CN100341941C - Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method - Google Patents
Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method Download PDFInfo
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Abstract
The present invention relates to a composite flame-retardant nanometer polyamide material of melamine cyanurate (MCA) and a preparation method thereof. The present invention is characterized in that melamine (MEL) and cyanuric acid (CA) are used as raw materials, polyamide is used as substrate resin, and water is used as a dispersion medium; under the action of a molecular compounding agent and a plasticizing agent of irreducible water, the in-situ synthesis MCA is prepared in an extrusion processing procedure, and the composite flame-retardant nanometer polyamide material is prepared. The introduction of the molecular compounding agent and the plasticizing agent of irreducible water suppress the violent evaporation of the water at a high temperature so as to solve the problem of water needed by the in-situ synthesis MCA in processing the polyamide at the high temperature. The in-situ synthesis MCA has a definite length-to-diameter ratio and is uniformly dispersed in the polyamide substrate resin on a nanometer scale.
Description
Technical field:
The present invention relates to a kind of trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and preparation method thereof, belong to the forming process field of flame-proofed polymer material.
Background technology:
Polymeric amide (nylon) is the engineering plastics of developing the earliest in the world, have excellent mechanical property, wear-resisting, oil resistant and common organic solvents, fine heat-resisting performance, be widely used in fields such as automobile, machinery instrument, electric, defence and military, aviations, especially be usually used in the comparison rigorous environment, as high humidity, high temperature, high-voltage etc.Yet the limiting oxygen index(LOI) of polymeric amide (LOI) low (about 23), very easily burning, thermal value is big, combustionvelocity is fast, can produce a large amount of dense smokes and molten drop, very easily propagating flame in the combustion processes, limited its application at some special dimensions greatly, the flame retardant resistance that therefore improves polymeric amide is extremely urgent.
Polymeric amide is fire-retardant to mainly contain following three kinds of methods: (1) adds flame-retardant additive in recombination process; (2) at grafting or the fire-retardant group of bonding on the polymer chain or on the surface; (3) carry out copolymerization with fire-retardant monomer.Owing to the operability of technology and the reason of production cost, the first method development is the rapidest, develop the multiple additive flame retardant that is suitable for polymeric amide, mainly contained halogenated flame retardant, inorganic combustion inhibitor, phosphorus flame retardant, nitrogen flame retardant and nitrogen phosphorus flame retardant etc.Halogenated flame retardant flame retarding efficiency height, consumption are few, performance impact to material is little, but the price of halogenated flame retardant significantly promotes in the recent period, and face the dioxin problem, generate a large amount of flue dust and corrodibility toxic gas when pyrolysis and the burning with the fire-retardant superpolymer of halogenated flame retardant (halogen-antimony system), its application is restricted greatly, and European Union has put into effect rules and forbids the application of halogenated flame retardant at some special dimensions in recent years.The non-halogen inexorable trend that has become the fire-retardant development of polymeric amide of fire retardant is developed the research focus that polymeric amide halogen-free flame retardants has efficiently become flame retardant area.Inorganic combustion inhibitor in the halogen-free flame-retardant system, phosphorus flame retardant etc. also all face variety of issue: the inorganic combustion inhibitor addition is big, and flame retarding efficiency is low, and the mechanical property of body material has been caused bigger infringement; Phosphorus flame retardant exists band look, poisonous, exudative high shortcoming.The nitrogen flame retardant is widely used in the fire-retardant of polymeric amide owing to nontoxic, no burn into flame retarding efficiency is high, melamine cyanurate (MCA) is typical case's representative of this based flame retardant.
Melamine cyanurate (MCA) powder white, nontoxic, tasteless, soapy feeling is arranged, proportion 1.5 is insoluble in water and most of organic solvent.As fire retardant, MCA not only has good flame retardant property, and the amount of being fuming is little, and work in-process also can play lubrication, is widely used in polymeric amide, Resins, epoxy, resol and the polyolefine material.Fire-retardant to polymeric amide, common 10～15% additions can reach UL94 V0 level.And good, non-blooming with resin compatible, the thermostability height, the adhesion mould, little to the material property negative impact, be polymeric amide ideal fire retardant.
