CN104292818A - Method of nano halogen-free flame retardant polyamide-6 - Google Patents

Method of nano halogen-free flame retardant polyamide-6 Download PDF

Info

Publication number
CN104292818A
CN104292818A CN201410453878.0A CN201410453878A CN104292818A CN 104292818 A CN104292818 A CN 104292818A CN 201410453878 A CN201410453878 A CN 201410453878A CN 104292818 A CN104292818 A CN 104292818A
Authority
CN
China
Prior art keywords
halogen
flame retardant
nano
free flame
polymeric amide
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.)
Granted
Application number
CN201410453878.0A
Other languages
Chinese (zh)
Other versions
CN104292818B (en
Inventor
何丹农
徐少洪
陈超
张春明
金彩虹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Original Assignee
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai National Engineering Research Center for Nanotechnology Co Ltd filed Critical Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority to CN201410453878.0A priority Critical patent/CN104292818B/en
Publication of CN104292818A publication Critical patent/CN104292818A/en
Application granted granted Critical
Publication of CN104292818B publication Critical patent/CN104292818B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to a preparation method of nano halogen-free flame retardant polyamide-6. The preparation method comprises the steps: firstly weighing polyamide-6, nano MCA halogen-free flame retardant agent and an antioxidant, and mixing uniformly the raw materials; and then preheating a double-screw extruder to the temperature of 185-280 DEG C, adding the uniformly-mixed raw materials into the double-screw extruder, and then carrying out granulation on the product, to obtain the nano halogen-free flame retardant polyamide-6. The prepared nano halogen-free flame retardant PA 6 has the advantages of good flame retardant effect, less adding amount of the flame retardant agent, small combustion smoke formation quantity, and no production of toxic and corrosive gases, and has mechanical properties higher than those of a common halogen-free flame retardant PA6 in markets.

