CN103408751A - Preparation method of MCA (Melamine Cyanurate) flame-retardant polyamide material - Google Patents
Preparation method of MCA (Melamine Cyanurate) flame-retardant polyamide material Download PDFInfo
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- CN103408751A CN103408751A CN2013102945025A CN201310294502A CN103408751A CN 103408751 A CN103408751 A CN 103408751A CN 2013102945025 A CN2013102945025 A CN 2013102945025A CN 201310294502 A CN201310294502 A CN 201310294502A CN 103408751 A CN103408751 A CN 103408751A
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Abstract
The invention relates to a preparation method of an MCA (Melamine Cyanurate) flame-retardant polyamide material. The preparation method is characterized by comprising the following steps of adding melamine salt of dicarboxylic acid and cyanuric acid salt of organic diamine into a polyamide monomer, dispersively mixing all the components by taking water as a medium and nano SiO2 and metal oxide as flame retardant synergists, then, carrying out in-situ polymerization to obtain flame-retardant polyamide, and finally, increasing the polymer molecular weight by using a solid-phase condensation polymerization method to obtain the polyamide material with favorable flame retardance and good mechanical property, wherein part of flame-retardant components can be connected to a polyamide chain, while the MCA formed in situ can be uniformly dispersed in a polyamide matrix, and the flame retardance of the polyamide material can be further improved because of the addition of the flame retardant synergists, namely the SiO2 and the metal oxide.
Description
Technical field
The present invention relates to a kind of preparation method of MCA Flameproof polyamide material, particularly relate to a kind of MCA of original position formation and contain synergistic flame retardant SiO
2Or the preparation method of the MCA Flameproof polyamide material of metal oxide.
Background technology
Polymeric amide (PA is commonly called as nylon) has the advantages such as wear resistance is good, rebound resilience is high, breaking tenacity is high, dyeability is good, proportion is little, both can be used as engineering plastics, also can be used as the important source material of synthon.In fields such as automobile, machinery instrument, electric, defence and military, aerospace, be widely used.But the limiting oxygen index(LOI) of polymeric amide (LOI) is between 21～22, and this has just limited its application in a lot of fields, therefore flame-retardant modified extremely urgent to polymeric amide.
Polymeric amide flame-retardant modified mainly contains following three kinds of approach: (1) blending fire retardant modification, namely in mechanically mixing, add fire retardant, and make it obtain flame retardant resistance; (2) copolymerization is flame-retardant modified, by molecular designing, is incorporated into flame retardant compositions on the polymeric amide molecular chain or in the polymerizing polyamide process, the flame retardance element original position is introduced, and makes material have flame-retarding characteristic; (3) after fabrics flame resistance, arrange, can be by grafting, roll cure, apply, the approach such as spraying makes fire retardant and fabric combine the acquisition flame retardant effect.After fabrics flame resistance, arrangement is simple, easy to operate with respect to first two method technique, processing is flexible, be applicable to the exploitation of fire-retardant product innovation, but flame-retardant after-finishing may cause the loss of fabric strength, and affect feel and the coloured light of fabric, also there is certain problem in its washing fastness in addition.The described fire retardant monomer reacted with monomer of polyamide of second method is in esse considerably less and price is high.What practical application was maximum is in this method of blending fire retardant.Wherein nitrogenated flame retardant melamine cyanurate (MCA) is widely used in the fire-retardant of polymeric amide because corrosion-free, nontoxic, flame retarding efficiency is higher, is the desirable fire retardant of polymeric amide.
