Method for preparing glass fiber-nylon composition

Abstract

To provide a method for preparing a glass fiber-nylon composition that can effectively improve the flame retardant properties of glass fiber-nylon composites.SOLUTION: The preparation of the composition includes the steps of: (1) condensing and polymerizing a compound represented by formula (I) in the presence of an inorganic acid and acetic anhydride to obtain a partially condensed polymer in which a portion forms a high-molecular-weight polymer; (2) reacting the partially condensed polymer with a rare earth inorganic salt to obtain a phosphonate; (3) mixing the phosphonate, an organic silicone flame retardant, and an inorganic silicone synergist to obtain a flame-retardant composition; (4) melt-extruding a raw material containing a first nylon, the flame-retardant composition, a lubricant, and an antioxidant in an extruder to obtain a flame-retardant masterbatch; and (5) melt-extruding a raw material containing a second nylon, glass fibers, the flame-retardant masterbatch, and additives in an extruder to obtain a composition.SELECTED DRAWING: Figure 1

Description

Description of Related Applications

[0001] This application is a divisional application of Patent Application No. 2024-65651, filed on April 15, 2024 (claiming priority from Patent Application No. CN202311730793.8, filed with the China National Intellectual Property Administration (CNIPA) on December 15, 2023). [Technical Field]

[0002] The present invention relates to a method for preparing a glass fiber-nylon composition. [Background technology]

[0003] Phosphorus-based flame retardants are halogen-free and have high flame retardancy and good electrical properties, making them widely used to improve the flame retardancy of glass fiber-reinforced nylon. Aluminum diethyl phosphinate is a typical flame retardant. Aluminum diethyl phosphinate has poor antioxidant properties and is prone to discoloration, smoke, and even scorching in air and at high temperatures. Aluminum diethyl phosphinate, with its high loading and small powder particle size, is prone to problems such as bridging, uneven feeding, and pellet breakage.

[0004] CN114672157A discloses a halogen-free flame-retardant masterbatch for glass fiber reinforced nylon, which contains nylon and a flame retardant prepared by mixing ammonium polyphosphate and tricresyl phosphate in a weight ratio of 1:3. When used in preparing glass fiber reinforced nylon, this flame retardant masterbatch is prone to releasing toxic gases and may cause phenomena such as bridging.

[0005] CN1763132A discloses a flame-retardant thermoplastic polyester resin composition, in which the polyester resin is different from nylon.

[0006] CN114364729A discloses a flame retardant composition containing (a) a hypophosphite and (b) a metal complex containing a metal Me selected from Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, Al, Sb, La, and Ce, a hydroxyl ligand, and a phosphorus-containing organic ligand. The flame retardant composition is prone to emitting toxic gases during use. Summary of the Invention

[0007] In light of this, an object of the present invention is to provide a flame-retardant composition that can effectively improve the flame retardant performance of glass fiber-nylon composites, does not generate toxic gases during use, and allows for smooth input of raw materials during processing. Furthermore, the flame-retardant composition has little effect on the mechanical properties of glass fiber-nylon composites. Furthermore, when applied to glass fiber-nylon composites, the flame-retardant composition does not undergo migration and is less corrosive to equipment. Another object of the present invention is to provide a method for preparing the flame-retardant composition. Another object of the present invention is to provide a flame-retardant masterbatch. Another object of the present invention is to provide a glass fiber-nylon composition. The above objects can be achieved by the following technical solutions.

[0008] In one aspect, the present invention provides a flame retardant composition comprising 40 to 60 parts by weight of a phosphonate, 5 to 15 parts by weight of an organosilicone flame retardant, and 2 to 8 parts by weight of an inorganic silicone synergist, The phosphonate is (1) A compound represented by formula (I) is subjected to condensation polymerization, and a part of the compound forms a polymer to obtain a partial condensation polymer; (2) Reacting rare earth inorganic salts with partial condensation polymers to obtain phosphonates A flame retardant composition obtained by the preparation method is provided.

[0009] TIFF2025183249000002.tif34170 (wherein R is selected from C1 to C6 alkyl groups and substituted or unsubstituted phenyl groups.) In the flame retardant composition of the present invention, the organic silicone flame retardant is preferably one or more selected from the group consisting of ladder-type siloxanes, cage-type silsesquioxanes, and silicone rubbers, and the inorganic silicone synergist is preferably one or more selected from the group consisting of wollastonite, layered silicates, nanosilica, and glass powder.

[0010] In the flame retardant composition according to the present invention, the inorganic silicone synergist is preferably an inorganic silicone synergist modified with a silane coupling agent, and the silane coupling agent is a one-end reactive polysiloxane coupling agent.

