CN105155018B - A kind of copolymerization 66 fiber of Flameproof polyamide and preparation method thereof - Google Patents
A kind of copolymerization 66 fiber of Flameproof polyamide and preparation method thereof Download PDFInfo
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- CN105155018B CN105155018B CN201510435341.6A CN201510435341A CN105155018B CN 105155018 B CN105155018 B CN 105155018B CN 201510435341 A CN201510435341 A CN 201510435341A CN 105155018 B CN105155018 B CN 105155018B
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Abstract
The present invention relates to a kind of copolymerization 66 fibers of Flameproof polyamide and preparation method thereof, more particularly to a kind of phosphorous reactive flame retardant, 66 copolymer of block Flameproof polyamide is made in aggregated reaction, then by method that after polyamide 66 copolymer granulated and dried, melt spinning prepares 66 fiber of Flameproof polyamide.Its main feature is that fire retardant and diamine or diol reaction are obtained into fire retardant performed polymer first, then fire retardant performed polymer and polyamide 66 prepolymer reaction are obtained into 66 copolymer of Flameproof polyamide, finally by 66 copolymer melt spinning of Flameproof polyamide, copolymerization 66 fiber of Flameproof polyamide is prepared.66 fibrous mechanical property of Flameproof polyamide made from this method is excellent, fire-retardant persistence is good, and limit oxygen index is more than 30%.This 66 fiber of Flameproof polyamide cannot be only used for making the Textile Filaments such as clothes, carpet, curtain and furniture cloth, it can also be used to manufacture the industrial long filament such as cord fabric, conveyer belt, fishing net, hawser and army fabric.
Description
Technical field
The invention belongs to Flameproof polyamide fiber synthesis technical field, be related to a kind of copolymerization 66 fiber of Flameproof polyamide and its
Preparation method, more particularly to a kind of phosphorous 66 fiber of reactive flame retardant performed polymer block copolymerization Flameproof polyamide and its preparation
Method.
Background technology
Fypro is one of synthetic fibers for putting into industrialized production earliest in the world, is known as polyamide fibre in China,
Foreign countries are also known as nylon, nylon, capron etc..As synthetic fibers, industrialized kind, Nylon66 are good with its earliest
The advantages that wearability well, hygroscopicity, resilience, dyeability, has all played very important work in civilian and industrial field
With.But the limit oxygen index of Nylon66 only has 21~23%, flame retardant property is poor, seriously limits it in every profession and trade
Application, therefore the research of 66 fiber of Flameproof polyamide has become the hot issue paid close attention at present.
The flame resistant method of Fypro and textile is roughly divided into that precursor is flame-retardant modified and two major class of flame-retardant after-finishing.Resistance
It is applied widely to fire afterfinish method, it is simple for process, but there are the shortcomings that fire-retardant persistence difference and poor fabric washability.Precursor hinders
Combustion is modified to be divided into as blending and modifying and modification by copolymerization, and blending and modifying is the side that flame retarding function is made it have using additive flame retardant
Method has the characteristics of easy to operate, widely applicable, but has larger impact to the mechanical property of fiber；Modification by copolymerization is poly-
The comonomer with anti-flammability is added in when amide monomer polymerize, so that fire-resistant copolyesters monomer polymerization is into polyamide macromolecular
Fire-retardant effect is played, but modification by copolymerization is faced with fire retardant the shortcomings of species is few, polymerization process is complicated, of high cost, therefore
Conceptual phase is in mostly.
Chinese patent (publication number CN1266445A) using reactive flame retardant 2- carboxyethyl phenyl phosphinic acids (CEPPA) with
66 polymer of Flameproof polyamide is made in the copolymerization of 66 salt, and flame retardant molecule is attached on polyamide 66 strand and improves product resistance
Persistence is fired, and then 66 fiber of Flameproof polyamide is made.Although be copolymerized it is flame-retardant modified can reach preferable flame retardant effect, resistance
The introducing of combustion agent certainly will have an impact the polymerization process of high molecular material, decline polymer molecular weight, influence polyamide 66 fibre
Tie up the progress of spinning process.In addition, fire retardant is usually randomly distributed in polymer matrix, for random copolymer, with
The increase of noncrystalline comonomer (fire retardant) concentration, fusing point monotonic decreasing, that is to say, that high with increasing for flame retardant agent content
Copolymer matrix fusing point continuously decreases, and so limits the use scope of high polymer.Therefore, fire retardant is first processed by the present invention
Fire retardant performed polymer, then fire retardant performed polymer and polyamide 66 performed polymer are copolymerized to obtain 66 copolymer material of block Flameproof polyamide
Material by melt spinning after 66 copolymer material Cast Strip of block Flameproof polyamide, pelletizing, drying, prepares copolymerization Flameproof polyamide 66
Fiber.
