CN104294392A - MCA flame-resistant polyamide 6 fibers and preparation method thereof - Google Patents
MCA flame-resistant polyamide 6 fibers and preparation method thereof Download PDFInfo
- Publication number
- CN104294392A CN104294392A CN201410545262.6A CN201410545262A CN104294392A CN 104294392 A CN104294392 A CN 104294392A CN 201410545262 A CN201410545262 A CN 201410545262A CN 104294392 A CN104294392 A CN 104294392A
- Authority
- CN
- China
- Prior art keywords
- mca
- preparation
- polyamide
- flameproof polyamide
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
The invention relates to MCA flame-resistant polyamide 6 fibers and a preparation method thereof. The MCA flame-resistant polyamide 6 fibers comprise the following raw material components in parts by weight: 72.32-85.66 parts of caprolactam, 5.44-10.88 parts of dicarboxylic melamine salt, 4.9-9.8 parts of organic diamine cyanurate and 4-7 parts of water. The preparation method comprises the following steps: mixing the raw materials in parts by weight, stirring and heating until the temperature reaches 250-270 DEG C and the pressure reaches 0.5-0.8MPa, carrying out heat preservation and pressure maintaining for 2-3 hours, releasing pressure, continuously reacting for 3-4 hours, and carrying out pressure reduction vacuumizing so as to obtain MCA flame-resistant polyamide 6 slices; and carrying out solid phase condensation polymerization and melt spinning on the MCA flame-resistant polyamide 6 slices so as to obtain the MCA flame-resistant polyamide 6 fibers. According to the MCA flame-resistant polyamide 6 fibers, MCA flame-resistant materials are environmentally friendly; by virtue of MCA in-situ polymerization, the preparation process is simplified, and the cost is low.
Description
Technical field
The invention belongs to fire resistance fibre and preparation field thereof, particularly a kind of MCA Flameproof polyamide 6 fiber and preparation method thereof.
Background technology
Daiamid-6 fiber is that one is widely used also known as polyamide fibre 6, the synthetic fiber of function admirable, have that good, the resistance to repeatedly morphotropism of ABRASION RESISTANCE, resilience are high, lower temperature resistance, alkaline-resisting chemical stability and easy dyeing, these performances are all that other general chemical fibre can not be compared.Daiamid-6 fiber is mainly used to do carpet, bunting, goods drape, conveyer belt, the knapsack in army, bedding and clothing and tent etc.Along with expanding economy, the raising of living standards of the people, the nylon carpet of middle class also can be more and more universal in China.The same with other chemical fibre, also there is inflammable shortcoming in daiamid-6 fiber.Which also limits the application of polyamide fibre 6.The research of fire-retardant polyamide fibre 6, production and application have become a problem very in the urgent need to address.
The research of fire-retardant polyamide fibre 6 and all rare report of industrialization product, Chinese patent (201220122279.7) reports a kind of method preparing fire-retardant polyamide fibre 6 carpet silk, described carpet yarn is the single thread be made up of the first polyamide fibre 6 varicosity fiber, the second polyamide fibre 6 varicosity fiber and fire resistance fibre that three beams color is different by this method, although this method improves fire resistance, but not the self flame retardance of polyamide fibre 6 causes, do not spin out fire-retardant Nylon 6 Monofilament, therefore need a kind of new Method and Technology to work out fire-retardant Nylon 6 Monofilament.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of MCA Flameproof polyamide 6 fiber and preparation method thereof, the MCA fire proofing environmental protection of this invention, and MCA in-situ polymerization simplifies preparation technology, and cost is low; MCA in-situ polymerization makes flame-retardant composition be uniformly distributed in daiamid-6 fiber with nano-scale, and flame retarding efficiency improves.
A kind of MCA Flameproof polyamide 6 fiber of the present invention, by weight, the raw material components of described MCA Flameproof polyamide 6 fiber is: caprolactam 72.32-85.66 part, melamine salt 5.44-10.88 part of dicarboxylic acids, the cyanurate of organic diamine 4.9 ~ 9.8 parts; 4 ~ 7 parts, water.
The preparation method of the melamine salt of described dicarboxylic acids is: moles of dicarboxylic acids and the melamine such as general, under 80-95 DEG C of condition, stirring reaction 1-5h centrifugal filtration, drying obtain the melamine salt of dicarboxylic acids.