[0011] In another aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: Step (1) of condensation-polymerizing the compound represented by formula (I) in the presence of an inorganic acid and acetic anhydride, so that a portion of the compound forms a polymer to obtain a partial condensation polymer; Step (2) of reacting a rare earth inorganic salt with a partial condensation polymer to obtain a phosphonate; Step (3) of obtaining the flame retardant composition by mixing raw materials including 40 to 60 parts by weight of a phosphonate, 5 to 15 parts by weight of an organic silicone flame retardant, and 2 to 8 parts by weight of an inorganic silicone synergist; a method for preparing the flame retardant composition, comprising:

[0012] TIFF2025183249000003.tif34170 (wherein R is selected from the group consisting of a C1 to C6 alkyl group and a substituted or unsubstituted phenyl group.)

[0013] According to the preparation method of the present invention, preferably, the molar ratio of the compound represented by formula (I) to acetic anhydride is (0.2-0.4):(0.1-0.3), the mass ratio of the compound represented by formula (I) to inorganic acid is 1:(1-5), and the molar ratio of the compound represented by formula (I) to rare earth element in the rare earth inorganic salt is (0.2-0.4):(0.08-0.35).

[0014] According to the preparation method of the present invention, preferably, in step (1), the compound represented by formula (I) is subjected to condensation polymerization in the presence of an inorganic acid and acetic anhydride at 110°C to 150°C for 5 to 15 hours, and in step (2), the rare earth inorganic salt is reacted with the partial condensation polymer at 70°C to 110°C for 2 to 10 hours.

[0015] In another aspect, the present invention provides a flame-retardant masterbatch comprising 25 to 40 parts by weight of a first nylon and 50 to 75 parts by weight of the flame-retardant composition according to any one of claims 1 to 3.

[0016] According to the flame-retardant masterbatch of the present invention, preferably, the flame-retardant masterbatch further comprises 0.5 to 5 parts by weight of a lubricant and 0.1 to 3 parts by weight of an antioxidant; the first nylon is obtained by polymerizing a diamine containing 5 to 18 carbon atoms with a dibasic acid containing 5 to 18 carbon atoms, or is obtained by polymerizing a polyamide containing 5 to 15 carbon atoms; the lubricant is one or more selected from aluminum stearate, lithium stearate, calcium stearate, magnesium stearate, silicone powder, polyamide wax, montan wax, ethylene bisstearamide, pentaerythritol stearate, and TAF lubricant; and the antioxidant is one or more selected from phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and metal salt antioxidants.

[0017] In another aspect, the present invention provides a glass fiber-nylon composition prepared from raw materials including 1 to 8 parts by weight of a second nylon, 0.5 to 6 parts by weight of a glass fiber, and 0.5 to 5 parts by weight of the flame-retardant masterbatch according to claim 7 or 8.

[0018] According to the glass fiber-nylon composition of the present invention, preferably, the raw material further contains 0.1 to 2 parts by weight of an auxiliary agent, and the auxiliary agent is one or more selected from the group consisting of an antioxidant, a lubricant, a stabilizer, and an antiseptic.

[0019] The flame-retardant composition of the present invention effectively improves the flame-retardant performance of glass fiber-nylon composites, does not generate toxic gases during use, and allows for smooth input of raw materials during processing. Furthermore, the flame-retardant composition has minimal effect on the mechanical properties of glass fiber-nylon composites. Furthermore, when applied to glass fiber-nylon composites, the flame-retardant composition does not cause migration and is less corrosive to equipment. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 shows XRD patterns of the phosphonate obtained by Preparation Example 1 and after treatment at different temperatures. [Figure 2] FIG. 1 is an ion mass spectrometry diagram of the partial condensation polymer of Preparation Example 1.

[0021] [Figure 3] FIG. 1 shows XRD patterns of the phosphonate obtained in Preparation Example 2 and after treatment at different temperatures. [Figure 4] FIG. 1 shows XRD patterns of the phosphonate obtained in Preparation Example 3 and after treatment at different temperatures. [Figure 5] FIG. 1 shows XRD patterns of the phosphonate obtained in Preparation Example 4 and after treatment at different temperatures. [Figure 6] FIG. 1 shows XRD patterns of the phosphonate obtained in Preparation Example 5 and after treatment at different temperatures. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be further described below with reference to specific examples, but the scope of protection of the present invention is not limited thereto.

[0023] In the present invention, the terms "first nylon" and "second nylon" both refer to nylon. The terms "first" and "second" simply distinguish between them and have no other meaning.

[0024] <Flame-retardant composition and method for preparing same> The flame retardant composition of the present invention includes a phosphonate, an organic silicone flame retardant, and an inorganic silicone synergist. The flame retardant composition of the present invention does not include a nitrogen-based flame retardant. In some embodiments, the flame retardant composition comprises a phosphonate, an organic silicone flame retardant, and an inorganic silicone synergist. In the present invention, the phosphonate is also referred to as an organic phosphorus metal salt, for example, an organic phosphorus rare earth salt.

