Flame retardant compositions, masterbatches, glass fiber-nylon compositions and preparation methods thereof

Abstract

To provide a flame retardant composition that can effectively improve the flame retardance of a glass fiber-nylon composite material, does not generate a toxic gas during use, and allows smooth raw material feeding during processing, and also to provide a preparation method of the flame retardant composition, a masterbatch, and a glass fiber-nylon composition.SOLUTION: A flame retardant composition comprises 40-60 pts.wt. of phosphonate, 5-15 pts.wt. of an organosilicon flame retardant, and 2-8 pts.wt. of an inorganic silicon synergist, wherein the phosphonate is obtained by a preparation method comprising: condensing a compound represented by a formula (I) such that some of the compounds form a polymer, thereby yielding a partially condensed product; and reacting a rare earth inorganic salt with the partially condensed product to form the phosphonate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a flame-retardant composition, a flame-retardant masterbatch, a glass fiber-nylon composition, and a preparation method.

Background Art

[0002] Phosphorus-based flame retardants do not contain halogen and have high flame retardancy efficiency and good electrical properties, so they are widely used in the flame retardant modification of glass fiber-reinforced nylon. Aluminum diethyl phosphinate is a typical flame retardant. Aluminum diethyl phosphinate is inferior in antioxidant properties and is prone to discoloration, smoke generation, and even charring under air environment and high temperature. Aluminum diethyl phosphinate has a large addition amount, a small powder particle size, and is prone to problems such as bridging, feed unevenness, and pellet breakage.

[0003] 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 the flame retardant masterbatch is used in the preparation of glass fiber-reinforced nylon, it is prone to releasing toxic gases and there is a risk of phenomena such as bridging.

[0004] CN1763132A discloses a flame-retardant thermoplastic polyester resin composition. The polyester resin of the composition is different from nylon.

[0005] CN114364729A discloses a flame-retardant composition containing (a) a hypophosphite, a metal Me selected from Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, Ti, Al, Sb, La, Ce, a hydroxy ligand, and (b) a metal complex containing a phosphorus-containing organic ligand. The flame-retardant composition is prone to releasing toxic gases during use.

Summary of the Invention

[0006] In view of this, the 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, and moreover, does not generate toxic gases during use, and has smooth raw material input during processing. Further, the flame-retardant composition has little influence on the mechanical properties of the glass fiber-nylon composite. In addition, when the flame-retardant composition is applied to the glass fiber-nylon composite, there is no migration phenomenon and the corrosiveness to equipment is also small. 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 are achieved by the following technical solutions.

[0007] In one aspect, the present invention provides a flame-retardant composition comprising 40 to 60 parts by weight of 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, wherein the phosphonate is (1) Condensing and polymerizing the compound represented by formula (I) so that some of the compounds form a multimer to obtain a partial condensation polymer, (2) Reacting a rare earth inorganic salt with the partial condensation polymer to obtain a phosphonate and provides a flame-retardant composition obtained by the preparation method.

[0008] TIFF2025096107000002.tif34170 (wherein R is selected from a C1-C6 alkyl group, a substituted or unsubstituted phenyl group). According to the flame-retardant composition of the present invention, preferably, the organic silicone flame retardant is one or more selected from ladder-type siloxane, cage-type silsesquioxane, and silicone rubber, and the inorganic silicone synergist is one or more selected from wollastonite, layered silicate, nanosilica, and glass powder.

[0009] According to the flame retardant composition of the present invention, preferably, the inorganic silicone synergist is an inorganic silicone synergist modified with a silane coupling agent, and the silane coupling agent is a one-terminal reactive polysiloxane coupling agent.

[0010] In another aspect, the present invention Step (1) of condensing and polymerizing the compound represented by formula (I) in the presence of an inorganic acid and acetic anhydride, and forming a multimer of some of the compounds to obtain a partially condensed polymer; Step (2) of reacting a rare earth inorganic salt with the partially condensed polymer to obtain a phosphonate; Step (3) of mixing a raw material containing 40 to 60 parts by weight of 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 the flame retardant composition A method for preparing the flame retardant composition is provided.

