CN109734898A - A kind of novel P-N-Si synergistic fire-resistant copolyesters polyamide 6 and preparation method thereof - Google Patents
A kind of novel P-N-Si synergistic fire-resistant copolyesters polyamide 6 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of novel P-N-Si synergistic fire-resistant copolyesters polyamide 6s and preparation method thereof.The preparation method of P-N-Si synergistic fire-resistant copolyesters polyamide 6 includes the following steps: that phosphonium flame retardant prepolymer, nitrogenous flame ratardant and Silicone-containing Flame Retardant are added in the polymerization process of polyamide 6 to get P-N-Si synergistic fire-resistant copolyesters polyamide 6 is arrived；The phosphonium flame retardant prepolymer is successively obtained through salt-forming reaction and prepolymerization reaction by phosphonium flame retardant with diamine.The present invention is reacted by using P-N-S-i synergistic flame-retardant system, by BCPPO derivative flame retardant oligomer, melamine cyanurate, Silicone-containing Flame Retardant with caprolactam, and P-N-Si synergistic has been prepared by copolymerization and has been copolymerized fire-resistant copolyesters polyamide 6.Due to synergistic effect, the flame retarding efficiency of fire retardant is high, in addition, the fire proofing that the method that the present invention is copolymerized obtains, guarantees molecular weight and mechanical property of material etc..
Description
Technical field
The present invention relates to a kind of P-N-Si synergistic fire-resistant copolyesters polyamide 6s and preparation method thereof, belong to fire proofing field.
Background technique
Polyamide (nylon) is the engineering plastics that dosage is maximum, purposes is most wide, polyamide 6 be most important nylon kind it
One, dosage is widely used greatly, high comprehensive performance, has excellent mechanical property, wearability, self-lubrication, corrosion resistance, energy
In face of more harsh use environment, it is commonly used for fibrous material and engineering plastics etc..The limit oxygen index of polyamide 6 is not high, resistance
Fuel efficiency fruit is undesirable, improves its flame retardant property and has a very important significance.
Currently, high molecular material is flame-retardant modified, there are three types of the methods of type: first, addition fire retardant is blended, and is being squeezed
Out be granulated when using twin-screw polyamide 6 is mixed with fire retardant high force dispersion realization it is flame-retardant modified, its main feature is that the scope of application
Extensively, easy to operate, but larger amount of addition is needed just to be able to achieve good flame retardant effect, the mechanical property of material can therefore by
To influence；Second, using reactive flame retardant, the flame-retardant monomer that can be reacted is added in polymerization technology for polyamide 6 and is copolymerized,
It is introduced directly into fire retardant on nylon molecules chain, it is not in move out to ask with dispersion that a small amount of addition, which can reach fire-retardant and fire retardant,
Topic, but suitable reactive flame retardant type is few, and processing technology is complex, at high cost；Third carries out fire-retardant post-processing, gathers
It is fire retardant in conjunction with fabric that 6 fabric of amide, which can be grafted by fire-retardant post-processing, roll the approach such as baking, spray application, from
And reaching fire-retardant, the method simple process is easy to operate, but will cause the strength loss and feel variation of fabric.
Be copolymerized fire-retardant with reactive flame retardant is the flame-retardant modified important method of nylon, is introduced in the molecule fire-retardant
Agent, makes product have intrinsically flame retarded effect, and flame retardant property is effective for a long time.But the polymerization temperature of nylon is higher, first has to select
Suitable reactive flame retardant is not decomposed in polymerization temperature；Secondly using fire retardant as comonomer, there can be no sealing ends
Situation, otherwise the molecular weight of polymer will be by extreme influence.Therefore it needs to provide a kind of novel synergistic fire-resistant copolyesters polyamides
Amine makes polymer while having excellent anti-flammability and mechanical property.
Summary of the invention
The object of the present invention is to provide a kind of P-N-Si synergistic fire-resistant copolyesters polyamide 6 and preparation method thereof, the present invention will
BCPPO derivative flame retardant prepolymer, melamine cyanurate, Silicone-containing Flame Retardant polymerize together with polyamide 6 salt to be prepared into
The P-N-Si synergistic fire-resistant copolyesters polyamide 6 of function admirable is arrived.
The preparation method of P-N-Si synergistic fire-resistant copolyesters polyamide 6 provided by the present invention, includes the following steps:
Be added in the polymerization process of polyamide 6 phosphonium flame retardant prepolymer, nitrogenous flame ratardant and Silicone-containing Flame Retardant to get
To the P-N-Si synergistic fire-resistant copolyesters polyamide 6.
