A polymer additive and a method for preparing the same, a polymer composition comprising the same

Abstract

The application provides a polymer additive and a preparation method thereof, a polymer composition containing the same, and the preparation method comprises the following steps: performing a free radical reaction on hypophosphite aqueous solution and an antioxidant in the presence of an initiator and ethylene to obtain diethyl hypophosphite aqueous solution; mixing the diethyl hypophosphite aqueous solution, metal salt aqueous solution and lye, and performing a reaction under the condition that the pH value is 3.5-3.8 to obtain diethyl hypophosphite metal salt slurry; mixing the diethyl hypophosphite metal salt slurry and a flocculating agent, stirring to obtain diethyl hypophosphite metal salt flocculate, and performing filtration, washing and drying to obtain the polymer additive. Through the design of the preparation method, the polymer additive with low acid value and high thermal stability can be obtained, the polymer additive is used as a flame retardant to prepare a polymer composition, the injection molding fouling can be reduced, the polymer composition has less water boiling precipitates, and the stability of the polymer composition under the condition of damp heat is improved.

Description

Technical Field

[0001] This invention belongs to the field of flame retardant technology, specifically relating to a polymer additive and its preparation method, and a polymer composition containing the same. Background Technology

[0002] Dialkylphosphinates are a general-purpose halogen-free and environmentally friendly flame retardant. They are characterized by good flame retardant properties, low addition amount, and minimal impact on the physical and electrical properties of the base resin. More importantly, materials using dialkylphosphinates as flame retardants have high CTI (relative tracking index) and low smoke production during combustion. They also possess superior mechanical and electrical properties, making them increasingly popular among manufacturers in the electrical and electronic equipment industry, with a very broad market prospect.

[0003] With the widespread application of dialkylphosphines, significant performance defects have become increasingly apparent. For example, research by Braun U et al. revealed that when dialkylphosphines are used to flame-retard PBT and polyamide, they decompose to release dialkylphosphinic acid during high-temperature processes. Specifically, when dialkylphosphines are used to flame-retard polyamide, the polyamide's numerous polar amide groups make it highly absorbent of water, resulting in a high water absorption rate. For instance, PA66 resin can achieve a water absorption rate of 2.7% at 23°C and 50% humidity. During extrusion or high-temperature injection molding, dialkylphosphines are inherently acidic and decompose to release dialkylphosphinic acid upon heating, easily promoting system decomposition and leading to significant gas emissions during processing. In repeated injection molding processes, severe mold fouling often occurs on the mold, severely affecting the product's appearance and requiring frequent mold cleaning, resulting in low production efficiency and hindering the widespread adoption of the product.

[0004] Currently, the main method to solve the problem of mold fouling in injection molding of dialkylphosphinate flame-retardant polyamide materials is to add an acid scavenger to the system to reduce its acidity. For example, EP2417191A1 discloses a halogen-free flame-retardant polyamide composition that adds 0.15-1 wt% calcium oxide, which neutralizes some acidic substances in the system, reduces the acidity of the system, and reduces the decomposition of the matrix resin, thereby effectively reducing the corrosiveness of the mold during high-temperature injection molding. Although this method helps to reduce mold fouling to some extent, calcium oxide is very hygroscopic, resulting in a high water absorption rate of the system, which is difficult to control during processing.

[0005] In the halogen-free flame-retardant thermoplastic polyamide composition disclosed in CN112409786A, a certain amount of ethylene copolymer is added as an adsorbent to reduce the amount of mold fouling generated during the injection molding process. CN114874616A discloses a halogen-free flame-retardant polyamide composite material that introduces a composite system of metal oxides and polyhydroxy components, resulting in a polyamide material with better anti-yellowing properties, lower mold fouling, and a higher number of consecutive mold opening and closing cycles. Although the above methods have a certain improvement effect on mold fouling of dialkylphosphinate flame-retardant polyamides, they all improve the acidity of the system and reduce mold fouling by adding external additives. While increasing costs, it is difficult to avoid the impact of new substances on other properties of the flame-retardant polyamide, such as the addition of inorganic metal oxides leading to a decrease in the mechanical properties of the material. Moreover, dialkylphosphinates themselves have insufficient heat resistance, exhibiting significant weight loss at temperatures above 300℃, causing decomposition during melt blending, extrusion, and other processing, affecting performance; and the method of adding external additives does not fundamentally solve the problem of insufficient heat resistance of dialkylphosphinates.

[0006] Therefore, providing a flame retardant additive with lower acidity and better thermal stability, so that polymer compositions using it have lower mold fouling and less additive precipitation, is a problem that urgently needs to be solved in the art. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a polymer additive and its preparation method, as well as a polymer composition containing the additive. By designing and interacting the raw materials, process steps, and parameters in the preparation method, a polymer additive with low acid value and high thermal stability can be obtained. When the polymer additive is used as a flame retardant to prepare a polymer composition, it not only effectively reduces mold fouling but also gives the polymer composition a lower content of water-boiling precipitates, thus extending its service life under humid and hot conditions.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing a polymer additive, the method comprising the following steps:

[0010] (1) An aqueous solution of hypophosphite and an antioxidant react with ethylene in the presence of an initiator to produce an aqueous solution of diethylphosphite;

[0011] (2) The diethylphosphonate aqueous solution, the metal salt aqueous solution and the alkaline solution are mixed and reacted under the condition of pH 3.5-3.8 to obtain diethylphosphonate metal salt slurry;

[0012] (3) The diethylphosphine metal salt slurry and flocculant are mixed and stirred to obtain diethylphosphine metal salt flocculants; the diethylphosphine metal salt flocculants are filtered, washed and dried to obtain the polymer additive.

[0013] This invention has found that by adding an antioxidant in step (1), the water-soluble acid value and organic acid value of the product can be effectively reduced. This is because the reaction between hypophosphite and ethylene is generally initiated by a free radical initiator. Hypophosphite contains pH bonds and has strong reducing properties. Therefore, free radical reaction and oxidation reaction occur simultaneously in step (1). The antioxidant introduced in this invention can donate electrons to the oxidant, thereby reducing it to a more stable substance. At the same time, the free radical reaction between hypophosphite and ethylene is a strong exothermic reaction, which is prone to uncontrollable phenomena and produces many side reactions during production. The antioxidant captures free radicals by reacting with them, neutralizing their activity, which can effectively slow down the exothermic effect and reduce the occurrence of side reactions, making the production process controllable.

