CN103408751B - A kind of preparation method of MCA fire-retardant polyamide material - Google Patents
A kind of preparation method of MCA fire-retardant polyamide material Download PDFInfo
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- CN103408751B CN103408751B CN201310294502.5A CN201310294502A CN103408751B CN 103408751 B CN103408751 B CN 103408751B CN 201310294502 A CN201310294502 A CN 201310294502A CN 103408751 B CN103408751 B CN 103408751B
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Abstract
The present invention relates to a kind of preparation method of MCA fire-retardant polyamide material, be characterized in monomer of polyamide, add the melamine salt of dicarboxylic acid, the cyanurate of organic diamine, and be medium with water, Nano-meter SiO_2
2be synergistic flame retardant with metal oxide, carry out dispersing and mixing, in-situ polymerization obtains Flameproof polyamide, and part flame-retardant composition can be made like this to receive on polyamide chains, and the MCA that original position is formed can be dispersed in polyamide substrate, synergistic flame retardant SiO
2flame retardant resistance can be made to improve further with adding of metal oxide, increase polymericular weight finally by process for solid state polycondensation, the polyamide material of obtained excellent flame retardancy, good mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of MCA fire-retardant polyamide material, particularly relate to the MCA of a kind of original position formation and contain synergistic flame retardant SiO
2or the preparation method of the MCA fire-retardant 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, and also can be used as the important source material of synthon.Be widely used in automobile, machinery instrument, electric, the field such as defence and military, aerospace.But the limiting oxygen index(LOI) of polymeric amide (LOI) is between 21 ~ 22, which limits its application in a lot of field, flame-retardant modified extremely urgent therefore to polymeric amide.
The flame-retardant modified of polymeric amide mainly contains following three kinds of approach: (1) blending fire retardant modification, namely adds fire retardant while mechanically mixing, makes it obtain flame retardant resistance; (2) copolymerization is flame-retardant modified, by molecular designing, is incorporated into by flame retardant compositions on polyamide molecule chain or in polyamide polymerization process and flame retardance element original position is introduced, make material have flame-retarding characteristic; (3) fabrics flame resistance Final finishing, by grafting, roll cure, apply, the approach such as spraying makes fire retardant combine acquisition flame retardant effect with fabric.Fabrics flame resistance Final finishing is simple, easy to operate relative 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 fire retardant monomer reacted with monomer of polyamide described in 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) due to corrosion-free, nontoxic, flame retarding efficiency is higher and be widely used in the fire-retardant of polymeric amide, is the desirable fire retardant of polymeric amide.
United States Patent (USP) (USPatent5,037,869) a kind of method preparing flame resistant polyamide resin material is reported, this method by polymeric amide, trimeric cyanamide or derivatives thereof and cyanuric acid, ethylene glycol or its condensation polymer and phthalic acid fat in presence of water melt blending extrude, 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.Thus the new technology and method developing fire-retardant polyamide material is needed.Chinese invention patent (ZL200510022046.4) is that polymeric amide is matrix resin, is dispersion medium with water, in extrusion process, realizes the fabricated in situ of MCA and the preparation of fire retarding polyamide nano-composite with trimeric cyanamide and cyanuric acid for raw material.The synthesis of MCA and the preparation of fire retarding polyamide nano-composite complete by the method in a procedure, enormously simplify the preparation technology of matrix material, though the method achieves 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 Nano-meter SiO_2
2, metal oxide; Polymeric amide does not form fine and close layer of charcoal in combustion, and molten drop problem does not improve.
Summary of the invention
The object of this invention is to provide a kind of preparation method of MCA fire-retardant polyamide material, particularly provide a kind of original position to form MCA and contain synergistic flame retardant SiO
2with the preparation method of the MCA fire-retardant polyamide material of metal oxide.Feature of the present invention abandons the method that fire retardant and polymkeric substance are directly blended in the past, directly obtained in polymer monomer polymerization process by MCA, make fire retardant be evenly distributed in polymeric matrix, significantly improve its flame retarding efficiency, in turn simplify the preparation technology of matrix material.In addition, Nano-meter SiO_2 is added in the process
2with metal oxide as synergistic flame retardant, Nano-meter SiO_2
2not only improve the mechanical property of polymeric amide to a certain extent, also improve working temperature and the ignition temperature of polymeric amide, slow down the heat release rate of material surface.Simultaneously due to SiO
2particle fusing point is high, is deposited on material layer of charcoal after burning, effectively prevent inflammable gas and contacts with the oxygen in air.Metal oxide is as the synergistic flame retardant of MCA, and have excellent cooperative flame retardant effect, when polyamide article burns, the layer of charcoal forming one deck densification at product surface can be effectively fire-retardant.
