CN104762688B - A kind of fire-retardant Nylon 66 and preparation method thereof - Google Patents
A kind of fire-retardant Nylon 66 and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fire-retardant Nylon 66 and preparation method thereof, fire-retardant Nylon 66 is polymerized by nylon salt, water and aminomethyl phenyl phosphinic acid.The present invention first by hydroxymethyl phenyl phosphinic acid, thionyl chloride and ether according to certain mol proportion reacting by heating in a kettle., the chloromethyl phenyl phosphinic acid prepared after completing are passed through ammonia in sodium hydroxide solution to carry out aminating reaction and prepares aminomethyl phenyl phosphinic acid, then is polymerized is formed fire-retardant Nylon 66 by nylon salt, water and aminomethyl phenyl phosphinic acid.Aminomethyl phenyl phosphinic acid is joined in the polymerization system of fire-retardant Nylon 66 by the present invention, make fire retardant and nylon66 fiber perfect adaptation, not only the mechanical performance of nylon66 fiber will not be had a negative impact, it is also possible to make nylon66 fiber have good flame retardant effect in the case of fire retardant adds seldom.
Description
Technical field
The invention belongs to novel flame redundant material technical field, relate to a kind of fire-retardant Nylon 66 and preparation method thereof, particularly relate to
And one carries out halogenating reaction respectively to hydroxymethyl phenyl phosphinic acid and aminating reaction prepares fire retardant aminomethyl phenyl phosphinic acid,
Then aminomethyl phenyl phosphinic acid and nylon salt and water are carried out the fire-retardant Nylon 66 that polyreaction prepares in reactor
And preparation method thereof.
Background technology
Along with development and the continuous expansion of application of China's synthetic material industry, fire retardant is at chemical building material, electronics
Before the every field such as electrical equipment, transportation, space flight and aviation, household furniture, interior decoration, clothing, food, lodging and transportion--basic necessities of life have wide market
Scape.Along with people's environmental protection, the enhancing day by day of safe and healthy consciousness, countries in the world start environment friendly flame retardant to open as research
Send out and the emphasis of application, and have been achieved for certain achievement.Effective element classification pressed by fire retardant, can be divided into phosphorus system, chlorine system, bromine
System and antimonio, aluminum base, boryl fire retardant etc..
The difference of fire retardant using method can be divided into addition type and response type, the fire retardant base that current market is used
This is based on additive flame retardant, can be divided into again melted interpolation and polymerization interpolation, and this kind of combustion adjuvant can only uniformly divide when adding
Cloth is in fire proofing, and this fire retardant phosphorus content is low, to reach good flame retardant effect, is necessary for increasing fire retardant
Addition, this will cause declining to a great extent of fire proofing performance.
Phosphinic acid salt flame retardant products density is relatively low, and amount of flame-retardant agent is less, has well in electronic apparatus industry
Application prospect.Clariant company of Germany, Pennwalt company of the U.S. and Ticona company are all to hypophosphite fire retardant
Develop and a lot of research should be used as.The synthetic method of various metal phosphinate fire retardants is found out the most successively.As
In the invention CN 98811621.9 of Clariant company in the basic conditions, from yellow phosphorus, alkyl halide, metal hydroxides
The method preparing metal phosphinate；And CN 200410104692.0, CN 102164934 A, CN 102164930 A, CN
The patents such as 1660858 A use the mode of radical reaction from phosphinic acid source, alkene or oxyalkylene, source metal preparation
The method of metal phosphinate fire retardant.The also exploitation to phosphinate flame retardant of domestic many scholars and company has been poured into a lot
Painstaking effort, and achieve a lot of achievement.As CN 101747368 A provides a kind of partially alkylated phosphinic acid nonalkali metal salt
Preparation method and application；CN 101830926 A provide a kind of from alkyl dichloro phosphorus use radical reaction prepare two
The synthetic process of alkylphosphinic acid metal salts.
Phosphinates based flame retardant is the most all based on phosphinate metal salt at present, and is applied to poly-terephthaldehyde more
Acid butanediol ester and nylon 6, nylon66 fiber in, respond well.About the research of non-metal phosphinate flame retardant, the most not
Many.Providing the preparation method of a kind of melamine hypophosphite fire retardant in Publication No. CN 101570518A, this method is from three
Poly cyanamid and phosphinic acid set out and use Aqueous phase to prepare.This method to be limited as raw material single, and by phosphinic acid strong reducing property
Impact, it is necessary to being simultaneously introduced tripolycyanamide and phosphinic acid, otherwise phosphinic acid are heated in air ambient and can be oxidized to phosphoric acid.