Traditional MCA is synthetic to be to be raw material with cyanuric acid (CA) and trimeric cyanamide (MEL), and hot water is done dispersion medium, realizes that as catalyzer the molecule of the two is compounded to form MCA (fine-chemical intermediate, 2001,31 (4): 27-28 at an alkali metal salt or its oxyhydroxide; The Hebei Academy of Sciences journal, 2000,17 (4): 219-223).There are the following problems in this reaction: reactant MEL, CA solubleness in water is little, bad dispersibility, and also the MCA that is generated has big plane hydrogen bond network structure, and hydrodynamic radius is big, therefore causes the system viscosity height, stirs difficulty, long reaction time.For reducing system viscosity, the ratio of water and raw material is usually up to more than 4/1 in the reaction, and reactor production efficiency is low, energy consumption is high, waste water is many, and the color and luster of product is dark.Thereby the alkali metal compound catalyzer of introducing in the reaction system easily residual product flame retardant properties that causes seriously descends, thereby must wash refiningly to head product, makes production cost rise complex process.In order to improve the synthesis technique of MCA, the molecule composite modification technology is introduced into the preparation process (Chinese invention patent ZL03135668.0) of MCA.This technology makes it participate in the reaction process of MEL-CA by introduce a kind of special properties-correcting agent in the reaction system of MEL and CA.This technology has been simplified the production technique of MCA greatly, and has significantly improved The comprehensive performance.But the dust problem of powder shaped fire retardant MCA work in-process, the homodisperse problem of MCA in matrix resin, and the MCA fire-retardant Nylon 6 have a flame drippage problem etc., also needs to improve, thereby need the new technology of the advanced fire-retardant nylon matrix material of development.United States Patent (USP) (US Patent 5,037,869) reported a kind of method for preparing the Flameproof polyamide resin material, this method is extruded nylon, trimeric cyanamide or derivatives thereof and cyanuric acid, ethylene glycol or its condensation polymer and phthalic ester melt blending in the presence of water, improve the flame retardant properties and the mechanical property of fire retardant material, but do not realized the nanometer of resultant MCA particle size and the nano-dispersed in matrix resin thereof.
Summary of the invention:
The objective of the invention is provides a kind of melamine cyanurate (MCA) fire retarding polyamide nano-composite and preparation method thereof at the deficiencies in the prior art.Its characteristics are that with trimeric cyanamide (MEL) and cyanuric acid (CA) be raw material, polymeric amide is a matrix resin, is dispersion medium with water, introduces the molecule recombiner simultaneously in system, in extrusion process, realize the preparation of the synthetic and fire retarding polyamide nano-composite of the original position of MCA.This method is unified in the preparation of the synthetic and fire retarding polyamide nano-composite of MCA in the process and finishes, simplified the preparation technology of matrix material greatly, generated in-situ MCA has certain length-to-diameter ratio, and is dispersed in the polyamide substrate resin with nanoscale.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial contains by weight:
Polymeric amide: 30～700 parts
Trimeric cyanamide: 0.1～150 part
Cyanuric acid: 0.1～150 part
Molecule recombiner: 0.05～50 part
Tie up the water softening agent: 0.05～50 part
Oxidation inhibitor: 0.001～10 part
Thermo-stabilizer: 0～10 part
Water: 0.5～50 part
Wherein, polyamide resin is at least a in nylon 6, nylon 66, nylon 6/ nylon 66 multipolymers, nylon 46, NYLON610, nylon 612, the nylon 1010;
The molecule recombiner is contract at least a in tetramethylolmethane, sorbyl alcohol, glucose, sucrose, the starch of hexanolactam, glycerol, polyvinyl alcohol, tetramethylolmethane, dipentaerythrityl ether, three;
Tie up the water softening agent and be at least a in triphenylphosphate, Tritolyl Phosphate, triphenyl phosphite, dioctyl phthalate (DOP), two 11 esters of phthalic acid, Dinonylphthalate, phthalic acid two (13) ester, diheptyl phthalate, the dibutyl phthalate;
Oxidation inhibitor is selected phenols, amine, phosphorous acid esters, at least a in the oxidation inhibitor such as thioesters class, phenols is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (abbreviation antioxidant 1010), 2,2-methylene radical-two (4-ethyl-6-tert-butyl phenol), β (4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) at least a in the benzene, amine is 4,4 '-two (α, α-Er Jiajibianji) pentanoic, N, N '-two (1,4-dimethyl amyl group)-and at least a in the Ursol D, phosphorous acid esters are three (2, the 4-di-t-butyl) phosphorous acid esters (oxidation inhibitor 168), distearyl pentaerythritol diphosphite (oxidation inhibitor 618), tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) at least a in the ester (oxidation inhibitor 626), the thioesters class is Tyox B (DLTP), at least a in the distearyl acid thiodipropionate (DSTDP);
Thermo-stabilizer is at least a in venus crystals, copper stearate, cuprous iodide, the copper sulfate.
