Polymer additives, methods for producing the same, and applications thereof

Abstract

The present invention aims to provide polymer additives, methods for producing the same, and applications thereof. [Solution] The present invention provides a polymer additive, a method for producing the same, and its applications. The production method includes the steps of: obtaining an aqueous solution of diethylphosphinic acid by reacting an aqueous hypophosphorous acid solution and an antioxidant with ethylene under the action of an initiator using free radicals; reacting the aqueous diethylphosphinic acid solution with sulfuric acid and a metal hydroxide, then adding an alkaline solution to obtain a diethylphosphinate slurry with a pH of 3.8 to 4.2; and mixing the diethylphosphinate slurry with a flocculant, stirring to obtain a diethylphosphinate aggregate, and filtering, washing, and drying it to obtain the polymer additive. The present invention makes it possible to obtain a polymer additive with a low acid value by designing the production method, and when used as a flame retardant in the production of polymer materials, it suppresses the precipitation of auxiliary agents during high-temperature processing, reduces the amount of scale, and yields a polymer composition with a low precipitate content after boiling, thereby improving its service life under high temperature and high humidity conditions.

Description

[Technical Field]

[0001] This invention belongs to the field of flame retardant technology, and more specifically, relates to polymer additives, methods for producing the same, and applications thereof. [Background technology]

[0002] Dialkylphosphinates are attracting significant attention from the industry as general-purpose halogen-free flame retardants due to their excellent flame retardancy, low additive requirements, minimal impact on the physical and electrical properties of the matrix resin, low smoke generation during combustion, and high CTI (Comparative Tracking Index). Furthermore, materials such as polyamides using dialkylphosphinates as flame retardants possess excellent mechanical and electrical properties, gaining increasing support from manufacturers in the electrical and electronic equipment industry, indicating a very broad market outlook.

[0003] A study by Braun U et al. revealed that when dialkylphosphinates are used to flame retard PBT and polyamides, they decompose into dialkylphosphinic acid during high-temperature processing.

[0004] When dialkylphosphinates are used to flame retard polyamides, the polyamides, which contain numerous polar amide groups, become highly absorbent and have a high water absorption rate. For example, PA66 resin can reach a water absorption rate of 2.7% at 23°C and 50% humidity. Dialkylphosphinates are inherently acidic and decompose upon heating in extrusion and high-temperature injection molding, producing acidic substances such as dialkylphosphinic acid. This accelerates the decomposition of the system and generates a large amount of gas during processing. In repeated injection molding processes, serious scaling often occurs in the molds, affecting the appearance of the product. The presence of scale necessitates frequent mold cleaning, reducing efficiency and hindering the effective promotion and use of the product.

[0005] Currently, the main method for solving the scaling problem in injection molding of dialkylphosphinate-based flame-retardant polyamide materials is to reduce the acidity by adding an acid scavenger to the system. For example, EP2417191A1 discloses a halogen-free flame-retardant polyamide composition in which calcium oxide is added to the system. This calcium oxide neutralizes acidic substances in the system, reducing the acidity of the system, thereby suppressing the decomposition of the matrix resin and reducing mold corrosion during high-temperature injection molding. While this method helps reduce scale, calcium oxide is highly hygroscopic, leading to a high water absorption rate in the system and making control during processing difficult.

[0006] CN112409786A allows for the production of halogen-free flame-retardant thermoplastic polyamides with reduced scale by adding a certain amount of ethylene copolymer to the system. CN114874616A, produced by adding metal oxides and polyhydroxy groups to the system, produces halogen-free flame-retardant thermoplastic polyamides with excellent resistance to yellowing and continuity of mold opening and closing cycles (low scale).

[0007] While the above technical solutions can improve the scaling of dialkylphosphinate-based flame-retardant polyamides to some extent, they all reduce scaling by increasing the acidity of the system through the addition of additives. This leads to increased costs and makes it difficult to avoid the impact of the addition of new substances on other properties of the flame-retardant polyamide. For example, the addition of inorganic metal oxides can lead to a decrease in the material's mechanical properties. Furthermore, because the inherent defects of dialkylphosphinates are not fundamentally improved, products containing them are prone to additive precipitation during high-temperature processing, which can clog processing equipment piping and cause surface defects in the product.

[0008] Therefore, providing novel low-acid polymer additives and using them to modify polymer materials for flame retardancy, thereby reducing additive precipitation during high-temperature processing and obtaining modified polymer materials with less scale and less additive precipitation, is an urgent problem to solve in this field. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] European Patent Application Publication No. 2417191 [Patent Document 2] Chinese Patent Application Publication No. 112409786 Specification [Patent Document 3] Chinese Patent Application Publication No. 114874616 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The present invention aims to provide a polymer additive, a method for producing the same, and its applications in order to solve the shortcomings of the prior art. By designing the materials and processes in the manufacturing method and their synergistic effects, a polymer additive with a low acid value can be obtained. When this polymer additive is used as a flame retardant in the manufacture of polymer materials, the precipitation of auxiliary agents during high-temperature processing can be suppressed or avoided, scale can be effectively reduced, and the content of precipitates after boiling in the manufactured polymer composition can be reduced, thereby improving the service life under high temperature and high humidity conditions.

[0011] To achieve this objective, the present invention employs the following technical solutions.

[0012] In a first aspect, the present invention provides a method for producing a polymer additive, the production method being: (1) A step in which an aqueous solution of hypophosphorous acid and an antioxidant are reacted with ethylene under the action of an initiator to obtain an aqueous solution of diethylphosphinic acid, Step (2) involves reacting the aforementioned aqueous solution of diethylphosphinic acid with sulfuric acid and a metal hydroxide, and then adding an alkaline solution to obtain a diethylphosphinate slurry with a pH of 3.8 to 4.2. The process includes (3) mixing the diethyl phosphinate slurry with a flocculant and stirring to obtain a diethyl hypophosphate aggregate, and then filtering, washing, and drying the diethyl hypophosphate aggregate to obtain the polymer additive.

[0013] In the research of the present invention, the reaction process between hypophosphorous acid and ethylene is generally carried out in the presence of a free radical initiator. Hypophosphorous acid has strong reducing properties due to the presence of pH bonds. Therefore, in the process of step (1), a free radical reaction and an oxidation reaction generally occur simultaneously. The present invention has found that by introducing an oxidizing agent in step (1) and donating electrons to the oxidizing agent, it is possible to reduce the substance to a stable material and achieve the oxidizing effect of the initiator. On the other hand, the free radical reaction between hypophosphorous acid and ethylene is a strongly exothermic reaction, and uncontrollable phenomena tend to occur during production, accompanied by many side reactions. Another mechanism of antioxidants is to react with free radicals to capture them and neutralize their activity. This effectively suppresses the exothermic effect, reduces the occurrence of side reactions, and makes the production process controllable. The present invention shows that by adding an antioxidant in step (1), the water-soluble acid value and organic acid value of the final product can be effectively reduced.

