CN106496548A - A kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof - Google Patents
A kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof Download PDFInfo
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- CN106496548A CN106496548A CN201610932353.4A CN201610932353A CN106496548A CN 106496548 A CN106496548 A CN 106496548A CN 201610932353 A CN201610932353 A CN 201610932353A CN 106496548 A CN106496548 A CN 106496548A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The present invention discloses a kind of organophosphor system copolymerization Flameproof polyamide and preparation method thereof.Preparation method of the present invention, specifically includes following steps：(A) organophosphor system flame-retardant monomer is reacted with diamines monomer, into salt；(B) salt for preparing diacid and diamines and/or binary amidic-salt, lactams, step (A), antioxidant, catalyst, deionized water add reactor, under nitrogen atmosphere, by regulating and controlling reaction temperature and pressure, prepared required organophosphor system copolymerization fire-retardant polyamide material in situ.The organophosphor system polyamide material that the present invention is prepared, the addition of reactive flame retardant are little, need not add synergistic flame retardant, and in preparation process, viscosity is controllable, and the product good mechanical performance that obtains, fire resistance are outstanding.Meanwhile, this preparation method also have concurrently environmental friendly simple, with low cost, the characteristics of operate easy to learn.
Description
Technical field
The invention belongs to flame-retardant high-molecular synthesis technical field, is related to a kind of preparation method of copolymerization Flameproof polyamide, special
It is not related to macromolecular material of the embedded polyamide molecule chain of a kind of phosphorous reactive flame retardant copolymerization and preparation method thereof.
Background technology
Polyamide is widely used in building, chemical industry, friendship because having excellent performance, such as high-strength, heat-resisting, wear-resisting, solvent resistant etc.
The fields such as logical and military affairs.But polyamide itself does not have anti-flammability, may cause or increase fire.Therefore, how
Modification is prepared the polyamide with good flame-retardance energy and is studied by tradesman always.
Generally there is two ways obtain fire-retardant polyamide material with modification：One kind is to add reactive flame retardant, in Buddhist nun
The functional group with flame retardant activity is introduced in imperial polymerization process；Another kind is after polymerizing polyamide, adds additive flame retardant
And related synergistic flame retardant, blending processing.The mode of latter of which physical blending can be subject to dispersiveness, compatibility, interface characteristics
Etc. the impact of factor, and the former is due to happens is that chemical reaction, there are no these.In addition to reach certain fire-retardant
Property, can be larger using the consumption of additive flame retardant, so as to cause the larger infringement of mechanical property and electric property, limit which
Application.And reactive flame retardant can solve these problems very well, its molecular structure copolymerization enters polyamide molecule main chain, does not exist
The problems such as volatilizing, migrate, oozing out, can provide reliable fire resistance within the materials'use life-span.
At present, conventional fire retardant mainly has halogenated flame retardant, phosphorus flame retardant, nitrogenated flame retardant, inorganic filler type resistance
Combustion agent etc..Halogen containing flame-retardant was once widely applied to the fire proofing of high polymer with its efficient fire resistance, but due to which
Toxic gas and smog can be produced in combustion process, had harm to environment and human body, gradually used by restriction.Phosphorous flame-retardant
Agent, especially organic phosphorus flame retardant have prospect to replace halogen containing flame-retardant very much.Phosphorus flame retardant can be simultaneously in condensed phase and gas phase
Work, its fire retardant mechanism is that fire retardant can produce the products such as phosphoric acid and polyphosphoric acid in combustion, promotes polymer dehydration
And charing, and vitreous protective layer is formed, prevent the heat between condensed phase and gas phase from transmitting with material.The combustion of phosphonium flame retardant
Burning process will not produce toxic and harmful, and raw smoke is also less, with preferable flame retardant effect.Especially response type phosphorous flame-retardant
Agent can be by way of polymerization, and entering needs, in fire-retardant macromolecular material molecular backbone, not migrate, do not ooze out and have for a long time
Effect.
The patent of Publication No. CN104231262A discloses a kind of preparation method of organophosphor copolymerization Flameproof polyamide, step
Suddenly it is：(1) in advance flame-retardant monomer is reacted with diamines monomer, prepares performed polymer；(2) by polymerized monomer, catalyst and institute
State performed polymer reactor is added according to certain order.In this patent, fire retardant used isOr with it
The derivative of matrix；Wherein described R1And R2It is the alkylidene of 1-10 carbon atom；Or R1And R2In any one be H；X1、X2
For the H or 1-4 halogen that may replace H on phenyl ring.The copolymerization fire block articles grade obtained in the present invention can reach UL94V-0 levels
Not, limited oxygen index is greatly improved, and up to 32, peak is up to 45 for minimum.
