CN104448299A - In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof - Google Patents
In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104448299A CN104448299A CN201310438994.0A CN201310438994A CN104448299A CN 104448299 A CN104448299 A CN 104448299A CN 201310438994 A CN201310438994 A CN 201310438994A CN 104448299 A CN104448299 A CN 104448299A
- Authority
- CN
- China
- Prior art keywords
- retardant
- attapulgite
- halogen
- composite material
- free flame
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a nylon 6 composite material, particularly an in-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and a preparation method thereof. The preparation method comprises the following step: carrying out in-situ polymerization on modified attapulgite, halogen-free flame retardant salt and caprolactam until the attapulgite forms a uniform solution in the caprolactam melt, thereby obtaining the halogen-free flame-retardant nylon 6/attapulgite nano composite material. The attapulgite can be uniformly dispersed in the nylon 6 base. The composite material has the advantages of high oxygen barrier efficiency, low flame retardant consumption, low cost, high flame-retardant efficiency, high mechanical properties and the like, does not generate any toxic or harmful gas after being combusted, does not pollute the environment, and can be used for flame-retardant spinning or as an engineering plastic.
Description
Technical field
The present invention relates to a kind of nylon 6 composite material, particularly one adopts in-situ polymerization halogen-free flame-retardant nylon 6/attapulgite clay nano composite material and preparation method thereof.
Background technology
Attapulgite is a kind of mineral being rich in magnalium, and its crystal theoretical chemical formula is (Mg, Al, Fe)
5si
8o
20(OH)
2(OH
2) 4H
2o.Attapulgite has the chain laminate structure of 2:1, its crystallization is needle-like, fibrous agrregate, the brilliant diameter of single fiber is at about 20nm, length can reach 1um, the chain laminate structure had is different from the layered silicates such as attapulgite, and this special structure gives the physical and chemical performances such as the absorption of attapulgite uniqueness, colloid, filling and anti-salt.Add a small amount of attapulgite in polymkeric substance and have good reinforced effects, in document " Attapulgite Filled Rigid PVC Plastics ", the interpolation of attapulgite can improve the flame retardant properties of polyvinyl chloride well.
Nylon 6 is fire-retardant to be realized mainly through two kinds of approach: use additive flame retardant and use reactive flame retardant.No matter be reactive flame retardant, or additive flame retardant, in raising polymer materials flame retardant resistance simultaneously, also other negative impacts can be produced to material itself and environment.As the amount of being fuming when reactive flame retardant can increase considerably material combustion, after material scrap, environmental pollution can be caused in natural circulation; Additive flame retardant usage quantity large (sometimes up to 50% ~ 60%), and due to its two-phase interface polarity difference, cause the mechanical property of material own significantly to decline, thus significantly limit the use range of material.Therefore, the novel flame redundant material meeting fire safety evaluating and environmental requirement is researched and developed significant.
Mainly by adding in nylon, inorganic combustion inhibitor or halogenated flame retardant realize current business-like fire-retardant nylon.As Chinese patent application CN102888095A name is called halogen-free reinforced nylon manufacture craft, the preparation of low temperature resistant halogen-free flame retardant nylon composite material is called with Chinese patent application CN101967277A name, fire retardant is made an addition in melted nylon particle, adopt twin screw extruder to prepare fire-retardant nylon material, make it obtain flame retardant resistance.Adopt fire-retardant Nylon 6 prepared by these class methods, the flame retardant amount added is large, cost is high, fine fire retardant is easily reunited and is formed focal point of stress in the course of processing, add that nylon 6 particle is through screw rod secondary processing degradation simultaneously, the purer nylon 6 of mechanical property of fire-retardant Nylon 6 declines greatly, can only be used for plastic industry; And during the burning of halogen system fire-retardant nylon, there is poisonous, obnoxious flavour release and problem of environmental pollution, forbidden in many developed countries.Also some reactive flame retardants are had, as Chinese patent application CN101450993A name is called that a kind of preparation method of halogen-free flame-retardant nylon 6 and Chinese patent application CN102675630A name are called a kind of preparation method of halogen-free flame-retardant nylon 6, with regard to single reaction type fire retardant in-situ polymerization, the main chain or the side chain that are attached to polymeric amide get on, make polymeric amide itself have flame-retardant composition, excellent flame retardant effect can not be reached.Chinese patent application CN201110363763.9, name is called that a kind of halogen-free flame-retardant long glass fiber reinforced nylon 6 and preparation method thereof discloses a kind of fire-retardant Nylon 6/attapulgite fire retardant material, attapulgite and nylon 6 are adopted the mode of blending extrusion, attapulgite can not good distribution in polymeric amide, material mechanical performance reduces, and is only applicable to engineering plastics.