[0025] The phosphonates according to the invention can be obtained by the following preparation method.

[0026] (1) The compound represented by formula (I) is condensation polymerized, and a part of the compound forms a polymer to obtain a partial condensation polymer.

[0027] (2) A rare earth inorganic salt is reacted with a partial condensation polymer to obtain a phosphonate.

[0028] TIFF2025183249000004.tif34170 (wherein R is selected from the group consisting of a C1 to C6 alkyl group and a substituted or unsubstituted phenyl group.) In the present invention, the phosphonate is obtained by filtering, washing, and drying the reaction product obtained by reacting a rare earth inorganic salt with a partial condensation polymer without separation, purification, or other treatments. Therefore, it is more appropriate to characterize the phosphonate of the present invention by its preparation method. It has been discovered that the use of the phosphonate of the present invention is more advantageous in improving the flame retardant performance of nylon.

[0029] The organic silicone flame retardant may be one or more selected from ladder-type siloxanes, cage-type silsesquioxanes, and silicone rubbers. Preferably, the organic silicone flame retardant is a ladder-type siloxane. Examples of ladder-type siloxanes include, but are not limited to, ladder-type phenyl siloxanes, ladder-type methyl siloxanes, and ladder-type methyl phenyl siloxanes. According to one embodiment of the present invention, the organic silicone flame retardant has the model number FCA-107 and is manufactured by Dow Corning.

[0030] The organic silicone flame retardant is contained in an amount of 5 to 15 parts by weight, preferably 7 to 13 parts by weight, and more preferably 10 to 12 parts by weight.

[0031] The inorganic silicone synergist is one or more selected from wollastonite, layered silicate, nanosilica, and glass powder. Preferably, the glass powder is low-melting-point glass powder. In some embodiments, the inorganic silicone synergist is wollastonite. In other embodiments, the inorganic silicone synergist is layered silicate. Examples of layered silicate include, but are not limited to, sepiolite, mica powder, and talc powder. In some embodiments, the inorganic silicone synergist is a composition of sepiolite, mica powder, and talc. The mass ratio of sepiolite, talc powder, and muscovite powder is (2-8):1:(0.2-0.8), preferably (4-6):1:(0.4-0.6).

[0032] The inorganic silicone synergist is present in an amount of 2 to 8 parts by weight, preferably 3 to 7 parts by weight, and more preferably 4 to 6 parts by weight.

[0033] The inorganic silicone synergist may be an inorganic silicone synergist modified with a silane coupling agent. The silane coupling agent may be a single-terminated reactive polysiloxane coupling agent. The silane coupling agent may be one or more selected from a butyl-terminated reactive polysiloxane coupling agent and a hydroxyalkyl-terminated reactive polysiloxane coupling agent. According to one embodiment of the present invention, the silane coupling agent may be purchased from JNC Corporation under the model number FM-0815J.

[0034] Specifically, an inorganic silicone synergist modified with a silane coupling agent can be obtained by mixing the inorganic silicone synergist and the silane coupling agent. The mass ratio of the inorganic silicone synergist to the silane coupling agent may be 1:(1-5), and preferably 1:(1.5-3).

[0035] The flame retardant composition according to the present invention comprises: (1) a step of condensation polymerization; (2) reacting a rare earth inorganic salt with a partial condensation polymer; (3) Mixing step and The compound is obtained by a preparation method comprising the steps of:

[0036] In the present invention, first, a partial condensation polymer is formed from the compound represented by formula (I), thereby increasing the degree of matching with a rare earth cation, thereby increasing the stability of the resulting organic rare earth salt, improving its high temperature resistance, reducing the occurrence of plate-out, and providing the resulting phosphonate with good flame retardancy.

[0037] Condensation polymerization step In the present invention, by condensation polymerizing a phosphonic acid compound, a portion of the compound forms a polymer, thereby obtaining a partial condensation polymer.

[0038] The compound is shown in formula (I).

[0039] TIFF2025183249000005.tif34170 (Here, R is selected from a C1 to C6 alkyl group and a substituted or unsubstituted phenyl group. Preferably, R is selected from a C1 to C3 alkyl group or a phenyl group. The substituent bonded to the phenyl group may be a C1 to C6 alkyl group, and preferably is a C1 to C3 alkyl group.) Illustrative examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, methylpropyl, pentyl, methylbutyl, dimethylpropyl, ethylpropyl, hexyl, methylpentyl, dimethylbutyl, ethylbutyl, cyclopropyl, and cyclopentyl groups.

[0040] The compound of Formula (I) may be reacted in the presence of an inorganic acid and acetic anhydride. In some embodiments, the inorganic acid is acetic acid.

[0041] The molar ratio of the compound represented by formula (I) to acetic anhydride may be (0.2-0.4):(0.1-0.3), preferably (0.25-0.35):(0.12-0.25), and more preferably (0.3-0.35):(0.13-0.2).