In above-mentioned preparation method, the phosphonium flame retardant prepolymer is by phosphonium flame retardant with diamine successively through anti-at salt
It should be obtained with prepolymerization reaction；
The molecular weight of the phosphor-containing flame-proof prepolymer is 1000~5000.
In above-mentioned preparation method, the temperature of the salt-forming reaction is 60~80 DEG C, and the time is 0.5~1.5h；
The temperature of the prepolymerization reaction is 150~170 DEG C, and pressure is 0.2~0.3MPa, and the time is 0.5~1h.
In above-mentioned preparation method, the diamine be ethylenediamine, propane diamine, hexamethylene diamine, decamethylene diamine, hendecane diamines and
At least one of dodecamethylene diamine；
The structural formula of the phosphonium flame retardant is as shown in formula I, as a kind of BCPPO derivative:
In formula I, R indicate the straight chained alkyl of C1~C3, unsaturated straight chain, branch or ring-type C3~C10 alkylidene or
Containing phenyl group, preferably contain phenyl group, such as the direct-connected alkyl-substituted phenyl of C1~C10 or the direct-connected alkyl-substituted benzene of C1~C7
Base, concretely aminomethyl phenyl, ethylphenyl, acrylic phenyl, butyl phenyl or n-heptyl phenyl；
The molar ratio of the phosphonium flame retardant and the diamine can be 1:1~1.2.
In above-mentioned preparation method, the nitrogenous flame ratardant can be melamine cyanurate；
The structural formula of the Silicone-containing Flame Retardant is as shown in formula II or formula III:
In formula II or formula III, R1、R2And R3Saturations or undersaturated straight chain, branch or the ring-type C3 of expression C1~C10~
The alkylidene of C10 contains phenyl group；
R3It is preferred that the saturations or undersaturated straight chain alkylidene of C1~C3, such as methylene or allylidene；
R1It is preferred that the saturations or undersaturated straight chain alkylidene of C1~C3, such as methylene, ethylidene or allylidene；
R2It is preferred that the saturations or undersaturated straight chain alkylidene of C1~C7, such as methylene, butylidene or heptamethylene.
In above-mentioned preparation method, the polymerization process of the polyamide 6 is as follows:
1) after caprolactam, catalyst, antioxidant and water mixing temperature be 160~200 DEG C, pressure be 0.6~
It is kept the temperature under conditions of 0.8Mpa；
2) after pressure release to normal pressure, the phosphonium flame retardant prepolymer, the nitrogenous flame ratardant and described siliceous fire-retardant is added
Agent carries out polymerization reaction up to the P-N-Si synergistic fire-resistant copolyesters polyamide 6 after being warming up to 235~260 DEG C；
The polymerization reaction carries out under vacuum conditions.
In above-mentioned preparation method, the mass ratio of each raw material are as follows: 100 parts of caprolactam, 0.1~1 part of catalyst, antioxidant
0.1~1 part, 5~10 parts of water, 0.1~10 part of phosphor-containing flame-proof prepolymer, 0.1~10 part of nitrogenous flame ratardant, Silicone-containing Flame Retardant 0.1
~10 parts；Concretely following 1) -7) any in:
1) 100 parts of caprolactam, 0.1~0.5 part of catalyst, 0.1~0.9 part of antioxidant, 5~8 parts of water, phosphor-containing flame-proof is pre-
0.1~8 part of polymers, 0.1~4 part of nitrogenous flame ratardant, 0.1~6 part of Silicone-containing Flame Retardant；
2) 100 parts of caprolactam, 0.5~1 part of catalyst, 0.9~1 part of antioxidant, 8~10 parts of water, phosphor-containing flame-proof pre-polymerization
8~10 parts of object, 4~10 parts of nitrogenous flame ratardant, 6~10 parts of Silicone-containing Flame Retardant；
3) 100 parts of caprolactam, it is 0.1 part of catalyst, 0.9 part of antioxidant, 5 parts of water, 3 parts of phosphor-containing flame-proof prepolymer, nitrogenous
3 parts of fire retardant, 6 parts of Silicone-containing Flame Retardant；
4) 100 parts of caprolactam, 1 part of catalyst, 0.8 part of antioxidant, 10 parts of water, 8 parts of phosphor-containing flame-proof prepolymer, nitrogenous resistance
0.1 part of agent, 10 parts of Silicone-containing Flame Retardant of combustion；
5) 100 parts of caprolactam, 0.5 part of catalyst, 0.1 part of antioxidant, 8 parts of water, 0.1 part of phosphor-containing flame-proof prepolymer contains
10 parts of nitrogen combustion inhibitor, 5 parts of Silicone-containing Flame Retardant；
6) 100 parts of caprolactam, it is 0.1 part of catalyst, 1 part of antioxidant, 10 parts of water, 10 parts of phosphor-containing flame-proof prepolymer, nitrogenous
10 parts of fire retardant, 0.1 part of Silicone-containing Flame Retardant；
7) 100 parts of caprolactam, 1 part of catalyst, 0.5 part of antioxidant, 5 parts of water, 4 parts of phosphor-containing flame-proof prepolymer, nitrogenous resistance
4 parts of agent, 10 parts of Silicone-containing Flame Retardant of combustion.
