CN106497027A - A kind of in-situ polymerization type N P synergistic fire-retardant nylons and preparation method thereof - Google Patents
A kind of in-situ polymerization type N P synergistic fire-retardant nylons and preparation method thereof Download PDFInfo
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- CN106497027A CN106497027A CN201610932376.5A CN201610932376A CN106497027A CN 106497027 A CN106497027 A CN 106497027A CN 201610932376 A CN201610932376 A CN 201610932376A CN 106497027 A CN106497027 A CN 106497027A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention discloses a kind of in-situ polymerization type N P synergistic fire-retardant nylons and preparation method thereof.Preparation method of the present invention, specifically includes following steps：(A) organophosphor system flame-retardant monomer and diamines monomer are reacted into salt；(B) by nitrogenated flame retardant emulsion dispersion, nitrogenated flame retardant emulsion is obtained；(C) by diacid and diamines or binary amidic-salt or its solution, salt made above or its solution, nitrogenated flame retardant emulsion, antioxidant, catalyst addition reactor, under inert atmosphere, by regulating and controlling reaction temperature and pressure, in-situ polymerization is obtained required N P synergistic fire-retardant nylon materials.The in-situ polymerization type fire-retardant nylon that the present invention is prepared, due to synergistic effect, the fire retardant total amount of interpolation needed for reducing.Whole preparation process viscosity is controllable, and mechanical performance and all good product of fire resistance is obtained, and, up to 94 V of UL, 0 ranks, limited oxygen index is more than 28% for vertical burn test.
Description
Technical field
The invention belongs to flame-retardant high-molecular synthesis technical field, be related to a kind of in-situ polymerization type N-P synergistic fire-retardant nylon and
Its preparation method.
Background technology
The features such as nylon (PA) is due to high mechanical strength, good, wear-resisting heat endurance, excellent solvent resistance, in machinery, hands over
The fields such as logical, electronic apparatus, military affairs, Aero-Space play an important role.But belong to the nylon of self-extinguishment macromolecular material,
Limited oxygen index value is usually no more than 23%, and vertical burn test grade is V-2 ranks, once it is ignited, can be high because of caloric value,
Burning velocity is fast, and molten drop is seriously waited and encourages the intensity of a fire, causes heavy losses to life is prepared, it is impossible to meet fire-retardant in practical application
Require.Therefore, the fire-retardant nylon of high comprehensive performance is developed, significant to expanding its application.
Method generally using the introducing fire retardant in matrix is come modified to flame retardance of polymer.According to method of modifying not
Together, the preparation method of fire-retardant nylon is divided into blending fire retardant modification, in-situ polymerization is flame-retardant modified and polymeric flame-retardant is modified.Blending fire retardant
Modification, due to process is simple, is the main method for preparing fire-retardant nylon at present.In order to reach required flame retardant effect, fire retardant adds
Amount is generally large, is difficult to realize the dispersed of fire retardant, can produce certain impact on the mechanical property of composite.And it is in situ
Polymeric flame-retardant nylon and polymeric flame-retardant nylon provide new thought for preparing fire-retardant nylon, and prospects for commercial application is bright.
Flame-retardant modified the referring to of in-situ polymerization is dispersed in additive flame retardant in nylon monomer, then in specified temp and pressure
It is polymerized under power, the excellent polymer composite of forming properties.If in system, the fire retardant addition type and response type
Coexist, then whole reaction also serves as the reaction of in-situ polymerization type.By polymerisation, fire retardant or chemical bond are incorporated into matrix, or
It is dispersed in matrix, is not in skewness problem that Blending Processes often occur substantially.
It is rarely employed the fire retardant of single variety in actual flame-retarded technology, but several fire retardants in order to reaching collaboration resistance
Fuel efficiency fruit.So-called synergistic is fire-retardant, exactly by two kinds or two or more effective flame-retardant compositions is allocated according to a certain percentage, passes through
Synergy, makes up the deficiency of single flame resistant method, the relation of balance flame retardant agent consumption, performance and cost, with meet environmental protection with
The requirement of safety.