The patent of Publication No. CN104262619A is related to a kind of phosphor-containing flame-proof polyamide and preparation method and application.System
Preparation Method includes：(1) being used for fire-retardant hypophosphites carries out prepolymerization reaction generation oligomer with diamine；(2) by oligomer
Prepolymerization reaction is carried out in a nitrogen atmosphere with dicarboxylate, prepolymer is obtained；(3) twice after prepolymerization reaction, by temperature
Raise, make air pressure be down to normal pressure；(4) temperature is raised, is pumped to vacuum, discharging obtains fire-retardant polyamide material.In this patent
Fire retardant used is
Wherein R1And R2For straight chain, the C of branched or ring-type1-C15Alkylidene,
C6-C15Arlydene or arylmethylene alkyl；M is metallic element, and when a is 1, M is lithium, sodium or potassium；When a is 2, M is calcium or magnesium.This
In invention, when reaching more than 0.48% with phosphorus content, Flameproof polyamide can be by UL-94 V-0 ranks, and LOI values also have bright
Aobvious raising.
The patent of Publication No. JPH09328543 is related to phosphorous polyamide copolymer of a kind of main chain and preparation method thereof.
Preparation method is that (1) phosphorous dicarboxylate is pre-reacted to salt with diamines；(2) salt and other comonomers (diacid and diamines,
Or caprolactam) polycondensation prepares polyamide copolymer.In this patent, the dicarboxylate is
Wherein R1For the straight or branched alkyl that carbon number is 1-8；
R2For H or methyl.When in obtained polyamide copolymer, phosphorus content is 6.48-6.58ppm, its limited oxygen index can reach
28.9-29.9%, with preferable fire resistance.But the polyamide material relative viscosity for preparing is only 0.78-0.82, the material
The mechanical property and other performance of sample also has larger room for promotion.
As previously discussed, although prior art proposes many phosphorous polyamide with good flame-retardance energy, but ability
The domain Flameproof polyamide all good to mechanical property, electric property and fire resistance still has strong demand.
Content of the invention
The purpose of the present invention is the situation for the present market of Flameproof polyamide mainly based on blending, prepares a kind of new
The organophosphor system copolymerization fire-retardant polyamide material of type.It is characterized in the characteristic and binary using two hydroxy-acid groups of flame-retardant monomer band
Amine into salt, then with dicarboxylic acids amine salt polycondensation, so as to prepare new organophosphor system copolymerization Flameproof polyamide.In this process
In, fire retardant addition is few and without the need for synergistic flame retardant, and the polyamide material for obtaining has excellent mechanics, electric property concurrently.
Technical scheme：
A kind of Flameproof polyamide, its formula is such as with following formula (1) Suo Shi：
Wherein, R is selected from H, C1-C5Alkyl, C6-C10Aryl, C3-C10Heteroaryl；R is preferably H, C1-C3Alkyl, C6-C8Virtue
Base or C3-C6Heteroaryl；
R1、R2It is each independently selected from straight chain, the C of branched or ring-type1-C10Alkylidene, C6-C15Arlydene or sub- aralkyl,
C3-C10Ester group；R1、R2Straight chain, the C of branched or ring-type are each independently preferably1-C5Alkylidene, C6-C10Arlydene or sub- aralkyl
Base, C3-C8Ester group；
R3、R4、R5It is each independently selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl
Base；R3、R4、R5C is each independently preferably3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
R6It is selected from C1-C10Alkylidene；R6Preferably C3-C9Alkylidene；
X represents 1-50；Y represents that 1-50, z represent 1-50；N represents 1-100；X is preferably 2-30, and y is preferably 2-30, and z is excellent
Elect 2-30 as, n is preferably 2-80, more preferably 5-50.
