CN105153415B - A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof - Google Patents
A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof Download PDFInfo
- Publication number
- CN105153415B CN105153415B CN201510435858.5A CN201510435858A CN105153415B CN 105153415 B CN105153415 B CN 105153415B CN 201510435858 A CN201510435858 A CN 201510435858A CN 105153415 B CN105153415 B CN 105153415B
- Authority
- CN
- China
- Prior art keywords
- fire
- retardant
- copolymer material
- nylon
- performed polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC*(*=N)P1(Clc(cccc2)c2C2=C1CCC=C2)=Cl Chemical compound CC*(*=N)P1(Clc(cccc2)c2C2=C1CCC=C2)=Cl 0.000 description 4
Landscapes
- Polyamides (AREA)
Abstract
The present invention relates to a kind of fire-retardant Nylon 66 copolymer material and preparation method thereof, and more particularly to a kind of phosphorous reactive flame retardant, block fire-retardant Nylon 66 copolymer material and preparation method thereof is obtained by polymerisation.Its main feature is that fire retardant and diamine or diol reaction are obtained fire retardant performed polymer first, fire retardant performed polymer and nylon66 fiber prepolymer reaction are then obtained into fire-retardant Nylon 66 copolymer material.Fire-retardant Nylon 66 copolymer material made from this method has the advantages that few fire retardant additive amount, good mechanical performance, fire-retardant persistence are good, and vertical burn test is up to 0 grade of UL94V, and limited oxygen index is more than 32%.Not only directly injection molding or film can be made in this fire-retardant Nylon 66 copolymer material, and fire resistance fibre can be also prepared through melt spinning for fields such as clothes, fabrics.
Description
Technical field
The invention belongs to fire-retardant nylon synthesis technical field, is related to a kind of fire-retardant Nylon 66 copolymer material and its preparation side
Method, more particularly to a kind of phosphorous reactive flame retardant performed polymer block fire-retardant Nylon 66 copolymer material and preparation method thereof.
Background technology
Nylon66 fiber is one of most widely used kind in engineering plastics, has excellent wearability, self lubricity and resistance to
Chemical corrosivity etc., but the limited oxygen index of nylon66 fiber only has 21~23%, fire resistance is poor, seriously limits it each
The application of industry, so the fire resistance for improving nylon66 fiber has important practical significance.
At present, the method for modifying flame of nylon66 fiber mainly has three kinds：First, fabric post-treatment method, this method is fire-retardant to hold
Long property is poor, and can influence the feel of fabric；Second, using additive flame retardant, i.e., by the method for mechanical mixture by fire retardant
It is added in nylon66 fiber matrix, it is this method positive effect, easy to operate, applied widely, but flame retardant particle is dispersed
Poor and easy reunion, has considerable influence to the mechanical performance and processing performance of polymer；3rd, using reactive flame retardant, i.e.,
Make it participate in polymerizeing as a kind of reaction monomers fire retardant addition polymerization reaction system, flame-retardant composition is attached to nylon66 fiber point
On sub- main chain or side chain, have the advantages that good heat endurance, small toxicity, flame retardant effect are lasting, and to the performance of nylon66 fiber
Influence small, be a kind of ideal method of modifying.
Chinese patent (publication number CN1266445A) using reactive flame retardant 2- carboxyethyl phenyl phosphinic acids (CEPPA) with
The copolymerization of 66 salt is made fire-retardant Nylon 66 polymer, and flame retardant molecule is aggregated on nylon66 fiber strand that to improve product fire-retardant persistently
Property.Chinese patent (publication number CN101805444A) is randomly common with terephthalic acid (TPA), ethylene glycol monomers using reactive flame retardant
It is poly- to obtain flame retardant polyester, obtain flame-retardant and anti-dripping polyester.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, so as to influence its mechanics
Performance.In addition, reactive flame retardant is usually randomly distributed in polymer matrix, for random copolymer, with non-knot
The increase of brilliant comonomer (fire retardant) concentration, fusing point monotonic decreasing, that is to say, that with increasing for flame retardant agent content, high polymer base
Bulk melting point gradually reduces, so as to limit the use scope of high polymer.Therefore, we, which are faced with, both needs a certain amount of fire retardant
Addition is also required to maintain the contradiction of the heat safe performance of nylon to reach flame retardant effect.Therefore, the present invention will be fire-retardant
Agent is first processed into fire retardant performed polymer, then fire retardant performed polymer and nylon66 fiber performed polymer are copolymerized to obtain block fire-retardant Nylon 66 and are total to
Polymer material.
