CN106633828B - A kind of halogen-free flame-retardant polyamide 66 and preparation method thereof - Google Patents

A kind of halogen-free flame-retardant polyamide 66 and preparation method thereof Download PDF

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CN106633828B
CN106633828B CN201710009055.2A CN201710009055A CN106633828B CN 106633828 B CN106633828 B CN 106633828B CN 201710009055 A CN201710009055 A CN 201710009055A CN 106633828 B CN106633828 B CN 106633828B
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retardant
polyamide
halogen
flame retardant
flame
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CN106633828A (en
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肖茹
李圆圆
刘可
刘畅
王华平
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Donghua University
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    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract

The present invention relates to a kind of halogen-free flame-retardant polyamides 66 and preparation method thereof, flame retardant salt is obtained by reacting between DPO base reactive phosphorus flame retardant and diamine first, then the components such as add phosphorus containing flame retardant and flame retardant salt are added during 66 salt are polymerized to polyamide 66 and halogen-free flame-retardant polyamide 66 is made, the strand of halogen-free flame-retardant polyamide 66 is made of polyamide segment and DPO base reactive phosphorus flame retardant segment, the content of P elements is 0.4~0.8wt%, the add phosphorus containing flame retardant containing 4~9wt% between strand in strand.The limit oxygen index of halogen-free flame-retardant polyamide 66 produced by the present invention is greater than 30%, tensile strength is 58~72MPa, elongation at break is 35~65%, the products such as gear, bearing and automobile component can be become by the methods of injection molding, Nylon66 can also be prepared into and be further processed into textile, army fabric and equipment etc..

Description

A kind of halogen-free flame-retardant polyamide 66 and preparation method thereof
Technical field
The invention belongs to Flameproof polyamide synthesis technical field, it is related to a kind of halogen-free flame-retardant polyamide 66 and its preparation side Method, in particular to a kind of halogen-free flame-retardant polyamide 66 and its preparation side that excellent combination property is prepared by introducing phosphorus flame retardant Method.
Background technique
Polyamide 66 is one of most widely used kind in engineering plastics, have excellent wearability, self-lubrication and Chemical corrosion resistance etc., but the limit oxygen index of polyamide 66 only has 21~23%, molten drop phenomenon is serious, flame retardant property compared with Difference seriously limits it in the application of every profession and trade, so improving the flame-retardant and anti-dripping performance of polyamide 66 has important reality Meaning.
Fire retardant suitable for polyamide 66 mainly has halogen system, nitrogen system, several major class of inorganic and phosphorus flame retardant, different resistances It is huge to fire agent difference in terms of fire retardant mechanism, flame retarding efficiency and to the influence of material property.Wherein halogenated flame retardant purposes is most It is maximum and flame retardant effect is preferably also for extensive, usage amount, but when halogenated flame retardant burns, releases a large amount of flue gases and toxic Gas has larger harm to environment and human body.Inorganic fire retardants is because thermal stability is good, volatility is low, corrosivity is low, almost non-toxic The advantages that, and it is widely used in flame retardant area, but usually require higher additive amount and can be only achieved preferable flame retardant effect.Phase Than in halogenated flame retardant and inorganic fire retardants, nitrogenated flame retardant has that stability is good, the advantages such as environmentally friendly, but nitrogen system hinders Combustion agent is introduced into polyamide with physical form mostly, there are problems that additive amount is big, is easily precipitated.Phosphorus flame retardant has thermostabilization Property good, not volatile, non-corrosive gas generate, duration of fire resistance persistently and low toxin, in recent years in Flameproof polyamide Field is widely used, but is mainly added in polyamide 66 in the form that physics adds at present.