Conventional organic phosphorus flame retardant mainly includes phosphate, phosphonate ester, aryl phosphine and phosphine oxide, phosphinate (salt) etc.
Relatively friendly to environment due to which, fire-retardant efficient, it is the preferred sub of halogenated flame retardant.Giving material good flame-retardance
Meanwhile, also with giving birth to, smoke is few, be difficult the features such as forming poisonous and rotten candle property gas.
Common nitrogenated flame retardant includes following several types:Melamine (ME), melamine polyphosphate (MPP), three
The compound with triazine structure such as poly cyanamid cyanurate (MCA) and modified melamine resin.Nylon is flame-retardant modified described at present
In nitrogenated flame retardant, MCA is most commonly seen.Used as additive flame retardant, how which is combined with nylon in the way of being blended, but
MCA agglomerated particle compact structures, difficulties in dispersion, can cause mechanical property to deteriorate.
The patent of Publication No. CN104499076A is related to a kind of preparation method of 6 fiber of Flameproof polyamide, and which is in oneself
Add MCA for fire retardant in acid amides polymerization process, in-situ polymerization prepares Flameproof polyamide 6 and cuts into slices, can so cause to be formed in situ
MCA be dispersed in polyamide 6 with nano-scale, then using solid phase polycondensation improve molecular weight, prepare fire resistance, power
Polyamide 6 section of good performance is learned, and 6 fibre of Flameproof polyamide with certain application prospect is obtained finally by melt spinning
Dimension.
The patent of Publication No. CN104177824A discloses a kind of novel phosphor nitrogen system halogen-free flame-retardant nylon 6 and its preparation side
Method, step is：(1) aluminum diethylphosphinate, macromolecular carbon forming agent, coupling agent, antioxidant are mixed with nylon 6 resin, is stirred
Uniformly；(2) mixture obtained in the first step is obtained phosphorous-nitrogen system bittern-free fire-retardant Nylon 6 using the method for high-temperature fusion blending.
In novel phosphor nitrogen system halogen-free flame-retardant nylon 6 that the present invention is provided and preparation method thereof, organic nitrogen-containing fire retardant is not used, used
Macromolecular carbon forming agent heat endurance high, meet the processing conditions of nylon 6, the macromolecular carbon forming agent be added to nylon 6 resin
In, aluminum diethylphosphinate is compounded with macromolecular carbon forming agent, improves heat endurance and the flame retardant effect of composite, Er Qieyou
Effect reduces the usage amount of aluminum diethylphosphinate, has saved cost.On the whole, this patent application or melt blending
Method, still suffers from the uneven problem of fire retardant dispersion.
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.Described in this patent, fire retardant 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 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. 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；R2
For 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.
The patent of Publication No. 104262169 is related to a kind of phosphor-containing flame-proof polyamide and preparation method and application.Prepare
Method includes：(1) being used for fire-retardant hypophosphites carries out prepolymerization reaction generation oligomer with diamine；(2) by oligomer with
Dicarboxylate carries out prepolymerization reaction in a nitrogen atmosphere, obtains prepolymer；(3) twice after prepolymerization reaction, by temperature liter
Height, makes air pressure be down to normal pressure；(4) temperature is raised, is pumped to vacuum, discharging obtains fire-retardant polyamide material.Institute in this patent
With fire retardant it 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-94V-0 ranks, and LOI values also have bright
Aobvious raising.
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 fire-retardant nylon of fire resistance.
Content of the invention
The purpose of the present invention is the scene for the present market of fire-retardant nylon mainly based on blending, and in-situ polymerization goes out one kind
New N-P synergistics fire-retardant nylon material.It is characterized in allowing reactive flame retardant to carry out precondensation, additive flame retardant with diamine
First be uniformly dispersed in solvent such as water, then again with polymerized monomer polycondensation, so as to prepare new N-P synergistics fire-retardant nylon material
Material.In this process, due to synergistic effect, fire retardant addition can greatly reduce.Additionally, polymerization can also cause fire-retardant
Agent is more evenly distributed in nylon matrix, chemical mode or physics mode, all good so as to obtain mechanical property, electric property etc.