Nylon 66 material market usage amount is huge, and use field relates to all trades and professions.Nylon66 fiber is as a kind of macromolecule
Material, it has obvious shortcoming in terms of fire resistance, and at present, the preparation of fire-retardant Nylon 66 mainly relies in nylon66 fiber
Adding fire retardant by physical method and prepare, this method can prepare fire resistance preferable fire-retardant Nylon 66 material.But
It is that it is disadvantageously, the amount of flame-retardant agent added is very big, and by the reprocessing to nylon66 fiber, the mechanicalness of nylon66 fiber
Can significantly decline, limit the use field of this fire-retardant Nylon 66 significantly.
The preparation method of a patent of invention CN 104211954 A halogen-free flame-proof nylon 66 having polymer, this invention first will be anti-
Answer type fire retardant DOPO derivant and binary acid or diamine to carry out reaction and generate salt, the most again by the salt generated and nylon salt
Carry out polyreaction and prepare halogen-free flame-proof nylon 66 having polymer.The fire-retardant Nylon 66 of this invention has certain anti-flammability, but its
Flame retardant molecule amount is big, and relative phosphorus content is little, and flame retardant effect is poor, and to make nylon66 fiber have preferable anti-flammability, it is fire-retardant
The addition of agent is relatively big, this rising having resulted in cost and the reduction of Mechanical Properties of Nylon 66.
Summary of the invention
The present invention relates to a kind of fire-retardant Nylon 66 and preparation method thereof, fire-retardant Nylon 66 is by nylon salt, water and aminomethyl
Phenyl phosphinic acid is polymerized.The present invention first by hydroxymethyl phenyl phosphinic acid, thionyl chloride and ether according to certain mol proportion instead
Answering reacting by heating in still, the chloromethyl phenyl phosphinic acid prepared after completing are passed through ammonia in sodium hydroxide solution, and to carry out ammonification anti-
Aminomethyl phenyl phosphinic acid should be prepared, then be polymerized formed fire-retardant nylon by nylon salt, water and aminomethyl phenyl phosphinic acid
66.Aminomethyl phenyl phosphinic acid is joined in the polymerization system of fire-retardant Nylon 66 by the present invention so that fire retardant is complete with nylon66 fiber
U.S. combination, not only will not have a negative impact to the mechanical performance of nylon66 fiber, it is also possible in the case of fire retardant adds seldom
Nylon66 fiber is made to have good flame retardant effect.
A kind of fire-retardant Nylon 66 of the present invention, it is polymerized by nylon salt, water and aminomethyl phenyl phosphinic acid；Described
The limited oxygen index of fire-retardant Nylon 66 is 30～35, and the limited oxygen index of common nylon 66 is 24, described aminomethyl phenyl time phosphine
The structural formula of acid is:
Aminomethyl phenyl phosphinic acid flame retardant molecule amount is little, and phosphorus content is high, good flame resistance, activity
Height, fully can be combined with organo-functional group, is conducive to enhancing product performance.
The present invention also proposes the preparation method of fire-retardant Nylon 66 as above, comprises the steps:
1) nylon salt is used under the conditions of 40～80 DEG C water dissolution in dissolution kettle, adds aminomethyl phenyl phosphinic acid,
It is passed through under nitrogen protection in reactor；
2) react 2～4 hours under temperature 220～240 DEG C, pressure 1.5～2.0MPa, when temperature is increased to 270 DEG C
Gradually release 1～2 hours are to 0.2～0.4MPa, keep temperature 270～280 DEG C, and pressure 0.2～0.4MPa reacts 2～4 hours,
Keep temperature to unload again and be depressed into-0.01～-0.05MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66.
