into no level, V-2 level, V-1 level and V-0 level, with no level indicating that the material is highly flammable, and the flame retardancy of the material is V-2 level. <V-1レベル<V-0レベルである。

[0070] The heat release rate (HRR) and total smoke release rate (TSR) of the copolyester are measured using a cone calorimetry test. 3 50kW / m on an FTT cone calorimeter according to the ISO 5660-1 standard. 2 The heat release rate (HRR), especially the peak heat release rate (p-HRR), is an important parameter for evaluating the flame retardant properties of materials in cone calorimetry tests; the lower the value, the higher the flame retardancy of the material; otherwise, it is low. The smaller the TSR, the lower the amount of smoke released by the material in a fire.

[0071] Example 1

[0072] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 7.98g of 4-(phenylethynyl)phthalic acid, 36.6g of 2,8-(2-hydroxyethoxy)carbonylphenanthrene potassium phosphinate, and 0.3g of antimony trioxide to a reaction vessel. Fill with nitrogen gas to remove the air from the vessel, pressurize to 0.1MPa, and heat to 240°C within 2 hours to initiate the esterification reaction. Control the pressure in the vessel at 0.3-0.4MPa and maintain this for 2-4 hours, then reduce the pressure to normal pressure to complete the esterification reaction. Then, carry out a polycondensation reaction at 240°C under low vacuum for 0.5-2 hours. Then, heat to 250-270°C and carry out a polycondensation reaction under high vacuum (pressure <80Pa) for 1-4 hours. Discharge the materials and cool with water.

[0073] The copolyester has an intrinsic viscosity [η] of 0.85 dL / g, a limiting oxygen index of 27.0%, a vertical burning level of V-2 level, and a peak heat release rate p-HRR of 320 kW / m in a cone calorimetry test. 2 The total smoke release rate (TSR) was 683 m 2 / m 2 is.

[0074] Example 2

[0075] Add 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 159.6g of 4-(phenylethynyl)phthalic acid, 25.2g of sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, 0.2g of manganese acetate, and 0.25g of germanium dioxide to a reaction vessel, fill with nitrogen gas to remove the air from the vessel, and react at 180-220°C under normal pressure for 2-6 hours until the transesterification reaction is complete. Then, carry out a polycondensation reaction at 240-250°C under low vacuum for 0.5-2 hours, and then a polycondensation reaction at 250-270°C under high vacuum (pressure <80Pa) for 1-4 hours. Discharge the material and cool with water.

[0076] The copolyester has an intrinsic viscosity [η] of 0.62 dL / g, a limiting oxygen index of 30.5%, a vertical burning level of V-2 level, and a peak heat release rate p-HRR of 312 kW / m in a cone calorimetry test. 2 The total smoke release rate (TSR) is 801m 2 / m 2 is.

[0077] Example 3

[0078] 388.0g of dimethyl terephthalate, 194g of dimethyl isophthalate, 400.0g of ethylene glycol, 79.8g of 4-(phenylethynyl)phthalic acid, 52.5g of potassium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 40.2g of sodium isophthalic acid-5-sulfonate, and 0.28g of isopropyl titanate are added to a reaction kettle, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 2, and then the materials are discharged.

[0079] The copolyester has an intrinsic viscosity [η] of 0.90 dL / g, a limiting oxygen index of 31.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 222 kW / m in the cone calorimetry test. 2 and TSR is 640m 2 / m 2 is.

[0080] Example 4

[0081] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 159.6g of 4-(phenylethynyl)phthalic acid, 38.7g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 0.2g of zinc acetate and 0.3g of antimony trioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0082] The copolyester has an intrinsic viscosity [η] of 0.88 dL / g, a limiting oxygen index of 31.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 298 kW / m in the cone calorimetry test. 2 and TSR is 728m 2 / m 2 is.

[0083] Example 5

[0084] 415.0g of terephthalic acid, 83.0g of phthalic acid, 220.0g of ethylene glycol, 176.4g of dimethyl 5-(phenylethynyl)-1,3-isophthalate, 47.5g of sodium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 65.9g of dimethyl 5-benzimidophenylacetylene-1,3-isophthalate, 9.4g of dimethyl 5-benzamido-1,3-isophthalate, 0.1g of antimony acetate, and 0.2g of titanium glycolate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0085] The copolyester has an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 32.0%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 238 kW / m in the cone calorimetry test. 2 and TSR is 709m2 / m 2 is.

[0086] Example 6

[0087] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 88.2g of dimethyl 5-(phenylethynyl)-1,3-isophthalate, 1.8g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, and 0.25g of titanium tartrate into a reaction kettle, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1, and then discharge the materials.

[0088] The copolyester has an intrinsic viscosity [η] of 1.27 dL / g, a limiting oxygen index of 30.0%, a vertical combustion level of V-2 level, and a p-HRR of 434 kW / m in a cone calorimetry test. 2 and TSR is 1473m 2 / m 2 is.

[0089] Example 7

[0090] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 65.9g of dimethyl 5-benzimidophenylacetylene-1,3-isophthalate, 38.7g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, and 0.3g of tetrabutyl titanate were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0091] The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 29.4%, a vertical combustion level of V-2 level, and a p-HRR of 266 kW / m in a cone calorimetry test. 2 and TSR is 770m 2 / m 2 is.

[0092] Example 8

[0093] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 131.7g of dimethyl 5-benzimidophenylacetylene-1,3-isophthalate, 28.6g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 25.5g of sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, 0.2g of magnesium acetate and 0.2g of titanium dioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0094] The copolyester has an intrinsic viscosity [η] of 0.95 dL / g, a limiting oxygen index of 33.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 248 kW / m in the cone calorimetry test. 2 and TSR is 690m 2 / m 2 is.

[0095] Example 9

[0096] 498.0g terephthalic acid, 220.0g ethylene glycol, 123.3g 5-benzimidophenylacetylene-1,3-dibenzoic acid, 42.6g potassium isophthalic acid-5-sulfonate, and 0.3g ethylene glycol antimony are added to a reaction kettle, and esterification and polycondensation are carried out according to the steps and conditions of Example 1, and then the materials are discharged.

[0097] The copolyester has an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 34.6%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 202 kW / m in the cone calorimetry test. 2 and TSR is 688m 2 / m 2 is.

[0098] Example 10

[0099] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 369.9g of 5-benzimidophenylacetylene-1,3-dibenzoic acid, 180.6g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, and 0.3g of tetrabutyl titanate into a reaction kettle, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1, and then discharge the materials.

[0100] The copolyester has an intrinsic viscosity [η] of 0.84 dL / g, a limiting oxygen index of 46.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 186 kW / m in the cone calorimetry test. 2 and TSR is 440m 2 / m 2 is.

[0101] Example 11

[0102] 415.0 g of terephthalic acid, 53.0 g of isophthalic acid, 30.0 g of phthalic acid, 220.0 g of ethylene glycol, 95.9 g of (E)-5-(benzylideneamino)benzene-1,3-diol, 16.1 g of magnesium (3-(2-hydroxyethoxy)-3-oxopropyl(phenyl)phosphinate), 12.9 g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 9.5 g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 0.27 g of titanium dioxide, and 0.03 g of silica were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0103] The copolyester has an intrinsic viscosity [η] of 0.60 dL / g, a limiting oxygen index of 32.5%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 482 kW / m in the cone calorimetry test. 2 and TSR is 917m 2 / m 2 is.