[0014] The present invention has found that the pH of the reaction system has a significant effect on the crystallization behavior in the additive precipitation process, and consequently on the acid value of the polymer additive. The present invention is designed to adjust the pH of the product in step (2), and by controlling the pH of the resulting diethylphosphinate slurry to 3.8-4.2, for example, 3.82, 3.85, 3.88, 3.9, 3.92, 3.95, 3.98, 4, 4.02, 4.05, 4.08, 4.1, 4.12, 4.15, 4.18, etc., a polymer additive with a low acid value can be produced while ensuring a high yield. If the pH of the slurry is too low, the acidity of the polymer additive becomes too high, reducing the yield. Conversely, if the pH is too high, the acidity of the polymer additive also increases, and if the pH rises further, the yield decreases further.

[0015] As a result of research, the present invention finds that introduction of a flocculant allows particle surfaces of a polymer additive to be fixed on molecular chains of the flocculant and form polymer crosslinks, thereby causing particles to aggregate and settle. Said flocculant can be adsorbed and bound to the polymer additive in the slurry obtained in step (2), effectively improving the filtering and washing effects of the polymer additive, while effectively reducing the acidity of the polymer additive after filtering and washing.

[0016] In summary, the present invention designs a method for producing a polymer additive, in which an antioxidant and a flocculant are used in the production process of the polymer additive, and the pH value of diethylphosphinate slurry is controlled to 3.8 to 4.2, thereby obtaining a polymer additive with low acid value. When this polymer additive is used as a flame retardant for producing a polymer composition, it can suppress or avoid precipitation of auxiliaries during high-temperature processing, significantly reduce scaling, and lower the content of precipitates in the polymer composition after boiling in water, thus greatly improving the service life of the polymer composition under high-temperature and high-humidity conditions.

[0017] The following are preferred technical solutions of the present invention, but they are not intended to limit the technical solutions provided by the present invention. The objects and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0018] Preferably, the antioxidant comprises any one or a combination of at least two selected from a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant; more preferably, it comprises any one or a combination of at least two selected from a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

[0019] More preferably, the antioxidants are pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 109). 8) comprising one or at least two of the following: tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,4-digylphenyl)pentaerythritol diphosphite ester (antioxidant 608), 2,6-di-tert-butyl-p-cresol (antioxidant BHT), β,β-distearylthiodipropionate (antioxidant DSTP), antioxidant 215, and antioxidant 225.

[0020] The antioxidant in the present invention may be a single component, such as any of the antioxidants listed above, or it may be a combination of multiple antioxidants, such as a combination of a hindered phenol antioxidant and a phosphite antioxidant. Typical combinations include composites obtained by mixing antioxidant 1010 and antioxidant 168 in different proportions, such as antioxidant 215 and antioxidant 225.

[0021] Preferably, the initiator comprises one or at least two of the following: organic peroxides, persulfates, azo initiators, and photoinitiators.

[0022] Preferably, the organic peroxide is diisobutyryl peroxide, benzoyl peroxide, bis(2-ethylhexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, tert-amyl peroxypivalate, dodecanoyl peroxide, bis(3,3,5-trimethylacetyl) peroxide, 2,5-dimethyl-2,5-di(2-ethylacetyl peroxide)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, peroxide-2-ethylhexanoate, tert-butylperoxy-2- The present invention comprises one or at least two of the following: ethylhexanoate, tert-butylperoxyisobutyrate, 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane, 1,1-di-tert-pentylcyclohexaneperoxide, 1,1-di-tert-butylcyclohexaneperoxide, di-tert-butylperoxide, di-tert-amylperoxide, dicumylperoxide, 2,5-di-tert-butylperoxide-2,5-dimethylhexane, tert-butylperoxyacetate, tert-amylperoxybenzoate, tert-butylperoxymaleate, and tert-butylperoxy-2-ethylhexanoate.

[0023] Preferably, the persulfate comprises one or at least two of the following: sodium persulfate, potassium persulfate, and ammonium persulfate.

[0024] Preferably, the azo initiator includes one or at least two of the following: azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, azobisisobutyramidazole hydrochloride, and azobisisobutyronitrile cyanoformamide.

[0025] Furthermore, the present invention does not impose any particular restrictions on the specific selection of photoinitiators, and all photoinitiators commonly used in the art are applicable.

[0026] Furthermore, the initiator described in step (1) of the present invention may be added all at once, added in several portions, or added continuously during the reaction process. In addition, in step (1), a portion of the initiator may be added in advance and the remainder added continuously during the reaction process.

[0027] Preferably, the mass percentage of hypophosphorous acid in the hypophosphorous acid aqueous solution is 20-70%, and may be, for example, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65%, and specific values ​​between the above numbers. Due to space limitations and for brevity, this invention does not comprehensively list all specific values ​​included in the above range, but 45-55% is more preferable.

[0028] Preferably, the mass ratio of hypophosphorous acid to antioxidant is 100:(0.02~1.2), and may be, for example, 100:0.04, 100:0.05, 100:0.06, 100:0.08, 100:0.1, 100:0.2, 100:0.3, 100:0.4, 100:0.5, 100:0.6, 100:0.7, 100:0.8, 100:0.9, 100:0.95, 100:1, 100:1.05, 100:1.1, or 100:1.15, and more preferably 100:(0.05~1).

[0029] Preferably, the mass ratio of hypophosphorous acid to the initiator is 100:(0.1~5), and may be, for example, 100:0.2, 100:0.5, 100:1, 100:1.5, 100:2, 100:2.5, 100:3, 100:3.5, 100:4, 100:4.5, or 100:4.8.

[0030] Preferably, the molar ratio of ethylene to hypophosphorous acid is (2-2.1):1, and may be, for example, 2.01:1, 2.02:1, 2.04:1, 2.05:1, 2.06:1, 2.08:1, or 2.09:1.

[0031] Preferably, the temperature of the free radical reaction is 60 to 105°C, and may be, for example, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 98°C, and specific values ​​between the above numbers. Due to space limitations and brevity, the present invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 70 to 100°C, and even more preferably 75 to 95°C.

[0032] The free radical reaction described in step (1) is carried out in the presence of an initiator. The reaction is considered complete and stopped when there is no significant change in the pressure of the reaction system.

[0033] Preferably, the free radical reaction is carried out under a protective atmosphere.

[0034] Preferably, the protective atmosphere includes a nitrogen gas atmosphere and / or an argon gas atmosphere.

[0035] Preferably, the metal hydroxide comprises one or at least two of the following: aluminum hydroxide, calcium hydroxide, copper hydroxide, zinc hydroxide, iron hydroxide, and titanium hydroxide, and more preferably aluminum hydroxide.

[0036] Preferably, the iron hydroxide includes ferrous hydroxide and / or iron(III) hydroxide.

[0037] By using the above-mentioned metal hydroxide, the cation in the obtained diethylphosphinate contains one of Al, Ca, Cu, Zn, Fe, or Ti, and is more preferably Al.