The content of the invention
The object of the present invention is to provide a kind of copolymerization 66 fibers of Flameproof polyamide and preparation method thereof, are especially to provide one kind
66 fiber of phosphonium flame retardant performed polymer block copolymerization Flameproof polyamide and preparation method thereof.The fire-retardant polyamides of copolymerization that the present invention obtains
66 fiber of amine not only has good flame retardant property, but also maintains its heat safe performance, this is because for block copolymerization
Object, when comonomer (fire retardant) content increases to very big, fusing point still maintains constant.Therefore, the copolymerization resistance that the present invention obtains
66 fiber of retardant polyamide can be not only used for the fields such as clothes, carpet, curtain, apply also for tensile strength of material and fracture
The special dimensions such as the military affairs that the mechanical properties such as intensity have higher requirements.
A kind of 66 fiber of copolymerization Flameproof polyamide of the present invention, is formed by 66 melt spinning of copolymerization Flameproof polyamide, should
Copolymerization Flameproof polyamide 66 molecular structural formula be：
Wherein, x >=30, y >=30；z≥2；3/100≤z/(x+y)≤10/100；
R is
The R1、R3For straight chain, branched or cricoid C1~C15Alkylidene；R2、R4For straight chain, branched or cricoid C1~
C15Alkyl or aryl；R5、R6For the C of straight chain1~C15Alkylidene.
As preferred technical solution：
A kind of copolymerization 66 fiber of Flameproof polyamide as described above, limit oxygen index is more than 30%；Fracture strength is
4.5~6.0cN/dtex, elongation at break 25~40%, Young's modulus are 25~40cN/dtex.
The present invention also provides a kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, first by fire retardant and diamine
Or dihydric alcohol polycondensation obtains fire retardant performed polymer, is then copolymerized fire retardant performed polymer and polyamide 66 performed polymer,
66 copolymer of block Flameproof polyamide is obtained, 66 copolymer of Flameproof polyamide obtains Flameproof polyamide 66 through Cast Strip, pelletizing and cuts into slices,
66 fiber of Flameproof polyamide is made in melt spinning after polyamide 66 chip drying；The fire retardant performed polymer for viscous liquid or
Person's semisolid, number-average molecular weight Mn are 103~104, and be the active function with carboxyl, amido or hydroxyl at molecule both ends
Group；
The structure of the fire retardant is：
Wherein：The R1、R3For straight chain, branched or cricoid C1~C15Alkylidene；R2、R4For straight chain, branched or annular
C1~C15Alkyl or aryl；
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above, the general formula of the diamine is H2N-R5-
NH2, the general formula of dihydric alcohol is HO-R6-OH；R5、R6For the C of straight chain1~C15Alkylidene.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above, specifically includes following steps：
(1) fire retardant, diamine or dihydric alcohol with water are uniformly mixed, are stirred to react, then are warming up at 90~130 DEG C
150~180 DEG C of further polymerizations, last decompression vacuum pumping, reaction terminate generation fire retardant performed polymer；The fire retardant, binary
The molar ratio of amine or dihydric alcohol and water is 1:1~1.5:2~2.5, the both ends of obtained flame-retardant agent performed polymer are with carboxyl, amido
Or the active function groups of hydroxyl；
(2) 90~99 mass parts, 66 salt, 0.1~1 mass parts adipic acid are made into 60%~80% aqueous solution, mixing is equal
Even addition autoclave is warming up to 210~230 DEG C, and when pressure is up to 1.7~2.0MPa, heat-insulation pressure keeping is gathered for a period of time
66 performed polymer of amide, the number-average molecular weight Mn of polyamide 66 performed polymer is 103~104, and at the both ends of polyamide 66 performed polymer point
As soon as not Wei carboxyl and amido active end group, having between such polyamide 66 performed polymer and fire retardant performed polymer can be mutual
The active end group of reaction.
