CN106750270A - A kind of N P synergistic fire-retardant Nylon 66s and preparation method thereof - Google Patents

A kind of N P synergistic fire-retardant Nylon 66s and preparation method thereof Download PDF

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CN106750270A
CN106750270A CN201611122802.5A CN201611122802A CN106750270A CN 106750270 A CN106750270 A CN 106750270A CN 201611122802 A CN201611122802 A CN 201611122802A CN 106750270 A CN106750270 A CN 106750270A
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fire
retardant
fire retardant
formula
nylon
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袁港
贾锐
李静维
李建学
黄杰
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Sichuan Dongcai Technology Group Co Ltd
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Sichuan Dongcai Technology Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen

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Abstract

The invention discloses a kind of N P synergistic fire-retardant Nylon 66s and preparation method thereof, it is characterized in that：9, the derivative of the oxide of 10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene 10 is obtained the fire retardant A containing P with diamine reaction, binary acid melamine salt and cyanuric acid binary amine salt equimolar mass mixing are obtained the fire retardant B containing N, by the reaction of fire retardant A, fire retardant B and nylon salt, fire retardant A and nylon66 fiber copolymerization, fire retardant B and nylon66 fiber in-situ polymerization, are obtained N P synergistic fire-retardant Nylon 66s；The melting range of the N P synergistic fire-retardant Nylon 66s is 255~265 DEG C, and relative viscosity scope is 2.0~3.0, and flame retardant rating is V0,70.0~82.0MPa of tensile strength, 3.5~5.0KJ/m of notch impact strength2, 100~120MPa of bending strength, smoke density be 10%~15%；Can be used for spinning and the manufacture of engineering plastics.

Description

A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof
Technical field
The invention belongs to organic high molecular compound polyamide and its preparation, be related to a kind of N-P synergistics fire-retardant Nylon 66 and Its preparation method.N-P synergistics fire-retardant Nylon 66 of the present invention is particularly well-suited to spinning and as engineering plastics.
Background technology
At present, the fire-retardant of nylon is realized by two kinds of approach：L () uses additive flame retardant by mechanical blending, will It realizes anti-flaming function in being added to nylon.(2) reactive flame retardant is used, nylon macromolecular chain is grafted to by chemical synthesis In, grafting mode can also be divided into be connected to nylon main chain or side chain can make up, nylon material in itself have flame-retardant composition with Corresponding anti-flaming function, can reach certain permanent fire retardant effect.Using this method, it prepares fire-retardant nylon fiber, fire-retardant nylon Plastics, all have more preferable flame retardant effect than the fire-retardant nylon of addition type, can also less influence on the original machinery of bulk material Mechanical property.Chinese patent (publication number CN104211954A and CN105153415A) employs the fire retardant DOPO of response type (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies) derivative and nylon66 fiber monomer copolymerization and obtain fire-retardant Nylon 66 Polymer, flame retardant molecule is introduced into polymer molecular chain so that the fire resistance of polymer keeps for a long time, but, in hair The bright middle P flame retardants for using can cause fire-retardant nylon anti-dropping effect worse and smoke density is higher.Chinese patent (publication number CN103387666A) employ melamine and cyanuric acid in-situ polymerization prepares fire-retardant nylon, the invention causes melamine Cyanuric acid can be uniformly dispersed in nylon resin, and part and nylon resin covalent linkage.So as to be hindered The combustion preferable nylon resin of persistence, but the N flame retardants that the invention is used need addition larger, also cause resin in itself Mechanical property be affected.So the mechanical property of the fire-retardant Nylon 66 of prior art is only：Tensile strength 55~ 65MPa, 2.8~3.4KJ/m of notch impact strength2, 95~105MPa of bending strength, poor-performing.
The present invention will contain N fire retardants and be polymerized together with nylon salt containing P fire retardant preparation and meanwhile have excellent flame retardant and The N-P synergistic fire-retardant Nylon 66s of mechanical property, current the method has not yet to see the report of any pertinent literature.
The content of the invention
The purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, there is provided a kind of N-P synergistics fire-retardant Nylon 66 and Its preparation method.The present invention will contain N (nitrogen) fire retardant monomers and containing P (phosphorus) flame-retardant monomers and nylon salt combined polymerization, be obtained one New copolymer nylon material --- N-P synergistic fire-retardant Nylon 66s are planted, the new N-P synergistics fire-retardant Nylon 66 is not changing substantially Become former pure nylon 66 resin in itself on the premise of excellent mechanical property, N and P flame-retardant monomers are accessed into nylon 66 resin macromolecular chain In so that nylon resin premium properties in itself is also maintained while it has fire resistance, more conducively it is in fiber art Application.
Present disclosure is：A kind of N-P synergistics fire-retardant Nylon 66, it is characterized in that：First synthesis 9,10- dihydro-9-oxies it is miscellaneous- The product that the derivative of 10- phospho hetero phenanthrenes -10- oxides (abbreviation DOPO) reacts with the diamine-fire retardant A containing P (phosphorus), The product that production of melamine reacts with the product binary acid melamine salt and cyanuric acid of binary acid reaction with diamine again Cyanuric acid binary amine salt, and binary acid melamine salt and cyanuric acid binary amine salt equimolar mass mixing thing be containing The fire retardant B of N (nitrogen), then together add reactor, fire retardant A to enter with nylon66 fiber fire retardant A, fire retardant B and nylon salt Row copolymerization, fire retardant B carries out in-situ polymerization with nylon66 fiber, and the N-P synergistics fire-retardant Nylon 66 is obtained；
The outward appearance of the N-P synergistics fire-retardant Nylon 66 is creamy white vitreous solid, and melting range is 255~265 DEG C, phase It is 2.0~3.0 to range of viscosities, flame retardant rating is V0,70.0~82.0MPa of tensile strength, notch impact strength 3.5~ 5.0KJ/m2, 100~120MPa of bending strength, smoke density be 10%~15%；
At least include following several segments in the main body basic structure of the N-P synergistics fire-retardant Nylon 66 macromolecular：
U segments (nylon66 fiber segment) areM=50~300 integer in formula；
W segments areN=1~15 integer in formula, R can be the straight chain alkane of saturation C1~C3 in formula The alkylidene of the C3~C10 of base or undersaturated straight chain, side chain or ring-type, R1It can be the straight chained alkyl or not of saturation C4~C12 The alkylidene of the C3~C10 of the straight chain, side chain or ring-type of saturation；
X segments areIn formula：n1=0~20 integers, R2=can be saturation C4~C12 Straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~C10 alkylidene；
Y segments (melaminecyanurate) are
Z segments are：
In formula：R2=can be the straight chained alkyl of saturation C4~C12 or the C3~C10 of undersaturated straight chain, side chain or ring-type Alkylidene；
The chemical structural formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies is
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies isIn formula：R can be saturation C1~C3 straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~ The alkylidene of C10；
The fire retardant A is
In formula：R can be the Asia of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3 Alkyl；R1It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The chemical structural formula of the melamine is
The chemical structural formula of the cyanuric acid is
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1Can be saturation C4~C12 straight chained alkyl or The alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, R in formula2It can be the straight chained alkyl of saturation C4~C12 Or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the binary acid melamine salt isIn formula：R2 It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The structural formula of the cyanuric acid binary amine salt isIn formula：R1Can be full With the straight chained alkyl of C4~C12 or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The fire retardant B is the equimolar mass mixing thing of binary acid melamine salt and cyanuric acid binary amine salt.
