A polymer additive, its preparation method and use

Abstract

The application provides a polymer additive and a preparation method and application thereof, and the preparation method comprises the following steps: free radical reaction of hypophosphorous acid aqueous solution and an antioxidant with ethylene under the action of an initiator to obtain diethyl hypophosphite aqueous solution; reaction of the diethyl hypophosphite aqueous solution, sulfuric acid and metal hydroxide, and then addition of lye to obtain diethyl hypophosphite slurry with a pH value of 3.8-4.2; mixing of the diethyl hypophosphite slurry and a flocculating agent, stirring to obtain diethyl hypophosphite flocculate, and then filtration, washing and drying to obtain the polymer additive. Through the design of the preparation method, the polymer additive with low acid value can be obtained, when the polymer additive is used as a flame retardant to prepare a polymer material, the additive precipitation in the high-temperature processing process can be inhibited, the mold dirt is reduced, the polymer composition prepared has a low water boiling precipitate content, and the service life of the polymer composition under the wet heat condition is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of flame retardants, and particularly relates to a polymer additive, a preparation method and application thereof. BACKGROUND

[0002] As a general halogen-free flame retardant, dialkyl phosphinic acid salt not only has good flame retardant performance, small addition amount, small influence on the physical and electrical properties of the base resin, but also has the characteristics of small smoke emission and high CTI (relative tracking index) during combustion, and is highly valued by the industry. At the same time, the dialkyl phosphinic acid salt flame-retardant polyamide material has superior mechanical and electrical properties, and is increasingly favored by electrical and electronic industry manufacturers, and has a very broad market prospect.

[0003] Braun U et al. found that dialkyl phosphinic acid salt decomposes dialkyl phosphinic acid during the process of flame-retardant PBT and polyamide.

[0004] When dialkyl phosphinic acid salt is used for flame-retardant polyamide, the polyamide contains a large number of polar amide groups, making the polyamide more prone to water absorption and having a high water absorption rate. For example, the water absorption rate of PA66 resin can reach 2.7% under the condition of 23℃ and 50% humidity. During the process of extrusion or injection molding at high temperature, the dialkyl phosphinic acid salt itself has a certain acidity, and the heat process also decomposes dialkyl phosphinic acid acid substances, which easily promotes the decomposition of the system, resulting in a large amount of gas during the processing. Serious mold fouling often occurs on the mold during repeated injection molding, affecting the appearance of the product. Due to the presence of mold fouling, the mold needs to be cleaned frequently, resulting in low efficiency, so that the product is difficult to be well promoted and used.

[0005] At present, the main method to solve the mold fouling problem of dialkyl phosphinic acid salt flame-retardant polyamide material injection molding is to add an acid absorber to the system to reduce the acidity of the system. For example, EP2417191A1 adds calcium oxide to the system, which neutralizes some acidic substances in the system, reduces the acidity of the system, and reduces the decomposition of the base resin, thereby effectively reducing the corrosiveness to the mold during high-temperature injection molding. Although this method helps to reduce mold fouling, calcium oxide is easily hygroscopic, resulting in a high water absorption rate of the system, which is difficult to control during processing.

[0006] CN112409786A adds a certain amount of ethylene copolymer to the system to prepare a halogen-free flame-retardant thermoplastic polyamide with low mold fouling. CN114874616A adds metal oxides and a multi-hydroxy system to the system to prepare a halogen-free flame-retardant thermoplastic polyamide with better yellowing resistance and more continuous mold opening and closing times (lower mold fouling).

[0007] The above technical solutions have certain improvement on the mold scale of the dialkyl hypophosphite salt flame-retardant polyamide, but are improved by adding an external additive to improve the acidity of the system and reduce the mold scale, which increases the cost and is difficult to avoid the influence of the addition of new substances on other properties of the flame-retardant polyamide. For example, the addition of inorganic metal oxides can reduce the mechanical properties of the material. Moreover, the nature defects of the dialkyl hypophosphite salt have not been fundamentally improved, which can cause the additive to be precipitated during high-temperature processing, thereby blocking the pipeline of the processing device and causing apparent defects of the product.

[0008] Therefore, how to provide a new type of polymer additive with low acidity, and use it for flame-retardant modification of a polymer material, can reduce the precipitation of the additive during high-temperature processing, and the modified polymer material has low mold scale and less additive precipitation, has become a problem to be solved in the field. SUMMARY

[0009] In view of the deficiencies of the prior art, the purpose of the present application is to provide a polymer additive and its preparation method and application. Through the design and joint action of the materials and process in the preparation method, a polymer additive with low acid value can be obtained. When the polymer additive is used as a flame retardant to prepare a polymer material, it can inhibit or avoid the precipitation of the additive during high-temperature processing, effectively reduce the mold scale, and the prepared polymer composition has low water boiling precipitate content, thereby improving its service life under humid heat conditions.

[0010] To achieve this purpose, the present application adopts the following technical solutions:

[0011] In a first aspect, the present application provides a preparation method of a polymer additive, which comprises the following steps:

[0012] (1) hypophosphorous acid aqueous solution and antioxidant are subjected to free radical reaction with ethylene under the action of an initiator to obtain a diethyl hypophosphite aqueous solution;

[0013] (2) the diethyl hypophosphite aqueous solution, sulfuric acid and metal hydroxide are subjected to reaction, and then a lye is added to obtain a diethyl hypophosphite salt slurry with a pH value of 3.8-4.2;

[0014] (3) the diethyl hypophosphite salt slurry and a flocculating agent are mixed and stirred to obtain a diethyl hypophosphite salt flocculate; the diethyl hypophosphite salt flocculate is filtered, washed and dried to obtain the polymer additive.

[0015] The present application researches and finds that the reaction process of hypophosphorous acid and ethylene is generally carried out in the presence of a free radical initiator, and hypophosphorous acid has strong reducing properties due to the presence of P-H bond, so the process of step (1) generally exists free radical reaction and oxidation reaction at the same time; the present application introduces an antioxidant in step (1), which can donate electrons to the oxidizing agent, thereby reducing it to a relatively stable substance, so as to achieve the effect of initiator oxidation performance. On the other hand, the free radical reaction of hypophosphorous acid and ethylene is a strong exothermic reaction, which is prone to uncontrollable phenomena in the production process, and many side reactions occur, and the other mechanism of action of the antioxidant is to capture free radicals in the form of free radical reaction, neutralize its activity, which can effectively slow down the exothermic effect and reduce the occurrence of side reactions, so that the production process can be controlled. The present application adds an antioxidant in the process of step (1), which can effectively reduce the water-soluble acid value and organic acid value of the final product.

