A polyester composition and use thereof

Abstract

The application provides a polyester composition and application thereof, which comprises the following components in parts by mass: polyester resin 40-99.5 parts, flame retardant 5-35 parts; the flame retardant comprises the following components in parts by mass: diethyl phosphinate 30-90 parts, ethyl phosphinate 0.01-3 parts, dialkyl phosphinate 5-67 parts, alkyl phosphinate 0.01-5.5 parts. The application introduces specific flame retardants, so that the flame retardants have excellent and efficient flame retardant effect, the polyester composition has excellent flame retardant performance, high flexibility, good toughness and bending performance, and excellent mechanical performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a polyester composition and its application. Background Technology

[0002] Polybutylene terephthalate (PBT) is a crystalline thermoplastic resin with a melting point of 225-235℃ and a heat distortion temperature exceeding 180℃. It can be used for extended periods below 140℃ and possesses excellent mechanical, electrical, heat, and chemical resistance properties. Polyethylene terephthalate (PET) is also crystalline and exhibits excellent performance in weather resistance, creep resistance, fatigue resistance, and abrasion resistance. It is also the toughest thermoplastic material.

[0003] Both PBT and PET possess excellent mechanical and processing properties, making them widely used in automobiles, connectors, and electrical appliance housings, and thus highly regarded polyester materials. Since the applications of PBT and PET are primarily concentrated in products with fire safety requirements, such as electrical appliances, automobiles, and home appliances, flame-retardant modification is particularly important. For example, CN102952381A discloses a glass fiber reinforced PBT / PET alloy material, comprising the following components: 22.5%-41% PBT, 22.5%-41% PET, 6%-20% compound flame retardant, 3%-15% antimony trioxide, 20%-30% glass fiber, 2%-10% toughening agent, 0.1%-1% antioxidant, and 0.1%-1% oxide; wherein the compound flame retardant is composed of brominated polystyrene, magnesium hypophosphite, and talc, which together with antimony trioxide form a flame retardant system, giving the material good flame retardancy; however, the flame retardant efficiency of brominated polystyrene is relatively low, and the compound flame retardant and antimony trioxide need to be added at a large amount to achieve the ideal flame retardant effect, while a high amount of flame retardant will seriously affect the mechanical properties of the material. Furthermore, although brominated polystyrene is an environmentally friendly flame retardant, it still contains halogens, which does not meet the requirements for use in high-environmental-standard halogen-free products.

[0004] Dialkyl phosphonates, as general-purpose halogen-free flame retardants, exhibit good flame retardant properties, low smoke emission during combustion, and minimal impact on the physical and electrical properties of the matrix polymer. This allows materials containing them to meet the application requirements of industries such as electrical appliances and energy storage. However, the flame retardant efficiency of dialkyl phosphonates is relatively low when used alone, and they usually need to be compounded with other flame retardants. For example, CN112724618A discloses a halogen-free flame-retardant reinforced PBT material with the following composition: 45%-55% PBT, 0.1%-0.5% coupling agent, 2%-5% composite toughening agent, 15%-25% composite flame retardant, 0.3%-1.5% antioxidant, and 0.1%-0.6% lubricant. The composite flame retardant consists of a halogen-free flame retardant and a synergistic flame retardant. The halogen-free flame retardant is aluminum diethylphosphonate and melamine polyphosphate, and the synergistic flame retardant is zinc borate. The combination of these three components achieves good flame retardant performance.

[0005] Although the combination of dialkylphosphines with melamine phosphates and melamine cyanurate can improve flame retardant properties, the ideal flame retardant effect can only be achieved when the addition amount in the polymer system is relatively large. Excessive addition of flame retardants can lead to a decrease in the toughness, flexibility, and other mechanical properties of polyester materials. Therefore, developing a polyester material with good flame retardant properties and excellent mechanical properties such as flexibility is an urgent problem to be solved in this field. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a polyester composition and its application, wherein the flame retardant can exert a highly efficient flame retardant effect, so that the polyester composition containing it has excellent flame retardant properties, high flexibility, good toughness and bending properties, and excellent mechanical properties.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a polyester composition comprising, by weight, the following components:

[0009] 40-99.5 parts of polyester resin

[0010] 5-35 parts flame retardant.

[0011] Based on a total mass of 100 parts, the flame retardant comprises the following components in parts by mass:

[0012]

[0013] The dialkylphosphinate has the structure shown in Formula I, and the alkylphosphinate has the structure shown in Formula II:

[0014]

[0015] R1, R2, and R3 are each independently selected from any one of substituted or unsubstituted C2-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, or substituted or unsubstituted C6-C18 aryl groups.