[0104] Example 12

[0105] 498.0g of terephthalic acid, 200.0g of ethylene glycol, 44.6g of (E)-5-(benzylideneamino)benzene-1,3-isophthalic acid dimethyl, 19.1g of (3,5-bis(methoxycarbonyl)phenyl) sodium phosphonate, 0.15g of zinc acetate, 0.3g of aluminum oxide and 0.1g of silica were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0106] The copolyester has an intrinsic viscosity [η] of 0.75 dL / g, a limiting oxygen index of 29.5%, a vertical flame resistance of V-2 level, and a p-HRR of 412 kW / m in a cone calorimetry test. 2 and TSR is 1055m 2 / m 2 is.

[0107] Example 13

[0108] 388.0g of dimethyl terephthalate, 194.0g of dimethyl isophthalate, 400.0g of ethylene glycol, 178.2g of (E)-5-(benzylideneamino)benzene-1,3-dimethyl isophthalate, 81.6g of potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 0.2g of aluminum acetate, and 0.25g of titanium citrate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, followed by discharging the materials.

[0109] The copolyester has an intrinsic viscosity [η] of 0.77 dL / g, a limiting oxygen index of 36.2%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 346 kW / m in the cone calorimetry test. 2 and TSR is 744m 2 / m2 is.

[0110] Example 14

[0111] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 109.5g of dimethyl 5-(2,5-dioxy-3-phenyl-2,5-dihydro-1H-pyrrol-1-yl)isophthalate, 25.8g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, and 0.25g of tetraethyl titanate into a reaction kettle, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1, and then discharge the materials.

[0112] The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 33.4%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 302 kW / m in the cone calorimetry test. 2 and TSR is 855m 2 / m 2 is.

[0113] Example 15

[0114] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 88.6g of (1-(3,5-bis(2-hydroxyethoxy)phenyl)-3-phenyl-1H-pyrrole-2,5-dione, 19.1g of (3,5-bis(methoxycarbonyl)phenyl) sodium phosphonate, and 0.3g of titanium potassium oxalate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0115] The copolyester has an intrinsic viscosity [η] of 0.78 dL / g, a limiting oxygen index of 32.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 398 kW / m in the cone calorimetry test. 2 and TSR is 926m 2 / m 2 is.

[0116] Example 16

[0117] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 47.0g of dimethyl 5-benzamido-1,3-isophthalate, 26.8g of potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 0.2g of magnesium acetate and 0.2g of potassium hexafluorotitanate were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0118] The copolyester has an intrinsic viscosity [η] of 1.2 dL / g, a limiting oxygen index of 28.6%, a vertical flame resistance of V-2 level, and a p-HRR of 465 kW / m in a cone calorimetry test. 2 and TSR is 970m 2 / m 2 is.

[0119] Example 17

[0120] Add 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 563.4g of dimethyl 5-benzamido-1,3-isophthalate, 17.8g of potassium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, 40.2g of sodium isophthalic acid-5-sulfonate, and 0.24g of tetraisopropyl orthotitanate into a reaction kettle, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 2, and then discharge the materials.

[0121] The copolyester has an intrinsic viscosity [η] of 0.90 dL / g, a limiting oxygen index of 42.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 195 kW / m in the cone calorimetry test. 2 and TSR is 468m 2 / m 2 is.

[0122] Example 18

[0123] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 171.0 g of 5-benzamido-1,3-isophthalic acid, 52.5 g of potassium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3 g of ethylene glycol antimony were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0124] The copolyester has an intrinsic viscosity [η] of 1.12 dL / g, a limiting oxygen index of 33.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 244 kW / m in the cone calorimetry test. 2 and TSR is 787m 2 / m 2 is.

[0125] Example 19

[0126] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 85.5g of 5-benzamido-1,3-isophthalic acid, 24.1g of sodium isophthalic acid-5-sulfonate, and 0.24g of tetrabutyl titanate are added to a reaction vessel, and esterification and polycondensation are carried out according to the steps and conditions of Example 2, and then the material is discharged.

[0127] The copolyester has an intrinsic viscosity [η] of 1.03 dL / g, a limiting oxygen index of 30.5%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 290 kW / m in the cone calorimetry test. 2 and TSR is 733m 2 / m 2 is.

[0128] Example 20

[0129] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 95.1g of N-(3,5-bis(2-hydroxyethoxy)phenyl)benzamide, 17.6g of dimethyl 5-(phenylethynyl)-1,3-isophthalate, 21.0g of potassium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, 31.7g of sodium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 0.2g of nickel acetate, and 0.2g of tetrabutoxygermanium were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, followed by discharging the materials.

[0130] The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 33.4%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 269 kW / m in the cone calorimetry test. 2 and TSR is 676m 2 / m 2 is.

[0131] Example 21

[0132] 468.0g of terephthalic acid, 30.0g of isophthalic acid, 220.0g of ethylene glycol, 142.7g of N-(3,5-bis(2-hydroxyethoxy)phenyl)benzamide, 90.3g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, 0.15g of magnesium acetate and 0.35g of aluminum hydroxide are added to a reaction kettle, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 1, and then the materials are discharged.

[0133] The copolyester has an intrinsic viscosity [η] of 0.74 dL / g, a limiting oxygen index of 34.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 241 kW / m in the cone calorimetry test. 2 and TSR is 532m 2 / m2 is.

[0134] Example 22

[0135] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 34.4g of 3,5-dihydroxy-N-phenylbenzamide, 28.0g of dimethyl 5-(3-cyanophenoxy)isophthalate, 28.6g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, 25.2g of sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, and 0.3g of titanium dioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0136] The copolyester has an intrinsic viscosity [η] of 0.79 dL / g, a limiting oxygen index of 34.0%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 235 kW / m in the cone calorimetry test. 2 and TSR is 664m 2 / m 2 is.

[0137] Example 23

[0138] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 47.6g of 3,5-bis(2-hydroxyethoxy)-N-phenylbenzamide, 61.4g of dimethyl 5-((diphenylphosphoryl)amino)isophthalate, 46.8g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 31.8g of sodium 3,5-dihydroxybenzenesulfonate, and 0.3g of tetrabutyl titanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, followed by discharging the materials.

[0139] The copolyester has an intrinsic viscosity [η] of 0.90 dL / g, a limiting oxygen index of 36.5%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 202 kW / m in the cone calorimetry test. 2 and TSR is 529m 2 / m 2 is.

[0140] Example 24

[0141] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 51.3g of N-(3-cyanophenyl)-3,5-bis(2-hydroxyethoxy)benzamide, 90.3g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, 10.2g of dimethyl 5-benzimido-1,3-isophthalate, 0.2g of manganese acetate, and 0.2g of tetraisopropyl orthotitanate are added to a reaction kettle, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 2, and then the materials are discharged.

[0142] The copolyester has an intrinsic viscosity [η] of 0.66 dL / g, a limiting oxygen index of 36.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 250 kW / m in the cone calorimetry test. 2 and TSR is 761m 2 / m 2 is.