Being undertaken composite by multiple inorganic and organic fire-retardant, while enhancing flame retardant effect, meet the requirement of environmental protection, reduce amount of flame-retardant agent, is a kind of efficient and lower-cost method.In recent years, along with the exploitation of the fire retardant of Halogen hypotoxicity, low flue dust, few additive, anti-dripping melt, the continuous reduction of nylon 6 cost and the release of cheap attapulgite resource and the fire-retardant polyamide fibre technique of applicable manufacture in addition, nylon 6 is flame-retarded will be increasingly universal.
Summary of the invention
The object of the invention is to solve that existing amount of flame-retardant agent is large, flame retardant effect is poor, the amount of being fuming large and high in cost of production technological difficulties, and provide that a kind of attapulgite and organic fire-retardant cooperative flame retardant, amount of flame-retardant agent are few, the preparation method of halogen-free flame-retardant nylon 6/attapulgite clay nano composite material that good flame retardation effect, fire-retardant life-span are long.
The technical scheme realizing the object of the invention is: a kind of halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, comprises the component of following mass parts:
Halogen-free flame-retardant nylon 6/attapulgite clay nano composite material of the present invention, preferably includes the component of following mass parts:
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, preferred described halogen-free flame retardants is organophosphorus system reactive flame retardant.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, preferred organophosphorus system reactive flame retardant is 2-carboxyethyl phenyl Hypophosporous Acid, 50 or two (p-carboxyphenyl) phenyl phosphine oxide.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, preferred described attapulgite modified nanoparticle is the attapulgite nano-particle through silane coupler modified process.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, preferred described silane coupling agent is a kind of in aminopropyl trimethoxysilane, aminopropyl triethoxysilane, phenylaminomethyl triethoxyl silane, phenylaminomethyl Trimethoxy silane or aminoethylaminopropyl Trimethoxy silane.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, described char-forming agent is a kind of in tetramethylolmethane, N.F,USP MANNITOL, sorbyl alcohol; Described charing promotor is wolframic acid or phospho-wolframic acid.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material preparation method, preferred described preparation method for by attapulgite modified with halogen-free flame retardants salt and hexanolactam in-situ polymerization, attapulgite is scattered in the nylon 6 containing fire retardant with nanoparticle morphology, and the molecular formula of described fire-retardant Nylon 6 is:
described x=1-200; Y=1-100.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material preparation method, comprises the steps: that (1) prepares halogen-free flame retardants salt; (2) attapulgite modified by silane coupling agent nanoparticle is used; (3) be 5-100 part hexanolactam by weight part, weight part is that 1-20 part water adds in reactor and is heated to 80-100 DEG C, vacuum hydro-extraction, more preferably secondary vacuum dehydration is carried out, namely 140 DEG C are reheated, continue vacuum hydro-extraction, to dewater rear releasing vacuum, added modified Nano attapulgite that weight part is 0.5-10 part, fire retardant salt that weight part is 1-15 part, weight part be the char-forming agent of 0.5-5 part and the charing promotor of 0.01-1 part, be stirred under air-proof condition and form uniform solution.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 3-5 time, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 1-2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 1-2h further, finally vacuumize 0.5-1h, reaction completes, and supplements nitrogen or rare gas element when discharging;
Described step (1) halogen-free flame retardants salt production process is: be dissolved in DMF by halogen-free flame retardants and hexanediamine, keeps water temperature 50-55 DEG C to react 3-5h, then cool, filter, obtain through absolute ethanol washing in thermostat water bath.