[0038] Preferably, when the molar amount of diethylphosphinic acid is set to 100%, the molar amount of the metal hydroxide is 30 to 50 mol%, and may be, for example, 32 mol%, 33 mol%, 33.3 mol%, 34 mol%, 35 mol%, 36 mol%, 38 mol%, 40 mol%, 42 mol%, 45 mol%, or 48 mol%, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, this invention does not comprehensively list all specific values ​​included in the above range.

[0039] Preferably, with the molar amount of diethylphosphinic acid set to 100%, the molar amount of sulfuric acid is 5 to 50 mol%, for example, 8 mol%, 10 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%, 28 mol%, 30 mol%, 32 mol%, 35 mol%, 38 mol%, 40 mol%, 42 mol%, 45 mol%, or 48 mol%, and any specific value between these numbers. Due to space limitations and brevity, this invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 8 to 30 mol%, and even more preferably, 10 to 15 mol%.

[0040] Preferably, the reaction temperature described in step (2) is 70 to 150°C, and may be, for example, 75°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 145°C, and specific values ​​between the above numbers. Due to space limitations and for brevity, the present invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 80 to 120°C, and even more preferably 90 to 100°C.

[0041] Preferably, the reaction time described in step (2) is 2 to 12 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 11.5 hours, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​that fall within the above range.

[0042] Preferably, the alkaline solution includes a sodium hydroxide solution and / or a potassium hydroxide solution.

[0043] The present invention does not impose any special restrictions on the mass concentration of the sodium hydroxide solution or potassium hydroxide solution, and it is sufficient to add the sodium hydroxide solution and / or potassium hydroxide solution so as to maintain the pH of the diethylphosphinate slurry obtained in step (2) at 3.8 to 4.2.

[0044] Preferably, the flocculant comprises a polyacrylamide flocculant, more preferably an anionic polyacrylamide and / or nonionic polyacrylamide, and even more preferably an anionic polyacrylamide.

[0045] As a preferred technical solution of the present invention, by using a polyacrylamide-based flocculant, the surface of polymer additive particles can be fixed to the molecular chains of the flocculant, thereby forming polymer crosslinks. In particular, when anionic polyacrylamide is added as a flocculant, it exhibits adsorption crosslinking and reinforcing effects, causing particles to aggregate and settle, improving the filtration and washing effect of the polymer additive, and reducing the acid value of the polymer additive after filtration and washing.

[0046] Preferably, with the theoretically obtained mass of the diethylphosphinate set as 100%, the mass of the flocculant is 0.01 to 0.5%, and may be, for example, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, 0.25%, 0.28%, 0.3%, 0.32%, 0.35%, 0.38%, 0.4%, 0.42%, 0.45%, or 0.48%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention does not comprehensively list all specific values ​​included in the above range.

[0047] The aforementioned "theoretically obtained mass of diethylphosphinate" is calculated based on the amounts of diethylphosphinic acid and metal hydroxide added in step (2).

[0048] Preferably, a flocculant solution can be obtained by mixing the flocculant and water at 20-30°C for 10-20 minutes, and then this flocculant solution can be mixed with a diethylphosphinate slurry and stirred. The mass ratio of flocculant to water is 1:10-1000, and may be, for example, 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, or 1:950.

[0049] Preferably, the mixing temperature described in step (3) is 40 to 60°C, and may be, for example, 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C, or 58°C, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​that fall within the above range.

[0050] Preferably, the number of washes in step (3) is four or more, for example, five, six, seven, eight, nine, ten, or twelve times, and more preferably five to ten times.

[0051] Preferably, the cleaning agent used for the cleaning is water.

[0052] A preferred technical solution of the present invention involves filtering the diethyl hypophosphate aggregate and then washing it multiple times. The number of washes is four or more, preferably five to ten times, which allows for more effective removal of impurities and acidic substances from the product, thereby obtaining the polymer additive with a low acid value.

[0053] Preferably, the mass ratio of water to solids in each of the washes is (1 to 10):1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and more preferably (1.5 to 6):1. The solids are solid products obtained by filtration.

[0054] Preferably, the drying temperature described in step (3) is 105 to 250°C, and may be, for example, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, or 240°C, and any specific value between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 110 to 150°C.

[0055] As a preferred technical solution of the present invention, the method for producing the polymer additive is: Step (1) to obtain an aqueous solution of diethylphosphinic acid by reacting an aqueous hypophosphorous acid solution and an antioxidant with ethylene under the action of an initiator using free radicals, under a protective atmosphere, Step (1) is a step in which the mass concentration of the hypophosphorous acid aqueous solution is 20-70%, the mass ratio of hypophosphorous acid, antioxidant and initiator is 100:(0.02-1.2):(0.1-5), the temperature of the free radical reaction is 60-100°C, and the reaction is terminated when the pressure of the system stops changing. Step (2) is a step in which the diethylphosphinic acid aqueous solution, sulfuric acid and metal hydroxide are reacted at 70-150°C for 2-12 hours, and then an alkaline solution is added to the system so that the pH is 3.8-4.2 to obtain a diethylphosphinate slurry. Here, if the molar amount of diethylphosphinic acid is taken as 100%, the molar amount of the metal hydroxide is 30-50 mol%, and the molar amount of sulfuric acid is 5-50 mol%, in step (2), Step (3) to obtain the polymer additive by mixing the diethyl phosphinate slurry with a flocculant solution at 40-60°C, stirring to obtain diethyl hypophosphate aggregates, filtering the diethyl hypophosphate aggregates, washing them four or more times, and drying them, The present invention includes step (3), wherein the mass of the flocculant is 0.01 to 0.5%, with the theoretically obtained mass of the diethylphosphinate being taken as 100%.

[0056] In a second aspect, the present invention provides a polymer additive manufactured by the manufacturing method described in the first aspect, wherein the water-soluble acid value of the polymer additive is 0.3 mg KOH / g or less, and the polymer additive is 95-98.98 parts by mass of diethylphosphinate, 1 to 3 parts by mass of ethylbutylphosphinate, 0.01 to 0.7 parts by mass of ethylphosphonate, 0.01 to 0.3 parts by mass of monoethylphosphinate, and It contains 0 to 3 parts by mass of alkali-insoluble substances. The alkali-insoluble substance is selected from one or at least two of the following: hydroxides, oxides, phosphates, phosphates, and other alkylphosphonates.

[0057] The polymer additive provided by the present invention has low acidity and a water-soluble acid value of 0.3 mg KOH / g or less. When used as a flame retardant in a polymer composition, it suppresses decomposition and the generation of dialkylphosphinic acid during high-temperature processes, thereby suppressing or avoiding the precipitation of the additive during high-temperature processing. This prevents blockage of equipment piping due to precipitates and reduces the amount of precipitates in the polymer composition after boiling. As a result, its stability under high-temperature and high-humidity conditions is greatly improved, its service life is extended, and the amount of scale during injection molding is reduced.