The common preparation method of Flameproof polyamide 66 is blending method and polymerization at present, and wherein polymerization includes copolymerization method again And situ aggregation method.Blending method processing technology is simple, and fire retardant additive amount is high, dispersion is uneven and is easily precipitated, to the mechanics of materials It can be affected.Being copolymerized flame-retardant modified is its flame-retardant modified important way, prepares Flameproof polyamide research by copolymerization process Less, the mechanical properties decrease of polyamide is larger when copolymerization method flame retarding process is complicated, additive amount is big.Situ aggregation method is to polymerize Fire retardant is introduced in the synthesis process of object to be scattered between substrate molecule chain, can effectively avoid drop caused by blending method secondary operation Solution, but it is also larger to reach the additive amount that fire-retardant purpose needs, and there are fire retardants to be easily precipitated, water-wash resistance poor, especially It is that there are fire retardants during drawing of fiber to be easily precipitated when being applied to fiber art, and flame retardant effect is deteriorated, fibrous mechanical property Decline, the problems such as feel is coarse.Reactive phosphorus flame retardant prepares Flameproof polyamide 66 in combustion by polymerization, main It to be gas phase fire retardation, weaker to polyamide crosslinking char forming ability although there is certain flame retardant effect, melting drip phenomenon is tight Again, the problem of usually causing scald or spot fire.Add phosphorus containing flame retardant prepares Flameproof polyamide 66 by blending method Predominantly condensed phase fire retardation, many phosphorus flame retardants need biggish additive amount to can be only achieved preferable flame retardant effect, power It is serious to learn performance decline, and further influences its application field.
Summary of the invention
The purpose of the present invention is overcome prior art polyamide 66 flame retardant property as made from modified poor or mechanical property The poor disadvantage of energy, provides a kind of halogen-free flame-retardant polyamide 66 and preparation method thereof of high comprehensive performance.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
A kind of halogen-free flame-retardant polyamide 66, the halogen-free flame-retardant polyamide 66 is by 66 strand of Flameproof polyamide and dispersion Add phosphorus containing flame retardant composition between 66 strand of Flameproof polyamide, 66 strand of Flameproof polyamide is by polyamide Segment and DPO base reactive phosphorus flame retardant segment form, and the content of P elements is 0.4 in 66 strand of Flameproof polyamide ~0.8wt%；
Content of the add phosphorus containing flame retardant in halogen-free flame-retardant polyamide 66 is 4~9wt%；
The structural formula of the polyamide segment is as follows:
The structural formula of the DPO base reactive phosphorus flame retardant segment is as follows:
In formula, R1For straight chain or the C of branching1~C15Alkylidene, R2For the C of straight chain3~C10Alkylidene or arlydene.
As a preferred technical scheme:
A kind of halogen-free flame-retardant polyamide 66 as described above, the add phosphorus containing flame retardant be aluminum diethylphosphinate, One of diethyl phosphinic acids zinc, methyl butyl phosphinic acids aluminium, methylcyclohexyl phosphinic acids aluminium or methylphenylphosphinic acid aluminium More than.
A kind of halogen-free flame-retardant polyamide 66 as described above, the limit oxygen index of the halogen-free flame-retardant polyamide 66 are greater than 30%, vertical burn test reaches UL94V-0 grades, self-extinguishing without fire in combustion testing, and no molten drop generates；
The endurance quality of the halogen-free flame-retardant polyamide 66 is good, washes 50 times, limit oxygen index is maintained at 28% or more；
The fusing point of the halogen-free flame-retardant polyamide 66 is 252~261 DEG C, and tensile strength is 58~72MPa, elongation at break It is 35~65%.
The present invention also provides a kind of preparation methods of halogen-free flame-retardant polyamide 66, and steps are as follows:
1) carry out salt-forming reaction is mixed evenly in DPO base reactive phosphorus flame retardant, diamine and solvent, resistance is made Fire agent salt；The structural formula of the DPO base reactive phosphorus flame retardant are as follows:
In formula, R1For straight chain or the C of branching1~C15Alkylidene；
The general structure of the diamine is H2N-R2-NH2, R2For the C of straight chain3~C10Alkylidene or arlydene；
The solvent is water or ethyl alcohol；
2) heat-insulation pressure keeping reaction is carried out after mixing add phosphorus containing flame retardant, 66 salt and water, is then unloaded and is depressed into normal pressure, institute The temperature for stating heat-insulation pressure keeping reaction is 210~230 DEG C, and pressure is 1.6~2.1MPa, and the time is 1~3h；It is pre- in this 66 salt of stage Polycondensation generates low molecular weight performed polymer；Heat-insulation pressure keeping reaction time it is too short 66 salt pre-polymerizations can be caused insufficient, influence in next step Polycondensation, overlong time may cause deshydroxy phenomenon, and the temperature of heat-insulation pressure keeping reaction is excessively high the possibility for decomposing performed polymer, temperature Spend it is low be unfavorable for 66 salt precondensations, need to extend the reaction time, the pressure of heat-insulation pressure keeping reaction is crossed conference and had to consersion unit Higher requirement needs equipment pressure resistance sufficiently high, increases production cost, and the volatilization of hypotony hexamethylene diamine influences polymerization and carries out；
3) flame retardant salt is added in the reaction system of step 2) after adjusting temperature and carries out polycondensation reaction, the polycondensation is anti- 240~260 DEG C of the temperature answered, time are 1~3h；In this stage, the process of polyamide 66 is polycondensed into low molecular weight performed polymer In, flame retardant salt also assists in the reaction bonded to polyamide 66 strand, and add phosphorus containing flame retardant is with physical aspect Be distributed in the polymerization process for being wherein not involved in polyamide, finally obtain on strand all contain with molecule interchain phosphorous flame-retardant at The Flameproof polyamide 66 divided；
4) post-processing obtains halogen-free flame-retardant polyamide 66.
