CN104292818B - The method of nanometer halogen-free anti-flaming polyamide-6 - Google Patents
The method of nanometer halogen-free anti-flaming polyamide-6 Download PDFInfo
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- CN104292818B CN104292818B CN201410453878.0A CN201410453878A CN104292818B CN 104292818 B CN104292818 B CN 104292818B CN 201410453878 A CN201410453878 A CN 201410453878A CN 104292818 B CN104292818 B CN 104292818B
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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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Polymers & Plastics (AREA)
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Abstract
First the preparation method that the present invention relates to a kind of nanometer halogen-free anti-flaming polyamide 6 weighs polyamide 6, nanometer MCA halogen-free flame retardants and antioxidant, and by these raw material mix homogeneously.Then double screw extruder is preheated to 185 280 DEG C, the raw material of mix homogeneously is added in double screw extruder, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide 6.The halogen free nanometer flame-proof PA 6 prepared, good flame retardation effect, fire retardant addition is few, and burning fuming amount is little, does not produce poisonous and mordant gas, and the halogen-free flameproof PA6 height that mechanical property is the most common.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of nanometer, halogen-free flame-retardant polyamide-6(nylon 6) preparation method.
Background technology
Polyamide-6(PA6) it is a kind of important engineering plastics, it is widely used in fields such as electronic apparatus, automobile and machineries, but polyamide-6 melted by heating in combustion to produce molten drop phenomenon more obvious, melt strength is low, and being easily generated substantial amounts of has molten of flame.When fire occurs, itself the most easily causes second-time burning while releasing amount of heat.Therefore, in the use of productive life, it is required to PA6 is carried out flame treatment.
The most conventional polyamide-6 fire retardant mainly has metal hydroxides, P-N type fire retardant and nitrogen based flame retardant etc..Metal hydroxides is a kind of environment friendly flame retardant, due to its abundance, cheap, does not produce the features such as corrosive gas, nontoxic, environmental friendliness, is widely used.Magnesium hydroxide is the current topmost fire retardant of polyamide-6, and its usage amount has exceeded 50%.P-N type fire retardant, as a kind of novel halogen-free flame retardants, has obtained the extensive concern of people with its excellent flame retarding efficiency.It can form porous foamed char in combustion, and this layer of charcoal can play heat insulation, oxygen barrier, press down cigarette and anti-molten drop effect, thus reaches good fire-retardant purpose.Nitrogen based flame retardant, mainly to form the non-flammable gases such as ammonia in catabolic process, dilutes and waters down imflammable gas or be covered in the effect of material surface and fire-retardant.Its major advantage is Halogen, low cigarette, is conducive to environmental conservation.Melamine cyanurate (MCA), as widely used a kind of nitrogenated flame retardant, in nylon, can play the most excellent fire resistance.
Above-mentioned three kinds of flame resistant methods all can reach the purpose of halogen-free flame-retardant polyamide-6, but owing to P-N type fire retardant the most on the market and nitrogen based flame retardant are a micron fire retardant, its grain diameter is micron level, particle diameter is excessive, and the best with the macromolecular material compatibility, utilize its Flameproof polyamide-6 can cause the decline of mechanical property；And magnesium hydroxide flame retardant is inefficient, addition needs very big, and meeting its mechanical property of extreme influence this strongly limits the use space of polyamide-6.
Summary of the invention
For the deficiencies in the prior art, the present invention provides one to utilize the method that nanoscale melamine cyanurate (MCA) carries out halogen-free flameproof to polyamide-6.
The preparation method of a kind of nanometer halogen-free anti-flaming polyamide-6, it is characterised in that comprise the following steps:
First polyamide-6 raw material of 100 weight portions is weighed, nano melamine cyanurate (MCA) halogen-free flame retardants of 2-20 weight portion, the antioxidant of 0.1-10 weight portion, and by these raw material mix homogeneously；Then double screw extruder being preheated to 185-280 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 100-400r/ min, product is carried out pelletize and i.e. obtains nanometer halogen-free anti-flaming polyamide-6.