The preparation method of a kind of MCA fire-retardant polyamide material of the present invention comprises:
Count by weight, 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 reactor, stir and heat up, mixing; Rotating speed is 100 ~ 400r/min, is warming up to 235 DEG C ~ 250 DEG C, and when pressure reaches 0.5MPa ~ 0.9MPa, reaction 6h ~ 9h, then passes through release and decompression vacuum pumping removing small molecules, obtain MCA fire-retardant polyamide material.
As preferred technical scheme:
The preparation method of a kind of MCA fire-retardant polyamide material as above, described monomer of polyamide is arbitrary a kind of monomer in nylon 1010, nylon 612, NYLON610, nylon66 fiber, nylon 46 or nylon 6.
The preparation method of a kind of MCA fire-retardant polyamide material as above, the melamine salt of described dicarboxylic acid and the cyanurate mol ratio of described organic diamine are 1:1, to ensure that number of functional groups is equal, do not affect follow-up polymerizable molecular amount.
The preparation method of a kind of MCA fire-retardant polyamide material as above, described metal oxide is Fe
2o
3, Al
2o
3or TiO
2, the synergistic effect certain to fire-retardant of MCA.
The preparation method of a kind of MCA fire-retardant polyamide material as above, after obtaining MCA fire-retardant polyamide material, is also further advanced by solid phase polycondensation and improves Flameproof polyamide molecular weight.
The preparation method of a kind of MCA fire-retardant polyamide material as above, described solid state polycondensation temperature is below fusing point 10 ~ 40 DEG C, and the polycondensation time is 12 ~ 36h.
Beneficial effect:
(1) MCA fire retardant material environmental protection, MCA in-situ polymerization simplifies preparation technology, and cost is low.
(2) MCA in-situ polymerization makes flame-retardant composition be uniformly distributed in polyamide substrate with nano-scale, and flame retarding efficiency improves, Nano-meter SiO_2
2with the synergistic fire retardation of metal oxide, while Flame Retardancy can significantly be improved, mechanical property is also improved to some extent.
(3) the Flame Retardancy energy prepared and good mechanical performance, have certain application prospect.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Mole hexanodioic acid and the trimeric cyanamide such as to get, at 80 DEG C, stirring reaction 4h centrifuging, drying obtain hexanodioic acid melamine salt.Mole hexanediamine such as to get and cyanuric acid stirring reaction 3h centrifuging at 60 DEG C, drying obtain cyanuric acid hexanediamine salt.By weight, in polymeric kettle, drop into 70.32 parts of hexanolactams, 10.88 parts of hexanodioic acid melamine salts, 9.8 parts of cyanuric acid hexanediamine salt, 1 part of SiO
2, 1 part of Fe
2o
3, the water of 7 parts, intensification melting is stirred, at 235 DEG C ~ 253 DEG C, during pressure 0.5MPa, reaction 6h.By row pressure, decompression vacuum pumping removing small molecules, discharging pelletizing, extraction obtain MCA Flameproof polyamide 6 resin.By dried flame-proof PA 6 resin at 200 DEG C of solid phase polycondensation 36h to increase molecular weight, the vertical combustion performance of sample reaches UL-94V-0 level.
Embodiment 2
Mole hexanodioic acid and the trimeric cyanamide, stirring reaction 2h at 90 DEG C such as to get, filter, drying obtains hexanodioic acid melamine salt.Mole hexanediamine such as to get and cyanuric acid stirring reaction 2.5h centrifuging at 70 DEG C, drying obtain cyanuric acid hexanediamine salt.By weight, in polymeric kettle, drop into 5.44 parts of hexanodioic acid melamine salts, 4.9 parts of cyanuric acid hexanediamine salt, 0.5 part of SiO
2with 0.5 part of TiO
2, get 84.66 parts of nylon salt solution and be placed in still, intensification melting is stirred, and passes into N
2excluding air, airtightly be warming up to 225 DEG C, pressure reaches 1.80Mpa, continues heating after heat-insulation pressure keeping 1h, slowly step-down simultaneously, temperature is 270 DEG C, when pressure is normal pressure, is again evacuated to-0.05MPa after heat-insulation pressure keeping 1h, extrude after aftercondensated 1.5h, blank, drying, lower solid phase polycondensation 12h at 240 DEG C again, obtain fire-retardant Nylon 66, the vertical combustion performance of sample reaches UL-94V-0 level.