[0058] The diethylphosphinate in the polymer additive is 95 to 98.98 parts by mass, and may be, for example, 95.5 parts by mass, 95.8 parts by mass, 96 parts by mass, 96.2 parts by mass, 96.5 parts by mass, 96.8 parts by mass, 96.9 parts by mass, 97 parts by mass, 97.2 parts by mass, 97.5 parts by mass, 97.8 parts by mass, 98 parts by mass, 98.2 parts by mass, 98.5 parts by mass, 98.8 parts by mass, or 98.9 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0059] Preferably, the mass percentage of diethylphosphinate in the polymer additive is 94% or more, and may be, for example, 94.5%, 95%, 95.5%, 95.8%, 96%, 96.2%, 96.5%, 96.8%, 96.9%, 97%, 97.2%, 97.5%, 97.8%, 98%, 98.2%, 98.5%, 98.8%, or 98.98%, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0060] The ethylbutylphosphinate in the polymer additive is 1 to 3 parts by mass, and may be, for example, 1.1 parts by mass, 1.2 parts by mass, 1.5 parts by mass, 1.6 parts by mass, 1.8 parts by mass, 2 parts by mass, 2.2 parts by mass, 2.5 parts by mass, 2.7 parts by mass, 2.8 parts by mass, or 2.9 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0061] The ethylphosphonate in the polymer additive is 0.01 to 0.7 parts by mass, and may be, for example, 0.02 parts by mass, 0.05 parts by mass, 0.1 parts by mass, 0.15 parts by mass, 0.2 parts by mass, 0.25 parts by mass, 0.3 parts by mass, 0.35 parts by mass, 0.4 parts by mass, 0.45 parts by mass, 0.5 parts by mass, 0.55 parts by mass, 0.6 parts by mass, or 0.65 parts by mass, and any specific value between these numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0062] The amount of monoethylphosphinate in the polymer additive is 0.01 to 0.3 parts by mass, and may be, for example, 0.02 parts by mass, 0.04 parts by mass, 0.05 parts by mass, 0.06 parts by mass, 0.08 parts by mass, 0.1 parts by mass, 0.12 parts by mass, 0.14 parts by mass, 0.15 parts by mass, 0.16 parts by mass, 0.18 parts by mass, 0.2 parts by mass, 0.22 parts by mass, 0.25 parts by mass, or 0.28 parts by mass, and any specific value between these numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0063] The alkali-insoluble substance in the polymer additive is 0 to 3 parts by mass, and may be, for example, 0.01 parts by mass, 0.02 parts by mass, 0.05 parts by mass, 0.08 parts by mass, 0.1 parts by mass, 0.15 parts by mass, 0.2 parts by mass, 0.25 parts by mass, 0.3 parts by mass, 0.4 parts by mass, 0.5 parts by mass, 0.6 parts by mass, 0.8 parts by mass, 1 part by mass, 1.2 parts by mass, 1.5 parts by mass, 1.8 parts by mass, 2 parts by mass, 2.2 parts by mass, 2.5 parts by mass, or 2.8 parts by mass, and any specific value between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0064] For example, the mass fractions of diethylphosphinate, ethylphosphonate, and monoethylphosphinate in the polymer additive can be obtained by liquid chromatography analysis. For instance, the test sample is dissolved in an aqueous sulfuric acid solution (30% mass concentration) five times the mass of the sample, and then diluted 10 to 30 times in the mobile phase for analysis. The mobile phase is prepared by adding 0.5% trifluoroacetic acid by volume to a mixture of water and methanol in a mass ratio of 9:1. A ShimNex CS C18 chromatography column is used, and the mass content of each component is calculated using the area percentage method at a flow rate of 0.6 mL / min.

[0065] For example, the mass fraction of alkali-insoluble substances in the polymer additive can be obtained by the following method: The test sample is mixed with an aqueous sodium hydroxide solution (mass concentration 3%) in a mass ratio of 1:100, stirred at 35°C for 30 minutes, filtered through filter paper with an accuracy of 2 μm or less, rinsed three times with water, dried the filter paper, and weighed. The increase in mass compared to the filter paper before filtration (dried filter paper) is the mass of the insoluble substance, and the mass ratio of the insoluble substance to the test sample is the mass content of the alkali-insoluble substance.

[0066] Preferably, the polymer additive is 96.5 to 98.5 parts by mass of diethylphosphinate, 1.1 to 2.8 parts by mass of ethylbutylphosphinate, 0.1 to 0.65 parts by mass of ethylphosphonate, 0.02 to 0.2 parts by mass of monoethylphosphinate, and 0 to 0.4 parts by mass of an alkali-insoluble substance.

[0067] Preferably, the cations in said diethylphosphinate, ethylbutylphosphinate, ethylphosphonate and monoethylphosphinate are the same, and Al 3+ , Ca 2+ , Cu 2+ , Zn 2+ , Fe 2+ , Fe 3+ or Ti 4+ is selected from any one or a combination of at least two of the above.

[0068] In the present invention, the water-soluble acid value of the polymer additive is 0.3 mg KOH / g or less, for example, 0.11 mg KOH / g, 0.12 mg KOH / g, 0.15 mg KOH / g, 0.18 mg KOH / g, 0.2 mg KOH / g, 0.22 mg KOH / g, 0.25 mg KOH / g, 0.28 mg KOH / g, or 0.29 mg KOH / g, and may also be any specific value between the above numerical values. Due to space constraints and for brevity, the present invention does not exhaustively list all specific values falling within said range. Preferably, the water-soluble acid value is 0.1 to 0.3 mg KOH / g.

[0069] Illustratively, the water-soluble acid value of the polymer additive can be determined by the following method. 1 g of a test sample is uniformly wetted with ethanol (the mass of ethanol is m メタノール ), water (the mass of water is m 水 ) is added, the mixture is boiled in water at 90°C for 1 h in a sealed container, then cooled to 25°C, after maintaining the temperature for 30 min, water is added to restore the total mass to that before boiling, the mixture is filtered to obtain a transparent filtrate with a mass of m1, and the acid value of the transparent filtrate is tested by potentiometric titration, wherein the concentration of the potassium hydroxide solution used for titration is 0.05 mol / L, and the water-soluble acid value of the polymer additive = tested acid value × (m 水 + m メタノール ) / m1.

[0070] Preferably, the water-soluble acid value of the polymer additive is 0.5 mg KOH / g or less, and may be, for example, 0.001 mg KOH / g, 0.01 mg KOH / g, 0.02 mg KOH / g, 0.022 mg KOH / g, 0.025 mg KOH / g, 0.028 mg KOH / g, 0.03 mg KOH / g, 0.032 mg KOH / g, 0.035 mg KOH / g, 0.038 mg KOH / g, 0.04 mg KOH / g, or 0.045 mg KOH / g, and specific values ​​between the above values. Due to space limitations and brevity, this invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 0.02 to 0.04 mg KOH / g.

[0071] For example, the organic acid value of the polymer additive can be determined by the following method: 1 g of the test sample is mixed with dichloromethane (the mass of dichloromethane is m). ジクロロメタン The mixture is uniformly moistened with ), boiled in a sealed container at 90°C for 1 hour, then cooled to 25°C and held at that temperature for 30 minutes. Dichloromethane is added up to the total mass before boiling, and the mixture is filtered to obtain a clear filtrate with a mass of m1. The test acid value of the clear filtrate is measured by potentiometric titration, where the concentration of the potassium hydroxide solution used for titration is 0.05 mol / L. The organic acid value of the polymer additive = test acid value × m ジクロロメタン It is / m1.