[0016] The total number of carbon atoms in R1 and R2 is ≥6.

[0017] The substituents in R1, R2, and R3 are each independently selected from at least one of C1-C8 straight-chain or branched alkyl groups and C6-C18 aryl groups.

[0018] M1 and M2 are each independently a cationic moiety; specifically, M1 m+ M2 represents an ion with a +m valence. n+ This represents an ion with a +n valence.

[0019] m and n are each independently selected from integers between 2 and 4, for example, they can be 2, 3 or 4.

[0020] This invention, through the design of four specific phosphonates and their compounding in specific amounts, synergistically enhances the flame retardant effect, endowing the flame retardant with excellent and efficient flame retardancy. When used in polyester flame retardancy, the polyester composition exhibits excellent flame retardant properties while also possessing high flexibility, good toughness and bending performance, demonstrating superior mechanical properties.

[0021] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0022] In the polyester composition of the present invention, the polyester resin is in the range of 40-99.5 parts by weight, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 98 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0023] The flame retardant is in the range of 5-35 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or 34 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0024] Based on a total mass of 100 parts of the flame retardant, the mass of diethylphosphonate is 30-90 parts, for example, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0025] Based on a total mass of 100 parts of the flame retardant, the mass of ethyl phosphonate is 0.01-3 parts, for example, 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, or 2.8 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0026] Based on a total mass of 100 parts of the flame retardant, the mass of the dialkylphosphinate is 5-67 parts, for example, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0027] Based on a total mass of 100 parts of the flame retardant, the mass of the hydrocarbon phosphonate is 0.01-5.5 parts, for example, 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, or 5.4 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0028] In this invention, the polyester resin comprises a condensation product of a dicarboxylic acid and / or its derivatives with a diol; wherein the dicarboxylic acid comprises any one or a combination of at least two of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids, preferably aromatic dicarboxylic acids. The diol comprises aliphatic diols and / or alicyclic diols.

[0029] Preferably, the dicarboxylic acid includes any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic acid, naphthalic acid, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, and hydrogenated phthalic acid; more preferably, any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic acid, and naphthalic acid.

[0030] The dicarboxylic acid derivatives include acyl halides (e.g., acyl chlorides), esters, acid anhydrides, etc., formed from dicarboxylic acids.

[0031] Preferably, the diol includes any one or a combination of at least two of ethylene glycol, propylene glycol, butanediol, hexanediol, and 1,4-cyclohexanediethanol.

[0032] Preferably, the polyester resin comprises any one or a combination of at least two of polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), poly(1,4-cyclohexanedimethyl terephthalate) (PCT), polyethylene 2,6-naphthalenedicarboxylate (PEN), and polybutylene 2,6-naphthalenedicarboxylate (PBN), and more preferably polyethylene terephthalate and / or polybutylene terephthalate.

[0033] Preferably, the intrinsic viscosity of the polyester resin is 0.5-1.2 dL / g, for example, it can be 0.6 dL / g, 0.7 dL / g, 0.8 dL / g, 0.9 dL / g, 1 dL / g, 1.1 dL / g or 1.2 dL / g, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0034] For example, the intrinsic viscosity of the polyester resin can be obtained by the method in standard ISO 1628-5:2015, tested at 25°C.

[0035] Preferably, the diethylphosphonate has the structure shown in Formula III, and the ethylphosphonate has the structure shown in Formula IV:

[0036]

[0037] In Formula III, M3 a+ The +a valence ion is represented, where a is an integer selected from 2 to 4, for example, it can be 2, 3 or 4. M3 is the cationic portion of diethylphosphonic acid salt, which can be a metal or a non-metal (e.g., amine cations, cations corresponding to melamine and its derivatives), preferably a metal; the M3 is further preferably any one of Al, Ca, Mg, Cu, Zn, Fe, Ti, more preferably Al.

[0038] In Equation IV, M4 b+ The +b valence ion is represented, where b is selected from an integer between 2 and 4, for example, it can be 2, 3, or 4. M4 is the cationic portion of ethylphosphonate, which can be a metal or a nonmetal (e.g., amine cations, cations corresponding to melamine and its derivatives), preferably a metal; the M4 is further preferably any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, more preferably Al.

[0039] In this invention, the dialkylphosphinate has the structure shown in Formula I, and the alkylphosphinate has the structure shown in Formula II.