The content of the invention
The object of the present invention is to provide a kind of fire-retardant Nylon 66 copolymer material and preparation method thereof, especially it is to provide one kind
Phosphonium flame retardant performed polymer block fire-retardant Nylon 66 copolymer material and preparation method thereof.The block nylon66 fiber that the present invention obtains is total to
Polymers not only has good fire resistance, but also maintains its heat safe performance, this is because for block copolymer, when
When comonomer (fire retardant) content increases to very big, fusing point still maintains constant.Meanwhile block copolymer overcomes random copolymerization
Is destroyed to material crystal structure, compared with pure nylon66 fiber, the fusing point and crystal property of fire-retardant Nylon 66 copolymer are equal the shortcomings that big
Without significant change, mechanical property does not have great changes yet.Therefore, the fire-retardant Nylon 66 copolymer that the present invention obtains can not only be used
In the raw material of plastics, film etc., fire resistance fibre can also be made through melt spinning, be applied to flame-retardant textile field.
A kind of fire-retardant Nylon 66 copolymer material of the present invention, molecular structural formula are：
Wherein, x >=30, y >=30；z≥2；3/100≤z/(x+y)≤10/100；
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 preferable technical solution：
A kind of fire-retardant Nylon 66 copolymer material as described above, its limited oxygen index more than 32%, survey by vertical combustion
Examination reaches UL94V-0 grades.
A kind of fire-retardant Nylon 66 copolymer material as described above, its number-average molecular weight Mn are 1.8 × 104~3.0 × 104,
The fusing point of material is 255~260 DEG C, and tensile strength is in 60~88MPa, and elongation at break is 100%~200%.
Present invention also offers a kind of preparation method of fire-retardant Nylon 66 copolymer material, first by fire retardant and diamine
Or dihydric alcohol polycondensation obtains fire retardant performed polymer, then fire retardant performed polymer and nylon66 fiber performed polymer are copolymerized, obtained
To block fire-retardant Nylon 66 copolymer material；The fire retardant performed polymer is viscous liquid or semisolid, number-average molecular weight
Mn is 103~104, and be the active function groups with carboxyl, amido or hydroxyl at molecule both ends；
The structure of the fire retardant is：
Wherein：The R1、R3For straight chain, branched or cricoid C1~C15Alkylidene；R2、R4For straight chain, branched or ring-type
C1~C15Alkyl or aryl；
A kind of preparation method of fire-retardant Nylon 66 copolymer material 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 of fire-retardant Nylon 66 copolymer material as described above, specifically includes following steps：
(1) fire retardant, diamine or dihydric alcohol are uniformly mixed with water, reaction are stirred at 90~130 DEG C, then be warming up to
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, when pressure is up to 1.7~2.0MPa, heat-insulation pressure keeping obtains Buddhist nun for a period of time
Imperial 66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 103~104, and be respectively one at the both ends of nylon66 fiber performed polymer
The active end group of a carboxyl and amido, just has the work that can be reacted to each other between such nylon66 fiber performed polymer and fire retardant performed polymer
Property end group.
(3) 3~9 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7~2.0MPa pressure, heating
To 240~260 DEG C, and gas reactor is slowly released to normal pressure within a period of time, fire retardant performed polymer and nylon66 fiber are pre- at this time
Aggressiveness takes place copolyreaction, reacts to each other between the active end group between two performed polymers, and strand gradually increases, and generation is embedding
Section nylon66 fiber copolymer；
(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
Mix, stand discharging, reaction product is fire-retardant Nylon 66 copolymer, due to that can produce a small amount of water in reaction process, suppresses reaction
Progress, suppress the growth of strand, vacuumize removing excessive moisture at this time so that polymer molecular weight further improves.
A kind of preparation method of fire-retardant Nylon 66 copolymer material as described above, in the step (1), is uniformly mixed 2
~3 it is small when, stirring reaction 2~3 it is small when, further polymerize 2~3 it is small when.
A kind of preparation method of fire-retardant Nylon 66 copolymer material as described above, first leads to before the middle heating of the step (2)
Enter N2Discharge air, closed heating.
A kind of preparation method of fire-retardant Nylon 66 copolymer material as described above, heat-insulation pressure keeping one in the step (2)
When the section time refers to that holding 1~3 is small.
A kind of preparation method of fire-retardant Nylon 66 copolymer material as described above, deflate in the step (3) one section when
Between refer to 2~4 it is small when.
A kind of preparation method of fire-retardant Nylon 66 copolymer material as described above, vacuumizes holding in the step (4)
When a period of time refers to that holding 0.5~1 is small.
Beneficial effect：
(1) fire retardant is added in nylon66 fiber polymerization process, flame-retardant composition is connected on nylon66 fiber strand, had fire-retardant
The advantages of agent 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) present invention obtains block fire-retardant Nylon 66 copolymer by polymerisation, its fusing point is kept approximately constant, and is being carried
While high flame resistance, its heat safe performance is maintained, is convenient for the following process process such as spinning, application prospect
It is wide.