The preparation method of fire-retardant Nylon 66 as above, is characterized in that, the raw materials quality ratio of described fire-retardant Nylon 66
Example is:
Aminomethyl phenyl phosphinic acid 0.5～10
Nylon salt 100
Water 100
The preparation method of fire-retardant Nylon 66 as above, described hydroxymethyl phenyl phosphinic acid, thionyl chloride and ether
Adding mol ratio is 1:1:3～10, and the chemical equation of correlated response is
The preparation method of fire-retardant Nylon 66 as above, described sodium hydroxide and the addition of chloromethyl phenyl phosphinic acid
Mol ratio is 1～1.2:1, and the concentration of sodium hydroxide solution is 2～50wt%.Relevant chemical equation is
The preparation method of fire-retardant Nylon 66 as above, described ether be methyl phenyl ethers anisole, diphenyl ether, Chloromethyl methyl ether,
Chloromethyl ether, ethyl vinyl ether, ethylene glycol monomethyl ether or glycol dimethyl ether.Ethers boiling point is relatively low, is a kind of conventional low
Temperature solvent.
The preparation method of fire-retardant Nylon 66 as above, the temperature of described reacting by heating is 40～80 DEG C, the response time
Being 3～6 hours, described cooling down to 20～30 DEG C filters.This reaction is temperature required low, and the time is short, can effectively control
Production cost, after cooling, Crystal solubility reduces precipitation, it is easier to carry out lock out operation；Described ammonia adds fashionable reaction pressure
Being 0.1～0.5MPa, excess of ammonia gas can ensure carrying out completely of reaction, and under the pressure of ammonia, is conducive to accelerating instead
The carrying out answered.
The preparation method of fire-retardant Nylon 66 as above, described reaction a period of time refers to 1～8 hour.
The preparation method of fire-retardant Nylon 66 as above, described repeatedly clean refer to wash number be 1～10 time until institute
State filtrate pH value and reach 6～8.The sodium hydroxide solution used in the preparation process of aminomethyl phenyl phosphinic acid is strong basicity,
If it can not be cleaned from fire retardant, it will the using effect of aminomethyl phenyl phosphinic acid is made a big impact.
The preparation method of fire-retardant Nylon 66 as above, described dry temperature is 50～100 DEG C, and drying time is 4
～8 hours.The fire retardant being fully dried, in use can be directly appended in production process, it is to avoid moisture introduces institute
The negative effect caused；The described filter paper used that filters is aperture 30～the qualitative filter paper of 120 microns.
Beneficial effect:
The preparation method of a kind of fire-retardant Nylon 66 of the present invention, design uniqueness, step is easy, and fire retardant addition is few, resistance
Combustion effects is obvious.
The fire-retardant Nylon 66 of the present invention, the fire retardant aminomethyl phenyl phosphinic acid used, is a kind of BACN, should
Flame retardant molecule amount is little, and phosphorus content is high.Phenyl in this flame retardant molecule structure, the nitrogen element in amino and the phosphorus of fire retardant
Element all has good flame retardant effect, by concentrating the combination of ignition-proof element so that this fire retardant is in the little feelings of addition
Fire proofing just can be made under condition to reach preferable flame retardant effect.Additionally, the amino in fire retardant can be with most of macromolecule materials
Functional group in material reacts, thus improves the compatibility and the adhesion of fire retardant and macromolecular material, can not only allow high score
Sub-material has preferable anti-flammability, moreover it is possible to improve the mechanical performance of macromolecular material to a certain extent.This fire retardant is processed
Convenient, relatively low to equipment requirements, production technology is easy, can control production cost significantly, more can ensure that the safety of production
Carry out.The fire retardant precision of preparation is high, and moisture is few, can directly add use.
The fire-retardant Nylon 66 of the present invention, by adding fire retardant aminomethyl phenyl phosphinic acid in the course of the polymerization process, this is fire-retardant
Agent fully can be combined with nylon66 fiber, and addition is few, good flame resistance.Use one-step method direct polymerization to prepare fire-retardant Nylon 66, have
Effect avoids the follow-up flame-retardant modified nylon66 fiber hydraulic performance decline caused of nylon66 fiber and the Cost Problems thus brought.Therefore, this
Bright have huge use value.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, art technology
The present invention can be made various changes or modifications by personnel, and these equivalent form of values fall within the application appended claims equally and limited
Fixed scope.