[0072] Preferably, the mass content of sulfate in the polymer additive is 100 to 700 ppm, and may be, for example, 120 ppm, 150 ppm, 200 ppm, 250 ppm, 270 ppm, 300 ppm, 350 ppm, 400 ppm, 420 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, or 680 ppm, as well as specific values ​​between these numbers. Due to space limitations and brevity, the present invention does not comprehensively list all specific values ​​within the above range, but 270 to 420 ppm is even more preferred.

[0073] For example, the mass content of sulfates in the polymer additive is measured by ion chromatography using an external standard method, referring to the method in accordance with standard EN 14582 - "Measurement of halogen content".

[0074] Preferably, the polymer additive D 50 The particle size is 1 to 100 μm, and may be, for example, 10 μm, 20 μm, 30 μm, 33 μm, 35 μm, 38 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 95 μm, or any specific value between the above numbers. Due to space limitations and for brevity, this invention does not comprehensively list all specific values ​​included in the above range, but is more preferably 20 to 60 μm, and even more preferably 33 to 38 μm.

[0075] D of the polymer additive 50 The particle size is defined as the particle size corresponding to a cumulative volume percentage of 50%, and can be measured using a laser diffraction particle size distribution analyzer according to the GB / T 19077-2016 particle size distribution laser diffraction method.

[0076] Preferably, the water content of the polymer additive is 0.01 to 1 wt%, and may be, for example, 0.02 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, or 0.9 wt%, and specific values ​​between the above values. Due to space limitations and brevity, the present invention does not comprehensively list all specific values ​​included in the above range, but more preferably it is 0.05 to 0.3 wt%, and even more preferably 0.1 to 0.25 wt%.

[0077] For example, the moisture content of the polymer additive can be obtained by measuring it using a Sartorius MA 35 infrared moisture analyzer from Germany, which automatically measures the moisture content after the sample has been left at 120°C for 30 minutes.

[0078] Preferably, the phosphorus content of the polymer additive is 22-25 wt%, and may be, for example, 22.2 wt%, 22.5 wt%, 22.8 wt%, 23 wt%, 23.2 wt%, 23.5 wt%, 23.8 wt%, 24 wt%, 24.2 wt%, 24.5 wt%, or 24.8 wt%, and specific values ​​between the above values. Due to space limitations and brevity, this invention does not comprehensively list all specific values ​​included in the above range. More preferably, it is 23-24 wt%.

[0079] For example, the phosphorus content of the polymer additive can be obtained by dissolving the test sample in an aqueous sulfuric acid solution (30% by mass) and measuring it according to standard GB / T 11893-1989 "Water quality - Measurement of total phosphorus - Ammonium molybdate spectrophotometric method".

[0080] In a third aspect, the present invention provides applying the polymer additive described in the second aspect to a polymer material.

[0081] Preferably, the polymer additive is used in the polymer material as a flame retardant.

[0082] Preferably, the polymer material comprises one or at least two of the following: polyamide, polyester, polyurethane, styrene polymer, polyolefin, polyphenylene ether, and polyacrylate, and more preferably, polyamide and / or polyester.

[0083] In a fourth aspect, the present invention provides a polymer composition comprising a polymer matrix and a polymer additive described in the second aspect.

[0084] Preferably, the polymer composition is 40 to 99 parts by mass of polymer matrix, and The polymer additive comprises 5 to 35 parts by mass.

[0085] Preferably, the polymer matrix may be 40 to 99 parts by mass, for example, 45 parts by mass, 50 parts by mass, 55 parts by mass, 60 parts by mass, 65 parts by mass, 70 parts by mass, 75 parts by mass, 80 parts by mass, 85 parts by mass, 90 parts by mass, 95 parts by mass, or 98 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0086] Preferably, the polymer additive is 5 to 35 parts by mass, and may be, for example, 6 parts by mass, 8 parts by mass, 10 parts by mass, 12 parts by mass, 15 parts by mass, 18 parts by mass, 20 parts by mass, 22 parts by mass, 25 parts by mass, 28 parts by mass, 30 parts by mass, 32 parts by mass, or 34 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0087] Preferably, the polymer matrix includes polyamide and / or polyester.

[0088] Preferably, the polyamide comprises one or at least two of the following: a polyamide resin and a polyamide elastomer.

[0089] The polyamide includes one or at least two of the following: a condensation product of a dicarboxylic acid and a diamine, a condensation product of an ω-amino acid, and a ring-opening polymerization product of a lactam. The dicarboxylic acid includes, but is not limited to, one or at least two of the following: adipic acid, sebacic acid, dodecanediic acid, terephthalic acid, and isophthalic acid. The diamine includes, but is not limited to, one or at least two of the following: pentanediamine, hexanediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine. The cyclic lactam includes, but is not limited to, one or at least two of the following: caprolactam, octyllactam, undecanelactam, and laurolactam. The aforementioned ω-amino acids include, but are not limited to, one or at least two combinations of ω-amino acids formed by ring-opening of the aforementioned cyclic lactams and aminobenzoic acids.

[0090] Preferably, the polyamide includes one or at least two of the following: polyamide 6 (polycaprolactam), polyamide 11 (polyundecanelactam), polyamide 12 (polydodecanolactam), polyamide 56 (polyhexamethylene adipate), polyamide 66 (polyadioxylenediamine), polyamide 610 (polyhexamethylene sevacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 1010 (polydecyldecanediamide), polyamide 1012 (polydodecyldecanediamide), polyamide 1212 (polydodecamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 10T (polydecamethylene terephthalamide), and PPA (polyphthalamide).

[0091] Preferably, the polyester comprises a condensation product of a dicarboxylic acid and / or its derivative with a diol, where the dicarboxylic acid includes, but is not limited to, one or at least two of the following: terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, and hydrogenated phthalic acid. The derivatives include acyl halides (acyl lorides), esters, acid anhydrides, etc., formed from the dicarboxylic acid. The diol includes, but is not limited to, one or at least two of the following: ethylene glycol, butanediol, and hexanediol.

[0092] For example, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0093] Furthermore, the polymer composition of the present invention may further contain other fillers and auxiliary agents that are recommended for addition in the art.

[0094] Preferably, the polymer composition further comprises a reinforcing agent and / or a filler.

[0095] Preferably, the reinforcing material includes glass fibers and / or carbon fibers.