Nylon material.
Technical scheme：
A kind of in-situ polymerization type N-P synergistic fire-retardant nylon, it are included with organic flame-retarding phosphorus copolymerized poly- shown in following formula (1)
Acid amides and the 1-10wt% relative to the in-situ polymerization type N-P synergistic fire-retardant nylon, the preferably nitrogenated flame retardant of 3-6wt%：
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 nitrogenated flame retardant is selected from melamine, melamine phosphate, melamine cyanurate and its derivative
Deng, preferably in the form of aqueous dispersions, preferably melamine cyanurate and its derivative, more preferably MCA (melamine cyanureas
Hydrochlorate) aqueous dispersions.
The preparation method of above-described in-situ polymerization type N-P synergistic fire-retardant nylon 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 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) allow the compound of formula (4) and the diacid of formula (5) and formula (6) diamines relative to whole polymerized monomer gross weights
React in the presence of the nitrogenated flame retardant of the 1-10wt% of amount, preferably 3-6wt%, or with the binary amidic-salt of formula (7) in phase
For the 1-10wt% of whole polymerized monomer gross weights, preferably in the presence of the nitrogenated flame retardant of 3-6wt% such as MCA emulsions
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；
Obtain the in-situ polymerization type N-P synergistic fire-retardant nylon containing formula (1) structure：
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), it is preferable that diamines monomer is slightly excessive, the PH for making obtained salting liquid is 7-9.Reaction temperature
40-70 DEG C is raised to by room temperature in 5-20min.
Preferably, diamines monomer described in step (A) 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 1:1.01-10, preferably 1:1.1-2, more preferably from about 1:1.5.
In step (B), it is preferable that by polymerized monomer, the product of step (A), nitrogenated flame retardant, antioxidant, urge
Agent, deionized water add reactor, under nitrogen atmosphere, regulate and control reaction temperature and pressure, in-situ polymerization type N-P association needed for being obtained
Effect fire-retardant nylon.
In step (B), further, the polymerized monomer binary acid be such as adipic acid, decanedioic acid, azelaic acid, 11
Docosandioic acid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or their derivative and other fat
One or more in race and aromatic dicarboxylic acid；Binary amine compound is such as hexamethylene diamine, nonamethylene diamine, decamethylene diamine, 11
Alkane diamines, dodecamethylene diamine and aliphatic C6-C20One kind in imino group diamines, aromatic diamine or alicyclic diamine or
Multiple；The binary amidic-salt be hexamethylene adipamide salt, adipyl pentanediamine salt, hexamethylene azelamide salt, decanedioyl oneself two
Amine salt, decanedioyl octamethylenediamine salt, suberoyl hexamethylene diamine salt, one or more of suberoyl octamethylenediamine salt.
In step (B), further, the nitrogenated flame retardant is selected from melamine, melamine phosphate, melamine
One or more in cyanurate and its derivative etc., preferably melamine cyanurate and its derivative.Nitrogenated flame retardant
It is preferred that used in the form of aqueous dispersions (emulsion), by nitrogenated flame retardant (such as melamine cyanurate) is added water
In (part by weight of nitrogenated flame retardant and water is as being 1:5～500, preferably 1:5～50), using homogeneous shearing stirrer or homogeneous
Agitator stirs (emulsification pretreatment) (such as 1-60 minutes, preferably from about 5-20 minutes) for (such as 5000-30000 rev/min) at a high speed
To prepare.
In step (B), further, the antioxidant is the compound such as p-phenylenediamine and EEDQ and its derivative,
2,6- di-tert-butyl-4-methy phenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic 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, step (A) gained product, nitrogenated flame retardant aqueous dispersions, catalyst, antioxidant, go
Ionized 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.