[0011] TIFF2025096107000003.tif34170(Here, R is selected from a C1-C6 alkyl group, a substituted or unsubstituted phenyl group.)

[0012] 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 to 0.4):(0.1 to 0.3), and the mass ratio of the compound represented by formula (I) to the inorganic acid is 1:(1 to 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 to 0.4):(0.08 to 0.35).

[0013] According to the preparation method of the present invention, preferably, in step (1), in the presence of an inorganic acid and acetic anhydride, the compound represented by formula (I) is condensed and polymerized at 110°C to 150°C for 5 to 15 h (hours), and in step (2), the rare earth inorganic salt and the partially condensed polymer are reacted at 70°C to 110°C for 2 to 10 h.

[0014] 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.

[0015] 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 and 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 lubricant TAF. The antioxidant is one or more selected from phenolic antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and metal salt antioxidants.

[0016] In another aspect, the present invention provides a glass fiber-nylon composition prepared from a raw material comprising 1 to 8 parts by weight of a second nylon, 0.5 to 6 parts by weight of glass fiber, and 0.5 to 5 parts by weight of the flame-retardant masterbatch according to claim 7 or 8.

[0017] According to the glass fiber-nylon composition of the present invention, preferably, the raw material further comprises 0.1 to 2 parts by weight of an auxiliary agent, and the auxiliary agent is one or more selected from antioxidants, lubricants, stabilizers, and preservatives.

[0018] The flame-retardant composition according to the present invention can effectively improve the flame-retardant performance of the glass fiber-nylon composite material, does not generate toxic gases during use, and has smooth raw material input during processing. In addition, the flame-retardant composition has little influence on the mechanical properties of the glass fiber-nylon composite material. Further, when the flame-retardant composition is applied to the glass fiber-nylon composite material, no migration phenomenon occurs and the corrosiveness to equipment is small.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

[0020]

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0021] Hereinafter, the present invention will be further described with reference to specific examples, but the protection scope of the present invention is not limited thereto.

[0022] Both the "first nylon" and the "second nylon" in the present invention mean nylon. The first and the second are only used to distinguish them and have no other meanings.

[0023] <Flame Retardant Composition and Its Preparation Method> The flame retardant composition according to the present invention contains a phosphonate, an organic silicone flame retardant, and an inorganic silicone synergist. The flame retardant composition according to the present invention does not contain a nitrogen-based flame retardant. In some embodiments, the flame retardant composition consists of 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, there is an organic rare earth phosphorus salt.

[0024] The phosphonate according to the present invention is obtained by the following preparation method.

[0025] (1) The compound represented by formula (I) is subjected to condensation polymerization so that a part of the compound forms a multimer to obtain a partial condensation polymer.

[0026] (2) A rare earth inorganic salt and a partial condensation polymer are reacted to obtain a phosphonate.

[0027] TIFF2025096107000004.tif34170 (Here, R is selected from an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group.) In the present invention, the reaction product obtained by reacting a rare earth inorganic salt and a partial condensation polymer is filtered, washed, and dried without performing treatments such as separation and purification to obtain a phosphonate. Therefore, it is more appropriate to characterize the phosphonate according to the present invention by the preparation method. It has been discovered that adopting the phosphonate according to the present invention is more advantageous for improving the flame retardancy performance of nylon.

[0028] The organic silicone flame retardant may be one or more selected from ladder-type siloxane, cage-type silsesquioxane, and silicone rubber. Preferably, it is ladder-type siloxane. Examples of ladder-type siloxane include, but are not limited to, ladder-type phenylsiloxane, ladder-type methylsiloxane, and ladder-type methylphenylsiloxane. According to an embodiment of the present invention, the organic silicone flame retardant has a model number of FCA-107 and is manufactured by Dow Corning.

[0029] The organic silicone flame retardant is 5 to 15 parts by weight, preferably 7 to 13 parts by weight, and more preferably 10 to 12 parts by weight.

[0030] The inorganic silicone synergist is one or more selected from wollastonite, layered silicate, nanosilica, and glass powder. Preferably, the glass powder is low-melting glass powder. In some embodiments, the inorganic silicone synergist is wollastonite. In some other embodiments, the inorganic silicone synergist is layered silicate. Examples of the 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 to 8):1:(0.2 to 0.8), preferably (4 to 6):1:(0.4 to 0.6).

