CN105153414A

CN105153414A - Permanent-flame-retardant nylon 6 material and preparation method therefor

Info

Publication number: CN105153414A
Application number: CN201510435315.3A
Authority: CN
Inventors: 肖茹; 刘可; 李圆圆; 朱德振; 姜铭汉; 王华平
Original assignee: Donghua University
Current assignee: Donghua University; National Dong Hwa University
Priority date: 2015-07-22
Filing date: 2015-07-22
Publication date: 2015-12-16
Anticipated expiration: 2035-07-22
Also published as: CN105153414B

Abstract

The invention relates to a permanent-flame-retardant nylon 6 material and a preparation method therefor and particularly relates to a preparation method for a block copolymerized flame-retardant nylon 6 material obtained through continuously and respectively carrying out two-step polymerization reaction on a phosphoric reactive flame retardant. The method is characterized by comprising the steps of firstly enabling the flame retardant to react with diamine or dibasic alcohol so as to obtain a flame retardant prepolymer, and then, enabling the flame retardant prepolymer to react and copolymerize with a prepolymer of nylon 6, thereby obtaining the permanent-flame-retardant nylon 6 material. The flame-retardant nylon 6 material prepared by the method has the characteristics of low flame retardant addition level and durable flame-retardant effect, the limiting oxygen index is over 30%, the vertical firing test reaches UL94V-0, and the mechanical properties are excellent; and the nylon 6 material can be subjected to injection molding directly or form films and can also become into fibers so as to further prepare flame-retardant fabrics.

Description

A kind of permanent fire retardant nylon 6 material and preparation method thereof

Technical field

The invention belongs to fire-retardant nylon synthesis technical field, relating to a kind of permanent fire retardant nylon 6 material and preparation method thereof, particularly relating to a kind of permanent fire retardant nylon 6 material containing fire retardant performed polymer being obtained by reacting block copolymerization of the two-stage polymerization by carrying out continuously and respectively and preparation method thereof.

Background technology

Nylon is one of most important engineering plastics, and nylon 6 is maximum, purposes kinds the most widely of usage quantity in nylon.Nylon 6 has good wear resistance, deformation resistant, rebound resilience and the excellent properties such as low temperature resistant, and can make fiber, film, engineering plastics etc., but the limiting oxygen index(LOI) of nylon 6 is 21 ~ 22%, flame retardant properties is undesirable, seriously limits the application of nylon 6.Therefore, the flame-retardant modified tool studying nylon 6 is of great significance.

At present, the flame-retardant modified of macromolecular material mainly contains three kinds of approach: the first, uses additive flame retardant, to nylon 6 mainly through blended method fire retardant joined realize in nylon 6 flame-retardant modified, be characterized in easy to use, widely applicable, but have considerable influence to the mechanical property of material.Second, use reactive flame retardant, namely fire retardant participates in reaction as a kind of reaction monomers, on the main chain that fire retardant is attached to nylon or side chain, make itself to there is flame-retardant composition, this method toxicity is little, flame retardant properties lasting, affect little on the use properties of material, but reactive flame retardant kind is few, complete processing is complicated, cost is higher, does not have additive flame retardant to use at present general.3rd, fabric post-treatment is fire-retardant, nylon 6 fabric can by flame-retardant after-finishing namely by grafting, roll cure, the approach such as spray application makes fire retardant be combined with fabric to obtain flame retardant effect, be characterized in that technique is simple, easy to operate, processing flexibly, but may cause the loss of fabric strength and affect its feel and washing fastness.