[0042] The mass ratio of the compound represented by formula (I) to acetic anhydride may be 1:(0.2 to 1.5), preferably 1:(0.4 to 1), and more preferably 1:(0.5 to 0.7).

[0043] When the amounts of the compound represented by formula (I) and acetic anhydride used are within the above ranges, a partial condensation polymer having an appropriate degree of polymerization can be obtained, and the degree of matching with rare earth ions can be improved.

[0044] The mass ratio of the inorganic acid to acetic anhydride is (1.5 to 8):1, preferably (2 to 6):1, and more preferably (3 to 4):1.

[0045] The reaction temperature in step (1) is 110 to 150° C., preferably 120 to 140° C. The reaction time is 5 to 15 hours, preferably 7 to 10 hours.

[0046] Specifically, the compound represented by formula (I) is added to a mixed solution containing an inorganic acid and acetic anhydride, and a condensation polymerization reaction is carried out to obtain a partial condensation polymer.

[0047] Reacting a rare earth inorganic salt with a partial condensation polymer The phosphonate is obtained by reacting the rare earth inorganic salt with the partial condensation polymer. Specifically, the rare earth inorganic salt is added to the partial condensation polymer. The rare earth inorganic salt may also be added to the partial condensation polymer in batches.

[0048] The rare earth element in the rare earth inorganic salt may be one or more selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium. Preferably, the rare earth element is one or more selected from lanthanum and cerium. The rare earth inorganic salt may be one or more selected from rare earth acetates, rare earth chlorides, and rare earth carbonates. In some embodiments, the rare earth elements are lanthanum and cerium. The molar ratio of lanthanum to cerium is 25:(50-100), preferably 25:(65-85).

[0049] The molar ratio of the compound represented by formula (I) to the rare earth element in the rare earth inorganic salt is (0.2-0.4):(0.08-0.35), preferably (0.25-0.35):(0.12-0.3), and more preferably (0.3-0.35):(0.15-0.3).

[0050] The reaction temperature in step (2) is 70 to 110° C., preferably 80 to 100° C. The reaction time is 2 to 10 hours, preferably 4 to 7 hours.

[0051] The amount of the phosphonate is 40 to 60 parts by weight, preferably 45 to 55 parts by weight, and more preferably 50 to 55 parts by weight.

[0052] Mixing Step The flame retardant composition is prepared by mixing raw materials including a phosphonate, an organic silicone flame retardant, and an inorganic silicone synergist. The types and proportions of each component are as described above. The mixing may be carried out using a high-speed mixer.

[0053] <Flame-retardant masterbatch and preparation method thereof> The flame-retardant masterbatch of the present invention includes a first nylon and a flame-retardant composition. In some embodiments, it further includes a lubricant and an antioxidant. The flame-retardant masterbatch of the present invention may consist solely of the aforementioned materials. The components of the flame-retardant composition have been described above, so they will not be repeated here.

[0054] The first nylon can be obtained by polymerizing a diamine containing 5 to 18 carbon atoms and a dibasic acid containing 5 to 18 carbon atoms, or can be obtained by polymerizing a polyamide containing 5 to 15 carbon atoms.

[0055] The diamine containing 5 to 18 carbon atoms may be an aliphatic diamine or an aromatic diamine. Preferably, the aliphatic diamine contains 6 to 15 carbon atoms. Examples of aliphatic diamines include, but are not limited to, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, and pentadecanediamine. Preferably, the aromatic diamine contains 8 to 16 carbon atoms. Examples of aromatic diamines include, but are not limited to, m-xylylenedimethylamine, p-xylylenedimethylamine, m-phenylenediethylamine, and p-phenylenediethylamine.

[0056] Preferably, the dibasic acid contains 6 to 15 carbon atoms. The dibasic acid may be an aliphatic dibasic acid or an aromatic dibasic acid. Examples of dibasic acids include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecanedioic acid.

[0057] Preferably, the polyamide contains 6 to 12 carbon atoms. Examples of polyamides include, but are not limited to, polycaprolactam, polyundecalactam, and polydodecalactam.

[0058] Examples of the first nylon include, but are not limited to, PA6, PA66, PA12, PA1315, and PAMXD6.

[0059] The amount of the first nylon used is 25 to 40 parts by weight, preferably 30 to 35 parts by weight, and more preferably 32 to 35 parts by weight.

[0060] The amount of the flame retardant composition used is 50 to 75 parts by weight, preferably 55 to 70 parts by weight, and more preferably 60 to 65 parts by weight.