Further, in step a, the addition of the polymerized monomer diamines and diacid or binary amidic-salt is described fire-retardant
8-100 times of monomer mass, preferably 10-40 times, more preferably 12-30 times；Nitrogenated flame retardant (melamine cyanurate) adds
1-10wt%, preferably 3-6wt% of the dosage relative to whole monomers (including polymerized monomer and flame-retardant monomer) gross mass；Described urge
Agent, antioxidant are respectively the 0.01%～1.0% of described polymerized monomer (or binary amidic-salt) quality, preferably 0.05-
0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；The addition of water preferably polymerized monomer (or binary acid amides
Salt) 10-60%, 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
Solution is added in polymerized monomer, is joined in the presence of nitrogenated flame retardant (preferably nitrogenated flame retardant emulsion) under catalyst action
With polymerisation.The fire resistance of the in-situ polymerization type N-P synergistic fire-retardant nylon for obtaining is satisfied by UL-94V-0 requirements.
WithAs a example by hexamethylene diamine, PA66 salt, MCA, the mechanism of the reaction
For：Flame-retardant monomer first reacts into salt with hexamethylene diamine, and then the salt or its solution generate fire-retardant with nylon salt and MCA in-situ polymerizations
Polyamide.The course of reaction that wherein flame-retardant monomer is copolymerized in PA66 can be written as：
The invention has the beneficial effects as follows：
When fire retardant (response type and addition type) quality in polymer raw total amount accounting more than 6% when, UL- can be reached substantially
94V-0 ranks, and limited oxygen index scope is 26%-33%, 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.
This patent makes emulsion by first dispersed in water for MCA, it is possible to reduce in polymerization process by emulsification
Agglomeration occur.
Fire-retardant nylon prepared by synergistic just can reach higher flame retarding efficiency when amount of flame-retardant agent is less, and few molten drop,
Do not separate out, next fire-retardant with gas phase and condensed phase collective effect mechanism, widen fire retardant range of choice.
The synergistic fire-retardant nylon of the present invention has good fire resistance and mechanics, electric property, can be prepared to close
Into fiber, to be further processed into the products such as clothes, decoration or injection mo(u)lding or melt cast molding, for automobile, electrical equipment,
The aspects such as communication, electronics, machinery.
Specific embodiment
The present invention is described in further detail with reference to instantiation.
The in-situ polymerization type N-P synergistic fire-retardant nylon of the present invention is included with organic flame-retarding phosphorus copolymerized shown in following formula (1)
Poly- nylon and the 1-10wt% relative to the organophosphor system copolymerization fire-retardant nylon, the preferably nitrogenated flame retardant of 3-6wt%：
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 in-situ polymerization type N-P synergistic fire-retardant nylon of the present invention, specifically includes following steps：
(A) by organophosphor system flame-retardant monomer and diamine reactant, amino excess is preferably made, into salt；
(B) product of step (A) and diacid and diamines or binary amidic-salt are made relative to whole polymerized monomers
React in the presence of the nitrogenated flame retardant of the 1-10wt% of gross weight, preferably 3-6wt%, prepare the resistance of in-situ polymerization type N-P synergistic
Combustion nylon.
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, diamines monomer described in step (A) 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, the product of step (A), nitrogenated flame retardant emulsion such as three
Poly cyanamid cyanurate emulsion, antioxidant, catalyst, deionized water add reactor, under nitrogen atmosphere, regulate and control reaction temperature
And pressure, in-situ polymerization type N-P synergistic fire-retardant nylon material needed for being obtained.
In step (B), further, the polymerized monomer binary acid be such as adipic acid, decanedioic acid, azelaic acid, ten
One docosandioic acid, dodecanedioic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or their derivative 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 diamines, dodecamethylene diamine and aliphatic C6-C20One kind in imino group diamines, aromatic diamine or alicyclic diamine
Or it is multiple；The binary acid amides 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.
In step (B), further, the nitrogenated flame retardant includes melamine, melamine phosphate, melamine
Amine cyanurate and its derivative etc., preferably melamine cyanurate and its derivative.Nitrogenated flame retardant emulsion passes through will
(such as melamine cyanurate is added to the water that (part by weight of nitrogenated flame retardant and water is as 1 to nitrogenated flame retardant:5～500,
It is preferred that 1:5～50), using homogeneous shearing stirrer or homogeneous agitator, (such as 5000-30000 rev/min) shearing is newborn at a high speed
Change (such as 1-60 minutes, preferably from about 5-20 minutes) to prepare.