United States Patent (USP) (US Patent5,037,869) reported a kind of method for preparing the Flameproof polyamide resin material, this method is extruded polymeric amide, trimeric cyanamide or derivatives thereof and cyanuric acid, ethylene glycol or its condensation polymer and phthalic acid fat melt blending under the existence of water, improve flame retardant properties and the mechanical property of material, but there is no the nanometer of realization response thing MCA particle size and the nano-dispersed in matrix resin thereof.Thereby the new technology and method of needs development Flameproof polyamide material.Chinese invention patent (ZL200510022046.4) is to take trimeric cyanamide and cyanuric acid to be raw material, and polymeric amide is matrix resin, and the water of take is dispersion medium, in extrusion process, realizes the preparation of the synthetic and fire retarding polyamide nano-composite of the original position of MCA.The method completes synthetic and preparation fire retarding polyamide nano-composite of MCA in a process, greatly simplified the preparation technology of matrix material, though the method has realized the nanometer of MCA particle size, but MCA nano-dispersed effect in matrix resin is undesirable, flame retarding efficiency improves little, do not add other synergistic flame retardant, as nanometer SiO
2, metal oxide; Polymeric amide does not form the dense char layer in combustion processes, the molten drop problem does not improve.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of MCA Flameproof polyamide material, particularly provide a kind of original position form MCA and contain synergistic flame retardant SiO
2Preparation method with the MCA Flameproof polyamide material of metal oxide.Characteristics of the present invention are to abandon the method for fire retardant and the direct blend of polymkeric substance in the past, by MCA, directly in the polymer monomer polymerization process, obtain, make fire retardant be evenly distributed in polymeric matrix, significantly improve its flame retarding efficiency, simplified again the preparation technology of matrix material.In addition, in this process, add nanometer SiO
2With metal oxide as synergistic flame retardant, nanometer SiO
2Not only improve to a certain extent the mechanical property of polymeric amide, also improved working temperature and the ignition temperature of polymeric amide, slowed down the heat release rate of material surface.Simultaneously due to SiO
2The particle fusing point is high, after burning, is deposited on material charcoal layer, has prevented that effectively inflammable gas from contacting with airborne oxygen.Metal oxide, as the synergistic flame retardant of MCA, has excellent cooperative flame retardant effect, and when polyamide article burnt, the charcoal layer that forms one deck densification at product surface can be effectively fire-retardant.
The preparation method of a kind of MCA Flameproof polyamide material of the present invention comprises:
Count by weight, the composition of raw materials component is:
Monomer of polyamide: 70.32～84.66 parts
The melamine salt of dicarboxylic acid: 5.44～10.88 parts
The cyanurate of organic diamine: 4.9～9.8 parts
SiO
2: 0.5～1 part
Metal oxide: 0.5～1 part
Water: 4～7 parts
By recipe ingredient, raw material is added to reactor, stir and heat up, mix; Rotating speed is 100～400r/min, is warming up to 235 ℃～250 ℃, and when pressure reached 0.5MPa～0.9MPa, reaction 6h～9h, then removed small molecules by release decompression vacuum pumping, obtains MCA Flameproof polyamide material.
As preferred technical scheme:
The preparation method of a kind of MCA Flameproof polyamide material as above, described monomer of polyamide is a kind of monomer arbitrarily in nylon 1010, nylon 612, NYLON610, nylon 66, nylon 46 or nylon 6.
The preparation method of a kind of MCA Flameproof polyamide material as above, the cyanurate mol ratio of the melamine salt of described dicarboxylic acid and described organic diamine is 1:1, equates to guarantee number of functional groups, does not affect follow-up polymerizable molecular amount.
The preparation method of a kind of MCA Flameproof polyamide material as above, described metal oxide is Fe
2O
3, Al
2O
3Or TiO
2, to fire-retardant certain synergistic effect of MCA.
The preparation method of a kind of MCA Flameproof polyamide material as above, after obtaining MCA Flameproof polyamide material, also improve the Flameproof polyamide molecular weight by solid phase polycondensation further.
The preparation method of a kind of MCA Flameproof polyamide material as above, described solid state polycondensation temperature are following 10～40 ℃ of fusing point, and the polycondensation time is 12～36h.
Beneficial effect:
(1) MCA fire retardant material environmental protection, the MCA in-situ polymerization has been simplified preparation technology, and cost is low.
(2) the MCA in-situ polymerization makes flame-retardant composition be uniformly distributed in polyamide substrate with nano-scale, and flame retarding efficiency improves, nanometer SiO
2With the synergistic fire retardation of metal oxide, when Flame Retardancy can significantly be improved, mechanical property also was improved to some extent.
(3) the Flame Retardancy energy and the good mechanical performance that prepare, have certain application prospect.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention be used to the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Mole hexanodioic acid and the trimeric cyanamide such as get, obtain the hexanodioic acid melamine salt in 80 ℃ of lower stirring reaction 4h centrifuging, drying.Mole hexanediamine and the cyanuric acid such as get and obtain cyanuric acid hexanediamine salt in 60 ℃ of lower stirring reaction 3h centrifuging, drying.By weight, in polymeric kettle, drop into 70.32 parts of hexanolactams, 10.88 parts of hexanodioic acid melamine salts, 9.8 portions of cyanuric acid hexanediamine salt, 1 part of SiO
2, 1 part of Fe
2O
3, the water of 7 parts, the intensification melting is stirred, at 235 ℃～253 ℃, during pressure 0.5MPa, reaction 6h.By row pressure, decompression vacuum pumping, remove small molecules, discharging pelletizing, extraction obtain MCA Flameproof polyamide 6 resins.By dried flame-proof PA 6 resin at 200 ℃ of solid phase polycondensation 36h to increase molecular weight, the vertical combustion performance of sample reaches the UL-94V-0 level.
