CN106496551A - A kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof - Google Patents
A kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of organophosphors system copolymerization Flameproof polyamide and preparation method thereof.Preparation method of the present invention, specifically includes following steps：(A) organophosphors system flame-retardant monomer and diamines monomer are reacted into salt；(B) salt described in diacid and diamidogen or binary amidic-salt or its solution, step (A) or its solution, antioxidant, catalyst, deionized water are added reactor, under nitrogen atmosphere, by regulating and controlling reaction temperature and pressure, organophosphors system copolymerization fire-retardant polyamide material needed for being obtained.The organophosphors system polyamide material that the present invention is prepared, the addition of reactive flame retardant is little, need not add synergistic flame retardant, and in preparation process, viscosity is controllable, the product good mechanical performance that obtains, fire resistance are outstanding, can be used to weaving, the every field such as insulant, tire cord, thin film.
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 the dispersibility, 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..Wherein front several can serve as reactive flame retardant.Halogen containing flame-retardant was once extensive with its efficient fire resistance
The fire proofing of high polymer is applied to, but as toxic gas and smog can be produced in its combustion process, to environment and human body
There is harm, gradually used by restriction.Phosphorus flame retardant, especially organic phosphorus flame retardant have prospect to replace halogen containing flame-retardant very much.
Phosphorus flame retardant can be worked in condensed phase and gas phase simultaneously, and its fire retardant mechanism is that fire retardant can produce phosphorus in combustion
The product such as acid and polyphosphoric acid, promotes polymer dehydration and carbonization, and forms vitreous protective layer, prevent between condensed phase and gas phase
Heat and material transmit.The combustion process of phosphonium flame retardant will not produce toxic and harmful, and raw smoke is also less, with compared with
Good flame retardant effect.Especially reactive phosphorus flame retardant can be by way of polymerization, and entering needs fire-retardant macromolecular material point
In sub- main chain, do not migrate, do not ooze out and permanently effective.
The patent of Publication No. CN104231262A discloses a kind of preparation method of organophosphors 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.Described in this patent, fire retardant isOr with it
The derivant 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
The fire retardant 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.Should
In invention, when reaching more than 0.48% with phosphorus content, Flameproof polyamide can be by UL-94V-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 diamidogen；(2) salt and other comonomers (diacid and diamidogen,
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
Domain still has strong demand to mechanical performance and all good Flameproof polyamide of fire resistance.
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 organophosphors 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 organophosphors 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；
X represents that 1-50, y represent that 1-50, n represent 1-100；X is preferably 2-30, and y is preferably 2-30, and n is preferably 2-80, more
It is preferred that 5-50.
The preparation method of above-described Flameproof polyamide, comprises the following steps：
(A) diamines monomer by organophosphors 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 is 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) diamine reactant of the compound of formula (4) and the diacid of formula (5) and formula (6), or the binary acyl with formula (7) allowed
Amine salt or its solution reaction,
Wherein, R4And R5It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl；R4With
R5It is preferably C3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
The polyamide of acquisition formula (1)：
Wherein, R, R1、R2、R3、R4、R5, x, y, n as defined above.
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), generally reacted in the presence of solvent such as water or organic solvent such as alcohols solvent, preferably
, diamines monomer slightly excessive (such as 0.1～10%, preferably the molar excess of 0.5-5%), the PH for making obtained saline solution is
7-9.Reaction temperature is raised to 40-70 DEG C by room temperature in 5-20min.
Preferably, diamines monomer described in step (A) be hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamidogen, 12
Alkane diamidogen, aliphatic C6-C20One or more in imino group diamidogen, aromatic diamine, alicyclic diamine.
In step (B), the mol ratio of the diamidogen of the diacid of formula (5) and formula (6) is not especially to limit, such as formula (5)
The mol ratio of the diamidogen of diacid and formula (6) can be 1:1.01-10, preferably 1:1.1-2, more preferably from about 1:1.5.
In step (B), it is preferred that by diacid and diamidogen or binary amidic-salt or its solution, the product of step (A)
(salt or saline solution), antioxidant, catalyst, deionized water add reactor, under nitrogen atmosphere, regulate and control reaction temperature and pressure,
Organophosphors system copolymerization Flameproof polyamide needed for being obtained.
In step (B), further, the polymerized monomer diacid be such as adipic acid, decanedioic acid, Azelaic Acid, 11
Docosandioic acid, dodecanedioic acid, p-phthalic acid, M-phthalic acid, phthalic acid or their derivant and other fat
One or more in race and aromatic dicarboxylic acid；Diamidogen is such as hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane diamidogen, 12
Alkane diamidogen and aliphatic C6-C20One or more in imino group diamidogen, aromatic diamine or alicyclic diamine；And two
First 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.