In step (B), further, the antioxidant 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, 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, step (A) gained product (salting liquid), nitrogenated flame retardant emulsion such as melamine
Cyanurate emulsion, catalyst, antioxidant, deionized water add reactor, vacuumize, inflated with nitrogen for several times so that reaction is just
Phase, 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 the polymerized monomer diamines and diacid or binary amidic-salt is described fire-retardant
8-100 times of monomer mass, preferably 10-40 times, more preferably 12-30 times；Nitrogenated flame retardant (melamine cyanurate) adds
1-10wt%, preferably 3-6wt% of the dosage relative to whole monomers (including polymerized monomer and flame-retardant monomer) gross mass；Described urge
Agent, antioxidant are respectively the 0.01%～1.0% of described polymerized monomer (or binary amidic-salt) quality, preferably 0.05-
0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；The addition of water preferably polymerized monomer (or binary acid amides
Salt) 10-60%, preferably 30-50%.
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, obtains salting liquid.
The MCA of polymerized monomer (including above-mentioned salting liquid and following nylon salts) gross mass 4% will be accounted in a certain amount of water
High speed shearing emulsification 10min, obtains finely dispersed MCA emulsions.
By nylon salt (hexamethylene adipamide salt) solution with account for nylon salt quality 4.0% (disregarding solvent, similarly hereinafter)
Salting liquid obtained above, MCA emulsions, 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, i.e. in-situ polymerization type N-P synergistic fire-retardant Buddhist nun cooling, pelletizing gas
Dragon, its relative viscosity are 2.26, and limited oxygen index is 27.8%, and flame retardant rating reaches UL94V-0 ranks.Wherein described organophosphor
It is that 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.
The 3%MCA of polymerized monomer gross mass will be accounted in a certain amount of water high speed emulsification pretreatment 6min, obtained finely dispersed
MCA emulsions.
By adipic acid, hexamethylene diamine according to 1:1.3 mass ratio configuration, molten with the salt obtained above of account for its weight 5%
Liquid, MCA emulsions, the catalyst toluene sulfonic acide of each accounting 1 ‰, antioxidant 2,6- di-tert-butyl-4-methy phenols, Yi Jizhan
Deionized water than 35% adds reactor, vacuumizes, inflated with nitrogen 3 times, and it is 0.3MPa finally to keep pressure in reactor.Heating
Reactor, 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 rise
, to 240 DEG C, in 1.5h, release of pressure is to normal pressure for temperature.Vacuumize as -0.06MPa, etc. mixing speed decline certain value and stable after, fill
Enter nitrogen to 0.3MPa, discharges material, is extracted, is dried to obtain final product, i.e. in-situ polymerization type N-P synergistic resistance cooling, pelletizing
Combustion nylon, its relative viscosity is 2.23, and limited oxygen index is 29.4%, and flame retardant rating reaches UL94V-0 ranks.Wherein described have
Machine phosphorous 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.
By account for polymerized monomer gross mass 3% MCA in a certain amount of water high speed emulsification pretreatment 5min, be uniformly dispersed
MCA emulsions.
It is 1 by mol ratio:1.4 heneicosanedioic acid, hexamethylene diamine and 5% salting liquid obtained above for accounting for its gross mass,
Double (3, the 5- di-tert-butyl-hydroxy phenyl) thioether of MCA emulsions, the catalyst sodium hypophosphite of each accounting 1 ‰, antioxidant with
And the deionized water of accounting 50% adds reactor, vacuumizes, inflated with nitrogen 4 times, it is 0.2MPa finally to keep pressure in reactor.
Heating response kettle, and keep high-speed stirred.When temperature of reaction kettle reaches 225 DEG C, when pressure is 1.7MPa, constant temperature and pressure 2h.So
After be warmed up to 255 DEG C, in 2h, release of pressure is to normal pressure.Vacuumize as -0.09MPa, etc. mixing speed decline certain value and stable after,
Nitrogen is filled with to 0.3MPa, discharges material, is extracted, is dried to obtain final product, i.e. in-situ polymerization type N-P synergistic cooling, pelletizing
Fire-retardant nylon, its relative viscosity are 2.2, and limited oxygen index is 30.3%, and flame retardant rating reaches UL94V-0.Wherein described organic
Phosphorous 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.