Another content of the invention is：A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, it is step that its feature is made It is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L distilled water, is heated to 80 DEG C, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is derived under (strength) stirring After thing is dispersed in distilled water, 50 DEG C (left and right) are cooled to, add 10 moles of diamines, stirring mixing (reacts it Completely), then be cooled to room temperature and standing separate out solids within 10 hours, suction filtration, solids with distillation water washing after, solids is Obtained fire retardant A；
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies is：
In formula：R can be the straight chained alkyl or undersaturated straight chain, side chain or ring of saturation C1~C3 The alkylidene of the C3~C10 of shape；
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1Can be saturation C4~C12 straight chained alkyl or The alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The fire retardant A is
In formula：R can be the Asia of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3 Alkyl；R1It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary In deionized water, melamine can be 1 with the mass ratio range of deionized water for acid dispersion：4~8, after stirring, Reacted 2~3 hours at 80~90 DEG C, suction filtration, solids is obtained binary acid melamine salt；
The chemical structural formula of the melamine is
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, in formula：R2Can be the straight chain alkane of saturation C4~C12 The alkylidene of the C3~C10 of base or undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the binary acid melamine salt isIn formula：R2 It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and binary Amine disperses in deionized water, and cyanuric acid can be 1 with the mass ratio range of deionized water：4~8, after stirring, Reacted 2~3 hours at 80~90 DEG C, suction filtration, solids is obtained cyanuric acid binary amine salt；
The chemical structural formula of the cyanuric acid is
The chemical structure of general formula of the diamine is H2N-R1-NH2, in formula：R1It can be the straight chained alkyl of saturation C4~C12 Or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the cyanuric acid binary amine salt isIn formula：R1 It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The preparation method of the fire retardant B is：At room temperature, by the binary acid melamine salt and the cyanuric acid It is uniform that binary amine salt carries out equimolar mass mixing in container, you can；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 5~10 mass parts fire retardant B, 65~75 matter obtained in 2~5 mass parts fire retardant A, step b obtained in step a Amount part nylon salt, 0~3 mass parts lactams, 0.1~0.3 mass parts of catalyst sodium hypophosphite, 0.1~0.5 mass parts ice vinegar Acid, 0~0.2 mass parts antioxidant, 0~0.5 mass parts heat stabilizer and 15~20 mass parts deionized waters, input are carried The reactor of agitator (automatically controlling) is 4. interior, and reactor is eliminated 4. after interior oxygen with (pure) nitrogen；200~220 DEG C of temperature, Polycondensation dehydration is carried out under 1.5~2.0MPa of pressure 2~3 hours, then slowly lay down reactor 4. interior pressure to atmospheric pressure, Temperature is increased to 265~300 DEG C simultaneously, under conditions of vacuum is -0.06~-0.09MPa, vacuum polymerization reaction is carried out 1~3 hour, stop stirring, be cooled to 255~275 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5~1 hour, Repressurization discharges resin melt, through being molded cooling and dicing, obtains N-P synergistics fire-retardant Nylon 66 (section)；
The outward appearance of the N-P synergistic fire-retardant Nylon 66s for obtaining is creamy white vitreous solid, and melting range is 255~265 DEG C, Relative viscosity scope is 2.0~3.0, and flame retardant rating is V0,70.0~82.0MPa of tensile strength, notch impact strength 3.5~ 5.0KJ/m2, 100~120MPa of bending strength, smoke density be 10%~15%；
" NH (the CH of the nylon salt (polyamide 66 salt)2)6NHCO(CH2)4The repetition number of CO " segments be 50~ 300, that is, the nylon66 fiber being commonly called as；
The heat stabilizer is phenyl hypophosphorous acid；
The antioxidant is any one in (China Chemical Industry in the market is commonly used) antioxidant 3114,1098 and 168；It is raw Producing enterprise has：Suqian Lian Sheng Chemical Co., Ltd.s, Qingdao moral reach will into Chemical Co., Ltd., the Qingdao limited public affairs of Jie get Jia new materials Department and Hangzhou Jing You Chemical Co., Ltd.s.
In another content of the invention：0~3 mass parts lactams preferably replaces with 0.1~3 matter described in step c Amount part lactams.
In another content of the invention：Lactams described in step c can be in caprolactam, 11 lactams and 12 One or more mixture in acid amides.
In another content of the invention：0~0.2 mass parts antioxidant described in step c preferably replaces with 0.1~ 0.2 mass parts antioxidant.
In another content of the invention：0~0.5 mass parts heat stabilizer described in step c preferably replaces with 0.1~ 0.5 mass parts heat stabilizer.
Compared with prior art, the present invention has following features and beneficial effect：
(1) method that together with nylon salt be polymerized for fire retardant containing N and flame-retardant monomer containing P by the present invention prepares N-P synergistics Fire-retardant Nylon 66 so that nylon resin premium properties in itself is also maintained while it has fire resistance, more conducively its The application of fiber art；This N-P synergistics fire-retardant Nylon 66 and preparation method thereof has had not yet to see paper, patent and other phases Close the report of document；
(2) the fire retardant A that the present invention is added is P flame retardants；Usual fire retardant B needs to add more than 10% fire-retardant nylon 66 can be only achieved preferably fire-retardant and mechanical property effect, and the present invention only needs to add the fire retardant B of 2% fire retardant A and 5% Can obtain the fire-retardant Nylon 66 of identical fire-retardant, anti-dropping and mechanical property effect.Due to fire retardant B additions in the present invention It is few so that the mechanical property of N-P synergistic fire-retardant Nylon 66s prepared by the present invention is than only adding the fire-retardant Nylon 66 of fire retardant B Mechanical property is excellent, the 70.0~82.0MPa of tensile strength of N-P synergistics fire-retardant Nylon 66 of the present invention, notch impact strength 3.5 ~5.0KJ/m2, 100~120MPa of bending strength, and 55~65MPa of tensile strength, the notch shock of existing fire-retardant Nylon 66 2.8~3.4KJ/m of intensity2, 95~105MPa of bending strength；
(3) the fire retardant B that the present invention is added is N flame retardants, and this causes the N-P synergistic fire-retardant Nylon 66s of present invention preparation , than only adding the fire-retardant Nylon 66 of fire retardant A or other P flame retardants much smaller, usual P systems are altogether for smoke density during burning The smoke density of poly- fire-retardant Nylon 66 is generally more than 20%, and the smoke density of the N-P synergistic fire-retardant Nylon 66s in the present invention is only 10%~15%, reduce smoke density more than 25%~50%.Fire-retardant Nylon 66 anti-dropping in the present invention is better than only addition resistance The fire-retardant Nylon 66 of combustion agent A, generally only adds the fire-retardant Nylon 66 of fire retardant A to drip, and fire-retardant Nylon 66 of the invention is not Drippage.Usual P systems copolymerization fire-retardant Nylon 66 ignites absorbent cotton so flame retardant rating typically can only achieve V2 grade due to drippage, and The flame retardant rating of the N-P synergistic fire-retardant nylons in invention can reach V0 grades；
(4) using the present invention, by choosing suitable fire retardant A and fire retardant B, this two based flame retardant has synergistic fire-retardant Effect.N-P synergistic flame retardants typically have fire-retardant, heat-insulated, oxygen barrier function, and raw smoke is few, and is not likely to produce toxic gas and corruption The features such as corrosion gas.In burning, the P flame retardants in N-P synergistic flame retardants can decompose the non-ignitibility liquid of generation phosphoric acid Film, when further burning, phosphoric acid flame retardant can be dehydrated generation metaphosphoric acid, and metaphosphoric acid fire retardant further generates poly- inclined phosphorus Acid.Because poly-metaphosphoric acid is strong dehydrating agent, make polymer be dehydrated and carbonize, polymer surfaces formed carbon membrane can intercept air with Heat, so as to play fire retardation.And the N flame retardants in N-P synergistic flame retardants absorb heat under heating condition, generation is decomposed non-ignitable Gas, to dilute combustible, reduce combustible surface temperature and oxygen barrier effect, and reduces burning velocity；In identical flame retardant effect In the case of, N-P synergistics fire-retardant Nylon 66 prepared by the present invention is than being individually added into fire-retardant Buddhist nun prepared by any kind fire retardant The cost of dragon 66 is low；
(5) product preparation process of the present invention is simple, and operation is easy, and easily operation, practical.
