AU2018100854A4 - An additive for polymer and preparation method thereof - Google Patents

Abstract

The invention claims an additive for polymer, wherein comprising: A, phosphonate containing two substituting groups, having the following structural formula (I), L - 0]j ', wherein R1 and R2 are the same or different and each represents H, C1-C6 alkyl or C6-C18 aryl, M is Al, m is 3, B: antimony metal element, wherein the metal element antimony in the total weight content of additive is 10-500 ppm. The invention contains a specific range content metal element antimony additive has simple preparation technique, low production cost, and it is used in the polymer, which can greatly improve the glowing filament performance of polymer, polymer molding composition GMIT can satisfy the GWIT not less than 855 degrees centigrade /0.8mm, and has high flame retardant property.

Description

An additive for polymer and preparation method thereof

Technology field

The invention claims an additive for polymer, specifically a dialkyl phosphinate salt containing trace metal element antimony and preparation method thereof.

Background technology

Dialkyl phosphinates, widely used as flame retardant, known can be obtained by different methods to synthesize. The patent DE4430932 claims disubstituted phosphinic acid metal salt flame retardant polyester as, DE19910232 US6248921 two patent claims a preparation method of disubstituted phosphinic acid metal salt. U.S. patent US6359171B1 claims a method for preparing aluminium dialkyl phosphinic acid, comprising the following steps: synthesizing monoalkyl phosphonate by the yellow phosphorus, then using free radical initiation vinylation after hydrolysis to obtain acid react with aluminium salt to obtain dialkyl aluminium hypophosphite flame retardant.

Thermoplastic plastic, which is widely applied to electronic appliances, automobile, building industry due to its excellent electrical performance and processing performance, in order to meet the requirement of inflaming retarding and environment-friendly requirements of the industry, usually added halogen-free flame retardant in the thermoplastic plastic to meet the requirement of the material.

Dialkyl phosphinic acid salt as a high efficiency halogen-free fire retardant, has high bulk density and small flame retardant dosage, good mechanical performance, good colour, iow smoke density, phase ratio electric leakage tracking index CTI {) value is high, and it is widely applied to polyamide, polyester, unsaturated resin, epoxy resin, polyurethane and other thermoplastic and thermosetting plastic.

The invention through research, unexpectedly found that when in the flame retardant containing a small amount of metal dialkyl phosphinate antimony element, not only can ensure the polymer composition with high flame resistance, also can greatly improve the glowing filament performance of polymer composition (GMIT), the polymer molding composition GMIT can satisfy the GWIT not less than 855 degrees centigrade to /0.8mm.

Invention contents

The purpose of the invention is to provide an additive for polymers, the additive by adding a little in the dialkyi phosphinate metal antimony element, the resulting polymer composition has excellent flame resistance and glowing filament performance (GMIT). Another object of the present invention is providing one of the above polymer used for the preparation method of the additive.

The invention is realized by the following technical solution:

An additive for polymer, comprising: A dialkyl phosphinate, having the following structural formula (I),

(i) wherein R1, R2 are the same or different and each represents H, C1-C6 alkyl or C6-C18 aryl, preferably ethyl, propyl, butyl, hexyl, or cyclohexyl; M is Al, m is 3; B: antimony metal element, wherein the metal element antimony weight content in the total additive is 10-500 ppm. preferably weight content is 25-400 ppm, more preferably the weight content is 40-300 ppm, more preferably is 50-200 ppm wt %.

Test method of the content by weight of the metal element antimony: taking 0.05 + 0.005 g additive for polymer sample, accurate to 0.001 g, and putting into microwave digestion tank, then adding 10 ml. ketopantoate the microwave digestion tank, such that it is completely immersed the sample, slowly dropping 1-2 ml. hydrogen peroxide, with the sample digesting acid react for 1-2 min, covering the cover, sealing the digestion tank in 220 degrees centigrade blast oven for digestion, the digestion time is 2h, after digestion, taking out the digestion pot, cooling to room temperature, tested, if still some particles without digestion, and then slowly dropping 1-2 ml. hydrogen peroxide digestion step, if the secondary digesting not completely, needs to be as sample digestion solution after filtering to obtain clarified solution, specifically, the microwave digestion solution in the dissolving tank by a filter film of 0.45 μ m is transferred to the volumetric flask, a digestion tank and the washing liquid is transferred to the volumetric flask, using the distilled water to dilute to the scale line 50 ml. with proper distilled water washing for many times by microwave, shaking evenly, measuring, using the Agilent Company is weight content of metal element antimony full automatic inductively coupled plasma atomic emission spectrograph analyzing sample 720ES to be tested, the final result is the average of three test values. the metal element antimony from antimony-containing compounds, antimony-containing compounds selected from antimony (III) oxide, antimony (V) oxide, antimony sulphide (III) sulfide, antimony (V), antimony sulfate, antimony acetate, antimony (III), iodide, antimony (III), antimony (III) propanol, triphenyl antimony (III), ethoxy antimony, propoxy antimony, methoxy antimony, 1-butyl-3-methyl hexafluoroantimonate, tri (4-bromophenyl) ammonium antimony, triphenyl antimony acetate (V), triphenyl antimony chloride (V), tetraphenyl antimony bromide (V) is one kind of or several kinds, source of metal antimony element indicated by this invention is not limited to the example, no matter which kind of format of using antimony-containing compounds, all of which can be detected using atomic emission spectroscopy, the weight content of metal element antimony is antimony metal element itself rather than to the antimony-containing compound is added metal antimony element as reference, calculating on the reference that the total weight of the antimony content of the metal elements expressed by ppm is for polymer additive of this invention. the polymer is polyester (e.g., PBT, PET), nylon (PA6, PA66 etc.), PPE, TPE, TPU or epoxy resin, preferably nylon 6.