[0014] Furthermore, this invention has found through research that the pH of the reaction system has a significant impact on the crystallization behavior of the additive precipitation process, thereby affecting the acid value of the product. This invention controls the pH of the system in step (2) to be 3.5-3.8, for example, 3.52, 3.55, 3.58, 3.6, 3.62, 3.65, 3.68, 3.7, 3.72, 3.75, 3.78, etc. Within this range, high-performance polymer additives can be prepared, especially those with low acid values ​​and excellent heat resistance. When used as flame retardants to prepare composite materials, they exhibit lower mold scale and water boil-out precipitate content. If the pH of the reaction system in step (2) is too low, it easily leads to excessively high acidity of the polymer additive and reduced thermal stability; if the pH of the reaction system is too high, it also leads to an increase in the acid value of the polymer additive, and further increases in pH will lead to a decrease in yield.

[0015] Furthermore, the main function of flocculants is to utilize the proximity of positively (negatively) charged groups and negatively (positively) charged, difficult-to-separate particles in water, thereby reducing their potential and making them unstable. Their polymerization properties then cause these particles to aggregate and be separated by physical or chemical methods. When the flocculant is used for flocculation of the polymer additives of this invention, it acts through adsorption bridging and reinforcement, fixing the surface of the polymer additive particles onto the molecular chains of the flocculant to form polymer bridges, thus causing the particles to aggregate and settle. The flocculant adsorbs and binds to the diethylphosphonic acid metal salt in the slurry obtained in step (2), effectively improving the filtration and washing effect of the polymer additives while reducing the acidity of the filtered and washed polymer additives.

[0016] In summary, this invention provides a specially designed method for preparing polymer additives. By using antioxidants and flocculants during the preparation process and controlling the pH value of the metathesis reaction to 3.5-3.8, a polymer additive with low acid value and excellent thermal stability is obtained. When used as a flame retardant in the preparation of polymer compositions, it can significantly reduce mold fouling, resulting in a lower content of water-boiling precipitates in the polymer composition. This greatly improves the stability of the polymer composition under humid and hot conditions and extends its service life.

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

[0018] Preferably, the hypophosphite comprises sodium hypophosphite and / or potassium hypophosphite, thereby yielding an aqueous solution of sodium diethylphosphite and / or potassium diethylphosphite.

[0019] It should be noted that the hypophosphite may be anhydrous hypophosphite and / or hypophosphite salt hydrate.

[0020] Preferably, the hypophosphite is sodium hypophosphite, and step (1) yields an aqueous solution of sodium diethylphosphite.

[0021] Preferably, the mass percentage of hypophosphite in the hypophosphite aqueous solution is 10-60%, for example, it can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or 55%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 30-40% is further preferred.

[0022] Preferably, the antioxidant includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants; more preferably, a combination of any one or at least two of hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0023] More preferably, the antioxidant comprises any one or a combination of at least two of the following: 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), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), 2,6-di-tert-butyl-p-cresol (antioxidant BHT), distearate β,β-thiodipropionate (antioxidant DSTP), antioxidant 215, and antioxidant 225.

[0024] The antioxidants in this invention can be single components, such as any of the antioxidants listed above, or multiple compound antioxidants, such as a combination of hindered phenolic antioxidants and phosphite antioxidants. A typical combination is a compound of antioxidant 1010 and antioxidant 168 in different proportions, such as antioxidant 215, antioxidant 225, etc.

[0025] Preferably, the mass ratio of hypophosphite to antioxidant is 100:(0.02-1.2), for example, it can be 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, etc., and more preferably 100:(0.05-1).

[0026] Preferably, the initiator includes any one or a combination of at least two of the following: organic peroxides, persulfates, azo initiators, and photoinitiators.

[0027] Preferably, the organic peroxide includes diisobutyryl peroxide, benzoyl peroxide, bis(2-ethylhexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, 1,1,3,3-tetramethylbutyl peroxypentanoate, tert-butyl peroxypentanoate, pentyl peroxypentanoate, dilauroyl peroxide, bis(3,3,5-trimethylacetyl) peroxide, 2,5-dimethyl-2,5-di(2-ethylacetylperoxide)hexane, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, and peroxide-2 -Any one or a combination of at least two of the following: tert-butyl ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-isobutyrate, 1,1-di-tert-butylperoxide-3,3,5-trimethylcyclohexane, 1,1-di-tert-pentylcyclohexane peroxide, 1,1-di-tert-butylcyclohexane peroxide, di-tert-butyl peroxide, di-tert-pentyl peroxide, dicumyl peroxide, 2,5-di-tert-butylperoxide-2,5-dimethylhexane, tert-butyl peracetate, tert-pentyl peroxide-benzoate, tert-butyl peroxide-maleic acid, and tert-butyl peroxide-2-ethylhexyl carbonate.

[0028] Preferably, the persulfate includes any one or a combination of at least two of sodium persulfate, potassium persulfate, and ammonium persulfate.

[0029] Preferably, the azo initiator includes any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, azobisisobutyramidazole hydrochloride, and azobisisobutyronitrile cyanoformamide.

[0030] It should be noted that the present invention does not impose any special restrictions on the specific selection of photoinitiators, and commonly used photoinitiators in the art are all applicable.

[0031] It should be noted that the initiator in step (1) of the present invention can be added all at once, or in batches, or continuously added during the reaction process; and in step (1), a portion of the initiator can be added in advance, and the remainder can be added continuously during the reaction process.

[0032] Preferably, the mass ratio of hypophosphite to initiator is 100:(0.1-5), for example, it can be 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, etc.

[0033] Preferably, the molar ratio of ethylene to hypophosphite is (2-2.1):1, for example, it can be 2.01:1, 2.02:1, 2.04:1, 2.05:1, 2.06:1, 2.08:1 or 2.09:1, etc.

[0034] Preferably, the temperature of the free radical reaction is 70-120°C, for example, it can be 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C or 115°C, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range. More preferably, it is 80-110°C, and even more preferably, it is 90-105°C.

[0035] The free radical reaction described in step (1) is carried out in the presence of an initiator. When the pressure of the reaction system no longer changes significantly, the reaction is considered complete and the reaction is stopped.

[0036] Preferably, the free radical reaction is carried out in a protective atmosphere.

[0037] Preferably, the protective atmosphere includes a nitrogen atmosphere and / or an argon atmosphere.

[0038] In this invention, the metal salt in step (2) is a water-soluble metal salt. Preferably, the metal salt includes metal sulfates and / or metal chlorides, and more preferably, metal sulfates.