The preparation method of above-described Flameproof polyamide is comprised the following steps：
(A) diamines monomer by organophosphor system flame-retardant monomer of formula (2) or derivatives thereof with formula (3) reacts；
Wherein, R is selected from H, C1-C5Alkyl, C6-C10Aryl, C3-C10Heteroaryl, R are preferably H, C1-C3Alkyl, C6-C8Virtue
Base, C3-C6Heteroaryl；
R1、R2It is each independently selected from straight chain, the C of branched or ring-type1-C10Alkylidene, C6-C15Arlydene or sub- aralkyl,
C3-C10Ester group, R1、R2Straight chain, the C of branched or ring-type are preferably independently of one another1-C5Alkylidene, C6-C10Arlydene or sub- virtue
Alkyl, C3-C8Ester group；
R3It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl, R3Preferably C3-C8
Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
Obtain the compound of following formula (4)：
(B) allow the compound of formula (4) anti-with the lactam monomers of the diamines and formula (8) of the diacid of formula (5) and formula (6)
Should, or the lactam monomers reaction of the binary amidic-salt with formula (7) and formula (8),
Wherein, R4And R5It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl, R4With
R5Respectively preferably C3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
R6It is selected from C1-C10Alkylidene, R6It is preferably C3-C9Alkylidene；
The polyamide of acquisition formula (1)：
Wherein, R, R1、R2、R3、R4、R5、R6As defined above；X represents that 1-50, y represent that 1-50, z represent 1-50, n tables
Show 1-100；Preferably, x represents that 2-30, y represent that 2-30, z represent that 2-30, n represent 2-80, more preferably 5-50.
Preferably, the diamines monomer of the flame-retardant monomer of formula (2) and formula (3) is according to 1:0.1-20, preferably 1:0.5-10, more
It is preferred that 1:The molar ratio reaction of 1-2.
In step (A), it is preferable that diamines monomer is relative to the excessive (example of organophosphor system flame-retardant monomer or derivatives thereof
Such as 0.1～10%, the preferred molar excess of 0.5-5%), the PH for making obtained salting liquid is 7-9.Reaction temperature is in 5-20min
Interior 40-70 DEG C is raised to by room temperature.
Preferably, in step (A) diamines monomer used be hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamines, 12
Alkane diamines, aliphatic C6-C20One or more in imino group diamines, aromatic diamine, alicyclic diamine.
In step (B), the mol ratio of the diamines of the diacid of formula (5) and formula (6) is not especially to limit, such as formula (5)
The mol ratio of the diamines of diacid and formula (6) can be 1:1-10, preferably 1:1-2, more preferably from about 1:1.5.
In step (B), it is preferable that by polymerized monomer (diacid and diamines or binary amidic-salt and lactams), step
(A) product (salt or salting liquid), antioxidant, catalyst, deionized water add reactor, and under nitrogen atmosphere, regulation and control are anti-
Temperature and pressure is answered, organophosphor system copolymerization Flameproof polyamide needed for being obtained.
In step (B), further, antioxidant used is the compound such as p-phenylenediamine and EEDQ and its derives
Thing, 2,6- di-tert-butyl-4-methy phenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyls) propionic acid) one or more in pentaerythritol ester etc..
Further, used catalyst is in sodium hypophosphite, toluene sulfonic acide, new ferrocene chiral polyamide part etc.
One or more.
It is further preferred that in step (B), specifically including following steps：
A. polymerized monomer, step (A) gained product, catalyst, antioxidant, deionized water are added reactor, is taken out
Vacuum, inflated with nitrogen are for several times so that initial reaction stage, and in kettle, pressure is 0.1-0.5MPa；
B. heating response kettle, is warming up to 200-250 DEG C, when pressure is 1.6-2.1MPa, maintains this reaction condition 30-
180min；
C. start slow pressure release to normal pressure at 230-280 DEG C, be then evacuated to -0.01 to -0.1MPa, then copolymer-1 0-
180min.
D. nitrogen, discharges material is finally filled with, cooling, pelletizing, is extracted, is dried to obtain final product.
Further, in step a, the polymerized monomer (including lactams and diacid and diamines or binary amidic-salt)
Addition is 8-100 times of the fire retardant quality, preferably 10-40 times, more preferably 12-30 times, wherein, diacid and diamines or two
First amidic-salt each relative to lactams mol ratio be 1:0.01-100, preferably 1:0.1-10, more preferably 1:0.5-5, makes
In the case of with diacid and diamines, the mol ratio of the two can be 1:1.01～10.0, preferably 1:1.1～2.0, more preferably from about 1:
1.1-1.5；The catalyst, antioxidant are respectively the 0.01%～1.0% of the polymerized monomer quality, preferably 0.05-
0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000.In system water addition (including individually add water,
The water that brings into the product of step (A) and the water that brings into binary amidic-salt) it is the 10～60% of reactant gross mass, preferably
30-50%.