In the invention, the dialkyl phosphate and antimony-containing compounds in the high-speed mixer and uniformly mixing to obtain additive for polymer; wherein said antimonial compound is antimony oxide (III), antimony (V) oxide, antimony sulphide (III) sulfide, antimony (V), antimony sulfate, antimony acetate, antimony selenide (III) iodide, antimony (III), antimony (III) propanol, triphenyl antimony (III), ethoxy antimony, propoxy antimony, methoxy antimony, 1-butyl-3-methyl hexafluoroantimonate, tri (4-bromophenyl) ammonium antimony, triphenyl antimony acetate (V), triphenyl antimony chloride (V), tetra-phenyl antimony bromide (V) is one kind of or several kinds.

The invention further claims the additive for polymer use as flame retardant.

The invention also claims an additive comprising the polymer used for the polymer material, comprising 5-25 parts by weight of additive for polymer, 50-75 by weight polymer or mixtures thereof. the polymer is polyester (PBT, PET), nylon (PA6, PA66 etc.), PPE, TPE, TPU or epoxy resin, preferably is nylon 6.

The polymer material of the invention can be designed according to different performance requirements of different material, and adding auxiliary agent. The further comprises auxiliary filler of 15-40 by weight and 0.1-5 by weight. filler of the invention is generally used for reinforced or filled polymer material, also can use two or more inorganic filler and/or reinforcing agent of mixture, preferably glass fibres, the auxiliary agent can be an additional component does not interfere with the desired properties but the other beneficial properties, such as antioxidants, lubricants, release agents, nucleating agents, colorants, light stabilizers.

Compared with the existing technology, the invention has the following beneficial effects: 1) This invention preparation containing specific range content metal element antimony dialkyl phosphinate obtained, as a polymer additive, the additive used in the polymer, not only can ensure the polymer composition with high flame resistance, also can greatly improve the glowing filament performance of polymer composition, polymer moulding composition GMIT can satisfy the GWIT not less than 855 degrees centigrade to /0.8mm. 2) according to the invention for polymer additive, the preparation process is simple, the production cost is low, it is convenient for production in a large scale.

Preferred Embodiment

By the following embodiments to further explain the present invention, the following embodiment is the embodiment preferred of the present invention, but the embodiment of the present invention is not limited by the following examples. in the following description of embodiments and the selected raw material in proportion, but not limited to these materials:

Component A is dialkyl hypophosphite: commercial metal antimony element content: not detected; PA6: commercially available, PA6:PA6M2000 (Guangdong Xinhui MITA Co., Ltd.) Antimony oxide (III): Xigema-Aodeliqi (Shanghai) Trading Co., Ltd.;

Antimony acetate: Xigema-Aodeliqi (Shanghai) Trading Co., Ltd.;

Antimony sulfate: Xigema-Aodeliqi (Shanghai) Trading Co., Ltd.;

Triphenyl antimony (III) : Xigema-Aodeliqi (Shanghai) Trading Co., Ltd.; glass fiber: ECS301-HP (Chongqing international Composite Material Co., Ltd.); antioxidant: 1010, commercially available.

The weight content of the invention is the metal element antimony test method: taking 0.05 + 0.005 g additive for polymer sample, accurate to 0.001 g, and putting into microwave digestion tank, then adding 10 mL ketopantoate the microwave digestion tank, so as to completely immerse the sample, slowly dropping 1-2 mL hydrogen peroxide, with the sample digesting acid react for 1-2 min, covering the cover, sealing the digestion tank in 220 degrees centigrade blast oven for digestion, the digestion time is 2h. after finishing digestion, taking out the digestion pot, cooling to room temperature, tested, if still some particles without digestion, and then slowly dropping 1-2 ml. hydrogen peroxide digestion step, if the secondary digesting not completely, needs to be as sample digestion solution after filtering to obtain clarified solution, specifically, the microwave digestion solution in the dissolving tank by a filter film of 0.45 μ m is transferred to the volumetric flask, many washing microwave digestion tank and the washing liquid is transferred to the volumetric flask by proper distilled water, then using distilled water to dilute to the scale line 50 mL, shaking evenly, measuring, using the Agilent Company is weight content of metal element antimony full automatic inductively coupled plasma atomic emission spectrograph analyzing sample 720ES to be tested, the final result is the average of three test values. The testing method of the invention the polymer composition GMIT reference GB/T 5169.11-1997.

