Rare earth-aluminum organic phosphinate and its preparation method, use and composition

Abstract

The present invention discloses a rare earth-aluminum organic phosphinate and its preparation method, use and composition. The preparation method of the present invention comprises the following steps: adding a promoter and an aluminum salt to a mixture of a rare earth alkyl phosphinate and water to obtain a rare earth-aluminum organic phosphinate; wherein the promoter is capable of generating H in water. + The rare earth-aluminum organic phosphinate prepared by the method of the present invention has good heat resistance and flame retardant properties.

Description

Technical Field

[0001] The present invention relates to a rare earth-aluminum organic phosphinate and a preparation method, application and composition thereof. Background Art

[0002] Alkyl phosphinates offer high thermal stability, high phosphorus content, and excellent flame retardancy. Commonly used alkyl phosphinate flame retardants include aluminum alkyl phosphinate and zinc alkyl phosphinate. When used with polymers with high melting points or high glass transition temperatures, aluminum alkyl phosphinates can generate smoke during extrusion or injection molding, posing a risk to personnel and the environment and affecting product performance. Zinc diethylphosphinate has a lower melting point.

[0003] CN101475706A discloses an organic phosphonate rare earth flame retardant, which is a salt of a rare earth element combined with an organic phosphonic acid structure. The organic phosphonate rare earth flame retardant has good temperature resistance, but its water resistance and flame retardancy still need to be improved.

[0004] CN117446767A discloses a method for preparing an infrared radiation composite phase aluminum phosphonate material, comprising preparing a solution A containing 0.1 to 1 mol / L Al(NO3)3·9H2O and a solution B containing 0.1 to 0.5 mol / L La(NO3)3·6H2O; mixing the solution A and the solution B, and controlling the Al 3+ with La 3+ The molar ratio of 1:(0.1-1) is 1 to obtain solution C; aqueous ammonia is added to solution C to adjust the pH of the solution to 3-5; the solution is then stirred at 50-100°C for 3-8 hours to obtain solution D; potassium phosphate and triethylenetriamine are dissolved in deionized water and thoroughly stirred to obtain solution E; solution E is added to solution D, followed by polyvinyl alcohol, and the mixture is stirred at 50-90°C for 2-6 hours to obtain solution F; solution F is freeze-dried and ground to obtain mixture G; mixture G is heated to 340-360°C at a rate of 14-16°C / min and held at this temperature for 1-3 hours; then heated to 1000-1200°C at a rate of 9-11°C / min, held at this temperature for 0.8-1.2 hours, and ground to obtain an infrared radiation composite phase aluminum phosphate material. This material has high reflectivity in the infrared range. Summary of the Invention

[0005] In view of this, one object of the present invention is to provide a method for preparing a rare earth-aluminum organophosphinate. The rare earth-aluminum organophosphinate prepared using the method of the present invention has good heat resistance and flame retardancy. Furthermore, the rare earth-aluminum organophosphinate of the present invention has good compatibility with polymers and low corrosiveness. Still further, the rare earth-aluminum organophosphinate of the present invention has good fluidity after being added to a polymer. Another object of the present invention is to provide a rare earth-aluminum organophosphinate. Yet another object of the present invention is to provide a use of the rare earth-aluminum organophosphinate. Yet another object of the present invention is to provide a composition.

[0006] The above purpose is achieved through the following technical solutions.

[0007] In one aspect, the present invention provides a method for preparing a rare earth-aluminum organic phosphinate, comprising the following steps:

[0008] Adding a promoter and an aluminum salt to a mixture of an alkyl phosphinate rare earth and water to obtain a rare earth-aluminum organic phosphinate; wherein the promoter is capable of generating H + of substance.

[0009] According to the preparation method of the present invention, preferably, the alkyl phosphinate in the alkyl phosphinate rare earth is as shown in formula (I):

[0010]

[0011] wherein R1 and R2 are independently selected from H, C1-C6 alkyl; and R1 and R2 are not H at the same time;

[0012] The accelerator is a water-soluble inorganic acid;

[0013] The aluminum salt is a water-soluble aluminum salt.

[0014] According to the preparation method of the present invention, preferably, the molar ratio of the promoter to the alkyl phosphinate rare earth is 0.2:(3-10), and the molar ratio of the alkyl phosphinate rare earth to the aluminum element in the aluminum salt is (0.4-10):2.

