CN104211955A - Halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and preparation method thereof - Google Patents
Halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and preparation method thereof Download PDFInfo
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- CN104211955A CN104211955A CN201310210839.3A CN201310210839A CN104211955A CN 104211955 A CN104211955 A CN 104211955A CN 201310210839 A CN201310210839 A CN 201310210839A CN 104211955 A CN104211955 A CN 104211955A
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Abstract
The invention relates to a nylon 6 composite material, and especially relates to a halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and a preparation method thereof. The preparation method comprises the following steps: modified organo montmorillonite is subjected to in situ polymerization with a halogen-free fire-retardant salt and caprolactam, and dispersed in the nylon 6 containing a fire retardant with a nano particles form. The flame-retardation composite material has the advantages of high efficiency oxygen permeability, less fire retardant amount, low cost, high flame retardation efficiency and high mechanical property. The halogen-free flame-retardation nylon 6 montmorillonite nanocomposite has the advantages of no toxicity, no harmful gas and no environment pollution after being combusted. Due to addition of organo montmorillonite, a unique lamellar and a char forming agent are combusted to form a charcoal layer to obstruct the contact of air and nylon 6, so that flame retardant synergism is realized.
Description
Technical field
The present invention relates to a kind of nylon 6 composite material, particularly a kind of halogen-free flame-retardant nylon 6/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.
Background technology
Nylon 6, it is the macromolecular compound containing amide group on main chain, the overall merit such as have that fusing point is high, wear resistance good, erosion resistance is strong and processing characteristics is excellent, is widely used in and makes tricot, tire cord, filter cloth, rope, fishnet, trolley part and wrapping material etc.But nylon 6 fiber belongs to meltbility combustible fibre, limiting oxygen index(LOI) (LOI) is about 21, along with the widespread use of fabric, the potentially dangerous of its fire also becomes increasingly conspicuous, in addition nylon 6 fabric burning easily forms melting, molten drop easily brings the secondary injury comprising and scald and wait, and therefore and anti-dropping modification fire-retardant to nylon 6 fiber has become the focus of research at present.
Mainly by adding in nylon, inorganic combustion inhibitor or halogenated flame retardant realize current business-like fire-retardant nylon.As in patent CN102453324A and CN101955659A, fire retardant is made an addition in melted nylon particle, twin screw extruder is adopted to prepare fire-retardant nylon material, nylon all receives impact to a certain degree in spinning property and mechanical property, be unfavorable for spinning, and the flame retardant amount added is large, cost is high; And during the burning of halogen system fire-retardant nylon, there is poisonous, obnoxious flavour release and problem of environmental pollution.Also some reactive flame retardants are had, as patent CN101450993A and CN102675630A, with regard to single reaction type fire retardant in-situ polymerization, fire retardant participates in reaction as reaction monomers, the main chain or the side chain that are attached to polymeric amide get on, and make polymeric amide itself have flame-retardant composition.But only use single reactive flame retardant to carry out copolymerization, excellent flame retardant effect can not be reached.Document " the preparation and property research of halogen-free flame-proof nylon 66 having/Nano composite material of montmorillonite " adopts single polynite, and the relatively pure nylon66 fiber of fire retardant material oxygen index improves little, and monomer nylon salt cost is relatively high.
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 polynite 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, burning drippage and high in cost of production technological difficulties, and provide that a kind of nano imvite cooperative flame retardant, amount of flame-retardant agent are few, the preparation method of good flame retardation effect and the low halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite of cost.
The technical scheme realizing the object of the invention is: a kind of halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, comprises the component of following mass parts:
Halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite of the present invention, preferably includes the component of following mass parts:
Above-mentioned halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, preferred described halogen-free flame retardants is organophosphorus system reactive flame retardant.
Above-mentioned halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, 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/Nano composite material of montmorillonite, preferred described modified organo montmorillonite nanoparticle is the organic montmorillonite nano particle through the process of enlargement layer spacing.
Above-mentioned halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, preferred described chain alkyl bromide is a kind of in tetradecyl triphenylphosphinebromide, hexadecyl tributyl phosphonium phosphine, hexadecyl triphenylphosphinebromide.
Above-mentioned halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, 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/Nano composite material of montmorillonite preparation method, preferred described preparation method is by modified organo montmorillonite and halogen-free flame retardants salt and hexanolactam in-situ polymerization, synthesis is scattered in the nylon 6 containing fire retardant with nanoparticle morphology, and the described molecular formula containing fire retardant nylon 6 is:
described X=1-200; Y=1-100.