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 of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, hexamethylene diamine are mixed with water, in 50 DEG C of uniformly mixed 2h under nitrogen protection, then at 90 DEG C
Stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer, its
For viscous liquid, 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, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively 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 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, it is pre- to obtain nylon66 fiber
Aggressiveness, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.5 × 103；
(3) 9 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7MPa pressure, are warming up to 240 DEG C,
And when 2 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=72, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 42.1%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.8 × 104, the fusing point of material is 255 DEG C, tensile strength in 62MPa,
Elongation at break is 103%.
Embodiment 2
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, hexamethylene diamine are mixed with water, in 80 DEG C of uniformly mixed 3h under nitrogen protection, then 130
Stirring reaction 3h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it 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 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 6.4 × 103；
(3) 3 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 2.0MPa pressure, are warming up to 260 DEG C,
And when 4 is small interior gas reactor of slowly releasing 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, reaction
Product is fire-retardant Nylon 66 copolymer, its molecular structural formula is：
Wherein：X+y=122, is the number of repeat unit of nylon66 fiber；Z=8, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 32.0%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 3.0 × 104, the fusing point of material is 260 DEG C, tensile strength in 86MPa,
Elongation at break is 198%.
Embodiment 3
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, hexamethylene diamine are mixed with water, in 60 DEG C of uniformly mixed 2.5h under nitrogen protection, then 95
Stirring reaction 2h at DEG C, then 160 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.8 × 103, the molar ratio of fire retardant BCPPO, hexamethylene diamine and water are 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 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 2.6 × 104；
(3) 8 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, are warming up to 250 DEG C,
And when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=68, is the number of repeat unit of nylon66 fiber；Z=6, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 40.6%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.8 × 104, the fusing point of material is 256 DEG C, tensile strength in 65MPa,
Elongation at break is 102%.
Embodiment 4
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, hexamethylene diamine are mixed with water, in 55 DEG C of uniformly mixed 3h under nitrogen protection, then 120
Stirring reaction 2.5h at DEG C, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, it is pre- that reaction terminates generation fire retardant
Aggressiveness, it is viscous liquid, and number-average molecular weight Mn is 2.5 × 103, the molar ratio of fire retardant CEMPP, hexamethylene diamine and water are 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 nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 9.2 × 103；
(3) 3.3 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 255
DEG C, and when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=104, is the number of repeat unit of nylon66 fiber；Z=10, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 33.8%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.6 × 104, the fusing point of material is 258 DEG C, tensile strength in 81MPa,
Elongation at break is 184%.
Embodiment 5
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, butanediol are mixed with water, in 70 DEG C of uniformly mixed 2h under nitrogen protection, then at 100 DEG C
Lower stirring reaction 2.5h, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it 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, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively 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 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.0 × 104；
(3) 5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, are warming up to 250 DEG C,
And when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=90, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 36.2%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.2 × 104, the fusing point of material is 258 DEG C, tensile strength 75MPa,
Elongation at break is 130%.
Embodiment 6
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, butanediol are mixed with water, in 80 DEG C of uniformly mixed 2h under nitrogen protection, then 120
Stirring reaction 2h at DEG C, then 165 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant CEPPA, butanediol and water are 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 nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 8.0 × 103；
(3) 8.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, is warming up to 245
DEG C, and when 2 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=75, is the number of repeat unit of nylon66 fiber；Z=7, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 40.9%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.9 × 104, the fusing point of material is 256 DEG C, tensile strength in 65MPa,
Elongation at break is 110%.
Embodiment 7
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, butanediol are mixed with water, in 70 DEG C of uniformly mixed 2h under nitrogen protection, then 130
Stirring reaction 2h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 1.6 × 103, the molar ratio of fire retardant BCPPO, butanediol and water are 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 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 6.5 × 103；
(3) 3.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, is warming up to 250
DEG C, and when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=121, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 33.3%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.9 × 104, the fusing point of material is 260 DEG C, tensile strength 82MPa,
Elongation at break is 185%.
Embodiment 8
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, butanediol are mixed with water, in 75 DEG C of uniformly mixed 2h under nitrogen protection, then 125
Stirring reaction 2h at DEG C, then 175 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 1.8 × 103, the molar ratio of fire retardant CEMPP, butanediol and water are 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 nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 7.2 × 103；
(3) 4.8 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 255
DEG C, and when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=98, is the number of repeat unit of nylon66 fiber；Z=8, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 35.4%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.4 × 104, the fusing point of material is 258 DEG C, tensile strength in 74MPa,
Elongation at break is 136%.
Embodiment 9
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, decamethylene diamine are mixed with water, in 80 DEG C of uniformly mixed 2h under nitrogen protection, then at 99 DEG C
Stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer, its
For semisolid, number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant DDP, decamethylene diamine and water are 1:1.1:2.4, gained
Fire retardant performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant DDP is：
(2) 91.9 mass parts, 66 salt, 0.6 mass parts adipic acid are made into 80% aqueous solution, is uniformly mixed and adds 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 1.8MPa, when heat-insulation pressure keeping 1 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 5.4 × 103；
(3) 7.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7MPa pressure, is warming up to 260
DEG C, and when 4 is small interior gas reactor of slowly releasing to normal pressure；
(4) 265 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=80, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 38.9%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.0 × 104, the fusing point of material is 257 DEG C, tensile strength in 68MPa,
Elongation at break is 155%.
