CN107501546A - A kind of high viscosity Flameproof polyamide 6 and preparation method thereof - Google Patents
A kind of high viscosity Flameproof polyamide 6 and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high viscosity Flameproof polyamide 6 and preparation method thereof.The preparation method of the high viscosity Flameproof polyamide 6 comprises the following steps：Phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant performed polymer through prepolymerization reaction and polymerisation successively in water；Fire retardant performed polymer is added in the polymerization process of polyamide 6 to produce.In-situ polymerization Flameproof polyamide 6 is due to the addition of fire retardant in the prior art, the problems such as fire retardant temperature tolerance is low, the big effect of steric hindrance is big be present, cause the viscosity of Flameproof polyamide 6 relatively low, polymerization is difficult, phenomena such as being even unable to pelletizing, thus being not suitable for existing in spinning or spinning a large amount of float thread.The method that the present invention prepares fire-retardant performed polymer by first carrying out prepolymerization reaction, overcome the problem of fire retardant heatproof is low, fire-retardant performed polymer is added in the middle and later periods of polymerization technique and solves the problems, such as that early stage adds fire retardant and makes polymer viscosity relatively low again, viscosity has reached 2.8~3.2pas, successfully prepares highly viscous Flameproof polyamide 6.
Description
Technical field
The present invention relates to a kind of high viscosity Flameproof polyamide 6 and preparation method thereof, belong to fire retardant preparation field.
Background technology
Polyamide has high-strength, wear-resisting etc. many excellent as one of most important engineering plastics and textile fiber material
Performance, it is widely used in building, weaves, the field such as military affairs, but the combustibility of polyamide have impact on its widely applies.Resistance
Most of polyamide substrate that also rests on is carried out to blending fire retardant and related synergistic flame retardant at present for the exploitation of retardant polyamide
On blending is granulated, the shortcomings of this mode such as add the bad dispersibility that flame retardant amount is more, fire retardant is in polyamide substrate,
Polyamide itself many performances such as are limited at the application that factor reduces blending class Flameproof polyamide.
The attention of researcher was obtained on copoly type Flameproof polyamide in recent years, its method prepared mainly uses
The fire retardant of reactivity carries out home position polymerization reaction together with monomer of polyamide, and in polyamide preparation process, polyamide divides greatly
Fire-retardant unit is introduced in subchain, realizes the permanent fire retardant of polyamide.At present, emerged in large numbers largely on copolymerization Flameproof polyamide
Patent, such as patent of invention 201310017151.3, to disclose a kind of inorganic modified MCA fire-retardant Nylon 6 compound
The preparation method of material, molten caprolactam is used first to prepare melamine cyanurate, then polymerize in the original location for reaction medium
During add water, the inorganic modifying component predecessor of inorganic component (or generation) and other auxiliary agents, it is finally obtained above-mentioned fire-retardant
Nylon 6 composite material.Patent of invention 201410489935.0 discloses a kind of preparation of organophosphor copolymerization fire-retardant polyamide material
Method, the previously prepared performed polymer containing fire retardant, monomer of polyamide, catalyst and above-mentioned performed polymer are subjected to copolyreaction,
Organophosphor copolymerization fire-retardant polyamide material is made.
It is copolymerized using the fire retardant or fire-retardant performed polymer of reactivity with monomer of polyamide and obtains Flameproof polyamide polymer
It is a kind of effective scheme for improving polyamide product fire resistance, but is copolymerized in Flameproof polyamide, due to fire retardant
Introduce, form substantial amounts of steric effect, make that copolymerization Flameproof polyamide viscosity is relatively low, it is necessary to which the process viscosified again, easily makes
The problems such as being mismatched into jaundice or Amino End Group, makes troubles for following process or spinning.
The content of the invention
It is fire-retardant poly- to solve copolymerization it is an object of the invention to provide a kind of high viscosity Flameproof polyamide 6 and preparation method thereof
The problem of acid amides viscosity is relatively low.
The reactants such as carboxylic phosphonic acids (phosphonium flame retardant) and diamine, dihydric alcohol are first passed through prepolymerization reaction shape by the inventive method
Into the fire-retardant performed polymer of low molecule amount, wherein, source of the carboxylic phosphonic acids as ignition-proof element phosphorus.Then, in polymerization technology for polyamide 6 technique
Middle and later periods adds above-mentioned fire-retardant performed polymer, while vacuumizes etc., finally obtains high viscous Flameproof polyamide 6 and cuts into slices.