[0039] Preferably, the metal in the metal salt includes any one or a combination of at least two of Al, Ca, Cu, Zn, Fe, and Ti, with Al being more preferred.

[0040] Preferably, the metal salt includes aluminum sulfate.

[0041] It should be noted that the metal salt can be anhydrous metal salt and / or metal salt hydrate.

[0042] Preferably, the mass percentage of the metal salt in the aqueous solution is 20-40%, for example, it can be 22%, 25%, 28%, 30%, 32%, 35% or 38%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0043] Preferably, the molar ratio of the metal salt to the diethylphosphonate is 1:(5.8-6.2), for example, it can be 1:5.82, 1:5.85, 1:5.88, 1:5.9, 1:5.92, 1:5.95, 1:5.98, 1:6, 1:6.02, 1:6.05, 1:6.08, 1:6.1, 1:6.12, 1:6.15 or 1:6.18, etc., and more preferably 1:6.

[0044] Preferably, the alkaline solution comprises sodium hydroxide solution and / or potassium hydroxide solution.

[0045] This invention does not impose any special restrictions on the mass concentration of sodium hydroxide solution or potassium hydroxide solution. It is only necessary to add sodium hydroxide solution and / or potassium hydroxide solution to maintain the pH of the reaction system obtained in step (2) at 3.5-3.8.

[0046] Preferably, the reaction temperature in step (2) is 20-80°C, for example, it can be 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C or 75°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but it is further preferred to be 40-60°C.

[0047] Preferably, the reaction time in step (2) is 0.1-5h, for example, it can be 0.2h, 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h or 4.5h, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0048] It should be noted that in step (2) of the present invention, the metal salt aqueous solution and the alkali solution are simultaneously added to the diethylphosphonate aqueous solution for reaction, or the metal salt aqueous solution, the alkali solution and the diethylphosphonate aqueous solution are continuously added to the reaction device (such as a stirred reaction vessel, a static mixer or a dynamic mixer) at a constant flow rate for thorough mixing reaction. When the metal salt aqueous solution and the alkali solution are simultaneously added to the diethylphosphonate aqueous solution for reaction, the reaction temperature is 20-80℃, preferably 30-70℃, and more preferably 40-60℃. The dropwise addition time of the metal salt aqueous solution and the alkali solution is 0.1-5h (e.g., 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, etc.), preferably 0.5-3h, and more preferably 1h-3h. When the metal salt aqueous solution, the alkali solution, and the diethylphosphonate aqueous solution are continuously added to the reaction vessel at a constant flow rate, the reaction temperature is 40-80℃, preferably 50-60℃, and the reaction space velocity is 0.1-2 / h (e.g., 0.2 / h, 0.5 / h, 0.8 / h, 1 / h, 1.2 / h, 1.5 / h, 1.8 / h, etc.), preferably 0.3-1 / h, and more preferably 0.5-0.8 / h.

[0049] Preferably, the flocculant includes any one or a combination of at least two of the following: polyacrylamide flocculants, starch flocculants, and chitosan flocculants.

[0050] More preferably, the flocculant includes anionic polyacrylamide and / or nonionic polyacrylamide.

[0051] As a preferred technical solution of the present invention, a polyacrylamide flocculant (preferably anionic polyacrylamide and / or nonionic polyacrylamide) is used, which can fix the surface of polymer additive particles on the molecular chain of the flocculant to form polymer bridges. In particular, when anionic polyacrylamide is added as a flocculant, it can produce adsorption bridging and reinforcement effects, thereby causing the particles to form aggregates and settle, improving the filtration and washing effect of polymer additives, and reducing the acid value of polymer additives after filtration and washing.

[0052] Preferably, based on the theoretically obtained mass of the diethylphosphonic acid metal salt as 100%, the mass of the flocculant is 0.01-0.5%, for example, it can be 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%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0053] The "theoretically obtained mass of diethylphosphonic acid metal salt" is calculated by the amount of diethylphosphonic acid salt and metal salt added in step (2).

[0054] Preferably, the flocculant and water are first mixed at 20-30°C for 10-20 minutes to obtain a flocculant solution, and then the flocculant solution is mixed with diethylphosphonic acid metal salt slurry and stirred. The mass ratio of flocculant to water is 1:(10-1000), 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, etc.

[0055] Preferably, the mixing temperature in step (3) is 40-60°C, for example, it can be 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C or 58°C, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0056] Preferably, the number of washing cycles in step (3) is ≥4 times, for example, 5, 6, 7, 8, 9, 10 or 12 times, and more preferably 5-10 times.

[0057] Preferably, the washing agent used for washing is water.

[0058] As a preferred technical solution of the present invention, the diethylphosphite metal salt flocculant is filtered and then washed multiple times, with the number of washings being ≥4 times, preferably 5-10 times, which can better remove impurities and acidic substances from the product and obtain the polymer additive with low acid value and better thermal stability.

[0059] Preferably, the mass ratio of water to solids in each wash is independently (1-10):1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, etc., and more preferably (1.5-6):1; the solids are the solid products obtained by filtration.

[0060] Preferably, the drying temperature in step (3) is 105-250℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 180℃, 200℃, 220℃ or 240℃, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 110-150℃ is further preferred.

[0061] As a preferred embodiment of the present invention, the preparation method of the polymer additive specifically includes the following steps:

[0062] (1) In a protective atmosphere, an aqueous solution of hypophosphite and an antioxidant are reacted with ethylene in the presence of an initiator to obtain an aqueous solution of diethylphosphite.

[0063] The hypophosphite aqueous solution contains 10-60% hypophosphite by mass, and the mass ratio of hypophosphite, antioxidant, and initiator is 100:(0.02-1.2):(0.1-5). The free radical reaction is carried out at a temperature of 70-120°C and terminated when the pressure of the system no longer changes.

[0064] (2) The diethylphosphonate aqueous solution, the metal salt aqueous solution and the alkaline solution are mixed and reacted at a pH of 3.5-3.8 and a temperature of 40-60°C to obtain a diethylphosphonate metal salt slurry;

[0065] The molar ratio of the metal salt to diethylphosphonate is 1:(5.9-6.1), and the mass percentage of the metal salt in the aqueous solution of the metal salt is 20-40%.

[0066] (3) The diethylphosphonic acid metal salt slurry and flocculant solution are mixed at 40-60℃ and stirred to obtain diethylphosphonic acid metal salt flocculants; the diethylphosphonic acid metal salt flocculants are filtered, washed ≥4 times, and dried to obtain the polymer additive.