[0015] According to the preparation method of the present invention, preferably, the accelerator is used in the form of an accelerator aqueous solution, and the accelerator aqueous solution is added dropwise to a mixture of alkyl phosphinate rare earth and water;

[0016] The aluminum salt is used in the form of an aluminum salt aqueous solution, which is added dropwise to a mixture of the alkyl phosphinate rare earth and water.

[0017] According to the preparation method of the present invention, preferably, after the accelerator and the aluminum salt are added, the reaction is carried out at 50 to 105° C. for 1 to 6 hours.

[0018] The preparation method according to the present invention preferably further comprises the following steps:

[0019] Mixing a first liquid containing water and a rare earth source with a second liquid containing a phosphorus-containing substance and water, and then reacting them at 50-105° C. to obtain an alkyl phosphinate rare earth;

[0020] The rare earth source is selected from one or more of rare earth chlorides, rare earth carbonates, rare earth oxides, rare earth nitrates, rare earth acetates, and rare earth hydroxides;

[0021] The phosphorus-containing substance is selected from one or more of alkyl phosphinate alkali metal salts, alkyl phosphinate ammonium salts, and alkyl phosphonic acid.

[0022] On the other hand, the present invention provides a rare earth-aluminum organic phosphinate, which is obtained by the above preparation method.

[0023] In another aspect, the present invention provides a use of the rare earth-aluminum organic phosphinate in improving the flame retardant properties of polymers.

[0024] In another aspect, the present invention provides a composition comprising the rare earth-aluminum organic phosphinate and an inorganic boron-based flame retardant.

[0025] According to the composition of the present invention, preferably, the composition further comprises a polymer; the polymer is selected from one or more of nylon, polybutylene terephthalate, polyethylene terephthalate, polyurethane, and acrylonitrile-styrene-butadiene copolymer.

[0026] The rare earth-aluminum organophosphinate prepared using the method of the present invention exhibits excellent heat resistance and flame retardancy. Furthermore, the rare earth-aluminum organophosphinate of the present invention exhibits good compatibility with polymers and low corrosiveness. Furthermore, the rare earth-aluminum organophosphinate of the present invention exhibits good fluidity when added to polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the infrared spectrum of the alkyl phosphinate rare earth obtained in Preparation Example 1.

[0028] Figure 2 This is the infrared spectrum of the alkyl phosphinate rare earth obtained in Preparation Example 2.

[0029] Figure 3 The XRD patterns of the rare earth-aluminum organic phosphinates obtained in Examples 1 and 2, and the alkyl phosphinate rare earth obtained in Preparation Example 2 are shown.

[0030] Figure 4 This is the XRD pattern of the rare earth-aluminum organic phosphinate and aluminum sulfate obtained in Example 1.

[0031] Figure 5 This is the XRD pattern of the rare earth-aluminum organic phosphinate and cerium sulfate obtained in Example 1.

[0032] Figure 6 This is the XRD pattern of the rare earth-aluminum organic phosphinate and cerium sulfate obtained in Example 2.

[0033] Figure 7 This is the SEM image of the alkyl phosphinate rare earth obtained in Preparation Example 2.

[0034] Figure 8 This is the SEM image of the alkyl phosphinate rare earth obtained in Preparation Example 3.

[0035] Figure 9 This is the SEM image of the rare earth-aluminum organic phosphinate obtained in Example 1.

[0036] Figure 10 This is the SEM image of the rare earth-aluminum organic phosphinate obtained in Example 2. DETAILED DESCRIPTION

[0037] The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0038] <Preparation Method of Rare Earth-Aluminum Organic Phosphinate>

[0039] The preparation method of the rare earth-aluminum organic phosphinate of the present invention comprises the following steps: adding a promoter and an aluminum salt to a mixed solution of alkyl phosphinate rare earth and water to obtain the rare earth-aluminum organic phosphinate.

[0040] The alkyl phosphinate in the alkyl phosphinate rare earth can be represented by formula (I):

[0041]

[0042] In formula (I), R1 and R2 are independently selected from H and C1-C6 alkyl groups; and R1 and R2 are not both H. Preferably, R1 and R2 are independently selected from H and C1-C3 alkyl groups; and R1 and R2 are not both H. More preferably, R1 and R2 are both ethyl groups.

[0043] Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl.

[0044] According to one embodiment of the present invention, the alkyl phosphinate is diethyl phosphinate.

