Organic aluminum phosphonate as well as preparation method and application thereof

Abstract

The invention provides organic aluminum phosphonate and a preparation method and application thereof.The organic aluminum phosphonate has the structure shown in the formula I. The organic aluminum phosphonate is amino trialkyl aluminum phosphonate, molecules of the organic aluminum phosphonate contain a specific content of crystal water and a specific crystal structure, and the organic aluminum phosphonate has excellent flame retardance and stability and can cooperate with dialkyl phosphinate to achieve the flame retardant effect; according to the present invention, the flame retardant is added, such that the polymer composition containing the flame retardant has advantages of excellent flame retardant property, excellent high temperature resistance, excellent high humidity resistance, no auxiliary agent precipitation problem in severe environments such as high temperature, high humidity and the like, excellent color value and excellent light transmittance, good processability, and high injection molding part qualification rate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flame retardants, and particularly relates to an organic aluminum phosphonate as well as a preparation method and application thereof. BACKGROUND

[0002] As a general halogen-free flame retardant, dialkyl phosphinic acid salt has good flame retardant performance, small addition amount, small influence on the physical properties and electrical properties of the base resin, small smoke emission during combustion, high CTI (tracking index), and is highly valued by the industry. In recent years, flame-retardant polyamides using dialkyl phosphinic acid salt have been increasingly favored by electrical and electronic industry manufacturers due to their superior mechanical and electrical properties, and have a very broad market prospect.

[0003] Aluminum diethylphosphinate is the most representative product among dialkyl phosphinic acid salts and has a wide range of applications in various plastics and elastomers, but its flame-retardant effect is not ideal when used alone and is usually used in combination with other flame retardants. For example, CN115505172A discloses a halogen-free flame retardant comprising, by weight percentage, 40-90% of aluminum diethylphosphinate, 1-60% of melamine poly(zinc phosphate) flame retardant, 1-40% of aluminum phosphite flame retardant, and 1-10% of silica aerogel; the halogen-free flame retardant has good flame-retardant performance and low smoke toxicity and smoke density when applied to nylon or polyester materials. CN116478532A discloses a polyamide composite comprising, by weight fraction, 30-60 parts of aliphatic polyamide resin, 6-18 parts of PA6T / 6I, 10-50 parts of glass fiber, 14-28 parts of flame retardant, and 0.3-1 part of antioxidant, wherein the flame retardant is selected from any one or several of a mixture of aluminum diethylphosphinate and aluminum phosphite, a mixture of aluminum diethylphosphinate and melamine polyphosphate; the polyamide composite has excellent performance in terms of flame-retardant performance and mechanical strength and helps to solve the problem of fiber floating on the surface of the product.

[0004] The flame retardant used in combination with aluminum diethylphosphinate mainly includes nitrogen-containing flame retardants such as melamine derivatives, and aluminum phosphite, and the combination of which can bring good flame-retardant synergy; however, the melamine derivatives will obviously precipitate in the product, which will bring negative effects on the sustained flame retardancy, appearance, mechanical properties and the like of the product. In comparison, the aluminum phosphite is not easy to precipitate and volatilize, has high phosphorus content, good thermal stability, and can solve the problem of fiber floating on the surface of the product, and is a widely used synergistic flame retardant in glass fiber reinforced engineering plastics. However, the dialkylphosphinic acid salt and the aluminum phosphite flame-retardant polyamide material are easily oxidized into phosphoric acid containing acidic groups in the high-temperature extrusion and injection molding process due to the strong reducing P-H bond in the aluminum phosphite, which causes the surrounding polymer to dehydrate and carbonize, resulting in a large color value of the obtained polymer, especially the whiteness is obviously affected, and the light transmittance of the obtained product is seriously reduced.

[0005] Therefore, it is an urgent problem to be solved in the field to develop a flame-retardant additive which has good flame-retardant effect, is not easy to precipitate, and does not bring negative effects on the color value and light transmittance of the polymer product. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide an organic aluminum phosphite and a preparation method and application thereof, the organic aluminum phosphite having a specific crystal water content and crystal form, and the structure of which is stable, can synergistically play a flame-retardant effect with dialkylphosphinic acid salt, and the polymer composition containing the same has excellent flame-retardant properties, does not have the problem of additive precipitation under high temperature and high humidity, and can maintain excellent color value and light transmittance.

[0007] To achieve this purpose, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides an organic aluminum phosphite, the organic aluminum phosphite having a structure as shown in Formula I:

[0009]

[0010] In Formula I, R is selected from any one of C1-C6 (for example, C1, C2, C3, C4, C5, C6) straight-chain or branched alkylene, phenylene.

[0011] In Formula I, c>3, 1≤d≤8, and 6b=3c+d; 1≤e≤3.

[0012] The organic phosphonate aluminum provided by the present application has a structure as shown in Formula I, which is an amino trialkylene phosphonic acid aluminum salt, and contains a specific content of crystal water in the molecule, has a specific crystal structure, and the crystal water structure is relatively stable and will not be separated at a temperature lower than 170 DEG C. The organic phosphonate aluminum has excellent flame retardancy and stability, can synergistically play a flame retardant effect with a dialkyl phosphinic acid salt, so that the polymer composition containing the same has excellent flame retardant performance and high temperature and high humidity resistance, and will not have the problem of additive precipitation in harsh environments such as high temperature and high humidity, while maintaining excellent color value and light transmittance, and the polymer composition has good processability and high qualified rate of injection molding parts.

[0013] The following is a preferred technical scheme of the present application, but is not a limitation on the technical scheme provided by the present application. Through the following preferred technical scheme, the purpose and beneficial effects of the present application can be better achieved and realized.

[0014] In the present application, the C1-C6 linear or branched alkylene group can be a linear or branched alkylene group of C1, C2, C3, C4, C5 or C6, for example, methylene, ethylene, linear or branched propylene, linear or branched butylene, linear or branched pentylene, linear or branched hexylene.