The MCA of polymerized monomer gross mass 2% will be accounted in a certain amount of water high speed emulsification pretreatment 5min, obtained finely dispersed
MCA emulsions.
By mol ratio 1:1.5 heneicosanedioic acid, octamethylenediamine are obtained with 6% above-mentioned for accounting for both the above monomer gross mass
Salting liquid, MCA emulsions, the catalyst toluene sulfonic acide of each accounting 1 ‰, four (β-(3,5- di-t-butyl -4- hydroxyls of antioxidant
Base phenyl) propionic acid) deionized water of pentaerythritol ester and accounting 40% adds reactor, vacuumizes, inflated with nitrogen 3 times, finally
It is 0.35MPa to keep pressure in reactor.Heating response kettle, and keep high-speed stirred.When temperature of reaction kettle reaches 230 DEG C, pressure
When being 1.8MPa by force, constant temperature and pressure 2h.Then 260 DEG C are warmed up to, and in 1h, release of pressure is to normal pressure.Vacuumize as -0.05MPa, wait and stir
Mix speed decline certain value and stable after, be filled with nitrogen to 0.3MPa, discharges material, is extracted, is dried to obtain cooling, pelletizing
Final product, i.e. in-situ polymerization type N-P synergistic fire-retardant nylon, its relative viscosity are 2.07, and limited oxygen index is 32.3%, fire-retardant
Grade reaches UL94V-0.Wherein described organophosphor system flame-retardant monomer is：
Embodiment 5
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.
The melamine phosphate of polymerized monomer gross mass 3% will be accounted in a certain amount of water high speed emulsification pretreatment 5min, obtained
Arrive finely dispersed melamine phosphate aqueous dispersions.
By mol ratio 1:1.5 heneicosanedioic acid, octamethylenediamine are obtained with 6% above-mentioned for accounting for both the above monomer gross mass
Salting liquid, melamine phosphate aqueous dispersions, the catalyst toluene sulfonic acide of each accounting 1 ‰, four (β-(3,5- of antioxidant
Di-tert-butyl-hydroxy phenyl) propionic acid) deionized water of pentaerythritol ester and accounting 40% adds reactor, and vacuumize, fill
Nitrogen 3 times, it is 0.35MPa finally to keep pressure in reactor.Heating response kettle, and keep high-speed stirred.Work as temperature of reaction kettle
230 DEG C are reached, 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, is filled with nitrogen to 0.3MPa, discharges material, cooling, pelletizing, extraction
Take, be dried to obtain final product, i.e. in-situ polymerization type N-P synergistic fire-retardant nylon, its relative viscosity is 2.17, and limited oxygen index is
31.7%, flame retardant rating reaches UL94V-0.Wherein described organophosphor system flame-retardant monomer is：
Embodiment 6
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=7.5, is dried to salt.
The MCA of polymerized monomer gross mass 2% will be accounted in a certain amount of water high speed emulsification pretreatment 5min, obtained finely dispersed
MCA emulsions.