As a preferred technical scheme:
A kind of preparation method of halogen-free flame-retardant polyamide 66 as described above, in step 1), DPO base response type phosphorus system The molar ratio of fire retardant and diamine is 1:1~1.2, and the mass ratio of DPO base reactive phosphorus flame retardant and solvent is 1:1~2； The stirring rate being mixed evenly is 50~400r/min, and the temperature of the salt-forming reaction is 60~90 DEG C, anti-at salt The time answered is 2~5h.
A kind of preparation method of halogen-free flame-retardant polyamide 66 as described above, in step 2), the heat-insulation pressure keeping reaction Stirring rate is 50~400r/min；In step 3), the addition time of the flame retardant salt is controlled in 0.5~1h；Polycondensation reaction In system, according to parts by weight, the additional amount of each component are as follows:
A kind of preparation method of halogen-free flame-retardant polyamide 66 as described above, also containing association in the reaction system in step 2) Imitate fire retardant and/or adipic acid；The additional amount of the synergistic flame retardant is 1~2 part, and the additional amount of the adipic acid is 0.1~1 Part.
A kind of preparation method of halogen-free flame-retardant polyamide 66 as described above, the add phosphorus containing flame retardant are diethyl Phosphinic acids aluminium, diethyl phosphinic acids zinc, methyl butyl phosphinic acids aluminium, methylcyclohexyl phosphinic acids aluminium or methylphenylphosphinic acid aluminium One or more of；
The synergistic flame retardant is zinc stannate, zinc borate, barium sulfate, antimony oxide, magnesium hydroxide, aluminium hydroxide or two One or more of silica.
A kind of preparation method of halogen-free flame-retardant polyamide 66 as described above, in step 4), the specific step of the post-processing Suddenly are as follows: system is evacuated down to -0.05~-0.1MPa, temperature is adjusted to 265~275 DEG C, stops stirring after keeping 0.5~3h It mixes, continues for vacuumizing to reach liquid-phase tackifying purpose, lead to nitrogen discharging after standing 10~20min.
The present invention is modified polyamide 66 using two kinds of fire retardants, a kind of to primarily serve gas phase fire retardation DPO base reactive phosphorus flame retardant, DPO base reactive phosphorus flame retardant are mainly connected on polyamide 66 strand, another It is the add phosphorus containing flame retardant for primarily serving condensed phase fire retardation, add phosphorus containing flame retardant is mainly in polyamide 66 point Between subchain.In the initial phase that polyamide 66 decomposes, DPO base reactive phosphorus flame retardant primarily serves the fire-retardant effect of gas phase, It is broken first since the P-O key bond energy in side group is lower, decomposes generation PO and HPO living radical in the gas phase and catch H the and OH free radical for catching high molecular material generation, interrupts chain combustion reaction, while DPO base reactive phosphorus flame retardant Heat is absorbed during sloughing moisture, the vapor of generation effectively reduces the concentration of oxygen and fuel gas, furthermore DPO base Reactive phosphorus flame retardant, which is introduced into polyamide 66 strand, obtains random copolymerization fire-retardant polyamide material, and random copolymerization is fire-retardant poly- The fusing point of amide can decrease, and the hot property by flame retardant can be changed and make to be increased by the heat-sinking capacity on flame retardant surface, because And can delay by the heating rate of flame retardant, although however DPO base reactive phosphorus flame retardant can burn in polyamide 66 Stage beginning plays preferable flame retardant effect, but phosphorus content is lower, general at charcoal effect, and condensed phase fire retardation is general, with Temperature increases, and copolyamide main chain is broken, it may occur that molten drop phenomenon.It is fire-retardant that add phosphorus containing flame retardant primarily serves synergistic Effect, mainly condensed phase is fire-retardant, thermally decomposes the stage in polyamide 66, add phosphorus containing flame retardant promotes polyamide 66 to decompose life At phosphoric acid, pyrophosphoric acid substance, layer of charcoal is promoted to generate in comburant surface dewatering, so that polyamide generates in combustion Fine and close and stable layer of charcoal, due to effective barrier of layer of charcoal, condensed phase fire retardation make single gas phase it is fire-retardant based on polyamides Amine in combustion molten drop low phenomenon the drawbacks of be effectively suppressed.By the present invention in that being hindered with DPO base response type phosphorus system Agent and add phosphorus containing flame retardant are fired, allows fire retardant in gas phase and condensed phase while playing a role, reach preferable resistance Fuel efficiency fruit.Further, since add phosphorus containing flame retardant is used as synergistic flame retardant, additive amount is less to be can reach preferably Effect, overcome traditional additive flame retardant additive amount it is excessive caused by material mechanical performance reduce and durability is poor etc. asks Topic, simultaneously because the fire-retardant effect of partial gas phase in additive flame retardant, the additive amount of reactive phosphorus flame retardant is also smaller, Overcome the existing melting drippage problem of single use.
