CN112280098A - Halogen-free flame retardant composition and two applications - Google Patents
Halogen-free flame retardant composition and two applications Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a halogen-free flame retardant composition which comprises the following components in parts by weight: 50-100 parts of anhydrous piperazine cyanurate; 0-50 parts of phosphorus-containing metal compound. The other purposes of the invention are to disclose the application of the halogen-free flame retardant composition in the high processing temperature flame-retardant thermoplastic resin and the application of the anhydrous piperazine cyanurate in the high processing temperature resin flame retardant. The halogen-free flame retardant composition is a flame retardant composition with a wide application range.
Description
Technical Field
The invention belongs to the technical field of flame retardant application, and particularly relates to a halogen-free flame retardant composition, application of anhydrous piperazine cyanurate in a high processing temperature resin flame retardant and application of the halogen-free flame retardant composition in a high processing temperature flame retardant thermoplastic resin.
Background
Fire use and control has been throughout the human civilization history, with concomitant development of flame retardant studies on materials. High molecular materials are closely related to human production life. The record of the flame retardance of natural polymer materials by adopting alum is recorded as early as 5 centuries before the yuan. With the recent modern times, along with the widespread use of synthetic polymer materials, the research on flame retardancy has also been rapidly developed.
Generally, there are two ways to implement flame retardancy of polymer materials: firstly, an additional flame retardant auxiliary agent is added, which is called physical blending flame retardant; and a flame-retardant unit is embedded in the polymer chain, which is called chemical modification flame-retardant. At present, most of flame-retardant polymer materials are realized by physical blending, because the physical blending flame retardance has the advantages of low cost and easy operation compared with chemical modification flame retardance. In the research of flame retardance of high polymer materials, the development and the use of flame retardants are important points.
As early as 1821, the basic elements of flame-retardant chemistry, mainly elements of main groups III, V and VII of the periodic Table of the elements, were identified by the French person Gay-Lussac. The flame retardant may be classified into a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a silicon flame retardant, a boron flame retardant, a sulfur flame retardant, a metal compound flame retardant, and the like, depending on the elements that play a major role. In addition to the halogen-based flame retardant, other flame retardants are also referred to as halogen-free flame retardants.
The halogen flame retardant has the advantages of high flame retardant efficiency and wide raw material sources. The disadvantage is that a large amount of corrosive toxic gases such as hydrogen halide, dioxin and the like are released in the combustion process, and secondary fire damage is caused.
The largest usage amount of aluminum hydroxide in the halogen-free flame retardant has the advantages of low cost, harmless combustion products and low flame retardant efficiency, and the large amount of aluminum hydroxide causes severe reduction of the mechanical properties of the material, has poor compatibility with a plurality of resins and has a narrow application range. Except for phosphorus flame retardants and nitrogen flame retardants, other halogen-free flame retardants are required to be used together with other flame retardants in a synergistic manner, and the application range is also limited.
Phosphorus and nitrogen can form a synergistic flame retardant effect, which is beneficial to forming a carbon layer with better quality. Wherein the phosphorus element mainly plays a role in promoting dehydration and carbon formation, and the nitrogen element plays a role in generating a flame-retardant gas and promoting the formation of a heat-insulating foam carbon layer. At present, more phosphorus and nitrogen flame retardants are compounded and used in intumescent flame retardants.
There are many reports in the literature of nitrogen-containing and phosphorus-containing compounds for use in intumescent flame retardants. Among them, ammonium polyphosphate (APP) flame retardants are being studied more. In addition to APP, flame retardants containing nitrogen and phosphorus compounds such as melamine polyphosphate (MPP) and piperazine phosphate have been reported. It is well known that MPP is limited in its range of use due to its relatively high price. Many other phosphorus-nitrogen compounds are limited by their heat resistance and cost performance, and cannot be applied in a wide range.
Patent document No. 91112732.1 discloses a polymer composition containing piperazine cyanurate, which is compounded with APP for use in PP resins, and UL94 flame retardant rating is V-0. However, the TGA data for the piperazine cyanurate salt prepared in this patent shows a significant weight loss (4.90 wt%) at 140 to 150℃, indicating that it cannot be used in polymers with higher processing temperatures. Further, the application of piperazine cyanurate to other thermoplastic resins such as ABS, PA, PBT, etc. is not described further, and the compositions formulated with ammonium polyphosphate or phosphate esters described in the patent documents can only be used for olefin-based polymer resins with lower processing temperatures.