Above-mentioned halogen-free flame-retardant nylon 6/attapulgite clay nano composite material preparation method, wherein attapulgite has the natural hydration zeopan of special bar-shaped, needle-shaped crystal structure, its microtexture comprises three level (1) excellent crystalline substance-ATP basic structural units, and long 1 μm, diameter is about 20nm; (2) the brilliant bundle of rod-formed by the rod crystalline substance gathering that countless tight is parallel; (3) aggregate-formed by the brilliant bundle of rod mutual gathering.Attapulgite has hydrophilic oleophobic properties as inorganic mineral, and specific surface area is large, easily reunites, and its surface, containing a large amount of polarity silicone hydroxyl and negative charge, is easy to modification; Preferred described step (2) is prepared attapulgite modified method and is: be dispersed in 5-250 parts by weight of toluene by 1 parts by weight of deionized water and 3-100 weight part nano-attapulgite, add 0.5-25 weight part containing amino silicane coupling agent, ultrasonic disperse 1-2h forms mixture; This mixture in mechanical stirring situation temperature 45-50 DEG C reaction 5 hours, wash drying and screening afterwards, obtain attapulgite modified.
The amide group (-CONH-) contained in the fire retardant salt that the present invention adopts, becomes at caprolactam polymerization in the process of nylon 6 and adds, can form fire retardant material, again due to the reactive group (-NH in molecule with better consistency and prepolymer
2), can polyreaction be carried out with hexanolactam and ignition-proof element (Si, P etc.) be introduced in polymkeric substance, thus reach permanent flame retardant effect.And have the attapulgite modified of amino group can be interconnected mainly through hydrogen bond with fire-retardant Nylon 6, because attapulgite is through surface modification, there is decorative layer on surface, and therefore attapulgite's surface decorative layer can be wound around mutually with fire-retardant Nylon 6, forms flexible interface layer.On the one hand, under stress, flexible interface layer plays a part to absorb crack growing ability and weaken crack to increase, and on the other hand, the relaxation property of interfacial layer, can eliminate the stress concentration of interface zone and reduce internal stress.Thus improve tensile strength, the toughness and moisture resistance etc. of matrix material simultaneously.
Fire-retardant principle: the present invention's fire retardant used is phosphorus system compounds, belong to expansion reaction type fire retardant, this reactive flame retardant can embed in base material in copolymerization mode and give base material with flame retardant resistance.The effect of fire retardant suppresses the generation of one or more component of combustion to reach the object stoping or slow down burning, it is fire-retardant that fire retardant mechanism of the present invention belongs to condensed phase, the Surface Creation porous carbon layer when burning, this carbon-coating difficulty combustion, heat insulation, oxygen barrier, combustible gas can be stoped again to enter burning gas phase, cause flameout.In combustion processes, thermal-oxidative degradation reaction all should mainly from intrinsic silicon, in nano composite material clay particle good distribution can trap heat from exterior conductive to intrinsic silicon, thus reduction heat conduction velocity.In addition, the blocking effect of nano composite material also can suppress thermal degradation products from the volatilization of interior.Nano composite material adds an oxygen enters into polymeric matrix inside passage from outside in addition, shown in arrow as thick in black in Fig. 1.Fully decentralized clay particle can to oxygen by produce blocking effect; Simultaneously the burn carbon-coating that formed and nano-attapulgite combines and forms finer and close layer of charcoal, is more conducive to the thermal conduction between barrier polymer and thermal source.
Halogen-free flame-retardant nylon 6/attapulgite clay nano composite material prepared by the present invention has fire-retardant and smoke-suppressing good, weather resistance is high, stable mechanical property, nontoxic and features such as good spinnability.