[0143] Example 25

[0144] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 46.7g of dimethyl 5-(3-cyanophenoxy)isophthalate, 40.1g of potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, and 0.3g of titanium citrate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0145] The copolyester has an intrinsic viscosity [η] of 0.88 dL / g, a limiting oxygen index of 30.0%, a vertical combustion level of V-2 level, and a p-HRR of 302 kW / m in a cone calorimetry test. 2 and TSR is 893m 2 / m 2 is.

[0146] Example 26

[0147] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 93.3g of dimethyl 5-(4-cyanophenoxy)isophthalate, 122.7g of dimethyl 5-((diphenylphosphoryl)amino)isophthalate, 190.8g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3g of antimony trioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0148] The copolyester has an intrinsic viscosity [η] of 0.75 dL / g, a limiting oxygen index of 39.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 242 kW / m in the cone calorimetry test. 2 and TSR is 598m 2 / m 2 is.

[0149] Example 27

[0150] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 94.5g of 4-(3,5-bis(2-hydroxyethoxy)phenoxy)benzonitrile, 63.6g of sodium 3,5-dihydroxybenzenesulfonate, and 0.25g of titanium glycolate into a reaction vessel, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1, and then discharge the materials.

[0151] The copolyester has an intrinsic viscosity [η] of 0.82 dL / g, a limiting oxygen index of 36.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 252 kW / m in the cone calorimetry test. 2 and TSR is 770m 2 / m 2 is.

[0152] Example 28

[0153] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 48.2g of 5-(benzenesulfonyl)isophthalic acid, 40.1g of potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 0.2g of cobalt acetate, and 0.25g of titanium tartrate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0154] The copolyester has an intrinsic viscosity [η] of 0.65 dL / g, a limiting oxygen index of 30.2%, a vertical flame retardation level of V-2, and a p-HRR of 268 kW / m in a cone calorimetry test. 2 and TSR is 690m 2 / m 2 is.

[0155] Example 29

[0156] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 159.0g of N-(3,5-dihydroxyphenyl)benzenesulfonamide, 28.1g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 47.7g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.25g of isopropyl titanate were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0157] The copolyester has an intrinsic viscosity [η] of 0.82 dL / g, a limiting oxygen index of 38.0%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 216 kW / m in the cone calorimetry test. 2 and TSR is 582m 2 / m 2 is.

[0158] Example 30

[0159] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 48.2g of 5-(benzenesulfonyl)isophthalic acid, 80.4g of sodium isophthalic acid-5-sulfonate, and 0.3g of tetrabutyl titanate are added to a reaction vessel, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 2, and then the materials are discharged.

[0160] The copolyester has an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 32.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 331 kW / m in the cone calorimetry test. 2 and TSR is 877m 2 / m 2 is.

[0161] Example 31

[0162] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 314.1g of dimethyl 5-(N-phenylsulfamoyl)isophthalate, 95.4g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, 0.2g of antimony acetate and 0.1g of titanium dioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0163] The copolyester has an intrinsic viscosity [η] of 0.94 dL / g, a limiting oxygen index of 40.5%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 177 kW / m in the cone calorimetry test. 2 and TSR is 530m 2 / m 2 is.

[0164] Example 32

[0165] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 101.7g of dimethyl 5-benzimide-1,3-isophthalate, 80.4g of sodium isophthalic acid-5-sulfonate, 0.2g of manganese acetate and 0.3g of potassium titanium oxalate are added to a reaction kettle, and esterification and polycondensation are carried out according to the steps and conditions of Example 2, and then the material is discharged.

[0166] The copolyester has an intrinsic viscosity [η] of 0.79 dL / g, a limiting oxygen index of 29.5%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 401 kW / m in the cone calorimetry test. 2 and TSR is 933m 2 / m 2 is.

[0167] Example 33

[0168] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 52.4g of methyl 4-(N-(4-(methoxycarbonyl)phenyl)sulfamoyl)benzoate, 40.2g of sodium isophthalic acid-5-sulfonate, 38.7g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 28.6g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 0.28g of titanium dioxide and 0.015g of zirconium dioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0169] The copolyester has an intrinsic viscosity [η] of 1.10 dL / g, a limiting oxygen index of 29.5%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 266 kW / m in the cone calorimetry test. 2 and TSR is 881m 2 / m 2 is.

[0170] Example 34

[0171] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 168.3g of methyl 2-cyano-4((4-methoxycarbonyl)phenyl)sulfonamido)benzoate, 81.6g of potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 0.2g of zinc acetate, and 0.3g of ethylene glycol antimony were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0172] The copolyester has an intrinsic viscosity [η] of 0.88 dL / g, a limiting oxygen index of 35.5%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 320 kW / m in the cone calorimetry test. 2 and TSR is 686m 2 / m 2 is.

[0173] Example 35

[0174] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 209.4g of methyl 4-(N-(4-(methoxycarbonyl)phenyl)sulfamoyl)benzoate, 24.5g of dimethyl 5-((diphenylphosphoryl)amino)isophthalate, 8.0g of sodium isophthalic acid-5-sulfonate, 180.6g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, and 0.26g of tetrabutyl titanate are added to a reaction kettle, and esterification and polycondensation are carried out according to the steps and conditions of Example 1, and then the materials are discharged.

[0175] The copolyester has an intrinsic viscosity [η] of 1.30 dL / g, a limiting oxygen index of 44.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 155 kW / m in the cone calorimetry test. 2 and TSR is 443m 2 / m 2 is.

[0176] Example 36

[0177] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 81.0g of 4,4'-azobenzenedicarboxylic acid, 64.5g of 2,8-(2-hydroxyethoxy)carbonylphenanthrene sodium hypophosphinate, and 0.3g of antimony acetate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0178] The copolyester has an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 30.0%, a vertical combustion level of V-2 level, and a p-HRR of 402 kW / m in a cone calorimetry test. 2 and TSR is 850m 2 / m 2 is.

[0179] Example 37

[0180] 498.0g isophthalic acid, 220.0g ethylene glycol, 81.0g 4,4'-azobenzenedicarboxylic acid, 32.6g potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 54.2g sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, 0.2g aluminum acetate and 0.25g titanium glycolate are added to a reaction kettle, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 1, and then the materials are discharged.

[0181] The copolyester has an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 33.8%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 220 kW / m in the cone calorimetry test. 2 and TSR is 617m 2 / m 2 is.

[0182] Example 38

[0183] Add 498.0g of terephthalic acid, 220.0g of ethylene glycol, 106.5g of N-(2-methyl-5-carbomethoxyphenyl)-4-carbomethoxybenzimide, 95.4g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3g of titanium acetylacetonate into a reaction kettle, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1, and then discharge the materials.

[0184] The copolyester has an intrinsic viscosity [η] of 0.66 dL / g, a limiting oxygen index of 33.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 322 kW / m in the cone calorimetry test. 2 and TSR is 885m 2 / m 2 is.

[0185] Example 39

[0186] 498.0g terephthalic acid, 220.0g ethylene glycol, 106.5g N-(2-methyl-5-carbomethoxyphenyl)-4-carbomethoxybenzimide, 80.4g sodium isophthalic acid-5-sulfonate, 0.28g antimony acetate are added to a reaction kettle, and esterification and polycondensation are carried out according to the steps and conditions of Example 1, and then the material is discharged.

[0187] The copolyester has an intrinsic viscosity [η] of 0.65 dL / g, a limiting oxygen index of 34.2%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 269 kW / m in the cone calorimetry test. 2 and TSR is 764m 2 / m 2 is.