A kind of fire-retardant Nylon 66 of the present invention, it is polymerized by nylon salt, water and aminomethyl phenyl phosphinic acid；Fire-retardant
The limited oxygen index of nylon66 fiber is 30～35, and the structural formula of described aminomethyl phenyl phosphinic acid is:
Embodiment 1
The preparation method of a kind of fire-retardant Nylon 66, first synthesis aminomethyl phenyl phosphinic acid, comprise the following steps:
1) hydroxymethyl phenyl phosphinic acid, thionyl chloride that mol ratio is 1:1:3 are heated instead in a kettle. with methyl phenyl ethers anisole
Should, the temperature of reacting by heating is 80 DEG C, and the response time is 3 hours, reaction terminate rear cooling down to 20 DEG C carry out filter prepare
Chloromethyl phenyl phosphinic acid crystal, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 2wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1:1, is passed through ammonia, and it is 0.1MPa that ammonia adds fashionable reaction pressure, after reacting 1 hour
Again filtering, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns, and cleans 1 time to filtrate with water
PH value reaches 8, then prepares aminomethyl phenyl phosphinic acid at temperature is 50 DEG C after dry 4 hours, aminomethyl phenyl phosphinic acid
Structural formula is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 40 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 0.5
Nylon salt 100
Water 100；
2) react 2 hours under temperature 220 DEG C, pressure 1.72MPa, when when temperature is increased to 270 DEG C, gradually release 1 is little
To 0.2MPa, keeping temperature 270 DEG C, pressure 0.2MPa reacts 2 hours, then keeps temperature to unload being depressed into-0.01MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 30.
Embodiment 2
A kind of preparation method of aminomethyl phenyl phosphinic acid, synthesis step is:
1) hydroxymethyl phenyl phosphinic acid, thionyl chloride that mol ratio is 1:1:10 are heated instead in a kettle. with diphenyl ether
Should, the temperature of reacting by heating is 80 DEG C, and the response time is 6 hours, reaction terminate rear cooling down to 30 DEG C carry out filter prepare
Chloromethyl phenyl phosphinic acid crystal, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 50wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1.1:1, is passed through ammonia, and it is 0.5MPa that ammonia adds fashionable reaction pressure, reacts 8 hours
After again filter, filter use filter paper be aperture 30～the qualitative filter paper of 120 microns, and with water clean 10 times to filter
Thing pH value reaches 7, then prepares aminomethyl phenyl phosphinic acid, aminomethyl phenyl phosphinic acid at temperature is 100 DEG C after dry 8 hours
Structural formula be:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 80 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 10
Nylon salt 100
Water 100；
2) react 4 hours under temperature 240 DEG C, pressure 2.0MPa, when when temperature is increased to 270 DEG C, gradually release 2 is little
To 0.4MPa, keeping temperature 280 DEG C, pressure 0.4MPa reacts 4 hours, then keeps temperature to unload being depressed into-0.05MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 35.
Embodiment 3
A kind of preparation method of aminomethyl phenyl phosphinic acid, synthesis step is:
1) hydroxymethyl phenyl phosphinic acid, thionyl chloride that mol ratio is 1:1:5 are added in a kettle. with chloromethyl ether
Thermal response, the temperature of reacting by heating is 50 DEG C, and the response time is 5 hours, and reaction terminates rear cooling down and filters to 25 DEG C
Preparing chloromethyl phenyl phosphinic acid crystal, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 5wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1.2:1, is passed through ammonia, and it is 0.3MPa that ammonia adds fashionable reaction pressure, reacts 3 hours
After again filter, filter use filter paper be aperture 30～the qualitative filter paper of 120 microns, and with water clean 5 times to filter
Thing pH value reaches 7.5, then prepares aminomethyl phenyl phosphinic acid, aminomethyl phenyl time phosphine at temperature is 80 DEG C after dry 6 hours
The structural formula of acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 60 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 3
Nylon salt 100
Water 100；
2) reacting 3 hours under temperature 230 DEG C, pressure 1.6MPa, when temperature is increased to 270 DEG C, gradually release 1.5 is little
Up to 0.3MPa, keeping temperature 275 DEG C, pressure 0.3MPa reacts 3 hours, then keeps temperature to unload being depressed into-0.02MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 31.
Embodiment 4
A kind of preparation method of aminomethyl phenyl phosphinic acid, synthesis step is:
1) by hydroxymethyl phenyl phosphinic acid that mol ratio is 1:1:8, thionyl chloride with Chloromethyl methyl ether in a kettle.