[0031] The inorganic silicone synergist is 2 to 8 parts by weight, preferably 3 to 7 parts by weight, more preferably 4 to 6 parts by weight.

[0032] The inorganic silicone synergist may be an inorganic silicone synergist modified with a silane coupling agent. The silane coupling agent may be a one-terminal reactive polysiloxane coupling agent. The silane coupling agent may be one or more selected from a butyl-terminal reactive polysiloxane type coupling agent and a hydroxyalkyl-terminal reactive polysiloxane type coupling agent. According to an embodiment of the present invention, the silane coupling agent has a model number of FM-0815J and can be purchased from JNC Corporation.

[0033] Specifically, by mixing the inorganic silicone synergist and the silane coupling agent, an inorganic silicone synergist modified with the silane coupling agent can be obtained. The mass ratio of the inorganic silicone synergist to the silane coupling agent may be 1:(1 to 5), preferably 1:(1.5 to 3).

[0034] The flame-retardant composition according to the present invention is (1) a step of condensation polymerization and (2) a step of reacting a rare earth inorganic salt with a partial condensation polymer and (3) a mixing step and is obtained by a preparation method including these steps.

[0035] The present invention first forms a partial condensation polymer from the compound represented by formula (I) to enhance the matching degree with rare earth cations, improve the stability of the resulting organic rare earth salt, enhance its high temperature resistance, reduce the occurrence of plate-out phenomenon, and the resulting phosphonate has good flame retardant performance.

[0036] Step of condensation polymerization In the present invention, by condensing and polymerizing phosphonic acid-based compounds, some compounds form multimers to obtain a partial condensation polymer.

[0037] The compound is represented by formula (I).

[0038] TIFF2025096107000005.tif34170(Here, R is selected from a C1-C6 alkyl group, a substituted or unsubstituted phenyl group. Preferably, R is selected from a C1-C3 alkyl group or a phenyl group. The substituent bonded to the phenyl group may be a C1-C6 alkyl group, preferably a C1-C3 alkyl group.) Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, butyl group, methylpropyl group, pentyl group, methylbutyl group, dimethylpropyl group, ethylpropyl group, hexyl group, methylpentyl group, dimethylbutyl group, ethylbutyl group, cyclopropyl group, cyclopentyl group.

[0039] The reaction of the compound represented by formula (I) may be carried out in the presence of an inorganic acid and acetic anhydride. In some embodiments, the inorganic acid is acetic acid.

[0040] 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), more preferably (0.3 - 0.35):(0.13 - 0.2).

[0041] The mass ratio of the compound represented by formula (I) to acetic anhydride may be 1:(0.2 - 1.5), preferably 1:(0.4 - 1), and more preferably 1:(0.5 - 0.7).

[0042] When the usage amounts of the compound represented by formula (I) and acetic anhydride are within the above ranges, a partial condensation polymer with an appropriate degree of polymerization can be obtained, and the matching degree with rare earth ions can be improved.

[0043] The mass ratio of the inorganic acid to acetic anhydride is (1.5 - 8):1, preferably (2 - 6):1, and more preferably (3 - 4):1.

[0044] The reaction temperature in step (1) is 110°C - 150°C, preferably 120°C - 140°C. The reaction time is 5 - 15 h, preferably 7 - 10 h.

[0045] 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.

[0046] Step of reacting a rare earth inorganic salt with a partially condensed polymer The rare earth inorganic salt and the partial condensation polymer are reacted to obtain a phosphonate. Specifically, the rare earth inorganic salt is added to the partial condensation polymer. The rare earth inorganic salt may be added to the partial condensation polymer in batches.

[0047] 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 or 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 the lanthanum element to the cerium element is 25:(50 - 100), preferably 25:(65 - 85).

[0048] 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).

[0049] The reaction temperature in step (2) is 70°C - 110°C, preferably 80°C - 100°C. The reaction time is 2 - 10 h, preferably 4 - 7 h.