Further, in step a, the polymerized monomer binary acid is such as adipic acid, decanedioic acid, azelaic acid, hendecane
Diacid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or their derivative and other aliphatic
With one or more in aromatic dicarboxylic acid；Binary amine compound is such as hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane
Diamines, dodecamethylene diamine and aliphatic C6-C20One kind or many in imino group diamines, aromatic diamine or alicyclic diamine
Kind；The binary amidic-salt is hexamethylene adipamide salt, adipyl pentanediamine salt, hexamethylene azelamide salt, hexamethylene sebacamide
Salt, decanedioyl octamethylenediamine salt, suberoyl hexamethylene diamine salt, one or more of suberoyl octamethylenediamine salt.In the polymerized monomer
Lactams is caprolactam, caprinolactam, 11 lactams, lauric lactam, and possesses the various interior acyl of lactams feature
One or more in amine monomers.
In the present invention, in advance fire retardant and diamines monomer preferably according to such as 1：(1-2) into salt, then by the salt for obtaining
Solution is added in polymerized monomer, participates in polymerisation under catalyst action.The polyamide material fire resistance for obtaining is satisfied by hindering
Combustion grade V-0 is required.
WithAs a example by hexamethylene diamine, PA66 salt, caprolactam, the reaction
Mechanism is：Flame-retardant monomer first reacts into salt with hexamethylene diamine, and then the salt is copolymerized into fire-retardant polyamides with nylon salt, caprolactam
Amine.Course of reaction can be written as：
The invention has the beneficial effects as follows：
As long as including the Flameproof polyamide for accounting for about 6% phosphor-containing flame-proof monomer of polymer quality, UL-94V- just can be reached substantially
0 rank, and limited oxygen index scope is 27%-32%, and low-smoke low-toxicity, efficient stable, viscosity be controllable, solves prior art
Disclosed in many phosphorous-containing monomers cannot realize the problem of higher degrees of polymerization when phosphorus content is increased.
Specific embodiment
The present invention is described in further detail with reference to instantiation.
The organophosphor system Flameproof polyamide molecular structure of the present invention is as shown in following formula 1：
Wherein, R is selected from H, C1-C5Alkyl, C6-C10Aryl, C3-C10Heteroaryl；R is preferably H, C1-C3Alkyl, C6-C8Virtue
Base or C3-C6Heteroaryl；
R1、R2It is each independently selected from straight chain, the C of branched or ring-type1-C10Alkylidene, C6-C15Arlydene or sub- aralkyl,
C3-C10Ester group；R1、R2Straight chain, the C of branched or ring-type are each independently preferably1-C5Alkylidene, C6-C10Arlydene or sub- aralkyl
Base, C3-C8Ester group；
R3、R3、R5It is each independently selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl
Base；R3、R4、R5C is each independently preferably3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
R6It is selected from C1-C10Alkylidene；R6Preferably C3-C9Alkylidene；
X represents 1-50；Y represents 1-50；Z represents 1-50；N represents 1-100；X is preferably 2-30, and y is preferably 2-30, and z is excellent
Elect 2-30 as, n is preferably 2-80, more preferably 5-50.
The preparation method of organophosphor system copolymerization Flameproof polyamide of the present invention, specifically includes following steps：
(A) by organophosphor system flame-retardant monomer and diamine reactant, amino excess is preferably made, generates salting liquid；
(B) product and diacid and diamines or binary amidic-salt and the lactams reaction of step (A) is made, is produced organic
Flame-retarding phosphorus copolymerized polyamide.
In step (A), it is preferable that diamines monomer is slightly excessive, the PH for making salting liquid is 7-9.Reaction temperature is in 5-
40-70 DEG C is raised to by room temperature in 20min.
Preferably, in step (A) diamines monomer used be hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamines, 12
Alkane diamines, aliphatic C6-C20One or more in imino group diamines, aromatic diamine, alicyclic diamine.
In step (B), it is preferable that by polymerized monomer (diacid and diamines or binary amidic-salt, lactams), step (A)
Product (salt or salting liquid), antioxidant, catalyst, deionized water add reactor, under nitrogen atmosphere, regulation and control reaction temperature
Degree and pressure, organophosphor system copolymerization fire-retardant polyamide material needed for being obtained.
In step (B), further, antioxidant used is the compound such as p-phenylenediamine and EEDQ and its derivative
Or polymer, 2,6- di-tert-butyl-4-methy phenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid) one or more in pentaerythritol ester etc..
Further, used catalyst is in sodium hypophosphite, toluene sulfonic acide, new ferrocene chiral polyamide part etc.
One or more.
