AU2018100240A4 - An additive for polymer and preparation method thereof - Google Patents

Abstract

The invention claims an additive for polymer, wherein comprising: A, phosphinate, containing two substituted groups having the following formula (1), I 0] MM. "k wherein R1 and R2 are the same or different and represents H, C1-C6 alkyl or C6-C18 aryl, M is Al, m is 3; B: sodium metal element, wherein sodium metal element weight content in the total additive is 100-900 ppm. The invention comprises a specific range content sodium metal element additive has simple preparation technique, low production cost, it is applied in polymer can greatly reduce the polymer composition resistant to thermal weight reduction rate, using PERKIN ELMER weight measurement device Pyris 1TGA, lower the melting point + 10 *C nitrogen atmosphere for 240 minutes, weight reduction rate is 0.101wt -0.250wt%, at the same time, it can maintain the polymer composition with excellent flame retardancy.

Description

An additive for polymer and preparation method thereof

Technology field he invention claims an additive for polymer, specifically claims a dialkyl phosphinate salt sodium containing trace metal elements and a preparation method thereof.

Background technology

Dialkyl phosphinates, widely used as flame retardant that is known to be through different methods to synthesize. The patent DE4430932 discloses disubstituted phosphinic acid metal salt used as flame retardant in polyester, DE19910232, US6248921 two patent claims a preparation method of disubstituted phosphinic acid metal salt. US patent US6359171B1 discloses a method for preparing aluminium dialkyl phosphinic acid, the method first uses the yellow phosphorus synthesizing monoalkyl ester, reacting to obtain dialkyl phosphinic acid aluminium and aluminium salt and then using free radical initiation vinylation after hydrolysis to obtain an acid.

Thermoplastic plastic, which is widely applied to electronic appliances because of its excellent electrical properties and processing property, automobile, building industry and so on, in order to meet the flame retardant requirements and environment requirements of industry, usually into the thermoplastic halogen-free flame retardant is added to satisfy the requirement of the material. ialkyl phosphinate salt as a high-efficient halogen-free flame retardant, with high bulk density, small dosage of flame retardant, good mechanical property, good colour and lustre, low smoke density, CTI (compared with leakage tracking index) 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 micro metal dialkyl phosphinate sodium element, not only can the polymer composition has high flame retardant property, can greatly reduce the polymer composition resistant to thermal weight reduction rate. ELMER using PERKIN heating weight measurement device Pyris 1TGA, lower the melting point + 10 °C nitrogen atmosphere for 240 minutes, the weight reducing rate is 0.101wt -0.250wt %.

Invention contents

The purpose of the invention is to provide an additive for polymers, the additive through adding trace metal in the dialkyl phosphinate sodium element can make the resulting polymer composition has excellent flame retardant property and remarkably reduce the thermal weight reduction rate.

Another object of the present invention is additive provides a preparation method of the polymer.

The invention is realized through the following technical solution:

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

wherein R1 and R2 are the same or different and represents H, C1-C6 alkyl or C6-C18 aryl, preferably ethyl, propyl, butyl, hexyl, or cyclohexyl; M is Al, m is 3; B: sodium metal element, wherein sodium metal element weight content in the total additive is 100-900 ppm. the preferable weight content is weight content is 200-890 ppm, more preferably 300-860 ppm, further preferably the weight content is 400-830 ppm.

Method for testing the weight content of sodium metal element additive sample 0.05 + 0.005 g for the polymer, accurate to 0.001 g, and putting into microwave digestion tank; then adding 10 ml_ ketopantoate to microwave digestion pot to make it completely immersing the sample, slowly dropping 1-2 mL hydrogen peroxide, the sample and digestion acid react for 1-2 min, cover upper cover, sealing the digestion tank in the 220 °C blast oven to digestion, the digestion time is 2h. after finishing digestion, taking out the digestion pot, cooling to room temperature, measuring, if still some particles not digesting, then slowly dropping 1-2 mL hydrogen peroxide repeating said digestion step, if the secondary digesting not completely, need to digestion liquid after clarifying solution is obtained by filtering the sample to be tested, specifically, the microwave digestion solution in the tank by 0.45 microns of filtering film is transferred to a volumetric flask, proper distilled water for many times washing microwave digestion pot and transferring the washing liquid to the volume bottle; and then diluted to 50 mL with distilled water, shaking evenly, measuring, full automatic inductive coupling plasma atomic emitting spectrograph analyzing with Agilent Company of 720ES weight content of sodium metal element in the sample to be tested, select test value for three times and the average is the final result. The metal sodium elements from sodium-containing compound, a sodium-containing compound selected from the group consisting of D-lactate, L-sodium lactate, sodium acetate, sodium sulfite, sodium hydroxide, sodium amide, sodium nitrate, sodium sulfide, sodium sulfate, sodium phosphate, sodium oxalate, tartrate dibasic dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium pyrosulfite, sodium silicate, sodium diacetate, sodium acrylate, acetylene, ethanol sodium, sodium citrate, sodium oleate, sodium salicylate, sodium methoxide, sodium benzene, sodium phenol. 1-butane sodium sulfonate, 1-sodium propane thiol, 1-dodecane sodium sulfonic acid, 1-nonane sodium sulfonate, 1-heptane sulfonic acid sodium, 1-decane sodium sulfonate, 2-sodium propane thiol, 2-naphthalene succinic acid, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, sodium dodecyl sulfate, sodium tert-butoxide in the one kind of or several, source of sodium metal element of the present invention is not limited to the example, no matter which kind of format using sodium-containing compounds, can be detected using atom emitting spectroscopy, the weight content of the sodium metal element is sodium metal element itself instead of sodium-containing compound is added sodium metal element as the reference, the weight content of the sodium metal elements expressed in terms of ppm is the total weight of the additive polymer used in this invention is reference calculating. the polymer is polyester (e.g., PBT, PET), nylon (PA6, PA66 etc.), PPE, TPE, TPU or epoxy resin, preferably a polyester.