Further, the antioxidant is the compound such as p-phenylenediamine and dihydroquinoline and its derivant, 2,6- bis- tertiary fourths
Base -4- methylphenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- di-tert-butyl-hydroxy phenyls)
Propanoic acid) one or more in pentaerythritol ester etc..
Further, the 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. by polymerized monomer diacid and diamidogen or binary amidic-salt or its solution, step (A) gained product, catalysis
Agent, antioxidant, deionized water add reactor, and evacuation, inflated with nitrogen are for several times so that initial reaction stage, and in kettle, pressure is 0.1-
0.5MPa；
B. reacting by heating 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 the polymerized monomer diacid and diamidogen or binary amidic-salt or its solution is
8-100 times of the fire retardant quality, preferably 12-30 times；The catalyst, antioxidant are respectively the polymerized monomer quality
0.01%～1.0%, preferably 0.05-0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；In system, water adds
Dosage (water, the water brought into of product with step (A) and the water that brings into binary amidic-salt including individually adding) is reactant
The 10～60% of gross mass, preferably 30-50%.
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
Add in polymerized monomer, under catalyst action, participate in polyreaction.The polyamide material fire resistance for obtaining is satisfied by fire-retardant etc.
Level UL-94V-0 is required.
WithAs a example by hexamethylene diamine, PA66 salt, the mechanism of the reaction is：Resistance
Combustion monomer first reacts into salt with hexamethylene diamine, and then the salt is copolymerized into Flameproof polyamide with nylon salt.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 reactant gross mass, UL- just can be reached substantially
94V-0 ranks, and limited oxygen index scope is 27%-32%, and low-smoke low-toxicity, efficient stable, viscosity be controllable, solves existing
Many phosphorous-containing monomers disclosed in technology 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 organophosphors 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, 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；
X represents that 1-50, y represent that 1-50, n represent 1-100；X is preferably 2-30, and y is preferably 2-30, and n is preferably 2-80, more
It is preferred that 5-50.
The preparation method of organophosphors system copolymerization Flameproof polyamide of the present invention, specifically includes following steps：
(A) by organophosphors system flame-retardant monomer and diamine reactant, amino excess is preferably made, generates saline solution；
(B) product and diacid and diamidogen or binary amidic-salt or its solution reaction of step (A) is made, is prepared organic
Flame-retarding phosphorus copolymerized polyamide.
In step (A), it is preferred that diamines monomer is slightly excessive, the PH for making saline solution is 7-9.Reaction temperature is in 5-
40-70 DEG C is raised to by room temperature in 20min.
Preferably, diamines monomer described in step (A) be hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamidogen, 12
Alkane diamidogen, aliphatic C6-C20One or more in imino group diamidogen, aromatic diamine, alicyclic diamine.
In step (B), it is preferred that by polymerized monomer, the product of step (A), antioxidant, catalyst, deionization
Water adds reactor, under nitrogen atmosphere, regulates and controls reaction temperature and pressure, organophosphors system copolymerization Flameproof polyamide material needed for being obtained
Material.
In step (B), further, the polymerized monomer binary acid be such as adipic acid, decanedioic acid, Azelaic Acid, ten
One docosandioic acid, dodecanedioic acid, p-phthalic acid, M-phthalic acid, phthalic acid or their derivant and other fat
One or more in fat race and aromatic dicarboxylic acid；Binary amine compound is such as hexamethylene diamine, nonamethylene diamine, decamethylene diamine, ten
One alkane diamidogen, dodecamethylene diamine and aliphatic C6-C20One kind in imino group diamidogen, aromatic diamine or alicyclic diamine
Or it is multiple；The binary amide salt compounds be such as polyhexamethylene adipamide, poly hexamethylene adipamide pentanediamine, poly- nonanedioyl oneself two
Amine, polyhexamethylene sebacamide, poly- decanedioyl octamethylenediamine, poly- suberoyl hexamethylene diamine, poly- dodecanoamide, poly- suberoyl octamethylenediamine
One or more in.
Further, the antioxidant is the compound such as p-phenylenediamine and dihydroquinoline and its derivant, 2,6- bis- tertiary fourths
Base -4- methylphenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- di-tert-butyl-hydroxy phenyls)
Propanoic acid) one or more in pentaerythritol ester etc..