It is further preferred that in step (B), specifically including following steps：
A. polymerized monomer, step (A) gained product, catalyst, antioxidant, deionized water are added reactor, is taken out
Vacuum, inflated with nitrogen are for several times so that initial reaction stage, and in kettle, pressure is 0.1-0.5MPa；
B. heating response kettle, is warming up to 200-250 DEG C, when pressure is 1.6-2.1MPa, maintains this reaction condition 30-
180min；
C. start slow pressure release to normal pressure at 230-280 DEG C, be then evacuated to -0.01 to -0.1MPa, then copolymer-1 0-
180min；
D. nitrogen, discharges material is finally filled with, cooling, pelletizing, is extracted, is dried to obtain final product.
Further, in step a, the addition of polymerized monomer (diacid/diamine or the binary amidic-salt+lactams) is
8-100 times of the fire retardant quality, preferably 10-40 times, more preferably 12-30 times, the catalyst, antioxidant are respectively described
0.01%～1.0%, preferably 0.05-0.5% of polymerized monomer (diacid/diamine or binary amidic-salt+lactams) quality, more excellent
0.08-0.2% is selected, more preferably e.g., from about 1/1000.The addition of water is preferably the 10-60%, preferably 30- of polymerized monomer
50%.
Further, in step a, the polymerized monomer binary acid is such as adipic acid, decanedioic acid, azelaic acid, hendecane
Diacid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or their derivative and other aliphatic
With one or more in aromatic dicarboxylic acid；Binary amine compound is such as hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane
Diamines, dodecamethylene diamine and aliphatic C6-C20One kind or many in imino group diamines, aromatic diamine or alicyclic diamine
Kind；The binary acid amides salt compounds are such as polyhexamethylene adipamide, poly hexamethylene adipamide pentanediamine, poly-hexamethylene azelamide,
Polyhexamethylene sebacamide, poly- decanedioyl octamethylenediamine, poly- suberoyl hexamethylene diamine, poly- dodecanoamide, poly- suberoyl octamethylenediamine etc..
Lactams in the polymerized monomer is caprolactam, caprinolactam, 11 lactams, lauric lactam, and possesses interior acyl
One or more in the various lactam monomers of amine feature.
Embodiments of the invention are as follows：
Using method used in following embodiments if no special instructions, is conventional method.
In following embodiments, material used, reagent etc., if no special instructions, obtain from market approach." % " presses matter
Amount fraction meter, unless otherwise prescribed.
Embodiment 1：
By flame-retardant monomer and hexamethylene diamine in aqueous according to mol ratio 1 at 60 DEG C：1.2 stirring reactions 0.5h, are adjusted molten
Liquid PH=7.2, is dried to salt.By mol ratio 1:1 nylon salt (hexamethylene adipamide salt) solution and caprolactam with account for the two
The salt obtained above of the 6.0% of gross mass, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant p-phenylenediamine, Yi Jizhan
Reactor is added than 40% deionized water, is vacuumized, inflated with nitrogen 5 times, it is 0.2MPa finally to keep pressure in reactor.Heating is anti-
Kettle is answered, high-speed stirred is kept, when temperature of reaction kettle reaches 220 DEG C, when pressure is 1.8MPa, constant temperature and pressure 1.5h.Then heat up
To 250 DEG C, in 1h, release of pressure is to normal pressure.Vacuumize as -0.05MPa, etc. mixing speed decline certain value and stable after, be filled with nitrogen
To 0.2MPa, discharges material, is extracted, is dried to obtain final product cooling, pelletizing gas, and its relative viscosity is 2.6, and limit oxygen refers to
Number is 28.3%, and flame retardant rating reaches UL94V-0 ranks.Organophosphor system flame-retardant monomer wherein used is：
Embodiment 2：
By flame-retardant monomer and hexamethylene diamine in aqueous according to mol ratio 1 at 45 DEG C：1.3 stirring reactions 1h, adjust solution
PH=7.8, is dried to salt.By adipic acid, hexamethylene diamine according to 1:1.2 mass ratio configuration, is 1 with adipic acid mol ratio:0.6
Caprinolactam and account for adipic acid, hexamethylene diamine and caprinolactam gross weight 7% salt obtained above, the catalysis of each accounting 1 ‰
The deionized water of agent toluene sulfonic acide, antioxidant 2,6- di-tert-butyl-4-methy phenols and accounting 35% adds reactor,
Vacuumize, inflated with nitrogen 3 times, it is 0.3MPa finally to keep pressure in reactor.Heating response kettle, keeps high-speed stirred, works as reaction
Kettle temperature degree reaches 215 DEG C, when pressure is 1.7MPa, constant temperature and pressure 1.6h.Then 240 DEG C are warmed up to, and in 1.5h, release of pressure is to normal pressure.