The preparation method of trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial contains following steps:
(1) water of tiing up water softening agent, 0.5～50 weight part of 0.05～50 weight part and the dry polymeric amide of 30～700 weight parts are added in the encloses container, stir, mix airtight then leaving standstill 5 minutes to 24 hours;
(2) trimeric cyanamide of 0.1～150 weight part, the cyanuric acid of 0.1～150 weight part, the molecule recombiner of 0.05～50 weight part, the oxidation inhibitor of 0.001～10 weight part and the thermo-stabilizer of 0～10 weight part are added in the above-mentioned encloses container, stir, mix:
(3) mixture with above-mentioned gained adds in the twin screw extruder, and in 225～270 ℃ of extruding pelletizations of temperature, the forcing machine rotating speed is 30～500 rev/mins, drying, and the pellet that obtains is injection molded into goods through injection moulding machine, and injection temperature is 230～270 ℃.
The present invention has the following advantages:
(1) environmental friendliness, less to the pollution of environment;
(2) preparation of the synthetic and fire retarding polyamide nano-composite of melamine cyanurate (MCA) is concentrated in the step finish, simplified the technological process of traditional preparation process MCA and corresponding flame-proof composite material greatly, have technology simple, easy to operate, efficient, energy-conservation, can realize mass-producing quantity-produced characteristics;
(3) generated in-situ MCA particle has certain length-to-diameter ratio (about 7.5) in matrix material, and is scattered in the polyamide substrate resin with nanoscale, and its radial dimension is 60～90 nanometers;
(4) Zhi Bei trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial flame retardant properties and good mechanical performance has broad application prospects.
Description of drawings
Fig. 1 is the SEM photo of fire-retardant Nylon 6 nano composite material sample brittle failure section
Wherein Fig. 1-a is for amplifying 10000 times photo, and Fig. 1-b is the photo of 5000 times of amplifications.The pattern photo shows that the generated in-situ MCA of reactive processing is the particle with certain length-to-diameter ratio, and its length-to-diameter ratio can reach 7.5, the radial dimension of particle is 60～300nm, most of at 80～90nm, and the MCA particle is uniformly dispersed in the nylon-6 matrix material, good with nylon 6 consistencies.
Embodiment:
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the foregoing invention content.
Embodiment 1:
Dinonylphthalate 0.05kg, water 0.5kg and nylon 6 30kg are placed an encloses container, stir, airtight leaving standstill 2 hours, add trimeric cyanamide 0.1kg, cyanuric acid 0.1kg, glycerol 0.05kg and four [β-(3 again, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.001kg, stir, mix, add in the twin screw extruder then, in 240 ℃ of extruding pelletizations of temperature, drying, the pellet that obtains is injection molded into the vertical combustion batten through injection moulding machine, and injection temperature is 240 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-2 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 50～70nm.