The invention through taking the dialkyl phosphate and sodium-containing compound in the high-speed mixer to mix uniformly to obtain the additive for polymer; wherein the sodium compound is sodium-containing compound is D-lactate, L-sodium lactate, sodium acetate, sodium sulfite, sodium hydroxide, sodium amide, sodium nitrate, sodium sulphide, sodium sulphate, sodium phosphate, sodium oxalate, sodium tartrate dibasic dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium pyrosulfite, sodium silicate, sodium diacetate, sodium acrylate, acetylene, ethanol sodium, sodium citrate, sodium oleate, sodium salicylate, sodium methoxide, sodium benzene, sodium phenol, 1-butane sulfonic acid sodium. 1-sodium propane thiol, 1-dodecane sodium sulfonic acid, 1-nonane sodium sulfonate, 1-heptane sulfonic acid sodium, 1-decane sodium sulfonate, 2-sodium propane thiol, 2-naphthalene succinic acid, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, sodium dodecyl sulfate, sodium tert-butoxide in the one kind of or several.

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

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

The polymer of the invention is material, according to the different performance requirements of material, adding different auxiliary agent. The further comprises 15-40 parts of filler and 0.1-5 parts of auxiliary agent by weight.

The 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 fibre.

The auxiliary agent can be an additional component does not interfere with the desired properties but improving other beneficial properties, such as antioxidant, lubricant, release agent, forming agents, colorants, light stabilizers.

The invention compared with the existing technology, has the following beneficial effects: 1) the invention is preparation method of dialkyl phosphinate sodium metal element containing specific range content obtained as a polymer additive, the additive used in the polymer, not only can ensure the polymer composition has high flame retardant property, it also can greatly reduce the polymer composition resistant to thermal weight reduction rate, using PERKIN ELMER weight measurement device PyrisITGA, lower the melting point +10 centigrade nitrogen atmosphere for 240 minutes, the weight reducing rate is 0.101wt -0.250wt %. 2) of the invention for the polymer additive, the preparation process is simple, the production cost is low, and it is convenient for large-scale production.

Preferred Embodiment

Below through specific embodiments to further explain the present invention, the following embodiments of the present invention better embodiment, but embodiments of the invention are not limited by the following examples. -the following description of embodiments and the selected raw material in proportion, but not limited the materials: component A dialkyl phosphate, commercially available sodium, metal element content: not detected; PBT, PBT 1100-211M (Taiwan vinblastine Group)

Sodium acetate, sigma-PETER-J-COWDERY-CORVAN (Shanghai) Trading Co., Ltd.; Sodium sulfate: sigma azulene-sulfonate PETER-J-COWDERY-CORVAN (Shanghai) Trading Co., Ltd.;

Sodium tert-butoxide; a sigma-PETER-J-COWDERY-CORVAN (Shanghai) Trading Co., Ltd.; crosslinked sodium benzene: sigma-PETER-J-COWDERY-CORVAN (Shanghai) Trading Co., Ltd.; glass fibre : ECS13-4.5-534 (Jushi Group) antioxidant: 1010, (jinhai yabao)

The weight content of the sodium metal element testing method: 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 to microwave digestion pot to make it completely immersing the sample, slowly dropping 1-2 mL hydrogen peroxide, the sample and digestion acid react for 1-2 min, cover upper cover, sealing the digestion tank in the 220 °C blast oven to digestion, the digestion time is 2h. after finishing digestion, taking out the digestion pot, cooling to room temperature, measuring, if still some particles not digesting, then slowly dropping 1-2 mL hydrogen peroxide repeating said digestion step, if the secondary digesting not completely, need to digestion liquid after clarifying solution is obtained by filtering the sample to be tested, specifically, the microwave digestion solution in the tank by 0.45 microns of filtering film is transferred to a volumetric flask, proper distilled water for many times washing microwave digestion pot and transferring the washing liquid to the volume bottle; and then diluted to 50 ml. with distilled water, shaking evenly, measuring, full automatic inductive coupling plasma atomic emitting spectrograph analyzing with Agilent Company of 720ES weight content of sodium metal element in the sample to be tested, select test value for three times and the average is the final result. The polymer composition of the invention heat-resistant weight reduction rate: PERKIN ELMER weight measurement device Pyris 1TGA is used to lower the melting point + 10 °C nitrogen atmosphere maintaining weight reduction rate in 240 minutes.