Disclosure of Invention
The invention aims to provide a halogen-free flame retardant composition with wide application range.
The invention is realized according to the following scheme.
The halogen-free flame retardant composition comprises the following components in parts by weight:
50-100 parts of anhydrous piperazine cyanurate;
0-50 parts of phosphorus-containing metal compound.
The 1wt% thermal weight loss temperature of the halogen-free flame retardant composition after TGA test is 230-350 ℃ (the test parameter is nitrogen atmosphere, the heating rate is 20 ℃ per minute, and the test temperature range is 30-750 ℃).
The phosphorus-containing metal compound is selected from phosphorus-containing calcium salt, phosphorus-containing magnesium salt, phosphorus-containing aluminum salt, phosphorus-containing sodium salt and phosphorus-containing potassium salt; preferably aluminum hypophosphite or aluminum dialkylphosphinate;
the selected phosphorus-containing metal compound has good thermal stability.
And may also include other halogen-free fire retardant in 1-50 weight portions, such as phosphate, red phosphorus coating, etc.
The anhydrous piperazine cyanurate is prepared by a reflux reaction of piperazine and cyanuric acid mixed in a liquid solvent.
In general recognition, the reaction is a salt-forming reaction of an organic acid (cyanuric acid) and an organic base (piperazine), and is mainly controlled by thermodynamics. However, in the course of the present study, the thermal stability of anhydrous piperazine cyanurate varies nonlinearly with the length of the reaction time, so it is possible and necessary to control the thermal stability of the product by controlling the length of the reaction time.
The remarkable improvement of the thermal stability enables the anhydrous piperazine cyanurate to be used not only in low processing temperature resins such as polyolefin, but also in the development of flame retardant materials of engineering plastics with higher processing temperature such as polyamide and polybutylene terephthalate. When the anhydrous piperazine cyanurate and the phosphorus-containing metal compound are mixed for flame retardance, the phosphorus-containing metal compound mainly provides an acid source to promote char formation, the anhydrous piperazine cyanurate mainly provides a gas source to cause a porous structure of a char layer, and meanwhile, P-N synergistic effect can be formed between element phosphorus and nitrogen, so that the flame retardance effect is better achieved.
Another object of the present invention is to provide an application of anhydrous piperazine cyanurate in high processing temperature thermoplastic resin flame retardant, and the processing temperature is 220-300 deg.C.
The halogen-free flame retardant composition is applied to the flame-retardant thermoplastic resin with high processing temperature, and comprises 100 parts by weight of thermoplastic resin and 10-60 parts by weight of halogen-free flame retardant composition.
The halogen-free flame retardant composition cannot realize a flame retardant effect when the dosage is too low, and seriously influences the mechanical property, the processing property and other characteristics of the polymer composition when the dosage is too high.
The thermoplastic resin is selected from one or more of ester-based polymer and amide-based polymer.
Polybutylene terephthalate, polycaprolactam are preferred.
The flame-retardant synergistic effect exists between the element phosphorus and the element nitrogen, and the carbonyl reaction activity and the phosphorylation rate of the oxygen-containing high polymer can be improved by the in-situ generated P-N bond, so that the carbon forming rate is further improved. The improvement of the carbon rate has a beneficial effect on flame retardance. Therefore, the selection of oxygen-containing thermoplastic resins (e.g., polyamides, thermoplastic polyesters, etc.) is more beneficial to the flame retardant effect of the halogen-free flame retardant composition than the selection of oxygen-free or low oxygen-containing resin (e.g., olefin polymers, etc.) systems.
Although the halogen-free flame retardant composition provided by the invention can be used for the resin with the processing temperature of 220-300 ℃, the resin with the lower processing temperature can enable the proportion of the components of the compound in the halogen-free flame retardant composition to have a wider selection window, and has positive effects on cost control and control of other properties. Meanwhile, compared with other oxygen-containing resin systems, in the polybutylene terephthalate and polycaprolactam system with lower processing temperature, the halogen-free flame retardant composition provided by the invention has the advantage that the flame retardant performance is obviously improved. Thus polybutylene terephthalate and polycaprolactam are preferred.