Embodiment 2
Mole hexanodioic acid and the trimeric cyanamide such as get, at 90 ℃ of lower stirring reaction 2h, filter, drying obtains the hexanodioic acid melamine salt.Mole hexanediamine and the cyanuric acid such as get and obtain cyanuric acid hexanediamine salt in 70 ℃ of lower stirring reaction 2.5h centrifuging, drying.By weight, in polymeric kettle, drop into 5.44 parts of hexanodioic acid melamine salts, 4.9 portions of cyanuric acid hexanediamine salt, 0.5 part of SiO
2With 0.5 part of TiO
2, to get 84.66 parts of nylon salt solution and be placed in still, the intensification melting is stirred, and passes into N
2Excluding air, airtightly be warming up to 225 ℃, pressure reaches 1.80Mpa, after heat-insulation pressure keeping 1h, continues heating, slowly step-down simultaneously, temperature is 270 ℃, when pressure is normal pressure, again after heat-insulation pressure keeping 1h, is evacuated to-0.05MPa, after aftercondensated 1.5h, extrude, blank, drying, at 240 ℃ of lower solid phase polycondensation 12h, obtain fire-retardant Nylon 66 again, the vertical combustion performance of sample reaches the UL-94V-0 level.
Embodiment 3
Mole m-phthalic acid and the trimeric cyanamide such as get, at 90 ℃ of lower stirring reaction 2.5h, filter, drying obtains the m-phthalic acid melamine salt.Mole mphenylenediamine and the cyanuric acid such as get and obtain cyanuric acid mphenylenediamine salt in 60 ℃ of lower stirring reaction 3h centrifuging, drying.By weight, in polymeric kettle, drop into 76.05 parts of hexanolactams, 10.23 parts of m-phthalic acid melamine salts, 8.30 portions of cyanuric acid mphenylenediamine salt, 0.78 part of SiO
2, 0.64 part of Fe
2O
3With 4 parts of water, the intensification melting is stirred, when 250 ℃, pressure are 0.9MPa, and reaction 9h.By release, decompression vacuum pumping, remove small molecules, the discharging pelletizing obtains MCA Flameproof polyamide 6 resins.By dried flame-proof PA 6 resin at 200 ℃ of solid phase polycondensation 36h to increase molecular weight, the flame retardant properties of sample is good, mechanical property is better.
Embodiment 4
Mole m-phthalic acid and the trimeric cyanamide such as get, at 90 ℃ of lower stirring reaction 2.5h, filter, drying obtains the m-phthalic acid melamine salt.Mole mphenylenediamine and the cyanuric acid such as get and obtain cyanuric acid mphenylenediamine salt in 70 ℃ of lower stirring reaction 2.5h centrifuging, drying.By weight, in polymeric kettle, drop into 8.76 parts of m-phthalic acid melamine salts, 7.12 portions of cyanuric acid mphenylenediamine salt, 0.5 part of SiO
2With 0.5 part of Al
2O
3, to get 83.12 parts of nylon salt wiring solution-formings and be placed in still, the intensification melting stirs and passes into N
2Excluding air, airtightly be warming up to 225 ℃, pressure reaches 1.70Mpa, after heat-insulation pressure keeping 1h, continues heating, simultaneously slowly step-down, temperature is that 275 ℃, pressure are while being normal pressure, again after heat-insulation pressure keeping 1h, be evacuated to-0.06MPa, after aftercondensated 1.5h, extrude, blank, drying, then at 220 ℃ of solid phase polycondensation 12h, obtain the fire-retardant Nylon 66 section, the vertical combustion performance of sample reaches the UL-94V-0 level.
Embodiment 5
By weight, in polymeric kettle, drop into 8.76 parts of m-phthalic acid melamine salts, 7.12 portions of cyanuric acid mphenylenediamine salt, 1 part of SiO
2, 1 part of Fe
2O
3With 82.12 parts of Nylon-1010 Salts.Vacuumize 10min and remove air in still.Be filled with carbon dioxide gas pressure and reach 50kpa, be heated to 180 ℃ of salt fusings.When temperature rises to 220 ℃, pressure, rise to 120kpa, start the venting dehydration after maintaining 1h.Along with dehydration reaction trend terminal, pressure also returns to normal pressure.While to reaction, finishing, temperature in the kettle can be heated to 240 ℃.In order to make as far as possible, dewatered, 240 ℃ of normal pressure emptying, until do not have tail gas to discharge.Discharging after reaction 6h.190 ℃ of solid phase polycondensation 18h after extracting drying, prepare FR Polyamide 1010 again, and the vertical combustion of sample is functional.