[0016] The present application researches and finds that the pH of the reaction system has a great influence on the crystallization behavior of the additive precipitation process, thereby affecting the acid value of the polymer additive; the present application designs the pH value of the product of step (2) reaction, controls the pH value of the obtained diethyl hypophosphite slurry to be 3.8-4.2, for example, it can be 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.; so that the prepared polymer additive has low acid value, and at the same time ensures that the product has high yield. If the pH value of the slurry is too low, it is easy to cause the acid value of the polymer additive to be too high, and the yield to be reduced; if the pH value of the slurry is too high, it will also cause the acid value of the polymer additive to increase, and further increase of the pH will also cause the yield to be further reduced.

[0017] The present application researches and finds that the introduction of flocculants can make the surface of polymer additive particles fixed on the molecular chain of flocculants, forming a bridge of polymer, so that the particles form a group and settle. The flocculants adsorb and combine with the polymer additive in the slurry obtained in step (2), which can effectively improve the filtering and washing effect of the polymer additive, and at the same time can effectively reduce the acidity of the polymer additive after filtering and washing.

[0018] In summary, the present application designs the preparation method of the polymer additive, uses antioxidants and flocculants in the preparation process of the polymer additive, and controls the pH value of the diethyl hypophosphite slurry to be 3.8-4.2, to prepare a polymer additive with low acid value. When the polymer additive is used as a flame retardant to prepare a polymer composition, it can inhibit or avoid the precipitation of auxiliary agents in the high-temperature processing process, significantly reduce the mold dirt, and make the polymer composition have a low water boiling precipitate content, greatly improving the service life of the polymer composition under humid heat conditions.

[0019] The following are preferred technical solutions of the present application, but not as a limitation of the technical solutions provided by the present application. Through the following preferred technical solutions, the purposes and beneficial effects of the present application can be better achieved and implemented.

[0020] Preferably, the antioxidant includes any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants, more preferably any one or a combination of at least two of hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants.

[0021] Further preferably, the antioxidant includes any one or a combination of at least two of tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl ester (antioxidant 1076), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (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), distearyl β,β-thiodipropionate (antioxidant DSTP), antioxidant 215, antioxidant 225.

[0022] The antioxidant in the present application can use a single component, such as any one of the above-listed antioxidants, or a plurality of compounded composite 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.

[0023] Preferably, the initiator includes any one or a combination of at least two of organic peroxides, persulfates, azo initiators, and photoinitiators.

[0024] Preferably, the organic peroxide includes any one of diisobutyryl peroxide, benzoyl peroxide, bis(2-ethylhexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxy-pivalate, t-butyl peroxy pivalate, t-amyl peroxy pivalate, dilauroyl peroxide, di(3,3,5-trimethylacetyl)peroxide, 2,5-dimethyl-2,5-di(2-ethylacetylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, 1,1-di-t-amyl peroxy cyclohexane, 1,1-di-t-butyl peroxy cyclohexane, di-t-butyl peroxide, di-t-amyl peroxide, dicumyl peroxide, 2,5-di-t-butyl peroxy-2,5-dimethylhexane, t-butyl peroxyacetate, t-amyl peroxybenzoate, t-butyl peroxy maleate, t-butyl peroxy-2-ethylhexyl carbonate, or a combination of at least two thereof.

[0025] Preferably, the persulfate salt includes any one of sodium persulfate, potassium persulfate, ammonium persulfate, or a combination of at least two thereof.

[0026] Preferably, the azo initiator includes any one of azobis isobutyronitrile, azobis isoheptanitrile, azobis isobutyramidine hydrochloride, azobis isobutylimidazoline hydrochloride, azoisobutyryl cyanamide, or a combination of at least two thereof.

[0027] It should be noted that the present application does not have any special limitation on the specific selection of the photoinitiator, and the photoinitiator commonly used in the art is applicable.

[0028] It should be noted that the initiator in step (1) of the present application can be added at one time, in batches, or continuously during the reaction process; and a part of the initiator in step (1) can be added in advance, and the remaining part can be continuously added during the reaction process.

[0029] Preferably, the mass percentage of hypophosphorous acid in the aqueous hypophosphorous acid solution is 20-70%, for example, it can be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range, and further preferably 45-55%.

[0030] Preferably, the mass ratio of the hypophosphorous acid and the 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., further preferably 100:(0.05-1).

[0031] Preferably, the mass ratio of the hypophosphorous acid and the 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.

[0032] Preferably, the molar ratio of the ethylene and the hypophosphorous acid 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.

[0033] Preferably, the temperature of the radical reaction is 60-105℃, for example, it can be 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or 98℃, and specific point values between the above-mentioned point values, limited by the length and for the sake of simplicity, the present application will not be exhaustively listed the specific point values included in the range, more preferably 70-100℃, further preferably 75-95℃.

[0034] The radical reaction in step (1) is carried out in the presence of an initiator, and when the pressure of the reaction system is basically no longer changed, it can be considered that the reaction is complete, and the reaction is stopped.

[0035] Preferably, the radical reaction is carried out in a protective atmosphere.

[0036] Preferably, the protective atmosphere includes a nitrogen atmosphere and / or an argon atmosphere.

[0037] Preferably, the metal hydroxide includes any one or a combination of at least two of aluminum hydroxide, calcium hydroxide, copper hydroxide, zinc hydroxide, iron hydroxide, and titanium hydroxide, more preferably aluminum hydroxide.

[0038] Preferably, the iron hydroxide includes ferrous hydroxide and / or ferric hydroxide.

[0039] By employing the above metal hydroxide, the cation in the resulting diethylphosphinic acid salt comprises any one of Al, Ca, Cu, Zn, Fe or Ti, more preferably Al.

[0040] Preferably, the molar amount of the metal hydroxide is 30-50 mol%, for example, it can be 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 point values between the above point values, the present application does not list the specific point values included in the range any more due to the limitation of the length and the consideration of simplicity.

[0041] Preferably, the molar amount of the sulfuric acid is 5-50 mol%, for example, it can be 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 specific point values between the above point values, the present application does not list the specific point values included in the range any more due to the limitation of the length and the consideration of simplicity, further preferably 8-30 mol%, more preferably 10-15 mol%.

[0042] Preferably, the temperature of the reaction in step (2) is 70-150°C, for example, it can be 75°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 145°C, and specific point values between the above point values, the present application does not list the specific point values included in the range any more due to the limitation of the length and the consideration of simplicity, further preferably 80-120°C, more preferably 90-100°C.