The present invention has positive effect: what (1) the present invention adopted is that the method for in-situ polymerization prepares halogen-free flame-retardant nylon 6/attapulgite clay nano composite material, fundamental difference is in the fire-retardant nylon of twin screw blending extrusion, between the fire retardant of anti-flaming nano composite material of preparation and nylon monomer chemical bond and, therefore flame retardant effect keeps good lasting.This anti-flaming nano composite material fire-retardant life-span is longer than twin screw blending extrusion fire retardant material, can not separate out fire retardant.And nano material good dispersity, be more conducive to spinning.
(2) addition that flame-proof composite material of the present invention has efficient oxygen barrier, amount of flame-retardant agent is less than twin screw blending extrusion, cost is low, flame retarding efficiency is high, mechanical property advantages of higher, does not produce poisonous, obnoxious flavour after burning, free from environmental pollution.Due to adding of organic attapulgite, the layer of charcoal combined barrier air formed after the chain laminate structure of its uniqueness and char-forming agent burn and the contact of nylon 6, play the effect of cooperative flame retardant.
(3) flame-proof composite material of the present invention adopts reactive flame retardant and attapulgite modified, and reactive flame retardant can embed in Nylon 6 Chains section, and attapulgite's surface decorative layer can be wound around mutually with fire-retardant Nylon 6, forms flexible interface layer.This flexible interface layer can alleviate the stress concentration that attapulgite adds nylon 6 to, maintains the original mechanical property of nylon, can spinning or as engineering plastics; Especially in nano composite material, attapulgite is more conducive to the oriented crystalline of material in drawing process, and the tensile strength for spinning can improve a lot.
(4) preparation technology of the present invention is easy, can polymeric kettle be utilized fully to be polymerized, and is convenient to produce, and can easily realize industrialization.
Accompanying drawing explanation
In order to make content of the present invention more easily be clearly understood, below according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is that flame retardant effect heat of the present invention intercepts schematic diagram.
Embodiment
(embodiment 1)
The preparation of step one, attapulgite modified nanoparticle
1 parts by weight of deionized water and 5 weight part nano-attapulgites are dispersed in 100 parts by weight of toluene, add 4 weight part aminopropyl trimethoxysilane, ultrasonic disperse 1h forms mixture; This mixture temperature 50 C in mechanical stirring situation reacts 5 hours, washs drying and screening afterwards, obtains attapulgite modified.Reaction equation is:
The preparation of step 2, fire retardant salt
Halogen-free flame retardants preparation method is: weight part 10 parts of 2-carboxyethyl phenyl Hypophosporous Acid, 50 and weight part 5 parts of hexanediamines are dissolved in N, in dinethylformamide, keep water temperature 55 DEG C to react 3-5h in thermostat water bath, then cool, filter, obtain through absolute ethanol washing.Reaction equation is:
The preparation of step 3, flame-proof composite material
Be 83.95 parts of hexanolactams by weight part, weight part is that 5 parts of deionized waters add in reactor and are heated to 100 DEG C, vacuum hydro-extraction, to dewater rear releasing vacuum, to add weight part be modified Nano attapulgite, the weight part of 1 part be fire retardant salt, the weight part of 9 parts is the tetramethylolmethane of 1 part and the wolframic acid of 0.05 part, is stirred to and forms uniform solution under air-proof condition.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 3-5 time, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 2h further, finally vacuumize 0.5h, reaction completes, and supplements nitrogen or rare gas element when discharging.Reaction equation
(embodiment 2)
The preparation of step one, attapulgite modified nanoparticle
1 parts by weight of deionized water and 5 weight part nano-attapulgites are dispersed in 100 parts by weight of toluene, add 4 weight part aminopropyl triethoxysilanes, ultrasonic disperse 1h forms mixture; This mixture temperature 50 C in mechanical stirring situation reacts 5 hours, washs drying and screening afterwards, obtains attapulgite modified.
The preparation of step 2, fire retardant salt
Halogen-free flame retardants preparation method is: two for weight part 4 parts (p-carboxyphenyl) phenyl phosphine oxide and weight part 2 parts of hexanediamines are dissolved in N, in dinethylformamide, keep water temperature 55 DEG C to react 3-5h in thermostat water bath, then cool, filter, obtain through absolute ethanol washing.