Embodiment 2:
Dioctyl phthalate (DOP) 3.6kg, water 11.0kg and nylon 66 200kg are placed an encloses container, stir, airtight leaving standstill 4 hours, add trimeric cyanamide 8.6kg, cyanuric acid 8.6kg, hexanolactam 1.8kg, tetramethylolmethane 3.6kg, three (2 again, the 4-di-t-butyl) phosphorous acid ester 0.18kg and copper stearate 0.10kg, stir, mix, add in the twin screw extruder then, in 260 ℃ of extruding pelletizations of temperature, drying obtains fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 260 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 60～80nm.
Embodiment 3:
Phthalic acid two 11 ester 50kg, water 50kg and nylon 66 700kg are placed an encloses container, stir airtight leaving standstill 6 hours, add trimeric cyanamide 150kg, cyanuric acid 150kg, dipentaerythrityl ether 50kg, three (2 again, the 4-di-t-butyl) phosphorous acid ester 10kg and venus crystals 10kg stir, and mix, add in the twin screw extruder then, in 260 ℃ of extruding pelletizations of temperature, drying obtains fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 260 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 60～300nm.
Embodiment 4:
Dioctyl phthalate (DOP) 5.4kg, water 16.5kg and nylon 6 300kg are placed an encloses container, stir, airtight leaving standstill 4 hours, add trimeric cyanamide 13.0kg, cyanuric acid 13.0kg, sorbyl alcohol 2.7kg, tetramethylolmethane 6.0kg, 4 again, 4 '-two (α, α-Er Jiajibianji) pentanoic 0.30kg and copper stearate 0.15kg, stir, mix, add then in the twin screw extruder, in 240 ℃ of extruding pelletizations of temperature, dry, obtain fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 240 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 80～90nm.
Embodiment 5:
With diheptyl phthalate 10kg, water 37.5kg and nylon 6/ nylon 66 multipolymer 500kg place an encloses container, stir, airtight leaving standstill 4 hours, add trimeric cyanamide 30kg again, cyanuric acid 30kg, polyvinyl alcohol 2.5kg, tetramethylolmethane 10kg, distearyl pentaerythritol diphosphite 0.3kg, Tyox B 0.2kg and CuI 0.3kg, stir, mix, add in the twin screw extruder then, in 260 ℃ of extruding pelletizations of temperature, dry, obtain fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 260 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 60～80nm.
Embodiment 6:
Phthalic acid two (13) ester 2kg, water 7.5kg and nylon 1010 copolymer 1 00kg are placed an encloses container, stir, airtight leaving standstill 4 hours, add trimeric cyanamide 6kg, cyanuric acid 6kg, sucrose 0.5kg, tetramethylolmethane 2kg, three (2 again, the 4-di-t-butyl) phosphorous acid ester 0.07kg, distearyl acid thiodipropionate 0.03kg and CuI0.06kg, stir, mix, add in the twin screw extruder then, in 230 ℃ of extruding pelletizations of temperature, drying obtains fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 230 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 70～90 nanometers.
Embodiment 7:
With triphenylphosphate 8.7kg, water 29.6kg and NYLON610 400kg place an encloses container, stir, airtight leaving standstill 4 hours, add trimeric cyanamide 27.8kg again, cyanuric acid 27.8kg, dipentaerythrityl ether 10.4kg, β (4-hydroxyl-3, the 5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester 0.30kg and N, N '-two (1,4-dimethyl amyl group)-and Ursol D 0.2kg, stir, mix, add in the twin screw extruder then, in 240 ℃ of extruding pelletizations of temperature, drying obtains fire-retardant pellet, be injection molded into the vertical combustion batten through injection moulding machine, injection temperature is 240 ℃.After testing, the vertical combustion performance of sample reaches UL94 V-0 level.Sem analysis shows that the radial dimension of MCA particle in the fire retardant material is 60～90nm.