Specific embodiment
The invention will be further described for example given below, but is not to be construed as to the scope of the present invention Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention It is whole, still fall within protection scope of the present invention.
The synthesis of Part I fire retardant A
The fire retardant A of embodiment 1-1~1-10 prepares basic technology：
Reactor 1. in, add 10 moles of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO) derivative Thing, 5L distilled water, are heated to 80 DEG C (temperature A), under strong stirring so that the miscellaneous -10- phospho hetero phenanthrenes -10- of 9,10- dihydro-9-oxies After oxide (DOPO) derivative is dispersed in distilled water, 50 DEG C (temperature B) left and right is cooled to, adds 10 moles of institute Diamine is stated, stirring mixing makes its reaction complete, is cooled to room temperature and standing separates out solids in 10 hours, suction filtration, solids And with water washing is distilled, solids is obtained fire retardant A；
It is DOPOMA, DOPOITA to choose miscellaneous -10- phospho hetero phenanthrenes -10- oxides (DOPO) derivative of 9,10- dihydro-9-oxies (DDP), its molecular structure is as follows：
The diamine of selection be 1,4- butanediamine, p-phenylenediamine, m-phenylene diamine (MPD), 1,6- hexamethylene diamines, 1,10- decamethylene diamines and 1,12- diamino dodecanes.
Embodiment 1-1：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOMA) and 1,6 hexamethylene diamines are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained fire-retardant Moles/time of agent A (1-1#) 10, it is standby.
Embodiment 1-2：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOITA) and 1,6 hexamethylene diamines are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, and resistance is obtained Combustion agent A (1-2#) 10 mole/time, it is standby.
Embodiment 1-3：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOMA) and p-phenylenediamine are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained fire-retardant 10 moles of agent A (1-3#), it is standby.
Embodiment 1-4：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOITA) and p-phenylenediamine are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained fire-retardant 10 moles of agent A (1-4#), it is standby.
Embodiment 1-5：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOMA) and m-phenylene diamine (MPD) are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained fire-retardant 10 moles of agent A (1-5#), it is standby.
Embodiment 1-6：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOITA) and m-phenylene diamine (MPD) are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained fire-retardant 10 moles of agent A (1-6#), it is standby.
Embodiment 1-7：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOMA) and 1,10- decamethylene diamine are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, and resistance is obtained 10 moles of combustion agent A (1-7#), it is standby.
Embodiment 1-8：
By the raw material proportioning of above-mentioned basic technology, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is chosen (DOPO) derivative (DOPOITA) and 1,10- decamethylene diamine are reactant, and design temperature A and B are respectively 80 DEG C and 50 DEG C, are obtained 10 moles of fire retardant A (1-8#), it is standby.
The synthesis of Part II fire retardant B
1st, the synthesis (embodiment R1~R4) of binary acid melamine salt
Prepare basic technology：Reactor 2. in, 10 moles of melamine and 10 moles of binary acid are dispersed in In ionized water, melamine can be 1 with the mass ratio range of deionized water：4~8, after stirring, at 80~90 DEG C After reaction 2~3 hours, suction filtration is that can obtain binary acid melamine salt；
The binary acid is adipic acid, decanedioic acid, terephthalic acid (TPA) and dodecanedioic acid.
Embodiment R1：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and adipic acid, is set as 80 DEG C of temperature Lower reaction 2 hours, is obtained 10 moles of melamine adipate (R1#), standby.
Embodiment R2：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and decanedioic acid, is set as 85 DEG C of temperature Lower reaction 2.5 hours, is obtained 10 moles of melamine adipate (R1#), standby.
Embodiment R3：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and terephthalic acid (TPA), is set as 90 DEG C At a temperature of react 3 hours, be obtained 10 moles of melamine adipate (R1#), it is standby.
Embodiment R4：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and dodecanedioic acid, and temperature is set as Reacted 3 hours at a temperature of 88 DEG C, 10 moles of melamine adipate (R#) is obtained, it is standby.
2nd, the synthesis (embodiment S1~S4) of cyanuric acid binary amine salt
Prepare basic technology：Reactor 3. in, 10 moles of cyanuric acid and 10 moles of diamine are dispersed in In ionized water, cyanuric acid can be 1 with the mass ratio range of deionized water：4~8, after stirring, at 80~90 DEG C After reaction 2~3 hours, suction filtration is that can obtain cyanuric acid binary amine salt；
The diamine is p-phenylenediamine, 1,6- hexamethylene diamines, 1,10- decamethylene diamines and 1,12- diamino dodecanes.
Embodiment S1：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose cyanuric acid and p-phenylenediamine, is set as 80 DEG C of temperature The lower reaction of degree 2 hours, is obtained 10 moles of melamine adipate (S1#), standby.
Embodiment S2：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and 1,6- hexamethylene diamine, is set as 84 DEG C At a temperature of react 2 hours, be obtained 10 moles of melamine adipate (S#), it is standby.
Embodiment S3：
By the raw material proportioning of above-mentioned basic technology, it is reactant to choose melamine and 1,10- decamethylene diamine, is set as 87 DEG C At a temperature of react 2.5 hours, be obtained 10 moles of melamine adipate (S3#), it is standby.
Embodiment S4：
By the raw material proportioning of above-mentioned basic technology, it is reactant, setting to choose melamine and 1,12- diamino dodecane To be reacted 3 hours at a temperature of 90 DEG C, 10 moles of melamine adipate (S4#) is obtained, it is standby.
3rd, the synthesis of the B of fire retardant
Prepare basic technology：At room temperature, the binary acid melamine salt and the cyanuric acid binary amine salt are existed Equimolar mass mixing is carried out in container uniform, you can.
Embodiment 2-1：
Choose 10 moles of R1# to mix with 10 moles of S1# equimolar uniform qualities, that is, obtain fire retardant B (2-1#) standby.