[0045] The rare earth element in the alkyl phosphinate is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium. Preferably, the rare earth element in the rare earth phosphite is selected from one or more of lanthanum, cerium and yttrium.

[0046] In the mixed solution of alkyl phosphinate rare earth and water, the mass ratio of alkyl phosphinate rare earth to water can be 1:(1.1-2.2); preferably 1:(1.3-2); more preferably 1:(1.4-1.9).

[0047] The temperature of the mixed solution of rare earth alkyl phosphinate and water may be 50 to 105°C, preferably 60 to 100°C, and more preferably 70 to 95°C.

[0048] The accelerator is capable of generating H + The accelerator may be an inorganic acid. Preferably, it is a water-soluble inorganic acid. Examples of inorganic acids include, but are not limited to, hydrogen chloride, sulfuric acid, acetic acid, and nitric acid. The inorganic acid may be used in the form of an aqueous solution. According to one embodiment of the present invention, the accelerator is hydrochloric acid.

[0049] The accelerator aqueous solution can be added dropwise to the mixture of the rare earth alkyl phosphinate and water. The concentration of the accelerator aqueous solution can be 0.5 to 3.5 mol / L, preferably 1 to 3 mol / L, and more preferably 1.5 to 2.5 mol / L.

[0050] The molar ratio of the promoter to the rare earth alkyl phosphinate can be 0.2:(3-10), preferably 0.2:(3.5-9). In certain embodiments, the molar ratio of the promoter to the rare earth alkyl phosphinate is 0.2:(4-5).

[0051] The aluminum salt is preferably an inorganic aluminum salt. Preferably, the aluminum salt is a water-soluble aluminum salt. The aluminum salt can be selected from one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, and aluminum acetate. According to one embodiment of the present invention, the aluminum salt is aluminum sulfate.

[0052] The aluminum salt can be used in the form of an aqueous solution. The aluminum salt aqueous solution can be added dropwise to a mixture of the rare earth alkyl phosphinate and water. The concentration of the aluminum salt aqueous solution can be 10 to 40 wt%, preferably 20 to 35 wt%, and more preferably 25 to 33 wt%.

[0053] The aluminum salt and the accelerator are added to the mixture of the alkyl phosphinate and water respectively. The aluminum salt and the accelerator do not contact each other before being added to the mixture. According to one embodiment of the present invention, the accelerator is added to the mixture of the alkyl phosphinate and water, and then the aluminum salt is added.

[0054] The molar ratio of the rare earth alkyl phosphinate to the aluminum in the aluminum salt can be (0.4-10):2, preferably (0.5-5):2. In certain embodiments, the molar ratio of the rare earth alkyl phosphinate to the aluminum in the aluminum salt is (0.8-1.2):2. In other embodiments, the molar ratio of the rare earth alkyl phosphinate to the aluminum in the aluminum salt is (1.8-2.2):2.

[0055] The reaction temperature may be 50 to 105°C, preferably 60 to 100°C, and more preferably 70 to 95°C.

[0056] The reaction time may be 1 to 6 hours, preferably 2 to 6 hours, and more preferably 3 to 5 hours.

[0057] In certain embodiments, the method further comprises the steps of filtering a reaction product obtained by reacting a mixture of a rare earth alkyl phosphinate and water, a promoter, and an aluminum salt to obtain a solid product, washing the solid product, and drying it at 90 to 150° C., preferably 100 to 130° C., to obtain a rare earth-aluminum organic phosphinate.

[0058] In certain embodiments, the method further comprises the following steps: mixing a first liquid containing water and a rare earth source with a second liquid containing a phosphorus-containing substance and water, and then reacting the mixture at 50-105° C. to obtain an alkyl phosphinate rare earth.

[0059] The rare earth source can be selected from one or more of rare earth chlorides, rare earth carbonates, rare earth oxides, rare earth nitrates, rare earth acetates, and rare earth hydroxides. In certain embodiments, the rare earth source is a rare earth carbonate, a rare earth oxide, or a rare earth hydroxide. In other embodiments, the rare earth source is a rare earth chloride, a rare earth nitrate, and a rare earth acetate.

[0060] The rare earth element in the rare earth source is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium. Preferably, the rare earth element is selected from one or more of lanthanum, cerium and yttrium.