To nylon, copolymerization is flame-retardant modified is its flame-retardant modified important way, by using reactive flame retardant, the flame-retardant modified nylon that not only can make is carried out to nylon and obtain excellent flame retardant properties, and reactive flame retardant is incorporated on the molecular backbone chain of nylon with the formal bond of chemical bond, so just can overcome that the fire retardant that other flame-retardant modified modes bring easily is separated out, flame retardant effect is lasting, to shortcomings such as Effect on Mechanical Properties are large.2-carboxyethyl phenyl phosphinic acid (CEPPA) is adopted to obtain fire-retardant Nylon 66 polymkeric substance with the monomer copolymerization of nylon66 fiber in patented technology CN1267475C, fire retardant CEPPA is attached on the molecular backbone chain of nylon66 fiber, obtain permanent fire retardant nylon66 fiber, have certain market in engineering plastics field.Patented technology CN104211954A adopts [(6-oxo-6H-dibenzo [c, e] [1,2] the own ring of oxygen phospha-6-base) methyl] monomer copolymerization of succinic acid (DDP) and nylon66 fiber obtains fire-retardant Nylon 66 polymkeric substance, fire retardant DDP is attached to the main chain of nylon66 fiber, makes the flame retardant properties of product effective lastingly; The researchist of Northcentral University (Yang Xiaofeng. phosphorous copolyamide and the research [D] with montmorillonite composite material thereof. Northcentral University, 2009) two (p-carboxyphenyl) phenylphosphine oxide (BCPPO) is introduced nylon66 fiber, what achieve nylon66 fiber is fire-retardant lastingly.But copolymerization is flame-retardant modified also exists shortcoming, the introducing of fire retardant will inevitably have impact to the polymerization process of macromolecular material on the one hand, and cause molecular weight to decline to some extent, this must affect its mechanical property, affects its result of use; On the other hand, usual copolymerization is flame-retardant modified is the random copolymers monomer direct polymerization of fire retardant and nylon being obtained nylon and fire retardant, fire retardant is random distribution in nylon, for random copolymers, along with the concentration of noncrystalline comonomer (fire retardant) increases, fusing point monotonic decreasing, we obtain fire-retardant nylon facing to both needing a certain amount of fire retardant modification, also need the contradiction of the resistant to elevated temperatures use properties maintaining nylon simultaneously, which limits the use of nylon.Have in the modification of other superpolymer and do not pass through direct condensation, but after fire retardant being done pre-treatment pulverize with macromolecular material in Blending Processes block on macromolecular material, the way of molecular weight is improved afterwards by solid phase polycondensation, but there is fire retardant skewness in macromolecular material in this method, the probability that fire retardant is attached to high polymer main chain is low, has the shortcomings such as impact to the mechanical property of material.

Summary of the invention

The object of this invention is to provide a kind of permanent fire retardant nylon 6 material and preparation method thereof, particularly relating to a kind of permanent fire retardant nylon 6 material containing fire retardant performed polymer being obtained by reacting block copolymerization of the two-stage polymerization by carrying out continuously and respectively and preparation method thereof.The present invention is obtained by reacting block copolymerization fire-retardant Nylon 6 by the two-stage polymerization carried out continuously and respectively, the fire-retardant Nylon 6 obtained changes the fusing point of nylon 6 hardly while improving its flame retardant properties, maintain its resistant to elevated temperatures use properties, this is because for segmented copolymer, when comonomer (fire retardant) content increases to very large, fusing point still remains unchanged.Meanwhile, segmented copolymer overcomes random copolymerization and destroys large shortcoming to material crystal structure, and compared with pure nylon 6, fusing point and the crystal property of fire-retardant Nylon 6 have no significant change, and its processing and mechanical property do not have large change yet.By fire-retardant Nylon 6 of the present invention poach 48h in boiling water, its mechanical property has almost no change compared with before non-boiling water treating with flame retardant properties.Therefore, the permanent fire retardant nylon 6 of what the present invention obtained have block copolymeric structure can be applied to has flame retardant properties requirement to material, has the special dimensions such as the military affairs of high request to the mechanical property such as tensile strength and breaking tenacity of material simultaneously.

A kind of permanent fire retardant nylon 6 material of the present invention, molecular structural formula is:

Wherein,

X >=50, y >=50 are the number of repeat unit of nylon 6;

Z >=2 are the number of repeat unit of fire retardant;

And 1/100≤z/ (x+y)≤1/10;

R is

Described R ₁, R ₃for the C of straight chain, branching or ring-type ₁~ C ₁₅alkylidene group; R ₂, R ₄for the C of straight chain, branching or ring-type ₁~ C ₁₅alkyl or aryl; R ₅, R ₆for the C of straight chain ₁~ C ₁₅alkylidene group;

As preferred technical scheme:

A kind of permanent fire retardant nylon 6 material as above, the limiting oxygen index(LOI) of described permanent fire retardant nylon 6 material is more than 30%, and vertical combustion test reaches UL94V-0 level.

A kind of permanent fire retardant nylon 6 material as above, the number-average molecular weight Mn of described permanent fire retardant nylon 6 material is 1.6 × 10 ⁴~ 2.4 × 10 ⁴, the fusing point of material is 220 ~ 225 DEG C, and tensile strength is 55 ~ 78MPa, and elongation at break is 150 ~ 250%.