The invention finds that the flame retardant formulas of the polybutylene terephthalate and the polycaprolactam have respective optimal ranges, when the optimal ranges are within the optimal ranges, the flame retardant property can reach V-0 level, the combustion time is short during the flame retardant test, and the flame retardant property can be reflected to be better.
Preferably, when the thermoplastic resin is polybutylene terephthalate, the weight portion of the polybutylene terephthalate is 100, and the halogen-free flame retardant composition is 18-50; in the halogen-free flame retardant composition, based on the total weight of the halogen-free flame retardant composition, 50-60 parts of anhydrous piperazine cyanurate and 40-50 parts of phosphorus-containing metal compound are used.
Preferably, when the thermoplastic resin is polycaprolactam, 100 parts of polycaprolactam and 15-60 parts of the halogen-free flame retardant composition are calculated according to the parts by weight; the halogen-free flame retardant composition comprises the following components in parts by weight: 50-100 parts of anhydrous piperazine cyanurate; 0-50 parts of phosphorus-containing metal compound.
Preferably, when the thermoplastic resin is polycaprolactam, 100 parts of polycaprolactam and 36-60 parts of the halogen-free flame retardant composition are calculated according to the parts by weight; the halogen-free flame retardant composition comprises the following components in parts by weight: 50-60 parts of anhydrous piperazine cyanurate; 40-50 parts of phosphorus-containing metal compound.
As regards the use of the halogen-free flame retardant composition in polycaprolactam, it may be the addition of pure anhydrous piperazine cyanurate. However, it was found that the addition of only pure anhydrous piperazine cyanurate caused dripping while the polycaprolactam resin was being flame retarded. If the addition amount is insufficient, the phenomenon that the cotton pad is ignited by the dropping matters can even occur. Tests show that in order to prevent the dripping phenomenon, a certain amount of phosphorus-containing metal compound needs to be added at the same time and is compounded with anhydrous piperazine cyanurate for use. The anti-dripping test effect is consistent with the aim trend of flame retardance and no dripping in the industry at present.
The ester-based polymer refers to a polyester product of a dicarboxylic acid and a dihydroxy compound, or a homopolymer or copolymer having both monohydroxymonocarboxylic acid compounds.
Dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Exemplary aromatic dicarboxylic acids that can be used herein include, but are not limited to, 2, 6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, mixtures thereof or derivatives thereof, and the like. Exemplary aliphatic dicarboxylic acids that may be used herein include, but are not limited to, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and cyclohexyldiacid, and the like, and derivatives thereof.
Dihydroxy compounds include, but are not limited to, aromatic dihydroxy compounds and aliphatic dihydroxy compounds. Aliphatic dihydroxy compounds are generally preferred. Exemplary aliphatic dihydroxy compounds that can be used herein include, but are not limited to, 1, 2-ethanediol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, allyl glycol, and the like, and derivatives thereof. Exemplary compounds that can be used herein that also have monohydroxymonocarboxylic acids include, but are not limited to, p-hydroxybenzoic acid and the like and derivatives thereof.
The amide-based polymer is: (a) condensation products of one or more dicarboxylic acids with one or more diamines, or (b) condensation products of one or more aminocarboxylic acids, or (c) ring-opening polymerization products of one or more cyclic lactams. Polycaprolactam is preferred because polycaprolactam is the most productive species of polyamide and is widely used.
The diamine may be selected from aliphatic diamines, alicyclic diamines, and aromatic diamines. Exemplary diamines that can be used herein include, but are not limited to: 1, 6-hexamethylenediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, undecanediamine, 1, 12-dodecanediamine, 2-methylpentanediamine, 2, 4-trimethylhexamethylenediamine, 2, 4, 4-trimethylhexamethylenediamine, 5-methylnonanediamine, 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, bis (p-aminocyclohexyl) methane, N-phenylthiopropionic acid, N-, 2-methyloctanediamine, trimethylhexamethylenediamine, m-xylylenediamine, p-xylylenediamine, and derivatives thereof.
The dicarboxylic acid may be selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Exemplary dicarboxylic acids for use herein include, but are not limited to, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, terephthalic acid, isophthalic acid, phthalic acid, glutaric acid, pimelic acid, suberic acid, 1, 4-cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, and derivatives thereof.