[0061] The phosphorus-containing substance can be selected from one or more of alkylphosphinic acid alkali metal salts, alkylphosphinic acid ammonium salts, and alkylphosphinic acid. Examples of alkylphosphinic acid alkali metal salts include, but are not limited to, sodium alkylphosphinic acid, potassium alkylphosphinic acid, and lithium alkylphosphinic acid.

[0062] The alkyl phosphinate contained in the phosphorus-containing substance may be represented by formula (I).

[0063] The alkylphosphonic acid may be represented by formula (II):

[0064]

[0065] In formula (II), R3 and R4 are independently selected from H and C1-C6 alkyl; and R3 and R4 are not both H. Preferably, R3 and R4 are independently selected from H and C1-C3 alkyl; and R1 and R2 are not both H. More preferably, R3 and R4 are both ethyl.

[0066] Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl.

[0067] According to one embodiment of the present invention, the alkylphosphonic acid is diethylphosphonic acid.

[0068] The reaction temperature may be 60 to 110°C, preferably 70 to 100°C, and more preferably 80 to 90°C.

[0069] The reaction time may be 1 to 8 hours, preferably 2 to 6 hours, and more preferably 3 to 4 hours.

[0070] In certain embodiments, the second liquid is added dropwise to the first liquid to mix the first and second liquids. The temperature of the first liquid may be 60-110°C, preferably 70-100°C, and more preferably 80-90°C.

[0071] In other embodiments, the first liquid is added dropwise to the second liquid to mix the first and second liquids. The temperature of the second liquid may be 60-110°C, preferably 70-100°C, and more preferably 80-90°C.

[0072] The molar ratio of the rare earth element in the rare earth source to the phosphorus-containing substance may be 1:(1-6), preferably 1:(2-5). In certain embodiments, the molar ratio of the rare earth element in the rare earth source to the phosphorus-containing substance is 1:(4-4.5).

[0073] In the first liquid, the mass ratio of the rare earth source to water may be 11:(15-50), preferably 11:(20-40).

[0074] In the second liquid, the mass ratio of the phosphorus-containing substance to water may be 10:(5-95), preferably 10:(10-90).

[0075] In certain embodiments, the process may further include filtering the reaction product obtained by reacting the first liquid and the second liquid, washing the product, and drying the washed product to obtain the alkyl phosphinate rare earth. The drying temperature may be 90 to 150° C., preferably 100 to 130° C.

[0076] <Rare earth-aluminum organic phosphinates and their uses>

[0077] The rare earth-aluminum organophosphinate of the present invention is prepared by the above method. The rare earth-aluminum organophosphinate can improve the flame retardancy of polymers. Therefore, the present invention also provides the use of the rare earth-aluminum organophosphinate in improving the flame retardancy of polymers.

[0078] The polymer may be selected from one or more of nylon, polybutylene terephthalate, polyethylene terephthalate, polyurethane, and acrylonitrile-styrene-butadiene copolymer. In certain embodiments, the polymer is preferably nylon. The nylon may be selected from one or more of PA6, PA66, PA11, PA12, PA6T, and a copolymer of PA6T and PA66. According to one embodiment of the present invention, the nylon is a copolymer of PA6T and PA66.

[0079] <Composition>

[0080] The flame-retardant composition of the present invention comprises the aforementioned rare earth-aluminum-containing organic phosphinate and an inorganic boron-based flame retardant. The inorganic boron-based flame retardant can be selected from one or more of borax, boric acid, zinc borate, calcium metaborate, ammonium metaborate, ammonium pentaborate, sodium metaborate, ammonium fluoroborate, and zinc fluoroborate. Preferably, the inorganic boron-based flame retardant is zinc borate. The present inventors have discovered that combining the aforementioned rare earth-aluminum-containing organic phosphinate with an inorganic boron-based flame retardant exhibits enhanced flame retardancy.

[0081] The amount of the rare earth-aluminum organic phosphinate used may be 5 to 30 parts by weight, preferably 10 to 25 parts by weight, and more preferably 15 to 20 parts by weight.

[0082] The amount of the inorganic boron flame retardant can be 0.3 to 5 parts by weight, preferably 0.5 to 3 parts by weight, and more preferably 1 to 2 parts by weight.

[0083] In certain embodiments, the composition of the present invention further comprises a polymer. The polymer may be selected from one or more of nylon, polybutylene terephthalate, polyethylene terephthalate, polyurethane, and acrylonitrile-styrene-butadiene copolymer. In certain embodiments, the polymer is preferably nylon. The nylon may be selected from one or more of PA6, PA66, PA11, PA12, PA6T, and copolymers of PA6T and PA66. According to one embodiment of the present invention, the nylon is a copolymer of PA6T and PA66. The amount of the polymer used may be 30 to 70 parts by weight, preferably 40 to 60 parts by weight, and more preferably 50 to 55 parts by weight.