Embodiment 2-2：
Choose 10 moles of R1# to mix with 10 moles of S2# equimolar uniform qualities, that is, obtain fire retardant B (2-2#) standby.
Embodiment 2-3：
Choose 10 moles of R1# to mix with 10 moles of S3# equimolar uniform qualities, that is, obtain fire retardant B (2-3#) standby.
Embodiment 2-4：
Choose 10 moles of R1# to mix with 10 moles of S4# equimolar uniform qualities, that is, obtain fire retardant B (2-4#) standby.
Embodiment 2-5：
Choose 10 moles of R2# to mix with 10 moles of S1# equimolar uniform qualities, that is, obtain fire retardant B (2-5#) standby.
Embodiment 2-6：
Choose 10 moles of R2# to mix with 10 moles of S3# equimolar uniform qualities, that is, obtain fire retardant B (2-6#) standby.
Embodiment 2-7：
Choose 10 moles of R3# to mix with 10 moles of S2# equimolar uniform qualities, that is, obtain fire retardant B (2-7#) standby.
Embodiment 2-8：
Choose 10 moles of R3# to mix with 10 moles of S4# equimolar uniform qualities, that is, obtain fire retardant B (2-8#) standby.
Embodiment 2-9：
Choose 10 moles of R4# to mix with 10 moles of S2# equimolar uniform qualities, that is, obtain fire retardant B (2-9#) standby.
Embodiment 2-10：
Choose 10 moles of R4# to mix with 10 moles of S3# equimolar uniform qualities, that is, obtain fire retardant B (2-10#) standby.
The synthesis of Part III N, P synergistic fire-retardant Nylon 66
Embodiment 3-1：
(1) the fire retardant B (2- prepared in fire retardant A (1-1#) 2kg and embodiment 2-1 prepared in Example 1-1 1#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 215 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.9MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 265 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.55, and flame retardant rating is V0, and tensile strength is 82MPa, and notch impact strength is 4.7KJ/m2, bending strength is 108.3MPa, and smoke density is 14.7%.
Embodiment 3-2：
(1) the fire retardant B (2- prepared in fire retardant A (1-2#) 2kg and embodiment 2-1 prepared in Example 1-1 2#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 210 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.72MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 266 DEG C, under conditions of vacuum is -0.07~-0.08MPa, vacuum polymerization is carried out and is reacted 1.5 hours, Stop stirring, be cooled to 260 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.6 hour.Repressurization discharge resin melts Body, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape solid, Melting range is 255~265 DEG C, and relative viscosity is 2.47, and flame retardant rating is V0, and tensile strength is 81MPa, notch impact strength It is 4.5KJ/m2, bending strength is 115.9MPa, and smoke density is 13.6%.
Embodiment 3-3：
(1) the fire retardant B (2- prepared in fire retardant A (1-3#) 2kg and embodiment 2-1 prepared in Example 1-1 3#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 209 DEG C, carry out polycondensation dehydration 2.5 hours under pressure 1.7MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 267 DEG C, vacuum be -0.08~-0.09MPa under conditions of, carry out vacuum polymerization react 1 hour, Stop stirring, be cooled to 260 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.65 hour.Repressurization discharge resin melts Body, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape solid, Melting range is 255~265 DEG C, and relative viscosity is 2.68, and flame retardant rating is V0, and tensile strength is 79MPa, notch impact strength It is 5KJ/m2, bending strength is 118.2MPa, and smoke density is 12.7%.
Embodiment 3-4：
(1) the fire retardant B (2- prepared in fire retardant A (1-4#) 2kg and embodiment 2-1 prepared in Example 1-1 4#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 211 DEG C, carry out polycondensation dehydration 2.5 hours under pressure 1.73MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 270 DEG C, under conditions of vacuum is -0.07~-0.08MPa, carry out vacuum polymerization reaction 1.7 small When, stop stirring, 258 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction after reacting 0.8 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 3.0, and flame retardant rating is V0, and tensile strength is 78MPa, and notch shock is strong It is 4.3KJ/m to spend2, bending strength is 116.7MPa, and smoke density is 13.5%.
Embodiment 3-5：
(1) the fire retardant B (2- prepared in fire retardant A (1-5#) 2kg and embodiment 2-1 prepared in Example 1-1 5#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 212 DEG C, carry out polycondensation dehydration 2.1 hours under pressure 1.75MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 267 DEG C, under conditions of vacuum is -0.06~-0.07MPa, carry out vacuum polymerization reaction 1.5 small When, stop stirring, 260 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.33, and flame retardant rating is V0, and tensile strength is 78.6MPa, breach punching Hit intensity is 4.2KJ/m2, bending strength is 118.6MPa, and smoke density is 14.5%.
Embodiment 3-6：
(1) the fire retardant B (2- prepared in fire retardant A (1-6#) 2kg and embodiment 2-1 prepared in Example 1-1 6#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 212 DEG C, carry out polycondensation dehydration 2.8 hours under pressure 1.74MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 269 DEG C, under conditions of vacuum is -0.07~-0.08MPa, carry out vacuum polymerization reaction 2.0 small When, stop stirring, 260 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction after reacting 0.5~1 hour.Repressurization is discharged Resin melt, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape Solid, melting range is 255~265 DEG C, and relative viscosity is 2.39, and flame retardant rating is V0, and tensile strength is 79MPa, breach punching Hit intensity is 4.5KJ/m2, bending strength is 111.4MPa, and smoke density is 13.5%.
Embodiment 3-7：
(1) the fire retardant B (2- prepared in fire retardant A (1-7#) 2kg and embodiment 2-1 prepared in Example 1-1 7#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 215 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.8MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 270 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1.0 hours, Stop stirring, be cooled to 265 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharge resin melts Body, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape solid, Melting range is 255~265 DEG C, and relative viscosity is 2.90, and flame retardant rating is V0, and tensile strength is 81.2MPa, and notch shock is strong It is 4.6KJ/m to spend2, bending strength is 117.6MPa, and smoke density is 14.3%.
Embodiment 3-8：
(1) the fire retardant B (2- prepared in fire retardant A (1-8#) 2kg and embodiment 2-1 prepared in Example 1-1 8#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 205 DEG C, carry out polycondensation dehydration 2.7 hours under pressure 1.67MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 266 DEG C, under conditions of vacuum is -0.08~-0.09MPa, carry out vacuum polymerization reaction 1.7 small When, stop stirring, 262 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.77, and flame retardant rating is V0, and N-P fire retardants mass content is 7%, is drawn Intensity is stretched for 78.1MPa, and notch impact strength is 4.3KJ/m2, bending strength is 119.4MPa, and smoke density is 14.2%.
Embodiment 3-9：
(1) the fire retardant B (2- prepared in fire retardant A (1-1#) 2kg and embodiment 2-1 prepared in Example 1-1 9#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 212 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.74MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 255~275 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.53, and flame retardant rating is V0, and tensile strength is 76.4MPa, breach punching Hit intensity is 4.5KJ/m2, bending strength is 115.6MPa, and smoke density is 14.1%.