[0188] Example 40

[0189] 498.0g of terephthalic acid, 270.0g of 1,3-propanediol, 182.3g of dimethyl 4,4'-((1,3-phenylene-5-cyano)dioxy)dibenzoate, 24.5g of dimethyl 5-((diphenylphosphoryl)amino)isophthalate, 47.7g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.2g of tetraisopropyl orthotitanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0190] The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 30.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 517 kW / m in the cone calorimetry test. 2 and TSR is 1295m 2 / m 2 is.

[0191] Example 41

[0192] 498.0g of isophthalic acid, 270.0g of 1,3-propanediol, 121.5g of dimethyl 4,4'-((1,3-phenylene-2-cyano)dioxy)dibenzoate, 95.4g of sodium 3,5-dihydroxybenzenesulfonate, 0.1g of antimony acetate, and 0.3g of aluminum oxide were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0193] The copolyester has an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 32.5%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 468 kW / m in the cone calorimetry test. 2 and TSR is 946m 2 / m 2 is.

[0194] Example 42

[0195] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 121.5g of dimethyl 4,4'-((1,3-phenylene-5-cyano)dioxy)dibenzoate, 47.7g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 180.6g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, and 0.3g of ethylene glycol antimony were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0196] The copolyester has an intrinsic viscosity [η] of 0.77 dL / g, a limiting oxygen index of 50.0%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 166 kW / m in the cone calorimetry test. 2 and TSR is 458m 2 / m 2 is.

[0197] Example 43

[0198] 498.0g of isophthalic acid, 220.0g of ethylene glycol, 152.1g of methyl 3-cyano-5((4-(methoxycarbonyl)phenyl)carbamoyl)benzoate, 47.7g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3g of potassium hexafluorotitanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0199] The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 34.6%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 270 kW / m in the cone calorimetry test. 2 and TSR is 701m 2 / m 2 is.

[0200] Example 44

[0201] 498.0g of terephthalic acid, 320.0g of 1,4-butanediol, 101.4g of methyl 3-cyano-5((4-(methoxycarbonyl)phenyl)carbamoyl)benzoate, 40.2g of sodium isophthalic acid-5-sulfonate, 0.2g of zinc acetate and 0.2g of tetraphenyl titanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0202] The copolyester has an intrinsic viscosity [η] of 0.99 dL / g, a limiting oxygen index of 28.0%, a vertical combustion level of V-2 level, and a p-HRR of 556 kW / m in a cone calorimetry test. 2 and TSR is 1252m 2 / m 2 is.

[0203] Example 45

[0204] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 46.8g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 64.5g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, and 0.3g of tetrabutyl titanate were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0205] The copolyester has an intrinsic viscosity [η] of 1.23 dL / g, a limiting oxygen index of 30.2%, a vertical flame resistance of V-2 level, and a p-HRR of 309 kW / m in a cone calorimetry test. 2 and TSR is 956m 2 / m 2 is.

[0206] Example 46

[0207] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 93.6g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 95.4g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 8.9g of potassium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, and 0.28g of titanium glycolate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0208] The copolyester has an intrinsic viscosity [η] of 1.04 dL / g, a limiting oxygen index of 35.2%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 253 kW / m in the cone calorimetry test. 2 and TSR is 858m 2 / m 2 is.

[0209] Example 47

[0210] 498.0g terephthalic acid, 220.0g ethylene glycol, 93.6g methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 40.2g sodium isophthalic acid-5-sulfonate, 0.2g zinc acetate and 0.3g ethylene glycol antimony were added to a reaction kettle, and esterification and polycondensation were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0211] The copolyester has an intrinsic viscosity [η] of 0.89 dL / g, a limiting oxygen index of 34.6%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 233 kW / m in the cone calorimetry test. 2 and TSR is 651m 2 / m 2 is.

[0212] Example 48

[0213] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 187.2g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 81.6g of potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 0.2g of manganese acetate, and 0.2g of potassium titanium oxalate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0214] The copolyester has an intrinsic viscosity [η] of 0.96 dL / g, a limiting oxygen index of 41.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 173 kW / m in the cone calorimetry test. 2 and TSR is 593m 2 / m 2 is.

[0215] Example 49

[0216] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 63.9g of 2,2'-(1,4-phenylene)bis(1H-benzimidazole-5-carboxylate methyl), 66.9g of 2,8-(2-hydroxyethoxy)carbonylphenanthrene potassium phosphinate, and 0.26g of orthotitanate tetraisopropyl were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, followed by discharging the materials.

[0217] The copolyester has an intrinsic viscosity [η] of 1.69 dL / g, a limiting oxygen index of 34.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 311 kW / m in the cone calorimetry test. 2 and TSR is 903m 2 / m 2 is.

[0218] Example 50

[0219] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 191.7 g of 2,2'-(1,4-phenylene)bis(1H-benzimidazole-5-carboxylate methyl), 52.5 g of potassium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3 g of titanium dioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0220] The copolyester has an intrinsic viscosity [η] of 1.04 dL / g, a limiting oxygen index of 40.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 199 kW / m in the cone calorimetry test. 2 and TSR is 620m 2 / m 2 is.

[0221] Example 51

[0222] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 261.9 g of 4-((4-cyanophenyl)ethynyl)phthalic acid, and 0.3 g of antimony trioxide were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0223] The copolyester has an intrinsic viscosity [η] of 1.22 dL / g, a limiting oxygen index of 34.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 292 kW / m in the cone calorimetry test. 2 and TSR is 1332m 2 / m 2 is.

[0224] Example 52

[0225] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 77.3 g of (E)-5-((4-cyanobenzylidene)amino)benzene-1,3-dimethyl isophthalate, and 0.28 g of antimony acetate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0226] The copolyester has an intrinsic viscosity [η] of 0.72 dL / g, a limiting oxygen index of 30.8%, a vertical flame resistance of V-0, no dripping in the test, and a p-HRR of 369 kW / m in the cone calorimetry test. 2 and TSR is 946m 2 / m 2 is.

[0227] Example 53

[0228] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 102.2 g of 2,2'-(1,4-phenylene)bis(1H-benzimidazole-5-carboxylate methyl), 59.9 g of 5-benzamido-1,3-isophthalic acid, and 0.3 g of tetrabutyl titanate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0229] The copolyester has an intrinsic viscosity [η] of 0.91 dL / g, a limiting oxygen index of 32.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 321 kW / m in the cone calorimetry test. 2 and TSR is 1257m 2 / m 2 is.

[0230] Example 54

[0231] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 76.6g of dimethyl 5-(3-cyanophenoxy)isophthalate, 65.9g of dimethyl 5-benzimidophenylacetylene-1,3-isophthalate, 0.2g of manganese acetate, and 0.2g of titanium glycolate were added to a reaction kettle, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2, and then the materials were discharged.

[0232] The copolyester has an intrinsic viscosity [η] of 0.68 dL / g, a limiting oxygen index of 31.0%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 312 kW / m in the cone calorimetry test. 2 and TSR is 1076m 2 / m 2 is.