[0043] Preferably, the time of the reaction in step (2) is 2-12h, for example, it can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 11.5h, and specific point values between the above point values, the present application does not list the specific point values included in the range any more due to the limitation of the length and the consideration of simplicity.

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

[0045] The present application does not have any special limitation on the mass concentration of sodium hydroxide solution and potassium hydroxide solution. It is only required to add sodium hydroxide solution and / or potassium hydroxide solution to maintain the pH of the diethylphosphinic acid salt slurry obtained in step (2) at 3.8-4.2.

[0046] Preferably, the flocculant comprises polyacrylamide flocculant, more preferably anionic polyacrylamide and / or non-ionic polyacrylamide, more preferably anionic polyacrylamide.

[0047] As a preferred technical solution of the present application, the use of polyacrylamide flocculant enables the polymer additive particle surface to be fixed on the molecular chain of the flocculant to form a polymer bridge. In particular, when anionic polyacrylamide is added as a flocculant, adsorption bridging and strengthening can be achieved, so that the particles form a collective and settle, thereby improving the effect of polymer additive filtration and washing and reducing the acid value of the polymer additive after filtration and washing.

[0048] Preferably, the mass of the flocculant is 0.01-0.5% based on 100% of the theoretical mass of the diethylphosphinic acid salt, 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%, and specific point values between the above point values. Due to the limitation of the length and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0049] The "theoretical mass of diethylphosphinic acid salt" is calculated based on the input amount of diethylphosphinic acid and metal hydroxide in step (2).

[0050] Preferably, the flocculant and water can be mixed at 20-30°C for 10-20 min to obtain a flocculant solution, and then the flocculant solution and the diethylphosphinic acid salt slurry are mixed and stirred. The mass ratio of the flocculant to water is 1:10-1000, for example, it can be 1:50, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:950, etc.

[0051] Preferably, the temperature of the mixing 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, and specific point values between the above point values. Due to the limitation of the length and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0052] Preferably, the number of times of washing in step (3) is ≥4, for example, it can be 5, 6, 7, 8, 9, 10 or 12 times, etc., and further preferably 5-10 times.

[0053] Preferably, the washing agent used in the washing is water.

[0054] As a preferred technical solution of the present application, the diethyl phosphinic acid salt flocculate is washed multiple times after filtration, and the number of times of washing is ≥4, preferably 5-10 times, which can better remove impurities and acidic substances in the product, and obtain the polymer additive with low acid value.

[0055] Preferably, the mass ratio of water to solid in each of the washings is independently (1-10):1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, etc., and further preferably (1.5-6):1. The solid is the solid product obtained by filtration.

[0056] 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 point values between the above point values, limited by the length and for the sake of simplicity, the present application will not enumerate the specific point values included in the range, and further preferably 110-150℃.

[0057] As a preferred technical solution of the present application, the preparation method of the polymer additive specifically comprises the following steps:

[0058] (1) In a protective atmosphere, a hypophosphorous acid aqueous solution and an antioxidant are subjected to a free radical reaction with ethylene under the action of an initiator to obtain a diethyl phosphinic acid aqueous solution;

[0059] In the formula, 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℃, and the reaction is terminated when the pressure of the system no longer changes;

[0060] (2) The diethyl phosphinic acid aqueous solution, sulfuric acid and metal hydroxide are reacted at 70-150℃ for 2-12h, and then a lye is added to make the pH of the system 3.8-4.2, to obtain a diethyl phosphinic acid salt slurry;

[0061] In the formula, the molar amount of the metal hydroxide is 30-50mol% and the molar amount of the sulfuric acid is 5-50mol%, based on 100% of the molar amount of the diethyl phosphinic acid.

[0062] (3) mixing the diethylphosphinate slurry and the flocculant solution at 40-60℃, stirring to obtain diethylphosphinate flocculate; filtering, washing ≥4 times, drying the diethylphosphinate flocculate to obtain the polymer additive;

[0063] wherein the mass of the flocculant is 0.01-0.5% based on 100% of the mass of the diethylphosphinate theoretically obtained.

[0064] In a second aspect, the present application provides a polymer additive, which is prepared by the preparation method as described in the first aspect, the water-soluble acid value of the polymer additive is ≤0.3mg KOH / g; the polymer additive comprises the following components in mass parts:

[0065]

[0066] The alkali insoluble substance is selected from any one or a combination of at least two of hydroxides, oxides, phosphates, phosphites, other alkyl phosphonates.

[0067] The polymer additive provided by the present application has lower acidity, and the water-soluble acid value is ≤0.3mg KOH / g. When it is used as a flame retardant in a polymer composition, it can inhibit the decomposition of dialkyl phosphinic acid during high-temperature process, inhibit or avoid the precipitation of auxiliary agents during high-temperature processing, thereby avoiding the blockage of device pipelines by precipitates, and making the polymer composition have lower water-boiling precipitate content, greatly improving its use stability under humid heat conditions, prolonging the service life, and reducing the amount of mold dirt produced during injection molding.

[0068] The mass parts of diethylphosphinate in the polymer additive are 95-98.98 parts, for example, can be 95.5 parts, 95.8 parts, 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, or 98.9 parts, and specific point values between the above point values. Due to the limitation of the length and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0069] Preferably, the mass percentage of diethylphosphinate in the polymer additive is ≥94%, for example, can be 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 point values between the above point values. Due to the limitation of the length and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0070] The mass fraction of ethyl butyl phosphinate in the polymer additive is 1-3 parts, for example, it can be 1.1 parts, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.7 parts, 2.8 parts or 2.9 parts, and specific point values between the above point values, for the sake of brevity and simplicity, the present application does not list the specific point values included in the range.

[0071] The mass fraction of ethyl phosphinate in the polymer additive is 0.01-0.7 parts, 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 or 0.65 parts, and specific point values between the above point values, for the sake of brevity and simplicity, the present application does not list the specific point values included in the range.

[0072] The mass fraction of monoethyl hypophosphite in the polymer additive is 0.01-0.3 parts, for example, it can be 0.02 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.15 parts, 0.16 parts, 0.18 parts, 0.2 parts, 0.22 parts, 0.25 parts or 0.28 parts, and specific point values between the above point values, for the sake of brevity and simplicity, the present application does not list the specific point values included in the range.

[0073] The mass fraction of alkali insoluble matter in the polymer additive is 0-3 parts, for example, it can be 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 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 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts or 2.8 parts, and specific point values between the above point values, for the sake of brevity and simplicity, the present application does not list the specific point values included in the range.