Embodiment 10
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, decamethylene diamine are mixed with water, in 80 DEG C of uniformly mixed 3h under nitrogen protection, then at 99 DEG C
Lower stirring reaction 2h, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is viscous liquid, and number-average molecular weight Mn is 1.5 × 103, the molar ratio of fire retardant CEPPA, decamethylene diamine 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 amido；
The structure of fire retardant is：
(2) 90.4 mass parts, 66 salt, 0.8 mass parts adipic acid are made into 65% aqueous solution, is uniformly mixed and adds high pressure
Reaction kettle, 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 3.0 × 104；
(3) 8.8 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 245
DEG C, and when 3 is small interior gas reactor of slowly releasing 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=78, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 40.3%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.9 × 104, the fusing point of material is 255 DEG C, tensile strength in 66MPa,
Elongation at break is 120%.
Embodiment 11
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, decamethylene diamine are mixed with water, in 50 DEG C of uniformly mixed 2h under nitrogen protection, then at 90 DEG C
Lower stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is viscous liquid, and number-average molecular weight Mn is 1.5 × 103, the molar ratio of fire retardant BCPPO, decamethylene diamine and water are 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) 90.8 mass parts, 66 salt, 0.6 mass parts adipic acid are made into 62% aqueous solution, is uniformly mixed and adds 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 1.9MPa, when heat-insulation pressure keeping 1 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 3.2 × 104；
(3) 8.6 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 245
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 262 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=77, is the number of repeat unit of nylon66 fiber；Z=3, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 41.6%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.9 × 104, the fusing point of material is 256 DEG C, tensile strength in 68MPa,
Elongation at break is 130%.
Embodiment 12
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, decamethylene diamine are mixed with water, in 55 DEG C of uniformly mixed 2h under nitrogen protection, then at 95 DEG C
Lower stirring reaction 2h, then 155 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is viscous liquid, and number-average molecular weight Mn is 1.8 × 103, the molar ratio of fire retardant CEMPP, decamethylene diamine and water are 1:1.1:
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) 96 mass parts, 66 salt, 0.8 mass parts adipic acid are made into 64% 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 218 DEG C, when pressure reaches 1.7MPa, when heat-insulation pressure keeping 1 is small, obtain nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.2 × 104；
(3) 3.2 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7MPa pressure, is warming up to 255
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 268 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=120, is the number of repeat unit of nylon66 fiber；Z=6, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 33.4%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.9 × 104, the fusing point of material is 260 DEG C, tensile strength in 85MPa,
Elongation at break is 192%.
Embodiment 13
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, propane diols are mixed with water, in 80 DEG C of uniformly mixed 3h under nitrogen protection, then at 130 DEG C
Lower stirring reaction 3h, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is semisolid, and number-average molecular weight Mn is 1.6 × 103, the molar ratio of fire retardant DDP, propane diols and water are 1:1.5:2.5, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 95.6 mass parts, 66 salt, 0.4 mass parts adipic acid are made into 65% aqueous solution, is uniformly mixed and adds high pressure
Reaction kettle, is first passed through N2Air is discharged, it is closed to be warming up to 212 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 1 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 7.8 × 103；
(3) 4 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, are warming up to 246 DEG C,
And when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.08MPa, keep 0.6 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=104, is the number of repeat unit of nylon66 fiber；Z=4, is the number of repeat unit of fire retardant.
The limited oxygen index of the fire-retardant Nylon 66 copolymer material is 34.2%, and vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.5 × 104, the fusing point of material is 258 DEG C, tensile strength in 76MPa,
Elongation at break is 178%.
Embodiment 14
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, propane diols are mixed with water, in 60 DEG C of uniformly mixed 2.5h under nitrogen protection, then 95
Stirring reaction 2h at DEG C, then 160 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.4 × 103, the molar ratio of fire retardant CEPPA, propane diols and water are 1:
1.2:2.1, 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) 93.3 mass parts, 66 salt, 0.7 mass parts adipic acid are made into 60% aqueous solution, is uniformly mixed and adds high pressure
Reaction kettle, is first passed through N2Air is discharged, it is closed to be warming up to 218 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 1.2 is small, obtain Buddhist nun
Imperial 66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.8 × 104；
(3) 6 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, are warming up to 249 DEG C,
And when 3 is small interior gas reactor of slowly releasing to normal pressure；
(4) 260 DEG C are warming up to again, is evacuated down to -0.06MPa, keep 1 it is small when after stop stirring, stand discharging, reaction
Product is fire-retardant Nylon 66 copolymer, its molecular structural formula is：
Wherein：X+y=87, is the number of repeat unit of nylon66 fiber；Z=9, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 38.1%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.2 × 104, the fusing point of material is 257 DEG C, tensile strength in 69MPa,
Elongation at break is 162%.