Embodiment 3-10：
(1) the fire retardant B (2- prepared in fire retardant A (1-2#) 2kg and embodiment 2-1 prepared in Example 1-1 10#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 205 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.70MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 271 DEG C, under conditions of vacuum is -0.07~-0.08MPa, vacuum polymerization is carried out and is reacted 2.5 hours, Stop stirring, be cooled to 266 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.9 hour.Repressurization discharge resin melts Body, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape solid, Melting range is 255~265 DEG C, and relative viscosity is 2.81, and flame retardant rating is V0, and tensile strength is 80.9MPa, and notch shock is strong It is 4.2KJ/m to spend2, bending strength is 113.5MPa, and smoke density is 15%.
Embodiment 3-11：
(1) the fire retardant B (2- prepared in fire retardant A (1-3#) 2kg and embodiment 2-1 prepared in Example 1-2 1#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 210 DEG C, carry out polycondensation dehydration 3 hours under pressure 1.72MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 3 hours, stopped Only stir, be cooled to 265 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 1 hour.Repressurization discharges resin melt, warp Shaping cooling and dicing and obtain the section of the N-P synergistics fire-retardant Nylon 66, outward appearance is presented opal glass shape solid, fusing point model It is 255~265 DEG C to enclose, and relative viscosity is 2.34, and flame retardant rating is V0, and tensile strength is 81.5MPa, and notch impact strength is 4.4KJ/m2, bending strength is 117.2MPa, and smoke density is 14.8%.
Embodiment 3-12：
(1) the fire retardant B (2- prepared in fire retardant A (1-4#) 2kg and embodiment 2-1 prepared in Example 1-3 2#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 217 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.80MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.06~-0.07MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 260 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.41, and flame retardant rating is V0, and tensile strength is 80.7MPa, and notch impact strength is 4.6KJ/m2, bending strength is 112.8MPa, and smoke density is 14.5%.
Embodiment 3-13：
(1) the fire retardant B (2- prepared in fire retardant A (1-5#) 2kg and embodiment 2-1 prepared in Example 1-4 3#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 220 DEG C, carry out polycondensation dehydration 2.9 hours under pressure 2.0MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 265 DEG C, under conditions of vacuum is -0.07~-0.08MPa, carry out vacuum polymerization reaction 1.6 small When, stop stirring, 260 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.35, and flame retardant rating is V0, and tensile strength is 79.3MPa, breach punching Hit intensity is 4.5KJ/m2, bending strength is 113.7MPa, and smoke density is 12.6%.
Embodiment 3-14：
(1) the fire retardant B (2- prepared in fire retardant A (1-6#) 2kg and embodiment 2-1 prepared in Example 1-5 4#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 211 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.74MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 265 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.17, and flame retardant rating is V0, and tensile strength is 82MPa, and notch impact strength is 4.6KJ/m2, bending strength is 114.3MPa, and smoke density is 13.7%.
Embodiment 3-15：
(1) the fire retardant B (2- prepared in fire retardant A (1-7#) 2kg and embodiment 2-1 prepared in Example 1-6 5#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 206 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.67MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 259 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.22, and flame retardant rating is V0, and tensile strength is 81.8MPa, and notch impact strength is 4.8KJ/m2, bending strength is 107.8MPa, and smoke density is 13.8%.
Embodiment 3-16：
(1) the fire retardant B (2- prepared in fire retardant A (1-8#) 2kg and embodiment 2-1 prepared in Example 1-7 6#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 219 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.95MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 269 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 267 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.46, and flame retardant rating is V0, tensile strength 77.9MPa, and notch impact strength is 3.8KJ/m2, bending strength is 116.1MPa, and smoke density is 13.9%.
Embodiment 3-17：
(1) the fire retardant B (2- prepared in fire retardant A (1-3#) 2kg and embodiment 2-1 prepared in Example 1-8 7#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 209 DEG C, carry out polycondensation dehydration 2.2 hours under pressure 1.73MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 273 DEG C, vacuum be -0.08~-0.09MPa under conditions of, carry out vacuum polymerization react 1 hour, Stop stirring, be cooled to 260 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharge resin melts Body, the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape solid, Melting range is 255~265 DEG C, and relative viscosity is 2.35, and flame retardant rating is V0, and tensile strength is 76.3MPa, and notch shock is strong It is 4.9KJ/m to spend2, bending strength is 120MPa, and smoke density is 14.4%.
Embodiment 3-18：
(1) the fire retardant B (2- prepared in fire retardant A (1-5#) 4kg and embodiment 2-1 prepared in Example 1-1 8#) it is well mixed under 5kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 217 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.90MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 275 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 255~275 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin Melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.65, and flame retardant rating is V0, and tensile strength is 85.4MPa, breach punching Hit intensity is 4.5KJ/m2, bending strength is 110.7MPa, and smoke density is 14.6%.
Embodiment 3-19：
(1) the fire retardant B (2- prepared in fire retardant A (1-1#) 2kg and embodiment 2-1 prepared in Example 1-1 9#) it is well mixed under 10kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 210 DEG C, carry out polycondensation dehydration 2 hours under pressure 1.73MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while Temperature is increased to 265 DEG C, under conditions of vacuum is -0.08~-0.09MPa, vacuum polymerization is carried out and is reacted 1 hour, stopped Only stir, be cooled to 260 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharges resin melt, The section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, outward appearance is presented opal glass shape solid, fusing point Scope is 255~265 DEG C, and relative viscosity is 2.44, and flame retardant rating is V0, and tensile strength is 75.3MPa, and notch impact strength is 3.5KJ/m2, bending strength is 105.1MPa, and smoke density is 10.3%.
Embodiment 3-20：
(1) the fire retardant B (2- prepared in fire retardant A (1-7#) 5kg and embodiment 2-1 prepared in Example 1-1 10#) it is well mixed under 10kg normal temperature.
(2) by the mixture of obtained fire retardant A and fire retardant B, 70kg nylon salts, 5kg lactams, 140g in (1) Catalyst sodium hypophosphite, 300g glacial acetic acid, 70g antioxidant 3114s, 350g heat stabilizer phenyl hypophosphorous acid and 17.5kg deionizations The reactor that water input is automatically controlled with agitator is 4. interior, and reactor is eliminated 4. after interior oxygen with pure nitrogen gas；In temperature 210 DEG C, carry out polycondensation dehydration 2.8 hours under pressure 1.72MPa, then slowly lay down reactor 4. interior pressure to atmospheric pressure, together When temperature is increased to 270 DEG C, vacuum be -0.08~-0.09MPa under conditions of, carry out vacuum polymerization react 1 hour, Stop stirring, be cooled to 255~275 DEG C, be passed through nitrogen, static balance terminates reaction after reacting 0.5 hour.Repressurization discharge tree Fat melt, and the section of the N-P synergistics fire-retardant Nylon 66 is obtained through being molded cooling and dicing, and outward appearance is presented opal glass shape and consolidates Body, melting range is 255~265 DEG C, and relative viscosity is 2.0, and flame retardant rating is V0, and tensile strength is 70MPa, and notch shock is strong It is 4.1KJ/m to spend2, bending strength is 100MPa, and smoke density is 10%.