[0074] Exemplarily, the mass fraction of diethyl hypophosphite, diethyl hypophosphite, ethyl phosphinate, monoethyl hypophosphite in the polymer additive can be obtained by liquid chromatography analysis test, for example, the sample to be tested is dissolved with 5 times the mass of sulfuric acid aqueous solution (mass concentration 30%), and then diluted 10-30 times with mobile phase for analysis test; the mobile phase uses a mixture of water and methanol with a mass ratio of 9:1, and 0.5% trifluoroacetic acid by volume is added, a ShimNex CSC18 chromatographic column is used, the flow rate is 0.6 mL / min; the mass content of each component is calculated by area normalization method.

[0075] Exemplarily, the mass fraction of alkali insoluble substance in the polymer additive is tested by the following method: the sample to be tested is mixed with sodium hydroxide aqueous solution (mass concentration 3%) at a mass ratio of 1:100, stirred at 35°C for 30 min, filtered with filter paper with a precision of ≤2 μm, and washed with water for 3 times, and then the filter paper is dried and weighed, the mass increase of the filter paper after the filtration is the mass of the insoluble substance, and the ratio of the mass of the insoluble substance to the mass of the sample to be tested is the mass content of the alkali insoluble substance.

[0076] Preferably, the polymer additive comprises the following components by mass fraction:

[0077]

[0078] Preferably, the cations in the diethylphosphinic acid salt, ethylbutylphosphinic acid salt, ethylphosphinic acid salt and monoethylphosphinic acid salt are the same and are selected from any one or a combination of at least two of Al 3+ , Ca 2+ , Cu 2+ , Zn 2+ , Fe 2+ , Fe 3+ or Ti 4+ .

[0079] In the present application, the water-soluble acid value of the polymer additive is ≤0.3 mg KOH / g, for example, it can be 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 or 0.29 mg KOH / g, and specific point values between the above point values, for the sake of brevity and simplicity, the present application does not exhaustively list the specific point values included in the range, and the preferred value is 0.1-0.3 mg KOH / g.

[0080] Exemplarily, the water-soluble acid value of the polymer additive can be tested by the following method: 1 g of the sample to be tested is uniformly moistened with ethanol (the mass of ethanol is m 乙醇 ), then water (the mass of water is m 水 ) is added, and after being boiled in water at 90°C for 1 h, it is cooled to 25°C and kept at this temperature for 30 min, and then water is added to the total mass before the boiling in water; filtration is performed, and the mass of the clear filtrate is m1, and the test acid value of the clear filtrate is measured by the potentiometric titration test method, wherein the concentration of the potassium hydroxide solution used for the titration is 0.05 mol / L, and the water-soluble acid value of the polymer additive = test acid value × (m 水 +m 乙醇 ) / m1.

[0081] 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, 0.01 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 the specific point values between the above-mentioned point values, for the sake of brevity and simplicity, the present application does not exhaustively list the specific point values included in the range, and further preferably 0.02-0.04 mg KOH / g.

[0082] Exemplarily, the organic acid value of the polymer additive can be tested by the following method: after 1 g of the sample to be tested is uniformly moistened with dichloromethane (the mass of dichloromethane is m 二氯甲烷 ), it is boiled at 90°C for 1 h in a closed state, cooled to 25°C and kept at a constant temperature for 30 min, and then dichloromethane is added to the total mass before boiling; after filtration, the mass of the clear filtrate is m1, and the clear filtrate is tested for the test acid value by the potentiometric titration method, wherein the concentration of the potassium hydroxide solution used for titration is 0.05 mol / L, and the organic acid value of the polymer additive = test acid value x m 二氯甲烷 / m1.

[0083] Preferably, the mass content of sulfate in the polymer additive is 100-700 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, 600 ppm, 650 ppm or 680 ppm, and the specific point values between the above-mentioned point values, for the sake of brevity and simplicity, the present application does not exhaustively list the specific point values included in the range, and further preferably 270-420 ppm.

[0084] Exemplarily, the mass content of sulfate in the polymer additive is measured by the method in the standard EN 14582-“Determination of halogen content” using ion chromatography technology by external standard method.

[0085] Preferably, the D 50The particle size is 1-100 μm, for example, it can be 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, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range, further preferably 20-60 μm, more preferably 33-38 μm.

[0086] The D of the polymer additive 50 The particle size is the particle size corresponding to the volume cumulative distribution percentage of 50%, which can be determined by referring to the standard GB / T 19077-2016 Particle Size Distribution Laser Diffraction Method, using a laser particle size analyzer.

[0087] 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 point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range, further preferably 0.05-0.3 wt%, more preferably 0.1-0.25 wt%.

[0088] Illustratively, the water content of the polymer additive can be tested by an infrared moisture analyzer, for example, using a MA 35 infrared moisture analyzer of Sartorius, Germany, the sample is placed at 120°C for 30 min, and the water content is automatically tested.

[0089] 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%, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range, further preferably 23-24 wt%.

[0090] Illustratively, the phosphorus content of the polymer additive can be tested by the following method: the sample to be tested is dissolved with sulfuric acid aqueous solution (mass concentration 30%), and the standard GB / T 11893-1989 "Determination of Total Phosphorus in Water-Ammonium Molybdate Spectrophotometric Method" is tested.

[0091] In a third aspect, the present application provides use of the polymer additive according to the second aspect in a polymer material.

[0092] Preferably, the polymer additive is used as a flame retardant in the polymer material.

[0093] Preferably, the polymer material comprises any one or a combination of at least two of a polyamide, a polyester, a polyurethane, a styrene-based polymer, a polyolefin, a polyphenylene ether, a polyacrylate, more preferably a polyamide and / or a polyester.

[0094] In a fourth aspect, the present application provides a polymer composition comprising a polymer matrix and the polymer additive according to the second aspect.

[0095] Preferably, the polymer composition comprises the following components in parts by mass:

[0096] polymer matrix 40-99 parts

[0097] the polymer additive 5-35 parts.

[0098] Preferably, the polymer matrix is in parts by mass of 40-99, for example, can be 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or 98 parts, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be exhaustively listed specific point values included in the range.

[0099] Preferably, the polymer additive is in parts by mass of 5-35, for example, can be 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, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be exhaustively listed specific point values included in the range.

[0100] Preferably, the polymer matrix comprises a polyamide and / or a polyester.

[0101] Preferably, the polyamide comprises any one or a combination of at least two of a polyamide resin, a polyamide elastomer.