[0067] Wherein, based on the theoretically obtained mass of the diethylphosphonic acid metal salt as 100%, the mass of the flocculant is 0.01-0.5%.

[0068] In a second aspect, the present invention provides a polymer additive, which is prepared by the preparation method described in the first aspect, wherein the water-soluble acid value of the polymer additive is ≤0.33 mg KOH / g; the polymer additive comprises the following components in parts by mass:

[0069]

[0070] The polymer additive provided by this invention has a low acid value and excellent thermal stability. Its water-soluble acid value is ≤0.33mg KOH / g. When used as a flame retardant in polymer compositions, it can inhibit the decomposition of dialkylphosphine acid at high temperatures, resulting in a lower content of water-boiling precipitates in the polymer composition. This effectively improves its stability under humid and hot conditions, extends its service life, and reduces the amount of mold fouling generated during injection molding.

[0071] The mass fraction of diethylphosphonate in the polymer additive is 96-99.88 parts, for example, 96 parts, 96.2 parts, 96.5 parts, 96.8 parts, 96.9 parts, 97 parts, 97.2 parts, 97.5 parts, 97.8 parts, 98 parts, 98.2 parts, 98.5 parts, 98.8 parts, 99 parts, 99.2 parts, 99.5 parts, 99.6 parts, or 99.8 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0072] Preferably, the mass percentage of diethylphosphonate in the polymer additive is ≥95%, for example, it can be 95.5%, 96%, 96.2%, 96.5%, 96.8%, 97%, 97.2%, 97.5%, 97.8%, 98%, 98.2%, 98.5%, 98.8%, 99%, 99.2%, 99.5%, 99.8%, or 99.88%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0073] The polymer additive contains 0.1-2 parts by mass of ethyl butyl phosphonate, for example, 0.12 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, or 1.8 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0074] The ethyl phosphonate in the polymer additive is 0.01-1 parts by mass, for example, 0.02 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts, or 0.95 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range.

[0075] The mass fraction of monoethylphosphonate in the polymer additive is 0.01-1 part, for example, it can be 0.02 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts or 0.95 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0076] For example, the mass fractions of diethylphosphonate, diethylphosphonate, ethylphosphonate, and monoethylphosphonate in the polymer additive can be obtained by liquid chromatography analysis. For instance, the sample to be tested is dissolved in a sulfuric acid aqueous solution (30% mass concentration) at 5 times its mass, and then diluted 10-30 times with the mobile phase for analysis. The mobile phase is a mixture of water and methanol at a mass ratio of 9:1, with 0.5% trifluoroacetic acid added by volume. A ShimNex CSC18 column is used at a flow rate of 0.6 mL / min. The mass fraction of each component is calculated using the area normalization method.

[0077] Preferably, the mass fraction of other phosphorus-containing compounds in the polymer additive is ≤1.2 parts, for example, it can be 0, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part or 1.1 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and it is further preferred to be 0.05-0.9 parts.

[0078] It should be noted that the other phosphorus-containing compounds are alkali-soluble and different from diethylphosphonic acid salts, ethylbutylphosphonic acid salts, ethylphosphonic acid salts, and monoethylphosphonic acid salts. Their mass fraction can be determined by NMR phosphorus spectroscopy. In the NMR phosphorus spectroscopy, the integral area of ​​the peaks other than diethylphosphonic acid salts, ethylbutylphosphonic acid salts, ethylphosphonic acid salts, and monoethylphosphonic acid salts represents the content of the other phosphorus-containing compounds.

[0079] Preferably, the polymer additive comprises the following components in parts by weight:

[0080]

[0081] Preferably, the cations in the diethylphosphonic acid salt, ethylbutylphosphonic acid salt, ethylphosphonic acid salt, and monoethylphosphonic acid salt are the same and are selected from Al. 3+ Ca 2+ Cu 2+ Zn 2+ Fe 2+ Fe 3+ or Ti 4+ Any one or at least two of them.

[0082] In this invention, the water-soluble acid value of the polymer additive is ≤0.33 mg KOH / g, for example, it can be 0.01 mg KOH / g, 0.1 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, 0.29 mg KOH / g, 0.3 mg KOH / g, 0.31 mg KOH / g, or 0.32 mg KOH / g, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range, but preferably 0.1-0.3 mg KOH / g.

[0083] For example, the water-soluble acid value of the polymer additive can be obtained by testing it as follows: 1g of the sample to be tested is diluted with ethanol (ethanol mass is m). 乙醇 After evenly wetting, add water (the mass of the water is m). 水 After boiling in water at 90℃ for 1 hour in a sealed container, the solution was cooled to 25℃ and held at that temperature for 30 minutes. Water was then added back to the total mass before boiling. The solution was filtered to obtain a clear filtrate with a mass of m1. The acid value of the filtrate was determined by potentiometric titration, using a 0.05 mol / L potassium hydroxide solution. The water-soluble acid value of the polymer additive was calculated as: (test acid value × m1) / m1. 水 +m 乙醇 ) / m1.

[0084] Preferably, the organic acid value of the polymer additive is ≤0.05 mg KOH / g, for example, it can be 0.001 mg KOH / g, 0.005 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, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 0.002-0.04 mg KOH / g is further preferred.

[0085] For example, the organic acid value of the polymer additive can be obtained by testing it as follows: 1g of the sample to be tested is treated with dichloromethane (the mass of dichloromethane is m). 二氯甲烷 After uniform wetting, boil in a sealed container at 90℃ for 1 hour, then cool to 25℃ and hold at that temperature for 30 minutes. Add dichloromethane to the total mass before boiling. Filter to obtain a clear filtrate with a mass of m1. The acid value of the filtrate is determined by potentiometric titration, using a 0.05 mol / L potassium hydroxide solution. The organic acid value of the polymer additive is calculated as: acid value × m1. 二氯甲烷 / m1.

[0086] Preferably, the sulfate content in the polymer additive is 100-600 ppm, for example, it can be 120 ppm, 150 ppm, 200 ppm, 250 ppm, 270 ppm, 300 ppm, 350 ppm, 400 ppm, 420 ppm, 450 ppm, 500 ppm, 550 ppm or 580 ppm, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 110-370 ppm is further preferred.

[0087] For example, the mass content of sulfate in the polymer additive is determined by ion chromatography using the external standard method, referring to the method in standard EN 14582:2007 - Determination of halogen content.