Present invention also offers a kind of preparation method of permanent fire retardant nylon 6 material, first fire retardant and diamine or dibasic alcohol polycondensation are obtained fire retardant performed polymer, then by fire retardant performed polymer and the nylon 6 performed polymer generation copolyreaction after pre-polymerization, permanent fire retardant nylon 6 material is obtained; Described fire retardant performed polymer is viscous liquid or semisolid, and number-average molecular weight Mn is 10 ³~ 10 ⁴, and be the active function groups with carboxyl, amido or hydroxyl at molecule two ends;

The structure of described fire retardant is:

Described R ₁, R ₃for the C of straight chain, branching or ring-type ₁~ C ₁₅alkylidene group; R ₂, R ₄for the C of straight chain, branching or ring-type ₁~ C ₁₅alkyl or aryl;

The preparation method of a kind of permanent fire retardant nylon 6 material as above, the general formula of described diamine is H ₂n-R ₅-NH ₂, the general formula of dibasic alcohol is HO-R ₆-OH; R ₅, R ₆for the C of straight chain ₁~ C ₁₅alkylidene group;

The preparation method of a kind of permanent fire retardant nylon 6 material as above, specifically comprises the following steps:

(1) fire retardant, diamine or dibasic alcohol are mixed with water, mix at 50 ~ 80 DEG C under nitrogen protection, then stirring reaction at 90 ~ 130 DEG C, then be warming up to 150 ~ 180 DEG C of polymerizations further, last decompression vacuum pumping, reaction terminates to generate fire retardant performed polymer; The mol ratio of described fire retardant, diamine or dibasic alcohol and water is 1:0.8 ~ 1.5:2 ~ 2.5, and the two ends of obtained flame-retardant agent performed polymer are the active function groups with carboxyl, amido or hydroxyl;

(2) 84.1 ~ 98.8 mass parts hexanolactams, 0.5 ~ 5 mass parts water and 0.1 ~ 1 mass parts hexanodioic acid are added reactor, stir and be warming up to 245 DEG C ~ 250 DEG C, when pressure reaches 0.5MPa ~ 0.9MPa, heat-insulation pressure keeping reacts for some time, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 10 ³~ 10 ⁴, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) fire retardant performed polymer described in 0.5 ~ 10 mass parts is added in described nylon 6 performed polymer, unlatching mixing speed is 200 ~ 400r/min, be warmed up to 235 DEG C ~ 240 DEG C, copolyreaction 6 ~ 8h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.05 ~-0.1MPa, stop stirring after keeping for some time, logical nitrogen discharging after leaving standstill 10 ~ 20min, gained reaction product is permanent fire retardant nylon 6 material, due to a small amount of moisture can be produced in reaction process, and the growth of Inhibitory molecules chain, now vacuumize removing excessive moisture, the molecular weight of polymkeric substance is increased further.

The preparation method of a kind of permanent fire retardant nylon 6 material as above, in step (1), mix 2 ~ 3h, stirring reaction 2 ~ 3h, is polymerized 2 ~ 3h further.

The preparation method of a kind of permanent fire retardant nylon 6 material as above, in step (2), stirs and heats up, and rotating speed is 200 ~ 400r/min; Heat-insulation pressure keeping reacts for some time, refers to heat-insulation pressure keeping reaction 2 ~ 4h.

The preparation method of a kind of permanent fire retardant nylon 6 material as above, in step (4), keeps for some time to refer to maintenance 0.5 ~ 1h.

The preparation method of a kind of permanent fire retardant nylon 6 material as above, stirs in step (2) and needs first to pass into N before heating up ₂discharge air in still, needs logical N in still when being added in reactor by fire retardant performed polymer in step (3) ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized.

Beneficial effect:

1, the present invention is by being attached to the performed polymer of reactive flame retardant on the main chain of nylon 6, develops permanent fire retardant nylon 6, has that fire retardant addition is few, good flame retardation effect and lasting, little to an Effect on Mechanical Properties advantage.

2, the present invention is obtained by reacting block copolymerization fire-retardant Nylon 6 by the two-stage polymerization carried out continuously and respectively, and while raising nylon 6 flame retardant resistance, its fusing point is almost constant, maintains its resistant to elevated temperatures use properties.

Embodiment

Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.