The cyclic lactam may be selected from aliphatic cyclic lactams. Exemplary lactams for use herein include, but are not limited to, caprolactam, enantholactam, nonanolactam, undecanolactam, dodecanolactam, tridecanolactam, and derivatives thereof.
The thermoplastic resins have somewhat different effects depending on their density, softening temperature, ratio of insoluble components to a solvent, degree of stereoregularity, presence or absence of catalyst residues, kind or mixing ratio of olefin as a raw material, kind of polymerization catalyst (for example, lewis acid catalyst, metallocene catalyst, etc.), etc., but they are effective in any of the above cases.
In order to improve the mechanical property of the thermoplastic resin, the thermoplastic resin also comprises 0-30 parts by weight of glass fiber, wherein the glass fiber is selected from one or more of high-alkali fiber, medium-alkali fiber, low-alkali fiber and alkali-free fiber.
A certain amount of processing aid can be added according to the processing performance and the use scene of the product, and if the ultraviolet absorber and the hindered amine light stabilizer are not required to be added in the use scene, the processing aid is not required to be added. The paint also comprises 0.1-5 parts by weight of processing aids, wherein the processing aids comprise one or a mixture of several of antioxidants, ultraviolet absorbers, hindered amine light stabilizers and lubricants.
The antioxidant includes, but is not limited to, 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) -propionic acid amide ], trisnonylphenyl phosphite, tris [ 2-t-butyl-4- (3-t-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl ] phosphite, tridecyl phosphite, octyldiphenyl phosphite, bis (decyl) monophenyl phosphite, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, stearyl chloride, pentaerythritol esters (which may be one or more of tetrakis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]) pentaerythritol esters.
The ultraviolet absorbers include, but are not limited to, 2, 4-dihydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, phenyl salicylate, resorcinol monobenzoate, 2, 4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, 2, 4-di-t-amylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, 2-ethyl-2-ethoxy oxanilide, 2-ethoxy-4-dodecyl oxanilide, ethyl-alpha-cyano-beta, beta-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-di-tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-s-triazine.
The hindered amine light stabilizers include, but are not limited to, 2, 2, 6, 6-tetramethyl-4-piperidyl stearate, 1, 2, 2, 6, 6-pentamethyl-4-piperidyl stearate, 2, 2, 6, 6-tetramethyl-4-piperidyl benzoate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, one or a mixture of more of bis (1, 2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate and tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 2, 3, 4-butane tetracarboxylate.
The lubricant comprises but is not limited to ricinoleic acid amide, pentaerythritol glyceryl monooleate, boron nitride, glycerol monostearate, glycerol monooleate, molybdenum disulfide, 12-tricosanone, paraffin, microcrystalline paraffin, amide wax, oxidized polyethylene, stearyl alcohol, butyl stearate, glyceryl stearate, N' -methylene bis stearamide and one or a mixture of more of aluminum distearate.
The invention has the following beneficial effects: the halogen-free flame retardant composition used in the invention can be applied to various high processing temperature thermoplastic resins, and the halogen-free flame retardant composition is compounded with the high processing temperature thermoplastic resins, so that the high processing temperature resins can not be hydrolyzed in the processing process because the flame retardant composition can not be decomposed into water in the processing process, the application range of the halogen-free flame retardant composition is expanded, meanwhile, the heat resistance of the halogen-free flame retardant composition can not be influenced by adding the phosphorus-containing metal compound in the composition, the flame retardant effect can be better improved, and the application range of the halogen-free flame retardant composition is also expanded.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention. In view of the above disclosure, it will be apparent to those skilled in the art that certain non-essential modifications and adaptations of the present invention can be made without departing from the scope of the invention.
The raw materials of the invention are all from commercial products.