Claims (6)
1. the preparation method of a MCA Flameproof polyamide material is characterized in that:
Count by weight, the composition of raw materials component is:
Monomer of polyamide: 70.32～84.66 parts;
The melamine salt of dicarboxylic acid: 5.44～10.88 parts;
The cyanurate of organic diamine: 4.9～9.8 parts;
SiO
2: 0.5～1 part;
Metal oxide: 0.5～1 part;
Water: 4～7 parts;
By recipe ingredient, raw material is added to reactor, stir and heat up, mix; Rotating speed is 100～400r/min, is warming up to 235 ℃～250 ℃, and when pressure reached 0.5MPa～0.9MPa, reaction 6h～9h, then removed small-molecule substance by release decompression vacuum pumping, obtains MCA Flameproof polyamide material.
2. the preparation method of a kind of MCA Flameproof polyamide material according to claim 1, is characterized in that, described monomer of polyamide is a kind of monomer arbitrarily in nylon 1010, nylon 612, NYLON610, nylon 66, nylon 46 or nylon 6.
3. the preparation method of a kind of MCA Flameproof polyamide material according to claim 1, is characterized in that, the cyanurate mol ratio of the melamine salt of described dicarboxylic acid and described organic diamine is 1:1.
4. the preparation method of a kind of Flameproof polyamide material according to claim 1, is characterized in that, described metal oxide is Fe
2O
3, Al
2O
3Or TiO
2.
5. the preparation method of a kind of MCA Flameproof polyamide material according to claim 1, is characterized in that, after obtaining MCA Flameproof polyamide material, also by solid phase polycondensation, improves the Flameproof polyamide molecular weight further.
6. the preparation method of a kind of MCA Flameproof polyamide material according to claim 5, is characterized in that, described solid state polycondensation temperature is following 10～40 ℃ of polymeric amide fusing point, and the polycondensation time is 12～36h.
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| CN201310294502.5A CN103408751B (en) | 2013-07-12 | 2013-07-12 | A kind of preparation method of MCA fire-retardant polyamide material |
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| CN103408751B CN103408751B (en) | 2016-01-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294392A (en) * | 2014-10-15 | 2015-01-21 | 东华大学 | MCA flame-resistant polyamide 6 fibers and preparation method thereof |
| CN105273182A (en) * | 2015-07-20 | 2016-01-27 | 杭州师范大学 | Preparation method of flame-retarding nylon 6 and uses thereof |
| CN116253990A (en) * | 2023-02-08 | 2023-06-13 | 苏州海聚高分子材料有限公司 | Halogen-free flame-retardant nylon composite material and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| EP0461097A1 (en) * | 1990-06-08 | 1991-12-11 | Monsanto Company | An improved process for preparing flame retardant polyamide molding resins containing melamine cyanurate |
| CN1786073A (en) * | 2005-11-10 | 2006-06-14 | 四川大学 | Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method |
| CN1860168A (en) * | 2003-10-03 | 2006-11-08 | E.I.内穆尔杜邦公司 | Flame resistant aromatic polyamide resin composition and articles therefrom |
| CN101450993A (en) * | 2007-12-05 | 2009-06-10 | 中国石油化工股份有限公司 | Method for preparing halogen free flame-retarded nylon 6 |
-
2013
- 2013-07-12 CN CN201310294502.5A patent/CN103408751B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0461097A1 (en) * | 1990-06-08 | 1991-12-11 | Monsanto Company | An improved process for preparing flame retardant polyamide molding resins containing melamine cyanurate |
| CN1860168A (en) * | 2003-10-03 | 2006-11-08 | E.I.内穆尔杜邦公司 | Flame resistant aromatic polyamide resin composition and articles therefrom |
| CN1786073A (en) * | 2005-11-10 | 2006-06-14 | 四川大学 | Trimeric cyanamide cyanureate fire retarding polyamide nano-composite meterial and its preparation method |
| CN101450993A (en) * | 2007-12-05 | 2009-06-10 | 中国石油化工股份有限公司 | Method for preparing halogen free flame-retarded nylon 6 |
Non-Patent Citations (1)
| Title |
|---|
| ZHI-YONG WU等: "Preparation and characterization of flame-retardant melamine cyanurate/polyamide 6 nanocomposites by in situ polymerization", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294392A (en) * | 2014-10-15 | 2015-01-21 | 东华大学 | MCA flame-resistant polyamide 6 fibers and preparation method thereof |
| CN105273182A (en) * | 2015-07-20 | 2016-01-27 | 杭州师范大学 | Preparation method of flame-retarding nylon 6 and uses thereof |
| CN116253990A (en) * | 2023-02-08 | 2023-06-13 | 苏州海聚高分子材料有限公司 | Halogen-free flame-retardant nylon composite material and preparation method thereof |
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