Beneficial effect
1) fire retardant that the present invention uses is phosphorus flame retardant, halogen is not contained, in the case where additive amount is less Reach preferable flame retardant effect, has the advantages that environmentally protective, efficient；
2) 66 excellent flame retardancy of halogen-free flame-retardant polyamide produced by the present invention, limit oxygen index are greater than 30%, vertical combustion It burns test and reaches UL94V-0 grades, self-extinguishing without fire in combustion testing, no molten drop generates；
3) 66 good mechanical performance of halogen-free flame-retardant polyamide produced by the present invention, tensile strength are 58~72MPa, and fracture is stretched Long rate is 35~65%, and the tensile strength of unmodified polyamide 66 is 65~75MPa or so, elongation at break 60%, generally The tensile strength of Flameproof polyamide 66 is 40~50MPa or so, and elongation at break decline is larger, generally less than 30%；
4) preparation method and simple process of halogen-free flame-retardant polyamide 66 of the present invention, easy to operate.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
Embodiment 1
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and water are mixed evenly with the stirring rate of 50r/min Flame retardant salt is made in 60 DEG C of progress salt-forming reaction 2h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine is 1: The mass ratio of 1, DPO base reactive phosphorus flame retardant and water is 1:1；The structural formula of DPO base reactive phosphorus flame retardant are as follows:
The structural formula of diamine is
2) reaction kettle according to parts by weight, is added in 4 parts of aluminum diethylphosphinates, 100 part of 66 salt and 20 parts of water, stirring is simultaneously 210 DEG C, stirring rate 50r/min are warming up to, when pressure reaches 1.6MPa, heat-insulation pressure keeping reacts 1h, then unloads and is depressed into often Pressure；
3) 4 parts of flame retardant salts are added in the reaction system of step 2) in 240 DEG C of conditions in 0.5h after adjusting temperature Lower progress polycondensation reaction 1h；
4) system is evacuated down to -0.05MPa, temperature is adjusted to 265 DEG C, stopped stirring after keeping 0.5h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 10min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.4wt%, between the strand of halogen-free flame-retardant polyamide 66 Aluminum diethylphosphinate containing 4wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 30.5%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 28.4%, nothing The fusing point of halogen Flameproof polyamide 66 is 261 DEG C, tensile strength 72MPa, elongation at break 65%.
Embodiment 2
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and ethyl alcohol are mixed evenly with the stirring rate of 80r/min Flame retardant salt is made in 63 DEG C of progress salt-forming reaction 2h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine is The mass ratio of 1:1, DPO base reactive phosphorus flame retardant and ethyl alcohol is 1:1.1；The structural formula of DPO base reactive phosphorus flame retardant Are as follows:
The structural formula of diamine is NH2-(CH2)5-NH2；
2) according to parts by weight, by 4 parts of diethyl phosphinic acids zinc, 1 part of zinc stannate, 99 part of 66 salt, 0.1 part of adipic acid and 22 Reaction kettle is added in part water, stirs and is warming up to 212 DEG C, stirring rate 100r/min, and when pressure reaches 1.7MPa, heat preservation is protected Pressure reaction 1.5h, then unloads and is depressed into normal pressure；
3) 5 parts of flame retardant salts are added in the reaction system of step 2) in 242 DEG C of conditions in 0.6h after adjusting temperature Lower progress polycondensation reaction 1.2h；
4) system is evacuated down to -0.06MPa, temperature is adjusted to 266 DEG C, stopped stirring after keeping 0.8h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 11min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.5wt%, between the strand of halogen-free flame-retardant polyamide 66 Diethyl phosphinic acids zinc containing 4wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 32.3%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 30.2%, nothing The fusing point of halogen Flameproof polyamide 66 is 259 DEG C, tensile strength 68MPa, elongation at break 62%.