Embodiment 1

A preparation method for permanent fire retardant nylon 6 material, specifically comprises the following steps:

(1) fire retardant DDP, hexanediamine are mixed with water; 2h is mixed at 50 DEG C under nitrogen protection; then stirring reaction 2h at 90 DEG C; be warming up to 150 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.8 × 10 ³, the mol ratio of fire retardant DDP, hexanediamine and water is 1:1.1:2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 90.7 mass parts hexanolactams, 4.0 mass parts water and 0.3 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 200r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.0 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 5.0 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.05MPa, stop stirring after keeping 0.5h, logical nitrogen discharging after leaving standstill 10min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=126 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 34.3%, and vertical combustion test reaches UL94V-0 level; The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.0 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 68MPa, and elongation at break is 193.6%.

Embodiment 2

(1) fire retardant CEPPA, hexanediamine are mixed with water; 3h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 3h at 130 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.5 × 10 ³, the mol ratio of fire retardant CEPPA, hexanediamine and water is 1:1.2:2.5, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 84.0 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 250 DEG C with rotating speed, and when pressure reaches 0.9MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 10 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 8h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.1MPa, stop stirring after keeping 1h, logical nitrogen discharging after leaving standstill 20min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=190 is the number of repeat unit of nylon 6;

Z=8 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 39.2%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.6 × 10 ⁴, the fusing point of material is 225 DEG C, and tensile strength is 78MPa, and elongation at break is 190%.

Embodiment 3

(1) fire retardant BCPPO, hexanediamine are mixed with water; 2.5h is mixed at 60 DEG C under nitrogen protection; then stirring reaction 2h at 95 DEG C; be warming up to 160 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.8 × 10 ³, the mol ratio of fire retardant BCPPO, hexanediamine and water is 1:1.2:2.1, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 92.9 mass parts hexanolactams, 0.8 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 300r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.6MPa, heat-insulation pressure keeping reaction 2.5h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 8.0 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 5.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 300r/min, be warmed up to 236 DEG C, copolyreaction 7h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.08MPa, stop stirring after keeping 0.8h, logical nitrogen discharging after leaving standstill 12min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=134 is the number of repeat unit of nylon 6;

Z=6 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 34.6%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 67MPa, and elongation at break is 160%.

Embodiment 4

(1) fire retardant CEMPP, hexanediamine are mixed with water; 3h is mixed at 70 DEG C under nitrogen protection; then stirring reaction 2h at 100 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.5 × 10 ³, the mol ratio of fire retardant CEMPP, hexanediamine and water is 1:1.2:2.1, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 93 mass parts hexanolactams, 1.2 mass parts water and 0.4 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 300r/min stirs and is warming up to 248 DEG C DEG C with rotating speed, and when pressure reaches 0.6MPaMPa, heat-insulation pressure keeping reaction 2.5h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 8.0 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 4.6 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 300r/min, be warmed up to 236 DEG C, copolyreaction 7h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=164 is the number of repeat unit of nylon 6;

Z=10 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 33.5%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.1 × 10 ⁴, the fusing point of material is 222 DEG C, and tensile strength is 63MPa, and elongation at break is 210%.

Embodiment 5

(1) fire retardant DDP, butyleneglycol are mixed with water; 2h is mixed at 70 DEG C under nitrogen protection; then stirring reaction 2.5h at 100 DEG C; be warming up to 170 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 1.7 × 10 ³, the mol ratio of fire retardant DDP, butyleneglycol and water is 1:1:2.2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 91.3 mass parts hexanolactams, 1.5 mass parts water and 0.7 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 250r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 3h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 9 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 6.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 350r/min, be warmed up to 240 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.1MPa, stop stirring after keeping 1h, logical nitrogen discharging after leaving standstill 15min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=162 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 35.8%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 64MPa, and elongation at break is 190%.

Embodiment 6

(1) fire retardant CEPPA, butyleneglycol are mixed with water; 2h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 120 DEG C; be warming up to 165 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.0 × 10 ³, the mol ratio of fire retardant CEPPA, butyleneglycol and water is 1:0.9:2.2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 87.5 mass parts hexanolactams, 3 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 260r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 2.8h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 8.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 260r/min, be warmed up to 235 DEG C, copolyreaction 6.5h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.05MPa, stop stirring after keeping 1h, logical nitrogen discharging after leaving standstill 18min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=177 is the number of repeat unit of nylon 6;

Z=7 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 37.7%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.7 × 10 ⁴, the fusing point of material is 220 DEG C, and tensile strength is 58MPa, and elongation at break is 240%.