The preparation of step 3, flame-proof composite material
Be 84 parts of hexanolactams by weight part, weight part is that 5 parts of deionized waters add in reactor and are heated to the complete rear releasing vacuum of 80 dehydration, to add weight part be modified Nano attapulgite, the weight part of 3 parts be fire retardant salt, the weight part of 4 parts is the tetramethylolmethane of 1 part and the wolframic acid of 0.01 part, is stirred to and forms uniform solution under air-proof condition.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 4 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 2h further, finally vacuumize 0.5h, reaction completes, and supplements nitrogen or rare gas element when discharging.
(embodiment 3)
The preparation of step one, attapulgite modified nanoparticle
1 parts by weight of deionized water and 5 weight part nano-attapulgites are dispersed in 100 parts by weight of toluene, add 4 weight part phenylaminomethyl triethoxyl silanes, ultrasonic disperse 1h forms mixture; This mixture temperature 50 C in mechanical stirring situation reacts 5 hours, washs drying and screening afterwards, obtains attapulgite modified.
The preparation of step 2, fire retardant salt
Halogen-free flame retardants preparation method is: weight part 15 parts of 2-carboxyethyl phenyl Hypophosporous Acid, 50 and weight part 5 parts of hexanediamines are dissolved in N, in dinethylformamide, keep water temperature 55 DEG C to react 3-5h in thermostat water bath, then cool, filter, obtain through absolute ethanol washing.
The preparation of step 3, flame-proof composite material
Be 90 parts of hexanolactams by weight part, weight part is that 5 parts of deionized waters add in reactor and are heated to 90 DEG C, vacuum hydro-extraction, post-heating is to 140 DEG C, continue vacuum hydro-extraction, to dewater rear releasing vacuum, to add weight part be modified Nano attapulgite, the weight part of 3 parts be fire retardant salt, the weight part of 6 parts is the tetramethylolmethane of 1 part and the wolframic acid of 0.05 part, is stirred to and forms uniform solution under air-proof condition.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 4 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 2h further, finally vacuumize 0.5h, reaction completes, and supplements nitrogen or rare gas element when discharging.
(embodiment 4)
The preparation of step one, attapulgite modified nanoparticle
1 parts by weight of deionized water and 5 weight part nano-attapulgites are dispersed in 100 parts by weight of toluene, add 4 weight part phenylaminomethyl Trimethoxy silanes, ultrasonic disperse 1h forms mixture; This mixture temperature 50 C in mechanical stirring situation reacts 5 hours, washs drying and screening afterwards, obtains attapulgite modified.
The preparation of step 2, fire retardant salt
Halogen-free flame retardants preparation method is: weight part 10 parts of 2-carboxyethyl phenyl Hypophosporous Acid, 50 and weight part 5 parts of hexanediamines are dissolved in N, in dinethylformamide, keep water temperature 55 DEG C to react 3-5h in thermostat water bath, then cool, filter, obtain through absolute ethanol washing.
The preparation of step 3, flame-proof composite material
Be 84.95 parts of hexanolactams by weight part, weight part is that 5 parts of deionized waters add in reactor and are heated to 80-100 DEG C, vacuum hydro-extraction, post-heating is to 140 DEG C, continue vacuum hydro-extraction, to dewater rear releasing vacuum, to add weight part be modified Nano attapulgite, the weight part of 4 parts be fire retardant salt, the weight part of 5 parts is the tetramethylolmethane of 1 part and the wolframic acid of 0.05 part, is stirred to and forms uniform solution under air-proof condition.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 4 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 2h further, finally vacuumize 0.5h, reaction completes, and supplements nitrogen or rare gas element when discharging.
(embodiment 5)
The preparation of step one, attapulgite modified nanoparticle
1 parts by weight of deionized water and 5 weight part nano-attapulgites are dispersed in 100 parts by weight of toluene, add 4 weight part aminoethylaminopropyl Trimethoxy silanes, ultrasonic disperse 1h forms mixture; This mixture temperature 50 C in mechanical stirring situation reacts 5 hours, washs drying and screening afterwards, obtains attapulgite modified.