[0040] In this invention, the C2-C8 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C2, C3, C4, C5, C6, C7, and C8, and exemplary include, but are not limited to: ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, neohexyl, 2-methylhexyl, 2-ethylhexyl, heptyl, octyl, etc.

[0041] In this invention, the C3-C8 cycloalkyl groups can all be C3, C4, C5, C6, C7, or C8 cycloalkyl groups, including monocycloalkyl, bridged cycloalkyl, and polycycloalkyl groups, and exemplary but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0042] In this invention, the C6-C18 aryl groups can all be aryl groups of C6, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, etc., including monocyclic aryl and fused-ring aryl groups, and exemplary of including but not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, indene, fluorene, etc.

[0043] In this invention, the C1-C8 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C1, C2, C3, C4, C5, C6, C7, and C8, and exemplary include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, 2-methylpentyl, 2-ethylpentyl, n-hexyl, neohexyl, 2-methylhexyl, 2-ethylhexyl, heptyl, octyl, etc.

[0044] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), they can be the same or different substituents; the same expression used below has the same meaning. Unless otherwise specified, the selection range of substituents is at least one of C1-C8 straight-chain or branched alkyl groups and C6-C18 aryl groups, which will not be elaborated further.

[0045] Preferably, R1 and R2 are each independently selected from any one of substituted or unsubstituted C2-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted phenyl groups.

[0046] Preferably, the substituents in R1 and R2 are each independently selected from at least one of C1-C6 straight-chain or branched alkyl groups and phenyl groups.

[0047] Preferably, R1 and R2 are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl.

[0048] In Formula I, the total number of carbon atoms in R1 and R2 is ≥6, for example, it can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., preferably the total number of carbon atoms in R1 and R2 is 6-14, and more preferably 8-12.

[0049] Preferably, the dialkylphosphonate comprises a combination of dialkylphosphonate A with the structure shown in Formula IA and ethylbutylphosphonate with the structure shown in Formula IB;

[0050]

[0051] Where M1 and m have the same definitions as in Equation I.

[0052] In Formula IA, R1' and R2' are each independently selected from any one of the following: substituted or unsubstituted C2-C8 (e.g., C3, C4, C5, C6, C7, etc.) straight-chain or branched alkyl groups; substituted or unsubstituted C3-C8 (e.g., C4, C5, C6, C7, etc.) cycloalkyl groups; and substituted or unsubstituted C6-C18 (e.g., C6, C9, C10, C12, C14, C15, C16, C17, C18, etc.) aryl groups.

[0053] In Formula IA, the total number of carbon atoms in R1' and R2' is ≥6, and if one of R1' and R2' is ethyl, the other is not butyl.

[0054] The substituents described in R1' and R2' are each independently selected from at least one of C1-C8 (e.g., C2, C3, C4, C5, C6, C7, etc.) straight-chain or branched alkyl groups and C6-C18 (e.g., C6, C9, C10, C12, C14, C15, C16, C17, C18, etc.) aryl groups.

[0055] Preferably, in formula IA, R1' and R2' are each independently selected from any one of substituted or unsubstituted C2-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, and substituted or unsubstituted phenyl groups.

[0056] Preferably, the substituents in R1' and R2' are each independently selected from at least one of C1-C6 straight-chain or branched alkyl groups and phenyl groups.

[0057] More preferably, R1' and R2' are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl. More preferably, they are selected from any one of n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, cyclohexyl, methylcyclohexyl, and phenyl.

[0058] Preferably, in formula IA, the total number of carbon atoms in R1' and R2' is ≥6, for example, it can be 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc. More preferably, the total number of carbon atoms in R1' and R2' is 6-14, more preferably 8-12.

[0059] Preferably, the dialkylphosphine A includes ethylpentylphosphine, ethylhexylphosphine, hexyloctylphosphine, ethylcyclohexylphosphine, ethylphenylphosphine, ethylphenethylphosphine, ethylheptylphosphine, dipropylphosphine, propylbutylphosphine, propylpentylphosphine, propylhexylphosphine, hexyloctylphosphine, propylcyclohexylphosphine, propylphenylphosphine, propylphenylpropylphosphine, propylheptylphosphine, dibutylphosphine, butylpentylphosphine, butylhexylphosphine, hexyloctylphosphine, butylcyclohexylphosphine, and butylphenylphosphine acid. The salt, butylphenyl butyl phosphinate, butylheptyl phosphinate, dicyclohexyl phosphinate, dihexyl phosphinate, diphenyl phosphinate, any one or a combination of at least two of the following: salt, butylphenyl butyl phosphinate, butylheptyl phosphinate, diisopropyl phosphinate, dibutyl butyl phosphinate, diisobutyl phosphinate, dibutyl isobutyl phosphinate, disec-butyl phosphinate, n-butyl sec-butyl phosphinate, isobutyl sec-butyl phosphinate, n-butylcyclohexyl phosphinate, isobutylcyclohexyl phosphinate, dicyclohexyl phosphinate, dihexyl phosphinate, diphenyl phosphinate, any one or a combination of at least two of the following: salt, butylphenyl butyl phosphinate, butylheptyl phosphinate, diisobutylcyclohexyl phosphinate, dicyclohexyl phosphinate, diphenyl phosphinate, diphenyl phosphinate.