Described halogen-free flame retardants nano melamine cyanurate (MCA) is long 500-800nm, the rod-like nano particle of wide 100nm.
Described antioxidant is three [2.4-di-tert-butyl-phenyl] phosphite ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, 2, 6-ditertbutylparacresol, N-cyclohexyl-p-ethoxyaniline, three (nonylated phenyl) phosphite ester, N-isopropyl-4-aminodiphenylamine, N-secondary octyl 4-aminodiphenylamine, octylated diphenylamine, 4, 4-bis-(propyloxy phenyl base) diphenylamines, hutanal-aniline condensation thing, 2, 2-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 1, 3, 5-(di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, 5H) the one in triketone or a combination thereof.
The advantage using method of the present invention to prepare halogen-free flame-retardant polyamide-6 is, owing to nano-meter flame retardants has bigger surface area, and the surface reaction activity of nanoparticle is more much bigger than micron particle, it is compared to the micron order MCA fire retardant commonly used on the market, nanometer MCA fire retardant has higher flame retarding efficiency, the flame retardant effect of 5 parts of nanometers MCA of interpolation can match in excellence or beauty and add polyamide-6 of 10 parts of micron MCA, can reach low dose of fire-retardant, see Fig. 1；On the other hand, excessive and with macromolecular material the compatibility of micron-sized MCA particle diameter is the best, the mechanical performance of material can be had a strong impact on, and the quantum size effect that nano-particle has due to it, small-size effect, skin effect etc., less to the mechanical property of macromolecular material, this shortcoming can be made to obtain perfect solution.
Accompanying drawing explanation
Fig. 1: nanometer MCA and micron MCA flame-proof PA 6 oxygen index (OI).
Detailed description of the invention
Further illustrate the present invention below by embodiment rather than limit the scope of the present invention.
Embodiment one:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 5 weight portions, the antioxidant of 0.1 weight portion, and by these raw material mix homogeneously.Then double screw extruder being preheated to 240 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 200r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Embodiment two:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 7 weight portions, the antioxidant of 0.2 weight portion, and by these raw material mix homogeneously.Then double screw extruder being preheated to 230 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 130r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Embodiment three:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 10 weight portions, the antioxidant of 0.5 weight portion, and by these raw material mix homogeneously.Then double screw extruder being preheated to 220 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 250r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Embodiment four:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 3 weight portions, the antioxidant of 1 weight portion, and by these raw material mix homogeneously.Then double screw extruder being preheated to 250 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 350r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Embodiment five:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 12 weight portions, the antioxidant of 2 weight portions, and by these raw material mix homogeneously.Then double screw extruder being preheated to 260 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 300r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Embodiment six:
First polyamide-6 raw material of 100 weight portions is weighed, the nanometer MCA halogen-free flame retardants of 5 weight portions, the antioxidant of 0.1 weight portion, and by these raw material mix homogeneously.Then double screw extruder being preheated to 235 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 120r/ min, product is carried out pelletize and i.e. obtains halogen free nanometer Flameproof polyamide-6.
