AU2018100153A4 - An additive for polymer and preparation method thereof - Google Patents
An additive for polymer and preparation method thereof Download PDFInfo
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- AU2018100153A4 AU2018100153A4 AU2018100153A AU2018100153A AU2018100153A4 AU 2018100153 A4 AU2018100153 A4 AU 2018100153A4 AU 2018100153 A AU2018100153 A AU 2018100153A AU 2018100153 A AU2018100153 A AU 2018100153A AU 2018100153 A4 AU2018100153 A4 AU 2018100153A4
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Abstract
The invention claims an additive for polymer, wherein comprising: A, phosphinate, containing two substituted groups having the following formula (I), -"'wherein RI and R2 are the same or different and represents H, C1-C6 alkyl or C6-Ci8 aryl, M is Al, m is 3, B: calcium metal element, wherein the metal weight content of calcium element in the total additive is 10-600 ppm. The invention comprises a specific range content metal calcium element additive is featured with simple preparation technique, low production cost, it is applied in polymer, which can greatly improve the anti-fatigue intensity of polymer composition product, but also can ensure the polymer composition has high flame retardant property.
Description
An additive for polymer and preparation method thereof
Technology field
The invention claims an additive for polymer, specifically claims a dialkyl phosphinate salt calcium containing micro metal element and 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.
Dialkyl 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 calcium element, not only can the polymer composition with high flame resistance, also can greatly improve the anti-fatigue intensity of polymer composition product.
Invention contents
The purpose of the invention is to provide an additive for polymers, the additive through adding trace metal in the dialkyl phosphinate calcium element can make the resulting polymer composition has the excellent inflaming retarding performance, it can make the polymer composition article has excellent fatigue resistance.
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 phosphinate, having the following structural formula (I),
(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: metal calcium element, weight content of the 10-600 ppm in the total additive wherein the metal calcium element, the preferable weight content is weight content is 50-500 ppm, more preferably 100-400 ppm, further preferably the weight content is 150-300 ppm. Testing method of the weight content of metal calcium element: taking 0.05 + 0.005g additive for polymer sample, accurate to 0.001 g, putting into microwave digestion tank, then adding 10 ml. ketopantoate to microwave digestion tank, to make it completely immersed sample, slowly dropping 1-2 ml. hydrogen peroxide, reacting the sample with digesting acid 1-2 min, cover upper cover sealing digestion tank in the 220 °C blast oven to digestion, the digestion time is 2h, after digestion. Taking out the digestion tank, cooling to the room temperature, tested, 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 tank and the washing liquid is transferred to a volumetric flask, then diluted to 50 ml. with distilled water, shaking up, tested, using Agilent Company is 720ES of full automatic inductive coupling plasma atomic emitting spectrograph analyzing weight calcium content of metal element in the sample to be detected, taking testing value for three times and the average is the final result.
The metal calcium element from the calcium-containing compound, the calcium-containing compound is selected from calcium oxide, calcium carbonate, calcium sulphate crystal whisker, calcium stearate or montanic acid calcium in the one kind of or several, source of this invention indicated by calcium metal element used is not limited to the example, no matter which kinds of calcium-containing compound, it is possible to use atoms emitting spectrum detected, the weight content of the calcium metal element is calcium metal element but not containing calcium compound adding metal calcium element as standard, the weight content of the calcium 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 nylon 6.
The invention through taking the dialkyl phosphate and the calcium-containing compound in the highspeed mixer to mix uniformly to obtain the additive for polymer; wherein the calcium-containing compound is selected from calcium oxide, calcium carbonate, calcium sulphate crystal whisker, calcium stearate or montanic acid calcium 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 nylon 6.
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 said auxiliary agent can be an additional component does not interfere with the desired properties but the 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 metal calcium element containing specific range content 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 anti-fatigue intensity of polymer composition product. 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 metal calcium element content: not detected; PA6: PA6M2000 (Guangdong Xinhui MITA chinlon Stock Co., Ltd.)
Glass fibre: ECS301-HP (Chongqing International Complex Material Co., Ltd.); Antioxidant: 1010, (Jinhai Yabao);
The embodiment of the invention and Comparative Example containing compound are commercially available.
The weight content of the calcium 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, reacting the sample with digesting acid 1-2 min, cover upper cover sealing 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 metal calcium element in the sample to be detected, taking three testing value of the average as a final result.
The polymer composition of the invention product fatigue strength testing method: taking device CIMTronic Ls-Dyna Mess Company 2000, according to DIN53442 and IS0178, calibration reference is about 50Mpa lower to broken number of bouts by starting the bending stress.
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 30s. V-1: duration of total combustion time after leaving the flame, continuous combustion time is no more than 30s, 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.
Not capable of classifying (ncl): Not meet the combustion level V-2.
Comparative Example 1-2 (D1-D2) and Example 1-11 (B1-B11)
According to the table 1, weighing the component A prepared above and the calcium-containing compound in the high speed mixer to mix uniformly to obtain the invention additive for polymer. wherein the invention additive for polymer metal calcium element content is to be adjusted and measured through actual adding quantity of the calcium compound in the preparation process.
Table 1 Comparative Example 1-2 (D1-D2) and Example 1-11 (B1-B11) for polymer additive
Comparative Example 3-5 ( CE3-5 ) , Example 12-22 ( B12-B22 )
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 doublescrew extruder, melting and extruding through a double-screw extruder in the water bath cooling, granulating to obtain the polymer composition, then measuring the UL-94 flame-retardant grade of the polymer composition, and the polymer composition product of fatigue strength, specific test data listed in Table 2.
Comparative Example 3-5 Table 2, embodiments of form 12-22 in specific proportions (parts by weight) and its test result
Claims (5)
1. An additive for polymer, wherein comprising: A, dialkyl phosphonate, having the following structural formula (I),
(1) 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: calcium metal element, wherein the metal weight content of calcium element in the total additive is 10-600 ppm.
2. The method according to claim 1 for the polymer additive, wherein the weight content of the calcium metal element in the total additive is 50-500 ppm, preferable weight content is 100-400 ppm, more preferably the content is 150-300 ppm by weight.
3. The method according to claim 1 or 2, a kind of additive for polymer, wherein the testing method of the weight content of metal calcium element, taking 0.05 + 0.005g additive sample for the polymer, 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, reacting the sample with digesting acid 1-2 min, cover upper cover sealing 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 metal calcium element in the sample to be detected, taking three testing value of the average as a 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 calcium metal elements from a calcium-containing compound, the calcium-containing compound is selected from calcium oxide, calcium carbonate, calcium sulphate crystal whisker, calcium stearate or montanic acid calcium in the one kind of or several.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPCT/CN2017/087391 | 2017-06-07 | ||
| PCT/CN2017/087391 WO2018214178A1 (en) | 2017-05-23 | 2017-06-07 | Additive for polymer and preparation method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2018100153A4 true AU2018100153A4 (en) | 2018-03-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2018100153A Ceased AU2018100153A4 (en) | 2017-06-07 | 2018-02-05 | An additive for polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU2018100153A4 (en) |
-
2018
- 2018-02-05 AU AU2018100153A patent/AU2018100153A4/en not_active Ceased
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| FGI | Letters patent sealed or granted (innovation patent) | ||
| MK22 | Patent ceased section 143a(d), or expired - non payment of renewal fee or expiry |