[0088] Preferably, the 1% thermogravimetric temperature of the polymer additive is ≥350°C, for example, it can be 355°C, 358°C, 360°C, 362°C, 365°C, 368°C, 370°C, 372°C, 375°C, 378°C, 382°C or 385°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 358-380°C is further preferred.

[0089] In this invention, the term "1% thermogravimetric temperature" refers to the temperature at which the polymer additive loses 1% of its weight under heating conditions, which can be obtained by testing with a thermogravimetric analyzer (TGA) in an air atmosphere.

[0090] Preferably, the D of the polymer additive 50 The particle size is 1-100μm, for example, it can be 10μm, 20μm, 30μm, 33μm, 35μm, 38μm, 40μm, 50μm, 60μm, 70μm, 80μm, 90μm or 95μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range. More preferably, it is 20-60μm, and even more preferably, it is 33-39μm.

[0091] The polymer additive D 50 The particle size is the particle size corresponding to a cumulative volume distribution percentage of 50%, which can be determined by laser particle size analyzer with reference to the standard GB / T 19077-2016 Particle Size Distribution Laser Diffraction Method.

[0092] Preferably, the water content of the polymer additive is 0.01-1 wt%, for example, it can be 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 for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range. More preferably, it is 0.05-0.3 wt%, and even more preferably, it is 0.1-0.25 wt%.

[0093] For example, the moisture content of the polymer additive can be obtained by testing with an infrared moisture analyzer, such as the Sartorius MA35 infrared moisture analyzer from Germany, which automatically tests the water content after the sample is placed at 120°C for 30 minutes.

[0094] Preferably, the phosphorus content of the polymer additive is 22-25 wt%, for example, it can be 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%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but it is more preferably 23-24 wt%.

[0095] For example, the phosphorus content of the polymer additive can be obtained by the following method: dissolving the sample to be tested in an aqueous sulfuric acid solution (30% by mass) and testing it according to the standard GB / T 11893-1989 "Determination of Total Phosphorus in Water by Ammonium Molybdate Spectrophotometric Method".

[0096] Thirdly, the present invention provides the application of the polymer additive as described in the second aspect in polymer materials.

[0097] Preferably, the polymer additive is used as a flame retardant in the polymer material.

[0098] Preferably, the polymer material includes any one or a combination of at least two of polyamide, polyester, polyurethane, styrene-based polymer, polyolefin, polyphenylene ether, and polyacrylate, more preferably polyamide and / or polyester.

[0099] Fourthly, the present invention provides a polymer composition comprising a polymer matrix and polymer additives as described in the second aspect.

[0100] Preferably, the polymer composition comprises, by weight, the following components:

[0101] 40-99 parts of polymer matrix

[0102] The polymer additive is 5-35 parts.

[0103] Preferably, the polymer matrix has a mass fraction of 40-99 parts, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 98 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0104] Preferably, the polymer additive is in the range of 5-35 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or 34 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0105] Preferably, the polymer matrix comprises polyamide and / or polyester.

[0106] Preferably, the polyamide includes any one or a combination of at least two of polyamide resin and polyamide elastomer.

[0107] As a polyamide, it includes any one or a combination of at least two of the following: condensation products of dicarboxylic acids and diamines, condensation products of ω-amino acids, and ring-opening polymerization products of lactams. The dicarboxylic acids exemplarily include, but are not limited to, any one or a combination of at least two of adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid. The diamines exemplarily include, but are not limited to, any one or a combination of at least two of pentanediamine, hexamethylenediamine, decanediamine, dodecanediamine, butanediamine, p-phenylenediamine, and m-phenylenediamine. The lactams exemplarily include, but are not limited to, any one or a combination of at least two of caprolactam, octanolactam, undecanolactam, and dodecalactam. The ω-amino acids exemplarily include, but are not limited to, any one or a combination of at least two of the ω-amino acids formed by ring-opening of the aforementioned lactams and aminobenzoic acid.

[0108] Preferably, the polyamide includes any one or a combination of at least two of the following: polyamide 6 (polycaprolactam), polyamide 11 (polyundecanolactam), polyamide 12 (polydodecanolactam), polyamide 56 (polypentyl adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene decanediamide), polyamide 612 (polyhexamethylene dodecyl diamine), polyamide 1010 (polydecyl decanediamide), polyamide 1012 (polydodecyl decanediamide), polyamide 1212 (polydodecyl dodecyl diamine), polyamide 6T (polyhexamethylene terephthalamide), polyamide 10T (polydecanediamide), and PPA (poly(p-phenylene terephthalamide)).

[0109] Preferably, the polyester comprises a condensation product of a dicarboxylic acid and / or its derivatives with a diol, wherein the dicarboxylic acid includes, but is not limited to, any one or a combination of 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; and the derivatives include acyl halides (acyl chlorides), esters, and anhydrides formed from the dicarboxylic acid. The diol includes, but is not limited to, any one or a combination of at least two of the following: ethylene glycol, butanediol, and hexanediol.

[0110] For example, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0111] It should be noted that the polymer composition of the present invention may also include any other fillers, other additives, etc. that are motivated to be added in the art.

[0112] Preferably, the polymer composition further includes reinforcing materials and / or fillers.

[0113] Preferably, the reinforcing material comprises glass fiber and / or carbon fiber.

[0114] Preferably, the mass fraction of the reinforcing material in the polymer composition is ≤45 parts. The mass fraction of the reinforcing material can be 0, 0.5, 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 42, or 44 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0115] Preferably, the filler comprises any one or a combination of at least two of the following: silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, and glass microspheres.

[0116] Preferably, the mass fraction of the filler in the polymer composition is ≤40 parts, and the mass fraction of the filler can be 0, 0.5, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35 or 38 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0117] Preferably, the polymer composition further includes 0-15 parts by weight of other additives, wherein the parts by weight of the other additives may be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0118] Preferably, the other additives include any one or a combination of at least two of antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, and colorants.

[0119] Preferably, the polymer composition further includes any one or a combination of at least two of the following: antioxidant, ultraviolet absorber, lubricant, nucleating agent, stabilizer, antistatic agent, and colorant.

[0120] Preferably, the mass fractions of the antioxidant, ultraviolet absorber, lubricant, and nucleating agent in the polymer composition are each independently 0.01-1.5 parts, for example, 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 1.2 parts, or 1.4 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0121] Preferably, the antioxidant in the polymer composition includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

[0122] For example, the antioxidants in the polymer composition include any one or a combination of at least two of the following: 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), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,4-dicumylphenyl) pentaerythritol diphosphite (antioxidant 608), 2,6-di-tert-butyl-p-cresol (antioxidant BHT), distearate β,β-thiodipropionate (antioxidant DSTP), antioxidant 215, and antioxidant 225.