Embodiment 7

(1) fire retardant BCPPO, butyleneglycol are mixed with water; 2h is mixed at 70 DEG C under nitrogen protection; then stirring reaction 2h at 130 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.6 × 10 ³, the mol ratio of fire retardant BCPPO, butyleneglycol and water is 1:1.1:2.3, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 90 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 210 ~ r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 4.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 280r/min, be warmed up to 236 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=198 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 34.4%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.1 × 10 ⁴, the fusing point of material is 222 DEG C, and tensile strength is 60MPa, and elongation at break is 230%.

Embodiment 8

(1) fire retardant CEMPP, butyleneglycol are mixed with water; 3h is mixed at 60 DEG C under nitrogen protection; then stirring reaction 2h at 120 DEG C; be warming up to 170 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.8 × 10 ³, the mol ratio of fire retardant CEMPP, butyleneglycol and water is 1:1.1:2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 88 mass parts hexanolactams, 5.5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 210 ~ r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 5.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 280r/min, be warmed up to 236 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=161 is the number of repeat unit of nylon 6;

Z=8 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.2%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.0 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 66MPa, and elongation at break is 250%.

Embodiment 9

(1) fire retardant DDP, decamethylene diamine are mixed with water; 2h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 99 DEG C; be warming up to 150 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.0 × 10 ³, the mol ratio of fire retardant DDP, decamethylene diamine and water is 1:1.1:2.4, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant DDP is:

(2) 91.9 mass parts hexanolactams, 0.8 mass parts water and 0.3 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 290r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 4 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 7 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.07MPa, stop stirring after keeping 0.8h, logical nitrogen discharging after leaving standstill 12min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=150 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.3%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.7 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 69MPa, and elongation at break is 180%.

Embodiment 10

(1) fire retardant CEPPA, decamethylene diamine are mixed with water; 3h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 99 DEG C; be warming up to 170 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.5 × 10 ³, the mol ratio of fire retardant CEPPA, decamethylene diamine and water is 1:1:2.2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 89.5 mass parts hexanolactams, 3.2 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 248 DEG C DEG C with rotating speed, and when pressure reaches 0.6MPa, heat-insulation pressure keeping reaction 3h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 7.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 6.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 7h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

(4) then, be evacuated down to-0.1MPa, stop stirring after keeping 0.9h, logical nitrogen discharging after leaving standstill 17min, gained reaction product is permanent fire retardant nylon 6 material, and its molecular structural formula is:

Wherein,

X+y=173 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.0%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 70MPa, and elongation at break is 190%.

Embodiment 11

(1) fire retardant BCPPO, decamethylene diamine are mixed with water; 2h is mixed at 50 DEG C under nitrogen protection; then stirring reaction 2h at 90 DEG C; be warming up to 150 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.5 × 10 ³, the mol ratio of fire retardant BCPPO, decamethylene diamine and water is 1:1:2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 93.4 mass parts hexanolactams, 2.5 mass parts water and 0.6 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 200r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 3.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=127 is the number of repeat unit of nylon 6;

Z=3 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 31.9%, and vertical combustion test reaches UL94V-0 level; The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.3 × 10 ⁴, the fusing point of material is 225 DEG C, and tensile strength is 77MPa, and elongation at break is 160%.

Embodiment 12

(1) fire retardant CEMPP, decamethylene diamine are mixed with water; 3h is mixed at 60 DEG C under nitrogen protection; then stirring reaction 2h at 105 DEG C; be warming up to 165 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 1.5 × 10 ³, the mol ratio of fire retardant CEMPP, decamethylene diamine and water is 1:1.2:2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 92.4 mass parts hexanolactams, 3.5 mass parts water and 0.7 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 200r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 3.4 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=137 is the number of repeat unit of nylon 6;

Z=5 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 31.3%, and vertical combustion test reaches UL94V-0 level; The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.7 × 10 ⁴, the fusing point of material is 225 DEG C, and tensile strength is 76MPa, and elongation at break is 170%.

Embodiment 13

(1) fire retardant DDP, propylene glycol are mixed with water; 3h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 3h at 130 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 1.6 × 10 ³, the mol ratio of fire retardant DDP, propylene glycol and water is 1:1.5:2.5, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 85.5 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 250 DEG C with rotating speed, and when pressure reaches 0.9MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 4.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 8h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=198 is the number of repeat unit of nylon 6;

Z=4 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 34.5%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.1 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 65MPa, and elongation at break is 230%.