[0015] Preferably, R is selected from any one of C1-C4 linear or branched alkylene group, and further preferably methylene or ethylene.

[0016] In the present application, b>1.6, for example, can be 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5 or 3.8, and specific point values between the above point values. Limited by the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range, and preferably, b is 3.

[0017] In Formula I, c>3, for example, can be 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2 or 5.5, and specific point values between the above point values. Limited by the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range, and preferably, 3.5≤c≤5.

[0018] In Formula I, 1≤d≤8, for example, d can be 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 5, 7, 7.5 or 7.9, and specific point values between the above point values. Limited by the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range, and preferably, 4≤d≤7.8.

[0019] In formula I, 1≤e≤3, for example, e can be 1.2, 1.5, 1.8, 2, 2.2, 2.5 or 2.8, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0020] As a preferred technical solution of the present application, in the structure shown in formula I, b represents the number of amino trialkylene phosphonic acid anions, c represents the number of aluminum ions, the values of b and c can be regulated by the ratio of the raw materials for providing amino trialkylene phosphonic acid anions (such as amino trialkylene phosphonic acid, water-soluble amino trialkylene phosphonic acid salt) and the raw materials for providing aluminum ions (such as aluminum salt, aluminum hydroxide, etc.). d represents the number of hydrogen ions, which can be regulated by the ratio of the raw materials for providing amino trialkylene phosphonic acid anions (such as amino trialkylene phosphonic acid, water-soluble amino trialkylene phosphonic acid salt), the raw materials for providing aluminum ions (such as aluminum salt, aluminum hydroxide, etc.) and the pH value in the preparation process. e represents the number of crystal water, which can be regulated by the concentration of the surfactant, the raw materials of amino trialkylene phosphonic acid anions (such as amino trialkylene phosphonic acid, water-soluble amino trialkylene phosphonic acid salt) in the solution.

[0021] Preferably, the average particle size of the aluminum organophosphate is 10-60 μm, for example, it can be 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm or 58 μm, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0022] Preferably, the D90 of the aluminum organophosphate is 10-60 μm, for example, it can be 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm or 58 μm, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range. 10 The particle size is 5-25 μm, for example, it can be 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm or 24 μm, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range, further preferably 10-20 μm.

[0023] Preferably, the D90 of the aluminum organophosphate is 10-60 μm, for example, it can be 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm or 58 μm, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range. 90 The particle size is 40-80 μm, for example, it can be 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm or 78 μm, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range, further preferably 48-65 μm.

[0024] In the present application, the term "average particle size" is also referred to as D 50 The particle size is the particle size corresponding to the volume cumulative distribution percentage of 50% of the aluminum organophosphonate. 10 The particle size, D 90 The particle sizes, D 10 , D 50 , D 90 The particle size can be determined by referring to the standard GB / T 19077-2016 Particle Size Distribution Laser Diffraction Method, using a laser particle size analyzer.

[0025] In a second aspect, the present application provides a preparation method of the aluminum organophosphonate according to the first aspect, which comprises the following steps:

[0026] The aqueous solution of the organic phosphonic acid is subjected to a neutralization reaction with an aqueous solution of an alkaline compound to obtain an aqueous solution of a water-soluble organic phosphonate salt;

[0027] The aqueous solution of the water-soluble organic phosphonate salt is subjected to a double decomposition reaction with an aluminum salt mixed solution to obtain the aluminum organophosphonate;

[0028] The organic phosphonic acid has a structure as shown in Formula II:

[0029]

[0030] wherein R has the same definition as in Formula I;

[0031] The mass percentage content of the organic phosphonic acid in the aqueous solution of the organic phosphonic acid is 5-20%; and the aluminum salt mixed solution comprises a water-soluble aluminum salt, a surfactant and water.

[0032] In the preparation method of the aluminum organophosphonate provided by the present application, by introducing a surfactant and controlling the process steps, the obtained aluminum organophosphonate has a specific crystal structure, and the content of crystal water is controlled, so that the crystal water structure is more stable.

[0033] In the present application, the mass percentage content of the organic phosphonic acid in the aqueous solution of the organic phosphonic acid is 5-20%, for example, it can be 6%, 8%, 10%, 12%, 14%, 15%, 16% or 18%, and specific point values between the above point values. Due to the limitation of the length and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range.

[0034] Preferably, the alkaline compound comprises sodium hydroxide and / or potassium hydroxide.

[0035] Preferably, the mass percentage of the basic compound in the aqueous solution of the basic compound is 20%-50%, for example, it can be 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, or 48%, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application does not enumerate the specific point values included in the range, and further preferably 35%-42%.

[0036] Preferably, the temperature of the neutralization reaction is 10-80℃, for example, it can be 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, or 75℃, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application does not enumerate the specific point values included in the range, and further preferably 20-50℃.

[0037] Preferably, the time of the neutralization reaction is 20-60min, for example, it can be 25min, 30min, 35min, 40min, 45min, 50min, or 55min, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application does not enumerate the specific point values included in the range.

[0038] Preferably, the pH value of the aqueous solution of the water-soluble organic phosphonate is 3-10, for example, it can be 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, or 9.5, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application does not enumerate the specific point values included in the range, and further preferably 4-9.5.

[0039] Preferably, the water-soluble aluminum salt includes any one or a combination of at least two of aluminum sulfate, aluminum sulfate hydrate, and aluminum chloride, and further preferably aluminum sulfate and / or aluminum sulfate hydrate.

[0040] Preferably, the molar amount of Al element in the aluminum salt mixed solution is denoted as n1, the molar amount of organic phosphonic acid in the aqueous solution of organic phosphonic acid is denoted as n2, n1 / n2=a·c / b, a is 0.98-1.02, for example, a can be 0.982, 0.985, 0.988, 0.99, 0.992, 0.995, 0.998, 0.999, 1, 1.002, 1.005, 1.008, 1.01, 1.012, 1.015, or 1.018, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application does not enumerate the specific point values included in the range, and further preferably 0.99-1.012. b and c have the same definition as in formula I.