In above-mentioned preparation method, in step 1), before the heat preservation, the method also includes following steps: it is described oneself
After lactams, the catalyst, the antioxidant and the water are mixed in reaction kettle, nitrogen is filled in reaction kettle, is then taken out
Vacuum, repeats to exhaust air 3~6 times；Inflated with nitrogen keeps 0.1~0.2MPa of pressure in kettle after completely removing air.
In above-mentioned preparation method, in step 1), the time of the heat preservation can be 1~2h；
In step 2), the time of the polymerization reaction can be 30~50min；
The vacuum degree of the vacuum condition can be 0.01~0.05KPa.
In above-mentioned preparation method, the antioxidant can be antioxidant 1010, antioxidant 1098 or antioxidant 1076 etc.；
The catalyst can be the sodium salt or sylvite of following acid: phosphoric acid, phosphorous acid and hypophosphorous acid；
In step 2), nitrogen is filled with after the polymerization reaction into kettle, opens lower discharge port, melt is obtained through cooling and dicing
Fire-resistant copolyesters polyamide 6 section.
Fire-resistant copolyesters polyamide 6 prepared by the present invention adds Silicone-containing Flame Retardant, flame retardant effect on the basis of N-P synergistic
Well, there is anti-dropping, flame retardant synthetic fibers can be made into, be spun into fabric, or be directly used as fire-resistant engineering plastics.
The present invention is by using P-N-S-i synergistic flame-retardant system, by BCPPO derivative flame retardant oligomer, melamine cyanogen
Lithate, Silicone-containing Flame Retardant are reacted with caprolactam, and P-N-Si synergistic has been prepared by copolymerization and has been copolymerized fire-resistant copolyesters polyamides
Amine 6.Due to synergistic effect, the flame retarding efficiency of fire retardant is high, in addition, the fire proofing that the method that the present invention is copolymerized obtains, guarantees
The molecular weight of material and mechanical property etc..
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Part in following embodiments refers to mass parts.
Embodiment 1, P-N-Si synergistic are copolymerized fire-resistant copolyesters polyamide 6
1, bis- (4- carboxyl phenyl) phenylethyl phosphine oxides (R is ethylo benzene in formula I) and hexamethylene diamine are added into reactor,
Molar ratio is 1:1.2, stirs 1.5h at 60 DEG C, is thoroughly mixed it.Then adjustment pressure is warming up to 170 DEG C to 0.2MPa,
Pre-polymerization 1h.It is cooled to room temperature and filters and be washed with deionized, obtain phosphor-containing flame-proof prepolymer, molecular weight 5000.
2, it is anti-that 5 parts of deionized waters, 100 parts of caprolactams, 1 part of catalyst sodium hypophosphite and 0.5 part are added into reaction kettle
Oxygen agent 1098 repeats vacuum nitrogen gas 6 times, eliminates air in kettle, inflated with nitrogen makes pressure 0.2MPa in kettle.Reaction kettle is heated,
Stirring is started simultaneously at, is warming up to 200 DEG C, pressure 0.8MPa, keeps 1h.It slowly adjusts pressure in kettle and 4 parts of trimerizations is added to normal pressure
Cyanamide cyanurate, 4 parts of phosphor-containing flame-proof prepolymers and 10 parts of methylamino dimethyl-silicons oxidation octanoic acid (R in formula III1For methylene
Base, R2For heptamethylene), be warming up to 235 DEG C, after pump vacuum to 0.01KPa, extract 30min.It is filled with nitrogen into kettle, opens
Lower discharge port, melt obtain fire-resistant copolyesters polyamide 6 section after cooling and dicing is dry.