Embodiment 14

(1) fire retardant CEPPA, propylene glycol are mixed with water; 2.5h is mixed at 60 DEG C under nitrogen protection; then stirring reaction 2h at 95 DEG C; be warming up to 160 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.4 × 10 ³, the mol ratio of fire retardant CEPPA, propylene glycol and water is 1:1.2:2.1, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 90.7 mass parts hexanolactams, 3 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 300r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.6MPa, heat-insulation pressure keeping reaction 2.5h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

Wherein,

X+y=138 is the number of repeat unit of nylon 6;

Z=9 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.0%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 64MPa, and elongation at break is 180%.

Embodiment 15

(1) fire retardant BCPPO, propylene glycol are mixed with water; 2h is mixed at 70 DEG C under nitrogen protection; then stirring reaction 2.5h at 100 DEG C; be warming up to 170 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.1 × 10 ³, the mol ratio of fire retardant BCPPO, propylene glycol and water is 1:0.9:2.1, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 91.3 mass parts hexanolactams, 2.5 mass parts water and 0.7 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 250r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 3h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 4.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

Wherein,

X+y=176 is the number of repeat unit of nylon 6;

Z=5 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 35.9%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 66MPa, and elongation at break is 210%.

Embodiment 16

(1) fire retardant CEMPP, propylene glycol are mixed with water; 2.5h is mixed at 65 DEG C under nitrogen protection; then stirring reaction 3h at 110 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.5 × 10 ³, the mol ratio of fire retardant CEMPP, propylene glycol and water is 1:1:2.1, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 91.3 mass parts hexanolactams, 4.5 mass parts water and 1.2 mass parts hexanodioic acids are added reactor, first pass into N ₂discharging air in still, is that 250r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 3h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 4.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 4.0 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 350r/min, be warmed up to 240 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=173 is the number of repeat unit of nylon 6;

Z=12 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 32.7%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.2 × 10 ⁴, the fusing point of material is 224 DEG C, and tensile strength is 68MPa, and elongation at break is 210%.

Embodiment 17

(1) fire retardant DDP, octamethylenediamine are mixed with water; 2h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 120 DEG C; be warming up to 165 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.4 × 10 ³, the mol ratio of fire retardant DDP, octamethylenediamine and water is 1:1.4:2.2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 87.7 mass parts hexanolactams, 3 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 260r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 2.8h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 9.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 7.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 260r/min, be warmed up to 235 DEG C, copolyreaction 6.5h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=174 is the number of repeat unit of nylon 6;

Z=5 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.8%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 68MPa, and elongation at break is 210%.

Embodiment 18

(1) fire retardant CEPPA, octamethylenediamine are mixed with water; 2h is mixed at 70 DEG C under nitrogen protection; then stirring reaction 2h at 130 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.0 × 10 ³, the mol ratio of fire retardant CEPPA, octamethylenediamine and water is 1:1.4:2.5, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 87.5 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 210 ~ r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.8 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 6.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 280r/min, be warmed up to 236 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=194 is the number of repeat unit of nylon 6;

Z=6 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 35.4%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.0 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 55MPa, and elongation at break is 250%.

Embodiment 19

(1) fire retardant BCPPO, octamethylenediamine are mixed with water; 2h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 99 DEG C; be warming up to 150 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.5 × 10 ³, the mol ratio of fire retardant BCPPO, octamethylenediamine and water is 1:1.2:2.4, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 88.9 mass parts hexanolactams, 3.8 mass parts water and 0.3 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 290r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 7.0 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=146 is the number of repeat unit of nylon 6;

Z=5 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.1%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 72MPa, and elongation at break is 180%.

Embodiment 20

(1) fire retardant CEMPP, octamethylenediamine are mixed with water; 2.5h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 3h at 110 DEG C; be warming up to 165 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.5 × 10 ³, the mol ratio of fire retardant CEMPP, octamethylenediamine and water is 1:1.1:2.3, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and amido;

The structure of fire retardant is:

(2) 88.9 mass parts hexanolactams, 4.5 mass parts water and 1.1 mass parts hexanodioic acids are added reactor, first pass into N ₂discharging air in still, is that 290r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.8MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 6.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 5.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=146 is the number of repeat unit of nylon 6;

Z=9 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 36.1%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.9 × 10 ⁴, the fusing point of material is 223 DEG C, and tensile strength is 68MPa, and elongation at break is 160%.