[0061] The lubricant may be one or more selected from aluminum stearate, lithium stearate, calcium stearate, magnesium stearate, silicone powder, polyamide wax, montan wax, ethylene bisstearamide, pentaerythritol stearate, and lubricant TAF. According to one embodiment of the present invention, the lubricant is a mixture of lithium stearate and silicone powder. The mass ratio of lithium stearate to silicone powder may be 1:(0.5-2), preferably 1:(0.8-1.5).

[0062] The amount of the lubricant used is 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, and more preferably 2 to 3 parts by weight.

[0063] The antioxidant may be one or more selected from phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and metal salt antioxidants. Illustrative examples of antioxidants include, but are not limited to, N,N'-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (Antioxidant 1098), pentaerythritol tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Antioxidant 1010), n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (Antioxidant 1076), tris(2,4-di-t-butylphenyl)phosphite (Antioxidant 168), bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite (Antioxidant 626), dilauryl thiodipropionate (Antioxidant DLTP), and distearyl thiodipropionate (Antioxidant DSTP).

[0064] The amount of the antioxidant used is 0.1 to 3 parts by weight, preferably 0.5 to 2.5 parts by weight, and more preferably 1 to 2 parts by weight.

[0065] A raw material containing a first nylon, a flame retardant composition, a lubricant, and an antioxidant is melt-extruded in a screw extruder to obtain a flame retardant masterbatch. Specifically, the first nylon and the antioxidant are uniformly mixed and then fed into the screw extruder. The uniformly mixed flame retardant composition and lubricant are then added to the screw extruder. The screw extruder is preferably a twin-screw extruder.

[0066] The temperature of the screw extruder is set to 150°C to 230°C, preferably 170°C to 210°C, and more preferably 180°C to 200°C.

[0067] The screw rotation speed is 150 to 220 rpm.

[0068] In some embodiments, the method further comprises cooling, pelletizing, sieving, and drying the extruded material.

[0069] <Glass fiber-nylon composition and its preparation method> The glass fiber-nylon composition of the present invention includes a flame-retardant masterbatch, a second nylon, and glass fibers. In some embodiments, it further includes an auxiliary agent. The glass fiber-nylon composition of the present invention may consist solely of the aforementioned components.

[0070] The details of the flame-retardant masterbatch are as described above and will not be repeated here.

[0071] The amount of the flame-retardant masterbatch used is 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, and more preferably 2 to 3 parts by weight.

[0072] The second nylon can be obtained by polymerizing a diamine containing 5 to 18 carbon atoms and a dibasic acid containing 5 to 18 carbon atoms, or can be obtained by polymerizing a polyamide containing 5 to 15 carbon atoms.

[0073] The diamine containing 5 to 18 carbon atoms may be an aliphatic diamine or an aromatic diamine. Preferably, the aliphatic diamine contains 6 to 15 carbon atoms. Examples of aliphatic diamines include, but are not limited to, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, and pentadecanediamine. Preferably, the aromatic diamine contains 8 to 16 carbon atoms. Examples of aromatic diamines include, but are not limited to, m-xylylenedimethylamine, p-xylylenedimethylamine, m-phenylenediethylamine, and p-phenylenediethylamine.

[0074] Preferably, the dibasic acid contains 6 to 15 carbon atoms. The dibasic acid may be an aliphatic dibasic acid or an aromatic dibasic acid. Examples of dibasic acids include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecanedioic acid.

[0075] Preferably, the polyamide contains 6 to 12 carbon atoms. Examples of polyamides include, but are not limited to, polycaprolactam, polyundecalactam, and polydodecalactam.

[0076] Examples of the second nylon include, but are not limited to, PA6, PA66, PA12, PA1315, and PAMXD6.

[0077] The second nylon is 1 to 8 parts by weight, preferably 2 to 6 parts by weight, and more preferably 4 to 5 parts by weight.

[0078] The amount of glass fiber is 0.5 to 6 parts by weight, preferably 1 to 5 parts by weight, and more preferably 2 to 4 parts by weight.

[0079] The auxiliary agent may be one or more selected from antioxidants, lubricants, stabilizers, and preservatives. Preferably, the auxiliary agent is an antioxidant. The antioxidant may be one or more selected from phenolic antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants. Examples of phenolic antioxidants include, but are not limited to, N,N'-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (Antioxidant 1098), pentaerythritol tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Antioxidant 1010), and n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (Antioxidant 1076). Examples of phosphorus-based antioxidants include, but are not limited to, tris(2,4-di-t-butylphenyl) phosphite (antioxidant 168), bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626), and antioxidant 627. Examples of thioether-based antioxidants include, but are not limited to, dilauryl thiodipropionate (antioxidant DLTP) and distearyl thiodipropionate (antioxidant DSTP). According to one embodiment of the present invention, the co-agent is phenyl tris(2,4-di-t-butyl) phosphite (antioxidant 168).

[0080] The amount of the auxiliary used may be 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight, and more preferably 0.5 to 0.8 parts by weight.