[0041] Preferably, the surfactant comprises an anionic surfactant, further preferably a sulfonic acid surfactant, more preferably a C8-C20 (e.g., C10, C12, C14, C16, C18, etc.) alkyl benzene sulfonate and / or a C8-C20 (e.g., C10, C12, C14, C16, C18, etc.) alkyl sulfonate.

[0042] Further preferably, the sulfonic acid surfactant comprises a dodecyl benzene sulfonate and / or a dodecyl sulfonate.

[0043] Preferably, the cation in the sulfonic acid surfactant comprises a sodium ion, a potassium ion, a calcium ion, or an ammonium ion, more preferably a sodium ion.

[0044] Preferably, the mass percentage of the water-soluble aluminum salt in the aluminum salt mixture is 10%-30%, for example, it can be 12%, 15%, 18%, 20%, 22%, 25%, or 28%, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range.

[0045] Preferably, the mass percentage of the surfactant in the aluminum salt mixture is 0.001%-0.1%, for example, it can be 0.002%, 0.005%, 0.008%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, or 0.09%, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range.

[0046] Preferably, the aluminum salt mixture is added to the water-soluble organic phosphonate salt solution and a metathesis reaction is carried out to obtain the aluminum organophosphonate.

[0047] Preferably, the aluminum salt mixture is added for 30-90 min, for example, it can be 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, or 85 min, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range.

[0048] Preferably, the temperature of the metathesis reaction is 10-100℃, for example, it can be 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃ or 95℃, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application does not list the specific point values included in the range, further preferably 40-95℃.

[0049] Preferably, the time of the metathesis reaction is 30-90min, for example, it can be 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application does not list the specific point values included in the range.

[0050] Preferably, after the metathesis reaction is completed, the step of post-treatment is further included, and the post-treatment includes filtering, washing and drying.

[0051] Preferably, the washing used in the washing includes water.

[0052] Preferably, the number of times of the washing is 1-5 times, for example, it can be 2 times, 3 times, 4 times, etc.

[0053] Preferably, the temperature of the drying is 105-150℃, for example, it can be 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃ or 145℃, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application does not list the specific point values included in the range.

[0054] In a third aspect, the present application provides an application of the aluminum organophosphonate as described in the first aspect in a polymer material.

[0055] Preferably, the aluminum organophosphonate is applied as a flame retardant additive in the polymer material.

[0056] In a fourth aspect, the present application provides a flame retardant composition, which includes a dialkyl phosphinic acid salt and the aluminum organophosphonate as described in the first aspect.

[0057] Preferably, the dialkyl phosphinic acid salt has a structure as shown in formula III:

[0058]

[0059] In formula III, R1, R2are each independently selected from any one of C1-C6 linear or branched alkyl, C3-C6 cycloalkyl, C6-C12 aryl.

[0060] In formula III, M n+ represents a +n-valent metal ion, n is 2 or 3.

[0061] In formula III, the C1-C6 linear or branched alkyl group can be a C1, C2, C3, C4, C5, C6 linear or branched alkyl group, exemplarily including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, etc. The C3-C6 cycloalkyl group can be a C3, C4, C5, C6 cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The C6-C12 aryl group can be a C6, C9, C10, C12 aryl group, for example, phenyl, naphthyl, biphenyl, etc.

[0062] Preferably, each of R1, R2 is independently selected from any one of C1-C4 linear or branched alkyl group.

[0063] Preferably, M n+ is Al 3+ or Zn 2+ , more preferably Al 3+ .

[0064] Preferably, the flame retardant composition comprises, in parts by mass: a dialkylphosphinic acid salt 40-95 parts, the aluminum organophosphonate 5-60 parts.

[0065] Preferably, the dialkylphosphinic acid salt is in parts by mass 40-95 parts, for example, can be 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be exhaustively listed specific point values included in the range.

[0066] Preferably, the aluminum organophosphonate is in parts by mass 5-60 parts, for example, can be 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be exhaustively listed specific point values included in the range.

[0067] In a fifth aspect, the present application provides a polymer composition, the polymer composition comprising a combination of a polymer matrix and a flame retardant additive, the flame retardant additive comprising any one of the aluminum organophosphonate as described in the first aspect or the flame retardant composition as described in the fourth aspect.

[0068] Preferably, the polymer composition comprises, in parts by mass:

[0069] polymer base 40-99 parts by mass

[0070] dialkylphosphinic acid salt 5-30 parts by mass

[0071] aluminum organophosphonate 0.1-15 parts by mass.

[0072] Preferably, the polymer base is 40-99 parts by mass, for example, it can be 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 point values between the above point values, the present application will not be exhausted to enumerate the specific point values included in the range, limited to the length and for the sake of simplicity.

[0073] Preferably, the dialkylphosphinic acid salt is 5-30 parts by mass, for example, it can be 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, or 28 parts, and specific point values between the above point values, the present application will not be exhausted to enumerate the specific point values included in the range, limited to the length and for the sake of simplicity.

[0074] Preferably, the aluminum organophosphonate is 0.1-15 parts by mass, for example, it can be 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 8 parts, 10 parts, 11 parts, 12 parts, or 14 parts, and specific point values between the above point values, the present application will not be exhausted to enumerate the specific point values included in the range, limited to the length and for the sake of simplicity.

[0075] Preferably, the polymer base includes any one or a combination of at least two of a polyamide, a polyester, a polyurethane, a styrene-based polymer, a polyolefin, a polyphenylene ether, a polyacrylate.

[0076] Preferably, the polyamide includes any one or a combination of at least two of a polyamide resin, a polyamide elastomer.