[0060] Preferably, based on a total mass of 100 parts of the flame retardant, the flame retardant includes 5-60 parts of dialkylphosphonate A. The mass of dialkylphosphonate A can be 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, or 58 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0061] Preferably, based on a total mass of 100 parts of the flame retardant, the flame retardant includes 0.05-7 parts of ethyl butyl phosphonate. The mass of the ethyl butyl phosphonate can be 0.08 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, or 6.5 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0062] Preferably, in Formula II, R3 is selected from any one of C2-C6 straight-chain or branched alkyl, C3-C6 cycloalkyl, and phenyl, and more preferably from any one of n-butyl, isobutyl, hexyl, cyclohexyl, and phenyl.

[0063] Preferably, the hydrocarbon phosphonate includes any one or a combination of at least two of n-butyl phosphonate, isobutyl phosphonate, n-hexyl phosphonate, cyclohexyl phosphonate, and phenyl phosphonate.

[0064] In this invention, M1 represents the cationic portion of the dialkylphosphinate with structure shown in Formula I, the dialkylphosphinate A with structure shown in Formula IA, and the ethylbutylphosphinate with structure shown in Formula IB. It can be a metal or a non-metal (e.g., amine cations, cations corresponding to melamine and its derivatives), preferably a metal.

[0065] Preferably, M1 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, and Al is more preferred.

[0066] In this invention, the cationic portion of the hydrocarbon-based phosphonate with the structure shown in Formula II, represented by M2, can be a metal or a non-metal (e.g., amine cations, cations corresponding to melamine and its derivatives), preferably a metal.

[0067] Preferably, M2 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, and even more preferably Al.

[0068] In this invention, the diethylphosphonate includes any one or a combination of at least two of diethylphosphonic acid metal salts and diethylphosphonic acid non-metal salts; exemplaryly, the non-metallic cation in the diethylphosphonic acid non-metal salt can be an amine cation, such as the cation corresponding to melamine and its derivatives. Preferably, the diethylphosphonate is a diethylphosphonic acid metal salt.

[0069] Preferably, the diethylphosphonate includes any one or a combination of at least two of aluminum diethylphosphonate, calcium diethylphosphonate, magnesium diethylphosphonate, copper diethylphosphonate, zinc diethylphosphonate, iron diethylphosphonate, and titanium diethylphosphonate, with aluminum diethylphosphonate being more preferred.

[0070] In this invention, the ethylphosphonate includes any one or a combination of at least two of ethylphosphonic acid metal salts and ethylphosphonic acid non-metal salts; exemplaryly, the non-metallic cation in the ethylphosphonic acid non-metal salt can be an amine cation, such as the cation corresponding to melamine and its derivatives. Preferably, the ethylphosphonate is an ethylphosphonic acid metal salt.

[0071] Preferably, the ethyl phosphonate includes any one or a combination of at least two of aluminum ethyl phosphonate, calcium ethyl phosphonate, magnesium ethyl phosphonate, copper ethyl phosphonate, zinc ethyl phosphonate, iron ethyl phosphonate, and titanium ethyl phosphonate, with aluminum ethyl phosphonate being more preferred.

[0072] Preferably, based on a total mass of 100 parts of the flame retardant, the flame retardant further includes 0.01-25 parts of phosphite. The mass of the phosphite can be 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, or 24 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0073] In this invention, the phosphite can be represented as (M5) c+ )2(HPO3)c, M5 c+ The +c valence ion is represented, where c is selected from an integer between 2 and 4, for example, it can be 2, 3, or 4. M5 is the cation portion of the phosphite, which can be a metal or a non-metal (e.g., amine cations, cations corresponding to melamine and its derivatives), preferably a metal; the M5 is further preferably any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti, more preferably Al.