Embodiment 2, P-N-Si synergistic are copolymerized fire-resistant copolyesters polyamide 6
1, bis- (4- carboxyl phenyl) phenylpropenyl phosphine oxides (R is propenylbenzene in formula I) and the last of the ten Heavenly stems are added into reactor
Diamines, molar ratio 1:1.1 stir 0.5h at 80 DEG C, are thoroughly mixed it.Then adjustment pressure is warming up to 0.2MPa
170 DEG C, pre-polymerization 1h.It is cooled to room temperature and filters and be washed with deionized, obtain phosphor-containing flame-proof prepolymer, molecular weight is
1000。
2, it is anti-that 10 parts of deionized waters, 100 parts of caprolactams, 0.1 part of catalyst potassium phosphite and 1 part are added into reaction kettle
Oxygen agent 1076 repeats vacuum nitrogen gas 3 times, eliminates air in kettle, keeps pressure 0.1MPa in kettle.Reaction kettle is heated, simultaneously
Start to stir, be warming up to 160 DEG C, pressure 0.6MPa, keeps 2h.It slowly adjusts pressure in kettle and 10 parts of melamines is added to normal pressure
Amine cyanurate, 10 parts of phosphor-containing flame-proof prepolymers and 0.1 part of allylamino dimethyl-silicon oxidation valeric acid (R in formula III1For Asia third
Alkenyl, R2For butylidene), be warming up to 260 DEG C, after pump vacuum to 0.05KPa, extract 50min.It is filled with nitrogen into kettle, beats
Lower discharge port is opened, melt obtains fire-resistant copolyesters polyamide 6 section after cooling and dicing is dry.
Embodiment 3, P-N-Si synergistic are copolymerized fire-resistant copolyesters polyamide 6
1, be added into reactor bis- (4- carboxyl phenyl) phenyl butane base phosphine oxides (R is butyl benzene in formula I) and oneself two
Amine, molar ratio 1:1.15 stir 1h at 70 DEG C, are thoroughly mixed it.Then adjustment pressure is warming up to 170 to 0.2MPa
DEG C, pre-polymerization 1h.It is cooled to room temperature and filters and be washed with deionized, obtain phosphor-containing flame-proof prepolymer, molecular weight 3500.
2, it is anti-that 8 parts of deionized waters, 100 parts of caprolactams, 0.5 part of catalyst sodium phosphate and 0.1 part are added into reaction kettle
Oxygen agent 1010 repeats vacuum nitrogen gas 5 times, eliminates air in kettle, keeps pressure 0.15MPa in kettle；Reaction kettle is heated, simultaneously
Start to stir, be warming up to 180 DEG C, pressure 0.7MPa, keeps 1h.It slowly adjusts pressure in kettle and 10 parts of melamines is added to normal pressure
Amine cyanurate, 0.1 part of phosphor-containing flame-proof prepolymer and 5 parts of allylamino dimethyl silanols (R in formula II3For allylidene),
Vacuum is pumped after being warming up to 255 DEG C to 0.03KPa, extracts 40min.It is filled with nitrogen into kettle, opens lower discharge port, melt is through cold
But after granulated and dried, fire-resistant copolyesters polyamide 6 section is obtained.
Embodiment 4, P-N-Si synergistic are copolymerized fire-resistant copolyesters polyamide 6
1, bis- (4- carboxyl phenyl) phenyl methyl phosphine oxides (R is methylbenzene in formula I) and dodecane are added into reactor
Diamines, molar ratio 1:1.1 stir 1.2h at 60 DEG C, are thoroughly mixed it.Then adjustment pressure is warming up to 0.2MPa
170 DEG C, pre-polymerization 1h.It is cooled to room temperature and filters and be washed with deionized, obtain phosphor-containing flame-proof prepolymer, molecular weight is
4500。
2, it is anti-that 10 parts of deionized waters, 100 parts of caprolactams, 1 part of catalyst potassium phosphite and 0.8 part are added into reaction kettle
Oxygen agent 1010 repeats vacuum nitrogen gas 4 times, eliminates air in kettle, rushing nitrogen makes pressure 0.2MPa in kettle.Reaction kettle is heated,
Stirring is started simultaneously at, is warming up to 190 DEG C, pressure 0.8MPa, keeps 1h.It slowly adjusts pressure in kettle and is added 0.1 part three to normal pressure
Poly cyanamid cyanurate, 8 parts of phosphor-containing flame-proof prepolymers and 10 parts of ethylamino dimethyl-silicons oxidation acetic acid (R in formula III1For sub- second
Base, R2For methylene), vacuum is pumped after being warming up to 245 DEG C to 0.03KPa, extracts 40min；Nitrogen is filled with into kettle, under opening
Discharge port, melt obtain fire-resistant copolyesters polyamide 6 section after cooling and dicing is dry.