[0077] As a polyamide, it includes any one or a combination of at least two of a condensation product of a dicarboxylic acid and a diamine, a condensation product of an omega-amino acid, a ring-opening polymerization product of a cyclic lactam. The dicarboxylic acid exemplarily includes, but is not limited to, any one or a combination of at least two of adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid. The diamine exemplarily includes, but is not limited to, any one or a combination of at least two of pentamethylene diamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, butanediamine, terephthaline, isophthaline. The cyclic lactam exemplarily includes, but is not limited to, any one or a combination of at least two of caprolactam, caprylolactam, undecanolactam, laurolactam. The omega-amino acid exemplarily includes, but is not limited to, any one or a combination of at least two of the omega-amino acid ring-opened from the aforementioned cyclic lactam, aminobenzoic acid.

[0078] Exemplarily, the polyamide includes any one or a combination of at least two of polyamide 6 (polycaprolactam), polyamide 11 (polyundecanolactam), polyamide 12 (polylauro lactam), polyamide 56 (polypentamethylene adipate), polyamide 66 (polyhexamethylene adipate), polyamide 610 (polydecamethylene adipate), polyamide 612 (polydodecamethylene adipate), polyamide 1010 (polydecamethylene sebacate), polyamide 1012 (polydecamethylene dodecanedioate), polyamide 1212 (polydodecamethylene dodecanedioate), polyamide 6T (polyterephthaloyl hexamethylene), polyamide 10T (polyterephthaloyl decamethylene), PPA (polyterephthaloyl paraphthaline).

[0079] Exemplarily, the polyamide elastomer includes hard segments from a polyamide and soft segments from a polyol, which includes a polyether polyol and / or a polyester polyol, preferably a polyether polyol.

[0080] Preferably, the polyester includes a condensation product of a dicarboxylic acid and / or a derivative thereof and a dihydric alcohol, wherein the dicarboxylic acid exemplarily includes, but is not limited to, any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, hydrogenated phthalic acid, and a derivative thereof including an acid halide (acid chloride), an ester, an anhydride, etc. formed from the dicarboxylic acid. The dihydric alcohol exemplarily includes, but is not limited to, any one or a combination of at least two of ethylene glycol, butylene glycol, hexanediol.

[0081] Exemplarily, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0082] Preferably, the polyurethane includes a polyurethane resin and / or a polyurethane elastomer.

[0083] Preferably, the polyurethane comprises a reaction product of a polyol and an isocyanate, wherein the polyol illustratively includes, but is not limited to, any one or a combination of at least two of a polyether polyol, a polyester polyol, a polylactone polyol, a polycarbonate polyol.

[0084] Preferably, the styrene-based polymer comprises any one or a combination of at least two of a styrene homopolymer (PS), a styrene-acrylate copolymer, a styrene-olefin copolymer, a styrene-olefin-acrylonitrile copolymer; the styrene-olefin copolymer illustratively includes, but is not limited to, any one or a combination of at least two of a styrene-(ethylene-propylene) diblock copolymer, a styrene-(ethylene-butylene)-ethylene triblock copolymer, a styrene-isoprene diblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene-ethylene-isoprene terpolymer.

[0085] Preferably, the polyolefin comprises any one or a combination of at least two of a polyethylene, an alpha olefin homopolymer, an alpha olefin copolymer, an ethylene-alpha olefin copolymer, an ethylene-alpha olefin-diene copolymer; wherein the alpha olefin illustratively includes, but is not limited to, any one or a combination of at least two of propylene, butene, pentene, hexene, heptene, octene; the diene illustratively includes, but is not limited to, any one or a combination of at least two of butadiene, isoprene, hexadiene.

[0086] Preferably, the dialkyl phosphinic acid salt has a structure as shown in Formula III, and further preferably comprises any one or a combination of at least two of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate.

[0087] It is noted that the polymer composition of the present application can further include any other auxiliary agent that is desirable in the art.

[0088] Preferably, the polymer composition further comprises 0-45 parts by mass of a reinforcing material, the parts by mass of the reinforcing material can be 0, 0.5, 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 42, or 44 parts, and specific point values between the above-mentioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and conciseness.

[0089] Preferably, the reinforcing material comprises glass fiber and / or carbon fiber.

[0090] Preferably, the polymer composition further includes 0-40 parts by mass of a filler, which can be 0, 0.5, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, or 38 parts by mass, and specific point values between the aforementioned point values, without the specific point values included in the range being exhaustively listed due to the limitation of the length and for the sake of brevity.

[0091] Preferably, the filler includes any one or a combination of at least two of silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass beads.

[0092] Preferably, the polymer composition further includes 0-15 parts by mass of other additives, which can be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14 parts by mass, and specific point values between the aforementioned point values, without the specific point values included in the range being exhaustively listed due to the limitation of the length and for the sake of brevity.

[0093] Preferably, the other additives include any one or a combination of at least two of an antioxidant, an ultraviolet absorber, a lubricant, a nucleating agent, a stabilizer, an antistatic agent, and a colorant.

[0094] Preferably, the parts by mass of the antioxidant, the ultraviolet absorber, the lubricant, and the nucleating agent in the polymer composition are each independently 0.01-2, such as 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, or 1.8, and specific point values between the aforementioned point values, without the specific point values included in the range being exhaustively listed due to the limitation of the length and for the sake of brevity.

[0095] Preferably, the antioxidant includes any one or a combination of at least two of a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

[0096] In one preferred technical solution, the polymer composition includes the following components by parts by mass:

[0097]

[0098] Preferably, the polymer matrix is present in the polymer composition in an amount of 40% to 99% by weight, for example 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98%, and specific values between the foregoing are included, subject to the limitation that the application is not intended to be exhausted by restricting the application to the specific embodiments shown and described.

[0099] The dialkylphosphinic acid salt and the organoaluminum phosphinate have synergistic flame retardant effect, preferably, the dialkylphosphinic acid salt is present in the polymer composition in an amount of 5% to 30% by weight, for example 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, or 28%, and specific values between the foregoing are included, subject to the limitation that the application is not intended to be exhausted by restricting the application to the specific embodiments shown and described, further preferably 6% to 20%.