Above-mentioned halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite preparation method, comprises the steps: that (1) prepares halogen-free flame retardants salt, (2) with cation exchange method modified organo montmorillonite nanoparticle, (3) by halogen-free flame retardants salt, organic montmorillonite nano particle, hexanolactam is mixed into mixture, then char-forming agent is added, charing promotor, then deionized water is added, between adjust ph to 7.3-7.7, above-mentioned aqueous 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, nitrogen or rare gas element is supplemented 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 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/Nano composite material of montmorillonite preparation method, the preparation method of preferred described step (2) modified organo montmorillonite nanoparticle: 5-100 weight part nano imvite is dispersed in mechanical stirring in 5-250 weight parts water, form stable suspension, add 0.05-25 weight part chain alkyl bromide and stir washing drying in 0.3-10 hour at 25-110 DEG C, obtain the organic nano imvite expanding layer.
The amide group (-CONH-) contained in the fire retardant 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 the monomer of polymkeric substance and ignition-proof element be introduced in polymkeric substance, thus reach permanent flame retardant effect.In addition organo montmorillonite improves its charring rate to a certain extent, organo montmorillonite layer of charcoal moves to nylon 6 layer of charcoal surface, the two combines and forms finer and close layer of charcoal, more be conducive to the thermal conduction between barrier polymer and thermal source, modified organo montmorillonite has good dispersiveness in the polymer simultaneously, montmorillonite layer structure is made to form good labyrinth effect, make to move towards roundabout by gas, external oxygen can be effectively stoped to be diffused into uncracked polymer surfaces, when burning can not get enough heat energy and oxygen, the polymkeric substance of burning just can put out certainly, thus polynite and fire retardant acting in conjunction reach good cooperative flame retardant effect.Halogen-free flame-retardant nylon 6 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 adopts a kind of chain alkyl bromide containing phosphine for expanding a layer organo montmorillonite, compares cetyl trimethylammonium bromide generally.Difference expands interlamellar spacing more greatly on the one hand, and make polynite through cationic exchange containing phosphine, finally increases matrix material and increase its flame retardant effect containing phosphine amount.
The present invention has positive effect: (1) flame-proof composite material of the present invention has efficient oxygen barrier, amount of flame-retardant agent is few, 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 organo montmorillonite, the layer of charcoal combined barrier air formed after the laminar structured and char-forming agent of its uniqueness burns and the contact of nylon 6, play the effect of cooperative flame retardant.
(2) flame-proof composite material of the present invention is owing to adopting reactive flame retardant, then uses nano imvite intercalation polymeric, maintains the original mechanical property of nylon, can spinning or as engineering plastics.
(3) 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
More easily be clearly understood to make content of the present invention, below according to specific embodiment also by reference to the accompanying drawings, the present invention is further detailed explanation, and wherein Fig. 1 remains carbon-coating after the not fire-retardant industrial tow of nylon 6 burns to sweep Electronic Speculum shape appearance figure at 1000 times of Flied emission rings; Fig. 2 remains carbon-coating after being halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite tow burning and sweeps Electronic Speculum shape appearance figure at 1000 times of Flied emission rings.
Embodiment
(embodiment 1)
The preparation of step one, modified organo montmorillonite nanoparticle
5 parts of organic montmorillonite nano particles are added mechanical stirring in 90 parts of water, form stable suspension, add 5 parts of chain alkyl bromide tetradecyl triphenylphosphinebromide and carry out cation exchange reaction, heating in water bath to 80 DEG C reaction 5h, suction filtration after exchange completes, and with in distilled water wash throw out to filtrate without Br
-ion.Gained organo montmorillonite is dried, and crosses 200 mesh sieves.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 share (removing) hexanediamine 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 the fire retardant salt of 9 parts by weight part, to be the modified organo montmorillonite nanoparticle of 1 part and weight part be weight part that the hexanolactam of 83.95 parts is mixed into mixture, then the tetramethylolmethane that weight part is 1 part is added, the wolframic acid of 0.05 part, then the deionized water that weight part is 5 parts is added, between adjust ph to 7.3-7.7, then above-mentioned aqueous mixture is put into stirring-type reactor, air-discharging 5 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping pre-dispersed polymerization 2h under spontaneous pressure, then slowly environmental stress is decompressed to, be heated to 260-280 DEG C simultaneously and react 2h further, vacuumize 0.5h, reaction completes, nitrogen or rare gas element is supplemented when discharging.Reaction equation is:
(embodiment 2)
The preparation of step one, modified organo montmorillonite nanoparticle
5 parts of organic montmorillonite nano particles are added mechanical stirring in 90 parts of water, form stable suspension, add 5 parts of chain alkyl bromide hexadecyl tributyl phosphonium phosphines and carry out cation exchange reaction, heating in water bath to 80 DEG C reaction 5h, suction filtration after exchange completes, and with in distilled water wash throw out to filtrate without Br
-ion.Gained organo montmorillonite is dried, and crosses 200 mesh sieves.