[0096] Preferably, the reinforcing material in the polymer composition is 45 parts by mass or less, and the reinforcing material may be 0, 0.5 parts by mass, 1 part by mass, 2 parts by mass, 5 parts by mass, 8 parts by mass, 10 parts by mass, 15 parts by mass, 20 parts by mass, 25 parts by mass, 30 parts by mass, 35 parts by mass, 40 parts by mass, 42 parts by mass, or 44 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0097] Preferably, the filler includes one or at least two of the following: silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0098] Preferably, the filler in the polymer composition is 40 parts by mass or less, and the filler may be 0, 0.5 parts by mass, 1 part by mass, 2 parts by mass, 5 parts by mass, 8 parts by mass, 10 parts by mass, 12 parts by mass, 15 parts by mass, 18 parts by mass, 20 parts by mass, 22 parts by mass, 25 parts by mass, 28 parts by mass, 30 parts by mass, 32 parts by mass, 35 parts by mass, or 38 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0099] Preferably, the polymer composition further comprises 0 to 15 parts by mass of other additives, the other additives of which may be 0, 0.1 parts by mass, 0.5 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 12 parts by mass, or 14 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0100] Preferably, the other additives include one or at least two of the following: antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, and colorants.

[0101] Preferably, the polymer composition further comprises one or at least two of the following: antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, and colorants.

[0102] Preferably, the antioxidant, ultraviolet absorber, lubricant, and nucleating agent in the polymer composition are each independently present in amounts of 0.01 to 1.5 parts by mass, for example, 0.05 parts by mass, 0.1 parts by mass, 0.2 parts by mass, 0.3 parts by mass, 0.4 parts by mass, 0.5 parts by mass, 0.6 parts by mass, 0.7 parts by mass, 0.8 parts by mass, 0.9 parts by mass, 1 part by mass, 1.2 parts by mass, or 1.4 parts by mass, and specific values ​​between these numerical values. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0103] Preferably, the antioxidant in the polymer composition includes one or at least two of the following: a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

[0104] For example, the antioxidants in the polymer composition are, independently, pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), and N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine The antioxidant comprises one or at least two of the following: (antioxidant 1098), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,4-digylphenyl)pentaerythritol diphosphite ester (antioxidant 608), 2,6-di-tert-butyl-p-cresol (antioxidant BHT), β,β-distearyl thiodipropionate (antioxidant DSTP), antioxidant 215, and antioxidant 225.

[0105] Preferably, the lubricant comprises one or at least two of the following: ester-based lubricants, alcohol-based lubricants, hydrocarbon-based lubricants, fatty acid-based lubricants, fatty acid amide-based lubricants, and metal soap-based lubricants.

[0106] Preferably, the polymer composition further comprises 0 to 15 parts by mass of a synergistic flame retardant, the synergistic flame retardant being 0, 0.1 parts by mass, 0.5 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 12 parts by mass, or 14 parts by mass, and specific values ​​between the above numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​included in the above range.

[0107] Preferably, the synergistic flame retardant comprises one or at least two of the following: melamine pyrophosphate, melamine pyrophosphate salt, zinc borate, zinc stannate, zinc sulfide, and boehmite.

[0108] A preferred technical solution involves the polymer composition, Polymer matrix 40-99 parts by mass, 5 to 35 parts by mass of the polymer additive, 0 to 45 parts by mass of reinforcing material, Synergistic flame retardant 0 to 15 parts by mass, Lubricant 0 to 1.5 parts by mass, It also contains 0 to 1.5 parts by mass of an antioxidant.

[0109] Preferably, the mass percentage of the polymer matrix in the polymer composition is 40% to 99%, and may be, for example, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98%, and specific values ​​between these numbers. Due to space limitations and for the sake of brevity, the present invention does not comprehensively list all specific values ​​that fall within the above range.

[0110] Preferably, the mass percentage of the polymer additive in the polymer composition is 5 to 35%, and may be, for example, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 34%, and specific values ​​between these numbers. Due to space limitations and brevity, the present invention does not comprehensively list all specific values ​​within the above range, but 6% to 20% is more preferable.

[0111] For example, a method for producing the polymer composition includes the steps of melt-blending each component of the polymer composition, extruding it, and obtaining the polymer composition.

[0112] Preferably, first, a polymer matrix, an optional filler, and an optional other auxiliary are premixed to obtain a premix, and then the premix, a polymer additive, and an optional reinforcing agent are melt-blended and extruded to obtain a polymer composition.

[0113] Preferably, the molten blend is carried out in a screw extruder.

[0114] Preferably, the screw extruder is a twin-screw extruder.

[0115] Preferably, the temperature of the screw extruder is 180 to 330°C, and may be, 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 above numbers. Due to space limitations and for the sake of brevity, this invention does not comprehensively list all specific values ​​that fall within the above range.

[0116] Preferably, the process further includes a granulation step and a drying step after the extrusion process.

[0117] Compared to conventional technologies, the present invention has the following beneficial effects.

[0118] The method for producing polymer additives provided by the present invention yields low-acid-value polymer additives through the design of materials such as antioxidants and flocculants, the design of the process and its parameters, and their synergistic effects. When this polymer additive is used as a flame retardant in the production of polymer compositions, it is possible to suppress or avoid the precipitation of auxiliary agents during high-temperature processing, prevent blockage of equipment piping by precipitates, significantly reduce the scale generated during injection molding, and reduce the precipitate content in the polymer composition after boiling, thereby significantly improving the stability and service life of the polymer composition under high-temperature and high-humidity conditions. [Modes for carrying out the invention]

[0119] The technical solutions of the present invention will be further described below in conjunction with specific embodiments. Those skilled in the art will understand that the embodiments described are merely for the purpose of facilitating the understanding of the present invention and should not be construed as limiting the invention.

[0120] The terms “include,” “contain,” “have,” “contain,” and other variations thereof as used herein are intended to mean non-exclusive inclusion. For example, a composition, step, method, product, or apparatus containing the enumerated elements may include, but is not limited to, other elements not expressly enumerated, or elements specific to such composition, step, method, product, or apparatus.