[0100] Preferably, the organoaluminum phosphinate of formula I is present in the polymer composition in an amount of 0.1% to 15% by weight, for example 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or 14%, and specific values between the foregoing are included, subject to the limitation that the application is not intended to be exhausted by restricting the application to the specific embodiments shown and described, further preferably 1% to 8%.

[0101] Preferably, the method for preparing the polymer composition comprises: melt blending the components of the polymer composition and then extruding to obtain the polymer composition.

[0102] Preferably, the polymer matrix, the dialkylphosphinic acid salt, the organoaluminum phosphinate, the optional reinforcing material, the optional filler, and the optional other additives are first premixed to obtain a premix; and then the premix is melt blended and extruded to obtain the polymer composition.

[0103] Preferably, the melt blending is performed in a screw extruder.

[0104] Preferably, the screw extruder is a twin-screw extruder.

[0105] Preferably, the temperature of the screw extruder is 180 to 330°C, for example 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, or 320°C, and specific values between the foregoing are included, subject to the limitation that the application is not intended to be exhausted by restricting the application to the specific embodiments shown and described.

[0106] Preferably, the extrusion is followed by the steps of granulation and drying.

[0107] Compared with the prior art, the present application has the following beneficial effects:

[0108] The organic aluminum phosphonate provided by the present application has a structure as shown in Formula I, is an amino trialkylene phosphonic acid aluminum salt, contains specific content of crystal water and specific crystal structure in the molecule, has excellent flame retardancy and stability, can synergistically play a flame retardant effect with dialkyl phosphinic acid salt, makes the polymer composition containing the same have excellent flame retardant performance and high temperature and high humidity resistance, does not have the problem of additive precipitation in harsh environments such as high temperature and high humidity, meanwhile, excellent color value and light transmittance are maintained, and the polymer composition has good processability and high qualified rate of injection molding parts. DETAILED DESCRIPTION

[0109] The technical solutions of the present application are further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0110] The terms "comprising", "including", "having", "containing", or any other similar term as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but can include other elements not explicitly listed or inherent to such composition, step, method, article, or apparatus.

[0111] In the following detailed description, the test methods of various parameters of the organic aluminum phosphonate are as follows:

[0112] (1)D 10 Particle size, D 50 Particle size, D 90 Particle size

[0113] The particle size is determined by referring to the standard GB / T 19077-2016 particle size distribution laser diffraction method, and using a laser particle size analyzer (LS-POP(6), Zhuhai OMEC).

[0114] (2) b, c, d

[0115] The test is performed by referring to HJ 776-2014 inductively coupled plasma mass spectrometry, and using an inductively coupled plasma spectrometer. Specifically, 0.2 g of the sample to be tested is added into 10 mL of sulfuric acid solution (30 wt%) and dissolved for 60 min to ensure complete dissolution of the sample. Then, the treated sample solution is diluted to 150 ppm, and then fed into an inductively coupled plasma spectrometer (ICP, model PerkinElmer 8300) for qualitative and quantitative analysis test.

[0116] (3) e

[0117] Take 10 mg of the sample to be tested in a thermogravimetric analyzer, heated at a temperature rate of 20 ℃ / min, the instrument will automatically record the mass of the sample at different temperatures, thereby obtaining the thermogravimetric curve. From the curve, a clear weight loss stage can be seen at 105-250 ℃, and the content of crystallization water can be calculated according to the proportion of weight loss.

[0118] The organic aluminum phosphonate and the preparation method thereof will be described in detail below with a plurality of examples as examples, but the organic aluminum phosphonate and the preparation method thereof are not limited to these examples.

[0119] In the following specific embodiments, the organic phosphonic acid (aminotrimethylenephosphonic acid, aminotriethylenephosphonic acid), the basic compound (NaOH), the soluble aluminum salt (aluminum sulfate octadecahydrate), and the surfactant (sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate) are all commercially available chemicals.

[0120] Example 1

[0121] An organic aluminum phosphonate A1 having the structure shown in formula I, R is methylene, and the preparation method is as follows:

[0122] An aqueous aminotrimethylenephosphonic acid solution 14950 g (aminotrimethylenephosphonic acid is 5 mol, mass content 10%) is added to a reactor, and an aqueous NaOH solution (NaOH mass content 40%) is added thereto, and a neutralization reaction is carried out at room temperature, so that the pH value of the obtained salt solution is 7.5; the salt solution is stirred and heated to 60 ℃, and an aqueous aluminum sulfate octadecahydrate solution 11100 g (aluminum sulfate octadecahydrate is 3.3333 mol, mass content 20%) is added thereto within 60 min, and 0.55 g of sodium dodecyl benzene sulfonate is contained therein, to generate a solid precipitate, which is cooled, filtered, washed with water, and dried, to obtain an organic aluminum phosphonate A1 of 1654.7 g, and the related parameters are shown in Table 1.

[0123] Example 2

[0124] An organic aluminum phosphonate A2 having the structure shown in formula I, R is methylene, and the preparation method is as follows:

[0125] An aqueous aminotrimethylenephosphonic acid solution 14950 g (aminotrimethylenephosphonic acid is 5 mol, mass content 10%) is added to a reactor, and an aqueous NaOH solution (NaOH mass content 40%) is added thereto, and a neutralization reaction is carried out at room temperature, so that the pH value of the obtained salt solution is 7.8; the salt solution is stirred and heated to 75 ℃, and an aqueous aluminum sulfate octadecahydrate solution 11100 g (aluminum sulfate octadecahydrate is 3.3333 mol, mass content 20%) is added thereto within 60 min, and 0.3 g of sodium dodecyl benzene sulfonate is contained therein, to generate a solid precipitate, which is cooled, filtered, washed with water, and dried, to obtain an organic aluminum phosphonate A2 of 1675.6 g, and the related parameters are shown in Table 1.