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 the fire retardant salt of 4 parts by weight part, to be the modified organo montmorillonite nanoparticle of 3 parts and weight part be weight part that the hexanolactam of 84 parts is mixed into mixture, then the tetramethylolmethane that weight part is 1 part is added, the wolframic acid of 0.01 part, then the deionized water that weight part is 5 parts is added, between adjust ph to 7.3-7.7, then above-mentioned aqueous 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 pre-dispersed polymerization 2h under spontaneous pressure, then slowly environmental stress is decompressed to, be heated to 260-270 DEG C simultaneously and react 2h further, vacuumize 1h, reaction completes, nitrogen or rare gas element is supplemented when discharging.
(embodiment 3)
The preparation of step one, organo montmorillonite
5 parts of polynites are added mechanical stirring in 90 parts of water, form stable suspension, add 5 parts of chain alkyl bromide hexadecyl triphenylphosphinebromide and carry out cation exchange reaction, heating in water bath to 80 DEG C reaction 5h, suction filtration after exchange completes, and with in distilled water wash throw out to filtrate without Br
-ion.Gained organo montmorillonite is dried, and crosses 200 mesh sieves.
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 the fire retardant salt of 6 parts by weight part, to be the organic montmorillonite nano particle of 3 parts and weight part be weight part that the hexanolactam of 90 parts is mixed into mixture, then the tetramethylolmethane that weight part is 1 part is added, the wolframic acid of 0.05 part, then the deionized water that weight part is 5 parts is added, between adjust ph to 7.3-7.7, then above-mentioned aqueous 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 pre-dispersed polymerization 2h under spontaneous pressure, then slowly environmental stress is decompressed to, be heated to 270-280 DEG C simultaneously and react 2h further, vacuumize 0.5h, reaction completes, nitrogen or rare gas element is supplemented when discharging.
(embodiment 4)
The preparation of step one, organo montmorillonite
5 parts of polynites are added mechanical stirring in 90 parts of water, forms stable suspension, add 5 parts of chain alkyl bromides and carry out cation exchange reaction, heating in water bath to 80 DEG C reaction 5h, has exchanged rear suction filtration, and with in distilled water wash throw out to filtrate without Br
-ion.Gained organo montmorillonite is dried, and crosses 200 mesh sieves.
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 the fire retardant salt of 5 parts by weight part, to be the organic montmorillonite nano particle of 4 parts and weight part be weight part that the hexanolactam of 84.95 parts is mixed into mixture, then the tetramethylolmethane that weight part is 1 part is added, the wolframic acid of 0.05 part, then the deionized water that weight part is 5 parts is added, between adjust ph to 7.3-7.7, then above-mentioned aqueous mixture is put into stirring-type reactor, air-discharging 5 times, 230-235 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping pre-dispersed polymerization 2h under spontaneous pressure, then slowly environmental stress is decompressed to, be heated to 260-280 DEG C simultaneously and react 2h further, vacuumize 0.5h, reaction completes, nitrogen or rare gas element is supplemented when discharging.
(embodiment 5)
The preparation of step one, organo montmorillonite
5 parts of polynites are added mechanical stirring in 90 parts of water, forms stable suspension, add 5 parts of chain alkyl bromides and carry out cation exchange reaction, heating in water bath to 80 DEG C reaction 5h, has exchanged rear suction filtration, and with in distilled water wash throw out to filtrate without Br
-ion.Gained organo montmorillonite is dried, and crosses 200 mesh sieves.
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 the fire retardant salt of 4 parts by weight part, to be the organic montmorillonite nano particle of 5 parts and weight part be weight part that the hexanolactam of 84.95 parts is mixed into mixture, then the tetramethylolmethane that weight part is 1 part is added, the wolframic acid of 0.05 part, then the deionized water that weight part is 5 parts is added, between adjust ph to 7.3-7.7, then above-mentioned aqueous mixture is put into stirring-type reactor, air-discharging 5 times, 230-240 DEG C is heated to reactor is airtight, to reactant heat-insulation pressure keeping pre-dispersed polymerization 2h under spontaneous pressure, then slowly environmental stress is decompressed to, be heated to 260-270 DEG C simultaneously and react 2h further, vacuumize 0.5h, reaction completes, nitrogen or rare gas element is supplemented when discharging.