Vacuumize as -0.06MPa, etc. mixing speed decline certain value and stable after, be filled with nitrogen to 0.3MPa, discharges material is cold
But, pelletizing, extract, be dried to obtain final product, its relative viscosity be 2.35, limited oxygen index is 29.2%, and flame retardant rating reaches
Arrive UL94V-0 ranks.Organophosphor system flame-retardant monomer wherein used is：
Embodiment 3：
By flame-retardant monomer and nonamethylene diamine in aqueous according to mol ratio 1 at 60 DEG C：1.5 stirring reactions 1h, adjust solution
PH=7.6, is dried to salt.It is 1 by mol ratio:1.2:1 heneicosanedioic acid, hexamethylene diamine, lauric lactam with account for three of the above
Double (3, the 5- bis- tertiary fourths of 8% salt obtained above of monomer gross mass, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant
Base -4- hydroxy phenyls) deionized water of thioether and accounting 50% adds reactor, vacuumizes, and inflated with nitrogen 4 times finally keeps
In reactor, pressure is 0.2MPa.Heating response kettle, and keep high-speed stirred.When temperature of reaction kettle reaches 225 DEG C, pressure is
During 1.7MPa, constant temperature and pressure 2h.Then 255 DEG C are warmed up to, and in 2h, release of pressure is to normal pressure.Vacuumize as -0.09MPa, wait stirring speed
Degree decline certain value and stable after, be filled with nitrogen to 0.3MPa, discharges material, is extracted, is dried to obtain finally cooling, pelletizing
Product, its relative viscosity are 2.5, and limited oxygen index is 31.4%, and flame retardant rating reaches UL94V-0.Organophosphor system wherein used
Flame-retardant monomer is：
Embodiment 4：
By fire retardant and hexamethylene diamine in aqueous according to mol ratio 1 at 52 DEG C：1.2 stirring reactions 50min, adjust solution
PH=7.4, is dried to salt.By mol ratio 1:1.1:0.5 heneicosanedioic acid, octamethylenediamine, 11 lactam monomers with account for above
The salt obtained above of the 8% of three kinds of monomer gross mass, the catalyst toluene sulfonic acide of each accounting 1 ‰, antioxidant four (β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid) deionized water of pentaerythritol ester and accounting 40% adds reactor, vacuumizes,
Inflated with nitrogen 3 times, it is 0.35MPa finally to keep pressure in reactor.Heating response kettle, and keep high-speed stirred.When reaction kettle temperature
Degree reaches 230 DEG C, when pressure is 1.8MPa, constant temperature and pressure 2h.Then 260 DEG C are warmed up to, and in 1h, release of pressure is to normal pressure.Vacuumize
For -0.05MPa, after declining certain value and stablize etc. mixing speed, nitrogen is filled with to 0.3MPa, discharges material, cools down, cut
Grain, extract, be dried to obtain final product, its relative viscosity be 2.35, limited oxygen index is 31.8%, and flame retardant rating reaches
UL94V-0.Organophosphor system flame-retardant monomer wherein used is：
Embodiment 5：
At 62 DEG C, by flame-retardant monomer with hexamethylene diamine in aqueous according to mol ratio 1：1.2 stirring reactions 0.5h, are adjusted molten
Liquid PH=7.8, is dried to salt.By mol ratio 1:1.15 nylon salt (hexamethylene adipamide salt) solution and caprolactam with account for
The salt obtained above of the 10.0% of the two gross mass, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant p-phenylenediamine add
Enter reactor, vacuumize, inflated with nitrogen 5 times, it is 0.2MPa finally to keep pressure in reactor.Heating response kettle, keeps high-speed stirring
Mix, when temperature of reaction kettle reaches 235 DEG C, when pressure is 1.95MPa, constant temperature and pressure 1.5h.Then 260 DEG C are warmed up to, are released in 1h
It is depressed into normal pressure.Vacuumize as -0.05MPa, etc. mixing speed decline certain value and stable after, be filled with nitrogen to 0.4MPa, row
Put material, cooling, pelletizing, extract, be dried to obtain final product organophosphor system copolymerization flame-retardant polyamide composition, P content is
0.80-0.84 mass %, its relative viscosity are 2.25, and limited oxygen index is 32.6%, and flame retardant rating reaches UL94V-0 ranks.