By 50% nylon salt (hexamethylene adipamide salt) solution and the above-mentioned salt, the MCA emulsifications that account for the salt quality 10.0%
Liquid, the deionized water of the catalyst sodium hypophosphite, antioxidant p-phenylenediamine and accounting 35% of each accounting 1 ‰ add reaction
Kettle adds reactor, vacuumizes, inflated with nitrogen 3 times, and it is 0.25MPa finally to keep pressure in reactor.Heating response kettle, keeps high
Speed stirring, when temperature of reaction kettle reaches 240 DEG C, when pressure is 1.95MPa, constant temperature and pressure 1.5h.Then 260 DEG C are warmed up to, 1h
Interior release of pressure is to normal pressure.Vacuumize as -0.05MPa, etc. mixing speed decline certain value and stable after, be filled with nitrogen extremely
0.4MPa, discharges material, are extracted, are dried to obtain final product cooling, pelletizing, and P content is 0.82-0.84 mass %, and which is relative
Viscosity is 2.28, and limited oxygen index is 33.5%, and flame retardant rating reaches UL94V-0 ranks.The fire-retardant list of wherein described organophosphor system
Body 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 1-6 is obtained
The test sample made of organophosphor system fire-retardant polyamide material be referred to as " FR-A "-" FR-F " 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, and the use of nitrogenated flame retardant, substantially can reduce phosphor-containing flame-proof monomer in the case where high fire-retardance rank is reached
Consumption, so as to cost is greatly reduced.When phosphor-containing flame-proof content of monomer is reached in 3-6%, Flameproof polyamide can pass through UL-
94 V-0 tests, LOI values are also improved therewith.Therefore may certify that, the present invention is using response type organic phosphorus flame retardant to polyamides
It is feasible and efficient that amine is flame-retardant modified, and nitrogenated flame retardant can act synergistically with response type organic phosphorus flame retardant, reduce
The high response type organic phosphorus flame retardant of price introduction volume in the polymer.The original position obtained by the scheme that the present invention is provided
Aggretion type N-P synergistic fire-retardant nylon material, while limited oxygen index is higher, its relative viscosity value is also higher.Due to end group
Exist, when will obtain more high-viscosity material, conventional solid technics of enhancing viscosity can be adopted, obtain 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 (9)
1. a kind of in-situ polymerization type N-P synergistic fire-retardant nylon, which is included with the organic flame-retarding phosphorus copolymerized polyamides shown in following formula (1)
Amine and the 1-10wt% relative to the in-situ polymerization type N-P synergistic fire-retardant nylon, the preferably nitrogenated flame retardant of 3-6wt%：
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. in-situ polymerization type N-P synergistic fire-retardant nylon according to claim 1, wherein, nitrogenated flame retardant is selected from melamine
One or more in amine, melamine phosphate, melamine cyanurate and its derivative, preferably melamine cyanurate
Salt and its derivative, more preferably MCA aqueous dispersions.
3. the preparation method of the in-situ polymerization type N-P synergistic fire-retardant nylon described in claim 1 or 2, 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 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) allow the compound of formula (4) and the diacid of formula (5) and formula (6) diamines relative to whole polymerized monomer gross weights
React in the presence of the nitrogenated flame retardant of 1-10wt%, preferably 3-6wt%；Or with the binary amidic-salt of formula (7) relative to
All the 1-10wt% of polymerized monomer gross weight, reacts preferably in the presence of the nitrogenated flame retardant of 3-6wt%,
Wherein, R4And R5It is selected from C3-C12Linearly, branched or cyclic alkylidene, C6-C10Arlydene, C3-C10Heteroaryl, is preferably selected from
C3-C8Linearly, branched or cyclic alkylidene, C6-C8Arlydene, C3-C8Heteroaryl；
Obtain the in-situ polymerization type N-P synergistic fire-retardant nylon containing formula (1) structure：
Wherein, R, R1、R2、R3、R4、R5, x, y, n as defined above.
4. preparation method according to claim 3, wherein, nitrogenated flame retardant selected from melamine, melamine phosphate,
One or more in melamine cyanurate and its derivative, preferably melamine cyanurate and its derivative or its water
Dispersion liquid, more preferably MCA aqueous dispersions.
5. the preparation method according to claim 3 or 4, 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.
6. the preparation method according to any one of claim 3-5, wherein, in step (A), diamines monomer slightly mistake
Amount, the PH for making obtained salting liquid are 7-9；Reaction temperature is raised to 40-70 DEG C by room temperature in 5-20min；And/or
Diamines monomer described in step (A) 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 polymerized monomer diacid and diamines or binary amidic-salt or its solution, the product of step (A), nitrogen system
Fire retardant aqueous dispersions, antioxidant, catalyst, deionized water add reactor, under inert atmosphere, regulate and control reaction temperature and pressure
By force, in-situ polymerization type N-P synergistic fire-retardant nylon material needed for being obtained.