The preparation of step 2, fire retardant salt
Halogen-free flame retardants preparation method is: weight part 10 parts of 2-carboxyethyl phenyl Hypophosporous Acid, 50 and weight part 5 parts of hexanediamines are dissolved in N, in dinethylformamide, keep water temperature 55 DEG C to react 3-5h in thermostat water bath, then cool, filter, obtain through absolute ethanol washing.
The preparation of step 3, flame-proof composite material
Be 74 parts of hexanolactams by weight part, weight part is that 5 parts of deionized waters add in reactor and are heated to 80-100 DEG C, vacuum hydro-extraction, post-heating is to 140 DEG C, continue vacuum hydro-extraction, to dewater rear releasing vacuum, to add weight part be modified Nano attapulgite, the weight part of 5 parts be fire retardant salt, the weight part of 4 parts is the tetramethylolmethane of 0.2 part and the wolframic acid of 0.05 part, is stirred to and forms uniform solution under air-proof condition.Between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 4 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 2h under spontaneous pressure, slowly be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 2h further, finally vacuumize 0.5h, reaction completes, and supplements nitrogen or rare gas element when discharging.
In order to investigate the effect of halogen-free flame-retardant nylon 6/attapulgite clay nano composite material mechanical property prepared by the present invention and flame retardant resistance, to the halogen-free flame-retardant nylon 6/attapulgite clay nano composite material prepared by above-described embodiment, carried out tensile strength by GB/T1040-2006 standard respectively with pure nylon 6, carried out notched Izod impact strength by GB/T1843-1996 standard, carried out limiting oxygen index(LOI) by GB/T2406-1993 standard, carried out vertical combustion test by ASTMD3801 standard, test result sees the following form one respectively.
Table one
Halogen-free flame-retardant nylon 6/attapulgite clay nano composite material section flame retardant properties prepared by the inventive method reaches UL94V0 rank, and fire retardant and polymeric amide form fire-retardant macromolecular chain.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. halogen-free flame-retardant nylon 6/attapulgite clay nano composite material of in-situ polymerization, comprises the component of following mass parts:
2. halogen-free flame-retardant nylon 6/the attapulgite clay nano composite material of in-situ polymerization according to claim 1, is characterized in that: the component with following mass parts:
3. halogen-free flame-retardant nylon 6/the attapulgite clay nano composite material of in-situ polymerization according to claim 1 and 2, is characterized in that: described halogen-free flame retardants is organophosphorus system reactive flame retardant.
4. halogen-free flame-retardant nylon 6/the attapulgite clay nano composite material of in-situ polymerization according to claim 3, is characterized in that: organophosphorus system reactive flame retardant is 2-carboxyethyl phenyl Hypophosporous Acid, 50 or two (p-carboxyphenyl) phenyl phosphine oxide.
5. halogen-free flame-retardant nylon 6/the attapulgite clay nano composite material of in-situ polymerization according to claim 1 and 2, is characterized in that: described attapulgite modified nanoparticle is the attapulgite nano-particle through silane coupler modified process.
6. halogen-free flame-retardant nylon 6/the attapulgite clay nano composite material of in-situ polymerization according to claim 1 and 2, is characterized in that: described char-forming agent is a kind of in tetramethylolmethane, N.F,USP MANNITOL, sorbyl alcohol; Described charing promotor is wolframic acid or phospho-wolframic acid.