[0081] The raw materials including the flame retardant masterbatch, the second nylon, the glass fiber and the auxiliary agent are extruded in an extruder and granulated to obtain a glass fiber-nylon composition.

[0082] The raw materials will be described below.

[0083] Lanthanum cerium carbonate: 25:75 molar ratio of elemental lanthanum to elemental cerium.

[0084] Layered silicate: A mixture of sepiolite fine powder, talc, and muscovite powder in a mass ratio of 5:1:0.5. Silane coupling agent: Model number FM-0815J, purchased from JNC Corporation Organic silicone flame retardant: Model FCA-107, purchased from Dow Corning Silicone powder: Model number KJ-B01, purchased from Hangzhou Kaijie Plastic Technology Co., Ltd. Glass fiber: Model number T-435N, purchased from Taishan Glass Fiber Co., Ltd. Auxiliary agent: Antioxidant 168 The measurement method will be explained below.

[0085] Tensile strength: Measured in accordance with the method specified in ISO527-1-2012.

[0086] Impact strength: Notch impact strength test is performed in accordance with the method specified in ISO179-1-2010.

[0087] Flame retardancy: Samples measuring 125 x 13 x 0.8 mm are prepared by injection molding, and vertical tests are carried out in accordance with the UL-94 standard.

[0088] (1) Clamp: Clamp 6 mm from the top end of the sample, point the lengthwise direction downward, and maintain the distance from the bottom end of the sample to the top surface of the specified cotton layer at 300±10 mm.

[0089] (2) Gas appliance: Methane flow rate is controlled to 105 milliliters per minute, back pressure is controlled to 10 millimeters of water column, and flame height is controlled to 20±1 millimeters.

[0090] (3) Combustion: Place the center of the flame at the midpoint of the lower edge of the sample, and maintain a distance of 10±1 mm from the top of the gas burner to the bottom of the sample for 10±0.5 seconds. If the shape and position of the sample change during combustion, adjust the gas burner accordingly. If the molten material falls during the test, the gas burner may be tilted up to 45°. After burning for 10±0.5 seconds, begin recording the afterburn time t1 while moving the burner at least 150 mm at a speed of 300 mm / min (minutes). After the afterburn stops, immediately continue burning for 10±0.5 seconds, recording the afterburn time t2 and the afterburn time t3 after the movement.

[0091] Migration property: A glass fiber-nylon composition sample (10 mm x 16 mm x 80 mm) is placed in a thermo-hygrostat (temperature of the thermo-hygrostat set to 85°C, relative humidity set to 85%), and after 168 hours, the condition of the sample surface is observed.

[0092] Corrosion: A glass fiber-nylon composition sample (50mm x 50mm) is placed in a glass beaker, and a 2cm x 2cm piece of red copper is inserted into the sample. The sample is then placed in a thermo-hygrostat (temperature of the thermo-hygrostat set to 85°C, relative humidity set to 85%), and after 168 hours, the state of corrosion on the copper surface is observed.

[0093] Preparation Example 1 15 g of acetic anhydride was added to 52.7 g of acetic acid, and then 28.8 g of methylphosphonic acid was added. The mixture was reacted at 130° C. for 8 hours, and then cooled to 80° C. to obtain a partial condensation polymer.

[0094] 52.5 g of lanthanum acetate was added in batches to the partial condensation polymer to form a white precipitate, and after all of the lanthanum acetate was added, the mixture was stirred at 80°C for 5 hours to obtain a reaction product, which was then filtered, washed, and dried to obtain a phosphonate.

[0095] Figure 1 shows the XRD patterns of the phosphonate obtained in Preparation Example 1 and its heat treatment in an air atmosphere at different temperatures for 120 minutes. As can be seen from Figure 1, the phosphonate obtained in Preparation Example 1 has good thermal stability.

[0096] Fig. 2 is an ion mass spectrometry diagram of the partial condensation polymer of Preparation Example 1. As can be seen from Fig. 2, the partial condensation polymer contains unpolymerized methylphosphonic acid and a methylphosphonic acid condensation polymer.

[0097] Preparation Example 2 15 g of acetic anhydride was added to 52.7 g of acetic acid, and then 28.8 g of methylphosphonic acid was added. The mixture was reacted at 130° C. for 8 hours, and then cooled to 90° C. to obtain a partial condensation polymer.

[0098] 62 g of cesium chloride was added in batches to the partial condensation polymer to form a white precipitate. After all the cesium chloride was added, the mixture was stirred at 90°C for 5 hours to obtain a reaction product, which was then filtered, washed, and dried to obtain the phosphonate.

[0099] Figure 3 shows the XRD patterns of the phosphonate obtained in Preparation Example 2 and its heat treatment in an air atmosphere at different temperatures for 120 minutes. As can be seen from Figure 3, the phosphonate obtained in Preparation Example 2 has good thermal stability.