[0050] The phosphonate is 40 - 60 parts by weight, preferably 45 - 55 parts by weight, and more preferably 50 - 55 parts by weight.

[0051] Mixing step Mix the raw materials containing phosphonate, organic silicone flame retardant, and inorganic silicone synergist to obtain the flame retardant composition. The types and formulations of each component are as described above. The mixing may be carried out with a high-speed mixer.

[0052] <Flame Retardant Masterbatch and Its Preparation Method> The flame-retardant masterbatch according to the present invention contains a first nylon and a flame-retardant composition. In some embodiments, it further contains a lubricant and an antioxidant. The flame-retardant masterbatch according to the present invention may consist only of the substances described above. Since the components of the flame-retardant composition are as described above, they will not be repeated here.

[0053] 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.

[0054] 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 the aliphatic diamine include, but are not limited to, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine. Preferably, the aromatic diamine contains 8 to 16 carbon atoms. Examples of the aromatic diamine include, but are not limited to, m-xylylenedimethylamine, p-xylylenedimethylamine, m-phenylenediethylamine, p-phenylenediethylamine.

[0055] 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 the dibasic acid include, but are not limited to, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid.

[0056] Preferably, the polyamide contains 6 to 12 carbon atoms. Examples of the polyamide include, but are not limited to, polycaprolactam, polyundecalactam, polydodecalactam.

[0057] Examples of the first nylon include, but are not limited to, PA6, PA66, PA12, PA1315, and PAMXD6.

[0058] 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.

[0059] 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.

[0060] 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 an 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 to 2), preferably 1:(0.8 to 1.5).

[0061] 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.

[0062] The antioxidant may be one or more selected from phenolic antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and metal salt antioxidants. Examples of antioxidants include 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), distearyl thiodipropionate (Antioxidant DSTP), but are not limited thereto.

[0063] 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.

[0064] Raw materials including the first nylon, the flame retardant composition, the lubricant, and the antioxidant are melt-extruded with a screw extruder to obtain a flame retardant masterbatch. Specifically, after uniformly mixing the first nylon and the antioxidant, they are put into a screw extruder, and then the uniformly mixed flame retardant composition and the lubricant are added to the screw extruder. The screw extruder is preferably a twin-screw extruder.

[0065] 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.

[0066] The screw rotation speed is 150 to 220 rpm.

[0067] In some embodiments, the method further includes the steps of cooling the extruded material, pelletizing it, screening it, and drying it.

[0068] <Glass fiber-nylon composition and method for preparing the same> The glass fiber-nylon composition according to the present invention comprises a flame retardant masterbatch, a second nylon, and glass fibers. In some embodiments, it further comprises an auxiliary agent. The glass fiber-nylon composition according to the present invention may consist of only the above-described components.

[0069] Since the details of the flame retardant masterbatch are as described above, they will not be repeated here.

[0070] 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.

[0071] 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 by polymerizing a polyamide containing 5 to 15 carbon atoms.

[0072] 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 the aliphatic diamine include, but are not limited to, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine. Preferably, the aromatic diamine contains 8 to 16 carbon atoms. Examples of the aromatic diamine include, but are not limited to, m-xylylenedimethylamine, p-xylylenedimethylamine, m-phenylenediethylamine, p-phenylenediethylamine.

[0073] 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 the dibasic acid 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.

[0074] Preferably, the polyamide contains 6 to 12 carbon atoms. Examples of the polyamide include, but are not limited to, polycaprolactam, polyundecalactam, and polydodecalactam.

[0075] Examples of the second nylon include, but are not limited to, PA6, PA66, PA12, PA1315, and PAMXD6.

[0076] 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.

[0077] The 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.

[0078] 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 auxiliary agent is phenyltris(2,4-di-t-butyl)phosphite (Antioxidant 168).

[0079] The amount of the auxiliary agent 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.

[0080] The raw materials including the flame retardant masterbatch, the second nylon, the glass fiber, and the auxiliary agent are extruded by an extruder and granulated to obtain a glass fiber-nylon composition.

[0081] Hereinafter, the raw materials will be described.

[0082] Lanthanum cerium carbonate: The molar ratio of lanthanum element to cerium element is 25:75.