(3) 3~9 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.7~2.0MPa pressure, risen
Temperature slowly releases gas reactor to normal pressure whithin a period of time to 240~260 DEG C, at this time fire retardant performed polymer and polyamide
66 performed polymers take place copolyreaction, react to each other between the active end group between two performed polymers, and strand gradually increases, raw
Into 66 copolymer of block polyamide；
(4) 260~275 DEG C are warming up to again, is evacuated down to -0.05~-0.1MPa, stop stirring after being kept for a period of time
It mixes, stands discharging, reaction product is 66 copolymer of Flameproof polyamide, due to that can generate a small amount of water in reaction process, inhibits anti-
The progress answered, inhibits the growth of strand, vacuumizes removing excessive moisture at this time so that polymer molecular weight further improves.
(5) by 66 chip drying of Flameproof polyamide for a period of time, directly or with other polyamide cut into slices after uniformly mixing, add
Enter to melt spinning machine and carry out melt spinning, drawing-off, obtain copolymerization 66 fiber of Flameproof polyamide.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above in the step (1), is uniformly mixed 2
~3 it is small when, be stirred to react 2~3 it is small when, further polymerize 2~3 it is small when；In the step (2) N is first passed through before heating2Discharge is empty
Gas, closed heating；When heat-insulation pressure keeping refers to that holding 1~3 is small for a period of time in the step (2)；Deflation one in the step (3)
Section the time refer to 2~4 it is small when.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above vacuumizes holding in the step (4)
When a period of time refers to that holding 0.5~1 is small.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above, when one section dry in the step (5)
Between when referring to that at 90~110 DEG C vacuum drying 12~24 is small.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above, in the step (5) directly melting spin
Silk be directly by Flameproof polyamide 66 cut into slices carry out melt spinning, with other polyamide section mix refer to will it is obtained it is fire-retardant gather
It is 1 that amide 66, which cuts into slices and cuts into slices with common polyamide 66 according to mass ratio,:1~3 after mixing, carries out melt spinning.
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described above, Flameproof polyamide in the step (5)
The spinning temperature of 66 sections is 285~300 DEG C, and drafting multiple is 3.2~4.0.
Advantageous effect：
(1) fire retardant is added in polyamide 66 polymerization process, flame-retardant composition is connected on polyamide 66 strand, is had
The advantages of fire retardant additive amount is few, flame retardant effect is lasting, small to Effect on Mechanical Properties.
(2) performed polymer is made in fire retardant, can be evenly dispersed in 66 salting liquids, be conducive to improve flame retarding efficiency.
(3) 66 fabric of copolymerization Flameproof polyamide and product that the present invention obtains have good feel and water-wash resistance,
Application prospect is good.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant DDP, hexamethylene diamine are mixed with water, nitrogen protection under 50 DEG C be uniformly mixed 2 it is small when, then 90
Be stirred to react at DEG C 2 it is small when, then be warming up to 150 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation fire retardant it is pre-
Aggressiveness, is viscous liquid, and number-average molecular weight Mn is 1.8 × 103, the molar ratio of fire retardant DDP, hexamethylene diamine and water are 1:
1.1:2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant is：
(2) 90 mass parts, 66 salt, 1 mass parts adipic acid are made into 60% aqueous solution, is uniformly mixed and adds in reaction under high pressure
Kettle is first passed through N2Air is discharged, it is closed to be warming up to 210 DEG C, when pressure reaches 1.7MPa, when heat-insulation pressure keeping 1 is small, obtain polyamide 66
Performed polymer；
(3) 9 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.7MPa pressure, is warming up to 240
DEG C, and when 2 is small interior slow releasing gas reactor to normal pressure；
(4) 260 DEG C are warming up to again, is evacuated down to -0.05MPa, keep 0.5 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) by Flameproof polyamide 66 cut into slices 90 DEG C vacuum drying 24 it is small when after, be added to melt spinning machine 290 DEG C into
Row melt spinning, drafting multiple 3.2 obtain copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=72 is the number of repeat unit of polyamide 66；Z=4 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 38.2%, fracture strength 4.52cN/dtex, fracture
Elongation is 25.36%, Young's modulus 25.17cN/dtex.