[0121] In the following specific embodiments, the test method for the parameters of the polymer additive is as follows. (1) Content test of diethylphosphinate, ethylbutylphosphinate, ethylphosphonate, and monoethylphosphinate The results were obtained by analysis using liquid chromatography (LC20A, Shimadzu Corporation, Japan). For diethylphosphinate, a commercially available standard sample was used; for ethylbutylphosphinate, a pure sample (prepared according to Example 4 of CN103172668A) was used as the standard sample; for ethylphosphinate, a pure sample (prepared according to Example 2 of CN104371142A) was used as the standard sample; and for monoethylphosphinate, a pure sample (prepared according to Example 1 of CN103172668A) was used as the standard sample. The test samples were dissolved in a sulfuric acid aqueous solution (30% by mass) five times their mass, diluted 20-fold in the mobile phase, and analyzed. The mobile phase was obtained by adding 0.5% by volume of trifluoroacetic acid to a 9:1 mixture of water and methanol, and the chromatography column was ShimNex CS C18 5μm, 4.6×250mm, with a flow rate of 0.6mL / min. The mass content of each component was calculated using the area percentage method. (2) Content of alkali-insoluble substances A 5g sample was taken, 500g of sodium hydroxide aqueous solution (3% by mass) was added, and the mixture was stirred at 35°C for 30 minutes. The mixture was then filtered through filter paper with an accuracy of 2μm or less, rinsed three times with 100g of water, dried, and its weight was measured. The increase in mass relative to the mass of the filter paper before filtration (dried filter paper) was defined as the mass of the insoluble substance, and the mass ratio of the insoluble substance to the test sample (5g) was defined as the mass content of the alkali-insoluble substance. (3) Water-soluble acid value Take 1 g of the test sample and measure 5.00 ± 0.01 g (m エタノール Add ethanol to the mixture and moisten evenly, then add 50±0.01g (m 水 Add room temperature water to the solution, stir in the bottle and weigh to determine the total weight as m0, boil in 90°C water in a sealed container for 1 hour, then cool to 25°C and hold the temperature for 30 minutes, add water until the total weight is m0, filter to obtain a clear filtrate with mass m1, measure the test acid value of the clear filtrate by potentiometric titration, where the concentration of the potassium hydroxide solution used for titration is 0.05 mol / L, and the water-soluble acid value of the polymer additive = test acid value × (m 水 +m メタノール ) / m1 was the value. (4) Organic acid value Take 1 g of the test sample and add 50.0 ± 0.01 g of dichloromethane (m ジクロロメタン In addition, the mixture is uniformly moistened, stirred in a bottle and weighed to a total weight of m0. After boiling in a sealed container at 90°C for 1 hour, it is cooled to 25°C and maintained at that temperature for 30 minutes. Dichloromethane is added until the total weight reaches m0, and the mixture is filtered to obtain a clear filtrate of mass m1. The test acid value of the clear filtrate is measured by potentiometric titration, where the concentration of the potassium hydroxide solution used for titration is 0.05 mol / L. The organic acid value of the polymer additive = test acid value × m ジクロロメタン It was / m1. (5) Mass content of sulfates The measurement was performed using ion chromatography with an external standard method, referring to the method specified in standard EN 14582:2007 - "Measurement of halogen content". (6)D 50 particle size A 0.1g sample was taken, moistened with 5g of ethanol, diluted with 50mL of water, and tested using a Mastersizer 3000 laser particle size distribution analyzer. (7) Moisture content The test samples were placed in an infrared moisture analyzer (MA 35, Sartorius, Germany), left at 105°C for 30 minutes, and then the moisture content was automatically measured. (8) Phosphorus content 0.1 g of the test sample was dissolved in 2 g of sulfuric acid aqueous solution (mass concentration 30%) and tested according to standard GB / T 11893-1989 "Water quality - Measurement of total phosphorus - Ammonium molybdate spectrophotometric method".

[0122] In the following specific embodiments of the present invention, all materials for which the manufacturing method is not shown are commercially available chemical substances. Specific information regarding some of these materials is as follows: TIFF2026153790000001.tif140160

[0123] The polymer additive and its manufacturing method described in the present invention will be explained in detail below using several examples, but the polymer additive and its manufacturing method are not limited to these examples.

[0124] Examples 1-9, Comparative Examples 1-5 A polymer additive and a method for producing the same, wherein the production method is as follows: (1) Place 39.6 kg of 50% hypophosphorous acid aqueous solution, 500 g of sodium persulfate, and m1 mass of antioxidant into an autoclave, purge three times with nitrogen gas, maintain an ethylene pressure of 1.5 MPa in a vacuum chamber, heat to temperature T1, maintain this temperature for 5.5 hours, and while maintaining the temperature, continuously add 3500 g of 10% sodium persulfate aqueous solution, then maintain at temperature T1 for 1.5 hours, cool and degass to obtain diethylphosphinic acid aqueous solution. (2) Mix the diethylphosphinic acid aqueous solution (6 mol of diethylphosphinic acid) obtained in step (1), the sulfuric acid aqueous solution (sulfuric acid mass content 30%, molar amount n1), and 2 mol of aluminum hydroxide, heat to a temperature T2 and stir for 8 hours to react, and adjust the pH value with sodium hydroxide solution (mass content 10%) to obtain a diethylphosphinate slurry. (3) At 50°C, an aqueous solution of a flocculant prepared with m² of anionic polyacrylamide and 50 g of water was added to the diethylphosphinate slurry obtained in step (2), stirred until flocculated, filtered, and the filtered cake was washed five times with three times its mass of water, and dried at 110°C to a constant weight to obtain the polymer additive.

[0125] Tables 1 and 2 show the specific process parameters of the manufacturing method and the relevant data for the obtained polymer additives. "--" indicates that the material was not added.

[0126] [Table 1]

[0127] [Table 2]

[0128] As can be seen from Table 1, the present invention designs a method for producing a polymer additive, and in particular, by using an antioxidant and a flocculant and controlling the pH value of the slurry, a low acid value polymer additive with a water-soluble acid value of 0.3 mg KOH / g or less was obtained. The polymer additive contained 95 to 98.98 parts by mass of diethylphosphinate, 1 to 3 parts by mass of ethylbutylphosphinate, 0.01 to 0.7 parts by mass of ethylphosphonate, 0.01 to 0.3 parts by mass of monoethylphosphinate, and 0 to 3 parts by mass of an alkali-insoluble substance.

[0129] In Table 2, in Comparative Examples 1 and 2, the pH value of the slurry exceeded the limits of the present invention; in Comparative Examples 3 and 4, no antioxidant was used; and in Comparative Example 5, no flocculant was added, resulting in a significant increase in both the water-soluble acid value and the organic acid value of the polymer additive.

[0130] The applications of the polymer additive described in this invention will be explained in detail below using examples of applications, but the applications of the polymer additive described are not limited to these examples.

[0131] Application Examples 1-9, Comparative Application Examples 1-5 In the polymer composition, specifically the polyamide composition, the types and amounts of each component are shown in Tables 3 and 4, and the unit of the amount of each component is "parts by mass".

[0132] The method for producing the polyamide composition includes the steps of: mixing polyamide 66, polyamide 6, glass fiber, polymer additive, MPP, antioxidant and lubricant according to the formulation to obtain a premix; and adding the premix to a twin-screw extruder, setting the screw rotation speed of the twin-screw extruder to 400 rpm, and setting the temperatures of zones 1 to 12 to 90°C, 180°C, 260°C, 250°C, 230°C, 230°C, 220°C, 220°C, 220°C, 220°C, 260°C, and 260°C, respectively, and then performing melt blending and extrusion granulation to obtain polyamide composition particles.

[0133] The following performance tests were conducted on the polyamide composition. (1) Test for phosphorus content by boiling in water: 50 g of polyamide composition particles were added to 500 mL of 90°C hot water, boiled for 1 hour, cooled to room temperature, filtered, and the phosphorus content of the filtrate was measured by ammonium molybdate spectrophotometric method in accordance with GB / T 11893-1989. (2) Scale testing method: Using an injection molding machine, polyamide composition particles were continuously injected into 150 molds at injection temperatures of 290°C, 285°C, 280°C, and 260°C. The molds were then removed, scale samples were collected, and their weight was measured using an analytical balance. (3) Amount of precipitate in the extrusion process: A cyclone separator with a jacketed cooling function was added to the vacuum line of a twin-screw extruder with a diameter of 75 mm and a length-to-diameter ratio of 48:1. The precipitate extracted by vacuum during the extrusion process was separated, and after continuously producing 2000 kg of product, the precipitate in the cyclone separator was weighed, and its weight was taken as the amount of extrusion during the extrusion process. If the separator became clogged, it would indicate that the amount of extrusion was too high, and the vacuum system would become clogged within 8 hours of the start of production. The data for each test are shown in Tables 3 and 4.