7. as described in as arbitrary in claim 1 ~ 6, the preparation method of the halogen-free flame-retardant nylon 6/attapulgite clay nano composite material of in-situ polymerization, comprises the steps: that (1) prepares halogen-free flame retardants salt, (2) attapulgite modified by silane coupling agent nanoparticle is used, (3) by weight part be 5-100 part hexanolactam, weight part is that 1-20 part deionized water adds in reactor and is heated to 80-100 DEG C, vacuum hydro-extraction, to dewater rear releasing vacuum, add the modified Nano attapulgite that weight part is 0.5-10 part, weight part is the fire retardant salt of 1-15 part, weight part is the char-forming agent of 0.5-5 part and the charing promotor of 0.01-1 part, be stirred under air-proof condition and form uniform solution, between adjust ph to 7.3-7.7, said mixture is put into stirring-type reactor air-discharging 3-5 time, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping 1-2h under spontaneous pressure, be decompressed to environmental stress, be heated to 260-280 DEG C simultaneously and react 1-2h further, finally vacuumize, reaction completes, discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310438994.0A CN104448299A (en) | 2013-09-24 | 2013-09-24 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310438994.0A CN104448299A (en) | 2013-09-24 | 2013-09-24 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104448299A true CN104448299A (en) | 2015-03-25 |
Family
ID=52895096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310438994.0A Pending CN104448299A (en) | 2013-09-24 | 2013-09-24 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104448299A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778438A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Stable type pbt material and preparation method thereof |
| CN105778437A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Composite silicon modified pbt material and preparing method thereof |
| CN105778440A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Environment-friendly pbt material and preparing method thereof |
| CN105778439A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Phosphorized pbt material and preparation method thereof |
| CN105778441A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Heat-preservation pbt material and preparing method thereof |
| CN105802150A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Hydrophobic anti-leakage pbt material and preparation method thereof |
| CN105802148A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material and preparation method thereof |
| CN105802147A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Flame-retardant pbt material and preparation method thereof |
| CN105802149A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Fiber-containing flexible pbt material and preparation method thereof |
| CN105802151A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material for roaster shell and preparation method of pbt mateiral |
| CN105838043A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Attapulgite-modified pbt material and preparation method thereof |
| CN105838042A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Insulating pbt material used for electronic equipment and preparation method thereof |
| CN105838041A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Composite calcareous pbt material and preparation method thereof |
| CN105860454A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Anti-oxidant pbt material and preparation method thereof |
| CN105860450A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Zinc oxide loaded pbt material and preparation method thereof |
| CN105860448A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Pbt material for automobile exterior part and preparing method thereof |
| CN105860452A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antimicrobial pbt material and preparation method thereof |
| CN105860451A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antistatic pbt material and preparation method thereof |
| CN105860453A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Outdoor sunlight-resistant pbt material and preparation method thereof |
| WO2017021355A1 (en) * | 2015-07-31 | 2017-02-09 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Flame-resistant polyamide as reaction product of a lactam, and method for the production and use thereof |
| CN112079601A (en) * | 2020-08-07 | 2020-12-15 | 安徽建筑大学 | Flame-retardant thermal insulation mortar for building construction and preparation method thereof |
| CN113087970A (en) * | 2020-01-08 | 2021-07-09 | 中国石油化工股份有限公司 | Halogen-free flame retardant and application thereof in preparation of halogen-free flame retardant PA6 |
| CN114702820A (en) * | 2022-04-02 | 2022-07-05 | 江苏扬农化工集团有限公司 | Natural mineral modified nylon composite material and preparation method thereof |
-
2013
- 2013-09-24 CN CN201310438994.0A patent/CN104448299A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017021355A1 (en) * | 2015-07-31 | 2017-02-09 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Flame-resistant polyamide as reaction product of a lactam, and method for the production and use thereof |
| CN105838041A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Composite calcareous pbt material and preparation method thereof |
| CN105802150A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Hydrophobic anti-leakage pbt material and preparation method thereof |
| CN105860454A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Anti-oxidant pbt material and preparation method thereof |
| CN105778441A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Heat-preservation pbt material and preparing method thereof |
| CN105860450A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Zinc oxide loaded pbt material and preparation method thereof |