Embodiment 2
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant CEPPA, hexamethylene diamine are mixed with water, nitrogen protection under 80 DEG C be uniformly mixed 3 it is small when, Ran Hou
Be stirred to react at 130 DEG C 3 it is small when, then be warming up to 180 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation it is fire-retardant
Agent performed polymer, is semisolid, and number-average molecular weight Mn is 2.5 × 103, the molar ratio of fire retardant CEPPA, hexamethylene diamine and water are 1:
1.2:2.5, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant is：
(2) 96.8 mass parts, 66 salt, 0.2 mass parts adipic acid are made into 80% aqueous solution, is uniformly mixed and adds in high pressure
Reaction kettle is first passed through N2Air is discharged, it is closed to be warming up to 230 DEG C, when pressure reaches 2.0MPa, when heat-insulation pressure keeping 3 is small, obtain polyamides
66 performed polymer of amine；
(3) 3 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 2.0MPa pressure, is warming up to 260
DEG C, and when 4 is small interior slow releasing gas reactor to normal pressure；
(4) 275 DEG C are warming up to again, is evacuated down to -0.1MPa, keep 1 it is small when after stop stirring, stand discharging, product
66 copolymer slice of Flameproof polyamide is obtained through Cast Strip, pelletizing；
(5) after Flameproof polyamide 66 is cut into slices when 110 DEG C of vacuum drying 12 are small, melt spinning machine is added at 300 DEG C
Melt spinning is carried out, drafting multiple 4.0 obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=122 is the number of repeat unit of polyamide 66；Z=8 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 30.2%, fracture strength 5.94cN/dtex, fracture
Elongation is 40.02%, Young's modulus 40.11cN/dtex.
Embodiment 3
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant BCPPO, hexamethylene diamine are mixed with water, nitrogen protection under 60 DEG C be uniformly mixed 2.5 it is small when, then
Be stirred to react at 95 DEG C 2 it is small when, then be warming up to 160 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation it is fire-retardant
Agent performed polymer, is viscous liquid, and number-average molecular weight Mn is 2.8 × 103, the molar ratio of fire retardant BCPPO, hexamethylene diamine and water
For 1:1.2:2.1, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant is：
(2) 91.8 mass parts, 66 salt, 0.2 mass parts adipic acid are made into 66% aqueous solution, is uniformly mixed and adds in high pressure
Reaction kettle is first passed through N2Air is discharged, it is closed to be warming up to 215 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 2 is small, obtain polyamides
66 performed polymer of amine；
(3) 8 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.8MPa pressure, is warming up to 250
DEG C, and when 3 is small interior slow releasing gas reactor to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.06MPa, keep 0.6 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) by Flameproof polyamide 66 cut into slices 100 DEG C vacuum drying 16 it is small when after, by Flameproof polyamide 66 cut into slices with commonly
Polyamide 66 section is 1 according to mass ratio:2 after mixing, is added to melt spinning machine and carries out melt spinning at 285 DEG C, leads
It is 3.4 to stretch multiple, obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=68 is the number of repeat unit of polyamide 66；Z=6 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 32.7%, fracture strength 5.42cN/dtex, fracture
Elongation is 31.08%, Young's modulus 35.56cN/dtex.
Embodiment 4
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant CEMPP, hexamethylene diamine are mixed with water, nitrogen protection under 55 DEG C be uniformly mixed 3 it is small when, Ran Hou
Be stirred to react at 120 DEG C 2.5 it is small when, then be warming up to 170 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation resistance
Agent performed polymer is fired, is viscous liquid, number-average molecular weight Mn is 2.5 × 103, mole of fire retardant CEMPP, hexamethylene diamine and water
Than for 1:1.2:2.4, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant is：
(2) 96 mass parts, 66 salt, 0.7 mass parts adipic acid are made into 75% aqueous solution, it is anti-to be uniformly mixed addition high pressure
Kettle is answered, is first passed through N2Air is discharged, it is closed to be warming up to 225 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 2 is small, obtain polyamide
66 performed polymers；
(3) 3.3 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.9MPa pressure, be warming up to
255 DEG C, and when 3 is small interior slow releasing gas reactor to normal pressure；
(4) 270 DEG C are warming up to again, is evacuated down to -0.08MPa, keep 0.8 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) after Flameproof polyamide 66 is cut into slices when 105 DEG C of vacuum drying 20 are small, melt spinning machine is added at 295 DEG C
Melt spinning is carried out, drafting multiple 3.9 obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=104 is the number of repeat unit of polyamide 66；Z=10 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 31.3%, fracture strength 5.62cN/dtex, fracture
Elongation is 35.05%, Young's modulus 36.39cN/dtex.