[0084] The composition of the present invention may further include one or more of an antioxidant, a lubricant, a nucleating agent, and glass fibers.

[0085] The amount of the antioxidant used may be 0.1 to 2 parts by weight, preferably 0.2 to 1.5 parts by weight, and more preferably 0.3 to 1 part by weight. The antioxidant may be antioxidant H10.

[0086] The amount of lubricant used can be 0.1 to 1 parts by weight, preferably 0.2 to 0.8 parts by weight, and more preferably 0.3 to 0.5 parts by weight. The lubricant can be wax powder. According to one embodiment of the present invention, the lubricant is AC540A produced by Honeywell.

[0087] The amount of the nucleating agent used can be 0.05 to 1 part by weight, preferably 0.1 to 0.5 part by weight, and more preferably 0.2 to 0.3 part by weight. The nucleating agent can be Cav102 produced by Klein.

[0088] The amount of glass fiber used may be 10 to 50 parts by weight, preferably 20 to 40 parts by weight, and more preferably 30 to 35 parts by weight.

[0089] The composition of the present invention can be prepared by the following method: extruding the raw materials through a twin-screw extruder to obtain a molding material, cooling the molding material, and then granulating it to obtain the composition.

[0090] Here are the raw materials:

[0091] PA6T / PA66 grade 1245 was purchased from Qingdao Sanli Benno New Materials Co., Ltd.

[0092] The glass fiber brand is ECS301UW, which was purchased from Chongqing International Composite Materials Co., Ltd.

[0093] Antioxidant H10, brand is Brüggemann.

[0094] Lubricant AC540A was purchased from Honeywell.

[0095] Nucleating agent Cav102 was purchased from Klein.

[0096] OP-1230, purchased from Klein.

[0097] OP-1240, purchased from Klein.

[0098] Here is the test method:

[0099] If the following test methods require processing into test pieces, the composition shall be dried and then processed into test pieces on an injection molding machine at 280°C, unless otherwise specified.

[0100] UL94: HB grade is evaluated using a horizontal burning test, and V0-V2 grade is evaluated using a 500W (125mm) vertical burning test.

[0101] Notched impact strength: tested using the method specified in ASTM D256.

[0102] GWIT is measured according to IEC-60695-2-12.

[0103] MVR: Determine the MVR at 325°C and 2.16 kg according to the method specified in GB / T 3682.1-2-2018.

[0104] Separation: Place a sample (50 mm × 50 mm × 20 mm) in a constant temperature and humidity chamber at 85°C and 85% relative humidity, and visually observe the surface condition of the sample after 168 hours.

[0105] Preparation Example 1

[0106] To 11.26 parts by weight of lanthanum cerium carbonate (75% by weight of lanthanum carbonate and 25% by weight of cerium carbonate), add 34 parts by weight of water, stir evenly, and heat to 80°C to obtain a first liquid. A second liquid consisting of 13.39 parts by weight of diethylphosphonic acid and 15 parts by weight of water is added dropwise to the first liquid. After the second liquid is added, the mixture is reacted at 80°C for 4 hours. The reaction product is filtered and then washed with water until the pH of the mother liquor is between 3 and 5. The washed solid product is dried to obtain a rare earth alkyl phosphinate.

[0107] Preparation Example 2

[0108] A 33wt% aqueous cerium chloride solution (the first liquid) was added dropwise to a 24wt% aqueous sodium diethylphosphinate solution (the second liquid) at 80°C. The molar ratio of sodium diethylphosphinate to cerium chloride was 4.5:1. After the addition was complete, the mixture was reacted at 80°C for 4 hours. The reaction product was filtered and then washed with water. The washed solid product was dried at 120°C to obtain a rare earth alkyl phosphinate.

[0109] Figure 2 The infrared spectrum of the alkyl phosphinate rare earth obtained in this preparation example is shown in FIG. 2800-2970 cm -1 The stretching vibration peaks of -CH3 and -CH2- are at 1400~800cm -1 The absorption peaks are those of PO and P=O.