| CN105802148A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material and preparation method thereof |
| CN105802147A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Flame-retardant pbt material and preparation method thereof |
| CN105860448A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Pbt material for automobile exterior part and preparing method thereof |
| CN105802151A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material for roaster shell and preparation method of pbt mateiral |
| CN105838043A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Attapulgite-modified pbt material and preparation method thereof |
| CN105838042A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Insulating pbt material used for electronic equipment and preparation method thereof |
| CN105778438A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Stable type pbt material and preparation method thereof |
| CN105778439A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Phosphorized pbt material and preparation method thereof |
| CN105778440A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Environment-friendly pbt material and preparing method thereof |
| CN105802149A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Fiber-containing flexible pbt material and preparation method thereof |
| CN105860452A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antimicrobial pbt material and preparation method thereof |
| CN105860451A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antistatic pbt material and preparation method thereof |
| CN105860453A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Outdoor sunlight-resistant pbt material and preparation method thereof |
| CN105778437A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Composite silicon modified pbt material and preparing method thereof |
| CN113087970A (en) * | 2020-01-08 | 2021-07-09 | 中国石油化工股份有限公司 | Halogen-free flame retardant and application thereof in preparation of halogen-free flame retardant PA6 |
| CN113087970B (en) * | 2020-01-08 | 2024-01-30 | 中国石油化工股份有限公司 | Halogen-free flame retardant and application thereof in preparation of halogen-free flame retardant PA6 |
| CN112079601A (en) * | 2020-08-07 | 2020-12-15 | 安徽建筑大学 | Flame-retardant thermal insulation mortar for building construction and preparation method thereof |
| CN112079601B (en) * | 2020-08-07 | 2022-07-29 | 广西德善新型科技材料有限公司 | Flame-retardant thermal insulation mortar for building construction and preparation method thereof |
| CN114702820A (en) * | 2022-04-02 | 2022-07-05 | 江苏扬农化工集团有限公司 | Natural mineral modified nylon composite material and preparation method thereof |
| CN114702820B (en) * | 2022-04-02 | 2023-08-08 | 江苏扬农化工集团有限公司 | Natural mineral modified nylon composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448299A (en) | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof | |
| CN102174247A (en) | Halogen-free flame retardant glass fiber reinforced polyester composite and preparation method thereof | |
| CN106832504A (en) | A kind of Graphene modified poly ethylene flame-proof composite material and preparation method thereof | |
| CN104211955A (en) | Halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and preparation method thereof | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN107936410A (en) | A kind of halogen-free flame-retardant wood-plastic composite material and preparation method thereof | |
| CN107868255A (en) | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification | |
| CN106497036A (en) | A kind of organophosphors system copolymerization flame-retardant polyamide composition and preparation method thereof | |
| CN103396600B (en) | High-performance is containing organosilicon non halogen flame retardant polyolefin composite | |
| CN1876730A (en) | Composite modifier surface modified brucite powder preparation method | |
| CN104448830A (en) | Phosphorus-silicon composite flame retardant as well as preparation method and application thereof | |
| CN106496550A (en) | A kind of organophosphors system fire-resistant copolyesters nylon composite and preparation method thereof | |
| CN109988407A (en) | A kind of highly effective flame-retardant makrolon material and preparation method thereof | |
| CN108203519A (en) | Alpha zirconium phosphate modified flame-retardant agent and its preparation method and application | |
| Huang et al. | Flame retardant polypropylene with a single molecule intumescent flame retardant based on chitosan | |
| CN105524301B (en) | A kind of preparation method of microencapsulation basic zirconium phosphate and the halogen-free flame retardant PC being made from it | |
| CN105907087A (en) | Flame retardant nylon material and preparation method thereof | |
| CN1793271A (en) | Single component mildew-proof flame retarded organic silicon sealing agent for machinery and preparation process thereof | |
| CN111690171A (en) | Flame retardant and flame-retardant PC plastic | |
| CN110819128A (en) | High-performance flame-retardant asphalt and preparation method thereof | |
| CN107216650A (en) | A kind of long glass fiber reinforced halogen-free reinforced nylon compound and preparation method thereof | |
| CN102382439B (en) | Modified polycarbonate and preparation method thereof | |
| CN109280259A (en) | A kind of distribution regulation is added with the EVA/PA6 flame retardant composite material and preparation method of OMMT | |
| CN109912842A (en) | A kind of preparation and application of efficient microcapsules composite flame-retardant agent | |
| CN105504802A (en) | Organic magnesium lithium silicate-nylon 6 composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
| RJ01 | Rejection of invention patent application after publication |