Embodiment 5
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant DDP, butanediol are mixed with water, nitrogen protection under 70 DEG C be uniformly mixed 2 it is small when, then 100
Be stirred to react at DEG C 2.5 it is small when, then be warming up to 170 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation fire retardant
Performed polymer, is semisolid, and number-average molecular weight Mn is 1.7 × 103, the molar ratio of fire retardant DDP, butanediol and water are 1:1:
2.2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 94.6 mass parts, 66 salt, 0.4 mass parts adipic acid are made into 68% aqueous solution, is uniformly mixed and adds in high pressure
Reaction kettle is first passed through N2Air is discharged, it is closed to be warming up to 215 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 1 is small, obtain polyamides
66 performed polymer of amine；
(3) 5 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.9MPa pressure, is warming up to 250
DEG C, and when 3 is small interior slow releasing gas reactor to normal pressure；
(4) 270 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.6 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) after Flameproof polyamide 66 is cut into slices when 110 DEG C of vacuum drying 14 are small, melt spinning machine is added at 290 DEG C
Melt spinning is carried out, drafting multiple 3.6 obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=90 is the number of repeat unit of polyamide 66；Z=4 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 35.4%, fracture strength 5.26cN/dtex, fracture
Elongation is 33.77%, Young's modulus 34.84cN/dtex.
Embodiment 6
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant CEPPA, butanediol are mixed with water, nitrogen protection under 80 DEG C be uniformly mixed 2 it is small when, Ran Hou
Be stirred to react at 120 DEG C 2 it is small when, then be warming up to 165 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation it is fire-retardant
Agent performed polymer, is viscous liquid, and number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant CEPPA, butanediol and water
For 1:1.1:2.2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 91 mass parts, 66 salt, 0.5 mass parts adipic acid are made into 65% aqueous solution, it is anti-to be uniformly mixed addition high pressure
Kettle is answered, is first passed through N2Air is discharged, it is closed to be warming up to 212 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 3 is small, obtain polyamide
66 performed polymers；
(3) 8.5 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.8MPa pressure, be warming up to
245 DEG C, and when 2 is small interior slow releasing gas reactor to normal pressure；
(4) 262 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.6 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) by Flameproof polyamide 66 cut into slices 100 DEG C vacuum drying 18 it is small when after, by Flameproof polyamide 66 cut into slices with commonly
Polyamide 66 section is 1 according to mass ratio:1 after mixing, is added to melt spinning machine and carries out melt spinning at 287 DEG C, leads
It is 3.4 to stretch multiple, obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=75 is the number of repeat unit of polyamide 66；Z=7 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 37.4%, fracture strength 5.36cN/dtex, fracture
Elongation is 36.25%, Young's modulus 34.36cN/dtex.
Embodiment 7
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant BCPPO, butanediol are mixed with water, nitrogen protection under 70 DEG C be uniformly mixed 2 it is small when, Ran Hou
Be stirred to react at 130 DEG C 2 it is small when, then be warming up to 180 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation it is fire-retardant
Agent performed polymer, is viscous liquid, and number-average molecular weight Mn is 1.6 × 103, the molar ratio of fire retardant BCPPO, butanediol and water
For 1:1.1:2.3, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 95.7 mass parts, 66 salt, 0.8 mass parts adipic acid are made into 70% aqueous solution, is uniformly mixed and adds in high pressure
Reaction kettle is first passed through N2Air is discharged, it is closed to be warming up to 220 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 2 is small, obtain polyamides
66 performed polymer of amine；
(3) 3.5 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.8MPa pressure, be warming up to
250 DEG C, and when 3 is small interior slow releasing gas reactor to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.06MPa, keep 0.8 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) after Flameproof polyamide 66 is cut into slices when 110 DEG C of vacuum drying 15 are small, melt spinning machine is added at 300 DEG C
Melt spinning is carried out, drafting multiple 3.8 obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=121 is the number of repeat unit of polyamide 66；Z=4 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 33.1%, fracture strength 5.47cN/dtex, fracture
Elongation is 36.28%, Young's modulus 34.15cN/dtex.