Embodiment 4：
A kind of N-P synergistics fire-retardant Nylon 66, first synthesizes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (referred to as DOPO the product that derivative) reacts with the diamine-fire retardant A containing P (phosphorus), then production of melamine is anti-with binary acid The product cyanuric acid binary amine salt that the product binary acid melamine salt and cyanuric acid answered react with diamine, and binary acid The equimolar mass mixing thing of melamine salt and cyanuric acid binary amine salt is the fire retardant B containing N (nitrogen), then by fire retardant A, fire retardant B and nylon salt together add reactor, and fire retardant A carries out copolymerization with nylon66 fiber, and fire retardant B is carried out with nylon66 fiber In-situ polymerization, is obtained the N-P synergistics fire-retardant Nylon 66；
The outward appearance of the N-P synergistics fire-retardant Nylon 66 is creamy white vitreous solid, and melting range is 255~265 DEG C, phase It is 2.0~3.0 to range of viscosities, flame retardant rating is V0,70.0~82.0MPa of tensile strength, notch impact strength 3.5~ 5.0KJ/m2, 100~120MPa of bending strength, smoke density be 10%~15%；
At least include following several segments in the main body basic structure of the N-P synergistics fire-retardant Nylon 66 macromolecular：
U segments (nylon66 fiber segment) areM=50~300 integer in formula；
W segments areN=1~15 integer in formula, R can be the straight chain alkane of saturation C1~C3 in formula The alkylidene of the C3~C10 of base or undersaturated straight chain, side chain or ring-type, R1It can be the straight chained alkyl or not of saturation C4~C12 The alkylidene of the C3~C10 of the straight chain, side chain or ring-type of saturation；
X segments areIn formula：n1=0~20 integers, R2=can be saturation C4~C12 Straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~C10 alkylidene；
Y segments (melaminecyanurate) are
Z segments are：
In formula：R2=can be the straight chained alkyl of saturation C4~C12 or the C3~C10 of undersaturated straight chain, side chain or ring-type Alkylidene；
The chemical structural formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies is
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies isIn formula：R can be saturation C1~C3 straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~ The alkylidene of C10；
The fire retardant A is
In formula：R can be the Asia of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3 Alkyl；R1It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The chemical structural formula of the melamine is
The chemical structural formula of the cyanuric acid is
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1Can be saturation C4~C12 straight chained alkyl or The alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, R in formula2It can be the straight chained alkyl of saturation C4~C12 Or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the binary acid melamine salt isIn formula： R2It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The structural formula of the cyanuric acid binary amine salt isIn formula：R1Can be The alkylidene of the straight chained alkyl of saturation C4~C12 or the C3~C10 of undersaturated straight chain, side chain or ring-type；
The fire retardant B is the equimolar mass mixing thing of binary acid melamine salt and cyanuric acid binary amine salt.
Embodiment 5：
A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, step is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L distilled water, is heated to 80 DEG C, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is derived under (strength) stirring After thing is dispersed in distilled water, 50 DEG C (left and right) are cooled to, add 10 moles of diamines, stirring mixing (reacts it Completely), then be cooled to room temperature and standing separate out solids within 10 hours, suction filtration, solids with distillation water washing after, solids is Obtained fire retardant A；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary In deionized water, cyanuric acid is 1 with the mass ratio range of deionized water for acid dispersion：4, after stirring, at 80 DEG C Reaction 3 hours, suction filtration, solids is obtained binary acid melamine salt；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and binary Amine disperses in deionized water, and cyanuric acid is 1 with the mass ratio range of deionized water：4, after stirring, 80~90 Reacted 3 hours at DEG C, suction filtration, solids is obtained cyanuric acid binary amine salt；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 5 mass parts fire retardant B, 65 mass parts nylon66 fibers obtained in 2 mass parts fire retardant A, step b obtained in step a Salt, 0.1 mass parts of catalyst sodium hypophosphite, 0.1 mass parts glacial acetic acid and 15 mass parts deionized waters, input is with stirring The reactor of device (automatically controlling) is 4. interior, and reactor is eliminated 4. after interior oxygen with (pure) nitrogen；200 DEG C of temperature, pressure 1.5~ Polycondensation dehydration is carried out under 2.0MPa 3 hours, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while by temperature liter Height under conditions of vacuum is -0.06~-0.09MPa, carries out vacuum polymerization and reacts 3 hours to 265 DEG C, stops stirring, drop Temperature is passed through nitrogen to 255 DEG C, and static balance terminates reaction after reacting 0.5 hour, repressurization discharge resin melt is cold through being molded But pelletizing, that is, be obtained N-P synergistics fire-retardant Nylon 66 (section).
Embodiment 6：
A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, step is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L distilled water, is heated to 80 DEG C, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is derived under (strength) stirring After thing is dispersed in distilled water, 50 DEG C (left and right) are cooled to, add 10 moles of diamines, stirring mixing (reacts it Completely), then be cooled to room temperature and standing separate out solids within 10 hours, suction filtration, solids with distillation water washing after, solids is Obtained fire retardant A；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary In deionized water, melamine is 1 with the mass ratio range of deionized water for acid dispersion：8, after stirring, at 90 DEG C Reaction 2 hours, suction filtration, solids is obtained binary acid melamine salt；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and binary Amine disperses in deionized water, and cyanuric acid is 1 with the mass ratio range of deionized water：8, after stirring, 80~90 Reacted 3 hours at DEG C, suction filtration, solids is obtained cyanuric acid binary amine salt；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 10 mass parts fire retardant B, 75 mass parts nylon66 fibers obtained in 5 mass parts fire retardant A, step b obtained in step a Salt, 3 mass parts lactams, 0.3 mass parts of catalyst sodium hypophosphite, 0.5 mass parts glacial acetic acid, 0.2 mass parts antioxidant 3114 (or 1098 or 168), 0.5 mass parts heat stabilizer and 20 mass parts deionized waters, input is with agitator (automatic control System) reactor it is 4. interior, eliminate reactor 4. after interior oxygen with (pure) nitrogen；Under 220 DEG C of temperature, 1.5~2.0MPa of pressure Carry out polycondensation dehydration 2 hours, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while temperature is increased into 300 DEG C, under conditions of vacuum is -0.06~-0.09MPa, carries out vacuum polymerization and react 1 hour, stop stirring, it is cooled to 275 DEG C, nitrogen is passed through, static balance terminates reaction after reacting 1 hour, repressurization discharges resin melt, through being molded cooling and dicing, i.e., N-P synergistics fire-retardant Nylon 66 (section) are obtained.
Embodiment 7：
A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, step is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L distilled water, is heated to 80 DEG C, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is derived under (strength) stirring After thing is dispersed in distilled water, 50 DEG C (left and right) are cooled to, add 10 moles of diamines, stirring mixing (reacts it Completely), then be cooled to room temperature and standing separate out solids within 10 hours, suction filtration, solids with distillation water washing after, solids is Obtained fire retardant A；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary In deionized water, melamine is 1 with the mass ratio range of deionized water for acid dispersion：6, after stirring, at 85 DEG C Reaction 2.5 hours, suction filtration, solids is obtained binary acid melamine salt；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and binary Amine disperses in deionized water, and cyanuric acid is 1 with the mass ratio range of deionized water：6, after stirring, 80~90 Reacted 2 hours at DEG C, suction filtration, solids is obtained cyanuric acid binary amine salt；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 7.5 mass parts fire retardant B, 70 mass parts Buddhist nuns obtained in 3.5 mass parts fire retardant A, step b obtained in step a Imperial 66 salt, 1.5 mass parts lactams, 0.2 mass parts of catalyst sodium hypophosphite, 0.3 mass parts glacial acetic acid, 0.1 mass parts antioxygen Agent 3114 (or 1098 or 168), 0.25 mass parts heat stabilizer and 17 mass parts deionized waters, input carry agitator The reactor of (automatically controlling) is 4. interior, and reactor is eliminated 4. after interior oxygen with (pure) nitrogen；210 DEG C of temperature, pressure 1.5~ Polycondensation dehydration is carried out under 2.0MPa 2.5 hours, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while by temperature 285 DEG C are increased to, under conditions of vacuum is -0.06~-0.09MPa, vacuum polymerization is carried out and is reacted 2 hours, stop stirring, 265 DEG C are cooled to, nitrogen is passed through, static balance terminates reaction, repressurization discharge resin melt, through shaping after reacting 0.8 hour Cooling and dicing, that is, be obtained N-P synergistics fire-retardant Nylon 66 (section).