The preparation method of the cyanurate of described organic diamine is: will wait mole organic diamine and cyanuric acid, and at 50-80 DEG C under condition, stirring reaction 1-5h centrifugal filtration, drying obtain the cyanurate of organic diamine.
The melamine salt of described dicarboxylic acids is the one in adipic acid melamine salt, M-phthalic acid melamine salt; The cyanurate of organic diamine is the one in cyanuric acid hexamethylene diamine salt, cyanuric acid m-phenylene diamine (MPD) salt.
The preparation method of a kind of MCA Flameproof polyamide 6 fiber of the present invention, comprising:
(1) by weight, by caprolactam 72.32-85.66 part, melamine salt 5.44-10.88 part of dicarboxylic acids, cyanurate 4.9-9.8 part of organic diamine; Water 4-7 part mixes, and stir and be heated to 250-270 DEG C, pressure reaches 0.5-0.8MPa, heat-insulation pressure keeping 2-3h, then continues reaction 3-4h after release, and decompression vacuum pumping removing Small molecular, obtains MCA retardant polyamide 6 and cut into slices;
(2) solid phase polycondensation thickening, melt spinning are carried out in above-mentioned MCA retardant polyamide 6 section, obtain MCA Flameproof polyamide 6 fiber.
In described step (1), the mol ratio of the melamine salt of dicarboxylic acids and the cyanurate of organic diamine is 1:1, to ensure that number of functional groups is equal, does not affect follow-up polymerizable molecular amount.
In described step (1), stir speed (S.S.) is 100 ~ 400r/min.
The reaction of described step (1) is carried out in a kettle..
In described step (2), solid state polycondensation temperature is 170-200 DEG C, and polycondensation reaction time is 12-36h.
Flameproof polyamide 6 molecular weight is improved by solid phase polycondensation.
In described step (2), the temperature of melt spinning is 260-265 DEG C, spins speed for 800-1000m/min, drafting multiple 3.0-4.0.
In caprolactam, the melamine salt of dicarboxylic acids, the cyanurate of organic diamine is added in the present invention, and be medium with water, carry out dispersion mixing, in-situ polymerization obtains Flameproof polyamide 6 and cuts into slices, part flame-retardant composition can be made like this to receive on polyamide 6 chain, and the MCA that original position is formed can be dispersed in polyamide 6 matrix, polymer molecular weight is increased again by process for solid state polycondensation, the polyamide 6 section of obtained excellent flame retardancy, good mechanical properties, prepare Flameproof polyamide 6 fiber finally by melt spinning, flame-retardant fiber is functional.
beneficial effect
(1) MCA fire proofing of the present invention environmental protection, MCA in-situ polymerization simplifies preparation technology, and cost is low;
(2) MCA in-situ polymerization of the present invention makes flame-retardant composition be uniformly distributed in daiamid-6 fiber with nano-scale, and flame retarding efficiency improves;
(3) fire resistance of daiamid-6 fiber prepared of the present invention and good mechanical performance, have certain application prospect.
Detailed description of the invention
Below in conjunction with specific 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 adipic acid and the melamine such as to get, at 80 DEG C, stirring reaction 4h centrifugal filtration, drying obtain adipic acid melamine salt.Mole hexamethylene diamine such as to get and cyanuric acid stirring reaction 3h centrifugal filtration at 60 DEG C, drying obtain cyanuric acid hexamethylene diamine salt.By weight, in polymeric kettle, drop into 72.32 parts of caprolactams, 10.88 parts of adipic acid melamine salts, 9.8 portions of cyanuric acid hexamethylene diamine salt, the water of 7 parts, intensification melting is stirred, temperature be 250 DEG C, pressure 0.5MPa time reaction 3h, later stage reacts 4 hours after unloading and being depressed into normal pressure, last decompression vacuum pumping removing Small molecular, discharging pelletizing, extraction obtain MCA Flameproof polyamide 6 and cut into slices, cut into slices dried flame-proof PA 6 at 170 DEG C of solid phase polycondensation 36h to increase molecular weight, limited oxygen index can reach more than 27.Adopt temperature to be 260 DEG C, melt spinning flame-proof PA 6 fiber is prepared in drawing-off cooling when spinning fast 800m/min.