The preparation method of high viscosity Flameproof polyamide 6 provided by the present invention, comprises the following steps：
(1) phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant through prepolymerization reaction and polymerisation successively in water
Performed polymer；
(2) the fire retardant performed polymer is added in the polymerization process of polyamide 6, produces the high viscosity Flameproof polyamide
6。
In above-mentioned preparation method, in step (1), the weight average molecular weight of the fire retardant performed polymer can be 2000~
4000。
In above-mentioned preparation method, in step (1), before the prepolymerization reaction, methods described also includes will be described phosphorous
Fire retardant, the diamine, the dihydric alcohol and the water mix the step of 0.5~1h；
The prepolymerization reaction and the polymerisation are carried out in an inert atmosphere, are carried out such as in nitrogen atmosphere.
In above-mentioned preparation method, in step (1), the temperature of the prepolymerization reaction can be 50~90 DEG C, and the time can be 0.5
~1.5h；
The temperature of the polymerisation can be 180~190 DEG C, and the time can be 1~2h；
The polymerisation can be carried out under 0.15~0.3MPa pressure, concretely 0.2MPa.
In above-mentioned preparation method, in step (1), the phosphonium flame retardant, the diamine, the dihydric alcohol with it is described
The mol ratio of water can be 1：1.1~1.2：1：50~100.
In above-mentioned preparation method, in step (1), the phosphonium flame retardant can be CEPPA, DDP or their derivative；
The structural formula of the CEPPA is as shown in formula I：
The derivative of the CEPPA is the sodium salt or sylvite of the CEPPA；
The structural formula of the DDP is as shown in formula II：
The derivative of the DDP is the sodium salt or sylvite of the DDP.
In above-mentioned preparation method, in step (1), the diamine can be ethylenediamine, propane diamine, butanediamine and pentanediamine
One or both of；
The dihydric alcohol is the dihydric alcohol that carbon number can be 2~10.
In above-mentioned preparation method, in step (2), the polymerization process of the polyamide 6 is as follows：
1) caprolactam is carried out melting under conditions of temperature is 200~230 DEG C, pressure is 0.5~0.6Mpa and gathered with water
Close；
2) continue to carry out the melt polymerization under conditions of temperature is 240~250 DEG C, pressure is 0.7~0.8Mpa；
3) after pressure release to normal pressure, the fire retardant performed polymer is added, continues the melt polymerization.
In above-mentioned preparation method, in step 1), the time of the melt polymerization is 4~5h；
The weight of the water is the 4~5% of the gross weight of the caprolactam and the water；
In step 2), the time of the melt polymerization is 4~5h；
In step 3), the temperature of the melt polymerization is 260~270 DEG C, and pressure be 0.3~0.5MPa, the time for 2~
4h；
The addition of the fire retardant performed polymer is the gross weight of the caprolactam, the water and the fire retardant performed polymer
The 4~15% of amount, concretely 4%, 6%, 8%, 10% or 15%.
In above-mentioned preparation method, after the melt polymerization terminates, methods described vacuumizes after also including pressure release to normal pressure
The step of；
The extraction time is 30~50min, and the vacuum after extraction is 0.01~50Kpa；
Pelletizing, extraction, drying are carried out after vacuumizing successively, Flameproof polyamide 6 is obtained and cuts into slices.
The viscosity for the polyamide 6 section that the above method of the present invention is prepared is 2.8~3.2pas, has high viscosity,
Limiting Oxygen Value number is 28~32, has anti-flammability.
The high viscous section of Flameproof polyamide 6 of the invention can be used for preparing Flameproof polyamide fiber.
The present invention has the advantages that：
In-situ polymerization Flameproof polyamide 6 is due to the addition of fire retardant in the prior art, there is that fire retardant temperature tolerance is low, steric hindrance
The problems such as effect is big greatly, causes the viscosity of Flameproof polyamide 6 relatively low, and polymerization is difficult, or even is unable to pelletizing, thus is not suitable for spinning
Or phenomena such as a large amount of float thread in spinning be present.The method that the present invention prepares fire-retardant performed polymer by first carrying out prepolymerization reaction, overcomes
The problem of fire retardant heatproof is low, fire-retardant performed polymer is added in the middle and later periods of polymerization technique again solving early stage addition fire retardant makes
The problem of polymer viscosity is relatively low, viscosity have reached 2.8~3.2pas, so as to successfully prepare highly viscous Flameproof polyamide
6。
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1, high viscous Flameproof polyamide 6
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant CEPPA, ethylenediamine, ethylene glycol and water 1：1.1：1：100 (mole) ratios mix, when mixing equal
Between be 0.5h；
1.2) after being well mixed, the stirring reaction 1h under nitrogen protection and temperature 50 C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 180 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 1h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 2000.