Embodiment 5, P-N-Si synergistic are copolymerized fire-resistant copolyesters polyamide 6
1, bis- (4- carboxyl phenyl) phenylheptan base phosphine oxides (R is n-heptylphenyl in formula I) and third are added into reactor
Diamines, molar ratio 1:1.1 stir 1h at 70 DEG C, are thoroughly mixed it.Then adjustment pressure is warming up to 170 to 0.2MPa
DEG C, pre-polymerization 1h.It is cooled to room temperature and filters and be washed with deionized, obtain phosphor-containing flame-proof prepolymer, molecular weight 4000.
2,5 parts of deionized waters of addition, 100 parts of caprolactams, 0.1 part of catalyst sodium hypophosphite and 0.9 part into reaction kettle
Antioxidant 1010 repeats vacuum nitrogen gas 3 times, eliminates air in kettle, inflated with nitrogen makes pressure 0.15MPa in kettle.Heating reaction
Kettle starts simultaneously at stirring, is warming up to 180 DEG C, pressure 0.8MPa, keeps 1h.It slowly adjusts pressure in kettle and is added 3 parts to normal pressure
Melamine cyanurate, 3 parts of phosphor-containing flame-proof prepolymers and 6 parts of methylamino dimethyl silanols (R in formula II3For methylene),
Vacuum is pumped after being warming up to 260 DEG C to 0.03KPa, extracts 40min；It is filled with nitrogen into kettle, opens lower discharge port, melt is through cold
But after granulated and dried, fire-resistant copolyesters polyamide 6 section is obtained.
The copolymerization flame resistant polyamide resin flame retardant property test that the various embodiments described above are obtained
I, the preparation of sample
The test sample made of the polyamide without fire retardant is referred to as " PA ", it will be by above-described embodiment 1-5 system
Test sample made of the flame resistant polyamide resin obtained is referred to as FR-1, FR-2, FR-3, FR-4 and FR-5.Above-mentioned all examinations
The test bars preparation process of sample is referring to GB/T 9352-2008 " compression moulding of plastics thermoplastic material sample " standard.
II, limit oxygen index (LOI) test
Limit oxygen index test is adopted referring to GB/T 2406.2-2009 " plastics oxygen index method measures burning behavior " standard
It is measured at room temperature with HC-2CZ type limit oxygen index analyzer.Batten specification: 130mm × 6.5mm × 3.0mm is used
Light method in top surface.
III, vertical combustion (UL-94) test
Table 1GB/T 2408-2008 tests grade reference standard
Vertical burn test reference GB/T 2408-2008 " the measurement Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance " standard,
It is tested at room temperature using CZF-2 type vertical combustion analyzer.Batten specification: 130mm × 13mm × 3.0mm.By batten
It being perpendicularly fixed on specimen holder, upper end holding part is divided into 6mm, and batten lower end is 300mm at a distance from absorbent cotton (6mm is thick),
Away from Bunsen burner (the high 20mm of flame, blue flame), removing after applying flame 10s to sample at the 150mm of batten bottom end, batten is recorded
Test data.After batten burning is extinguished, lights again according to the above method, record test data respectively.Table 1 is test result grade
Reference standard.
IV, flame test result
The test result of limit oxygen index and vertical combustion is as shown in table 2.
2 flame test result of table
| Sample | LOI (%) | UL-94 grade |
| PA | 23.0 | V-2 |
| FR-1 | 27.8 | V-1 |
| FR-2 | 29.3 | V-0 |
| FR-3 | 28.1 | V-0 |
| FR-4 | 29.2 | V-0 |
| FR-5 | 28.6 | V-0 |
By in table 2 results, it can be seen that the polyamide after copolymerization has good anti-flammability, limit oxygen index LOI is equal
It 28% or so, improves a lot than the polyamide without fire-retardant processing, all slices all reach UL-94V-1 or more
It is horizontal.