Embodiment 3
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and water are mixed evenly with the stirring rate of 100r/min Flame retardant salt is made in 66 DEG C of progress salt-forming reaction 3h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine is The mass ratio of 1:1.1, DPO base reactive phosphorus flame retardant and water is 1:1.2；The structural formula of DPO base reactive phosphorus flame retardant Are as follows:
The structural formula of diamine is NH2-(CH2)10-NH2；
2) according to parts by weight, 5 parts of methyl butyl phosphinic acids aluminium, 97 part of 66 salt, 1 part of adipic acid and 25 parts of water are added anti- Kettle is answered, stir and is warming up to 213 DEG C, stirring rate 200r/min, when pressure reaches 1.8MPa, heat-insulation pressure keeping reacts 2h, Then it unloads and is depressed into normal pressure；
3) 4 parts of flame retardant salts are added in the reaction system of step 2) in 245 DEG C of conditions in 0.7h after adjusting temperature Lower progress polycondensation reaction 1.5h；
4) system is evacuated down to -0.06MPa, temperature is adjusted to 268 DEG C, stopped stirring after keeping 1h, continue for It vacuumizes to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 12min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.4wt%, between the strand of halogen-free flame-retardant polyamide 66 Methyl butyl phosphinic acids aluminium containing 5wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 33.6%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 32.9%, nothing The fusing point of halogen Flameproof polyamide 66 is 257 DEG C, tensile strength 64MPa, elongation at break 53%.
Embodiment 4
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and water are mixed evenly with the stirring rate of 150r/min Flame retardant salt is made in 68 DEG C of progress salt-forming reaction 3h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine is The mass ratio of 1:1.1, DPO base reactive phosphorus flame retardant and water is 1:1.3；The structural formula of DPO base reactive phosphorus flame retardant Are as follows:
The structural formula of diamine is NH2-(CH2)10-NH2；
2) according to parts by weight, by 4 parts of methylcyclohexyl phosphinic acids aluminium, 2 parts of zinc borates, 98 part of 66 salt, 0.5 part of adipic acid Reaction kettle is added with 28 parts of water, stirs and is warming up to 215 DEG C, stirring rate 300r/min, when pressure reaches 1.8MPa, protects 2h is reacted in warm pressure maintaining, then unloads and is depressed into normal pressure；
3) 4 parts of flame retardant salts are added in the reaction system of step 2) in 248 DEG C of conditions in 0.8h after adjusting temperature Lower progress polycondensation reaction 1.8h；
4) system is evacuated down to -0.07MPa, temperature is adjusted to 270 DEG C, stopped stirring after keeping 1.2h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 13min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.4wt%, between the strand of halogen-free flame-retardant polyamide 66 Methylcyclohexyl phosphinic acids aluminium containing 4wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 31.3%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 29.8%, nothing The fusing point of halogen Flameproof polyamide 66 is 258 DEG C, tensile strength 66MPa, elongation at break 46%.
Embodiment 5
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and ethyl alcohol are mixed with the stirring rate of 200r/min equal It is even that flame retardant salt is made in 70 DEG C of progress salt-forming reaction 2.5h, wherein mole of DPO base reactive phosphorus flame retardant and diamine Than for 1:1.2, the mass ratio of DPO base reactive phosphorus flame retardant and ethyl alcohol is 1:1.4；DPO base reactive phosphorus flame retardant Structural formula are as follows:
The structural formula of diamine is NH2-(CH2)3-NH2；
2) according to parts by weight, 6 parts of methylphenylphosphinic acid aluminium, 1 part of barium sulfate, 98 part of 66 salt and 30 parts of water are added anti- Kettle is answered, stir and is warming up to 217 DEG C, stirring rate 400r/min, when pressure reaches 1.6MPa, heat-insulation pressure keeping reacts 2h, Then it unloads and is depressed into normal pressure；
3) 5 parts of flame retardant salts are added in the reaction system of step 2) in 250 DEG C of conditions in 0.8h after adjusting temperature Lower progress polycondensation reaction 2h；
4) system is evacuated down to -0.07MPa, temperature is adjusted to 271 DEG C, stopped stirring after keeping 1.4h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 13min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.5wt%, between the strand of halogen-free flame-retardant polyamide 66 Methylphenylphosphinic acid aluminium containing 6wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 34.6%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generate, and endurance quality is good, wash 50 times, limit oxygen index be 33.7% with On, the fusing point of halogen-free flame-retardant polyamide 66 is 255 DEG C, tensile strength 61MPa, elongation at break 48%.