Piperazine, pura chemical technology ltd, changzhou, 99% anhydrous piperazine;
cyanuric acid, Shanghai Aladdin Biotechnology Ltd, cyanuric acid, 98%;
PA6 resin, Jiangsu Haiyang chemical fiber Co., Ltd., HY2500 i;
PA66 resin: huafeng group Ltd, PA66 EP-158;
PBT resin, southeast star synthetic materials ltd, 1090;
aluminum hypophosphite, Weifang Dakang chemical Limited, aluminum hypophosphite;
ammonium polyphosphate, institute of fine chemical engineering research and design, Sichuan province, ammonium polyphosphate APP-II;
aluminum diethylphosphinate, craine, OP 1230;
melamine polyphosphate: sichuan province, institute of research and design of Fine chemical engineering, HNP-12N;
red phosphorus master batch: southwest expert chemical industries ltd, REDNIC 20450N 3 (red phosphorus coating);
antioxidant: hubei Xin Rundji chemical Co., Ltd., antioxidant 1010 (pentaerythritol esters);
lubricant: jusheng science and technology Co., Ltd, aluminum distearate;
glass fiber: chongqingxin giant New Material Co., Ltd., ECS303W-3 (alkali-free fiber);
preparation of anhydrous piperazine cyanurate: in a 5L flask equipped with a stirrer, a reflux condenser and a thermo-well tube, 193.8 g of piperazine and 2500 mL of water were added at room temperature, and stirred until all was dissolved. 580.8 g of cyanuric acid were added with stirring. The reaction system is heated to a reflux state, but the violent boiling phenomenon is avoided, the temperature is maintained, and the stirring reaction is carried out for 7 hours. Cooling the reaction mixture, filtering to obtain anhydrous piperazine cyanurate as white powdery solid, and drying for later use.
The product TGA data indicated a 1% thermogravimetric loss temperature between 230 ℃ and 260 ℃. Product elemental analysis data (C% =34.7, N% =32.78, H% = 4.391) indicated that no water molecules were present in the product and piperazine and cyanuric acid were present in the molecular structure at a ratio of the amount of species of 1: 2. The infrared spectrum of the product is 2000-3600cm-1In the range, an absorption peak is present, but not the presence of a hydrohydroxy group, but a stretching vibration peak of a secondary amine bond.
The anhydrous piperazine cyanurate is compounded with a phosphorus-containing metal compound, preferably with aluminum hypophosphite or dialkyl aluminum phosphinate, and the TGA data of the compounded composition shows that the 1 percent of the thermogravimetric loss temperature is 230-350 ℃.
The preparation method of the halogen-free flame retardant composition comprises the following steps: weighing anhydrous piperazine cyanurate, a phosphorus-containing metal compound or ammonium polyphosphate according to the table 1, adding the weighed anhydrous piperazine cyanurate, the phosphorus-containing metal compound or ammonium polyphosphate into a high-speed mixer for mixing, then adding the mixture into a double-screw extruder, blending the mixture at the temperature of 170-250 ℃, extruding and granulating the mixture, and performing TGA test.
The preparation method of the flame-retardant resin comprises the following steps: weighing anhydrous piperazine cyanurate, flame-retardant thermoplastic resin, phosphorus-containing metal compound or ammonium polyphosphate, processing aid and glass fiber according to the following table 1, pouring the mixture into a high-speed mixer for mixing, adding the mixture and/or the glass fiber into a double-screw extruder, blending at the temperature of 170-250 ℃, and extruding and granulating to obtain the flame-retardant resin granules. And then, carrying out injection molding on the dried granules at the temperature of 180-260 ℃ to obtain a sample strip meeting the test standard, and carrying out combustion performance test.
And (4) testing standard:
combustion performance: UL94 test for plastic burning performance, or GB/T2408 and 2008 horizontal and vertical methods for measuring the burning performance of plastic. The used combustion sample bar is strip-shaped, and the size is as follows: the length is 125mm plus or minus 5mm, the width is 13.0mm plus or minus 0.5mm, and the thickness is 1.55mm plus or minus 0.05 mm. One set had 5 splines. Based on the behavior of the test specimens, the materials were classified into V-0, V-1 and V-2 classes (V stands for vertical combustion) according to the criteria shown in the following table.
Fourier transform infrared analysis method (IR): the powder sample is prepared by potassium bromide tabletting, and the polymer composition sample is prepared by hot tabletting. The scanning wave number range is 400-4000 cm-1。
Thermogravimetric analysis method (TGA): in nitrogen atmosphere, the heating rate is 20 ℃ per minute, and the test temperature range is 30-750 ℃. The test temperature range substantially covers the range of temperature intervals in which an actual fire occurs.
Examples and comparative examples
The examples and comparative examples were prepared by weighing the materials in the parts by weight shown in Table 1, and sample preparation and performance characterization were performed according to the above-described flame retardant thermoplastic resin preparation method.