Embodiment 8~14：
A kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, step is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L distilled water, is heated to 80 DEG C, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is derived under (strength) stirring After thing is dispersed in distilled water, 50 DEG C (left and right) are cooled to, add 10 moles of diamines, stirring mixing (reacts it Completely), then be cooled to room temperature and standing separate out solids within 10 hours, suction filtration, solids with distillation water washing after, solids is Obtained fire retardant A；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary In deionized water, melamine can be 1 with the mass ratio range of deionized water for acid dispersion：Any in 4~8, stirring is equal After even, reacted 2~3 hours at 80~90 DEG C, suction filtration, solids is obtained binary acid melamine salt；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and binary Amine disperses in deionized water, and cyanuric acid can be 1 with the mass ratio range of deionized water：Any in 4~8, stirring is equal After even, reacted 2~3 hours at 80~90 DEG C, suction filtration, solids is obtained cyanuric acid binary amine salt；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 5~10 mass parts fire retardant B, 65~75 matter obtained in 2~5 mass parts fire retardant A, step b obtained in step a Amount part nylon salt, 0~3 mass parts lactams, 0.1~0.3 mass parts of catalyst sodium hypophosphite, 0.1~0.5 mass parts ice vinegar Acid, 0~0.2 mass parts antioxidant 3114 (or 1098 or 168), 0~0.5 mass parts heat stabilizer and 15~20 mass parts Deionized water, reactor of the input with agitator (automatically controlling) is 4. interior, and reactor is eliminated 4. after interior oxygen with (pure) nitrogen； Polycondensation dehydration is carried out under 200~220 DEG C of temperature, 1.5~2.0MPa of pressure 2~3 hours, then slowly lay down reactor 4. interior pressure is to atmospheric pressure, while temperature is increased to 265~300 DEG C, in the condition that vacuum is -0.06~-0.09MPa Under, carry out vacuum polymerization and react 1~3 hour, stop stirring, 255~275 DEG C are cooled to, it is passed through nitrogen, static balance reaction Terminate reaction after 0.5~1 hour, repressurization discharge resin melt through being molded cooling and dicing, that is, is obtained N-P synergistic fire-retardant nylons 66 (sections)；
The specific mass parts consumption (unit of mass parts of each component raw material in each embodiment：Gram) see the table below：
In above-described embodiment 5~14：
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies described in step a is：
In formula：R can be the straight chained alkyl or undersaturated straight chain, side chain or ring of saturation C1~C3 The alkylidene of the C3~C10 of shape；
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1Can be saturation C4~C12 straight chained alkyl or The alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The fire retardant A is
In formula：R can be the Asia of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3 Alkyl；R1It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The chemical structural formula of melamine is described in step b
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, in formula：R2Can be the straight chain alkane of saturation C4~C12 The alkylidene of the C3~C10 of base or undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the binary acid melamine salt isIn formula： R2It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The chemical structural formula of the cyanuric acid is
The chemical structure of general formula of the diamine is H2N-R1-NH2, in formula：R1It can be the straight chained alkyl of saturation C4~C12 Or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The chemical structural formula of the cyanuric acid binary amine salt isIn formula：R1 It can be the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
" NH (the CH of nylon salt described in step c (polyamide 66 salt)2)6NHCO(CH2)4The repetition number of CO " segments is 50~300, that is, the nylon66 fiber being commonly called as；
The lactams can be the mixed of one or more in caprolactam, 11 lactams and 12 lactams Compound；
The antioxidant is Suqian Lian Sheng Chemical Co., Ltd.s, Qingdao moral reaches will into Chemical Co., Ltd., Qingdao Jie get Jia New material Co., Ltd and Hangzhou Jing You Chemical Co., Ltd.s produce 3114,1098,168 products；
The heat stabilizer is phenyl hypophosphorous acid；
The outward appearance that step c is obtained N-P synergistic fire-retardant Nylon 66s is creamy white vitreous solid, and melting range is 255~265 DEG C, relative viscosity scope is 2.0~3.0, and flame retardant rating is V0,70.0~82.0MPa of tensile strength, notch impact strength 3.5 ~5.0KJ/m2, 100~120MPa of bending strength, smoke density be 10%~15%.
In above-described embodiment：It is especially not dated in the percentage for being used, be quality (weight) percentage or Well known to a person skilled in the art percentage；In the ratio for being used, do not indicate especially, be quality (weight) ratio； The weight portion can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, concentration etc.) and each component numerical quantity in each step etc. are Scope, any point is applicable.
Compared with technology, the raw material are the technology contents being not specifically delineated in present invention and above-described embodiment Commercially available prod.
The invention is not restricted to above-described embodiment, can implement and with the good result described in present invention.

Claims (8)

1. a kind of N-P synergistics fire-retardant Nylon 66, it is characterized in that：First miscellaneous -10- phospho hetero phenanthrenes -10- the oxidations of synthesis 9,10- dihydro-9-oxies Product-fire retardant the A containing P of the derivative of thing and diamine reaction, then production of melamine and binary acid reaction product The product cyanuric acid binary amine salt that binary acid melamine salt and cyanuric acid react with diamine, and binary acid melamine The equimolar mass mixing thing of salt and cyanuric acid binary amine salt is the fire retardant B containing N, then by fire retardant A, fire retardant B with Nylon salt together adds reactor, and fire retardant A carries out copolymerization with nylon66 fiber, and fire retardant B carries out in-situ polymerization with nylon66 fiber, makes Obtain the N-P synergistics fire-retardant Nylon 66；
The outward appearance of the N-P synergistics fire-retardant Nylon 66 is creamy white vitreous solid, and melting range is 255~265 DEG C, is glued relatively Degree scope is 2.0~3.0, and flame retardant rating is V0,70.0~82.0MPa of tensile strength, 3.5~5.0KJ/ of notch impact strength m2, 100~120MPa of bending strength, smoke density be 10%~15%；
At least include following several segments in the main body basic structure of the N-P synergistics fire-retardant Nylon 66 macromolecular：
U segments (nylon66 fiber segment) areM=50~300 integer in formula；
W segments areN=1~15 integer in formula, R is the straight chained alkyl or not of saturation C1~C3 in formula The alkylidene of the C3~C10 of the straight chain, side chain or ring-type of saturation, R1It is the straight chained alkyl or undersaturated straight of saturation C4~C12 The alkylidene of the C3~C10 of chain, side chain or ring-type；
X segments areIn formula：n1=0~20 integers, R2=it is the straight chain of saturation C4~C12 The alkylidene of the C3~C10 of alkyl or undersaturated straight chain, side chain or ring-type；
Y segments (melaminecyanurate) are
Z segments are：
In formula：R2=for saturation C4~C12 straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~C10 alkylene Base；
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies isIn formula：R for saturation C1~C3 straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~ The alkylidene of C10；
The fire retardant A is
In formula：R is the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3；R1 It is the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1It is the straight chained alkyl or unsaturation of saturation C4~C12 Straight chain, side chain or ring-type C3~C10 alkylidene；
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, R in formula2Straight chained alkyl or insatiable hunger for saturation C4~C12 The alkylidene of the C3~C10 of the straight chain, side chain or ring-type of sum；
The chemical structural formula of the binary acid melamine salt isIn formula：R2It is full With the straight chained alkyl of C4~C12 or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The structural formula of the cyanuric acid binary amine salt is
In formula：R1It is the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
The fire retardant B is the equimolar mass mixing thing of binary acid melamine salt and cyanuric acid binary amine salt.