Embodiment 6
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and water are mixed evenly with the stirring rate of 235r/min Flame retardant salt is made in 73 DEG C of progress salt-forming reaction 2.5h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine For 1:1.2, the mass ratio of DPO base reactive phosphorus flame retardant and water is 1:1.5；The structure of DPO base reactive phosphorus flame retardant Formula are as follows:
The structural formula of diamine is NH2-(CH2)8-NH2；
2) according to parts by weight, by the mixture of 6 parts of aluminum diethylphosphinates and diethyl phosphinic acids zinc (mass ratio 1: 1), reaction kettle is added in 2 parts of antimony oxides, 97 part of 66 salt and 33 parts of water, stirs and is warming up to 220 DEG C, stirring rate 150r/ Min, when pressure reaches 1.9MPa, heat-insulation pressure keeping reacts 2.5h, then unloads and is depressed into normal pressure；
3) 5 parts of flame retardant salts are added in the reaction system of step 2) in 252 DEG C of conditions in 0.6h after adjusting temperature Lower progress polycondensation reaction 2.2h；
4) system is evacuated down to -0.08MPa, temperature is adjusted to 272 DEG C, stopped stirring after keeping 1.5h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 14min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.5wt%, between the strand of halogen-free flame-retardant polyamide 66 The mixture of aluminum diethylphosphinate containing 6wt% and diethyl phosphinic acids zinc；Wherein, the structural formula of polyamide segment is such as Under:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 35.2%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 34.1%, nothing The fusing point of halogen Flameproof polyamide 66 is 254 DEG C, tensile strength 60MPa, elongation at break 46%.
Embodiment 7
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and ethyl alcohol are mixed with the stirring rate of 268r/min equal It is even that flame retardant salt is made in 75 DEG C of progress salt-forming reaction 3h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine For 1:1, the mass ratio of DPO base reactive phosphorus flame retardant and ethyl alcohol is 1:1.6；The structure of DPO base reactive phosphorus flame retardant Formula are as follows:
The structural formula of diamine is
2) according to parts by weight, by the mixture (mass ratio of 7 parts of methyl butyl phosphinic acids aluminium and methylcyclohexyl phosphinic acids Reaction kettles are added for 1:2), 1 part of magnesium hydroxide, 98 part of 66 salt, 1 part of adipic acid and 35 parts of water, stir and are warming up to 223 DEG C, stir Mixing rate is 200r/min, and when pressure reaches 2.0MPa, heat-insulation pressure keeping reacts 2.5h, then unloads and is depressed into normal pressure；
3) 6 parts of flame retardant salts are added in the reaction system of step 2) in 255 DEG C of conditions in 0.8h after adjusting temperature Lower progress polycondensation reaction 2.5h；
4) system is evacuated down to -0.08MPa, temperature is adjusted to 273 DEG C, stopped stirring after keeping 1.8h, continue to hold Continuous to vacuumize to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 15min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.6wt%, between the strand of halogen-free flame-retardant polyamide 66 The mixture of methyl butyl phosphinic acids aluminium containing 7wt% and methylcyclohexyl phosphinic acids；Wherein, the structural formula of polyamide segment It is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 35.6%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 34.3%, nothing The fusing point of halogen Flameproof polyamide 66 is 253 DEG C, tensile strength 60MPa, elongation at break 42%.