[0134] [Table 3]

[0135] [Table 4]

[0136] As can be seen from the data in Table 3, when the polymer additive provided by the present invention is used as a flame retardant in a polyamide composition, the precipitation of auxiliary agents during extrusion can be effectively suppressed, reducing the risk of clogging, significantly reducing the scale generated during injection molding to 7.2 mg or less, reducing the phosphorus content of the polyamide composition after boiling to 490 mg or less, reducing the amount of precipitate after boiling, and improving the stability and service life of the polyamide composition under high temperature and high humidity conditions.

[0137] As can be seen from the test data in Table 4, the polymer additives in Comparative Examples 1 to 10 have high acid values. Therefore, when used as flame retardants in polyamide compositions, a large amount of additive precipitates during extrusion, which easily causes pipe blockage. In addition, a large amount of scale is produced during injection molding, the phosphorus content increases after boiling, and stability under high temperature and high humidity conditions is significantly insufficient.

[0138] While the applicant has illustrated the polymer additives of the present invention, their manufacturing methods, and their applications through the above examples, the applicant declares that the present invention is not limited to the above examples, that is, it does not mean that one must rely on the above examples to carry out the present invention. Those skilled in the art will understand that any improvements to the present invention, equivalent substitutions of each raw material in the product of the present invention, addition of auxiliary components, selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A method for producing polymer additives, wherein the production method is: Step (1) involves reacting an aqueous hypophosphorous acid solution and an antioxidant with ethylene under the action of an initiator to obtain an aqueous diethylphosphinic acid solution, Step (2) involves reacting the aforementioned aqueous solution of diethylphosphinic acid with sulfuric acid and a metal hydroxide, and then adding an alkaline solution to obtain a diethylphosphinate slurry with a pH of 3.8 to 4.

2. A method for producing a polymer additive, comprising the steps (3) of: mixing the diethyl phosphinate slurry with a flocculant and stirring to obtain a diethyl hypophosphate aggregate; and filtering, washing, and drying the diethyl hypophosphate aggregate to obtain the polymer additive.

2. The antioxidant comprises one or at least two of the following: a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant, preferably comprising one or at least two of the following: a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant. Preferably, the antioxidant comprises one or at least two of the following: pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-digylphenyl)pentaerythritol diphosphite ester, 2,6-di-tert-butyl-p-cresol, and β,β-distearyl thiodipropionate. Preferably, the manufacturing method according to claim 1, characterized in that the initiator comprises one or at least two of the following: an organic peroxide, a persulfate, an azo initiator, and a photoinitiator.

3. The mass percentage of hypophosphorous acid in the aforementioned aqueous hypophosphorous acid solution is 20 to 70%, preferably 45 to 55%. Preferably, the mass ratio of hypophosphorous acid to antioxidant is 100:(0.02 to 1.2), and more preferably 100:(0.05 to 1). Preferably, the mass ratio of hypophosphorous acid to the initiator is 100:(0.1 to 5), characterized in that, the manufacturing method according to claim 1.

4. The temperature of the free radical reaction is 60 to 105°C, preferably 70 to 100°C, and more preferably 75 to 95°C. Preferably, the free radical reaction is carried out under a protective atmosphere. Preferably, the protective atmosphere includes a nitrogen gas atmosphere and / or an argon gas atmosphere, as described in claim 1.

5. The metal hydroxide comprises one or at least two of the following: aluminum hydroxide, calcium hydroxide, copper hydroxide, zinc hydroxide, iron hydroxide, and titanium hydroxide, and is preferably aluminum hydroxide. Preferably, if the molar amount of diethylphosphinic acid is 100%, the molar amount of the metal hydroxide is 30 to 50 mol%, Preferably, with respect to the molar amount of diethylphosphinic acid being 100%, the molar amount of sulfuric acid is 5 to 50 mol%, more preferably 8 to 30 mol%, and even more preferably 10 to 15 mol%. Preferably, the reaction temperature in step (2) is 70 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 100°C. Preferably, the reaction time in step (2) is 2 to 12 hours, as described in claim 1.

6. The flocculant comprises a polyacrylamide flocculant, preferably an anionic polyacrylamide and / or nonionic polyacrylamide, and more preferably an anionic polyacrylamide. Preferably, with the mass of the theoretically obtained diethylphosphinate being taken as 100%, the mass of the flocculant is 0.01 to 0.5%. Preferably, the mixing temperature described in step (3) is 40 to 60°C. Preferably, the manufacturing method according to claim 1, characterized in that the number of washes in step (3) is four or more times.

7. A polymer additive obtained by a manufacturing method described in any one of claims 1 to 6, wherein the water-soluble acid value of the polymer additive is 0.3 mg KOH / g or less. Preferably, the polymer additive is 95 to 98.98 parts by mass of diethylphosphinate, 1 to 3 parts by mass of ethylbutylphosphinate, 0.01 to 0.7 parts by mass of ethylphosphonate, 0.01 to 0.3 parts by mass of monoethylphosphinate, and It contains 0 to 3 parts by mass of alkali-insoluble substance, The polymer additive is characterized in that the alkali-insoluble substance is selected from one or at least two of the following: hydroxides, oxides, phosphates, phosphates, and other alkylphosphonates.

8. The water-soluble acid value of the polymer additive is 0.1 to 0.3 mg KOH / g. Preferably, the organic acid value of the polymer additive is 0.05 mg KOH / g or less, and more preferably 0.02 to 0.04 mg KOH / g. Preferably, the sulfate content in the polymer additive is 100 to 700 ppm, more preferably 270 to 420 ppm. Preferably, the polymer additive D ５０ The particle size is 1 to 100 μm, more preferably 20 to 60 μm, and even more preferably 33 to 38 μm. Preferably, the water content of the polymer additive is 0.01 to 1 wt%, more preferably 0.05 to 0.3 wt%, and even more preferably 0.1 to 0.25 wt%. Preferably, the polymer additive has a phosphorus content of 22 to 25 wt%, more preferably 23 to 24 wt%, as described in claim 7.

9. Preferably, the polymer additive is used as a flame retardant in the polymer material, characterized in that the application of the polymer additive according to claim 7 in a polymer material.

10. A polymer composition comprising a polymer matrix and the polymer additive described in claim 7, Preferably, the polymer composition is 40 to 99 parts by mass of polymer matrix, and The polymer additive comprises 5 to 35 parts by mass, Preferably, the polymer composition is characterized in that the polymer matrix comprises polyamide and / or polyester.