2. a kind of N-P synergistics fire-retardant Nylon 66 and preparation method thereof, it is characterized in that step is as follows：
A, prepare fire retardant A：
Reactor 1. in, add 10 moles of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 5L to steam Distilled water, is heated to 80 DEG C, makes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative dispersed under agitation After in the distilled water, 50 DEG C are cooled to, add 10 moles of diamines, stirring mixing, then be cooled to room temperature and standing 10 hours Solids is separated out, suction filtration, after solids is with distillation water washing, solids is obtained fire retardant A；
The chemical structure of general formula of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide derivatives of 9,10- dihydro-9-oxies is：In formula：R for saturation C1~C3 straight chained alkyl or undersaturated straight chain, side chain or ring-type C3~ The alkylidene of C10；
The chemical structure of general formula of the diamine is H2N-R1-NH2, R in formula1It is the straight chained alkyl or unsaturation of saturation C4~C12 Straight chain, side chain or ring-type C3~C10 alkylidene；
The fire retardant A is
In formula：R is the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C1~C3；R1 It is the alkylidene of the C3~C10 of the straight chained alkyl or undersaturated straight chain, side chain or ring-type of saturation C4~C12；
B, prepare fire retardant B：
By binary acid melamine salt and cyanuric acid binary amine salt according to equimolar mass mixing, that is, fire retardant B is obtained；
The preparation method of the binary acid melamine salt is：Reactor 2. in, by equimolar melamine and binary acid point Dissipate in deionized water, melamine is 1 with the mass ratio range of deionized water：4~8, after stirring, at 80~90 DEG C Lower reaction 2~3 hours, suction filtration, solids is obtained binary acid melamine salt；
The chemical structure of general formula of the binary acid is HOOC-R2- COOH, in formula：R2It is the straight chained alkyl or not of saturation C4~C12 The alkylidene of the C3~C10 of the straight chain, side chain or ring-type of saturation；
The chemical structural formula of the binary acid melamine salt isIn formula：R2It is full With the straight chained alkyl of C4~C12 or the alkylidene of the C3~C10 of undersaturated straight chain, side chain or ring-type；
The preparation method of the cyanuric acid binary amine salt is：Reactor 3. in, by equimolar cyanuric acid and diamine point Dissipate in deionized water, cyanuric acid is 1 with the mass ratio range of deionized water：4~8, after stirring, at 80~90 DEG C Lower reaction 2~3 hours, suction filtration, solids is obtained cyanuric acid binary amine salt；
The chemical structure of general formula of the diamine is H2N-R1-NH2, in formula：R1It is the straight chained alkyl or unsaturation of saturation C4~C12 Straight chain, side chain or ring-type C3~C10 alkylidene；
The chemical structural formula of the cyanuric acid binary amine salt isIn formula：R1It is saturation The alkylidene of the C3~C10 of the straight chained alkyl of C4~C12 or undersaturated straight chain, side chain or ring-type；
The preparation method of the fire retardant B is：At room temperature, by the binary acid melamine salt and the cyanuric acid binary It is uniform that amine salt carries out equimolar mass mixing in container, you can；
C, preparation N-P synergistic fire-retardant Nylon 66s：
Take 5~10 mass parts fire retardant B, 65~75 mass parts obtained in 2~5 mass parts fire retardant A, step b obtained in step a Nylon salt, 0~3 mass parts lactams, 0.1~0.3 mass parts of catalyst sodium hypophosphite, 0.1~0.5 mass parts glacial acetic acid, 0 ~0.2 mass parts antioxidant, 0~0.5 mass parts heat stabilizer and 15~20 mass parts deionized waters, input is with stirring The reactor of device is 4. interior, and reactor is eliminated 4. after interior oxygen with nitrogen；Under 200~220 DEG C of temperature, 1.5~2.0MPa of pressure Carry out polycondensation dehydration 2~3 hours, then slowly lay down reactor 4. interior pressure to atmospheric pressure, while temperature is increased to 265~300 DEG C, under conditions of vacuum is -0.06~-0.09MPa, carries out vacuum polymerization and react 1~3 hour, stop stirring Mix, be cooled to 255~275 DEG C, be passed through nitrogen, static balance terminates reaction, repressurization discharge resin after reacting 0.5~1 hour Melt, through being molded cooling and dicing, that is, is obtained N-P synergistic fire-retardant Nylon 66s；
The antioxidant is any one in antioxidant 3114,1098 and 168；
The heat stabilizer is phenyl hypophosphorous acid.
3. N-P synergistic fire-retardant Nylon 66s as described in claim 2 and preparation method thereof, it is characterized in that：0~3 described in step c Mass parts lactams replaces with 0.1~3 mass parts lactams.
4. N-P synergistic fire-retardant Nylon 66s as described in Claims 2 or 3 and preparation method thereof, it is characterized in that：Described in step c Lactams can be one or more the mixture in caprolactam, 11 lactams and 12 lactams.
5. N-P synergistic fire-retardant Nylon 66s as described in Claims 2 or 3 and preparation method thereof, it is characterized in that：0 described in step c ~0.2 mass parts antioxidant replaces with 0.1~0.2 mass parts antioxidant.
6. N-P synergistic fire-retardant Nylon 66s as described in claim 4 and preparation method thereof, it is characterized in that：0 described in step c~ 0.2 mass parts antioxidant replaces with 0.1~0.2 mass parts antioxidant.
7. N-P synergistic fire-retardant Nylon 66s as described in claim 2,3 or 6 and preparation method thereof, it is characterized in that：Institute in step c State 0~0.5 mass parts heat stabilizer and replace with 0.1~0.5 mass parts heat stabilizer.
8. N-P synergistic fire-retardant Nylon 66s as described in claim 5 and preparation method thereof, it is characterized in that：0 described in step c~ 0.5 mass parts heat stabilizer replaces with 0.1~0.5 mass parts heat stabilizer.
CN201611122802.5A 2016-12-08 2016-12-08 A kind of N P synergistic fire-retardant Nylon 66s and preparation method thereof Pending CN106750270A (en)

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Application publication date: 20170531