Further, the 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. by polymerized monomer diacid and diamidogen or binary amidic-salt or its solution, step (A) gained product, catalysis
Agent, antioxidant, deionized water add reactor, and evacuation, inflated with nitrogen are for several times so that initial reaction stage, and in kettle, pressure is 0.1-
0.5MPa；
B. reacting by heating 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 the polymerized monomer is 8-100 times of the fire retardant quality, preferably
10-40 times, more preferably 12-30 times；The catalyst, antioxidant are respectively described polymerized monomer (or binary amidic-salt) quality
0.01%～1.0%, preferably 0.05-0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；In system, water adds
10-60%, preferably 30-50% of the dosage for reactant gross mass.
Embodiments of the invention are as follows：
Using method used in following embodiments if no special instructions, is conventional method.
Material, reagent described in following embodiments 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 40 DEG C：1.2 stirring reactions 0.5h, are adjusted molten
Liquid PH=7.2, is dried to salt.By 50% nylon salt (hexamethylene adipamide salt) solution with account for the above-mentioned of the salt quality 6.0%
The salt that obtains, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant p-phenylenediamine add reactor, evacuation, inflated with nitrogen 5
Secondary, it is 0.2MPa finally to keep pressure in reactor.Reacting by heating kettle, keeps high-speed stirred, when temperature of reaction kettle reaches 220
DEG C, when pressure is 1.8MPa, constant temperature and pressure 1.5h.Then 250 DEG C are warmed up to, and in 1h, release of pressure is to normal pressure.Evacuation for-
0.05MPa, after declining certain value and stablize etc. mixing speed, is filled with nitrogen to 0.2MPa, discharges material, cooling, pelletizing, extraction
Take, be dried to obtain final product, its relative viscosity is 2.3, and limited oxygen index is 27.5%, and flame retardant rating reaches UL94V-0 levels
Not.Wherein described organophosphors system flame-retardant monomer is：
Embodiment 2：
By flame-retardant monomer and hexamethylene diamine in aqueous according to mol ratio 1 at 50 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 mol ratio than configuration, above-mentioned salt with account for the two quality above 7%,
The catalyst toluene sulfonic acide of each accounting 1 ‰, antioxidant 2,6- di-tert-butyl-4-methy phenols and accounting 35% go from
Sub- water addition reactor, evacuation, inflated with nitrogen 3 times, it is 0.3MPa finally to keep pressure in reactor.Reacting by heating kettle, keeps
High-speed stirred, when temperature of reaction kettle reaches 215 DEG C, when pressure is 1.7MPa, constant temperature and pressure 1.6h.Then 240 DEG C are warmed up to,
In 1.5h, release of pressure is to normal pressure.Evacuation is -0.06MPa, after declining certain value and stablize etc. mixing speed, is filled with nitrogen extremely
0.3MPa, discharges material, are extracted, are dried to obtain final product cooling, pelletizing, and its relative viscosity is 2.1, and limited oxygen index is
29%, flame retardant rating reaches UL94V-0 ranks.Wherein described organophosphors system flame-retardant monomer 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.By mol ratio 1:1.1 heneicosanedioic acids and hexamethylene diamine and with account for the two gross mass above 8% on
State double (3, the 5- di-tert-butyl-hydroxy phenyl) thioethers of salt, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant and account for
Deionized water addition reactor than 40%, evacuation, inflated with nitrogen 4 times, it is 0.2MPa finally to keep pressure in reactor.Heating
Reactor, and keep high-speed stirred.When temperature of reaction kettle reaches 245 DEG C, when pressure is 1.7MPa, constant temperature and pressure 2h.Then rise
, to 255 DEG C, in 2h, release of pressure is to normal pressure for temperature.Evacuation is -0.09MPa, after declining certain value and stablize etc. mixing speed, is filled with
To 0.3MPa, discharges material, is extracted, is dried to obtain final product cooling, pelletizing nitrogen, and its relative viscosity is 2.0, limit oxygen
Index is 32.2%, and flame retardant rating reaches UL94V-0.Wherein described organophosphors system flame-retardant monomer is：
Embodiment 4：
By fire retardant and hexamethylene diamine in aqueous according to mol ratio 1 at 42 DEG C：1.2 stirring reactions 50min, adjust solution
PH=7.4, is dried to salt.By mol ratio 1:1.15 heneicosanedioic acid and octamethylenediamine and account for the 8% of the two gross mass above
Above-mentioned salt, the catalyst toluene sulfonic acide of each accounting 1 ‰, four (β-(3,5- di-tert-butyl-hydroxy phenyl) third of antioxidant
Acid) deionized water of pentaerythritol ester and accounting 40% adds reactor, evacuation, inflated with nitrogen 3 times finally to keep reactor
Interior pressure is 0.35MPa.Reacting by heating kettle, and keep high-speed stirred.When temperature of reaction kettle reaches 230 DEG C, pressure is 1.8MPa
When, constant temperature and pressure 2h.Then 260 DEG C are warmed up to, and in 1h, release of pressure is to normal pressure.Evacuation is -0.05MPa, declines etc. mixing speed