[0074] The phosphite includes any one or a combination of at least two of metal phosphite salts and non-metal phosphite salts; for example, the non-metallic cation in the non-metallic phosphite salt can be an amine cation, such as the cation corresponding to melamine and its derivatives. Preferably, the phosphite is a metal phosphite salt.

[0075] Preferably, the phosphite includes any one or a combination of at least two of aluminum phosphite, calcium phosphite, magnesium phosphite, copper phosphite, zinc phosphite, iron phosphite, and titanium phosphite.

[0076] As a preferred embodiment of the present invention, based on a total mass of 100 parts of the flame retardant, the flame retardant comprises the following components in parts by mass:

[0077]

[0078] In this invention, the method for preparing the flame retardant includes: mixing diethylphosphonate, ethylphosphonate, dialkylphosphonate, alkylphosphonate, and optionally diphosphite to obtain the flame retardant.

[0079] In this invention, the diethylphosphonate, ethylphosphonate, dialkylphosphonate, alkylphosphonate, and phosphite can be purchased from the market or prepared by synthetic methods known in the art.

[0080] It is understood that the flame retardant of the present invention (based on a total mass of 100%) comprises the following components by mass percentage:

[0081]

[0082] Preferably, the flame retardant (based on a total mass percentage of 100%) comprises the following components by mass percentage:

[0083]

[0084] Accordingly, the mass fraction of diethylphosphonate in the polyester composition can be understood as (5-35 parts) × (30%-90%), that is, the polyester composition includes 1.5-31.5 parts of diethylphosphonate by mass fraction, and the mass fraction of diethylphosphonate can be 2 parts, 4 parts, 5 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts or 30 parts, etc.

[0085] Similarly, the polyester composition includes 0.0005-1.05 parts by weight of ethyl phosphonate, wherein the parts by weight of ethyl phosphonate may be 0.001 parts, 0.005 parts, 0.008 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part, etc.

[0086] The polyester composition comprises 0.25-23.45 parts by weight of dialkylphosphinate, wherein the parts by weight of dialkylphosphinate may be 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 4 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, or 23 parts, etc.

[0087] Preferably, the polyester composition comprises 0.0025-2.45 parts by weight of ethyl butyl phosphite, wherein the weight of ethyl butyl phosphite may be 0.003 parts, 0.005 parts, 0.01 parts, 0.02 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, or 2.4 parts, etc.

[0088] Preferably, the polyester composition comprises 0.25-21 parts by weight of dialkylphosphinate A, wherein the parts by weight of dialkylphosphinate A may be 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 4 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, or 20 parts, etc.

[0089] The polyester composition comprises 0.0005-1.925 parts by weight of a hydrocarbon phosphonate, wherein the hydrocarbon phosphonate may be present in parts by weight of 0.001, 0.005, 0.008, 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.5, 1.6, 1.8, or 1.9.

[0090] The polyester composition comprises 0-8.75 parts by weight of phosphite, wherein the parts by weight of phosphite may be 0.0005 parts, 0.001 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, or 8.5 parts, etc.

[0091] It should be noted that the polyester composition of the present invention may also include any fillers, other additives, other auxiliaries, etc. that are motivated to be added in the art.

[0092] Preferably, the polyester composition further comprises 10-45 parts by weight of reinforcing material, wherein the parts by weight of the reinforcing material may be 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 42, or 44 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0093] Preferably, the reinforcing material comprises glass fiber and / or carbon fiber, with glass fiber being more preferred.

[0094] Preferably, the glass fiber includes any one or a combination of at least two of the following: alkali-free glass fiber (E glass fiber), medium-alkali glass fiber (C glass fiber), high-alkali glass fiber (A glass fiber), special glass fiber (S glass fiber), low-dielectric glass fiber (D glass fiber), and quartz glass fiber.

[0095] Preferably, the diameter of the glass fiber is 0.1-50 μm, for example, it can be 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 35 μm, 40 μm or 45 μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 5-20 μm is further preferred.

[0096] Preferably, the polyester composition further includes antioxidants and / or lubricants.

[0097] Preferably, the polyester composition further comprises 0.01-1 parts by weight of an antioxidant, wherein the antioxidant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, or 0.9 parts by weight, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0098] Preferably, the antioxidant includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0099] Preferably, the polyester composition further comprises 0.01-1 parts by weight of lubricant, wherein the parts by weight of lubricant may be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts or 0.9 parts, and specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0100] Preferably, the lubricant includes any one or a combination of at least two of the following: ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, and metal soap lubricants.

[0101] Preferably, the polyester composition further includes any one or a combination of at least two of the following: filler, synergistic flame retardant, colorant, UV absorber, and toughening agent.