2nd, high viscous Flameproof polyamide 6 is prepared
2.1) by caprolactam and deionized water melting mixing, the amount of water accounts for the 4% of whole weight；
2.2) frit reaction thing is warming up to 200 DEG C of reactions, polymerization pressure 0.5MPa, reacts 4h；Then temperature is raised to
240 DEG C, pressure is raised to 0.7MPa, reacts 4h, unloads and be depressed into normal pressure；
2.3) start agitator, high-speed stirred, add fire retardant performed polymer, addition accounts for the 4% of percentage by weight, continues
260 DEG C are heated to, boosts to 0.3MPa, 2h is reacted, unloads and be depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 0.01KPa, extracts time 30min；
2.5) pelletizing, extraction, drying, obtain high viscous Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by the present embodiment is 3.2pas, and Limiting Oxygen Value number is 28.
Embodiment 2, high viscous Flameproof polyamide 6
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant DDP, ethylenediamine, ethylene glycol and water with 1：1.2：1：50 (mole) ratios mix, when mixing equal
Between be 1h；
1.2) after being well mixed, the stirring reaction 1h at nitrogen protection, 90 DEG C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 190 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 2h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 3000.
2nd, high viscous Flameproof polyamide 6 is prepared
2.1) by caprolactam and deionized water melting mixing, the amount of water accounts for the 5% of whole weight；
2.2) frit reaction thing is warming up to 230 DEG C of reactions, polymerization pressure 0.6MPa, reacts 5h；Then temperature is raised to
250 DEG C, pressure is raised to 0.8MPa, reacts 5h, unloads and be depressed into normal pressure；
2.3) starting agitator, high-speed stirred, add fire retardant performed polymer, addition accounts for the 15% of percentage by weight, after
It is continuous to be heated to 270 DEG C, 0.5MPa is boosted to, 4h is reacted, unloads and be depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 50KPa, extracts time 50min；
2.5) pelletizing, extraction, drying, obtain high viscous Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by the present embodiment is 2.8pas, and Limiting Oxygen Value number is 32.
Embodiment 3, high viscous Flameproof polyamide 6
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant DDP sodium salts, propane diamine, propane diols and water with 1：1.15：1：70 (mole) ratios mix, mixing
Time is 0.5h；
1.2) after being well mixed, the stirring reaction 1h at nitrogen protection, 55 DEG C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 182 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 1.5h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 2500.
2nd, high viscous Flameproof polyamide 6 is prepared
2.1) by caprolactam and deionized water melting mixing, the amount of water accounts for the 4% of whole weight；
2.2) frit reaction thing is warming up to 210 DEG C of reactions, polymerization pressure 0.5MPa, reacts 4.5h；Then by temperature liter
To 246 DEG C, pressure is raised to 0.75MPa, reacts 4h, unloads and be depressed into normal pressure；
2.3) start agitator, high-speed stirred, add fire retardant performed polymer, addition accounts for the 6% of percentage by weight, continues
265 DEG C are heated to, boosts to 0.5MPa, 3.5h is reacted, unloads and be depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 0.01KPa, extracts time 45min；
2.5) pelletizing, extraction, drying, obtain high viscous Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by the present embodiment is 3.1pas, and Limiting Oxygen Value number is 30.
Embodiment 4, high viscous Flameproof polyamide 6
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant CEPPA sylvite, butanediamine, pentanediamine, butanediol and water with 1：0.6：0.5：1：70 (moles)
Ratio mixes, and it is 50min to mix the equal time；
1.2) after being well mixed, the stirring reaction 1.5h at nitrogen protection, 60 DEG C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 185 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 1.5h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 4000.