[0102] As a polyamide, it includes any one or a combination of at least two of condensation products of a dicarboxylic acid and a diamine, condensation products of an omega-amino acid, ring-opening polymerization products of a cyclic lactam. The dicarboxylic acid exemplarily includes, but is not limited to, any one or a combination of at least two of adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid. The diamine exemplarily includes, but is not limited to, any one or a combination of at least two of pentamethylene diamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, butanediamine, p-phenylenediamine, m-phenylenediamine. The cyclic lactam exemplarily includes, but is not limited to, any one or a combination of at least two of caprolactam, caprylolactam, undecanolactam, laurolactam. The omega-amino acid exemplarily includes, but is not limited to, any one or a combination of at least two of the omega-amino acid ring-opened from the aforementioned cyclic lactam, aminobenzoic acid.

[0103] Preferably, the polyamide includes any one or a combination of at least two of polyamide 6 (polycaprolactam), polyamide 11 (polyundecanolactam), polyamide 12 (polylauro lactam), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecanediamide), polyamide 1010 (polydecamethylene sebacamide), polyamide 1012 (polydecamethylene dodecanediamide), polyamide 1212 (polydodecamethylene dodecanediamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 10T (polydecamethylene terephthalamide), PPA (poly-p-phenylenediamine terephthalamide).

[0104] Preferably, the polyester includes condensation products of a dicarboxylic acid and / or its derivatives and a dihydric alcohol, wherein the dicarboxylic acid exemplarily includes, but is not limited to, any one or a combination of at least two of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, hydrogenated isophthalic acid, hydrogenated phthalic acid, and derivatives including acyl halides (acid chlorides), esters, acid anhydrides, etc. formed from the dicarboxylic acid. The dihydric alcohol exemplarily includes, but is not limited to, any one or a combination of at least two of ethylene glycol, butylene glycol, hexanediol.

[0105] Exemplarily, the polyester includes polyethylene terephthalate (PET) and / or polybutylene terephthalate (PBT).

[0106] It is to be noted that the polymer composition of the present application can further include any other fillers, other auxiliary agents, etc. that are motivated to be added in the art.

[0107] Preferably, the polymer composition further includes a reinforcing material and / or a filler.

[0108] Preferably, the reinforcing material comprises glass fibers and / or carbon fibers.

[0109] Preferably, the mass parts of the reinforcing material in the polymer composition is < 45 parts, which can be 0, 0.5, 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 42, or 44 parts, and specific point values between the aforementioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and consideration.

[0110] Preferably, the filler comprises any one or a combination of at least two of silica, talc, titanium dioxide, barium sulfate, kaolin, calcium sulfate, boehmite, mica, magnesium carbonate, glass microbeads.

[0111] Preferably, the mass parts of the filler in the polymer composition is < 40 parts, which can be 0, 0.5, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, or 38 parts, and specific point values between the aforementioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and consideration.

[0112] Preferably, the polymer composition further comprises 0-15 parts of other additives in mass parts, which can be 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, or 14 parts, and specific point values between the aforementioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and consideration.

[0113] Preferably, the other additives comprise any one or a combination of at least two of antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, colorants.

[0114] Preferably, the polymer composition further comprises any one or a combination of at least two of antioxidants, ultraviolet absorbers, lubricants, nucleating agents, stabilizers, antistatic agents, colorants.

[0115] Preferably, the mass parts of the antioxidants, ultraviolet absorbers, lubricants, nucleating agents in the polymer composition are each independently 0.01-1.5 parts, which can be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, or 1.4 parts, and specific point values between the aforementioned point values, the present application does not exhaustively list the specific point values included in the range for the sake of brevity and consideration.

[0116] Preferably, the antioxidant in the polymer composition comprises any one or a combination of at least two of hindered amine antioxidants, hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants.

[0117] Illustratively, the antioxidant in the polymer composition comprises any one or a combination of at least two of tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) pentaerythritol ester (antioxidant 1010), n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexylenediamine (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), distearyl β,β-thiodipropionate (antioxidant DSTP), antioxidant 215, antioxidant 225.

[0118] Preferably, the lubricant comprises any one or a combination of at least two of ester lubricants, alcohol lubricants, hydrocarbon lubricants, fatty acid lubricants, fatty acid amide lubricants, metal soap lubricants.

[0119] Preferably, the polymer composition further comprises 0-15 parts by mass of a synergistic flame retardant, the parts by mass 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, and specific point values between the above point values, the specific point values included in the range are not exhaustively listed in the present disclosure due to the limitation of the length and the consideration of simplicity.

[0120] Preferably, the synergistic flame retardant comprises any one or a combination of at least two of melamine polyphosphate, melamine polyphosphate salt, zinc borate, zinc stannate, zinc sulfide, boehmite.

[0121] In one preferred technical solution, the polymer composition comprises the following components by parts by mass:

[0122]

[0123]

[0124] Preferably, the mass percentage of the polymer matrix in the polymer composition is 40% to 99%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 98%, and specific point values between the above point values, the specific point values included in the range are not listed exhaustively due to the limitation of the length and for the sake of simplicity.

[0125] Preferably, the mass percentage of the polymer additive in the polymer composition is 5% to 35%, for example, it can be 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, or 34%, and specific point values between the above point values, the specific point values included in the range are not listed exhaustively due to the limitation of the length and for the sake of simplicity, further preferably 6% to 20%.

[0126] Illustratively, the preparation method of the polymer composition comprises: melt blending and then extruding the components of the polymer composition to obtain the polymer composition.

[0127] Preferably, the polymer matrix, optionally the filler, and optionally other additives are first premixed to obtain a premix; and then the premix, the polymer additive, and optionally the reinforcing material are melt blended and then extruded to obtain the polymer composition.

[0128] Preferably, the melt blending is carried out in a screw extruder.

[0129] Preferably, the screw extruder is a twin-screw extruder.

[0130] Preferably, the temperature of the screw extruder is 180 to 330°C, for example, it can be 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 point values between the above point values, the specific point values included in the range are not listed exhaustively due to the limitation of the length and for the sake of simplicity.

[0131] Preferably, the extrusion further comprises the steps of granulation and drying.

[0132] Compared with the prior art, the present application has the following beneficial effects:

[0133] The polymer additive prepared by the method has low acid value, and when the polymer additive is used as a flame retardant to prepare a polymer composition, the additive can be inhibited or avoided from being precipitated during high-temperature processing, the precipitate can be avoided from blocking the device pipeline, the mold dirt generated during injection molding is significantly reduced, the polymer composition has low water boiling precipitate content, and the stability and service life of the polymer composition under humid heat conditions are greatly improved. DETAILED DESCRIPTION

[0134] The technical solutions of the present application are further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application, and should not be regarded as specific limitations on the present application.