[0102] Preferably, the filler comprises any one or a combination of at least two of the following: silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0103] Preferably, the filler in the polyester composition is ≤40 parts by mass, for example, it can be 0, 0.1, 0.5, 1, 2, 5, 8, 10, 15, 20, 25, 30, 35 or 38 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0104] Preferably, the synergistic flame retardant includes any one or a combination of at least two of melamine polyphosphate, melamine polyphosphate, and borate.

[0105] For example, the melamine polyphosphate includes magnesium melamine polyphosphate and / or zinc melamine polyphosphate; the borate includes zinc borate.

[0106] Preferably, the mass fraction of the synergistic flame retardant in the polyester composition is ≤15 parts, for example, it can be 0, 0.1, 0.5, 1, 2, 4, 5, 6, 8, 10, 12 or 14 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0107] Preferably, the colorant and ultraviolet absorber in the polyester composition each have a mass fraction of 0-2 parts, for example, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.2 parts, 1.5 parts, or 1.8 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0108] Preferably, the colorant includes inorganic and / or organic colorants; depending on its solubility and coloring properties, the colorant may include pigments and / or dyes.

[0109] For example, the colorant includes any one or a combination of at least two of titanium dioxide, ultramarine blue, iron oxide, zinc sulfide, carbon black, phthalocyanine, quinacridone, perylene black, and aniline black.

[0110] Preferably, the ultraviolet absorber includes any one or a combination of at least two of the following: hydroxybenzoic acid ester ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, substituted acrylonitrile ultraviolet absorbers, triazine ultraviolet absorbers, and hindered amine ultraviolet absorbers.

[0111] Preferably, the toughening agent in the polyester composition is 0-10 parts by weight, for example, 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8 or 9 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0112] In a preferred embodiment, the polyester composition comprises the following components in parts by weight:

[0113]

[0114] The polyester resin is the matrix material. Preferably, the mass percentage of polyester resin in the polyester composition is 40%-99.5%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0115] The flame retardant exerts a highly efficient flame retardant effect. Preferably, the flame retardant content in the polyester composition is 5%-35% by mass, for example, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 34%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 6%-25% is further preferred.

[0116] The reinforcing material can regulate the mechanical properties of the polyester composition and achieve a reinforcing effect. Preferably, the mass percentage of the reinforcing material in the polyester composition is 10%-45%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, or 44%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0117] For example, the method for preparing the polyester composition includes: melt-blending a polyester resin, a flame retardant and optionally a reinforcing material and then extruding the mixture to obtain the polyester composition.

[0118] Preferably, the melt blending process further includes a premixing step, which includes: mixing polyester with other additives to obtain a premix; the other additives include any one or a combination of at least two of lubricants, antioxidants, fillers, synergistic flame retardants, colorants, and ultraviolet absorbers.

[0119] Preferably, the melt blending is carried out in a screw extruder.

[0120] Preferably, the screw extruder is a twin-screw extruder.

[0121] Preferably, the temperature of the screw extruder is 80-300℃, for example, it can be 90℃, 100℃, 120℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃ or 290℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0122] Preferably, the extrusion process further includes granulation and drying steps.

[0123] In a second aspect, the present invention provides the use of the polyester composition as described in the first aspect in automotive parts, energy storage devices, connectors or electronic appliances.

[0124] Compared with the prior art, the present invention has the following beneficial effects:

[0125] The polyester composition provided by the present invention, by introducing a specific flame retardant, exhibits excellent and efficient flame retardant effect, giving the polyester composition excellent flame retardant properties, while also having high flexibility, good toughness and bending properties, and excellent performance in terms of mechanical properties. Detailed Implementation

[0126] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0127] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not limited to those elements and may also include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0128] In the following specific embodiments of the present invention, all materials used are commercially available chemicals, and specific information is as follows:

[0129] Brand factory PET PET YS-Y01 Hainan Yisheng Petrochemical Co., Ltd. PBT PBT 1200-211M Chang Chun Chemical Company, Taiwan Fiberglass ECS10-03-568H China Jushi Co., Ltd. lubricant TR044W Struktol, Germany Antioxidant 1098 RIANOX 1098 Tianjin Lianlong New Materials Co., Ltd. Antioxidant 168 RIANOX 168 Tianjin Lianlong New Materials Co., Ltd.

[0130] The components of the flame retardant used in the following specific embodiments of the present invention are shown in Table 1. The amount of each component in Table 1 is in parts by mass.