[0110] Preparation Example 3

[0111] A 30wt% aqueous solution of yttrium trichloride (the first liquid) was added dropwise to a 10wt% aqueous solution of sodium diethylphosphinate (the second liquid) at 80°C. The molar ratio of sodium diethylphosphinate to yttrium trichloride was 3.16:1. After the addition was complete, the mixture was reacted at 80°C for 3 hours. The reaction product was filtered, and the filter cake was then dried at 125°C to obtain a rare earth alkyl phosphinate.

[0112] Example 1

[0113] 2.12 kg of the rare earth alkyl phosphinate obtained by the method of Preparation Example 2 was dispersed in 3.0 kg of water, stirred, and heated to 75°C to obtain a mixed solution. 100 mL of 2 mol / L hydrochloric acid was then added dropwise to the mixed solution, followed by a 33 wt% aqueous solution of aluminum sulfate. The amount of aluminum sulfate used was 1.32 kg. After the addition of the aqueous solution of aluminum sulfate, the mixture was reacted at 75°C for 5 hours to obtain a reaction product. The reaction product was cooled and filtered to obtain a solid product. The solid product was washed and then dried at 120°C to obtain a rare earth-aluminum organic phosphinate.

[0114] The TG curve shows that the thermal weight loss temperature of 1 wt% of the rare earth-aluminum organic phosphinate obtained in this example is 338.3°C.

[0115] Depend on Figure 3 It can be seen that the XRD pattern of the product of Example 1 is different from that of Preparation Example 2, and the raw material alkyl phosphinate rare earth has reacted. Figure 4 It can be seen that there is no aluminum sulfate (standard card number 30-43) phase in the product of Example 1. Figure 5 It can be seen that most of the diffraction peaks of the product of Example 1 are inconsistent with those of cerium sulfate (standard card number 73-1675). The diffraction peak at around 2θ = 10° is similar in attribution to the diffraction peak of cerium diethylphosphinate. This indicates that when aluminum sulfate is used, the existing reaction system does not form an insoluble precipitate of rare earth sulfate.

[0116] Figure 9 This is the SEM image of the rare earth-aluminum organic phosphinate obtained in Example 1. It can be seen from the image that the product morphology is irregular block or columnar, and some columnar particles have uneven surfaces, overgrown small grains, and small fragment particles attached. Figure 7 This is a SEM image of the rare earth alkyl phosphinate obtained in Preparation Example 2. Its microscopic morphology is a rounded rectangular strip crystal with a smooth surface and clear outlines, which is different from the morphology of the product in Example 1. This indicates that the crystal form has changed after reacting with aluminum sulfate.

[0117] Example 2

[0118] 4.24 kg of the rare earth alkyl phosphinate obtained by the method of Preparation Example 2 was dispersed in 8.0 kg of water, stirred, and heated to 95°C to obtain a mixed solution. 100 mL of 2 mol / L hydrochloric acid was then added dropwise to the mixed solution, followed by a 33 wt% aqueous solution of aluminum sulfate. The amount of aluminum sulfate used was 1.32 kg. After the addition of the aqueous solution of aluminum sulfate, the mixture was reacted at 95°C for 4 hours to obtain a reaction product. The reaction product was cooled and filtered to obtain a solid product. The solid product was washed and then dried at 120°C to obtain a rare earth-aluminum organic phosphinate.

[0119] The TG curve shows that the thermal weight loss temperature of 1 wt% of the rare earth-aluminum organic phosphinate obtained in this example is 379.7°C.

[0120] Example 3

[0121] Except that the alkyl phosphinate rare earth is obtained by the method of Preparation Example 1, the rest is the same as Example 1.

[0122] Example 4

[0123] Except that the alkyl phosphinate rare earth is obtained by the method of Preparation Example 1, the rest is the same as Example 2.

[0124] Example 5

[0125] The preparation process was the same as in Example 1, except that 1.81 kg of the alkyl phosphinate rare earth was obtained by the method of Preparation Example 3.

[0126] Examples 6 to 10 and Comparative Examples 1 to 5

[0127] 53 parts by weight of PA6T / PA66, 0.3 parts by weight of antioxidant H10, 0.5 parts by weight of lubricant AC540C, and 0.2 parts by weight of nucleating agent Cav102 were mixed and placed in a twin-screw extruder (model: KTS35 / 44D). The materials shown in Table 1 were mixed and then fed into the twin-screw extruder through a first side feed port at 310-330°C. 30 parts by weight of glass fiber was added to the twin-screw extruder through a second side feed port. The mixture was extruded through the twin-screw extruder to obtain a molding material. The molding material was cooled in a water bath and then pelletized to obtain a composite.