7. the preparation method according to any one of claim 3-6, wherein, in step (B), the polymerized monomer is energy
Enough participate in copolymerization diacid and diamines, diacid be adipic acid, decanedioic acid, azelaic acid, heneicosanedioic acid, dodecanedioic acid, to benzene
In dioctyl phthalate, M-phthalic acid, phthalic acid or their derivative and other aliphatic and aromatic dicarboxylic acid one
Plant or multiple；And binary amine compound is hexamethylene diamine, nonamethylene diamine, decamethylene diamine, hendecane diamines, dodecamethylene diamine and fat
Fat race C6-C20One or more in imino group diamines, aromatic diamine or alicyclic diamine；The binary amidic-salt, be
Hexamethylene adipamide salt, adipyl pentanediamine salt, hexamethylene azelamide salt, hexamethylene sebacamide salt, decanedioyl octamethylenediamine salt, pungent
Two acyl hexamethylene diamine salt, one or more of suberoyl octamethylenediamine salt.
In step (B), the nitrogenated flame retardant selected from melamine, melamine phosphate, melamine cyanurate and its
One or more in derivative etc., preferably melamine cyanurate and its derivative.Nitrogenated flame retardant is preferably dissipated with moisture
The form of liquid (emulsion) is used, and by nitrogenated flame retardant (such as melamine cyanurate) to be added to the water, (nitrogen system is fire-retardant
Agent is such as 1 with the part by weight of water:5～500, preferably 1:5～50), using homogeneous shearing stirrer or homogeneous agitator high speed
(such as 5000-30000 rev/min) is stirred (emulsification pretreatment) (such as 1-60 minutes, preferably from about 5-20 minutes) to prepare.
In step (B), the antioxidant is the compound such as p-phenylenediamine and EEDQ and its derivative, 2,6- di-t-butyls-
4- methylphenols, double (3,5- di-tert-butyl-hydroxy phenyl) thioethers, four (β-(3,5- di-tert-butyl-hydroxy phenyl) third
Acid) one or more in pentaerythritol ester；And/or
In step (B), the catalyst is sodium hypophosphite, toluene sulfonic acide, in new ferrocene chiral polyamide part one
Plant or multiple.
8. the preparation method according to any one of claim 3-7, wherein, in step (B), specifically includes following steps：
A. by diacid and diamines or binary amidic-salt or its solution, step (A) gained product, nitrogenated flame retardant, 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.
9. preparation method according to claim 8, wherein, the polymerized monomer diamines and diacid or binary amidic-salt plus
Enter that amount is the flame-retardant monomer quality 8-100 times, preferably 10-40 times, more preferably 12-30 times；Nitrogenated flame retardant (melamine
Cyanurate) addition relative to whole monomers (including polymerized monomer and flame-retardant monomer) gross mass 1-10wt%, preferably
3-6wt%；The catalyst, antioxidant are respectively the 0.01%～1.0% of described polymerized monomer (or binary amidic-salt) quality,
It is preferred that 0.05-0.5%, more preferably 0.08-0.2%, more preferably e.g., from about 1/1000；The addition of water is preferably polymerized monomer
The 10-60% of (or binary amidic-salt), preferably 30-50%.
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| CN113861413A (en) * | 2020-12-25 | 2021-12-31 | 四川大学 | Phosphorus-nitrogen-containing flame-retardant copolymerized nylon and preparation method and application thereof |
| CN113861413B (en) * | 2020-12-25 | 2023-09-26 | 四川大学 | Flame-retardant copolymerized nylon containing phosphorus and nitrogen as well as preparation method and application thereof |
| CN113651955A (en) * | 2021-08-16 | 2021-11-16 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin with good processability and preparation method and application thereof |
| CN115572387A (en) * | 2022-09-28 | 2023-01-06 | 浙江恒逸石化研究院有限公司 | Preparation method of low-melting-point copolymerized flame-retardant polyamide |
| CN115572387B (en) * | 2022-09-28 | 2023-11-24 | 浙江恒逸石化研究院有限公司 | Preparation method of low-melting-point copolymerized flame-retardant polyamide |
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