Claims (2)
1. trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial is characterized in that the recipe ingredient of this matrix material is by weight:
Polymeric amide: 30～700 parts
Trimeric cyanamide: 0.1～150 part
Cyanuric acid: 0.1～150 part
Molecule recombiner: 0.05～50 part
Tie up the water softening agent: 0.05～50 part
Oxidation inhibitor: 0.001～10 part
Thermo-stabilizer: 0～10 part
Water: 0.5～50 part
Wherein, polyamide resin is at least a in nylon 6, nylon 66, nylon 6/ nylon 66 multipolymers, nylon 46, NYLON610, nylon 612, the nylon 1010; The molecule recombiner is contract at least a in tetramethylolmethane, sorbyl alcohol, glucose, sucrose, the starch of hexanolactam, glycerol, polyvinyl alcohol, tetramethylolmethane, dipentaerythrityl ether, three; Tie up the water softening agent and be at least a in triphenylphosphate, Tritolyl Phosphate, triphenyl phosphite, Dinonylphthalate, phthalic acid two (13) ester, diheptyl phthalate, the dibutyl phthalate.
2. according to the preparation method of the described trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial of claim 1, it is characterized in that this method contains following steps:
(1) water of tiing up water softening agent, 0.5～50 weight part of 0.05～50 weight part and the dry polymeric amide of 30～700 weight parts are added in the encloses container, stir, mix airtight then leaving standstill 5 minutes to 24 hours;
(2) trimeric cyanamide of 0.1～150 weight part, the cyanuric acid of 0.1～150 weight part, the molecule recombiner of 0.05～50 weight part, the oxidation inhibitor of 0.001～10 weight part and the thermo-stabilizer of 0～10 weight part are added in the above-mentioned encloses container, stir, mix;
(3) mixture with above-mentioned gained adds in the twin screw extruder, and in 225～270 ℃ of extruding pelletizations of temperature, the forcing machine rotating speed is 30～500 rev/mins, drying, and the pellet that obtains is injection molded into goods through injection moulding machine, and injection temperature is 230～270 ℃.
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| CN101302305B (en) * | 2008-07-07 | 2011-11-02 | 贵州省冶金设计研究院 | Use of diantimony trioxide as nylon main flame retardant, and product and preparation thereof |
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| CN103408750A (en) * | 2013-07-12 | 2013-11-27 | 东华大学 | Preparation method of melamine cyanurate flame-retardant polyamide material |
| CN103408751B (en) * | 2013-07-12 | 2016-01-06 | 东华大学 | A kind of preparation method of MCA fire-retardant polyamide material |
| CN104153035B (en) * | 2014-07-24 | 2016-08-31 | 江苏红豆实业股份有限公司 | Fire-retardant nice and cool recycled polyester filament fiber and production method thereof |
| CN104499076A (en) * | 2014-12-12 | 2015-04-08 | 广东新会美达锦纶股份有限公司 | Preparation method of flame-retarded polyamide 6 fiber |
| CN106349690A (en) * | 2016-10-09 | 2017-01-25 | 上海金发科技发展有限公司 | PA/AS-based resin compound and preparation method thereof |
| CN112538192B (en) * | 2020-12-07 | 2022-10-18 | 安徽融英新材料科技有限公司 | Modified nano MCA composite flame retardant, preparation method thereof and application thereof in preparation of halogen-free flame-retardant nylon composition for spinning |
| CN112831092B (en) * | 2021-02-03 | 2022-09-09 | 山东迈特新材料科技有限公司 | Preparation method of modified melamine cyanurate |
| CN115637042A (en) * | 2022-11-04 | 2023-01-24 | 杭州明日新材料科技有限公司 | Nitrogen-series flame-retardant nylon modified material with high glowing filament ignition temperature |
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Assignee: Shantou Northwest Aviation Articles Co., Ltd. Assignor: Sichuan University Contract record no.: 2012990000132 Denomination of invention: Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method Granted publication date: 20071010 License type: Exclusive License Open date: 20060614 Record date: 20120326 |