Reacting by heating, the temperature of reacting by heating is 50 DEG C, and the response time is 4 hours, and reaction terminates rear cooling down and carried out to 20 DEG C
Filter prepares chloromethyl phenyl phosphinic acid crystal, and filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 30wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1.2:1, is passed through ammonia, and it is 0.3MPa that ammonia adds fashionable reaction pressure, reacts 7 hours
After again filter, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns, and cleans 8 times until mistake with water
Screening pH value reaches 6, then prepares aminomethyl phenyl phosphinic acid, aminomethyl phenyl time phosphine at temperature is 100 DEG C after dry 4 hours
The structural formula of acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 50 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 5
Nylon salt 100
Water 100；
2) reacting 3.5 hours under temperature 225 DEG C, pressure 1.8MPa, when temperature is increased to 270 DEG C, gradually release 1 is little
Up to 0.3MPa, keeping temperature 275 DEG C, pressure 0.3MPa reacts 2.5 hours, then keeps temperature to unload being depressed into-0.03MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 32.
Embodiment 5
A kind of preparation method of aminomethyl phenyl phosphinic acid, synthesis step is:
1) hydroxymethyl phenyl phosphinic acid, thionyl chloride that mol ratio is 1:1:6 are heated instead in a kettle. with methyl phenyl ethers anisole
Should, the temperature of reacting by heating is 60 DEG C, and the response time is 6 hours, reaction terminate rear cooling down to 20 DEG C carry out filter prepare
Chloromethyl phenyl phosphinic acid crystal, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 40wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1:1, is passed through ammonia, and it is 0.5MPa that ammonia adds fashionable reaction pressure, after reacting 2 hours
Again filtering, filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns, and cleans 3 times to filtrate with water
PH value reaches 8, then prepares aminomethyl phenyl phosphinic acid at temperature is 50 DEG C after dry 4 hours, aminomethyl phenyl phosphinic acid
Structural formula is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 55 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 5
Nylon salt 100
Water 100；
2) reacting 3 hours under temperature 235 DEG C, pressure 1.6MPa, when temperature is increased to 270 DEG C, gradually release 1.2 is little
Up to 0.25MPa, keeping temperature 275 DEG C, pressure 0.2MPa reacts 2 hours, then keeps temperature to unload being depressed into-0.04MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 32.
Embodiment 6
A kind of preparation method of aminomethyl phenyl phosphinic acid, synthesis step is:
1) by hydroxymethyl phenyl phosphinic acid that mol ratio is 1:1:9, thionyl chloride with glycol dimethyl ether in a kettle.
Reacting by heating, the temperature of reacting by heating is 50 DEG C, and the response time is 5 hours, and reaction terminates rear cooling down and carried out to 26 DEG C
Filter prepares chloromethyl phenyl phosphinic acid crystal, and filtering the filter paper used is aperture 30～the qualitative filter paper of 120 microns；
2) chloromethyl phenyl phosphinic acid crystal is joined in the sodium hydroxide solution that concentration is 45wt%, sodium hydroxide with
The mol ratio of chloromethyl phenyl phosphinic acid is 1.1:1, is passed through ammonia, and it is 0.2MPa that ammonia adds fashionable reaction pressure, reacts 5 hours
After again filter, filter use filter paper be aperture 30～the qualitative filter paper of 120 microns, and with water clean 6 times to filter
Thing pH value reaches 7.5, then prepares aminomethyl phenyl phosphinic acid, aminomethyl phenyl time phosphine at temperature is 90 DEG C after dry 7 hours
The structural formula of acid is:
Then prepare fire-retardant Nylon 66, comprise the following steps:
1) nylon salt is used under the conditions of 70 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
Being passed through in reactor under gas shielded, raw materials quality ratio is:
Aminomethyl phenyl phosphinic acid 6
Nylon salt 100
Water 100；
2) react 4 hours under temperature 235 DEG C, pressure 1.5MPa, when when temperature is increased to 270 DEG C, gradually release 2 is little
To 0.24MPa, keeping temperature 270 DEG C, pressure 0.4MPa reacts 4 hours, then keeps temperature to unload being depressed into-0.02MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66, the pole of fire-retardant Nylon 66
Limited oxygen index is 33.