[0083] Layered silicate: A mixture of sepiolite fine powder, talc, and muscovite powder with a mass ratio of 5:1:0.5 Silane coupling agent: Model number FM-0815J, purchased from JNC Corporation Organic silicone flame retardant: Model number FCA-107, purchased from Dow Corning Silicone powder: Model number KJ-B01, purchased from Hangzhou Kajie Plastic Technology Co., Ltd Glass fiber: Model number T-435N, purchased from Taishan Fiberglass Co., Ltd Auxiliary agent: Antioxidant 168 The following describes the measurement methods.

[0084] Tensile strength: Measured in accordance with the method specified in ISO527-1-2012

[0085] Impact strength: Conduct a notch impact strength test in accordance with the method specified in ISO179-1-2010

[0086] Flame retardant performance: Samples of 125×13×0.8 mm are prepared by injection molding, and a vertical test is carried out in accordance with the UL-94 standard

[0087] (1) Clamp: Clamp 6 mm from the upper end of the sample, with the length direction downward, and maintain the distance from the lower end of the sample to the upper surface of the specified cotton layer at 300±10 mm

[0088] (2) Gas appliance: Control the methane flow rate at 105 milliliters per minute, the back pressure at 10 millimeters of water column, and the flame height at 20±1 millimeter

[0089] (3) Combustion: Place the center of the flame at the midpoint of the lower edge of the sample, set the distance from the top of the gas burner to the lower end of the sample to 10 ± 1 mm, and maintain it for 10 ± 0.5 seconds. If the shape and position of the sample change during combustion, adjust the gas burner accordingly. If the melt drops during the test, the gas burner may be tilted up to 45°. After burning for 10 ± 0.5 seconds, while moving the burner at a speed of 300 mm / min (minute) by at least 150 mm, start recording the afterburn time t1. After the afterburn stops, immediately burn for 10 ± 0.5 seconds and record the afterburn time t2 and the afterburn time t3 after movement.

[0090] Migration property: Place a glass fiber-nylon composition sample (10 mm × 16 mm × 80 mm) in a thermostatic and humidistatic chamber (set the temperature of the thermostatic and humidistatic chamber to 85 °C and the relative humidity to 85%), and observe the state of the sample surface after 168 h.

[0091] Corrosiveness: Place a glass fiber-nylon composition sample (50 mm × 50 mm) in a glass beaker, insert a 2 cm × 2 cm copper sheet into the sample, then place it in a thermostatic and humidistatic chamber (set the temperature of the thermostatic and humidistatic chamber to 85 °C and the relative humidity to 85%), and observe the corrosion state of the copper surface after 168 h.

[0092] Preparation Example 1 Put 15 g of acetic anhydride into 52.7 g of acetic acid, add 28.8 g of methylphosphonic acid, react at 130 °C for 8 h, and cool down to 80 °C to obtain a partial condensation polymer.

[0093] Add 52.5 g of lanthanum acetate to the partial condensation polymer in batches to form a white precipitate. After adding all the lanthanum acetate, react for 5 h with stirring at a temperature of 80 °C to obtain a reaction product. Filter, wash, and dry the reaction product in sequence to obtain a phosphonate.

[0094] Figure 1 shows the XRD patterns of the phosphonate obtained in Preparation Example 1 and after heat-treating it at different temperatures for 120 min in an air atmosphere. As can be seen from Figure 1, the phosphonate obtained in Preparation Example 1 has good thermal stability.

[0095] Figure 2 is the ion mass spectrometry diagram of the partial condensation polymer of Preparation Example 1. As can be seen from Figure 2, the partial condensation polymer contains unreacted methylphosphonic acid and methylphosphonic acid condensation polymer.

[0096] Preparation Example 2 15 g of acetic anhydride was put into 52.7 g of acetic acid, and 28.8 g of methylphosphonic acid was added, followed by reacting at 130 °C for 8 h and then cooling to 90 °C to obtain a partial condensation polymer.

[0097] 62 g of cerium chloride was added batchwise to the partial condensation polymer to form a white precipitate. After all the cerium chloride was added, the reaction was carried out for 5 h with stirring at 90 °C to obtain a reaction product. The reaction product was filtered, washed, and dried in sequence to obtain a phosphonate.