Claims (1)
1. the preparation method of a nanometer halogen-free anti-flaming polyamide-6, it is characterised in that comprise the following steps:
First polyamide-6 raw material of 100 weight portions is weighed, nano melamine cyanurate (MCA) halogen-free flame retardants of 2-20 weight portion, the antioxidant of 0.1-10 weight portion, and by these raw material mix homogeneously；Then double screw extruder being preheated to 185-280 DEG C, added by the raw material of mix homogeneously in double screw extruder, controlling screw speed is 100-400r/ min, product is carried out pelletize and i.e. obtains nanometer halogen-free anti-flaming polyamide-6；
Described halogen-free flame retardants nano melamine cyanurate (MCA) is long 500-800nm, the rod-like nano particle of wide 100nm；
Described antioxidant be three [2,
4-di-tert-butyl-phenyl] phosphite ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, 2, 6-ditertbutylparacresol, N-cyclohexyl-p-ethoxyaniline, three (nonylated phenyl) phosphite ester, N-isopropyl-4-aminodiphenylamine, N-secondary octyl 4-aminodiphenylamine, octylated diphenylamine, 4, 4-bis-(propyloxy phenyl base) diphenylamines, hutanal-aniline condensation thing, 2, 2-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), 1, 3, 5-(di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, 5H) the one in triketone or a combination thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410453878.0A CN104292818B (en) | 2014-09-09 | 2014-09-09 | The method of nanometer halogen-free anti-flaming polyamide-6 |
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| CN201410453878.0A CN104292818B (en) | 2014-09-09 | 2014-09-09 | The method of nanometer halogen-free anti-flaming polyamide-6 |
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| CN104292818A CN104292818A (en) | 2015-01-21 |
| CN104292818B true CN104292818B (en) | 2016-08-17 |
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| CN109957243A (en) * | 2017-12-14 | 2019-07-02 | 凯赛(乌苏)生物材料有限公司 | A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method |
| CN109957244A (en) * | 2017-12-14 | 2019-07-02 | 凯赛(乌苏)生物材料有限公司 | A kind of thermoplastic halogen-free flame retarding enhancing biology base PA56 and PA66 composite material and preparation method |
| CN114085520B (en) * | 2021-11-30 | 2024-06-21 | 上海试四化学品有限公司 | Modified high-flame-retardant temperature nylon 66 and preparation method thereof |
Citations (8)
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|---|---|---|---|---|
| US5510059A (en) * | 1994-02-08 | 1996-04-23 | Nissan Chemical Industries, Ltd. | Surface-treated melamine cyanurate powder and process for its production |
| CN101074317A (en) * | 2007-06-25 | 2007-11-21 | 辽宁大学 | Production of trimeric-cyanamide cyanurate fire-retardant nylon material |
| CN101914220A (en) * | 2010-08-27 | 2010-12-15 | 北京工商大学 | Method for preparing nano melamine cyanurate acid (MCA) |
| CN102363672A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | MCA (Melamine Cyanurate) flame-retardant polycaprolactam compound material and preparation method thereof |
| CN102363671A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | Flame-retardant master batch for nylon carrier and preparation method thereof |
| CN102757393A (en) * | 2012-07-05 | 2012-10-31 | 同济大学 | Method for synthesizing nano-scale melamine cyanurate (MCA) through hydrothermal method |
| CN103013104A (en) * | 2012-12-26 | 2013-04-03 | 上海金发科技发展有限公司 | Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof |
| CN103910999A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | High-glowing nylon 6 composition and preparation method thereof |
-
2014
- 2014-09-09 CN CN201410453878.0A patent/CN104292818B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510059A (en) * | 1994-02-08 | 1996-04-23 | Nissan Chemical Industries, Ltd. | Surface-treated melamine cyanurate powder and process for its production |
| CN101074317A (en) * | 2007-06-25 | 2007-11-21 | 辽宁大学 | Production of trimeric-cyanamide cyanurate fire-retardant nylon material |
| CN101914220A (en) * | 2010-08-27 | 2010-12-15 | 北京工商大学 | Method for preparing nano melamine cyanurate acid (MCA) |
| CN102363672A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | MCA (Melamine Cyanurate) flame-retardant polycaprolactam compound material and preparation method thereof |
| CN102363671A (en) * | 2011-06-30 | 2012-02-29 | 深圳市科聚新材料有限公司 | Flame-retardant master batch for nylon carrier and preparation method thereof |
| CN102757393A (en) * | 2012-07-05 | 2012-10-31 | 同济大学 | Method for synthesizing nano-scale melamine cyanurate (MCA) through hydrothermal method |
| CN103013104A (en) * | 2012-12-26 | 2013-04-03 | 上海金发科技发展有限公司 | Halogen-free filling flame-retardant nylon 6 composite material and preparation method thereof |
| CN103910999A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | High-glowing nylon 6 composition and preparation method thereof |
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