[0128] The properties of the compositions are shown in Table 1.

[0129] Table 1

[0130]

[0131] Note: Each set of UL94 tests is conducted five times. X*A means that the results of the five tests are grade A for X times.

[0132] Corrosion test

[0133] PA6T / PA66, antioxidant H10, lubricant AC540C, and nucleating agent Cav102 were mixed uniformly and placed in a twin-screw extruder (model: KTS35 / 44D). A brass block with a mass of m1 was placed on the die head of the twin-screw extruder. Anhydrous zinc borate and a flame retardant (selected from an organic phosphinate, OP-1230, or OP-1240) were mixed and then added to the twin-screw extruder through a first side feed port at 310-330°C. Glass fiber was added to the twin-screw extruder through a second side feed port. The extruder extruded the mixture to obtain a molding material. The molding material was cooled in a water bath and then pelletized.

[0134] The total weight of the raw materials (PA6T / PA66, antioxidant H10, lubricant AC540C, nucleating agent Cav102, anhydrous zinc borate, flame retardant and glass fiber) is 25 kg.

[0135] The mass of the brass block on the die after granulation was measured and recorded as m2. The loss of the brass block was calculated according to the formula (m1-m2) / m1, and the corrosiveness of the composition was judged based on the loss of the brass block.

[0136] The selection and proportion of each raw material are shown in Table 2, and the corrosiveness is shown in Table 2.

[0137] Table 2

[0138]

[0139] The present invention is not limited to the above-mentioned embodiments. Any modification, improvement, or substitution that can be conceived by those skilled in the art without departing from the essential content of the present invention shall fall within the scope of the present invention.

Claims

1. A method for preparing a rare earth-aluminum organic phosphinate, characterized in that: The steps include: Adding a promoter and an aluminum salt to a mixture of a rare earth alkyl phosphinate and water to obtain a rare earth-aluminum organic phosphinate; The alkyl phosphinate in the alkyl phosphinate rare earth is as shown in formula (I): wherein R1 and R2 are independently selected from H, C1-C6 alkyl; and R1 and R2 are not H at the same time; The rare earth element in the alkylphosphinate rare earth is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium; The accelerator is a water-soluble inorganic acid; The aluminum salt is a water-soluble aluminum salt.

2. The preparation method according to claim 1, characterized in that The molar ratio of the accelerator to the alkyl phosphinate rare earth is 0.2:(3-10), and the molar ratio of the alkyl phosphinate rare earth to the aluminum element in the aluminum salt is (0.4-10):

2.

3. The preparation method according to claim 1, characterized in that The accelerator is used in the form of an accelerator aqueous solution, which is added dropwise to a mixture of alkyl phosphinate rare earth and water; The aluminum salt is used in the form of an aluminum salt aqueous solution, which is added dropwise to a mixture of the alkyl phosphinate rare earth and water.

4. The preparation method according to claim 1, characterized in that After the accelerator and aluminum salt are added, the reaction is carried out at 50-105°C for 1-6 hours.

5. The preparation method according to claim 1, characterized in that The following steps are also included: Mixing a first liquid containing water and a rare earth source with a second liquid containing a phosphorus-containing substance and water, and then reacting them at 50-105° C. to obtain an alkyl phosphinate rare earth; The rare earth source is selected from one or more of rare earth chlorides, rare earth carbonates, rare earth oxides, rare earth nitrates, rare earth acetates, and rare earth hydroxides; The phosphorus-containing substance is selected from one or more of alkylphosphinic acid alkali metal salts, alkylphosphinic acid ammonium salts, and alkylphosphinic acid.

6. A rare earth-aluminum organic phosphinate, characterized in that: The rare earth-aluminum organic phosphinate is prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the rare earth-aluminum organic phosphinate according to claim 6 in improving the flame retardant properties of polymers.

8. A composition, characterized in that The composition comprises the rare earth-aluminum organic phosphinate according to claim 6 and an inorganic boron-based flame retardant.

9. The composition according to claim 8, characterized in that The composition further comprises a polymer; the polymer is selected from one or more of nylon, polybutylene terephthalate, polyethylene terephthalate, polyurethane, and acrylonitrile-styrene-butadiene copolymer.

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