[0098] Figure 3 shows the XRD patterns of the phosphonate obtained in Preparation Example 2 and after heat-treating it at different temperatures for 120 min in an air atmosphere. As can be seen from Figure 3, the phosphonate obtained in Preparation Example 2 has good thermal stability.

[0099] Preparation Example 3 24 g of acetic anhydride was put into 52.7 g of acetic acid, 28.8 g of methylphosphonic acid was added, and the mixture was reacted at 130 °C for 8 h and then cooled to 90 °C to obtain a partial condensation polymer.

[0100] 42 g of lanthanum acetate was added batchwise to the partial condensation polymer to form a white precipitate. After all the lanthanum acetate was added, the reaction was carried out for 5 h with stirring at 90 °C to obtain a reaction product. The reaction product was filtered, washed, and dried in sequence to obtain a phosphonate.

[0101] Figure 4 shows the XRD patterns of the phosphonate obtained in Preparation Example 3 and after heat-treating it at different temperatures in an air atmosphere for 120 min. As can be seen from Figure 4, the phosphonate obtained in Preparation Example 3 has good thermal stability.

[0102] Preparation Example 4 15 g of acetic anhydride was put into 90 g of acetic acid, and 28.8 g of methylphosphonic acid was added, followed by reacting at 130 °C for 8 h. After cooling to 90 °C, a partial condensation polymer was obtained.

[0103] 38.4 g of lanthanum carbonate was added batchwise to the partial condensation polymer to form a white precipitate. After adding all of the lanthanum carbonate, the reaction was carried out at 90 °C with stirring for 5 h to obtain a reaction product. The reaction product was filtered, washed, and dried in sequence to obtain a phosphonate.

[0104] Figure 5 shows the XRD patterns of the phosphonate obtained in Preparation Example 4 and after heat-treating it at different temperatures in an air atmosphere for 120 min. As can be seen from Figure 5, the phosphonate obtained in Preparation Example 4 has good thermal stability.

[0105] Preparation Example 5 15 g of acetic anhydride was put into 90 g of acetic acid, and 48 g of phenylphosphonic acid was added, followed by reacting at 130 °C for 8 h, and then cooling to 90 °C to obtain a partial condensation polymer.

[0106] 52 g of lanthanum acetate was added batchwise to the partial condensation polymer to form a white precipitate. After adding all of the lanthanum acetate, the reaction was carried out at 90 °C with stirring for 5 h to obtain a reaction product. The reaction product was filtered, washed, and dried in sequence to obtain a phosphonate.

[0107] Figure 6 shows the XRD patterns of the phosphonate obtained in Preparation Example 5 and after heat-treating it at different temperatures in an air atmosphere for 120 min. As can be seen from Figure 6, the phosphonate obtained in Preparation Example 5 has good thermal stability.

[0108] Data shown in Table 1 were obtained from the thermogravimetric analysis diagrams of the phosphonates obtained in Preparation Examples 1 to 5.

[0109] TIFF2025096107000006.tif112170 Examples 1 to 2 The inorganic silicone synergist was put into a high-speed mixer, and a silane coupling agent was added to the high-speed mixer to obtain an inorganic silicone synergist modified with the silane coupling agent. The mass ratio of the inorganic silicone synergist to the silane coupling agent was 1:2.

[0110] 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 were mixed to obtain a flame retardant composition.

[0111] Details of the types of phosphonates and inorganic silicone synergists are shown in Table 2.

[0112] TIFF2025096107000007.tif29170 Comparative Example 1 It was the same as in Example 1 except that the phosphonate was replaced with aluminum diethylphosphinate.

[0113] Comparative Example 2 It was the same as in Example 2 except that the phosphonate was replaced with a mixture of aluminum diethylphosphinate and melamine polyphosphate (MPP) at a mass ratio of 3:1.

[0114] Examples 3 to 4 and Comparative Examples 3 to 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, put into a twin-screw extruder, and then 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 uniformly mixed and added to the twin-screw extruder.