[0100] Preparation Example 3 24 g of acetic anhydride was added to 52.7 g of acetic acid, and 28.8 g of methylphosphonic acid was added thereto. The mixture was reacted at 130° C. for 8 hours, and then cooled to 90° C. to obtain a partial condensation polymer.

[0101] 42 g of lanthanum acetate was added in batches to the partial condensation polymer to form a white precipitate. After all of the lanthanum acetate was added, the mixture was stirred at 90°C for 5 hours to obtain a reaction product, which was then filtered, washed, and dried to obtain a phosphonate.

[0102] Figure 4 shows the XRD patterns of the phosphonate obtained in Preparation Example 3 and its heat treatment in an air atmosphere at different temperatures for 120 minutes. As can be seen from Figure 4, the phosphonate obtained in Preparation Example 3 has good thermal stability.

[0103] Preparation Example 4 15 g of acetic anhydride was added to 90 g of acetic acid, and then 28.8 g of methylphosphonic acid was added. The mixture was reacted at 130° C. for 8 hours, and then cooled to 90° C. to obtain a partial condensation polymer.

[0104] 38.4 g of lanthanum celsium carbonate was added in batches to the partial condensation polymer to form a white precipitate. After all of the lanthanum celsium carbonate was added, the mixture was stirred at 90°C for 5 hours to obtain a reaction product, which was then filtered, washed, and dried to obtain the phosphonate.

[0105] Figure 5 shows the XRD patterns of the phosphonate obtained in Preparation Example 4 and its heat treatment in an air atmosphere at different temperatures for 120 minutes. As can be seen from Figure 5, the phosphonate obtained in Preparation Example 4 has good thermal stability.

[0106] Preparation Example 5 15 g of acetic anhydride was added to 90 g of acetic acid, and 48 g of phenylphosphonic acid was added thereto, followed by reaction at 130° C. for 8 hours and then cooling to 90° C. to obtain a partial condensation polymer.

[0107] 52 g of lanthanum acetate was added in batches to the partial condensation polymer to form a white precipitate, and after all of the lanthanum acetate was added, the mixture was stirred at 90°C for 5 hours to obtain a reaction product, which was then filtered, washed, and dried to obtain a phosphonate.

[0108] Figure 6 shows the XRD patterns of the phosphonate obtained in Preparation Example 5 and its heat treatment in an air atmosphere at different temperatures for 120 minutes. As can be seen from Figure 6, the phosphonate obtained in Preparation Example 5 has good thermal stability.

[0109] The data shown in Table 1 were obtained from the thermogravimetric analysis diagrams of the phosphonates obtained in Preparation Examples 1 to 5.

[0110] TIFF2025183249000006.tif112170 Examples 1 and 2 The inorganic silicone synergist was placed in a high-speed mixer, and the silane coupling agent was added to the high-speed mixer to obtain a silane coupling agent-modified inorganic silicone synergist, and the mass ratio of the inorganic silicone synergist to the silane coupling agent was 1:2.

[0111] A flame retardant composition was obtained by mixing 50 parts by weight of phosphonate, 10 parts by weight of an organic silicone flame retardant, and 5 parts by weight of an inorganic silicone synergist modified with a silane coupling agent.

[0112] Details of the types of phosphonates and inorganic silicone synergists are given in Table 2.

[0113] TIFF2025183249000007.tif29170 Comparative Example 1 Same as Example 1 except that the phosphonate was replaced with aluminum diethylphosphinate.

[0114] Comparative Example 2 Same as Example 2, except that the phosphonate was replaced with aluminum diethylphosphinate and melamine polyphosphate (MPP) in a 3:1 mass ratio.

[0115] Examples 3-4 and Comparative Examples 3-4 32 parts by weight of the first nylon and 1 part by weight of N,N'-bis-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098) were uniformly mixed and placed in a twin-screw extruder. 65 parts by weight of the flame retardant composition, 1 part by weight of silicone powder, and 1 part by weight of lithium stearate were then uniformly mixed and added to the twin-screw extruder.

[0116] The materials in the twin-screw extruder were melted and extruded, cooled, pelletized, sieved, and dried to obtain a flame-retardant masterbatch. Specifically, the extruder's temperature zones were divided into 12 zones, with the 12th zone being the machine head. The temperatures of zones 1 through 11 were 180°C, 200°C, 200°C, 200°C, 200°C, 200°C, 190°C, 190°C, 190°C, 180°C, and 180°C, respectively, and the machine head temperature was 200°C. The screw rotation speed was 150-220 rpm.

[0117] Details of the first nylon and the type of flame retardant composition are shown in Table 3.