Embodiment 2
Mole adipic acid and the melamine, stirring reaction 2h at 90 DEG C such as to get, filter, drying obtains adipic acid melamine salt.Mole hexamethylene diamine such as to get and cyanuric acid stirring reaction 2.5h centrifugal filtration at 70 DEG C, drying obtain cyanuric acid hexamethylene diamine salt.By weight, in polymeric kettle, drop into 5.44 parts of adipic acid melamine salts, 4.9 portions of cyanuric acid hexamethylene diamine salt 85.66 parts of caprolactams are placed in still, intensification melting is stirred, and passes into N
2deaeration, airtight be warming up to 270 DEG C, pressure unloads after reacting 3 hours when being 0.80Mpa and is depressed into normal pressure and continues reaction 4 hours, extrude after being finally evacuated to-0.05MPa aftercondensated 1.5h, blank, extraction, drying, solid phase polycondensation 12h 200 DEG C time again, obtain Flameproof polyamide 6 to cut into slices, limited oxygen index can reach more than 27.Adopt temperature to be 265 DEG C, melt spinning flame-proof PA 6 fiber is prepared in drawing-off cooling when spinning fast 1000m/min.
Embodiment 3
Mole M-phthalic acid and the melamine, stirring reaction 2.5h at 90 DEG C such as to get, filter, drying obtains M-phthalic acid melamine salt.Mole m-phenylene diamine (MPD) such as to get and cyanuric acid stirring reaction 3h centrifugal filtration at 60 DEG C, drying obtain cyanuric acid m-phenylene diamine (MPD) salt.By weight, in polymeric kettle, drop into 77.47 parts of caprolactams, 10.23 parts of M-phthalic acid melamine salts, 8.30 parts of cyanuric acid m-phenylene diamine (MPD) salt, 4 parts of water, intensification melting is stirred, 250 DEG C, pressure be 0.8MPa time reaction 3h, continue reaction 4h by unloading to be depressed into after normal pressure, last decompression vacuum pumping removes hydrone, and discharging pelletizing, extraction obtain MCA Flameproof polyamide 6 and cut into slices.Cut into slices dried flame-proof PA 6 at 200 DEG C of solid phase polycondensation 36h to increase molecular weight, its limited oxygen index can reach more than 27.Adopt temperature to be 265 DEG C, melt spinning flame-proof PA 6 fiber is prepared in drawing-off cooling when spinning fast 800m/min.
Embodiment 4
Mole M-phthalic acid and the melamine, stirring reaction 2.5h at 90 DEG C such as to get, filter, drying obtains M-phthalic acid melamine salt.Mole m-phenylene diamine (MPD) such as to get and cyanuric acid stirring reaction 2.5h centrifugal filtration at 70 DEG C, drying obtain cyanuric acid m-phenylene diamine (MPD) salt.By weight, in polymeric kettle, drop into 8.76 parts of M-phthalic acid melamine salts, 7.12 portions of cyanuric acid m-phenylene diamine (MPD) salt, and 84.12 parts of caprolactams are placed in still, intensification melting stirs and passes into N
2deaeration, airtightly be warming up to 260 DEG C, 3h is reacted when pressure is 0.70Mpa, then be slowly depressurized to normal pressure and continue reaction 4h, extrude after reaction 1.5h when being finally evacuated to-0.06MPa, blank, extraction, drying, and when temperature is 190 DEG C solid phase polycondensation 12h, obtain Flameproof polyamide 6 cut into slices, its limited oxygen index can reach more than 27.Adopt temperature to be 265 DEG C, melt spinning flame-proof PA 6 fiber is prepared in drawing-off cooling when spinning fast 800m/min.
Claims (10)
1. MCA Flameproof polyamide 6 fiber, it is characterized in that: by weight, the raw material components of described MCA Flameproof polyamide 6 fiber is: caprolactam 72.32-85.66 part, melamine salt 5.44-10.88 part of dicarboxylic acids, the cyanurate of organic diamine 4.9 ~ 9.8 parts; Water 4-7 part.
2. a kind of MCA Flameproof polyamide 6 fiber according to claim 1, it is characterized in that: the preparation method of the melamine salt of described dicarboxylic acids is: moles of dicarboxylic acids and the melamine such as general, under 80-95 DEG C of condition, stirring reaction 1-5h centrifugal filtration, drying obtain the melamine salt of dicarboxylic acids.