2nd, high viscous Flameproof polyamide 6 is prepared
2.1) by caprolactam and deionized water melting mixing, the amount of water accounts for the 4.5% of whole weight；
2.2) frit reaction thing is warming up to 225 DEG C of reactions, polymerization pressure 0.6MPa, reacts 4.5h；Then by temperature liter
To 248 DEG C, pressure is raised to 0.75MPa, reacts 4.5h, unloads and be depressed into normal pressure；
2.3) start agitator, high-speed stirred, add fire retardant performed polymer, addition accounts for the 8% of percentage by weight, continues
267 DEG C are heated to, boosts to 0.4MPa, 3h is reacted, unloads and be depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 0.1KPa, extracts time 45min；
2.5) pelletizing, extraction, drying, obtain high viscous Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by the present embodiment is 3.1pas, and Limiting Oxygen Value number is 29.
Embodiment 5, high viscous Flameproof polyamide 6
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant DDP, ethylenediamine, propane diamine, decanediol and water with 1：0.5：0.62：1：The ratio of 70 (moles)
Mixing, it is 1h to mix the equal time；
1.2) after being well mixed, the stirring reaction 1.2h at nitrogen protection, 70 DEG C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 188 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 1.5h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 3600.
2nd, high viscous Flameproof polyamide 6 is prepared
2.1) by caprolactam and deionized water melting mixing, the amount of water accounts for the 4.2% of whole weight；
2.2) frit reaction thing is warming up to 220 DEG C of reactions, polymerization pressure 0.55MPa, reacts 4h；Then temperature is raised to
245 DEG C, pressure is raised to 0.7MPa, reacts 4.5h, unloads and be depressed into normal pressure；
2.3) starting agitator, high-speed stirred, add fire retardant performed polymer, addition accounts for the 10% of percentage by weight, after
It is continuous to be heated to 270 DEG C, 0.4MPa is boosted to, 3.5h is reacted, unloads and be depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 10KPa, extracts time 50min；
2.5) pelletizing, extraction, drying, obtain high viscous Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by the present embodiment is 2.8pas, and Limiting Oxygen Value number is 31.
Comparative example 1,
1st, fire retardant performed polymer is prepared：
1.1) by fire retardant DDP, ethylenediamine, propane diamine, decanediol and water with 1：0.5：0.62：1：The ratio of 70 (moles)
Mixing, it is 1h to mix the equal time；
1.2) after being well mixed, the stirring reaction 1.2h at nitrogen protection, 70 DEG C；
1.3) after stirring reaction, 0.2MPa is pressurized to, further heats up to 188 DEG C and polymerize instead under nitrogen protection
Should, fire retardant performed polymer is prepared after reacting 1.5h；
1.4) weight average molecular weight of the fire retardant performed polymer prepared is 3600.
2nd, Flameproof polyamide 6 is prepared
2.1) caprolactam, fire retardant performed polymer and deionized water melting mixing, the amount of water are accounted for into whole weight
4.2%, fire retardant performed polymer addition accounts for the 10% of percentage by weight；
2.2) frit reaction thing is warming up to 220 DEG C of reactions, polymerization pressure 0.55MPa, reacts 4h；Then temperature is raised to
245 DEG C, pressure is raised to 0.7MPa, reacts 4.5h, unloads and be depressed into normal pressure；
2.3) start agitator, high-speed stirred, continue to be heated to 270 DEG C, boost to 0.4MPa, react 3.5h, unload
It is depressed into normal pressure；
2.4) finally vacuumize, reaction vacuum is 10KPa, extracts time 50min；
2.5) pelletizing, extraction, drying, obtain Flameproof polyamide 6 and cut into slices.
The viscosity of section obtained by this comparative example is 2.0pas, and Limiting Oxygen Value number is 31.
As can be seen that the early stage of polymeric flame-retardant polyamide 6 adds fire retardant performed polymer, obtained Flameproof polyamide in the original location
6 viscosity is substantially less than the present invention and the viscous of the Flameproof polyamide 6 that fire retardant performed polymer obtains is added in the middle and later periods of polymerization technique
Spend (2.8~3.2), the method that the present invention prepares fire-retardant performed polymer by first carrying out prepolymerization reaction, it is low to overcome fire retardant heatproof
The problem of, successfully prepare highly viscous Flameproof polyamide 6.
Above example is only to introduce the preferred case of the present invention, to those skilled in the art, without departing substantially from this
Any obvious changes and improvements carried out in the range of spirit, it is regarded as the part of the present invention.