Embodiment 3
Mole m-phthalic acid and the trimeric cyanamide, stirring reaction 2.5h at 90 DEG C such as to get, filter, drying obtains m-phthalic acid melamine salt.Mole mphenylenediamine such as to get and cyanuric acid stirring reaction 3h centrifuging at 60 DEG C, drying obtain cyanuric acid mphenylenediamine salt.By weight, in polymeric kettle, drop into 76.05 parts of hexanolactams, 10.23 parts of m-phthalic acid melamine salts, 8.30 parts of cyanuric acid mphenylenediamine salt, 0.78 part of SiO
2, 0.64 part of Fe
2o
3with 4 parts of water, intensification melting stir, 250 DEG C, pressure be 0.9MPa time, reaction 9h.By release, decompression vacuum pumping removing small molecules, discharging pelletizing obtains MCA Flameproof polyamide 6 resin.By dried flame-proof PA 6 resin at 200 DEG C of solid phase polycondensation 36h to increase molecular weight, the excellent flame retardancy of sample, mechanical property is better.
Embodiment 4
Mole m-phthalic acid and the trimeric cyanamide, stirring reaction 2.5h at 90 DEG C such as to get, filter, drying obtains m-phthalic acid melamine salt.Mole mphenylenediamine such as to get and cyanuric acid stirring reaction 2.5h centrifuging at 70 DEG C, drying obtain cyanuric acid mphenylenediamine salt.By weight, in polymeric kettle, drop into 8.76 parts of m-phthalic acid melamine salts, 7.12 parts of cyanuric acid mphenylenediamine salt, 0.5 part of SiO
2with 0.5 part of Al
2o
3, get 83.12 parts of nylon salt wiring solution-formings and be placed in still, intensification melting stirs and passes into N
2excluding air, airtightly be warming up to 225 DEG C, pressure reaches 1.70Mpa, continues heating after heat-insulation pressure keeping 1h, simultaneously slowly step-down, when temperature is 275 DEG C, pressure is normal pressure, again be evacuated to-0.06MPa after heat-insulation pressure keeping 1h, extrude after aftercondensated 1.5h, blank, drying, then at 220 DEG C of solid phase polycondensation 12h, obtain fire-retardant Nylon 66 section, the vertical combustion performance of sample reaches UL-94V-0 level.
Embodiment 5
By weight, in polymeric kettle, drop into 8.76 parts of m-phthalic acid melamine salts, 7.12 parts 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 DEG C of salt fusings.When temperature rise to 220 DEG C, pressure rises to 120kpa, starts venting dehydration after maintaining 1h.Along with dehydration reaction trend terminal, pressure also returns to normal pressure.At the end of reaction, temperature in the kettle can be heated to 240 DEG C.In order to make dehydration complete as far as possible, 240 DEG C of normal pressure emptying, until do not have tail gas to discharge.Discharging after reaction 6h.190 DEG C of solid phase polycondensation 18h after extracting drying, prepare FR Polyamide 1010 again, and the vertical combustion performance of sample is good.
Claims (6)
1. a preparation method for MCA fire-retardant polyamide material, is characterized in that:
Count by weight, 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 reactor, stir and heat up, mixing; Rotating speed is 100 ~ 400r/min, is warming up to 235 DEG C ~ 250 DEG C, and when pressure reaches 0.5MPa ~ 0.9MPa, reaction 6h ~ 9h, then passes through release and decompression vacuum pumping removing small-molecule substance, obtain MCA fire-retardant polyamide material.
2. the preparation method of a kind of MCA fire-retardant polyamide material according to claim 1, is characterized in that, described monomer of polyamide is arbitrary a kind of monomer in nylon 1010, nylon 612, NYLON610, nylon66 fiber, nylon 46 or nylon 6.
3. the preparation method of a kind of MCA fire-retardant polyamide material according to claim 1, is characterized in that, the melamine salt of described dicarboxylic acid and the cyanurate mol ratio of described organic diamine are 1:1.
4. the preparation method of a kind of MCA fire-retardant 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 fire-retardant polyamide material according to claim 1, is characterized in that, after obtaining MCA fire-retardant polyamide material, is also further advanced by solid phase polycondensation and improves Flameproof polyamide molecular weight.
6. the preparation method of a kind of MCA fire-retardant polyamide material according to claim 5, is characterized in that, described solid state polycondensation temperature is below polymeric amide fusing point 10 ~ 40 DEG C, and the polycondensation time is 12 ~ 36h.
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Families Citing this family (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)
| 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 |
| 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 |
|---|
| Preparation and characterization of flame-retardant melamine cyanurate/polyamide 6 nanocomposites by in situ polymerization;Zhi-Yong Wu等;《Journal of Applied Polymer Science》;20090424;第113卷;2109-2116页 * |
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