[0233] Example 55

[0234] 582.0g of dimethyl terephthalate, 400.0g of ethylene glycol, 44.1g of dimethyl 5-(phenylethynyl)-1,3-isophthalate, 44.6g of dimethyl (E)-5-(benzylideneamino)benzene-1,3-isophthalate, 54.8g of dimethyl 5-(2,5-dioxy-3-phenyl-2,5-dihydro-1H-pyrrol-1-yl)isophthalate, 0.2g of magnesium acetate, 0.27g of titanium dioxide and 0.03g of silica are added to a reaction kettle, and esterification and polycondensation reactions are carried out according to the steps and conditions of Example 2, and then the materials are discharged.

[0235] The copolyester has an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 31.8%, a vertical flame resistance of V-0 level, no dripping in the test, and a p-HRR of 284 kW / m in the cone calorimetry test. 2 and TSR is 1105m 2 / m 2 is.

[0236] Comparative Example 1

[0237] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 0.2g of zinc acetate, and 0.3g of antimony trioxide were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting PET polyester had an intrinsic viscosity [η] of 0.80dL / g, a limiting oxygen index of 22.0%, no vertical combustion level, and a large amount of dripping during testing. In a cone calorimetry test, the p-HRR was 735kW / m. 2 and TSR is 1756m 2 / m 2 is.

[0238] Comparative Example 2

[0239] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 159.6 g of 4-(phenylethynyl)phthalic acid, 0.2 g of zinc acetate, and 0.3 g of antimony trioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.95 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, a small amount of dripping during testing, and a p-HRR of 471 kW / m in a cone calorimetry test. 2 and TSR is 1939m 2 / m 2 is.

[0240] Comparative Example 3

[0241] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 38.7 g of sodium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 0.2 g of zinc acetate, and 0.3 g of antimony trioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.84 dL / g, a limiting oxygen index of 25.5%, no vertical flame level, and significant dripping during testing. In a cone calorimetry test, the p-HRR was 392 kW / m. 2 and TSR is 1077m 2 / m 2 is.

[0242] Comparative Example 4 (Comparison with Example 2)

[0243] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 25.2 g of sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, 0.2 g of manganese acetate, and 0.25 g of germanium dioxide were added to a reaction vessel, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The material was then discharged. The copolyester had an intrinsic viscosity [η] of 0.60 dL / g, a limiting oxygen index of 24.0%, no vertical flame level, and a large amount of dripping during testing. In a cone calorimetry test, the peak heat release rate (p-HRR) was 655 kW / m. 2 The total smoke release rate (TSR) is 1634m 2 / m 2 is.

[0244] Comparative Example 5 (Comparison with Examples 3 and 13)

[0245] 388.0 g of dimethyl terephthalate, 194 g of dimethyl isophthalate, 400.0 g of ethylene glycol, and 0.28 g of isopropyl titanate were added to a reactor, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.64 dL / g, a limiting oxygen index of 21.0%, no vertical flame level, and a large amount of dripping in the test. In the cone calorimetry test, the p-HRR was 821 kW / m. 2 and TSR is 1850m 2 / m 2 is.

[0246] Comparative Example 6 (Comparison with Example 3)

[0247] 388.0 g of dimethyl terephthalate, 194 g of dimethyl isophthalate, 400.0 g of ethylene glycol, 79.8 g of 4-(phenylethynyl)phthalic acid, and 0.28 g of isopropyl titanate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 25.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 605 kW / m in the cone calorimetry test. 2 and TSR is 1764m 2 / m 2 is.

[0248] Comparative Example 7 (Comparison with Example 3)

[0249] 388.0 g of dimethyl terephthalate, 194 g of dimethyl isophthalate, 400.0 g of ethylene glycol, 52.5 g of potassium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 40.2 g of sodium isophthalic acid-5-sulfonate, and 0.28 g of isopropyl titanate were added to a reactor, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.82 dL / g, a limiting oxygen index of 27.5%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 484 kW / m in the cone calorimetry test. 2 and TSR is 1062m 2 / m 2 is.

[0250] Comparative Example 8 (Comparison with Examples 8 and 9)

[0251] Add 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 131.7 g of dimethyl 5-benzimidophenylacetylene-1,3-isophthalate, 0.2 g of magnesium acetate, and 0.2 g of titanium dioxide to a reactor, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1. After that, the material is discharged. The copolyester has an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 30.0%, a vertical flame level of V-2, drips in the test, and a p-HRR of 436 kW / m in the cone calorimetry test. 2 and TSR is 1240m 2 / m 2 is.

[0252] Comparative Example 9 (Comparison with Examples 8 and 22)

[0253] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 28.6 g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, 25.5 g of sodium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, 0.2 g of magnesium acetate, and 0.2 g of titanium dioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.74 dL / g, a limiting oxygen index of 26.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 488 kW / m in the cone calorimetry test. 2 and TSR is 1055m 2 / m 2 is.

[0254] Comparative Example 10 (Comparison with Example 9)

[0255] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 42.6 g of potassium isophthalic acid-5-sulfonate, and 0.3 g of ethylene glycol antimony were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.68 dL / g, a limiting oxygen index of 25.0%, a vertical flame level of V-2, and a large amount of dripping in the test. In a cone calorimetry test, the p-HRR was 560 kW / m. 2 and TSR is 1325m 2 / m 2 is.

[0256] Comparative Example 11 (Comparison with Example 13)

[0257] 388.0 g of dimethyl terephthalate, 194.0 g of dimethyl isophthalate, 400.0 g of ethylene glycol, 178.2 g of (E)-5-(benzylideneamino)benzene-1,3-dimethyl isophthalate, 0.2 g of aluminum acetate, and 0.25 g of titanium citrate were added to a reactor, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.74 dL / g, a limiting oxygen index of 31.0%, a vertical flame level of V-0, no dripping in the test, and a p-HRR of 458 kW / m in the cone calorimetry test. 2 and TSR is 1221m 2 / m 2 is.

[0258] Comparative Example 12 (Comparison with Examples 13, 34, and 48)

[0259] 388.0 g of dimethyl terephthalate, 194.0 g of dimethyl isophthalate, 400.0 g of ethylene glycol, 81.6 g of potassium 3,5-di(6-(methoxycarbonyl)-1H-benzimidazol-2-yl)benzenesulfonate, 0.2 g of aluminum acetate, and 0.25 g of titanium citrate were added to a reaction vessel, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.78 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 505 kW / m in the cone calorimetry test. 2 and TSR is 1174m 2 / m 2 is.

[0260] Comparative Example 13 (Comparison with Example 15)

[0261] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 88.6 g of (1-(3,5-bis(2-hydroxyethoxy)phenyl)-3-phenyl-1H-pyrrole-2,5-dione, and 0.3 g of potassium titanium oxalate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The material was then discharged. The copolyester had an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 28.5%, a vertical flame level of V-2, and dripping in the test. The p-HRR in the cone calorimetry test was 480 kW / m. 2 and TSR is 1335m 2 / m 2 is.

[0262] Comparative Example 14 (Comparison with Example 15)

[0263] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 19.1 g of sodium (3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3 g of potassium titanium oxalate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.75 dL / g, a limiting oxygen index of 24.0%, no vertical flame level, and a large amount of dripping in the test. In the cone calorimetry test, the p-HRR was 652 kW / m. 2 and TSR is 1486m 2 / m 2 is.