Claims (9)
1. a preparation method for fire-retardant Nylon 66, is characterized in that, comprises the steps:
1) nylon salt is used under the conditions of 40～80 DEG C water dissolution in dissolution kettle, add aminomethyl phenyl phosphinic acid, at nitrogen
It is passed through in reactor under gas shielded；
2) react 2～4 hours under temperature 220～240 DEG C, pressure 1.5～2.0MPa, when temperature is increased to 270 DEG C gradually
Release 1～2 hours, to 0.2～0.4MPa, keep temperature 270～280 DEG C, and pressure 0.2～0.4MPa reacts 2～4 hours, then protects
Hold temperature to unload and be depressed into-0.01～-0.05MPa；
3) discharging under nitrogen pressure, melt water-bath cooling, pelletizing prepare finished product fire-retardant Nylon 66；
The synthesis step of described aminomethyl phenyl phosphinic acid is:
By hydroxymethyl phenyl phosphinic acid, thionyl chloride and ether reacting by heating in a kettle., reaction terminates rear cooling down and carries out
Filter and prepare chloromethyl phenyl phosphinic acid crystal；
Chloromethyl phenyl phosphinic acid crystal is joined in sodium hydroxide solution, is passed through ammonia, again enters after reaction a period of time
Row filters, and by the most cleaned screening of water, prepares aminomethyl phenyl phosphinic acid after drying；
The structural formula of described aminomethyl phenyl phosphinic acid is:
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, the raw material of described fire-retardant Nylon 66
Mass ratio is:
Aminomethyl phenyl phosphinic acid 0.5～10；
Nylon salt 100；
Water 100.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, described hydroxymethyl phenyl time phosphine
Acid, thionyl chloride are 1:1:3～10 with the addition mol ratio of ether；Described sodium hydroxide and chloromethyl phenyl phosphinic acid crystal
Mol ratio is 1～1.2:1, and the concentration of sodium hydroxide solution is 2～50wt%.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, described ether is methyl phenyl ethers anisole, hexichol
Ether, Chloromethyl methyl ether, chloromethyl ether, ethyl vinyl ether, ethylene glycol monomethyl ether or glycol dimethyl ether.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, it is characterised in that the temperature of described reacting by heating is
40～80 DEG C, the response time is 3～6 hours, and described cooling down to 20～30 DEG C filters；Described ammonia adds to be made instead
Answering pressure is 0.1～0.5MPa.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, described reaction a period of time refers to 1
～8 hours；Described repeatedly clean refer to wash number be 1～10 time until described filtrate pH value reaches 6～8.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, described dry temperature be 50～
100 DEG C, drying time is 4～8 hours.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, the described filter paper used that filters is
Aperture 30～the qualitative filter paper of 120 microns.
The preparation method of fire-retardant Nylon 66 the most according to claim 1, is characterized in that, the limit oxygen of described fire-retardant Nylon 66
Index is 30～35.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332987A (en) * | 1963-06-24 | 1967-07-25 | Pennsalt Chemicals Corp | Aminoalkylphosphinic acids |
| CN1059148A (en) * | 1990-08-17 | 1992-03-04 | 赫彻斯特股份公司 | The method for making of aminomethane phosphonic acids and amino methyl-phospho acid |
| CN102675630A (en) * | 2011-03-18 | 2012-09-19 | 上海枫化兆质新材料科技有限公司 | Preparation method of halogen-free flame-retardant nylon 6 |
| CN104211954A (en) * | 2013-05-30 | 2014-12-17 | 辽宁银珠化纺集团有限公司 | Preparation method of halogen-free flame retardant nylon 66 polymer |
-
2015
- 2015-04-09 CN CN201510164733.3A patent/CN104762688B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332987A (en) * | 1963-06-24 | 1967-07-25 | Pennsalt Chemicals Corp | Aminoalkylphosphinic acids |
| CN1059148A (en) * | 1990-08-17 | 1992-03-04 | 赫彻斯特股份公司 | The method for making of aminomethane phosphonic acids and amino methyl-phospho acid |
| CN102675630A (en) * | 2011-03-18 | 2012-09-19 | 上海枫化兆质新材料科技有限公司 | Preparation method of halogen-free flame-retardant nylon 6 |
| CN104211954A (en) * | 2013-05-30 | 2014-12-17 | 辽宁银珠化纺集团有限公司 | Preparation method of halogen-free flame retardant nylon 66 polymer |
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