[0123] Preferably, the lubricant includes any one or a combination of at least two of the following: ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, and metal soap lubricants.

[0124] Preferably, the polymer composition further comprises 0-15 parts by weight of a synergistic flame retardant, wherein the mass parts of the synergistic flame retardant can be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14 parts, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0125] Preferably, the synergistic flame retardant includes any one or a combination of at least two of melamine polyphosphate, melamine polyphosphate salt, zinc borate, zinc stannate, zinc sulfide, and boehmite.

[0126] In a preferred embodiment, the polymer composition comprises the following components in parts by weight:

[0127]

[0128] Preferably, the polymer matrix in the polymer composition has a mass percentage content of 40%-99%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0129] Preferably, the polymer additive in the polymer composition has a mass percentage content of 5%-35%, for example, it can be 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 34%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 6%-20% is further preferred.

[0130] For example, the method for preparing the polymer composition includes: melting and blending the components of the polymer composition and then extruding them to obtain the polymer composition.

[0131] Preferably, the melt blending is carried out in a screw extruder.

[0132] Preferably, the screw extruder is a twin-screw extruder.

[0133] Preferably, the temperature of the screw extruder is 180-330℃, for example, it can be 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃ or 320℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0134] Preferably, the extrusion process further includes granulation and drying steps.

[0135] Compared with the prior art, the present invention has the following beneficial effects:

[0136] The polymer additive preparation method provided by this invention, through the design of materials such as antioxidants and flocculants, the design of process steps and parameters, and their combined effect, can yield a polymer additive with low acid value and high thermal stability. When the polymer additive is used as a flame retardant in the preparation of polymer compositions, it can significantly reduce mold fouling generated during injection molding and give the polymer composition a low content of water-boiling precipitates, greatly improving the stability of the polymer composition under humid and hot conditions and extending its service life. Detailed Implementation

[0137] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0138] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not limited to those elements and may also include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0139] In the following specific embodiments, the testing methods for the parameters of the polymer additives are as follows:

[0140] (1) Content test of diethylphosphonic acid, ethylbutylphosphonic acid, ethylphosphonic acid, and monoethylphosphonic acid

[0141] The results were obtained using a liquid chromatograph (LC20A, Shimadzu, Japan). Diethylphosphonate used a commercially available standard, ethylbutylphosphonate used its pure form (prepared according to Example 4 of CN103172668A), ethylphosphonate used its pure form (prepared according to Example 2 of CN104371142A), and monoethylphosphonate used its pure form (prepared according to Example 1 of CN103172668A). The test samples were dissolved in 5 times their mass of sulfuric acid aqueous solution (30% mass concentration), and then diluted 20 times with the mobile phase for analysis. The mobile phase consisted of a 9:1 mixture of water and methanol, with 0.5% trifluoroacetic acid added by volume. A ShimNex CS C18 5μm column (4.6 × 250 mm) was used, with a flow rate of 0.6 mL / min. The mass content of each component was calculated using the area normalization method.

[0142] (2) Content of other phosphorus-containing compounds

[0143] The sample to be tested was mixed with a deuterated aqueous solution of deuterated sodium hydroxide (mass concentration 10%) at a mass ratio of 1:30 to completely dissolve the sample. After filtration, the resulting clear liquid was analyzed by nuclear magnetic resonance (NMR) using a Bruker NMR spectrometer (AVANCENEO 400MHz). The phosphorus NMR spectrum was integrated, and the percentage of the integrated area of ​​peaks other than those of diethylphosphonic acid salt, ethylbutylphosphonic acid salt, ethylphosphonic acid salt, and monoethylphosphonic acid salt was considered as the content of the other phosphorus-containing compounds.

[0144] (3) Water-soluble acid value

[0145] Take 1g of the sample to be tested and add 5.00±0.01g (m 乙醇 After uniformly wetting with ethanol, add 50±0.01g (m 水 Weigh room temperature water, including the bottle and stirring, to a total weight of m0. Boil the solution in a sealed container at 90℃ for 1 hour, then cool to 25℃ and hold at that temperature for 30 minutes. Add water to bring the total weight to m0. Filter the solution to obtain a clear filtrate with a mass of m1. Determine the acid value of the filtrate using potentiometric titration. The concentration of the potassium hydroxide solution used in the titration is 0.05 mol / L. The water-soluble acid value of the polymer additive = test acid value × (m1 / m2) / m2. 水 +m 乙醇 ) / m1.

[0146] (4) Organic acid value

[0147] Take 1g of the sample to be tested and add 50.0±0.01g (m 二氯甲烷After uniformly wetting the polymer additive in dichloromethane, weigh the total weight m0 with the bottle and stirring. Boil in a sealed container at 90℃ for 1 hour, then cool to 25℃ and hold at that temperature for 30 minutes. Add dichloromethane to bring the total weight to m0. Filter to obtain a clear filtrate with a mass m1. Determine the acid value of the filtrate using potentiometric titration. The concentration of the potassium hydroxide solution used in the titration is 0.05 mol / L. The organic acid value of the polymer additive = test acid value × m. 二氯甲烷 / m1.

[0148] (5) Sulfate content

[0149] The method was adopted in EN 14582:2007 - Determination of halogen content, using ion chromatography with external standard method.

[0150] (6)D 50 Particle size

[0151] Take 0.1g of the sample to be tested, moisten it with 5g of ethanol, then dilute it with 50mL of water, and test it using a Mastersizer3000 laser particle size analyzer.

[0152] (7) Moisture content

[0153] The sample to be tested was placed in an infrared moisture analyzer (MA35 model, Sartorius, Germany) and placed at 105℃ for 30 minutes before the water content was automatically measured.

[0154] (8) Phosphorus content

[0155] Take 0.1g of the sample to be tested, add 2g of sulfuric acid aqueous solution (mass concentration 30%) to dissolve it, and test it according to the standard GB / T 11893-1989 "Determination of Total Phosphorus in Water by Ammonium Molybdate Spectrophotometric Method".

[0156] (9) 1% thermogravimetric temperature

[0157] Take 10mg of the sample to be tested and test it using a thermogravimetric analyzer (TGA, Netzsch TG 209F3, Germany). The heating rate is 20℃ / min, the protective gas is nitrogen, and the purging gas is air. The temperature corresponding to a 1% weight loss is measured.