[0264] Comparative Example 15 (Comparison with Example 18)

[0265] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 171.0 g of 5-benzamido-1,3-isophthalic acid, and 0.3 g of ethylene glycol antimony were added to a reactor, and transesterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.95 dL / g, a limiting oxygen index of 31.0%, a vertical flame rating of V-0, no dripping in the test, and a p-HRR of 350 kW / m in the cone calorimetry test. 2 and TSR is 986m 2 / m 2 is.

[0266] Comparative Example 16 (Comparison with Examples 18 and 50)

[0267] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 52.5 g of potassium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, and 0.3 g of ethylene glycol antimony were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.86 dL / g, a limiting oxygen index of 26.0%, a vertical flame level of V-2, and a large amount of dripping in the test. In a cone calorimetry test, the p-HRR was 587 kW / m. 2 and TSR is 1256m 2 / m 2 is.

[0268] Comparative Example 17 (Comparison with Example 19)

[0269] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 85.5 g of 5-benzamido-1,3-isophthalic acid, and 0.24 g of tetrabutyl titanate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.85 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 456 kW / m in the cone calorimetry test. 2 and TSR is 1258m 2 / m 2 is.

[0270] Comparative Example 18 (Comparison with Example 19)

[0271] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 24.1 g of sodium isophthalic acid-5-sulfonate, and 0.24 g of tetrabutyl titanate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.88 dL / g, a limiting oxygen index of 24.0%, no vertical flame level, and significant dripping during testing. In a cone calorimetry test, the p-HRR was 605 kW / m. 2 and TSR is 1359m 2 / m 2 is.

[0272] Comparative Example 19 (Comparison with Example 19)

[0273] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 120.6 g of sodium isophthalic acid-5-sulfonate, and 0.24 g of tetrabutyl titanate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 27.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 476 kW / m in the cone calorimetry test. 2 and TSR is 1095m 2 / m 2 is.

[0274] Comparative Example 20 (Comparison with Examples 19, 20, and 21)

[0275] 468.0 g of terephthalic acid, 30.0 g of isophthalic acid, 220.0 g of ethylene glycol, 142.7 g of N-(3,5-bis(2-hydroxyethoxy)phenyl)benzamide, 0.15 g of magnesium acetate, and 0.35 g of aluminum hydroxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.92 dL / g, a limiting oxygen index of 29.5%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 388 kW / m in the cone calorimetry test. 2 and TSR is 1065m 2 / m 2 is.

[0276] Comparative Example 21 (Comparison with Examples 21 and 24)

[0277] Add 468.0 g of terephthalic acid, 30.0 g of isophthalic acid, 220.0 g of ethylene glycol, 90.3 g of sodium 2,8-di(5-methoxycarbonyl-1H-benzimidazol-2-yl)anthraxaphosphinate, 0.15 g of magnesium acetate, and 0.35 g of aluminum hydroxide to a reactor, and carry out esterification and polycondensation reactions according to the steps and conditions of Example 1. After discharging the material, the copolyester has an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, drips in the test, and a p-HRR of 480 kW / m in the cone calorimetry test. 2 and TSR is 1153m 2 / m 2 is.

[0278] Comparative Example 22 (Comparison with Example 22)

[0279] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 34.4 g of 3,5-dihydroxy-N-phenylbenzamide, 28.0 g of dimethyl 5-(3-cyanophenoxy)isophthalate, and 0.3 g of titanium dioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.72 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 536 kW / m in the cone calorimetry test. 2 and TSR is 1159m 2 / m 2 is.

[0280] Comparative Example 23 (Comparison with Example 24)

[0281] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 51.3 g of N-(3-cyanophenyl)-3,5-bis(2-hydroxyethoxy)benzamide, 10.2 g of dimethyl 5-benzimido-1,3-isophthalate, 0.2 g of manganese acetate, and 0.2 g of tetraisopropyl orthotitanate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 26.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 492 kW / m in the cone calorimetry test. 2 and TSR is 1204m 2 / m 2 is.

[0282] Comparative Example 24 (Comparison with Examples 28 and 30)

[0283] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 48.2 g of 5-(benzenesulfonyl)isophthalic acid, and 0.3 g of tetrabutyl titanate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 27.5%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 510 kW / m in the cone calorimetry test. 2 and TSR is 1126m 2 / m 2 is.

[0284] Comparative Example 25 (Comparison with Example 28)

[0285] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 40.1 g of potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, 0.2 g of cobalt acetate, and 0.25 g of titanium tartrate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.63 dL / g, a limiting oxygen index of 24.0%, no vertical flame level, and a large amount of dripping in the test. In the cone calorimetry test, the p-HRR was 651 kW / m. 2 and TSR is 1247m 2 / m 2 is.

[0286] Comparative Example 26 (Comparison with Examples 30, 32, and 39)

[0287] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 80.4 g of sodium isophthalic acid-5-sulfonate, and 0.3 g of tetrabutyl titanate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.85 dL / g, a limiting oxygen index of 26.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 525 kW / m in the cone calorimetry test. 2 and TSR is 1237m 2 / m 2 is.

[0288] Comparative Example 27 (Comparison with Example 31)

[0289] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 314.1 g of dimethyl 5-(N-phenylsulfamoyl)isophthalate, 0.2 g of antimony acetate, and 0.1 g of titanium dioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.76 dL / g, a limiting oxygen index of 34.0%, a vertical flame level of V-0, no dripping in the test, and a p-HRR of 805 kW / m in the cone calorimetry test. 2 and TSR is 956m 2 / m 2 is.

[0290] Comparative Example 28 (Comparison with Examples 31 and 38)

[0291] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 95.4 g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, 0.2 g of antimony acetate, and 0.1 g of titanium dioxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.77 dL / g, a limiting oxygen index of 27.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 963 kW / m in the cone calorimetry test. 2 and TSR is 1022m 2 / m 2 is.

[0292] Comparative Example 29 (Comparison with Example 32)

[0293] 582.0 g of dimethyl terephthalate, 400.0 g of ethylene glycol, 101.7 g of dimethyl 5-benzimido-1,3-isophthalate, 0.2 g of manganese acetate, and 0.3 g of potassium titanium oxalate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 2. The resulting copolyester had an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 25.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 956 kW / m in the cone calorimetry test. 2 and TSR is 1350m 2 / m 2 is.

[0294] Comparative Example 30 (Comparison with Example 34)

[0295] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 168.3 g of methyl 2-cyano-4((4-methoxycarbonyl)phenyl)sulfonamido)benzoate, 0.2 g of zinc acetate, and 0.3 g of ethylene glycol antimony were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.74 dL / g, a limiting oxygen index of 30.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 743 kW / m in the cone calorimetry test. 2 and TSR is 967m 2 / m 2 is.

[0296] Comparative Example 31 (Comparison with Examples 38 and 39)

[0297] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 106.5 g of N-(2-methyl-5-carbomethoxyphenyl)-4-carbomethoxybenzimide, and 0.3 g of titanium acetylacetonate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.65 dL / g, a limiting oxygen index of 27.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 565 kW / m in the cone calorimetry test. 2 and TSR is 1239m 2 / m 2 is.