Embodiment 8
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and water are mixed evenly with the stirring rate of 300r/min Flame retardant salt is made in 80 DEG C of progress salt-forming reaction 4h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine is The mass ratio of 1:1, DPO base reactive phosphorus flame retardant and water is 1:1.7；The structural formula of DPO base reactive phosphorus flame retardant are as follows:
The structural formula of diamine is
2) according to parts by weight, by 7 parts of aluminum diethylphosphinates, diethyl phosphinic acids zinc and methyl butyl phosphinic acids aluminium Reaction kettle is added in mixture (mass ratio 1:1:1), 95 part of 66 salt, 0.5 part of adipic acid and 38 parts of water, stirs and is warming up to 226 DEG C, stirring rate 350r/min, when pressure reaches 2.0MPa, heat-insulation pressure keeping reacts 3h, then unloads and is depressed into normal pressure；
3) 6 parts of flame retardant salts are added in the reaction system of step 2) in 258 DEG C of conditions in 0.9h after adjusting temperature Lower progress polycondensation reaction 2.8h；
4) system is evacuated down to -0.09MPa, temperature is adjusted to 274 DEG C, stopped stirring after keeping 2h, continue for It vacuumizes to reach liquid-phase tackifying purpose, logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 16min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.6wt%, between the strand of halogen-free flame-retardant polyamide 66 The mixture of aluminum diethylphosphinate containing 7wt%, diethyl phosphinic acids zinc and methyl butyl phosphinic acids aluminium；Wherein, polyamides The structural formula of amine segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 35.9%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 34.8%, nothing The fusing point of halogen Flameproof polyamide 66 is 253 DEG C, tensile strength 59MPa, elongation at break 40%.
Embodiment 9
A kind of preparation method of halogen-free flame-retardant polyamide 66, steps are as follows:
1) DPO base reactive phosphorus flame retardant, diamine and ethyl alcohol are mixed with the stirring rate of 400r/min equal It is even that flame retardant salt is made in 90 DEG C of progress salt-forming reaction 5h, wherein the molar ratio of DPO base reactive phosphorus flame retardant and diamine For 1:1.1, the mass ratio of DPO base reactive phosphorus flame retardant and ethyl alcohol is 1:2；The structure of DPO base reactive phosphorus flame retardant Formula are as follows:
The structural formula of diamine is NH2-(CH2)3-NH2；
2) according to parts by weight, by 9 parts of aluminum diethylphosphinates, the mixture (quality of 1 part of aluminium hydroxide and silica Than reaction kettle is added for 1:1), 99 part of 66 salt, 1 part of adipic acid and 40 parts of water, stirs and be warming up to 230 DEG C, stirring rate is 400r/min, when pressure reaches 2.1MPa, heat-insulation pressure keeping reacts 3h, then unloads and is depressed into normal pressure；
3) 8 parts of flame retardant salts are added in the reaction system of step 2) in 260 DEG C of conditions in 1.0h after adjusting temperature Lower progress polycondensation reaction 3h；
4) system is evacuated down to -0.1MPa, temperature is adjusted to 275 DEG C, stopped stirring after keeping 3h, continue for taking out Vacuum is to reach liquid-phase tackifying purpose, and logical nitrogen discharges to obtain halogen-free flame-retardant polyamide 66 after standing 20min.
The strand of final halogen-free flame-retardant polyamide 66 obtained is by polyamide segment and DPO base reactive phosphorus flame retardant Segment composition, phosphorus content in 66 strand of Flameproof polyamide are 0.8wt%, between the strand of halogen-free flame-retardant polyamide 66 Aluminum diethylphosphinate containing 9wt%；Wherein, the structural formula of polyamide segment is as follows:
The structural formula of DPO base reactive phosphorus flame retardant segment is as follows:
Test shows that the limit oxygen index of halogen-free flame-retardant polyamide 66 is 36.7%, and vertical burn test reaches UL94V-0 Grade, self-extinguishing without fire in combustion testing, no molten drop generates, and endurance quality is good, washes 50 times, limit oxygen index 35.4%, nothing The fusing point of halogen Flameproof polyamide 66 is 252 DEG C, tensile strength 58MPa, elongation at break 35%.

Claims (9)

1. a kind of preparation method of halogen-free flame-retardant polyamide 66, characterized in that steps are as follows:
1) carry out salt-forming reaction is mixed evenly in DPO base reactive phosphorus flame retardant, diamine and solvent, fire retardant is made Salt；The structural formula of the DPO base reactive phosphorus flame retardant are as follows:
In formula, R1For straight chain or the C of branching1~C15Alkylidene；
The general structure of the diamine is H2N-R2-NH2, R2For the C of straight chain3~C10Alkylidene or arlydene；
The solvent is water or ethyl alcohol；
2) heat-insulation pressure keeping reaction is carried out after mixing add phosphorus containing flame retardant, 66 salt and water, is then unloaded and is depressed into normal pressure, the guarantor The temperature of warm pressure maintaining reaction is 210~230 DEG C, and pressure is 1.6~2.1MPa, and the time is 1~3h；
3) flame retardant salt is added in the reaction system of step 2) after adjusting temperature and carries out polycondensation reaction, the polycondensation reaction 240~260 DEG C of temperature, the time is 1~3h；
4) post-processing obtains halogen-free flame-retardant polyamide 66；
Phosphorus content is 0.4~0.8wt% in 66 strand of halogen-free flame-retardant polyamide, and the add phosphorus containing flame retardant is in nothing Content in halogen Flameproof polyamide 66 is 4~9wt%.