Wherein described organophosphor system flame-retardant monomer is：
1. the preparation of sample
The test sample being made up of the polyamide material for being not added with fire retardant is referred to as " PA ", above-described embodiment 1-5 is obtained
The test sample made of organophosphor system fire-retardant polyamide material be referred to as " FR-A "-" FR-E " successively.
The test bars preparation process of above-mentioned all samples is with reference to GB/T 9532-2008《Plastics thermoplastic material is tried
The compression moulding of sample》Standard.
2. limited oxygen index (LOI) test
Limited oxygen index test is with reference to GB/T 2406.2-2009《Plastics determine burning behavior with oxygen index method》Standard, adopts
It is measured with type limited oxygen index analyzer at room temperature.Batten specification：80mm*10mm*4mm.
3.UL-94 is tested
Vertical burn test is with reference to GB/T 2408-2008《Plastics Combustion method for testing performance Horizontal Bridgman Method and normal beam technique》Mark
Standard, is measured at room temperature using CFZ-5 type vertical combustion analyzers.Batten specification：125mm*13.2mm*3.2mm.By sample
Bar is perpendicularly fixed on specimen holder, and upper end holding part is divided into 6mm, and batten lower end is 300mm with the distance of absorbent cotton (4mm is thick),
Apply flame according at the 10mm of batten bottom, record batten test data.After batten burning is extinguished, the standard according to the form below 1 is again
Secondary light, record test data.
Table 1 determines grade reference standard
4. test result
The presence that organophosphor flame retarding construction be can be seen that by example fire resistance test result, improves polyamide
Fire resistance.When flame-retardant monomer content reaches more than 6%, Flameproof polyamide can be tested by the V-0 of UL-94, LOI values
Improve therewith.Therefore may certify that, the present invention using response type organic phosphorus flame retardant flame-retardant modified to polyamide be feasible and
Efficiently.The organophosphor system copolymerization fire-retardant polyamide material obtained by the scheme that the present invention is provided, limited oxygen index are higher
Meanwhile, its relative viscosity value is also higher.Due to the presence of end group, when will obtain more high-viscosity material, conventional solid can be adopted
Technics of enhancing viscosity, obtains various required viscosity numbers.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not intended to limit, for those skilled in the art
Member, the present invention can have various modifications and variations.Every any modification that within the spirit and principles in the present invention, is made, etc.
With replacement, improvement etc., should be included in protection scope of the present invention.
Claims (7)
1. a kind of organophosphor system copolymerization Flameproof polyamide, its formula is such as with following formula (1) Suo Shi：
Wherein, R is selected from H, C1-C5Alkyl, C6-C10Aryl, C3-C10Heteroaryl；R is preferably H, C1-C3Alkyl, C6-C8Aryl, C3-
C6Heteroaryl；
R1、R2It is each independently selected from straight chain, the C of branched or ring-type1-C10Alkylidene, C6-C15Arlydene or sub- aralkyl, C3-C10
Ester group；R1、R2Straight chain, the C of branched or ring-type are preferably independently of one another1-C5Alkylidene, C6-C10Arlydene or sub- aralkyl,
C3-C8Ester group；
R3、R4、R5It is each independently selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl；
R3、R4、R5C is preferably independently of one another3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
R6It is selected from C1-C10Alkylidene；R6Preferably C3-C9Alkylidene；
X represents 1-50；Y represents 1-50；Z represents 1-50；N represents 1-100；Preferably, x represents 2-30；Y represents 2-30；Z is represented
2-30；N represents 2-80, more preferably 5-50.
2. the preparation method of the Flameproof polyamide described in claim 1, comprises the following steps：
(A) diamines monomer by organophosphor system flame-retardant monomer of formula (2) or derivatives thereof with formula (3) reacts；
Wherein, R is selected from H, C1-C5Alkyl, C6-C10Aryl, C3-C10Heteroaryl, R are preferably H, C1-C3Alkyl, C6-C8Aryl, C3-
C6Heteroaryl；
R1、R2It is each independently selected from straight chain, the C of branched or ring-type1-C10Alkylidene, C6-C15Arlydene or sub- aralkyl, C3-
C10Ester group, R1、R2Straight chain, the C of branched or ring-type are preferably independently of one another1-C5Alkylidene, C6-C10Arlydene or sub- aralkyl
Base, C3-C8Ester group；
R3It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl, R3It is preferred that C3-C8Linearly, prop up
Change or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl, obtains the compound of following formula (4)：
(B) compound of formula (4) and the lactam monomers of the diacid, the diamines of formula (6) and formula (8) of formula (5) are allowed to react, or with
The lactam monomers reaction of the binary amidic-salt of formula (7) and formula (8),
Wherein, R4And R5It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl, R4And R5Excellent
Elect C as3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
R6It is selected from C1-C10Alkylidene, R6Preferably C3-C9Alkylidene；
The polyamide of acquisition formula (1)：
Wherein, R, R1、R2、R3、R4、R5、R6As defined above；X represents that 1-50, y represent that 1-50, z represent that 1-50, n represent 1-
100；Preferably, x represents that 2-30, y represent that 2-30, z represent that 2-30, n represent 2-80, more preferably 5-50.