[0298] Comparative Example 32 (Comparison with Example 41)

[0299] 498.0 g of isophthalic acid, 270.0 g of 1,3-propanediol, 0.1 g of antimony acetate, and 0.3 g of aluminum oxide were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 19.0%, no vertical combustion level, and a large amount of dripping in the test. In the cone calorimetry test, the p-HRR was 1093 kW / m. 2 and TSR is 2056m 2 / m 2 is.

[0300] Comparative Example 33 (Comparison with Example 41)

[0301] 498.0 g of isophthalic acid, 270.0 g of 1,3-propanediol, 121.5 g of dimethyl 4,4'-((1,3-phenylene-2-cyano)dioxy)dibenzoate, 0.1 g of antimony acetate, and 0.3 g of aluminum oxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 28.5%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 650 kW / m in the cone calorimetry test. 2 and TSR is 1422m 2 / m 2 is.

[0302] Comparative Example 34 (Comparison with Example 41)

[0303] 498.0 g of isophthalic acid, 270.0 g of 1,3-propanediol, 95.4 g of sodium 3,5-dihydroxybenzenesulfonate, 0.1 g of antimony acetate, and 0.3 g of aluminum oxide were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.79 dL / g, a limiting oxygen index of 26.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 741 kW / m in the cone calorimetry test. 2 and TSR is 1255m 2 / m 2 is.

[0304] Comparative Example 35 (Comparison with Examples 46 and 47)

[0305] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 93.6 g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, and 0.28 g of titanium glycolate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.84 dL / g, a limiting oxygen index of 28.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 502 kW / m in the cone calorimetry test. 2 and TSR is 1231m 2 / m 2 is.

[0306] Comparative Example 36 (Comparison with Example 46)

[0307] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 95.4 g of sodium 3,5-bis(methoxycarbonyl)phenyl)phosphonate, 8.9 g of potassium (3-(2-hydroxyethoxy)-3-oxopropyl)(phenyl)phosphinate, and 0.28 g of titanium glycolate were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.75 dL / g, a limiting oxygen index of 26.5%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 540 kW / m in the cone calorimetry test. 2 and TSR is 1147m 2 / m 2 is.

[0308] Comparative Example 37 (Comparison with Example 47)

[0309] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 40.2 g of sodium isophthalic acid-5-sulfonate, 0.2 g of zinc acetate, and 0.3 g of ethylene glycol antimony were added to a reactor, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.80 dL / g, a limiting oxygen index of 25.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 608 kW / m in the cone calorimetry test. 2 and TSR is 1423m 2 / m 2 is.

[0310] Comparative Example 38 (Comparison with Example 48)

[0311] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 187.2 g of methyl 2-(4-(methoxycarbonyl)phenyl)-1H-benzimidazole-5-carboxylate, 0.2 g of manganese acetate, and 0.2 g of potassium titanium oxalate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.81 dL / g, a limiting oxygen index of 33.0%, a vertical flame level of V-0, no dripping in the test, and a p-HRR of 386 kW / m in the cone calorimetry test. 2 and TSR is 977m 2 / m 2 is.

[0312] Comparative Example 39 (Comparison with Example 49)

[0313] 498.0 g of terephthalic acid, 220.0 g of ethylene glycol, 63.9 g of 2,2'-(1,4-phenylene)bis(methyl 1H-benzimidazole-5-carboxylate), and 0.26 g of tetraisopropyl orthotitanate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1. The resulting copolyester had an intrinsic viscosity [η] of 0.84 dL / g, a limiting oxygen index of 27.0%, a vertical flame level of V-2, dripping in the test, and a p-HRR of 598 kW / m in the cone calorimetry test. 2 and TSR is 1425m 2 / m 2 is.

[0314] Comparative Example 40 (Comparison with Example 49)

[0315] 498.0g of terephthalic acid, 220.0g of ethylene glycol, 66.9g of potassium 2,8-(2-hydroxyethoxy)carbonylphenanthrenephosphinate, and 0.26g of tetraisopropyl orthotitanate were added to a reaction vessel, and esterification and polycondensation reactions were carried out according to the steps and conditions of Example 1, and then the materials were discharged.

[0316] The copolyester has an intrinsic viscosity [η] of 0.70 dL / g, a limiting oxygen index of 25.0%, a vertical flame resistance of V-2 level, dripping in the test, and a p-HRR of 624 kW / m in the cone calorimetry test. 2 and TSR is 1244m 2 / m 2 is.

[0317] 1 to 5 further exemplarily illustrate the fourth embodiment of the present invention.

[0318] Figure 1 shows the dynamic rheology of the copolyester prepared in Example 4 of the present invention and the pure PET prepared in Comparative Example 1. For thermoplastic polymers, the higher the complex viscosity at high temperatures, the higher the melt viscosity and melt strength during combustion, which in turn indicates a stronger anti-drip capability. For pure PET, the complex viscosity gradually decreases with increasing temperature, demonstrating shear-thinning rheological behavior. For the copolyester, the complex viscosity decreases and then increases with increasing temperature, demonstrating a "U"-shaped change curve, indicating that the copolyester undergoes a self-crosslinking reaction at high temperatures. This self-crosslinking reaction effectively improves the melt viscosity and strength of the copolyester during combustion, thereby providing anti-drip properties.

[0319] 2 shows the thermogravimetric curves of the copolyester containing phenylacetylene self-crosslinking functional groups and sodium phosphinate ion groups prepared in Example 4 of the present invention, pure PET prepared in Comparative Example 1, the copolyester containing only phenylacetylene self-crosslinking functional groups prepared in Comparative Example 2, and the copolyester containing only sodium phosphinate ion groups prepared in Comparative Example 3. As can be seen from FIG. 2, in a nitrogen atmosphere, the copolyester of Example 4 of the present invention not only maintains high thermal stability, but also has a much higher residual carbon content (26.6 wt%) at a high temperature (700°C) than pure PET (11.8 wt%), Comparative Example 2 (14.9 wt%), and Comparative Example 3 (17.5 wt%). The carbon residues of Example 4, Comparative Example 2, and Comparative Example 3 were increased by 14.8 wt%, 3.1 wt%, and 5.7 wt%, respectively, compared to that of pure PET. However, the increase in carbon residues of Example 4 was greater than the sum of the increases in carbon residues of Comparative Examples 2 and 3. This indicates that the high-temperature self-crosslinking functional groups and ionic groups have a synergistic flame-retardant effect, further improving the carbon-forming ability of the copolyester prepared in this invention.

[0320] Figure 3 shows digital photographs of the vertical flame test of the copolyester prepared in Example 4 of the present invention and the pure PET prepared in Comparative Example 1. As can be seen from the photographs, the PET did not self-extinguish after ignition, producing a large amount of dripping and earning a test grade of "None." The copolyester prepared in the present invention quickly self-extinguished within 10 seconds after ignition, producing no dripping and earning a test grade of "V-0." Meanwhile, Comparative Example 2 only achieved a V-2 grade, and Comparative Example 3 earned a grade of "None" and still produced dripping during the test. This demonstrates that the copolyester prepared in the present invention has superior flame retardancy and drip resistance compared to copolyesters containing only high-temperature self-crosslinking functional groups or copolyesters containing only ionic groups.