Description

The method of nanometer halogen-free anti-flaming polymeric amide-6
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
Polymeric amide-6(PA6) be a kind of important engineering plastics, be widely used in fields such as electronic apparatus, automobile and machineries, but polymeric amide-6 in combustion melted by heating to produce molten drop phenomenon comparatively obvious, melt strength is low, and easily producing a large amount of has molten of flame.When fire occurs, itself also easily causes secondary combustion while releasing amount of heat.Therefore, in the use of productive life, all need to carry out fire-retardant finish to PA6.
Polymeric amide-6 fire retardant conventional at present mainly contains 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 corrosive gases, nontoxic, and the features such as environmental friendliness, are widely used.Magnesium hydroxide is the topmost fire retardant of current polymeric amide-6, and its usage quantity has exceeded 50%.P-N type fire retardant, as a kind of novel halogen-free flame retardants, obtains 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 object.Nitrogen based flame retardant, mainly to form the non-flammable gases such as ammonia in decomposition course, dilutes and waters down inflammable gas or be covered in the effect of material surface and fire-retardant.Its major advantage is Halogen, low cigarette, be conducive to environment protection.Melamine cyanurate (MCA), as widely used a kind of nitrogenated flame retardant, in nylon, can play very excellent flame retardant properties.
Above-mentioned three kinds of flame resistant methods all can reach the object of halogen-free flame-retardant polyamide-6, but because at present P-N type fire retardant on the market and nitrogen based flame retardant are a micron fire retardant, its grain diameter is micron level, particle diameter is excessive, and good not with macromolecular material consistency, utilize its Flameproof polyamide-6 can cause the decline of mechanical property; And magnesium hydroxide flame retardant efficiency is not high, addition needs very large, and its mechanical property of meeting extreme influence, this strongly limits the usage space of polymeric amide-6.
Summary of the invention
For the deficiencies in the prior art, the invention provides one and utilize nano level melamine cyanurate (MCA) polymeric amide-6 to be carried out to the method for halogen-free flameproof.
A preparation method for nanometer halogen-free anti-flaming polymeric amide-6, is characterized in that, comprises the following steps:
First take polymeric amide-6 raw material of 100 weight parts, nano melamine cyanurate (MCA) halogen-free flame retardants of 2-20 weight part, the antioxidant of 0.1-10 weight part, and these raw materials are mixed; Then twin screw extruder is preheated to 185-280 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 100-400r/ min, carries out granulation namely obtain nanometer halogen-free anti-flaming polymeric amide-6 to product.
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] phosphorous acid ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2, 6-ditertbutylparacresol, N-cyclohexyl-p-ethoxyaniline, three (nonylated phenyl) phosphorous acid ester, N-sec.-propyl-4-aminodiphenylamine, N-secondary octyl 4-aminodiphenylamine, octylated diphenylamine, 4, 4-bis-(propyloxy phenyl base) pentanoic, butyraldehyde-n-aniline condensation thing, 2, 2-methylene-bis (4-methyl-6-tert-butylphenol), 1, 3, 5-(di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, one 5H) in triketone or its combination.
The advantage adopting method of the present invention to prepare halogen-free flame-retardant polyamide-6 is, because nano-meter flame retardants has larger surface-area, and the surface reaction activity of nanoparticle is more much bigger than micron particle, be compared to micron order MCA fire retardant conventional on the market, nanometer MCA fire retardant has higher flame retarding efficiency, add the flame retardant effect of 5 parts of nanometer MCA can to match in excellence or beauty the polymeric amide-6 of interpolation 10 parts of micron MCA, can reach low dose of fire-retardant, see Fig. 1; On the other hand, micron-sized MCA particle diameter is excessive and good not with the consistency of macromolecular material, the mechanical property of material can be had a strong impact on, and quantum size effect, small-size effect, surface effects etc. that nano particle has due to it, 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.
Embodiment
Further illustrate the present invention below by embodiment, instead of limit the scope of the invention.
Embodiment one:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 5 weight parts, the antioxidant of 0.1 weight part, and these raw materials are mixed.Then twin screw extruder is preheated to 240 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 200r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.
Embodiment two:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 7 weight parts, the antioxidant of 0.2 weight part, and these raw materials are mixed.Then twin screw extruder is preheated to 230 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 130r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.
Embodiment three:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 10 weight parts, the antioxidant of 0.5 weight part, and these raw materials are mixed.Then twin screw extruder is preheated to 220 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 250r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.
Embodiment four:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 3 weight parts, the antioxidant of 1 weight part, and these raw materials are mixed.Then twin screw extruder is preheated to 250 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 350r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.
Embodiment five:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 12 weight parts, the antioxidant of 2 weight parts, and these raw materials are mixed.Then twin screw extruder is preheated to 260 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 300r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.
Embodiment six:
First take polymeric amide-6 raw material of 100 weight parts, the nanometer MCA halogen-free flame retardants of 5 weight parts, the antioxidant of 0.1 weight part, and these raw materials are mixed.Then twin screw extruder is preheated to 235 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 120r/ min, product is carried out granulation and namely obtains halogen free nanometer Flameproof polyamide-6.

Claims (3)

1. a preparation method for nanometer halogen-free anti-flaming polymeric amide-6, is characterized in that, comprises the following steps:
First take polymeric amide-6 raw material of 100 weight parts, nano melamine cyanurate (MCA) halogen-free flame retardants of 2-20 weight part, the antioxidant of 0.1-10 weight part, and these raw materials are mixed; Then twin screw extruder is preheated to 185-280 DEG C, adds in twin screw extruder by the raw material mixed, controlling screw speed is 100-400r/ min, carries out granulation namely obtain nanometer halogen-free anti-flaming polymeric amide-6 to product.
2. the preparation method of nanometer halogen-free anti-flaming polymeric amide-6 according to claim 1, is characterized in that, described halogen-free flame retardants nano melamine cyanurate (MCA) is long 500-800nm, the rod-like nano particle of wide 100nm.
3. the preparation method of nanometer halogen-free anti-flaming polymeric amide-6 according to claim 1, it is characterized in that, described antioxidant is three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, 2, 6-ditertbutylparacresol, N-cyclohexyl-p-ethoxyaniline, three (nonylated phenyl) phosphorous acid ester, N-sec.-propyl-4-aminodiphenylamine, N-secondary octyl 4-aminodiphenylamine, octylated diphenylamine, 4, 4-bis-(propyloxy phenyl base) pentanoic, butyraldehyde-n-aniline condensation thing, 2, 2-methylene-bis (4-methyl-6-tert-butylphenol), 1, 3, 5-(di-tert-butyl-4-hydroxyl benzyl) guanamine, 4, 6-(1H, 3H, one 5H) in triketone or its combination.
CN201410453878.0A 2014-09-09 2014-09-09 The method of nanometer halogen-free anti-flaming polyamide-6 Expired - Fee Related CN104292818B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410453878.0A CN104292818B (en) 2014-09-09 2014-09-09 The method of nanometer halogen-free anti-flaming polyamide-6