[0158] In the following specific embodiments of the present invention, all materials for which no preparation method is provided are commercially available chemicals. Specific information about some of the materials is as follows:

[0159] Brand, Manufacturer Antioxidant 1010 RIANOX 1010, Tianjin Lialong New Materials Co., Ltd. Antioxidant 168 RIANOX 168, Tianjin Lialong New Material Co., Ltd. Flocculant: Anionic polyacrylamide Gongyi Xinqi Polymer Co., Ltd. Polyamide 66 (PA66) PA66 M2000, Guangdong Xinhui Meida Nylon Co., Ltd. Polyamide 6 (PA6) PA6 EPR24, Shenma Industrial Co., Ltd. Melamine polyphosphate (MPP) BUDIT 3141, Budenheim GmbH, Germany Fiberglass ECS10-03-568H, China Jushi Co., Ltd. lubricant TR044W, Struktol GmbH, Germany Antioxidant 1098 RIANOX 1098, Tianjin Lialong New Material Co., Ltd.

[0160] The polymer additives and their preparation methods described in this invention will be detailed below using several examples, but the polymer additives and their preparation methods are not limited to these examples.

[0161] Examples 1-11, Comparative Examples 1-4

[0162] A polymer additive and its preparation method are described below:

[0163] (1) 31.8 kg of solid sodium hypophosphite monohydrate, 50 kg of water, 500 g of sodium persulfate, antioxidant 1010 with mass m1 and antioxidant 168 with mass m2 were placed in a high pressure vessel, purged with nitrogen three times, and ethylene was constant pressured to 1.5 MPa through a pressure reducer. The vessel was heated to 95°C and kept at that temperature for 4 h. 2500 g of sodium persulfate aqueous solution with mass content of 20% was continuously added during the 4 h holding period. The vessel was then kept at 95°C for 1 h, cooled and vented to obtain sodium diethylphosphite aqueous solution.

[0164] (2) Dilute the sodium diethylphosphonate aqueous solution obtained in step (1) to a mass content of 20% (containing 6 mol of sodium diethylphosphonate), heat to temperature T1, continuously add aluminum sulfate aqueous solution (1 mol of aluminum sulfate, mass content of 28%) over 1 hour, and adjust the pH value with potassium hydroxide solution (mass content of 5%) to obtain aluminum diethylphosphonate slurry;

[0165] (3) Add an aqueous flocculant solution of anionic polyacrylamide and 50g water with a mass of m3 to the aluminum diethylphosphonate slurry obtained in step (2) at 50℃, stir until flocculation, filter, wash the filter cake with 3 times the mass of water 5 times, and dry at 110℃ to constant weight to obtain polymer additive.

[0166] The specific process parameters of the preparation method and the relevant data of the polymer additives obtained are shown in Tables 1 and 2.

[0167] Table 1

[0168]

[0169]

[0170] Table 2

[0171]

[0172]

[0173] As shown in Table 1, the present invention designs a method for preparing polymer additives, particularly by using antioxidants and flocculants and controlling the pH value in the metathesis reaction system of step (2), to prepare polymer additives with low acid value and high thermal stability. The water-soluble acid value is ≤0.33 mg KOH / g, and the 1% thermal weight loss temperature is ≥350℃. The polymer additive comprises the following components by mass: 96-99.88 parts of diethylphosphonate, 0.1-2 parts of ethylbutylphosphonate, 0.01-1 parts of ethylphosphonate, and 0.01-1 parts of monoethylphosphonate.

[0174] In Table 2, the pH value of the reaction system in step (2) of Comparative Examples 1-2 exceeded the range of 3.5-3.8 specified in this invention. No antioxidant was used in Comparative Example 3 and no flocculant was added in Comparative Example 4, which resulted in a significant increase in both the water-soluble acid value and the organic acid value of the polymer additive, a decrease in the 1% thermal weight loss temperature, and a decrease in thermal stability.

[0175] The application of the polymer additives described in this invention will be detailed below using application examples, but the application of the polymer additives is not limited to these application examples.

[0176] Application Example 1-11, compared with Application Example 1-4

[0177] A polymer composition, specifically a polyamide composition, wherein the types and amounts of each component are shown in Tables 3 and 4, and the amount of each component is in parts by mass.

[0178] The preparation method of the polyamide composition includes: mixing polyamide 66, polyamide 6, glass fiber, polymer additives, antioxidants and lubricants according to the formulation to obtain a premix; adding the premix to a twin-screw extruder, wherein the screw speed of the twin-screw extruder is 380 rpm, and the temperatures of zones 1-12 are 90℃, 180℃, 260℃, 250℃, 230℃, 230℃, 220℃, 220℃, 220℃, 220℃, 260℃ and 260℃ respectively; and after melt mixing and extrusion granulation, polyamide composition particles are obtained.

[0179] The following performance tests were performed on the polyamide composition:

[0180] (1) Test of phosphorus content by boiling in water: Take 50g of polyamide composition particles, add them to 500mL of hot water at 90℃, boil for 1h, cool to room temperature, filter, and determine the phosphorus content of the filtrate by the ammonium molybdate spectrophotometric method in GB / T 11893-1989.

[0181] (2) Mold fouling test method: Using an injection molding machine, the polyamide composition particles were continuously injected into 150 molds at injection temperatures of 290℃, 285℃, 280℃ and 260℃. The mold fouling sample collected in the last mold was removed and weighed using an analytical balance.

[0182] The test data are shown in Tables 3 and 4.

[0183] Table 3

[0184]

[0185] Table 4

[0186]

[0187]

[0188] According to the data in Tables 3 and 4, the polymer additives provided by this invention, when used as flame retardants in polyamide compositions, significantly reduce mold fouling generated during injection molding, resulting in mold fouling ≤ 8.0 mg. Furthermore, the phosphorus content in the polyamide composition after boiling is ≤ 527 ppm, which reduces the content of precipitates after boiling, improves the stability of the polyamide composition under humid and hot conditions, and extends its service life.

[0189] According to the test data in Table 4, the polymer additives in Comparative Examples 1-4 have high acid values ​​and poor thermal stability, resulting in excessive mold fouling, high phosphorus content in boiling water, and insufficient stability under humid and hot conditions when used as flame retardants in polyamide compositions.