Embodiment 15
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, propane diols are mixed with water, in 70 DEG C of uniformly mixed 2h under nitrogen protection, then 100
Stirring reaction 2.5h at DEG C, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, it is pre- that reaction terminates generation fire retardant
Aggressiveness, it is semisolid, and number-average molecular weight Mn is 2.1 × 103, the molar ratio of fire retardant BCPPO, propane diols and water are 1:1.1:
2.1, 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) 95.9 mass parts, 66 salt, 0.3 mass parts adipic acid are made into 62% aqueous solution, is uniformly mixed and adds 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 nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 5.8 × 103；
(3) 3.8 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, is warming up to 245
DEG C, and when 4 is small interior gas reactor of slowly releasing to normal pressure；
(4) 266 DEG C are warming up to again, is evacuated down to -0.06MPa, keep 0.7 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=115, is the number of repeat unit of nylon66 fiber；Z=5, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 34.6%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.8 × 104, the fusing point of material is 259 DEG C, tensile strength in 80MPa,
Elongation at break is 178%.
Embodiment 16
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, propane diols are mixed with water, in 75 DEG C of uniformly mixed 2h under nitrogen protection, then 115
Stirring reaction 2.5h at DEG C, then 175 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, it is pre- that reaction terminates generation fire retardant
Aggressiveness, it is semisolid, and number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant CEMPP, propane diols and water are 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) 91 mass parts, 66 salt, 0.2 mass parts adipic acid are made into 66% 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 3 is small, obtain nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 6.2 × 104；
(3) 8.8 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 255
DEG C, and when 4 is small interior gas reactor of slowly releasing to normal pressure；
(4) 267 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.8 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=71, is the number of repeat unit of nylon66 fiber；Z=10, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 40.1%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.8 × 104, the fusing point of material is 255 DEG C, tensile strength in 61MPa,
Elongation at break is 112%.
Embodiment 17
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, octamethylenediamine are mixed with water, in 80 DEG C of uniformly mixed 2h under nitrogen protection, then at 120 DEG C
Lower stirring reaction 2h, then 165 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is viscous liquid, and number-average molecular weight Mn is 2.4 × 103, the molar ratio of fire retardant DDP, octamethylenediamine and water are 1:1.4:
2.2, 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) 91 mass parts, 66 salt, 0.7 mass parts adipic acid are made into 68% 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 220 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 1.5 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 2.7 × 103；
(3) 8.3 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, is warming up to 242
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 268 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, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=74, is the number of repeat unit of nylon66 fiber；Z=5, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 39.5%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.9 × 104, the fusing point of material is 255 DEG C, tensile strength in 62MPa,
Elongation at break is 106%.
Embodiment 18
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, octamethylenediamine are mixed with water, in 70 DEG C of uniformly mixed 2h under nitrogen protection, then 130
Stirring reaction 2h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant, octamethylenediamine and water is 1:1.4:
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) 95 mass parts, 66 salt, 0.8 mass parts adipic acid are made into 66% 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 1.5 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 6.8 × 103；
(3) 4.2 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 250
DEG C, and when 3 is small interior gas reactor of slowly releasing to normal pressure；
(4) 270 DEG C are warming up to again, is evacuated down to -0.09MPa, keep 0.8 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=106, is the number of repeat unit of nylon66 fiber；Z=6, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 35.4%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.6 × 104, the fusing point of material is 259 DEG C, tensile strength in 73MPa,
Elongation at break is 172%.
Embodiment 19
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, octamethylenediamine are mixed with water, in 80 DEG C of uniformly mixed 2h under nitrogen protection, then at 99 DEG C
Lower stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is semisolid, and number-average molecular weight Mn is 2.5 × 103, the molar ratio of fire retardant BCPPO, octamethylenediamine and water are 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) 92.7 mass parts, 66 salt, 0.3 mass parts adipic acid are made into 68% aqueous solution, is uniformly mixed and adds high pressure
Reaction kettle, is first passed through N2Air is discharged, it is closed to be warming up to 212 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 2 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 1.5 × 104；
(3) 7 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, are warming up to 246 DEG C,
And when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 263 DEG C are warming up to again, is evacuated down to -0.05MPa, keep 0.7 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=78, is the number of repeat unit of nylon66 fiber；Z=5, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 38.2%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.0 × 104, the fusing point of material is 256 DEG C, tensile strength in 71MPa,
Elongation at break is 149%.