Certain value and stable after, be filled with nitrogen to 0.3MPa, discharges material, is extracted, is dried to obtain final product cooling, pelletizing, its
Relative viscosity is 2.05, and limited oxygen index is 31.5%, and flame retardant rating reaches UL94V-0.The fire-retardant list of wherein described organophosphors system
Body is：
Embodiment 5
At 65 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=7.3, is dried to salt.By 50% nylon salt (hexamethylene adipamide salt) solution with account for the above-mentioned of the salt quality 10.0%
Salt, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant p-phenylenediamine addition reactor, evacuation, inflated with nitrogen 3 times, finally
It is 0.25MPa to keep pressure in reactor.Reacting by heating kettle, keeps high-speed stirred, when temperature of reaction kettle reaches 240 DEG C, pressure
For 1.95MPa when, constant temperature and pressure 1.5h.Then 260 DEG C are warmed up to, and in 1h, release of pressure is to normal pressure.Evacuation is -0.05MPa, waits and stirs
Mix speed decline certain value and stable after, be filled with nitrogen to 0.4MPa, discharges material, is extracted, is dried to obtain cooling, pelletizing
Final product, P content are 0.82-0.86wt.%, and its relative viscosity is 2.25, and limited oxygen index is 34.0%, and flame retardant rating reaches
Arrive UL94V-0 ranks.Wherein described organophosphors 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 organophosphors 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 organophosphors 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 organophosphors 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 organophosphors 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 each independently preferably1-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 each independently preferably3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
X represents that 1-50, y represent that 1-50, n represent 1-100；X is preferably 2-30, and y is preferably 2-30, and n is preferably 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 organophosphors 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 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-
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；R3Preferably C3-C8Linearly,
Branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
Obtain the compound of following formula (4)：
(B) diamine reactant of the compound of formula (4) and the diacid of formula (5) and formula (6), or the binary amidic-salt with formula (7) allowed
Or its solution reaction,
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；
The polyamide of acquisition formula (1)：
Wherein, R, R1、R2、R3、R4、R5, x, y, n as defined above.
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 slightly excessive, makes to be obtained
Saline solution PH be 7-9；Reaction temperature is raised to 40-70 DEG C by room temperature in 5-20min；And/or
In step (A), the diamines monomer is hexamethylene diamine, decamethylene diamine, nonamethylene diamine, hendecane diamidogen, dodecamethylene diamine, fat
Fat race C6-C20One or more in imino group diamidogen, aromatic diamine, alicyclic diamine；And/or
In step (B), change that diacid and diamidogen or binary amidic-salt or its solution, the product of step (A) are formula (4)
Compound, antioxidant, catalyst, deionized water add reactor, under nitrogen atmosphere, regulate and control reaction temperature and pressure, needed for being obtained
Organophosphors system copolymerization fire-retardant polyamide material.
5. the preparation method according to any one of claim 2-4, in step (B), the polymerized monomer diacid is for oneself
Diacid, decanedioic acid, Azelaic Acid, heneicosanedioic acid, dodecanedioic acid, p-phthalic acid, M-phthalic acid, phthalic acid or he
Derivant and other aliphatic and aromatic dicarboxylic acid in one or more；Diamidogen is hexamethylene diamine, nonamethylene diamine, the last of the ten Heavenly stems two
Amine, hendecane diamidogen, dodecamethylene diamine and aliphatic C6-C20In imino group diamidogen, aromatic diamine or alicyclic diamine
One or more；And 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.
The antioxidant is the compound such as p-phenylenediamine and dihydroquinoline and its derivant, 2,6- di-tert-butyl-4-methy phenols,
Double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester
In one or more；And/or
The 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 polymerized monomer be diacid and diamidogen or binary amidic-salt or its solution, step (A) gained product, catalyst,
Antioxidant, deionized water add reactor, and evacuation, inflated with nitrogen are for several times so that initial reaction stage, and in kettle, pressure is 0.1-
0.5MPa；
B. reacting by heating 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, the polymerized monomer diacid and diamidogen or binary acyl
The addition of amine salt or its solution is 8-100 times of the flame-retardant monomer quality, preferably 10-40 times, more preferably 12-30 times；Institute
The 0.01%-1.0% that catalyst, antioxidant are respectively the diacid and diamidogen or binary amidic-salt or its solution quality is stated, excellent
Select 0.05-0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；In system, the addition of water is the total matter of reactant
The 10-60% of amount, preferably 30-50%.
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