[0118] TIFF2025183249000008.tif23170 Examples 5-6 and Comparative Examples 5-6 2.5 parts by weight of flame-retardant masterbatch, 4.5 parts by weight of nylon 66, 3 parts by weight of glass fiber, and 0.5 parts by weight of additive were uniformly mixed and extruded in a twin-screw extruder to form granules. The granulated material was sieved and dried to obtain a glass fiber-nylon composition. The extruder's temperature zones were divided into 12 areas, with the 12th area being the machine head. The temperatures of the first through 11th areas were 180°C, 200°C, 200°C, 200°C, 200°C, 200°C, 190°C, 190°C, 190°C, 180°C, and 180°C, respectively, and the machine head temperature was 200°C. The screw rotation speed was 150-220 rpm.

[0119] The types of flame retardant master batches, the performance of the glass fiber-nylon composition and the expressions during processing are shown in Table 4.

[0120] TIFF2025183249000009.tif63170 The present invention is not limited to the above-described embodiments. Any modifications, improvements, substitutions, etc. that may occur to those skilled in the art are included within the scope of the present invention, provided that they do not deviate from the spirit of the present invention.

Claims

1. Step (1) of condensation-polymerizing the compound represented by formula (I) in the presence of an inorganic acid and acetic anhydride, so that a part of the compound forms a polymer to obtain a partial condensation polymer; Step (2) of reacting a rare earth inorganic salt with a partial condensation polymer to obtain a phosphonate; Step (3) mixing raw materials including 40 to 60 parts by weight of a phosphonate, 5 to 15 parts by weight of an organic silicone flame retardant, and 2 to 8 parts by weight of an inorganic silicone synergist to obtain a flame retardant composition; Step (4) of melt-extruding a raw material containing 25 to 40 parts by weight of a first nylon, 50 to 75 parts by weight of the flame-retardant composition, 0.5 to 5 parts by weight of a lubricant, and 0.1 to 3 parts by weight of an antioxidant, using a screw extruder to obtain a flame-retardant masterbatch; Step (5) of extruding and granulating a raw material containing 1 to 8 parts by weight of a second nylon, 0.5 to 6 parts by weight of a glass fiber, 0.5 to 5 parts by weight of the flame-retardant masterbatch, and 0.1 to 2 parts by weight of an auxiliary agent in an extruder to obtain a glass fiber-nylon composition, wherein the auxiliary agent is one or more selected from the group consisting of an antioxidant, a lubricant, a stabilizer, and an antiseptic; A method for preparing a glass fiber-nylon composition, comprising: (wherein R is selected from C1 to C6 alkyl groups and substituted or unsubstituted phenyl groups.)

2. 2. The method according to claim 1, wherein in step (1), the molar ratio of the compound represented by formula (I) to acetic anhydride is (0.2-0.4):(0.1-0.3), the mass ratio of the compound represented by formula (I) to the inorganic acid is 1:(1-5), and the molar ratio of the compound represented by formula (I) to the rare earth element in the rare earth inorganic salt is (0.2-0.4):(0.08-0.35).

3. In step (1), the compound represented by formula (I) is subjected to condensation polymerization in the presence of an inorganic acid and acetic anhydride at 110-150°C for 5-15 hours; 2. The method according to claim 1, wherein in step (2), the rare earth inorganic salt and the partial condensation polymer are reacted at 70-110°C for 2-10 hours.

4. 2. The method of claim 1, wherein in step (3), the organic silicone flame retardant is one or more selected from the group consisting of ladder-type siloxane, cage-type silsesquioxane, and silicone rubber, and the inorganic silicone synergist is one or more selected from the group consisting of wollastonite, layered silicate, nanosilica, and glass powder.

5. 2. The method of claim 1, wherein in step (3), the inorganic silicone synergist is a silane coupling agent-modified inorganic silicone synergist, and the silane coupling agent is a one-end reactive polysiloxane coupling agent.

6. 2. The method of claim 1, wherein in step (4), the first nylon is obtained by polymerizing a diamine containing 5 to 18 carbon atoms and a dibasic acid containing 5 to 18 carbon atoms, or by polymerizing a polyamide containing 5 to 15 carbon atoms.

7. 2. The method of claim 1, wherein in step (4), the lubricant is one or more selected from aluminum stearate, lithium stearate, calcium stearate, magnesium stearate, silicone powder, polyamide wax, montan wax, ethylene bisstearamide, pentaerythritol stearate, and lubricant TAF.

8. 2. The method of claim 1, wherein in step (4), the lubricant is a mixture of lithium stearate and silicone powder, in which the mass ratio of lithium stearate to silicone powder is 1:(0.5-2).

9. 2. The method according to claim 1, wherein the antioxidant is one or more selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and metal salt antioxidants.

10. The preparation method according to claim 1, characterized in that the second nylon is obtained by polymerizing a diamine containing 5 to 18 carbon atoms and a dibasic acid containing 5 to 18 carbon atoms, or by polymerizing a polyamide containing 5 to 15 carbon atoms.

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