[0115] After melting, extruding, and cooling the substance in the twin-screw extruder, it was pelletized, sieved, and dried in sequence to obtain the flame-retardant masterbatch. As specific parameters, the temperature zone of the extruder was divided into 12 areas, and the 12th area was the machine head. The temperatures of the 1st to 11th areas were 180 °C, 200 °C, 200 °C, 200 °C, 200 °C, 200 °C, 190 °C, 190 °C, 190 °C, 180 °C, 180 °C respectively, and the temperature of the machine head was 200 °C. The screw rotation speed was 150 - 220 rpm.

[0116] The details of the types of the first nylon and the flame-retardant composition were shown in Table 3.

[0117] TIFF2025096107000008.tif23170 Examples 5 to 6 and Comparative Examples 5 to 6 2.5 parts by weight of the 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 the auxiliary agent were uniformly mixed and then extruded and granulated with a twin-screw extruder. The granulated material was sieved and dried to obtain the glass fiber-nylon composition. The temperature zone of the extruder was divided into 12 areas, and the 12th area was the machine head. The temperatures of the 1st to 11th areas were 180 °C, 200 °C, 200 °C, 200 °C, 200 °C, 200 °C, 190 °C, 190 °C, 190 °C, 180 °C, 180 °C respectively, and the temperature of the machine head was 200 °C. The screw rotation speed was 150 - 220 rpm.

[0118] The types of the flame-retardant masterbatch, the performance of the glass fiber-nylon composition, and the performance during the processing were shown in Table 4.

[0119] TIFF2025096107000009.tif63170 The present invention is not limited to the above embodiments. All deformations, improvements, substitutions, etc. that can be conceived by those skilled in the art without departing from the spirit of the present invention are included in the scope of the present invention.

Claims

1. A flame retardant composition comprising 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. (1) The phosphonate is produced by condensation polymerization of a compound represented by formula (I) such that a portion of the compound forms a polymer to obtain a partial condensation polymer, (2) reacting a rare earth inorganic salt with a partial condensation polymer to obtain a phosphonate; The flame retardant composition is obtained by the above preparation method. (wherein R is selected from C1 to C6 alkyl groups and substituted or unsubstituted phenyl groups).

2. 2. The flame retardant composition according to claim 1, wherein the organic silicone flame retardant is one or more selected from the group consisting of ladder-type siloxanes, cage-type silsesquioxanes, and silicone rubbers, and the inorganic silicone synergist is one or more selected from the group consisting of wollastonite, layered silicate, nanosilica, and glass powder.

3. 2. The flame retardant composition according to claim 1, wherein the inorganic silicone synergist is an inorganic silicone synergist modified with a silane coupling agent, and the silane coupling agent is a one-end reactive polysiloxane coupling agent.

4. A step (1) of condensation-polymerizing the compound represented by formula (I) in the presence of an inorganic acid and acetic anhydride to obtain a partial condensation polymer by forming a part of the compound into a polymer; (2) reacting a rare earth inorganic salt with a partial condensation polymer to obtain a phosphonate; (3) mixing raw materials including 40-60 parts by weight of a phosphonate, 5-15 parts by weight of an organic silicone flame retardant, and 2-8 parts by weight of an inorganic silicone synergist to obtain the flame retardant composition; 2. A method for preparing the flame retardant composition of claim 1, comprising: (wherein R is selected from C1 to C6 alkyl groups and substituted or unsubstituted phenyl groups).

5. 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 to 5); The preparation method according to claim 4, wherein 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).

6. 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 h; The preparation method according to claim 4, wherein in step (2), the rare earth inorganic salt and the partial condensation polymer are reacted at 70°C to 110°C for 2 to 10 hours.

7. 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.

8. 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 and 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 bisstearic acid amide, pentaerythritol stearate ester, and lubricant TAF; The flame-retardant master batch according to claim 7, 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.

9. 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.

10. 10. The glass fiber-nylon composition of claim 9, wherein the raw material further comprises 0.1 to 2 parts by weight of an auxiliary agent, the auxiliary agent being one or more selected from the group consisting of an antioxidant, a lubricant, a stabilizer, and a preservative.

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