[0126] Example 3

[0127] An organic phosphonate aluminum A3 having the structure shown in Formula I, R is methylene, and the preparation method is as follows:

[0128] Amino trimethylene phosphonic acid aqueous solution 14950 g (amino trimethylene phosphonic acid is 5 mol, mass content 10%) is added into a reactor, NaOH aqueous solution (NaOH mass content 40%) is added into it, neutralization reaction is carried out at room temperature, so that the pH value of the obtained salt solution is 7.8; the salt solution is stirred and heated to 80°C, aluminum sulfate octadecahydrate aqueous solution 11100 g (aluminum sulfate octadecahydrate is 3.3333 mol, mass content 20%) is added within 60 min, and 0.2 g of sodium dodecyl benzene sulfonate is contained therein, solid precipitate is generated, cooling, filtration, water washing, and drying are carried out, so that organic phosphonate aluminum A3 is obtained, a total of 1697.9 g, and the related parameters are shown in Table 1.

[0129] Example 4

[0130] An organic phosphonate aluminum A4 having the structure shown in Formula I, R is methylene, and the preparation method is as follows:

[0131] Amino trimethylene phosphonic acid aqueous solution 14950 g (amino trimethylene phosphonic acid is 5 mol, mass content 10%) is added into a reactor, NaOH aqueous solution (NaOH mass content 40%) is added into it, neutralization reaction is carried out at room temperature, so that the pH value of the obtained salt solution is 9.4; the salt solution is stirred and heated to 65°C, aluminum sulfate octadecahydrate aqueous solution 12820 g (aluminum sulfate octadecahydrate is 3.85 mol, mass content 20%) is added within 60 min, and 0.3 g of sodium dodecyl benzene sulfonate is contained therein, solid precipitate is generated, cooling, filtration, water washing, and drying are carried out, so that organic phosphonate aluminum A4 is obtained, a total of 1692 g, and the related parameters are shown in Table 1.

[0132] Example 5

[0133] An organic phosphonate aluminum A5 having the structure shown in Formula I, R is methylene, and the preparation method is as follows:

[0134] Amino-trimethylene phosphonic acid aqueous solution 14950g (amino-trimethylene phosphonic acid 5mol, mass content 10%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 4.5; the salt solution was heated to 45°C under stirring, aluminum sulfate octadecahydrate aqueous solution 9824g (aluminum sulfate octadecahydrate 2.95mol, mass content 20%) was added into the salt solution within 60min, and 0.3g of sodium dodecyl benzene sulfonate was contained in the aluminum sulfate octadecahydrate aqueous solution, solid precipitate was generated, and the solid precipitate was cooled, filtered, washed with water, and dried to obtain 1656g of organic aluminum phosphonate A5, and the related parameters are shown in Table 1.

[0135] Example 6

[0136] An organic aluminum phosphonate A6 having the structure shown in Formula I, R is ethylene, and the preparation method is as follows:

[0137] Amino-trimethylene phosphonic acid aqueous solution 14950g (amino-trimethylene phosphonic acid 5mol, mass content 10%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 4.5; the salt solution was heated to 45°C under stirring, aluminum sulfate octadecahydrate aqueous solution 9824g (aluminum sulfate octadecahydrate 2.95mol, mass content 20%) was added into the salt solution within 60min, and 0.3g of sodium dodecyl benzene sulfonate was contained in the aluminum sulfate octadecahydrate aqueous solution, solid precipitate was generated, and the solid precipitate was cooled, filtered, washed with water, and dried to obtain 1656g of organic aluminum phosphonate A5, and the related parameters are shown in Table 1.

[0138] Comparative Example 1

[0139] An organic aluminum phosphonate D1, and the preparation method is as follows:

[0140] Amino-trimethylene phosphonic acid aqueous solution 14950g (amino-trimethylene phosphonic acid 5mol, mass content 10%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 4.5; the salt solution was heated to 45°C under stirring, aluminum sulfate octadecahydrate aqueous solution 9824g (aluminum sulfate octadecahydrate 2.95mol, mass content 20%) was added into the salt solution within 60min, and 0.3g of sodium dodecyl benzene sulfonate was contained in the aluminum sulfate octadecahydrate aqueous solution, solid precipitate was generated, and the solid precipitate was cooled, filtered, washed with water, and dried to obtain 1656g of organic aluminum phosphonate A5, and the related parameters are shown in Table 1.

[0141] Comparative Example 2

[0142] An organic aluminum phosphonate D2, and the preparation method is as follows:

[0143] Amino triethylene phosphonic acid aqueous solution 3789g (amino triethylene phosphonic acid 5mol, mass content 45%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 7.5; the salt solution was heated to 60°C under stirring, aluminum sulfate octadecahydrate aqueous solution 11100g (aluminum sulfate octadecahydrate 3.3333mol, mass content 20%) was added into the salt solution within 60min, solid precipitate was generated, and the precipitate was cooled, filtered, washed with water, and dried to obtain 1936.5g of organic aluminum phosphonate D2, and the related parameters are shown in Table 1.

[0144] Comparative Example 3

[0145] An organic aluminum phosphonate D3 was prepared by the following method:

[0146] Amino triethylene phosphonic acid aqueous solution 17350g (amino triethylene phosphonic acid 5mol, mass content 10%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 4.0; the salt solution was heated to 60°C under stirring, aluminum sulfate octadecahydrate aqueous solution 3247g (aluminum sulfate octadecahydrate 1.95mol, mass content 40%) was added into the salt solution within 60min, and the aluminum sulfate octadecahydrate aqueous solution contained 0.3g of sodium dodecyl benzene sulfonate, solid precipitate was generated, and the precipitate was cooled, filtered, washed with water, and dried to obtain 1332g of organic aluminum phosphonate D3, and the related parameters are shown in Table 1.