[0131] Table 1

[0132]

[0133] The dipropyl aluminum phosphonate in Table 1 includes di-n-propyl aluminum phosphonate and n-propyl isopropyl aluminum phosphonate, with a molar ratio of 94.8:4.3. All aluminum salts in Table 1 are commercially available chemicals or can be prepared by methods known in the art.

[0134] Examples 1-11, Comparative Examples 1-8

[0135] A polyester composition, the types and amounts of each component are shown in Tables 2 and 3, and the unit of amount of each component is "parts by mass".

[0136] The preparation method of the polyester composition includes: placing all components except glass fiber and flame retardant in a mixer according to the formula amount, mixing at 200 rpm for 3 minutes to obtain a premix; adding the premix into a twin-screw extruder through the main feed port, adding glass fiber into the twin-screw extruder through the first side feed port, adding flame retardant into the twin-screw extruder through the second side feed port, performing melt blending, and then extruding, granulating, drying and cooling to obtain the polyester composition; wherein the screw speed of the twin-screw extruder is 300 rpm, and the temperatures from the feeding section to the die head are 90℃, 180℃, 240℃, 240℃, 210℃, 210℃, 210℃, 210℃, 210℃, 210℃, 230℃, and 240℃ respectively.

[0137] The following performance tests were performed on the polyester composition:

[0138] (1) Flame retardancy: 125mm×13mm×1.6mm and 125mm×13mm×0.8mm specimens were made by injection molding and tested according to the method in standard ANSI / UL-94-1985;

[0139] (2) Deflection: The material is made into a 80mm×20mm×4mm spline and tested according to the method in standard GB / T9341-2008;

[0140] The test data are shown in Tables 2 and 3.

[0141] Table 2

[0142]

[0143]

[0144] Table 3

[0145]

[0146]

[0147] Based on the aforementioned performance test data, it can be seen that the present invention, through the design of phosphonates and their compounding in specific amounts, can synergistically enhance the flame retardant effect of flame retardants, so that the polyester composition containing them not only has excellent flame retardant properties, achieving V0 flame retardant effect for 1.6mm boards and V0-V1 flame retardant effect for 0.8mm boards, but also has a deflection ≥5.4, exhibiting excellent toughness and bending properties.

[0148] Comparing the data in Tables 2 and 3, it can be seen that flame retardants D1-D6 do not contain the four types of phosphonates specified in this invention, or the amount of phosphonates used exceeds the scope of this invention. Consequently, the components cannot exert a synergistic flame-retardant effect, leading to a decrease in the flame-retardant properties of the polyester compositions in Comparative Examples 1-6. In Comparative Examples 7 and 8, the amount of flame retardant was increased. Although the flame retardancy was improved, the flexibility decreased, and the toughness and bending properties of the material deteriorated.

[0149] The applicant declares that the present invention illustrates the polyester composition and its application through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyester composition, characterized in that, The polyester composition comprises the following components in parts by weight: 40-99.5 parts of polyester resin 5-35 parts flame retardant; Based on a total mass of 100 parts, the flame retardant comprises the following components in parts by mass: 30-90 parts of diethylphosphine salt Ethylphosphonate 0.01-3 parts 5-67 parts of dihydrophosphine salt Hydroxyl phosphonates 0.01-5.5 parts; The dialkylphosphinate is a combination of dialkylphosphinate A with the structure shown in Formula IA and ethylbutylphosphinate with the structure shown in Formula IB, or is ethylbutylphosphinate with the structure shown in Formula IB. Formula IA; Formula IB; The hydrocarbon-based phosphonate has the structure shown in Formula II: Formula II; R1', R2', and R3 are each independently selected from any one of substituted or unsubstituted C2-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C8 cycloalkyl groups, and substituted or unsubstituted C6-C18 aryl groups; The total number of carbon atoms in R1' and R2' is ≥6, and if one of R1' and R2' is ethyl, the other is not butyl; The substituents described in R1', R2', and R3 are each independently selected from at least one of C1-C8 straight-chain or branched alkyl groups and C6-C18 aryl groups; M1 m+ M2 represents an ion with a +m valence. n+ This represents an ion with a +n valence. m and n are each independently selected from integers between 2 and 4.

2. The polyester composition according to claim 1, characterized in that, The polyester resin includes any one or a combination of at least two of the following: polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, and polyethylene 2,6-naphthalenedicarboxylate.

3. The polyester composition according to claim 2, characterized in that, The polyester resin is polyethylene terephthalate and / or polybutylene terephthalate.