Embodiment 8
A kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide, specifically includes following steps：
(1) fire retardant CEMPP, butanediol are mixed with water, nitrogen protection under 75 DEG C be uniformly mixed 2 it is small when, Ran Hou
Be stirred to react at 125 DEG C 2 it is small when, then be warming up to 175 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation it is fire-retardant
Agent performed polymer, is viscous liquid, and number-average molecular weight Mn is 1.8 × 103, the molar ratio of fire retardant CEMPP, butanediol and water
For 1:1.1:2.2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 95 mass parts, 66 salt, 0.2 mass parts adipic acid are made into 72% aqueous solution, it is anti-to be uniformly mixed addition high pressure
Kettle is answered, is first passed through N2Air is discharged, it is closed to be warming up to 225 DEG C, when pressure reaches 2.0MPa, when heat-insulation pressure keeping 2 is small, obtain polyamide
66 performed polymers；
(3) 4.8 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.9MPa pressure, be warming up to
255 DEG C, and when 3 is small interior slow releasing gas reactor to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.7 it is small when after stop stirring, stand discharging, production
Object obtains 66 copolymer slice of Flameproof polyamide through Cast Strip, pelletizing；
(5) after Flameproof polyamide 66 is cut into slices when 100 DEG C of vacuum drying 18 are small, melt spinning machine is added at 296 DEG C
Melt spinning is carried out, drafting multiple 3.7 obtains copolymerization 66 fiber of Flameproof polyamide.Its molecular structural formula is：
Wherein：X+y=98 is the number of repeat unit of polyamide 66；Z=8 is the number of repeat unit of fire retardant.
The limit oxygen index of 66 fiber of copolymerization Flameproof polyamide is in 34.6%, fracture strength 5.34cN/dtex, fracture
Elongation is 34.48%, Young's modulus 32.56cN/dtex.
Claims (9)
1. a kind of copolymerization 66 fiber of Flameproof polyamide, which is characterized in that it is formed by 66 melt spinning of copolymerization Flameproof polyamide, should
Copolymerization Flameproof polyamide 66 molecular structural formula be：
Wherein, x >=30, y >=30；z≥2；3/100≤z/(x+y)≤10/100；
R is
The R1For straight chain, branched or cricoid C1~C15Alkylidene；R3For straight chain, branched or cricoid C1~C15Alkylene
Base；R2、R4For straight chain, branched or cricoid C1~C15Alkyl or aryl；R5、R6For the C of straight chain1~C15Alkylidene；
The limit oxygen index of 66 fiber of Flameproof polyamide is more than 30%；The fracture of 66 fiber of Flameproof polyamide is strong
It spends for 4.5~6.0cN/dtex, elongation at break is 25~40%, and Young's modulus is 25~40cN/dtex.
2. according to a kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide as described in claim 1, which is characterized in that first
Fire retardant and diamine or dihydric alcohol polycondensation are obtained into fire retardant performed polymer, then by fire retardant performed polymer and polyamide 66 pre-polymerization
Body is copolymerized, and obtains 66 copolymer of Flameproof polyamide, and 66 copolymer of Flameproof polyamide obtains fire-retardant poly- through Cast Strip, pelletizing
Amide 66 is cut into slices, and 66 fiber of Flameproof polyamide is made in melt spinning after 66 chip drying of Flameproof polyamide；The fire retardant
Performed polymer is viscous liquid or semisolid, and number-average molecular weight Mn is 103~104, and molecule both ends be with carboxyl,
The active function groups of amido or hydroxyl；
The structural formula of the fire retardant is：
Wherein：The R1For straight chain, branched or cricoid C1~C15Alkylidene；R3For straight chain, branched or cricoid C1~C15's
Alkylidene；R2、R4For straight chain, branched or cricoid C1~C15Alkyl or aryl.
3. a kind of preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 2, which is characterized in that described two
The general formula of first amine is H2N-R5-NH2, the general formula of dihydric alcohol is HO-R6-OH；R5、R6For the C of straight chain1~C15Alkylidene.