[0147] Comparative Example 4

[0148] An organic aluminum phosphonate D4 was prepared by the following method:

[0149] Amino trimethylene phosphonic acid aqueous solution 3738g (amino trimethylene phosphonic acid 5mol, mass content 40%) was added into a reactor, NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, neutralization reaction was carried out at room temperature, and the pH value of the obtained salt solution was 7.8; the salt solution was heated to 75°C under stirring, aluminum sulfate octadecahydrate aqueous solution 11100g (aluminum sulfate octadecahydrate 3.3333mol, mass content 20%) was added into the salt solution within 60min, and the aluminum sulfate octadecahydrate aqueous solution contained 0.3g of sodium dodecyl benzene sulfonate, solid precipitate was generated, and the precipitate was cooled, filtered, washed with water, and dried to obtain 1613.6g of organic aluminum phosphonate D4, and the related parameters are shown in Table 1.

[0150] Comparative Example 5

[0151] An organic aluminum phosphonate D5 was prepared by the following method:

[0152] Amino-trimethylene phosphonic acid aqueous solution 3738 g (amino-trimethylene phosphonic acid 5 mol, mass content 40%) was added into a reactor, and NaOH aqueous solution (NaOH mass content 40%) was added into the reactor, and a neutralization reaction was carried out at room temperature, so that the pH value of the obtained salt solution was 7.8; the salt solution was heated to 75°C under stirring, and aluminum sulfate octadecahydrate aqueous solution 11100 g (aluminum sulfate octadecahydrate 3.3333 mol, mass content 20%) was added into the salt solution within 60 min, a solid precipitate was generated, and the precipitate was cooled, filtered, washed with water, and dried to obtain 1730 g of aluminum organophosphate D5, and the related parameters are shown in Table 1.

[0153] Table 1

[0154]

[0155] The application of the organic phosphorus flame retardant described in the application will be described in detail below by taking application examples as examples, but the application of the organic phosphorus flame retardant is not limited to these application examples.

[0156] In the following application examples, the specific information of the materials used is as follows:

[0157] Grade, manufacturer Polyamide 66 (PA66) PA66 U4800 NC01 SS, Inventa-Polymer Co., Ltd. Polyamide 6 (PA6) HY2800A, Haiyang Chemical Fiber Group Glass fiber ECS301HP-3-H, Chongqing International Composite Material Co., Ltd. Aluminum diethylphosphinate Commercially available Synergistic flame retardant A1-A6 Examples 1-6 Synergistic flame retardant D1-D5 Comparative examples 1-5 Aluminum phosphite Commercially available Melamine polyphosphate Commercially available Antioxidant 1098 Commercially available Antioxidant 168 Commercially available

[0158] Application Examples 1-6 and Comparative Application Example 1-7

[0159] A polyamide composition includes the following components in parts by mass:

[0160]

[0161]

[0162] In the application examples 1-6 and comparative application example 1-7, the synergistic flame retardant is the organic phosphonate aluminum, aluminum phosphite, and melamine polyphosphate provided in the examples 1-6 and comparative examples 1-5, respectively.

[0163] The preparation method of the polyamide composition is as follows: the polyamide 66, polyamide 6, glass fiber, aluminum diethyl phosphinate, synergistic flame retardant, and two antioxidants are mixed according to the formula amount to obtain a premix; the premix is added to a twin-screw extruder, the screw rotation speed of the twin-screw extruder is 300 rpm, the barrel temperature of the twin-screw extruder is 180°C, 230°C, 260°C, 240°C, 240°C, 230°C, 230°C, and 230°C in zones 1-8, respectively, the head temperature is 260°C, and the polyamide composition particles are obtained by melt mixing and extrusion granulation.

[0164] The polyamide composition is tested for the following properties:

[0165] (1) Flame Retardancy: The sample to be tested is made into a 125mm x 13mm x 0.8mm sample bar by injection molding, and tested according to the method in the standard ANSI / UL-94-1985;

[0166] (2) Whiteness: The sample to be tested is made into a 80mm diameter x 4mm thick disc by injection molding, and tested using a colorimeter (USVIS / 565, Hunterlab Company, USA), which specifically includes: calibrating the colorimeter before testing, then placing the test disc in the test window, covering the back plate, and pressing the test button to test;

[0167] (3) Light transmittance: The sample to be tested is made into a 15mm diameter x 4mm thick disc by injection molding, and tested using a light transmittance and haze meter (DH-13, Caipu Technology (Zhejiang) Co., Ltd.), and calculated to obtain; wherein G is the light transmittance, %; Gt is the incident light flux; Gd is the total transmitted light flux through the sample product;

[0168] (4) Precipitation: a test disc with a length of 80mm, a width of 50mm, and a thickness of 4mm is obtained by injection molding, and the sample is placed in a constant temperature and humidity chamber under the condition of a temperature of 85℃ and a humidity of 85% for 168h; after the test is completed, the sample is taken out, visually inspected, and then detected for precipitation using a scanning electron microscope (SEM, model S-3400N, Beijing Tianmei Scientific Instrument Co., Ltd.).