3. a kind of MCA Flameproof polyamide 6 fiber according to claim 1, it is characterized in that: the preparation method of the cyanurate of described organic diamine is: will wait mole organic diamine and cyanuric acid, at 50-80 DEG C under condition, stirring reaction 1-5h centrifugal filtration, drying obtain the cyanurate of organic diamine.
4. a kind of MCA Flameproof polyamide 6 fiber according to claim 1, is characterized in that: the melamine salt of described dicarboxylic acids is the one in adipic acid melamine salt, M-phthalic acid melamine salt; The cyanurate of organic diamine is the one in cyanuric acid hexamethylene diamine salt, cyanuric acid m-phenylene diamine (MPD) salt.
5. a preparation method for MCA Flameproof polyamide 6 fiber as described in as arbitrary in claim 1-4, comprising:
(1) by caprolactam, the melamine salt of dicarboxylic acids, the cyanurate of organic diamine, water mixes, stir and be heated to 250-270 DEG C, pressure reaches 0.5-0.8MPa, heat-insulation pressure keeping 2-3h, then continue reaction 3-4h after release, decompression vacuum pumping, obtains MCA retardant polyamide 6 and cuts into slices;
(2) solid phase polycondensation, melt spinning are carried out in above-mentioned MCA retardant polyamide 6 section, obtain MCA Flameproof polyamide 6 fiber.
6. the preparation method of a kind of MCA Flameproof polyamide 6 fiber according to claim 5, is characterized in that: in described step (1), the mol ratio of the melamine salt of dicarboxylic acids and the cyanurate of organic diamine is 1:1.
7. the preparation method of a kind of MCA Flameproof polyamide 6 fiber according to claim 5, is characterized in that: in described step (1), stir speed (S.S.) is 100 ~ 400r/min.
8. the preparation method of a kind of MCA Flameproof polyamide 6 fiber according to claim 5, is characterized in that: the reaction of described step (1) is carried out in a kettle..
9. the preparation method of a kind of MCA Flameproof polyamide 6 fiber according to claim 5, is characterized in that: in described step (2), solid state polycondensation temperature is 170-200 DEG C, and polycondensation reaction time is 12-36h.
10. the preparation method of a kind of MCA Flameproof polyamide 6 fiber according to claim 5, is characterized in that: in described step (2), the temperature of melt spinning is 260-265 DEG C, spins speed for 800-1000m/min, drafting multiple 3.0-4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410545262.6A CN104294392A (en) | 2014-10-15 | 2014-10-15 | MCA flame-resistant polyamide 6 fibers and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410545262.6A CN104294392A (en) | 2014-10-15 | 2014-10-15 | MCA flame-resistant polyamide 6 fibers and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104294392A true CN104294392A (en) | 2015-01-21 |
Family
ID=52314333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410545262.6A Pending CN104294392A (en) | 2014-10-15 | 2014-10-15 | MCA flame-resistant polyamide 6 fibers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104294392A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220268A (en) * | 2015-09-15 | 2016-01-06 | 郎溪和心化纤织造有限公司 | A kind of POLYAMIDE YARNS with high efficiency flame retardance |
| CN105273182A (en) * | 2015-07-20 | 2016-01-27 | 杭州师范大学 | Preparation method of flame-retarding nylon 6 and uses thereof |
| CN107383863A (en) * | 2017-08-17 | 2017-11-24 | 中央军委后勤保障部军需装备研究所 | A kind of high CTI high-strength anti-flamings polyamide material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056392A (en) * | 2005-08-24 | 2007-03-08 | Toray Ind Inc | Flame retardant polyamide fiber and flame retardant fabric |
| 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 |
| CN103031638A (en) * | 2012-12-14 | 2013-04-10 | 常熟市凯鑫地毯有限公司 | Carpet yarn manufacture method |
| CN103387666A (en) * | 2013-07-12 | 2013-11-13 | 东华大学 | Preparation method of fire-retardant nylon 66 material |
| CN103408751A (en) * | 2013-07-12 | 2013-11-27 | 东华大学 | Preparation method of MCA (Melamine Cyanurate) flame-retardant polyamide material |
-
2014