A kind of 4. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 2, which is characterized in that specific bag
Include following steps：
(1) fire retardant, diamine or dihydric alcohol with water are uniformly mixed, are stirred to react at 90~130 DEG C, then are warming up to 150
~180 DEG C further polymerization, last decompression vacuum pumping, reaction terminate generation fire retardant performed polymer, the fire retardant, diamine or
The molar ratio of dihydric alcohol and water is 1:1~1.5:2~2.5；
(2) 90~99 mass parts nylon salts, 0.1~1 mass parts adipic acid are made into 60%~80% aqueous solution, mixing is equal
Even addition autoclave is warming up to 210~230 DEG C, when pressure is up to 1.7~2.0MPa, and heat-insulation pressure keeping for a period of time, is gathered
66 performed polymer of amide；
(3) 3~9 mass parts fire retardant performed polymers are added in polyamide 66 performed polymer under 1.7~2.0MPa pressure, be warming up to
240~260 DEG C, and gas reactor is slowly released whithin a period of time to normal pressure；
(4) 260~275 DEG C are warming up to again, is evacuated down to -0.05~-0.1MPa, stop stirring after being kept for a period of time, it is quiet
Discharging is put, Cast Strip, pelletizing obtain 66 copolymer slice of Flameproof polyamide；
(5) 66 copolymer slice of Flameproof polyamide is dried into a period of time, directly or with the section of other polyamide uniformly mixed
Afterwards, after being added to melt spinning machine progress melt spinning, drawing-off, copolymerization 66 fiber of Flameproof polyamide is obtained.
A kind of 5. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 4, which is characterized in that the step
Suddenly in (1), be uniformly mixed 2~3 it is small when, be stirred to react 2~3 it is small when, further polymerize 2~3 it is small when；It is risen in the step (2)
Wen Qianxian is passed through N2Discharge air, closed heating；When heat-insulation pressure keeping refers to that holding 1~3 is small for a period of time in the step (2)；
Deflate in the step (3) a period of time refer to 2~4 it is small when.
A kind of 6. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 4, which is characterized in that the step
Suddenly holding a period of time is vacuumized in (4) when referring to that holding 0.5~1 is small.
A kind of 7. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 4, which is characterized in that the step
Suddenly when dry a period of time refers to that vacuum drying 12~24 is small at 90~110 DEG C in (5).
A kind of 8. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 4, which is characterized in that the step
Suddenly direct melt spinning is that directly Flameproof polyamide 66 is cut into slices to carry out melt spinning in (5), is mixed with the section of other polyamide
Refer to by Flameproof polyamide 66 obtained cut into slices with common polyamide 66 cut into slices according to mass ratio be 1:1~3 after mixing, into
Row melt spinning.
A kind of 9. preparation method for being copolymerized 66 fiber of Flameproof polyamide according to claim 4, which is characterized in that the step
Suddenly the spinning temperature that Flameproof polyamide 66 is cut into slices in (5) is 285~300 DEG C, and drafting multiple is 3.2~4.0.
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| CN107573504B (en) * | 2017-08-17 | 2020-11-10 | 中央军委后勤保障部军需装备研究所 | Moisture-absorbing flame-retardant nylon and fiber and preparation method thereof |
| CN107686553B (en) * | 2017-08-17 | 2020-02-07 | 中央军委后勤保障部军需装备研究所 | High-viscosity flame-retardant polyamide 66 and preparation method thereof |
| CN107460561B (en) * | 2017-08-17 | 2020-06-09 | 中央军委后勤保障部军需装备研究所 | Antibacterial flame-retardant polyamide 66 fabric and preparation method thereof |
| CN110318111A (en) * | 2019-08-09 | 2019-10-11 | 四川斯派恩新材料有限公司 | A kind of low water absorption High-temperature-ressemi-aromatic semi-aromatic polyamide fiber and preparation method thereof |
| CN112679730B (en) * | 2019-10-17 | 2022-08-19 | 华峰集团有限公司 | Halogen-free flame-retardant polyamide and preparation method and product thereof |
| CN112225892B (en) * | 2020-09-15 | 2021-10-08 | 东华大学 | Copolymerization flame-retardant polyamide and preparation method thereof |
| CN112144141B (en) * | 2020-09-15 | 2021-10-26 | 东华大学 | Copolymerized flame-retardant polyamide fiber and preparation method thereof |
| CN114989422A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide material for industrial yarn, preparation method thereof and fiber |
| CN114989419A (en) * | 2022-06-21 | 2022-09-02 | 浙江理工大学 | Polyamide for industrial yarn, preparation method thereof and fiber |
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| CN104211954B (en) * | 2013-05-30 | 2016-10-05 | 辽宁银珠化纺集团有限公司 | A kind of preparation method of halogen-free flame-proof nylon 66 having polymer |
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