3. preparation method according to claim 2, wherein, the diamines monomer of the flame-retardant monomer of formula (2) and formula (3) according to
1:0.1-20, preferably 1:0.5-10, more preferably 1:The molar ratio reaction of 1-2.
4. the preparation method according to Claims 2 or 3, wherein, in step (A), diamines monomer is relative to organophosphor
It is that flame-retardant monomer or derivatives thereof is excessive, the PH for making obtained salting liquid is 7-9；Reaction temperature is in 5-20min by room temperature liter
Arrive 40-70 DEG C；And/or
In step (A), diamines monomer used is hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamines, dodecamethylene diamine, fat
Race C6-C20One or more in imino group diamines, aromatic diamine, alicyclic diamine；And/or
In step (B), by diacid and diamines or binary amidic-salt, lactam monomers, the product of step (A), antioxidant,
Catalyst, deionized water add reactor, under nitrogen atmosphere, regulate and control reaction temperature and pressure, organophosphor system copolymerization needed for being obtained
Fire-retardant polyamide material.
5. the preparation method according to any one of claim 2-4, wherein, in step (B), antioxidant used is to benzene
The compound such as diamines and EEDQ and its derivative, 2,6- di-tert-butyl-4-methy phenols, double (3,5- di-t-butyl -4- hydroxyls
Base phenyl) thioether, one or more in four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester；And/or
Used catalyst is sodium hypophosphite, toluene sulfonic acide, one or more in new ferrocene chiral polyamide part.
6. the preparation method according to any one of claim 2-5, wherein, in step (B), specifically includes following steps：
A. by diacid and diamines or binary amidic-salt, lactam monomers, step (A) gained product, catalyst, antioxidant,
Deionized water add reactor, vacuumize, inflated with nitrogen for several times so that initial reaction stage, in kettle pressure be 0.1-0.5MPa；
B. heating response kettle, is warming up to 200-250 DEG C, when pressure is 1.6-2.1MPa, maintains this reaction condition 30-180min；
C. start slow pressure release to normal pressure at 230-280 DEG C, be then evacuated to -0.01 to -0.1MPa, then copolymer-1 0-
180min.
D. nitrogen, discharges material is finally filled with, cooling, pelletizing, is extracted, is dried to obtain final product.
7. preparation method according to claim 6, wherein, in step a, polymerized monomer (diacid and diamines or the binary
Amidic-salt, lactams) addition be 8-100 times of the flame-retardant monomer quality, preferably 10-40 times, more preferably 12-30 times,
Wherein, diacid and diamines and/or binary amidic-salt each relative to lactams mol ratio be 1:0.01-100, preferably 1:0.1-
10, more preferably 1:0.5-5；The catalyst, antioxidant be respectively the polymerized monomer (diacid and diamines or binary amidic-salt,
Lactams) quality 0.01%-1.0%, preferably 0.05-0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000.
The addition of water is preferably the 10-60%, preferably 30-50% of polymerized monomer (or binary amidic-salt)；And/or
In step a, the polymerized monomer is the diacid and diamines that can participate in copolymerization, and diacid is adipic acid, decanedioic acid, nonyl two
Acid, heneicosanedioic acid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or their derivative and its
One or more in his aliphatic and aromatic dicarboxylic acid；And binary amine compound is hexamethylene diamine, nonamethylene diamine, the last of the ten Heavenly stems two
Amine, hendecane diamines, dodecamethylene diamine and aliphatic C6-C20In imino group diamines, aromatic diamine or alicyclic diamine
One or more；The binary amidic-salt, is hexamethylene adipamide salt, adipyl pentanediamine salt, hexamethylene azelamide salt, the last of the ten Heavenly stems two
Acyl hexamethylene diamine salt, decanedioyl octamethylenediamine salt, suberoyl hexamethylene diamine salt, one or more of suberoyl octamethylenediamine salt.
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