[0321] Figure 4 is a curve showing the heat release rate of a cone calorimetry test for the copolyester prepared in Example 4 of the present invention and the pure PET, copolyester containing only high-temperature self-crosslinking functional groups, and copolyester containing only ionic groups prepared in Comparative Examples 1 to 3. The peak heat release rate (p-HRR) is an important parameter for evaluating the flame retardant properties of a material; the lower the value, the higher the flame retardancy of the material. As can be seen from the comparison of the curves in this figure, the p-HRR of Example 4 of the present invention is 298 kW / m 2 This is a 59.5% decrease compared to pure PET, and is 471 kW / m in Comparative Example 2. 2 and 392 kW / m in Comparative Example 3 2 This explains why the copolyester prepared in this invention exhibits better flame retardancy.

[0322] 5 is a curve diagram showing the total smoke release (TSR) in a cone calorimetry test for the copolyester prepared in Example 4 of the present invention and the pure PET, copolyester containing only high-temperature self-crosslinking functional groups, or copolyester containing only ionic groups prepared in Comparative Examples 1 to 3. As can be seen from the comparison of the curves in this figure, the copolyester of the present invention has a TSR of 728 m 2 / m 2 This is a 58.5% decrease compared to pure PET, and is also 1939m in Comparative Example 2. 2 / m 2 and 1077 m of Comparative Example 3 2 / m 2 It is much lower and exhibits better smoke suppression performance.

[0323] In the description herein, a description that refers to the term "one embodiment," "one example," or the like means that the specific feature, structure, material, or characteristic described with reference to that embodiment / example is included in at least one embodiment / example of the present disclosure. In the description, exemplary expressions of the above terms do not necessarily refer to the same embodiment / example. Where there is no conflict, the specific feature, structure, material, or characteristic described may be combined in any suitable manner in any one or more embodiments / examples.

[0324] The above description is merely a specific embodiment of the present disclosure, and the scope of protection of the present disclosure is not limited thereto. Any changes or substitutions that a person skilled in the art can easily make within the technical scope disclosed in the present disclosure should be included in the scope of protection of the present disclosure. Therefore, the scope of protection of the present disclosure should be based on the scope of protection of the claims.

Claims

1. Contains structural units represented by the following [I], [II], [III] and [IV]: Structural unit [I] 【Chemistry 1】 (In the formula, R １ represents an arylene group) Structural unit [II] 【Chemistry 2】 (In the formula, R ２ represents an alkylene group) The structural unit [III] has a structure selected from formulas [A] to [R], 【Transformation 3】 (In formulas [A] to [R], R ３ , R ４ is a carbonyl group, an O atom or 【Chemistry 4】 a is an integer from 2 to 12, and R ３ , R ４ are the same or different, and X １ , X ２ is any one of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, and X １ , X ２ are the same or different, and Y １ is an O atom or a S atom) The structural unit [IV] is represented by the formula [A １ ]~[F １ and 【Transformation 5】 (Formula [A １ ]~[F １ ] Medium, R ５ , R ６ is a carbonyl group, an O atom or 【Transformation 6】 a is an integer from 2 to 12, and R ５ , R ６ are the same or different, and R ７ is C １ ~C １２ is an alkyl group, an aryl group, or a benzyl group of the formula R ８ is C １ ~C ８ is an alkylene or arylene group represented by the formula: ２ is an O atom or a S atom, and Y ３ is an O atom, an S atom, a secondary amino group (HN<), a nitrogen methyl group (CH ３ N<) or nitrogen ethyl group (C ２ H ５ N<), where M is a cation having n positive charges derived from any of the metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, or Zn, provided that n satisfies the chemical valence of the metal atom and n is an integer from 1 to 3. A copolyester in which the number of structural units of [III] is 2 to 60% of the number of structural units of [I], and the number of structural units of [IV] is 0.1 to 60% of the number of structural units of [I].

2. 2. The copolyester according to claim 1, wherein the intrinsic viscosity [η] is 0.20 to 3.50 dL / g, the limiting oxygen index is 23.0 to 60.0%, and the vertical burning level is V-2 to V-0.

3. 2. The copolyester according to claim 1, wherein the intrinsic viscosity [η] is 0.30 to 3.20 dL / g, the limiting oxygen index is 24.0 to 55.0%, and the vertical burning level is V-2 to V-0.

4. 10. A method for preparing the copolyester according to claim 1, comprising esterifying polyester monomers of a dibasic acid / dibasic acid ester and a dihydric alcohol, and a catalyst, based on the blending ratio, by a direct esterification method or an ester exchange method, and then subjecting the resulting polyester monomers to a polycondensation reaction, the method comprising the steps of: A preparation method in which 2 to 60% of a monomer from which the structural unit [III] is derived and 0.1 to 60% of a monomer from which the structural unit [IV] is derived are added relative to the number of moles of a dibasic acid or a dibasic acid ester of a polyester monomer.

5. The method for preparing the copolyester according to claim 4, wherein the monomer used to derive the structural unit [III] is at least one of the structures represented by the following general formula: 【Transformation 7】 (In the formula, Z １ , Z ２ is a carboxyl group, an ester group, a hydroxyl group or 【Transformation 8】 a is an integer from 2 to 12; Z １ , Z ２ are the same or different, and X １ , X ２ is any one of an H atom, a hydroxy group, a methyl group, an ethyl group, a cyano group, a methoxy group, a phenylethynyl group, and a phenyl group, and X １ , X ２ are the same or different, and Y １ is an O atom or a S atom)

6. 5. The method for preparing the copolyester according to claim 4, wherein the monomer used to derive the structural unit [IV] is at least one of the structures of the following general formula: 【Chemistry 9】 (In the formula, Z １ , Z ２ is a carboxyl group, an ester group, a hydroxyl group or 【Chemistry 10】 a is an integer from 2 to 12; Z １ , Z ２ are the same or different, and Z ３ is C ２ ~C ８ is an alkylene group of the formula R ７ is C １ ~C １２ is an alkyl group, an aryl group, or a benzyl group of the formula R ８ is C １ ~C ８ is an alkylene or arylene group represented by the formula: ２ is an O atom or a S atom, and Y ３ is any one of an O atom, an S atom, a secondary amino group, a nitrogen methyl group, and a nitrogen ethyl group, and M is a cation having n positive charges derived from any one of metal atoms Li, Na, K, Mg, Ca, Mn, Co, Ni, Ba, Fe, Cs, and Zn, provided that n satisfies the chemical valence of the metal atom and is an integer of 1 to 3.

7. 6. The method for preparing a copolyester according to claim 5, wherein the ester group of the monomer from which the structural unit [III] is derived is any one of a methyl ester group or an ethyl ester group obtained by esterifying a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentylene glycol ester group, a glycerol ester group, and a pentaerythritol ester group obtained by esterifying a polyhydric alcohol.

8. 7. The method for preparing a copolyester according to claim 6, wherein the ester group of the monomer from which the structural unit [IV] is derived is any one of a methyl ester group or an ethyl ester group obtained by esterifying a monohydric alcohol, or an ethylene glycol ester group, a propylene glycol ester group, a butanediol ester group, a pentylene glycol ester group, a glycerol ester group, and a pentaerythritol ester group obtained by esterifying a polyhydric alcohol.

9. 2. The application of the copolyester according to claim 1, which is a standalone application in the field of fibers, nonwoven fabrics, engineering plastics, membrane materials, container materials, self-repairing materials, shape memory materials or 3D printer materials, or is used as a functional additive for modifying polymeric materials.

Images