- 2014-10-15 CN CN201410545262.6A patent/CN104294392A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056392A (en) * | 2005-08-24 | 2007-03-08 | Toray Ind Inc | Flame retardant polyamide fiber and flame retardant fabric |
| 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 |
| CN103031638A (en) * | 2012-12-14 | 2013-04-10 | 常熟市凯鑫地毯有限公司 | Carpet yarn manufacture method |
| CN103387666A (en) * | 2013-07-12 | 2013-11-13 | 东华大学 | Preparation method of fire-retardant nylon 66 material |
| CN103408751A (en) * | 2013-07-12 | 2013-11-27 | 东华大学 | Preparation method of MCA (Melamine Cyanurate) flame-retardant polyamide material |
Non-Patent Citations (1)
| Title |
|---|
| 邬智勇: ""原位聚合型阻燃尼龙6的制备、性能及应用研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273182A (en) * | 2015-07-20 | 2016-01-27 | 杭州师范大学 | Preparation method of flame-retarding nylon 6 and uses thereof |
| CN105220268A (en) * | 2015-09-15 | 2016-01-06 | 郎溪和心化纤织造有限公司 | A kind of POLYAMIDE YARNS with high efficiency flame retardance |
| CN107383863A (en) * | 2017-08-17 | 2017-11-24 | 中央军委后勤保障部军需装备研究所 | A kind of high CTI high-strength anti-flamings polyamide material and preparation method thereof |
| CN107383863B (en) * | 2017-08-17 | 2020-03-24 | 中央军委后勤保障部军需装备研究所 | high-CTI high-strength flame-retardant polyamide material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102199807B (en) | Method for producing phosphorus copolymerized flame-retarding terylene high-strength industrial yarns | |
| CN101450993B (en) | Method for preparing halogen free flame-retarded nylon 6 | |
| CN105155018A (en) | Copolymerized flame-retardant polyamide 66 fiber and preparation method thereof | |
| CN103215686A (en) | Preparation method of halogen-free flame retardant recycled polyester fiber | |
| CN104499076A (en) | Preparation method of flame-retarded polyamide 6 fiber | |
| CN104294392A (en) | MCA flame-resistant polyamide 6 fibers and preparation method thereof | |
| CN116355209B (en) | Preparation method and application of high-whiteness meta-aramid polymer | |
| KR102104658B1 (en) | HIGH PERFORMANCE POLYAMIDE, SPINNING DOPE COMPOSITION and MOLD COMPRISING THEREOF | |
| CN112663167A (en) | Flame-retardant polyester fiber and preparation method thereof | |
| CN105696100A (en) | Green carbon source copolymerized anti-flaming polylactic acid fiber and preparation method thereof | |
| CN103387666B (en) | A kind of preparation method of fire-retardant Nylon 66 material | |
| CN105696103B (en) | Carpet silk fire-retardant fiber of ultraviolet resistant nylon 6 of copoly type and preparation method thereof | |
| RU2116393C1 (en) | Filaments and films with increased thermal stability, method for producing such filaments and films and fabric manufactured from such filaments | |
| CN103408751B (en) | A kind of preparation method of MCA fire-retardant polyamide material | |
| CN103387665B (en) | A kind of preparation method of fire-retardant polyamide material | |
| JP6873768B2 (en) | I Ching meta-type total aromatic polyamide fiber with excellent flame retardancy and its manufacturing method | |
| CN106432722B (en) | A kind of high-performance fiber and preparation method thereof | |
| GB2068984A (en) | Fibre and method of making the fibre | |
| JP2018154943A (en) | Meta-type wholly aromatic polyamide fiber having excellent flame retardancy and method for producing the same | |
| CN102585188B (en) | Novel phosphorus-containing thermotropic liquid crystal copolyester and preparation method and application thereof | |
| CN102584610B (en) | Bisphenol 2 (m-amino p-hydroxy phenyl) ether hydrochloride and preparation method and application thereof | |
| CN115262030B (en) | Flame-retardant noctilucent fiber and preparation method thereof | |
| CN105671672B (en) | Containing only carbon, hydrogen, the flame-proof polylactic acid fiber of the element of oxygen three and preparation method thereof | |
| CN114230786B (en) | Preparation method and application of superfine poly-p-phenylene terephthamide powder | |
| CN115850692B (en) | High-temperature-resistant nylon and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150121 |
|
| RJ01 | Rejection of invention patent application after publication |