Embodiment 20
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, octamethylenediamine are mixed with water, in 75 DEG C of uniformly mixed 2h under nitrogen protection, then 105
Stirring reaction 2h at DEG C, then 160 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is semisolid, and number-average molecular weight Mn is 1.9 × 103, the molar ratio of fire retardant CEMPP, octamethylenediamine and water are 1:1.2:
2.2, 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) 94 mass parts, 66 salt, 0.5 mass parts adipic acid are made into 70% 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 214 DEG C, when pressure reaches 1.75MPa, when heat-insulation pressure keeping 2 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 3.3 × 103；
(3) 5.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.75MPa pressure, is warming up to 248
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 267 DEG C are warming up to again, is evacuated down to -0.05MPa, keep 0.8 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=93, is the number of repeat unit of nylon66 fiber；Z=7, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 37.7%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.3 × 104, the fusing point of material is 257 DEG C, tensile strength in 66MPa,
Elongation at break is 115%.
Embodiment 21
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant DDP, ethylene glycol are mixed with water, in 80 DEG C of uniformly mixed 3h under nitrogen protection, then at 99 DEG C
Stirring reaction 2h, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer, its
For viscous liquid, number-average molecular weight Mn is 2.7 × 103, the molar ratio of fire retardant DDP, ethylene glycol and water are 1:1:2.2, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 92.5 mass parts, 66 salt, 0.3 mass parts adipic acid are made into 66% aqueous solution, is uniformly mixed and adds high pressure
Reaction kettle, is first passed through N2Air is discharged, it is closed to be warming up to 211 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 1 is small, obtain nylon
66 performed polymers, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.2 × 103；
(3) 7.2 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.8MPa pressure, is warming up to 242
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.8 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=72, is the number of repeat unit of nylon66 fiber；Z=7, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 39.3%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 1.9 × 104, the fusing point of material is 256 DEG C, tensile strength in 69MPa,
Elongation at break is 144%.
Embodiment 22
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEPPA, ethylene glycol are mixed with water, in 50 DEG C of uniformly mixed 2h under nitrogen protection, then at 90 DEG C
Lower stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer,
It is viscous liquid, and number-average molecular weight Mn is 3.1 × 103, the molar ratio of fire retardant, ethylene glycol and water is 1:1:2, gained resistance
Combustion agent performed polymer both ends are respectively the active end group of a carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 93 mass parts, 66 salt, 0.5 mass parts adipic acid are made into 80% 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 211 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 2 is small, obtain nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 4.9 × 104；
(3) 6.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7MPa pressure, is warming up to 242
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 265 DEG C are warming up to again, is evacuated down to -0.08MPa, keep 0.7 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=80, is the number of repeat unit of nylon66 fiber；Z=12, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 37.0%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.1 × 104, the fusing point of material is 257 DEG C, tensile strength in 70MPa,
Elongation at break is 154%.
Embodiment 23
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant BCPPO, ethylene glycol are mixed with water, in 80 DEG C of uniformly mixed 3h under nitrogen protection, then 130
Stirring reaction 3h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is semisolid, and number-average molecular weight Mn is 2.1 × 103, the molar ratio of fire retardant BCPPO, ethylene glycol and water are 1:1.1:
2.5, 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, 0.5 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 214 DEG C, when pressure reaches 1.8MPa, when heat-insulation pressure keeping 1 is small, obtain nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 2.5 × 104；
(3) 4.5 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 246
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 266 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 0.8 it is small when after stop stirring, stand discharging, instead
It is fire-retardant Nylon 66 copolymer to answer product, its molecular structural formula is：
Wherein：X+y=102, is the number of repeat unit of nylon66 fiber；Z=5, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 36.3%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.5 × 104, the fusing point of material is 258 DEG C, tensile strength in 72MPa,
Elongation at break is 170%.
Embodiment 24
A kind of preparation method of fire-retardant Nylon 66 copolymer material, specifically includes following steps：
(1) fire retardant CEMPP, ethylene glycol are mixed with water, in 70 DEG C of uniformly mixed 3h under nitrogen protection, then 125
Stirring reaction 2h at DEG C, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is semisolid, and number-average molecular weight Mn is 2.0 × 103, the molar ratio of fire retardant CEMPP, ethylene glycol and water are 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) 96 mass parts, 66 salt, 0.6 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 224 DEG C, when pressure reaches 1.9MPa, when heat-insulation pressure keeping 1 is small, obtain nylon66 fiber
Performed polymer, the number-average molecular weight Mn of nylon66 fiber performed polymer is 3.5 × 104；
(3) 3.4 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.9MPa pressure, is warming up to 268
DEG C, and when 2 is small interior gas reactor of slowly releasing to normal pressure；
(4) 273 DEG C are warming up to again, is evacuated down to -0.07MPa, keep 1 it is small when after stop stirring, stand discharging, reaction
Product is fire-retardant Nylon 66 copolymer, its molecular structural formula is：
Wherein：X+y=111, is the number of repeat unit of nylon66 fiber；Z=10, is the number of repeat unit of fire retardant.