4. The polyester composition according to claim 1, characterized in that, R1' and R2' are each independently selected from any one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, phenethyl, phenylpropyl, phenylbutyl, pentyl, 2-methylpentyl, 2-ethylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, heptyl, octyl, phenyl, methylphenyl, and dimethylphenyl.

5. The polyester composition according to claim 4, characterized in that, R1' and R2' are each independently selected from any one of n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, cyclohexyl, methylcyclohexyl, and phenyl.

6. The polyester composition according to claim 1, characterized in that, The dialkylphosphonate A includes any one or a combination of at least two of the following: ethylpentylphosphonate, ethylhexylphosphonate, hexyloctylphosphonate, ethylcyclohexylphosphonate, ethylphenylphosphonate, ethylphenylethylphosphonate, ethylheptylphosphonate, dipropylphosphonate, propylbutylphosphonate, propylpentylphosphonate, propylhexylphosphonate, hexyloctylphosphonate, propylcyclohexylphosphonate, propylphenylphosphonate, propylphenylpropylphosphonate, propylheptylphosphonate, dibutylphosphonate, butylpentylphosphonate, butylhexylphosphonate, hexyloctylphosphonate, butylcyclohexylphosphonate, butylphenylphosphonate, butylphenylbutylphosphonate, butylheptylphosphonate, dicyclohexylphosphonate, dihexylphosphonate, and diphenylphosphonate.

7. The polyester composition according to claim 6, characterized in that, The dialkylphosphonate A includes any one or a combination of at least two of the following: di-n-propylphosphonate, di-n-propylisopropylphosphonate, di-isopropylphosphonate, di-n-butylphosphonate, di-isobutylphosphonate, di-sec-butylphosphonate, di-n-butylsec-butylphosphonate, isobutylsec-butylphosphonate, di-n-butylcyclohexylphosphonate, isobutylcyclohexylphosphonate, dicyclohexylphosphonate, di-n-hexylphosphonate, and diphenylphosphonate.

8. The polyester composition according to claim 1, characterized in that, Based on a total mass of 100 parts, the flame retardant includes 5-60 parts of dihydrophosphine A.

9. The polyester composition according to claim 1, characterized in that, Based on a total mass of 100 parts, the flame retardant includes 0.05-7 parts of ethyl butyl phosphonate.

10. The polyester composition according to claim 1, characterized in that, R3 is selected from any one of C2-C6 straight-chain or branched alkyl groups, C3-C6 cycloalkyl groups, and phenyl groups.

11. The polyester composition according to claim 10, characterized in that, R3 is selected from any one of n-butyl, isobutyl, hexyl, cyclohexyl, and phenyl.

12. The polyester composition according to claim 1, characterized in that, The hydrocarbon phosphonates include any one or a combination of at least two of the following: n-butyl phosphonate, isobutyl phosphonate, n-hexyl phosphonate, cyclohexyl phosphonate, and phenyl phosphonate.

13. The polyester composition according to claim 1, characterized in that, M1 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

14. The polyester composition according to claim 13, characterized in that, M1 is Al.

15. The polyester composition according to claim 1, characterized in that, The M2 is selected from any one of Al, Ca, Mg, Cu, Zn, Fe, and Ti.

16. The polyester composition according to claim 15, characterized in that, M2 is Al.

17. The polyester composition according to claim 1, characterized in that, Based on a total mass of 100 parts of the flame retardant, the flame retardant also includes 0.01-25 parts of phosphite.

18. The polyester composition according to claim 17, characterized in that, The phosphite includes any one or a combination of at least two of aluminum phosphite, calcium phosphite, magnesium phosphite, copper phosphite, zinc phosphite, iron phosphite, and titanium phosphite.

19. The polyester composition according to claim 1, characterized in that, The polyester composition further includes 10-45 parts by weight of reinforcing material.

20. The polyester composition according to claim 19, characterized in that, The reinforcing material includes glass fiber and / or carbon fiber.

21. The polyester composition according to claim 20, characterized in that, The reinforcing material is glass fiber.

22. The polyester composition according to claim 1, characterized in that, The polyester composition further includes 0.01-1 parts by weight of antioxidant.

23. The polyester composition according to claim 1, characterized in that, The polyester composition further includes 0.01-1 parts by weight of lubricant.

24. The polyester composition according to claim 1, characterized in that, The polyester composition further includes any one or a combination of at least two of the following: filler, synergistic flame retardant, colorant, UV absorber, and toughening agent.

25. The use of a polyester composition as described in any one of claims 1-24 in automotive parts, energy storage devices, connectors, or electronic and electrical appliances.

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