The combustion performance of the invention: UL94 plastic combustion performance test; Measuring the UL 94 flame rating for the test sample of each polymer composition with thickness 1.5 mm of test sample, the following is a burn rating of UL 94: V-0: sample leaves the flame, continuous combustion time is not longer than the continuous combustion time 10 s, 5 spline 10 times ignition when the sum does not exceed 50 s, there is no melt drop, flame spread to clamp, sample after the igniting end of afterglow burning time is not longer than 30 s. V-1: duration of total combustion time after leaving the flame, continuous combustion time is no more than 30 s, 5 spline 10 times ignition is not more than 250 s, after the sample is ignited afterglow burning time is not longer than 60 s, other standard like V-0. V-2: sample leaves the flame, continuously during the combustion process, drop and drop will not ignite absorbent cotton indicator, other standard V-1.

Is not capable of classifying (ncl) does not meet the combustion level V-2.

Comparative Example 1-2 (D1-D2) and Example 1-11 (B1-B11)

The rockably table 1, weighing the said preparation of component A and a sodium containing compound in high speed mixer to mix uniformly to obtain the invention additive for polymer.

Wherein the invention additive for polymer sodium metal element content is to be adjusted and measured by an actual added quantity of the sodium compound in the preparation process.

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

Sodium acetate Sodium sulfate Sodium tert-butoxide; crosslinked sodium benzene

Comparative Example 3-5, Example 12-22

According to table 2: weighing each component in the high speed stirring mixing machine after uniformly mixing in the double-screw extruder; the glass fibre through side feeding system of double-screw extruder, melting and extruding through a double-screw extruder, cooling in the water bath, granulating, to obtain the polymer composition; and measuring the UL-94 flame retardant grade and thermal weight reduction rate, the specific test data listed in Table 2.

Claims (5)

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

wherein R1 and R2 are the same or different and represents H, C1-C6 alkyl or C6-C18 aryl, M is Al, m is 3; B: sodium metal element, wherein sodium metal element weight content in the total additive is 100-900 ppm.

2. The method according to claim 1 for the polymer additive, wherein the weight content of the sodium metal element in the total additive is 200-890 ppm, preferable weight content is 300-860 ppm, more preferably the content is 400-830 ppm by weight.

3. The method according to claim 1 or 2 for the polymer additive, wherein the test method of sodium weight content of metal elements: 0.05 + 0.005 g additive for polymer sample, accurate to 0.001 g. putting into microwave digestion tank, then adding 10 ml_ ketopantoate to microwave digestion pot to make it completely immersing the sample, slowly dropping 1-2 ml. hydrogen peroxide, the sample and digestion acid react for 1-2 min, cover upper cover, sealing a digestion tank, in the 220 °C blast oven to digestion, the digestion time is 2h, after finishing the digestion, taking out the digestion pot, cooling to room temperature, measuring, if still some particles not digesting, then slowly dropping 1-2 mL hydrogen peroxide repeating said digesting step, to be measured; if the secondary is not digested completely, the digestion liquid after clarifying solution is obtained by filtering the sample to be tested, specifically, the microwave digestion solution in the tank by 0.45 microns of filtering film is transferred to a volumetric flask, proper distilled water for many times washing microwave digestion tank and the washing liquid is transferred to the volumetric flask, and then diluted to 50 ml. with distilled water, shaking evenly, measuring, full automatic inductive coupling plasma atomic emitting spectrograph analyzing with Agilent Company of 720ES weight content of sodium metal element in the sample to be tested, select test value for three times and the average is the final result.

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

5. The method according to claim 1 for the polymer additive, wherein the sodium metal elements from a sodium-containing compound, a sodium-containing compound selected from the group consisting of D-lactate, L-sodium lactate, sodium acetate, sodium sulfite, sodium oxide, sodium amide, sodium nitrate, sodium sulphide, sodium sulphate, sodium phosphate, sodium oxalate, sodium tartrate dihydrate, sodium chlorite, sodium selenite, sodium metasilicate, sodium pyrosulfite, sodium silicate, sodium diacetate, sodium acrylate, acetylene, sodium ethoxide, sodium citrate, sodium oleate, sodium salicylate, sodium methoxide, sodium benzene, sodium phenol, 1-butane sodium sulfonate, 1-sodium propane thiol, 1-dodecane sodium sulfonic acid, 1-nonane sodium sulfonate, 1- heptane sulfonic acid sodium, 1-decane sodium sulfonate, 2-sodium propane thiol, 2- naphthalene succinic acid, sodium succinate, sodium pyruvate, sodium propionate, sodium xylene sulfonate, sodium dodecyl sulfate, sodium tert-butoxide in the one kind of or several.