[0190] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the polymer additives and their preparation methods, as well as the polymer compositions comprising them. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a polymer additive, characterized in that, The preparation method includes the following steps: (1) An aqueous solution of hypophosphite and an antioxidant react with ethylene in the presence of an initiator to produce an aqueous solution of diethylphosphite; (2) The diethylphosphonate aqueous solution, the metal salt aqueous solution and the alkaline solution are mixed and reacted under the condition of pH 3.5-3.8 to obtain diethylphosphonate metal salt slurry; (3) Mix the diethylphosphine metal salt slurry and flocculant, stir, and obtain diethylphosphine metal salt flocculant; filter, wash and dry the diethylphosphine metal salt flocculant to obtain the polymer additive; The flocculant includes anionic polyacrylamide.

2. The preparation method according to claim 1, characterized in that, The hypophosphite includes sodium hypophosphite and / or potassium hypophosphite.

3. The preparation method according to claim 1, characterized in that, The hypophosphite aqueous solution contains 10-60% hypophosphite by mass.

4. The preparation method according to claim 3, characterized in that, The hypophosphite aqueous solution contains 30-40% hypophosphite by mass.

5. The preparation method according to claim 1, characterized in that, The antioxidants include any one or a combination of at least two of the following: hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

6. The preparation method according to claim 5, characterized in that, The antioxidant is any one or a combination of at least two of the following: hindered phenolic antioxidants, phosphite antioxidants, and thioester antioxidants.

7. The preparation method according to claim 6, characterized in that, The antioxidants include any one or a combination of 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, 2,6-di-tert-butyl-p-cresol, and distearate β,β-thiodipropionate.

8. The preparation method according to claim 1, characterized in that, The mass ratio of hypophosphite to antioxidant is 100:(0.02-1.2).

9. The preparation method according to claim 8, characterized in that, The mass ratio of hypophosphite to antioxidant is 100:(0.05-1).

10. The preparation method according to claim 1, characterized in that, The initiator includes any one or a combination of at least two of the following: organic peroxides, persulfates, azo initiators, and photoinitiators.

11. The preparation method according to claim 1, characterized in that, The mass ratio of hypophosphite to initiator is 100:(0.1-5).

12. The preparation method according to claim 1, characterized in that, The free radical reaction is carried out at a temperature of 70-120℃.

13. The preparation method according to claim 12, characterized in that, The free radical reaction is carried out at a temperature of 80-110℃.

14. The preparation method according to claim 13, characterized in that, The free radical reaction is carried out at a temperature of 90-105℃.

15. The preparation method according to claim 1, characterized in that, The free radical reaction is carried out in a protective atmosphere.

16. The preparation method according to claim 15, characterized in that, The protective atmosphere includes a nitrogen atmosphere and / or an argon atmosphere.

17. The preparation method according to claim 1, characterized in that, The metal salts include metal sulfates and / or metal chlorides.

18. The preparation method according to claim 17, characterized in that, The metal salt is a metal sulfate.

19. The preparation method according to claim 1, characterized in that, The metal salt contains any one or a combination of at least two of the following metals: Al, Ca, Cu, Zn, Fe, and Ti.

20. The preparation method according to claim 19, characterized in that, The metal in the metal salt is Al.

21. The preparation method according to claim 1, characterized in that, The alkaline solution includes sodium hydroxide solution and / or potassium hydroxide solution.

22. The preparation method according to claim 1, characterized in that, The reaction temperature in step (2) is 20-80℃.

23. The preparation method according to claim 22, characterized in that, The reaction temperature in step (2) is 40-60℃.

24. The preparation method according to claim 1, characterized in that, Based on the theoretically obtained mass of the diethylphosphonic acid metal salt as 100%, the mass of the flocculant is 0.01-0.5%.

25. The preparation method according to claim 1, characterized in that, The mixing temperature in step (3) is 40-60℃.

26. The preparation method according to claim 1, characterized in that, The number of times the washing is performed in step (3) is ≥ 4.

27. A polymer additive, characterized in that, The polymer additive is prepared by the preparation method according to any one of claims 1-26, and the water-soluble acid value of the polymer additive is ≤0.33 mg KOH / g; The polymer additive comprises the following components in parts by weight: 96-99.88 parts of diethylphosphonate 0.1-2 parts of ethyl butyl phosphine salt 0.01-1 part of ethylphosphonate 0.01-1 part of monoethylphosphonate.

28. The polymer additive according to claim 27, characterized in that, The water-soluble acid value of the polymer additive is 0.1-0.3 mg KOH / g.

29. The polymer additive according to claim 27, characterized in that, The organic acid value of the polymer additive is ≤0.05 mg KOH / g.

30. The polymer additive according to claim 29, characterized in that, The organic acid value of the polymer additive is 0.002-0.04 mg KOH / g.

31. The polymer additive according to claim 27, characterized in that, The mass content of sulfate in the polymer additive is 100-600 ppm.

32. The polymer additive according to claim 31, characterized in that, The mass content of sulfate in the polymer additive is 110-370 ppm.

33. The polymer additive according to claim 27, characterized in that, The polymer additive has a 1% thermal weight loss temperature ≥350℃.

34. The polymer additive according to claim 27, characterized in that, The polymer additive D 50 The particle size is 1-100 μm.

35. The polymer additive according to claim 34, characterized in that, The polymer additive D 50 The particle size is 20-60 μm.

36. The polymer additive according to claim 35, characterized in that, The polymer additive D 50 The particle size is 33-39 μm.

37. The polymer additive according to claim 27, characterized in that, The water content of the polymer additive is 0.01-1 wt%.

38. The polymer additive according to claim 37, characterized in that, The water content of the polymer additive is 0.05-0.3 wt%.

39. The polymer additive according to claim 38, characterized in that, The water content of the polymer additive is 0.1-0.25 wt%.

40. The polymer additive according to claim 27, characterized in that, The phosphorus content of the polymer additive is 22-25 wt%.

41. The polymer additive according to claim 40, characterized in that, The phosphorus content of the polymer additive is 23-24 wt%.

42. The use of a polymer additive as described in any one of claims 27-41 as a flame retardant in polymer materials.

43. A polymer composition, characterized in that, The polymer composition comprises a polymer matrix and a polymer additive as described in any one of claims 27-41.

44. The polymer composition according to claim 43, characterized in that, The polymer composition comprises the following components in parts by weight: 40-99 parts of polymer matrix The polymer additive is 5-35 parts.

45. The polymer composition according to claim 44, characterized in that, The polymer matrix includes polyamide and / or polyester.

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