Table 1: specific composition of flame retardant materials and test results (parts by weight) thereof in examples and comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Anhydrous piperazine cyanurate | 20 | 20 | 25 | 20 | 18 | 18 |
| Aluminum hypophosphite | ||||||
| Aluminium diethylphosphinate | 20 | 25 | 20 | 18 | 18 | |
| Polyphosphoric acid melamine salts | ||||||
| Ammonium polyphosphate | ||||||
| Red phosphorus master batch | 5 | |||||
| 1% weight loss TGA/. degree.C | 260 | 314 | 314 | 314 | 312 | 314 |
| PBT | ||||||
| PA6 | 100 | 100 | 100 | 100 | 100 | |
| PA66 | 100 | |||||
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Glass fiber | 30 | 30 | 30 | 30 | 30 | 30 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Total time of vertical combustion, s | 8 | 11 | 7 | 15 | 8 | 15 |
| Whether or not to drip | Is that | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
| Cotton pad for igniting dripping object | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
TABLE 1
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Anhydrous piperazine cyanurate | 12 | 18 | 24 | 30 | 18 |
| Aluminum hypophosphite | 8 | 12 | 16 | 20 | 12 |
| Aluminium diethylphosphinate | |||||
| Polyphosphoric acid melamine salts | |||||
| Ammonium polyphosphate | |||||
| Red phosphorus master batch | 5 | ||||
| 1% weight loss TGA/. degree.C | 295 | 295 | 295 | 295 | 293 |
| PBT | 100 | 100 | 100 | 100 | 100 |
| PA6 | |||||
| PA66 | |||||
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Glass fiber | 30 | 30 | 30 | 30 | 30 |
| Flame retardant rating | V-1 | V-0 | V-0 | V-0 | V-0 |
| Total time of vertical combustion, s | 76 | 16 | 7 | 6 | 8 |
| Whether or not to drip | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
| Cotton pad for igniting dripping object | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
Continuing with Table 1:
| comparative example 1 | Comparison ofExample 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Anhydrous piperazine cyanurate | 20 | 20 | 18 | |||
| Aluminum hypophosphite | 30 | |||||
| Aluminium diethylphosphinate | 40 | |||||
| Polyphosphoric acid melamine salts | 20 | 40 | ||||
| Ammonium polyphosphate | 20 | 12 | ||||
| Red phosphorus master batch | ||||||
| 1% weight loss TGA/. degree.C | 318 | 272 | 279 | 330 | 375 | 301 |
| PBT | 100 | 100 | ||||
| PA6 | 100 | 100 | ||||
| PA66 | 100 | 100 | ||||
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Glass fiber | 30 | 30 | 30 | 30 | 30 | 30 |
| Flame retardant rating | V-2 does not pass through | V-2 does not pass through | NA | V-2 | NA | NA |
| Total time of vertical combustion, s | Not to be extinguished | Not to be extinguished | NA | 13 | NA | NA |
| Whether or not to drip | Is that | Whether or not | NA | Is that | NA | NA |
| Cotton pad for igniting dripping object | Is that | Whether or not | NA | Is that | NA | NA |
Note: NA indicates that no specimen bar can be obtained by the method for producing a flame-retardant resin of the present invention.
From examples 1 and 2, the addition of the phosphorus-containing metal compound is effective in preventing the occurrence of the dripping phenomenon.
As can be seen from examples 2 and 4, the compound of the anhydrous piperazine cyanurate and the phosphorus-containing metal compound has better use effect in PA 6.
It can be seen from example 5/6/8/11 that the flame retardant property of the present invention is improved by the combination of anhydrous piperazine cyanurate and phosphorus-containing metal compound, but other halogen-free flame retardants can be added to further improve the flame retardant property.
As can be seen from examples 7-10, the flame retardant properties increased with increasing amounts of the halogen-free flame retardant composition.
As can be seen from comparative examples 1 and 2, the flame retardant effect of the anhydrous piperazine cyanurate compounded with melamine polyphosphate or ammonium polyphosphate is not good.
As can be seen from comparative example 3, the system cannot even prepare sample strips when the anhydrous piperazine cyanurate is compounded with ammonium polyphosphate.
From comparative example 5 it can be seen that at such high addition levels, no bars could be prepared after 40 parts of melamine polyphosphate in PA 66.
As can be seen from comparative example 6, with 30 parts of aluminum hypophosphite added to PBT, no bars could be made.