[0169] The test results are shown in Table 2:

[0170] Table 2

[0171] Synergistic flame retardant Flame retardancy Whiteness L value Transmittance (%) Precipitation condition Application example 1 Organic aluminum phosphonate A1 V-0 73.9 61 No precipitation Application example 2 Organic aluminum phosphonate A2 V-0 74.2 72 No precipitation Application example 3 Organic aluminum phosphonate A3 V-0 73.7 67 No precipitation Application example 4 Organic aluminum phosphonate A4 V-0 72.8 69 No precipitation Application example 5 Organic aluminum phosphonate A5 V-0 72.1 59 No precipitation Application example 6 Organic aluminum phosphonate A6 V-0 71.0 58 No precipitation Comparative application example 1 Organic aluminum phosphonate D1 V-0 67.5 40 No precipitation Comparative application example 2 Organic aluminum phosphonate D2 V-1 68.9 52 No precipitation Comparative application example 3 Organic aluminum phosphonate D3 V-2 57.3 67 No precipitation Comparative application example 4 Organic aluminum phosphonate D4 V-0 67.8 46 No precipitation Comparative application example 5 Organic aluminum phosphonate D5 V-1 68.5 50 No precipitation Comparative application example 6 Aluminum phosphite V-0 53.3 33 No precipitation Comparative application example 7 Melamine polyphosphate V-0 69.0 36 Obvious precipitation

[0172] According to the data in Table 2, the organic aluminum phosphonate provided in Examples 1-6 has the structure shown in Formula I, and contains a specific proportion of crystal water in the molecular structure, which is stable in structure and can synergistically exert excellent flame retardant performance with aluminum diethyl phosphinate, so that the polyamide composition containing it achieves V-0 level flame retardation, while the L value is ≥71 and the light transmittance is ≥58%, maintaining excellent color value and light transmittance, and without the problem of additive precipitation in a double 85 high temperature and high humidity environment.

[0173] The organic aluminum phosphonates in Comparative Examples 1-5 do not have the structure shown in Formula I, resulting in a decrease in the flame retardant performance, whiteness, and light transmittance of the polyamide composition containing them in Comparative Application Examples 1-5 to varying degrees.

[0174] ​According to the application examples 1-6 and the comparative application examples 6-7, compared with aluminum phosphite and melamine polyphosphate, the organic aluminum phosphonate provided by the application not only has excellent performance in synergistic flame retardancy, but also overcomes the defect that melamine polyphosphate is easy to precipitate, and effectively avoids the negative influence of aluminum phosphite on the whiteness and light transmittance of polymer products. Therefore, the organic aluminum phosphonate with the structure of formula I provided by the application has excellent comprehensive performance as a flame retardant aid.

[0175] The applicant declares that the organic aluminum phosphonate, the preparation method and the application thereof of the application are illustrated by the above examples, but the application is not limited to the above examples, that is, it does not mean that the application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the application, equivalent replacement of each raw material of the product of the application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the application.

Claims

1. An aluminum organophosphonate characterized in that, The organic aluminum phosphonate has a structure as shown in Formula I: wherein R is selected from any one of C1-C6 linear or branched alkylene, phenylene; c>3, 1≤d≤8, and 6b=3c+d; 1≤e≤3。 2. The aluminum organophosphonate of claim 1, wherein, The R is selected from any one of C1-C4 linear or branched alkylene, preferably methylene or ethylene.

3. The aluminum organophosphonate of claim 1, wherein, The b is 3; and / or, 3.5≤c≤5; and / or, 4≤d≤7.

8.

4. The aluminum organophosphonate of claim 1, wherein, The average particle size of the organic aluminum phosphonate is 10-60 μm.

5. A process for the preparation of the aluminum organophosphonate according to any one of claims 1 to 4, characterized in that The preparation method comprises the following steps: neutralizing the aqueous organic phosphonic acid solution with an aqueous alkaline compound solution to obtain an aqueous organic phosphonate solution; The aqueous organic phosphonate solution is subjected to a metathesis reaction with an aluminum salt mixture to obtain the organic aluminum phosphonate; The organic phosphonic acid has a structure as shown in Formula II: wherein R has the same definition as in Formula I; The mass percentage of the organic phosphonic acid in the aqueous organic phosphonic acid solution is 5%-20%; The aluminum salt mixture comprises a water-soluble aluminum salt, a surfactant, and water.

6. The production method according to claim 5, wherein The alkaline compound comprises sodium hydroxide and / or potassium hydroxide; Preferably, the mass percentage of the alkaline compound in the aqueous alkaline compound solution is 20%-50%; Preferably, the temperature of the neutralization reaction is 10-80°C, further preferably 20-50°C; Preferably, the pH value of the aqueous organic phosphonate solution is 3-10, further preferably 4.2-9.

5.

7. The preparation method according to claim 5, characterized in that, The water-soluble aluminum salt comprises any one of aluminum sulfate, aluminum sulfate hydrate, aluminum chloride, or a combination of at least two thereof; Preferably, the surfactant comprises an anionic surfactant, further preferably a sulfonic surfactant; Preferably, the mass percentage of the water-soluble aluminum salt in the aluminum salt mixture is 10%-30%; Preferably, the mass percentage of the surfactant in the aluminum salt mixture is 0.001%-0.1%; Preferably, the temperature of the metathesis reaction is 10-100°C, further preferably 40-95°C; Preferably, the time of the metathesis reaction is 30-90 min; Preferably, the metathesis reaction is followed by a post-treatment step, which comprises filtration, washing, and drying.

8. Use of the organic aluminum phosphonate according to any one of claims 1-4 in a polymeric material; Preferably, the organic aluminum phosphonate is used as a flame retardant additive in the polymeric material.

9. A flame retardant composition characterized in that, The flame retardant composition comprises a dialkyl phosphinic acid salt and the organic aluminum phosphonate according to any one of claims 1-4.

10. A polymer composition characterized in that, The polymeric composition comprises a combination of a polymeric matrix and a flame retardant additive, which comprises any one of the organic aluminum phosphonate according to any one of claims 1-4 or the flame retardant composition according to claim 9; Preferably, the polymeric composition comprises the following components in parts by mass: polymeric matrix 40-99 parts dialkyl phosphinic acid salt 5-30 parts the organic aluminum phosphonate 0.1-15 parts; Preferably, the polymeric matrix comprises any one of polyamide, polyester, polyurethane, styrene-based polymer, polyolefin, polyphenylene ether, polyacrylate, or a combination of at least two thereof. Preferably, the dialkylphosphinic acid salt comprises any one of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate or a combination of at least two thereof. Preferably, the dialkylphosphinic acid salt comprises any one of aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate or a combination of at least two thereof.

Images