The invention UL94 the combustion performance plastic combustion property test;

The test sample measurement from the test sample to the UL 94 flame rating with a thickness 1.5 mm of each polymer composition, following is a combustion level of UL 94: V-0 spline, sustained combustion time after the flame is not long continuous combustion time total 10 times starting at 10 s, 5 sample strips and not more than 50 s, there is no melt drop falls, no flame spread to clamp, sample the igniting the afterglow after finishing burning time is not longer than 30 s. V-1 spline, sustained combustion time after the flame is not long continuous combustion time total 10 times starting at 30 s, 5 sample strips and not more than 250 s, the sample ignites the afterglow after finishing burning time is not longer than 60 s, other standard like V-0. V-2 spline from the flame burns continuously after drop occurs in the process, and the melt drops will ignite absorbent cotton indicator, other standard V-1.

Not capable of classifying (TIR) does not satisfy the combustion level V-2.

Example 1-2 (D1-D2) and Example 1-11 (B1-B11) according to the composition of Table 1 rockably, weighing component A and an antimony-containing compound in high-speed mixer mixing uniformly to obtain the additive for polymer. wherein the invention for polymer additive metal element antimony content is to be adjusted and measured by the actual amount of antimony compound added in the preparation process.

Table 1 the ratio of 1-2 (D1-D2) and Example 1-11 (B1-B11) for polymer additive

Comparative Example 3-5, Example 12-22 in Table 2: weighing each component in the high speed stirring and mixing machine after uniformly mixing in the double-screw extruder; the glass fibre by side feeding system of double-screw extruder, melting and extruding through a double-screw extruder in the water bath cooling, granulating to obtain the polymer composition; and measuring the UL-94 flame retardant grade and GMIT, specific test data are listed in Table 2. Comparative Example 3-5 Table 2, embodiments of components 12-22 in specific proportions (parts by weight) and testing result

Claims (5)

1. An additive for polymer, comprising: A, a dialkyl phosphinate, having the following structural formula (I),

(0 wherein R1, R2 are the same or different and each represents H, C1-C6 alkyl or C6-C18 aryl, M is Al, m is 3, B: antimony metal element, wherein the metal element antimony weight content in the total additive is 10-500 ppm.

2. The method according to claim 1, the mentioned a kind of additive for polymer, wherein the weight content of the metal antimony element in the total additive is 25-400 ppm, preferable weight content is 40-300 ppm, more preferably is 50-200 ppm wt %.

3. The method according to one of claim 2 1 additive for polymer, wherein, the testing method of the content by weight of the metal element antimony: taking 0.05 + 0.005 g additive for polymer sample, accurate to 0.001 g. putting into microwave digestion tank, then adding 10 ml_ ketopantoate the microwave digestion tank, so as to completely immerse the sample, slowly dropping 1-2 mL hydrogen peroxide, the sample with the acid for reacting for 1-2 min, covering the cover, sealing a digestion tank, in the 220 degrees centigrade blast oven for digestion, the digestion time is 2h, after digestion, taking out the digestion pot, cooling to room temperature, tested, if still some particles without digestion, and then slowly dropping 1-2 mL hydrogen peroxide digestion step, tested; If a secondary has not digesting completely, it needs to make the digestion solution after filtering to obtain the clear solution sample to be tested, specifically, dissolving tank in the microwave digestion solution by a filter film of 0.45 μ m is transferred to the volumetric flask, many washing microwave digestion tank and the washing liquid is transferred to the volumetric flask by proper distilled water, then using distilled water to dilute to the scale line 50 ml_, shaking evenly, measuring, using the Agilent Company is weight content of metal element antimony full automatic inductively coupled plasma atomic emission spectrograph analyzing sample 720ES to be tested, the final result is the average of three test values.

4. The method according to claim 1, the mentioned a kind of additive for polymer, wherein R1, R2 is ethyl, propyl, butyl, hexyl, or cyclohexyl.

5. The method according to claim 1, the mentioned a kind of additive for polymer, wherein the metal element antimony from antimony-containing compounds, antimony-containing compounds selected from antimony (III) oxide, antimony (V) oxide, antimony sulphide (III), antimony sulphide (V), antimony sulfate, antimony acetate, antimony selenide (III) iodide, antimony (III), antimony (III) propanol, triphenyl antimony (III), ethoxy antimony, propoxy antimony, methoxy antimony, 1-butyl-3-methyl hexafluoroantimonate, tri (4-bromophenyl) ammonium antimony, triphenyl antimony acetate (V), triphenyl antimony chloride (V), tetraphenyl antimony bromide (V) is one kind of or several kinds.