For the limited oxygen index of the fire-retardant Nylon 66 copolymer material 34.5%, vertical burn test reaches UL94V-0 grades；Resistance
The number-average molecular weight Mn for firing nylon66 fiber copolymer material is 2.7 × 104, the fusing point of material is 259 DEG C, tensile strength in 79MPa,
Elongation at break is 182%.
Claims (8)
1. a kind of fire-retardant Nylon 66 copolymer material, it is characterised in that molecular structural formula is：
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 number-average molecular weight Mn of the fire-retardant Nylon 66 copolymer material is 1.8 × 104~3.0 × 104, the fire-retardant nylon
For the limited oxygen index of 66 copolymer materials more than 32%, vertical burn test reaches UL94V-0 grade, and the fusing point of material is 255~
260 DEG C, tensile strength is in 60~88MPa, and elongation at break is 100~200%.
2. the preparation method of a kind of fire-retardant Nylon 66 copolymer material according to claim 1, it is characterised in that first will
Fire retardant obtains fire retardant performed polymer with diamine or dihydric alcohol polycondensation, then sends out fire retardant performed polymer and nylon66 fiber performed polymer
Raw copolyreaction, obtains fire-retardant Nylon 66 copolymer material；The fire retardant performed polymer is viscous liquid or semisolid, is counted
Average molecular weight Mn is 103~104, and be the active function groups with carboxyl, amido or hydroxyl at molecule both ends；
The structure 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. the preparation method of a kind of fire-retardant Nylon 66 copolymer material according to claim 2, it is characterised 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 of fire-retardant Nylon 66 copolymer material according to claim 2, it is characterised in that specific bag
Include following steps：
(1) fire retardant, diamine or dihydric alcohol are uniformly mixed with water, reaction are stirred at 90~130 DEG C, then be 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, 66 salt, 0.1~1 mass parts adipic acid are made into 60%~80% aqueous solution, is uniformly mixed and adds
Enter autoclave, be warming up to 210~230 DEG C, when pressure is up to 1.7~2.0MPa, heat-insulation pressure keeping for a period of time, obtains nylon66 fiber
Performed polymer；
(3) 3~9 mass parts fire retardant performed polymers are added in nylon66 fiber performed polymer under 1.7~2.0MPa pressure, be warming up to
240~260 DEG C, and gas reactor is slowly released to normal pressure within a period of time；
(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, reaction product is fire-retardant Nylon 66 copolymer.
A kind of 5. preparation method of fire-retardant Nylon 66 copolymer material according to claim 4, it is characterised in that the step
Suddenly in (1), be uniformly mixed 2~3 it is small when, stirring reaction 2~3 it is small when, further polymerize 2~3 it is small when.
A kind of 6. preparation method of fire-retardant Nylon 66 copolymer material according to claim 4, it is characterised in that the step
Suddenly in (2) N is first passed through before heating2Discharge air, closed heating.
A kind of 7. preparation method of fire-retardant Nylon 66 copolymer material according to claim 4, it is characterised in that the step
Suddenly when heat-insulation pressure keeping refers to that holding 1~3 is small for a period of time in (2).
A kind of 8. preparation method of fire-retardant Nylon 66 copolymer material according to claim 4, it is characterised in that the step
Suddenly deflate in (3) a period of time refer to 2~4 it is small when；Holding is vacuumized in the step (4) and refers to holding 0.5~1 for a period of time
Hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510435858.5A CN105153415B (en) | 2015-07-22 | 2015-07-22 | A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510435858.5A CN105153415B (en) | 2015-07-22 | 2015-07-22 | A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153415A CN105153415A (en) | 2015-12-16 |
| CN105153415B true CN105153415B (en) | 2018-04-17 |
Family
ID=54794487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510435858.5A Expired - Fee Related CN105153415B (en) | 2015-07-22 | 2015-07-22 | A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153415B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837816B (en) * | 2016-04-22 | 2018-02-16 | 宁波好点烟具有限公司 | A kind of fire-retardant Nylon 66 and preparation method thereof |
| CN106750270A (en) * | 2016-12-08 | 2017-05-31 | 四川东材科技集团股份有限公司 | A kind of N P synergistic fire-retardant Nylon 66s and preparation method thereof |
| CN106633828B (en) * | 2017-01-06 | 2019-07-02 | 东华大学 | A kind of halogen-free flame-retardant polyamide 66 and preparation method thereof |
| CN106832911B (en) * | 2017-01-06 | 2019-06-11 | 东华大学 | A kind of Flameproof polyamide 66 and preparation method thereof |