Claims (10)
1. a kind of preparation method of high viscosity Flameproof polyamide 6, comprises the following steps：
(1) phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant pre-polymerization through prepolymerization reaction and polymerisation successively in water
Body；
(2) the fire retardant performed polymer is added in the polymerization process of polyamide 6, produces the high viscosity Flameproof polyamide 6.
2. preparation method according to claim 1, it is characterised in that：It is described before the prepolymerization reaction in step (1)
The step of method also includes the phosphonium flame retardant, the diamine, the dihydric alcohol and the water mixing 0.5~1h；
The prepolymerization reaction and the polymerisation are carried out in an inert atmosphere.
3. preparation method according to claim 1 or 2, it is characterised in that：In step (1), the temperature of the prepolymerization reaction
For 50~90 DEG C, the time is 0.5~1.5h；
The temperature of the polymerisation is 180~190 DEG C, and the time is 1~2h；
The polymerisation is carried out under 0.15~0.3MPa pressure.
4. according to the preparation method any one of claim 1-3, it is characterised in that：In step (1), the phosphor-containing flame-proof
Agent, the diamine, the mol ratio of the dihydric alcohol and the water are 1：1.1~1.2：1：50~100.
5. according to the preparation method any one of claim 1-4, it is characterised in that：In step (1), the phosphor-containing flame-proof
Agent is CEPPA, DDP or their derivative；
The structural formula of the CEPPA is as shown in formula I：
The derivative of the CEPPA is the sodium salt or sylvite of the CEPPA；
The structural formula of the DDP is as shown in formula II：
The derivative of the DDP is the sodium salt or sylvite of the DDP.
6. according to the preparation method any one of claim 1-5, it is characterised in that：In step (1), the diamine is
One or both of ethylenediamine, propane diamine, butanediamine and pentanediamine；
The dihydric alcohol is the dihydric alcohol that carbon number is 2~10.
7. according to the preparation method any one of claim 1-6, it is characterised in that：In step (2), the polyamide 6
Polymerization process it is as follows：
1) caprolactam carries out melt polymerization with water under conditions of temperature is 200~230 DEG C, pressure is 0.5~0.6Mpa；
2) continue to carry out the melt polymerization under conditions of temperature is 240~250 DEG C, pressure is 0.7~0.8Mpa；
3) after pressure release to normal pressure, the fire retardant performed polymer is added, continues the melt polymerization.
8. preparation method according to claim 7, it is characterised in that：In step 1), time of the melt polymerization for 4~
5h；
The weight of the water is the 4~5% of the gross weight of the caprolactam and the water；
In step 2), the time of the melt polymerization is 4~5h；
In step 3), the temperature of the melt polymerization is 260~270 DEG C, and pressure is 0.3~0.5MPa, and the time is 2~4h；
The addition of the fire retardant performed polymer is the gross weight of the caprolactam, the water and the fire retardant performed polymer
4~15%.
9. the preparation method according to claim 7 or 8, it is characterised in that：After the melt polymerization terminates, methods described is also
The step of including being vacuumized after pressure release to normal pressure；
The extraction time is 30~50min, and the vacuum after extraction is 0.01~50KPa.
10. high viscosity Flameproof polyamide 6 prepared by method any one of claim 1-9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734898A (en) * | 2019-01-10 | 2019-05-10 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of novel P-N-Si synergistic fire-resistant copolyesters polyamide 6 and preparation method thereof |
| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
| CN114874265A (en) * | 2022-05-10 | 2022-08-09 | 厦门稀土材料研究所 | Rare earth flame-retardant complex and preparation method and application thereof |
| CN116120544A (en) * | 2023-02-01 | 2023-05-16 | 中化学科学技术研究有限公司 | Melamine flame-retardant composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499076A (en) * | 2014-12-12 | 2015-04-08 | 广东新会美达锦纶股份有限公司 | Preparation method of flame-retarded polyamide 6 fiber |
| CN105155019A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 fiber and preparation method thereof |
| CN105155033A (en) * | 2015-07-22 | 2015-12-16 | 东华大学 | Flame-retardant polyamide 6 composite fiber and preparation method thereof |
| CN106675007A (en) * | 2017-01-06 | 2017-05-17 | 东华大学 | Flame-retarded polyamide 6 and preparation method thereof |
-
2017
- 2017-08-17 CN CN201710707060.0A patent/CN107501546B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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