[0135] As used herein, the terms "comprising", "including", "containing", "having" or any other similar forms are intended to cover non-exclusive inclusions. For example, a composition, step, method, article, or device that comprises listed elements does not necessarily limit those elements only, but can also include other elements not explicitly listed or inherent to such composition, step, method, article, or device.

[0136] In the following detailed description, the test method of the parameters of the polymer additive is as follows:

[0137] (1) Content test of diethyl phosphinate, ethyl butyl phosphinate, ethyl phosphinate, and monoethyl phosphinate

[0138] The liquid chromatograph (LC20A, Shimadzu, Japan) is used for analysis and test, wherein, the diethyl phosphinate uses a commercially available standard sample, the ethyl butyl phosphinate uses a pure product (reference CN103172668A embodiment 4) as a standard sample, the ethyl phosphinate uses a pure product (reference CN104371142A embodiment 2) as a standard sample, and the monoethyl phosphinate uses a pure product (reference CN103172668A embodiment 1) as a standard sample; the sample to be tested is dissolved with 5 times of mass of sulfuric acid aqueous solution (mass concentration 30%), and then diluted 20 times with a mobile phase for analysis and test; the mobile phase uses a mixture of water and methanol with a mass ratio of 9:1, and 0.5% of trifluoroacetic acid is added; the chromatographic column uses ShimNex CS C18 5μm, 4.6*250mm, and the flow rate is 0.6mL / min; the mass content of each component is calculated according to the area normalization method.

[0139] (2) Content of alkali insoluble matter

[0140] Take 5g of the sample to be tested, stir with 500g of aqueous sodium hydroxide solution (3% by mass) at 35°C for 30min, filter with filter paper with a precision of ≤2μm, and rinse with 100g of water for 3 times. After drying the filter paper, weigh it. The mass increase relative to the filter paper before filtration (dry filter paper) is the mass of the insoluble substance. The ratio of the mass of the insoluble substance to the mass of the sample to be tested (5g) is the mass content of the alkali-insoluble substance.

[0141] (3) Water-soluble acid value

[0142] Take 1g of the sample to be tested, uniformly wet with 5.00±0.01g (m 乙醇 ) of ethanol, then add 50±0.01g (m 水 ) of water at room temperature, weigh the total mass m0 with the bottle and stirring, and then boil in water at 90°C for 1h in a closed state. After cooling to 25°C and constant temperature for 30min, add water to the total mass m0. Filter to obtain the clear filtrate with a mass of m1. Measure the test acid value of the clear filtrate by the potentiometric titration test method. The concentration of the potassium hydroxide solution used for titration is 0.05mol / L. The water-soluble acid value of the polymer additive is test acid value×(m 水 +m 乙醇 ) / m1.

[0143] (4) Organic acid value

[0144] Take 1g of the sample to be tested, uniformly wet with 50.0±0.01g (m 二氯甲烷 ) of dichloromethane, then weigh the total mass m0 with the bottle and stirring, and then boil at 90°C for 1h in a closed state. After cooling to 25°C and constant temperature for 30min, add dichloromethane to the total mass m0. Filter to obtain the clear filtrate with a mass of m1. Measure the test acid value of the clear filtrate by the potentiometric titration test method. The concentration of the potassium hydroxide solution used for titration is 0.05mol / L. The organic acid value of the polymer additive is test acid value×m 二氯甲烷 / m1.

[0145] (5) Mass content of sulfate radical

[0146] Refer to the method in the standard EN 14582:2007-“Determination of halogen content”, and measure by ion chromatography technology with external standard method.

[0147] (6) D 50 Particle size

[0148] Take 0.1g of the sample to be tested, wet with 5g of ethanol, and then dilute with 50mL of water. Test by Mastersizer3000 laser particle size analyzer.

[0149] (7) Water content

[0150] The sample to be tested was placed in an infrared moisture analyzer (Model MA 35, Sartorius, Germany) and automatically tested for water content after being placed at 105℃ for 30 min.

[0151] (8) Phosphorus content

[0152] 0.1 g of the sample to be tested was dissolved in 2 g of aqueous sulfuric acid (30% by mass), and tested according to the standard GB / T 11893-1989 "Determination of Total Phosphorus in Water - Ammonium Molybdate Spectrophotometric Method".

[0153] In the following specific embodiments of the present application, all materials for which no preparation method is provided are commercially available chemicals, and specific information for some of the materials is as follows:

[0154] Grade, manufacturer Antioxidant 1076 RIANOX 1076, commercially available Antioxidant 1010 RIANOX 1010, commercially available Antioxidant 608 Revonox 608, commercially available Flocculating agent: anionic polyacrylamide Xinqi Polymer Co., Ltd., Gongyi Polyamide 66 (PA66) PA66 M2000, Guangdong Xinhui Meda Nylon Co., Ltd. Polyamide 6 (PA6) PA6 EPR24, Shenma Industrial Co., Ltd. Melamine polyphosphate (MPP) BUDIT 3141, Budenheim, Germany Glass fiber ECS10-03-568H, China Jushi Co., Ltd. Lubricant TR044W, Struktol, Germany Antioxidant 1098 RIANOX 1098, commercially available Antioxidant 168 RIANOX 168, commercially available

[0155] The polymer additive and the preparation method thereof will be described in detail below with multiple examples as examples, but the polymer additive and the preparation method thereof are not limited to these examples.

[0156] Examples 1-9, Comparative Examples 1-5

[0157] A polymer additive and a preparation method thereof, the preparation method being as follows:

[0158] (1) 39.6 kg of a 50% by mass aqueous hypophosphorous acid solution, 500 g of sodium persulfate, and an antioxidant with a mass of m1 were placed in an autoclave, replaced with nitrogen for 3 times, ethylene was passed through a pressure reducer to a constant pressure of 1.5 MPa, heated to a temperature of T1, and kept at the temperature for 5.5 h; 3500 g of a 10% by mass aqueous sodium persulfate solution was continuously added during the keeping process, and then kept at the temperature T1 for another 1.5 h, cooled, and vented to obtain an aqueous diethyl hypophosphite solution;

[0159] (2) The aqueous diethyl hypophosphite solution (6 mol of diethyl hypophosphite) obtained in step (1), an aqueous sulfuric acid solution (30% by mass of sulfuric acid, n1 mol of sulfuric acid), and 2 mol of aluminum hydroxide were mixed, heated to a temperature T2, stirred for 8 h, and adjusted to a pH value with a sodium hydroxide solution (10% by mass) to obtain a diethyl hypophosphite salt slurry;

[0160] (3) The diethyl hypophosphite salt slurry obtained in step (2) was added with a flocculant aqueous solution prepared from an anionic polyacrylamide with a mass of m2 and 50 g of water at 50℃, stirred to a flocculation state, filtered, and the filter cake was washed with 3 times the mass of water for 5 times, and dried at 110℃ to a constant weight to obtain the polymer additive.