Embodiment 21

(1) fire retardant DDP, ethylene glycol are mixed with water; 3h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 2h at 99 DEG C; be warming up to 170 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 2.7 × 10 ³, the mol ratio of fire retardant DDP, ethylene glycol and water is 1:1:2.2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 87.5 mass parts hexanolactams, 3.2 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 248 DEG C with rotating speed, and when pressure reaches 0.6MPa, heat-insulation pressure keeping reaction 3h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 8.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 8.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 7h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=161 is the number of repeat unit of nylon 6;

Z=7 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 37.6%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.7 × 10 ⁴, the fusing point of material is 220 DEG C, and tensile strength is 58MPa, and elongation at break is 210%.

Embodiment 22

(1) fire retardant CEPPA, ethylene glycol are mixed with water; 2h is mixed at 50 DEG C under nitrogen protection; then stirring reaction 2h at 90 DEG C; be warming up to 150 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is viscous liquid, and number-average molecular weight Mn is 3.1 × 10 ³, the mol ratio of fire retardant CEPPA, ethylene glycol and water is 1:1:2, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 91.2 mass parts hexanolactams, 4.0 mass parts water and 0.8 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 200r/min stirs and is warming up to 245 DEG C with rotating speed, and when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction 2h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 5.5 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 9.5 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 200r/min, be warmed up to 235 DEG C, copolyreaction 6h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=114 is the number of repeat unit of nylon 6;

Z=12 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 38.7%, and vertical combustion test reaches UL94V-0 level; The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 1.6 × 10 ⁴, the fusing point of material is 221 DEG C, and tensile strength is 66MPa, and elongation at break is 190%.

Embodiment 23

(1) fire retardant BCPPO, ethylene glycol are mixed with water; 3h is mixed at 80 DEG C under nitrogen protection; then stirring reaction 3h at 130 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.1 × 10 ³, the mol ratio of fire retardant BCPPO, ethylene glycol and water is 1:1.1:2.5, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 88 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 250 DEG C with rotating speed, and when pressure reaches 0.9MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 8.0 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 6.0 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 8h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=194 is the number of repeat unit of nylon 6;

Z=5 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 35.2%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.1 × 10 ⁴, the fusing point of material is 224 DEG C, and tensile strength is 65MPa, and elongation at break is 210%.

Embodiment 24

(1) fire retardant CEMPP, ethylene glycol are mixed with water; 3h is mixed at 75 DEG C under nitrogen protection; then stirring reaction 3h at 120 DEG C; be warming up to 180 DEG C of polymerizations further again; last decompression vacuum pumping; reaction terminates to generate fire retardant performed polymer, and it is semi-solid, and number-average molecular weight Mn is 2.2 × 10 ³, the mol ratio of fire retardant CEMPP, ethylene glycol and water is 1:1.2:2.5, and obtained flame-retardant agent performed polymer two ends are respectively the active end group of a carboxyl and hydroxyl;

The structure of fire retardant is:

(2) 89 mass parts hexanolactams, 5 mass parts water and 1 mass parts hexanodioic acid are added reactor, first pass into N ₂discharging air in still, is that 400r/min stirs and is warming up to 250 DEG C with rotating speed, and when pressure reaches 0.9MPa, heat-insulation pressure keeping reaction 4h, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer, the number-average molecular weight Mn of nylon 6 performed polymer is 8.0 × 10 ³, and the active end group of a carboxyl and amido is respectively at the two ends of nylon 6 performed polymer, be just provided with the active end group that can react to each other between such nylon 6 performed polymer and fire retardant performed polymer;

(3) 5.0 mass parts fire retardant performed polymers are added in nylon 6 performed polymer, and lead to N in still ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized, unlatching mixing speed is 400r/min, be warmed up to 240 DEG C, copolyreaction 8h, make fire retardant performed polymer and the copolymerization of nylon 6 performed polymer, fire retardant performed polymer can be dispersed in nylon 6 performed polymer uniformly under high velocity agitation, and can react to each other between the active end group between two performed polymers, molecular chain increases gradually;

Wherein,

X+y=167 is the number of repeat unit of nylon 6;

Z=11 is the number of repeat unit of fire retardant;

The limiting oxygen index(LOI) of this permanent fire retardant nylon 6 material is 34.6%, and vertical combustion test reaches UL94V-0 level.The number-average molecular weight Mn of permanent fire retardant nylon 6 material is 2.1 × 10 ⁴, the fusing point of material is 224 DEG C, and tensile strength is 68MPa, and elongation at break is 230%.