2. a kind of preparation method of halogen-free flame-retardant polyamide 66 according to claim 1, which is characterized in that in step 1), The molar ratio of the DPO base reactive phosphorus flame retardant and diamine be 1:1~1.2, DPO base reactive phosphorus flame retardant with it is molten The mass ratio of agent is 1:1~2；The stirring rate being mixed evenly is 50~400r/min, the temperature of the salt-forming reaction Degree is 60~90 DEG C, and the time of salt-forming reaction is 2~5h.
3. a kind of preparation method of halogen-free flame-retardant polyamide 66 according to claim 1, which is characterized in that in step 2), The stirring rate of the heat-insulation pressure keeping reaction is 50~400r/min；In step 3), the addition time of the flame retardant salt is controlled In 0.5~1h；In polycondensation reaction system, according to parts by weight, the additional amount of each component are as follows:
4. a kind of preparation method of halogen-free flame-retardant polyamide 66 according to claim 3, which is characterized in that in step 2) Also contain synergistic flame retardant and/or adipic acid in reaction system；The additional amount of the synergistic flame retardant be 1~2 part, it is described oneself two The additional amount of acid is 0.1~1 part.
5. a kind of preparation method of halogen-free flame-retardant polyamide 66 according to claim 4, which is characterized in that the addition type Phosphorus flame retardant is aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl butyl phosphinic acids aluminium, methylcyclohexyl phosphinic acids aluminium Or one or more of methylphenylphosphinic acid aluminium；
The synergistic flame retardant is zinc stannate, zinc borate, barium sulfate, antimony oxide, magnesium hydroxide, aluminium hydroxide or titanium dioxide One or more of silicon.
6. a kind of preparation method of halogen-free flame-retardant polyamide 66 according to claim 1, which is characterized in that in step 4), The specific steps of the post-processing are as follows: system is evacuated down to -0.05~-0.1MPa, temperature is adjusted to 265~275 DEG C, is protected Stop stirring after holding 0.5~3h, continue for vacuumizing to reach liquid-phase tackifying purpose, logical nitrogen goes out after standing 10~20min Material.
7. halogen-free flame-retardant polyamide 66 made from a kind of preparation method as described in any one of claims 1 to 6, it is characterized in that: The halogen-free flame-retardant polyamide 66 is by 66 strand of Flameproof polyamide and is dispersed in adding between 66 strand of Flameproof polyamide Adding type phosphorus flame retardant composition, 66 strand of Flameproof polyamide is by polyamide segment and DPO base reactive phosphorus flame retardant Segment forms, and the content of P elements is 0.4~0.8wt% in 66 strand of Flameproof polyamide；
Content of the add phosphorus containing flame retardant in halogen-free flame-retardant polyamide 66 is 4~9wt%；
The structural formula of the polyamide segment is as follows:
The structural formula of the DPO base reactive phosphorus flame retardant segment is as follows:
In formula, R1For straight chain or the C of branching1~C15Alkylidene, R2For the C of straight chain3~C10Alkylidene or arlydene.
8. a kind of halogen-free flame-retardant polyamide 66 according to claim 7, which is characterized in that the add phosphorus containing flame retardant For aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl butyl phosphinic acids aluminium, methylcyclohexyl phosphinic acids aluminium or aminomethyl phenyl One or more of phosphinic acids aluminium.
9. a kind of halogen-free flame-retardant polyamide 66 according to claim 7, which is characterized in that the halogen-free flame-retardant polyamide 66 Limit oxygen index be greater than 30%, vertical burn test reaches UL94V-0 grade, self-extinguishing without fire in combustion testing, the generation of no molten drop；
The endurance quality of the halogen-free flame-retardant polyamide 66 is good, washes 50 times, limit oxygen index is maintained at 28% or more；
The fusing point of the halogen-free flame-retardant polyamide 66 is 252~261 DEG C, and tensile strength is 58~72MPa, elongation at break 35 ~65%.
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