The mechanical performance index of the fire-resistant copolyesters polyamide 6 section of embodiment 1-5 preparation is as shown in table 3.
By in table 3 results, it can be seen that the addition of fire retardant influences the preparation of the performance of slice less, to show P-N-
The every mechanical property that not only ensure that Flameproof polyamide is added in Si synergistic flame retardant, but also substantially increases anti-flammability, table
Bright P-N-Si has synergistic well.
3 fire-retardant Nylon 6 chip property index of table
Claims (10)
1. a kind of preparation method of P-N-Si synergistic fire-resistant copolyesters polyamide 6, includes the following steps:
Phosphonium flame retardant prepolymer, nitrogenous flame ratardant and Silicone-containing Flame Retardant is added in the polymerization process of polyamide 6 to get institute is arrived
State P-N-Si synergistic fire-resistant copolyesters polyamide 6.
2. preparation method according to claim 1, it is characterised in that: the phosphonium flame retardant prepolymer is by phosphonium flame retardant
It is successively obtained through salt-forming reaction and prepolymerization reaction with diamine.
3. preparation method according to claim 2, it is characterised in that: the temperature of the salt-forming reaction is 60~80 DEG C, when
Between be 0.5~1.5h；
The temperature of the prepolymerization reaction is 150~170 DEG C, and pressure is 0.2~0.3MPa, and the time is 0.5~1h.
4. preparation method according to claim 2 or 3, it is characterised in that: the diamine be ethylenediamine, propane diamine, oneself
At least one of diamines, decamethylene diamine, hendecane diamines and dodecamethylene diamine；
The structural formula of the phosphonium flame retardant is as shown in formula I:
In formula I, R indicates the alkylidene of the straight chained alkyl of C1~C3, unsaturated straight chain, branch or ring-type C3~C10 or containing benzene
Group；
The molar ratio of the phosphonium flame retardant and the diamine is 1:1~1.2.
5. preparation method described in any one of -4 according to claim 1, it is characterised in that: the nitrogenous flame ratardant is melamine
Amine cyanurate；
The structural formula of the Silicone-containing Flame Retardant is as shown in formula II or formula III:
In formula II or formula III, R1、R2And R3Indicate saturations or undersaturated straight chain, branch or the ring-type C3~C10 of C1~C10
Alkylidene or contain phenyl group.
6. preparation method according to any one of claims 1-5, it is characterised in that: the polymerization process of the polyamide 6
It is as follows:
1) temperature is 160~200 DEG C, pressure is 0.6~0.8Mpa's after caprolactam, catalyst, antioxidant and water mixing
Under the conditions of kept the temperature；
2) after pressure release to normal pressure, the phosphonium flame retardant prepolymer, the nitrogenous flame ratardant and the Silicone-containing Flame Retardant is added, rises
Temperature is to progress polymerization reaction after 235~260 DEG C up to the P-N-Si synergistic fire-resistant copolyesters polyamide 6；
The polymerization reaction carries out under vacuum conditions.
7. preparation method according to claim 6, it is characterised in that: the mass ratio of each raw material are as follows: 100 parts of caprolactam,
0.1~1 part of catalyst, 0.1~1 part of antioxidant, 5~10 parts of water, 0.1~10 part of phosphor-containing flame-proof prepolymer, nitrogenous flame ratardant 0.1
~10 parts, 0.1~10 part of Silicone-containing Flame Retardant.
8. preparation method according to claim 6 or 7, it is characterised in that: in step 1), time of the heat preservation is 1~
2h；
In step 2), the time of the polymerization reaction is 30~50min；
The vacuum degree of the vacuum condition is 0.01~0.05KPa.
9. preparation method a method according to any one of claims 6-8, it is characterised in that: the antioxidant is antioxidant
1010, antioxidant 1098 or antioxidant 1076；
The catalyst is the sodium salt or sylvite of following acid: phosphoric acid, phosphorous acid and hypophosphorous acid.
10. the P-N-Si synergistic fire-resistant copolyesters polyamide 6 of any one of claim 1-9 the method preparation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111410739A (en) * | 2020-04-29 | 2020-07-14 | 东华大学 | Green long-acting flame-retardant nylon 6 copolymer and preparation method thereof |
| CN112920410A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
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| CN111410739A (en) * | 2020-04-29 | 2020-07-14 | 东华大学 | Green long-acting flame-retardant nylon 6 copolymer and preparation method thereof |
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| CN112920410A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
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