Claims (12)
1. The halogen-free flame retardant composition is characterized by comprising the following components in parts by weight:
50-100 parts of anhydrous piperazine cyanurate;
0-50 parts of phosphorus-containing metal compound.
2. The halogen-free flame retardant composition of claim 1, wherein the halogen-free flame retardant composition has a 1wt% thermogravimetric loss temperature of 230 ℃ to 350 ℃ after TGA test (test parameters are nitrogen atmosphere, temperature rise rate is 20 ℃ per minute, and test temperature range is 30 ℃ to 750 ℃).
3. The halogen-free flame retardant composition of claim 1, wherein the phosphorus-containing metal compound is selected from the group consisting of phosphorus-containing calcium salts, phosphorus-containing magnesium salts, phosphorus-containing aluminum salts, phosphorus-containing sodium salts, phosphorus-containing potassium salts; aluminum hypophosphite or dialkylaluminum phosphinate is preferred.
4. The halogen-free flame retardant composition of claim 1, further comprising 1-50 parts of other halogen-free flame retardant, such as phosphate, phosphate ester, red phosphorus coating, etc.
5. The application of anhydrous piperazine cyanurate in high-processing-temperature thermoplastic resin flame retardant, and the processing temperature is 220-300 deg.C.
6. Use of the halogen-free flame retardant composition according to any of claims 1-4 for flame retarding thermoplastic resins at high processing temperatures.
7. The use of the halogen-free flame retardant composition of claim 6 in the flame retarding of thermoplastic resins at high processing temperatures comprises the following components in parts by weight: 100 parts of thermoplastic resin and 10-60 parts of halogen-free flame retardant composition.
8. The use of the halogen-free flame retardant composition according to claim 7 for flame retarding a thermoplastic resin at a high processing temperature, wherein the thermoplastic resin is selected from one or more of ester-based polymers and amide-based polymers; polybutylene terephthalate, polycaprolactam are preferred.
9. The use of the halogen-free flame retardant composition of claim 8 in the flame retarding of thermoplastic resins at high processing temperatures, wherein when the thermoplastic resin is polybutylene terephthalate, the weight parts of polybutylene terephthalate are 100 parts, and the halogen-free flame retardant composition is 18-50 parts; in the halogen-free flame retardant composition, based on the total weight of the halogen-free flame retardant composition, 50-60 parts of anhydrous piperazine cyanurate and 40-50 parts of phosphorus-containing metal compound are used.
10. The use of the halogen-free flame retardant composition of claim 8 for flame retarding a thermoplastic resin at high processing temperatures, wherein when the thermoplastic resin is polycaprolactam, the halogen-free flame retardant composition comprises, by weight, 100 parts polycaprolactam and 15 to 60 parts halogen-free flame retardant; the halogen-free flame retardant composition comprises the following components in parts by weight: 50-100 parts of anhydrous piperazine cyanurate; 0-50 parts of phosphorus-containing metal compound.
11. The use of the halogen-free flame retardant composition of claim 10 for flame retarding a thermoplastic resin at high processing temperatures, wherein when the thermoplastic resin is polycaprolactam, the halogen-free flame retardant composition comprises, by weight, 100 parts polycaprolactam and 36-60 parts halogen-free flame retardant; the halogen-free flame retardant composition comprises the following components in parts by weight: 50-60 parts of anhydrous piperazine cyanurate; 40-50 parts of phosphorus-containing metal compound.
12. The use of the halogen-free flame retardant composition according to claim 7 for flame retarding thermoplastic resins at high processing temperature, further comprising 0-30 parts by weight of glass fibers, wherein the glass fibers are selected from one or more of high alkali fibers, medium alkali fibers, low alkali fibers and alkali-free fibers; the paint also comprises 0.1 to 5 weight parts of processing aid, wherein the processing aid is one or a mixture of several of antioxidant, ultraviolet absorbent, hindered amine light stabilizer and lubricant.
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| CN113831731A (en) * | 2021-10-22 | 2021-12-24 | 安徽众诚塑胶科技有限公司 | Flame-retardant nylon master batch and preparation method thereof |
| CN114644838A (en) * | 2022-01-11 | 2022-06-21 | 山东玥能新材料科技有限公司 | Method for preparing black phosphorus-piperazine compound composite material |
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