In order to investigate the effect of halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite mechanical property prepared by the present invention and flame retardant resistance, to the halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite 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/Nano composite material of montmorillonite section flame retardant properties prepared by the inventive method reaches UL94V0 rank, and fire retardant and polymeric amide form fire-retardant macromolecular chain.
Fig. 1: remain carbon-coating after the industrial tow burning of nylon 6 and sweep Electronic Speculum shape appearance figure at 1000 times of Flied emission rings
Fig. 2: remain carbon-coating after halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite tow burning and sweep Electronic Speculum shape appearance figure at 1000 times of Flied emission rings
As can be seen from Fig. 1, Fig. 2, after former nylon 6 industrial yarn burning, the ignition residue of fiber is comparatively loose, and after fire-retardant finish, the residue of sample becomes fine and close, and maintains fibriilar shape.There is hemispherical projections thing in carbide surface.This mainly accelerates the dehydration of fiber due to the fire retardant of grafting, and define more melting carbon-coating, the carbon-coating of the cracked gas of simultaneously overflowing to melting plays expansion.This carbon-coating and nano imvite work in coordination with the thermal conduction between barrier polymer and thermal source, stop external oxygen to be diffused into uncracked polymer surfaces simultaneously, and when burning can not get enough oxygen and heat energy, the polymkeric substance of burning just can put out certainly.
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 (10)
1. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, is characterized in that the component comprising following mass parts:
2. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite, is characterized in that the component comprising following mass parts:
3. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite 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/Nano composite material of montmorillonite 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/Nano composite material of montmorillonite according to claim 1 and 2, is characterized in that: described modified organo montmorillonite nanoparticle is the organic montmorillonite nano particle through the process of enlargement layer spacing.
6. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite according to claim 5, is characterized in that: described chain alkyl bromide is a kind of in tetradecyl triphenylphosphinebromide, hexadecyl tributyl phosphonium phosphine, hexadecyl triphenylphosphinebromide.
7. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite according to claim 1 or 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.
8. one kind as arbitrary in claim 1 ~ 7 as described in halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite preparation method, it is characterized in that: described preparation method is for by modified organo montmorillonite and halogen-free flame retardants salt and hexanolactam in-situ polymerization, synthesis is scattered in the nylon 6 containing fire retardant with nanoparticle morphology, and the described molecular formula containing fire retardant nylon 6 is:
described X=1-200; Y=1-100.
9. halogen-free flame-retardant nylon 6/Nano composite material of montmorillonite the preparation method as described in as arbitrary in claim 1 ~ 7, is characterized in that: comprise the steps: that (1) prepares halogen-free flame retardants salt, (2) with cation exchange method ester/modified montmorillonite nano particle, (3) by halogen-free flame retardants salt, organic montmorillonite nano particle, hexanolactam is mixed into mixture, then char-forming agent is added, charing promotor, then deionized water is added, between adjust ph to 7.3-7.7, above-mentioned aqueous 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, nitrogen or rare gas element is supplemented 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 55 DEG C to react 3-5h, then cool, filter, obtain through absolute ethanol washing in thermostat water bath.
10. halogen-free flame-retardant nylon 6 according to claim 9/Nano composite material of montmorillonite preparation method, it is characterized in that: the preparation method of described step (2) modified organo montmorillonite nanoparticle: 5-100 weight part nano imvite is dispersed in mechanical stirring in 5-250 weight parts water, form stable suspension, add 0.05-25 weight part chain alkyl bromide and stir washing drying in 0.3-10 hour at 25-110 DEG C, obtain the organic nano imvite expanding layer.
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| CN104744690A (en) * | 2015-04-09 | 2015-07-01 | 泰索新材料科技（杭州）有限公司 | Flame-retardant nylon 6 and preparation method thereof |
| CN106496548A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof |
| CN106496551A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof |
| CN106497036A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system copolymerization flame-retardant polyamide composition and preparation method thereof |
| CN106496550A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system fire-resistant copolyesters nylon composite and preparation method thereof |
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| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
| CN114350139A (en) * | 2022-02-17 | 2022-04-15 | 广东中塑新材料有限公司 | Polyamide LDS composite material and synthetic method thereof |
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| CN106497036A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system copolymerization flame-retardant polyamide composition and preparation method thereof |
| CN106496550A (en) * | 2016-10-25 | 2017-03-15 | 成都拓利科技股份有限公司 | A kind of organophosphors system fire-resistant copolyesters nylon composite and preparation method thereof |
| CN106867109A (en) * | 2017-03-09 | 2017-06-20 | 常州塑金高分子科技有限公司 | A kind of low VOC PP composite materials and preparation method thereof |
| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
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