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410453878.0A CN104292818B (en) 2014-09-09 2014-09-09 The method of nanometer halogen-free anti-flaming polyamide-6

Publications (2)

Publication Number Publication Date
CN104292818A true CN104292818A (en) 2015-01-21
CN104292818B CN104292818B (en) 2016-08-17

Family

ID=52312786

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410453878.0A Expired - Fee Related CN104292818B (en) 2014-09-09 2014-09-09 The method of nanometer halogen-free anti-flaming polyamide-6

Country Status (1)

Country Link
CN (1) CN104292818B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN114085520A (en) * 2021-11-30 2022-02-25 上海试四化学品有限公司 Modified high-flame-retardant-temperature nylon 66 and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
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)
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
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
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
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)
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
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
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨明山 等: "《塑料改性工艺、配方与应用》", 31 July 2006, article "聚乙烯的无机阻燃剂阻燃" *
辛忠: "《材料添加剂化学》", 31 January 2010, article "第2篇 材料加工添加剂" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN114085520A (en) * 2021-11-30 2022-02-25 上海试四化学品有限公司 Modified high-flame-retardant-temperature nylon 66 and preparation method thereof

Also Published As

Publication number Publication date
CN104292818B (en) 2016-08-17

Similar Documents

Publication Publication Date Title
CN101293983B (en) Expansion flame-proof polypropelene composition and preparation method thereof
CN110041612B (en) Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof
CN102134352B (en) Expansion type flame-retardant polypropylene composite material and preparation method thereof
CN101338201B (en) Organic-inorganic composite flame retardants with mesoporous molecular sieve and method for preparing same
CN101376727A (en) Expansion flame-retardant polypropylene / organic clay nano composite material and preparation
CN102604372B (en) Polyamide composite material with flame retardance and heat conduction and preparation method thereof
CN103087414A (en) Composite intumescent flame retardant inflaming retarding general polypropylene and preparation method thereof
CN103012904B (en) Halogen-free flame-retardant master batch
CN101759900B (en) Halogen-free flame-retardant and anti-static polyethylene material, pipe and preparing method thereof
CN105482349A (en) High temperature resistant halogen-free flame retardant ABS composition
CN102796319A (en) Expansion type flame-retardant polypropylene composition
CN102477184A (en) High-glossiness flame-retardant polypropylene composite and preparation method thereof
CN107304268A (en) A kind of anti-flaming polyolefin composition and preparation method thereof
CN103849039A (en) Nano flame retardant modified polyethylene composite material and preparation method thereof
CN104530587A (en) PVC composition specially used for high-rise buildings
CN103183901A (en) Housing material for halogen-free flame retardant storage battery and preparation method thereof
CN103102593A (en) Supported metal oxide catalytic synergistic inorganic flame retardant polypropylene composite material and preparation method thereof
CN103333423B (en) Compound flame-retardant polystyrene composition and preparation method thereof
CN105566811A (en) Composite halogen-free flame-retardant smoke suppression agent of PVC wood-plastic composite material and preparation method and application of agent
CN104292818A (en) Method of nano halogen-free flame retardant polyamide-6
CN102229719A (en) Nano mesoporous molecular sieve synergistic intumescent flame retardant flame-retardant polypropylene
CN102153811B (en) Polypropylene composite material with fire retardance and toughening performance
CN104086884A (en) Flame retardant polypropylene material and preparation method thereof
CN103849045A (en) Polyethylene inorganic nanometer flame retardant master batches and preparation method thereof
CN102585355B (en) A kind of dispersing method of halogen-free polypropylene flame redardant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160817

Termination date: 20190909