| CN107189062A (en) * | 2017-06-29 | 2017-09-22 | 四川东方绝缘材料股份有限公司 | A kind of low melting point fire-resistant copolyesters nylon and preparation method thereof |
| CN107501545A (en) * | 2017-08-17 | 2017-12-22 | 中央军委后勤保障部军需装备研究所 | A kind of low regain Flameproof polyamide and preparation method thereof |
| CN109705341B (en) * | 2019-01-10 | 2021-04-16 | 军事科学院系统工程研究院军需工程技术研究所 | P-N-Si synergistic flame-retardant copolymerized polyamide 66 and preparation method thereof |
| CN110218311B (en) * | 2019-05-09 | 2021-01-12 | 金发科技股份有限公司 | Flame-retardant semi-aromatic polyamide and preparation method thereof |
| CN112920410B (en) * | 2021-01-29 | 2022-05-27 | 浙江恒逸石化研究院有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
| CN113234320A (en) * | 2021-04-30 | 2021-08-10 | 福建融海新材料科技有限公司 | Anti-aging heat insulation strip and preparation process thereof |
| CN113956291A (en) * | 2021-11-05 | 2022-01-21 | 湖南世博瑞高分子新材料有限公司 | Diacid monomer, copolymerization flame retardant nylon prepared from diacid monomer and copolymerization flame retardant nylon and method |
| CN113980267A (en) * | 2021-11-24 | 2022-01-28 | 中化学科学技术研究有限公司 | High-viscosity intrinsic flame-retardant polyamide and preparation method thereof |
| CN114591623B (en) * | 2022-04-26 | 2023-08-11 | 华润化学材料科技股份有限公司 | Flame-retardant nylon elastomer material with high impact toughness and preparation method thereof |
| CN115160562B (en) * | 2022-07-22 | 2024-05-21 | 濮阳市盛通聚源新材料有限公司 | Phosphorus-containing flame-retardant high-temperature-resistant copolymerized nylon and preparation method thereof |
| CN118006118A (en) * | 2024-01-24 | 2024-05-10 | 昆山运城塑业有限公司 | Halogen-free flame-retardant biaxially oriented nylon film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231262A (en) * | 2014-09-23 | 2014-12-24 | 江苏瑞美福实业有限公司 | Preparation method for organic phosphorus copolymerized antiflaming polyamide material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921472A (en) * | 2010-08-18 | 2010-12-22 | 苏州奔腾塑业有限公司 | High impact-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof |
-
2015
- 2015-07-22 CN CN201510435858.5A patent/CN105153415B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231262A (en) * | 2014-09-23 | 2014-12-24 | 江苏瑞美福实业有限公司 | Preparation method for organic phosphorus copolymerized antiflaming polyamide material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153415A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105153415B (en) | A kind of fire-retardant Nylon 66 copolymer material and preparation method thereof | |
| CN105153414B (en) | A kind of permanent fire retardant nylon 6 material and preparation method thereof | |
| CN105155018B (en) | A kind of copolymerization 66 fiber of Flameproof polyamide and preparation method thereof | |
| CN104231262B (en) | A kind of preparation method of organophosphor copolymerization fire-retardant polyamide material | |
| Chujo et al. | A novel nonionic hydrogel from 2-methyl-2-oxazoline | |
| JP7343610B2 (en) | Flame-retardant semi-aromatic polyamide and its manufacturing method | |
| CN108424641A (en) | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening | |
| CN106496549A (en) | A kind of organophosphor system fire-resistant copolyesters nylon and preparation method thereof | |
| CN116333279B (en) | Polycarbonate toughening resin | |
| CN105155019B (en) | A kind of fiber of Flameproof polyamide 6 and preparation method thereof | |
| US20170283557A1 (en) | Process of making hydrophilic polyamide without excessive foaming | |
| CN109322008B (en) | Method for improving performance stability of spandex product | |
| KR102206786B1 (en) | Polyamide terpolymer for the production of transparent articles | |
| CN111995746B (en) | Bio-based high-temperature-resistant polyamide composite material, low-temperature pre-polycondensation preparation method and application thereof | |
| JPWO2016182001A1 (en) | Polyamide elastomer, medical device, and method for producing polyamide elastomer | |
| CN112759760B (en) | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof | |
| CN103965467A (en) | Tough nylon and preparation method thereof | |
| CN115572387B (en) | Preparation method of low-melting-point copolymerized flame-retardant polyamide | |
| CN107531896A (en) | The manufacture method of polyamide elastomer, Medical Devices and polyamide elastomer | |
| CN106589351A (en) | Semi-aromatic transparent nylon material PA6I and preparing method thereof | |
| AU2021106204A4 (en) | Flame retardant semi aromatic polyamide and preparation method thereof | |
| CN116355204A (en) | Nylon polymer and preparation method thereof | |
| CN113698594B (en) | Polyamide resin and preparation method thereof | |
| CN115725068A (en) | Polyamide elastomer based on pentamethylene diamine and preparation method and application thereof | |
| CN116948168A (en) | Flame-retardant antistatic high-temperature-resistant nylon and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180417 Termination date: 20200722 |