[0161] The specific process parameters of the preparation method and the related data of the prepared polymer additive are shown in Table 1 and Table 2; “--” represents that the material is not added.

[0162] Table 1

[0163]

[0164]

[0165] Table 2

[0166]

[0167] As shown in Table 1, the preparation method of the polymer additive is designed, and especially by using the antioxidant and the flocculating agent and controlling the pH value of the slurry, the polymer additive with low acid value is prepared, and the water-soluble acid value of the polymer additive is ≤0.3 mgKOH / g. The polymer additive includes the following components in mass parts: 95-98.98 parts of diethyl phosphinate, 1-3 parts of ethyl butyl phosphinate, 0.01-0.7 parts of ethyl phosphonate, 0.01-0.3 parts of monoethyl phosphinate, and 0-3 parts of alkali-insoluble matter.

[0168] In Table 2, the pH value of the slurry in Comparative Examples 1-2 exceeds the limited range of the present application, the antioxidant is not used in Comparative Examples 3-4, and the flocculating agent is not added in Comparative Example 5, which leads to the significant increase of the water-soluble acid value and the organic acid value of the polymer additive.

[0169] The application of the polymer additive will be described in detail below by taking application examples as examples, but the application of the polymer additive is not limited to these application examples.

[0170] Application Examples 1-9, Comparative Application Examples 1-5

[0171] A polymer composition, specifically a polyamide composition, the types and amounts of the components are shown in Table 3 and Table 4, and the amount of each component is “mass parts”.

[0172] The preparation method of the polyamide composition includes: mixing polyamide 66, polyamide 6, glass fiber, polymer additive, MPP, antioxidant and lubricant according to the formula amount to obtain a premix; adding the premix to a double screw extruder, the screw rotation speed of the double screw extruder is 400 rpm, and the temperatures of the 1-12 zones are 90℃, 180℃, 260℃, 250℃, 230℃, 230℃, 220℃, 220℃, 220℃, 220℃, 260℃, and 260℃ respectively, and the polyamide composition particles are obtained by melt mixing, extruding and granulating.

[0173] The polyamide composition is tested for the following properties:

[0174] (1) Water boiling phosphorus content test: 50 g of polyamide composition particles is added into 500 mL of hot water at 90 ℃, and boiled for 1 h, cooled to room temperature, filtered, and the filtrate is measured for phosphorus content by the ammonium molybdate spectrophotometric method of GB / T 11893-1989;

[0175] (2) Mold dirt test method: using an injection molding machine, polyamide composition particles are continuously injection molded at 150 molds at an injection molding temperature of 290 ℃, 285 ℃, 280 ℃, and 260 ℃, and the mold dirt sample collected in the last mold is weighed using an analytical balance;

[0176] (3) Extrusion process release amount: a cyclone separator with a jacketed cooling is added to the vacuum pipeline of a double-screw extruder with a diameter of 75 mm and a length-diameter ratio of 48:1 to separate the released substances during the extrusion process, and the released substances in the cyclone separator are weighed after 2000 kg of products are continuously produced, which is the release amount of the extrusion process; wherein, blockage represents that the release amount is too large, resulting in blockage of the vacuum system within 8 h of production.

[0177] The test data are shown in Tables 3 and 4.

[0178] Table 3

[0179]

[0180] Table 4

[0181]

[0182] According to the data in Table 3, the polymer additive provided by the application as a flame retardant used in the polyamide composition can effectively inhibit the release of auxiliary agents during the extrusion process, reduce the risk of blockage, significantly reduce the mold dirt generated by injection molding, make the mold dirt ≤7.2 mg, and the water boiling phosphorus content of the polyamide composition ≤490 ppm, reduce the content of water boiling release, and improve the stability and service life of the polyamide composition under humid heat conditions.

[0183] According to the test data in Table 4, the polymer additives of Comparative Examples 1-5 have high acid values, which leads to obvious release of auxiliary agents during the extrusion process when they are used as flame retardants in the polyamide composition, which easily causes pipe blockage problems, and more mold dirt is generated by injection molding, and the water boiling phosphorus content is increased, indicating that the stability under humid heat conditions is obviously insufficient.

[0184] The applicant states that the polymer additive of the present application and the preparation method and application thereof are illustrated by the above-mentioned examples, but the present application is not limited to the above-mentioned examples, i.e. it does not mean that the present application must rely on the above-mentioned examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for the preparation of a polymer additive, characterized in that The preparation method comprises the following steps: (1) hypophosphorous acid aqueous solution and an antioxidant are subjected to a free radical reaction with ethylene under the action of an initiator to obtain a diethyl hypophosphite aqueous solution; (2) the diethyl hypophosphite aqueous solution, sulfuric acid and a metal hydroxide are subjected to a reaction, and then a lye is added to obtain a diethyl hypophosphite slurry with a pH value of 3.8-4.2; (3) the diethyl hypophosphite slurry and a flocculating agent are mixed and stirred to obtain diethyl hypophosphite flocculate; the diethyl hypophosphite flocculate is filtered, washed and dried to obtain the polymer additive; The antioxidant comprises any one or a combination of at least two of a hindered amine antioxidant, a hindered phenol antioxidant, a phosphite antioxidant and a thioester antioxidant. The flocculating agent comprises an anionic polyacrylamide and / or a nonionic polyacrylamide.

2. The production method according to claim 1, characterized by, The antioxidant comprises any one or a combination of at least two of a hindered phenol antioxidant, a phosphite antioxidant and a thioester antioxidant.

3. The preparation method according to claim 1, characterized in that, The antioxidant includes any one of or a combination of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N, N' - bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, 2,6-di-tert-butyl-p-cresol, distearyl-β,β-thiodipropionate.

4. The method of claim 1, wherein, The initiator comprises any one or a combination of at least two of an organic peroxide, a persulfate, an azo initiator and a photoinitiator.