Claims

1. a permanent fire retardant nylon 6 material, is characterized in that, its molecular structural formula is:

Wherein,

X >=50, y >=50; Z >=2; And 1/100≤z/ (x+y)≤1/10;

R is

Described R ₁, R ₃for the C of straight chain, branching or ring-type ₁~ C ₁₅alkylidene group; R ₂, R ₄for the C of straight chain, branching or ring-type ₁~ C ₁₅alkyl or aryl; R ₅, R ₆for the C of straight chain ₁~ C ₁₅alkylidene group.

2. a kind of permanent fire retardant nylon 6 material according to claim 1, is characterized in that, the limiting oxygen index(LOI) of described permanent fire retardant nylon 6 material is more than 30%, and vertical combustion test reaches UL94V-0 level.

3. a kind of permanent fire retardant nylon 6 material according to claim 1, is characterized in that, the number-average molecular weight Mn of described permanent fire retardant nylon 6 material is 1.6 × 10 ⁴~ 2.4 × 10 ⁴, the fusing point of material is 220 ~ 225 DEG C, and tensile strength is 55 ~ 78MPa, and elongation at break is 150 ~ 250%.

4. the preparation method of a permanent fire retardant nylon 6 material, it is characterized in that: first fire retardant and diamine or dibasic alcohol polycondensation are obtained fire retardant performed polymer, then by fire retardant performed polymer and the nylon 6 performed polymer generation copolyreaction after pre-polymerization, permanent fire retardant nylon 6 material is obtained; Described fire retardant performed polymer is viscous liquid or semisolid, and number-average molecular weight Mn is 10 ³~ 10 ⁴, and be the active function groups with carboxyl, amido or hydroxyl at molecule two ends;

The structure of described fire retardant is:

Wherein: described R ₁, R ₃for the C of straight chain, branching or ring-type ₁~ C ₁₅alkylidene group; R ₂, R ₄for the C of straight chain, branching or ring-type ₁~ C ₁₅alkyl or aryl.

5. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 4, is characterized in that, the general formula of described diamine is H ₂n-R ₅-NH ₂, the general formula of dibasic alcohol is HO-R ₆-OH; R ₅, R ₆for the C of straight chain ₁~ C ₁₅alkylidene group.

6. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 4, is characterized in that, specifically comprise the following steps:

(1) fire retardant, diamine or dibasic alcohol are mixed with water, mix at 50 ~ 80 DEG C under nitrogen protection, then stirring reaction at 90 ~ 130 DEG C, then be warming up to 150 ~ 180 DEG C of polymerizations further, last decompression vacuum pumping, reaction terminates to generate fire retardant performed polymer; The mol ratio of described fire retardant, diamine or dibasic alcohol and water is 1:0.8 ~ 1.5:2 ~ 2.5;

(2) 84.1 ~ 98.8 mass parts hexanolactams, 0.5 ~ 10 mass parts water and 0.1 ~ 1 mass parts hexanodioic acid are added reactor, stir and be warming up to 245 DEG C ~ 250 DEG C, when pressure reaches 0.5MPa ~ 0.9MPa, heat-insulation pressure keeping reacts for some time, then unload and be depressed into normal pressure, obtain nylon 6 performed polymer;

(3) added in described nylon 6 performed polymer by fire retardant performed polymer described in 0.5 ~ 10 mass parts, unlatching mixing speed is 200 ~ 400r/min, is warmed up to 235 DEG C ~ 240 DEG C, copolyreaction 6 ~ 8h, makes fire retardant performed polymer and the copolymerization of nylon 6 performed polymer;

(4) then, be evacuated down to-0.05 ~-0.1MPa, stop stirring after keeping for some time, logical nitrogen discharging after leaving standstill 10 ~ 20min, gained reaction product is permanent fire retardant nylon 6 material.

7. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 6, is characterized in that, in step (1), mix 2 ~ 3h, stirring reaction 2 ~ 3h, is polymerized 2 ~ 3h further.

8. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 6, is characterized in that, in step (2), stirs and heats up, and rotating speed is 200 ~ 400r/min; Heat-insulation pressure keeping reacts for some time, refers to heat-insulation pressure keeping reaction 2 ~ 4h.

9. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 6, is characterized in that, in step (4), keeps for some time to refer to maintenance 0.5 ~ 1h.

10. the preparation method of a kind of permanent fire retardant nylon 6 material according to claim 6, is characterized in that, stirs in step (2) and needs first to pass into N before heating up ₂discharge air in still, needs logical N in still when being added in reactor by fire retardant performed polymer in step (3) ₂protection fire retardant performed polymer and nylon 6 performed polymer not oxidized.