5. The preparation method according to claim 1, characterized in that, The mass percentage content of hypophosphorous acid in the hypophosphorous acid aqueous solution is 20-70%.

6. The production method according to claim 5, wherein The mass percentage content of hypophosphorous acid in the hypophosphorous acid aqueous solution is 45-55%.

7. The preparation method according to claim 5, characterized in that, The mass ratio of hypophosphorous acid to the antioxidant is 100:(0.02-1.2).

8. The preparation method according to claim 7, characterized in that, The mass ratio of hypophosphorous acid to the antioxidant is 100:(0.05-1).

9. The preparation method according to claim 5, characterized in that, The mass ratio of hypophosphorous acid to the initiator is 100:(0.1-5).

10. The method of claim 1, wherein, The temperature of the free radical reaction is 60-105℃.

11. The method of claim 10, wherein, The temperature of the free radical reaction is 70-100℃.

12. The method of claim 11, wherein, The temperature of the free radical reaction is 75-95℃.

13. The method of claim 1, wherein, The free radical reaction is carried out in a protective atmosphere.

14. The method of claim 13, wherein, The protective atmosphere comprises a nitrogen atmosphere and / or an argon atmosphere.

15. The method of claim 1, wherein, The metal hydroxide comprises any one or a combination of at least two of aluminum hydroxide, calcium hydroxide, copper hydroxide, zinc hydroxide, iron hydroxide and titanium hydroxide.

16. The method of claim 15, wherein, The metal hydroxide comprises aluminum hydroxide.

17. The method of claim 1, wherein, The molar amount of the metal hydroxide is 30-50 mol% based on 100% of the molar amount of the diethyl hypophosphite.

18. The method of claim 1, wherein, The molar amount of the sulfuric acid is 5-50 mol% based on 100% of the molar amount of the diethyl hypophosphite.

19. The method of claim 18, wherein, The molar amount of the sulfuric acid is 8-30 mol% based on 100% of the molar amount of the diethyl hypophosphite.

20. The method of claim 19, wherein, The molar amount of the sulfuric acid is 10-15 mol% based on 100% of the molar amount of the diethyl hypophosphite.

21. The method of claim 1, wherein, The temperature of the reaction in step (2) is 70-150℃.

22. The method of claim 21, wherein, The temperature of the reaction in step (2) is 80-120℃.

23. The method of claim 22, wherein, The temperature of the reaction in step (2) is 90-100℃.

24. The method of claim 1, wherein, The reaction time in step (2) is 2-12 h.

25. The method of claim 1, wherein, The flocculating agent comprises an anionic polyacrylamide.

26. The method of claim 1, wherein, The mass of the flocculating agent is 0.01-0.5% based on 100% of the theoretically obtained mass of the diethyl hypophosphite salt.

27. The method of claim 1, wherein, The temperature of the mixing in step (3) is 40-60℃.

28. The method of claim 1, wherein, The washing in step (3) is performed for ≥4 times.

29. A polymer additive characterized in that, The polymer additive is prepared by the preparation method according to any one of claims 1-28, and has a water-soluble acid value of ≤0.3 mg KOH / g; The polymer additive comprises the following components in parts by mass: diethylphosphinic acid salt 95-98.98 parts ethylbutylphosphinic acid salt 1-3 parts ethylphosphinic acid salt 0.01-0.7 parts monoethylphosphinic acid salt 0.01-0.3 parts alkali-insoluble substance 0-3 parts; The alkali-insoluble substance is selected from any one or a combination of at least two of hydroxide, oxide, phosphate, phosphite, and other alkylphosphinic acid salt. The water-soluble acid value of the polymer additive is tested by the following method: 1 g of the sample to be tested is uniformly wetted with 5.00±0.01 g (m 乙醇 ) ethanol, then 50±0.01 g (m 水 ) normal temperature water is added, the total weight m0 is weighed with the bottle and stirring, after being boiled in water at 90℃ for 1 h, it is cooled to 25℃ and kept at constant temperature for 30 min, then water is added to the total weight m0; filtration is performed, the mass of the clear filtrate is m1, the test acid value is measured by the potentiometric titration method, 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=(m 水 +m 乙醇 ) / m1.

30. The polymer additive of claim 29, wherein, The polymer additive has a water-soluble acid value of 0.1-0.3 mg KOH / g.

31. The polymer additive of claim 29, wherein, The polymer additive has an organic acid value of ≤0.05 mg KOH / g. The organic acid value of the polymer additive was obtained by testing as follows: Take 1 g of the sample to be tested, add 50.0 ± 0.01 g (m 二氯甲烷 After uniformly wetting the sample in dichloromethane, weigh the total weight m0 with the bottle and stirring. Boil the sample 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 the solution 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 is calculated as: (Test acid value × m) 二氯甲烷 / m1.

32. The polymer additive of claim 31, wherein, The polymer additive has an organic acid value of 0.02-0.04 mg KOH / g.

33. The polymer additive of claim 29, wherein, The polymer additive has a mass content of sulfate of 100-700 ppm.

34. The polymer additive of claim 33, wherein, The polymer additive has a mass content of sulfate of 270-420 ppm.

35. The polymer additive of claim 29, wherein, D of the polymer additive 50 Particle size is 1-100 μm.

36. The polymer additive of claim 35, wherein, D of the polymer additive 50 Particle size is 20-60 μm.

37. The polymer additive of claim 36, wherein, D of the polymer additive 50 Particle size is 33-38 μm.

38. The polymer additive of claim 29, wherein, The polymer additive has a water content of 0.01-1 wt%.

39. The polymer additive of claim 38, wherein, The polymer additive has a water content of 0.05-0.3 wt%.

40. The polymer additive of claim 39, wherein, The polymer additive has a water content of 0.1-0.25 wt%.

41. The polymer additive of claim 29, wherein, The polymer additive has a phosphorus content of 22-25 wt%.

42. The polymer additive of claim 41, wherein, The polymer additive has a phosphorus content of 23-24 wt%.

43. Use of the polymer additive according to any one of claims 29-42 in a polymer material.

44. Use of the polymer additive according to claim 43 in a polymer material, characterized in that, The polymer additive is used as a flame retardant in the polymer material.

45. A polymer composition characterized in that, The polymer composition comprises a polymer matrix and the polymer additive according to any one of claims 29-42.

46. The polymer composition according to claim 45, characterized in that The polymer composition comprises the following components in parts by mass: polymer matrix 40-99 parts The polymer additive 5-35 parts.

47. The polymer composition of claim 45, wherein The polymer matrix comprises a polyamide and / or a polyester.

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