CN109796629A - Novel N-P-S expansion type phosphor flame retardant and preparation method thereof - Google Patents
Novel N-P-S expansion type phosphor flame retardant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the preparation methods of several Novel Intumescent Flame Retardants.Its technical issues that need to address is that tri- kinds of N, P, S effective ignition-proof elements are assembled in single intramolecular, design synergistic intumescent flame retardant in a kind of novel molecular, it is added in carbonate polymer simultaneously, realize a small amount of highly effective flame-retardant polycarbonate, and it is environment-friendly and low-toxicity, so that flame retardant effect is reached best.Reaction process is that first the substances such as the organic amine containing sulfonic acid or phenol are added dropwise in aqueous slkali；Hexachlorocyclotriph,sphazene is dissolved in solvent, and is added dropwise in the aqueous solution of sulfonate, is down to room temperature after back flow reaction 48h, adjusts pH to neutrality with dilute hydrochloric acid, standing overnight is precipitated inorganic salts largely.Inorganic salts are filtered out, neutral alumina absorption is added in filtrate and falls foreign pigment, filtrate is collected by filtration；Reverse phase precipitating reagent is added in filtrate, product is precipitated, decompression filters, and filter cake freeze-day with constant temperature is arrived product of the invention.
Description
Technical field:
The invention belongs to the synthesis technical fields of Novel Intumescent Flame Retardant, are related to several Novel Intumescent Flame Retardants
Preparation method and its as Polycarbonate flame retardant material flame retardant property test.
Background technique:
High molecular material is widely used in all kinds of household chemicals and industrial chemical, since it is with inflammability, increases
Flame enrichment calamity odds has buried serious security risk to the daily life of consumer.Therefore, in job site and residence
It is middle to use the fire proofing for being added to fire retardant, reliable safety guarantee will be provided to people's production and life.Polycarbonate
(PC) be a kind of high comprehensive performance thermoplastic engineering plastic, because excellent in cushion effect, light transmittance is high, and processing dimension is stablized
The advantages that property is good, easy coloring, is widely used in the industries such as electronics, electric appliance, aerospace, machinery.Although the flame retardant property of pure PC
Reach 94V-2 grades of UL, but still is difficult to meet certain application fields, such as television set, computer, automobile component, construction material
Requirement to PC flame retardant property, it is therefore desirable to which the more efficient fire retardant of research carries out PC flame-retardant modified.
Common PC fire retardant has following a few major class: halogen system, phosphorus system, silicon systems, sulfonate system, boron system, phosphorus-nitrogen system and polymerization
Object/inorganic nano combined etc..With the raising of environmental requirement, gesture can not for the trend of halogen-free flame retardants substitution halogenated flame retardant
Gear.Although phosphorus flame retardant is most widely used, but influence the impact strength of material because fire retardant additive amount is big, reduce
The hydrolytic stability and heat distortion temperature of PC；Although silicon-series five-retardant can satisfy fire-retardant, environmentally friendly and transparent requirement, still
Production cost is higher；Although sulfonate flame retardant additive amount is small, hydrolytic stability is poor, in the product long-term fire-retardant steady
It is qualitative poor；Boron flame retardant needs and other types fire retardant compounding can be only achieved required flame-retardancy requirements；Phosphorus-nitrogenated flame retardant
Research have become hot spot, but not yet realize industrialized production and scale application；The resistance of nano combined and other inorganic systems
Combustion agent is affected to the transparency of material.
Currently, the requirement with the progress and people of flame-retarded technology to fire proofing is increasingly harsh, above-described list
One type fire retardant has been unable to meet industry requirement, has relevant expert and scholar to propose the concept of cooperative flame retardant, i.e., will be single
Type fire retardant Composite carries out efficient combination with other fire retardants, makes to include multiple effective ignition-proof elements in a system,
These ignition-proof elements can be cooperateed with mutually, to form a new highly effective flame-retardant system.
Expansion type flame retardant is exactly the example for realizing synergistic effect perfection.Expansion type flame retardant (IFR) is a kind of
It is the composite flame-retardant agent mainly formed containing nitrogen and phosphorus element, it integrates acid source, charcoal source, gas source, foaming and intumescing when because being heated,
Therefore referred to as expansion type flame retardant.Environment friendly flame retardant of the expansion type flame retardant as a kind of high-efficiency low-toxicity, is acknowledged as realizing
Non-halogen one of the effective way of fire retardant, therefore the great application potential in high molecular material flame retardant area.
The Chinese patent of Publication No. CN 102977575A discloses a kind of sulfonate salt flame and preparation method thereof, should
Class sulfonate salt flame two kinds of effective ignition-proof elements containing N, S, using Cyanuric Chloride as raw material, respectively with tarine, to amino
Benzene sulfonic acid and 2,5- disulfonic acid base benzene sulfonic acid, which reacts, is made three kinds of different types of sulfonate salt flames.The invention realize by N,
The purpose of cooperative flame retardant is realized in two kinds of element fusions of S in an intramolecular, and flame retardant molecule structure is simple, and synthetic method is novel,
But the based flame retardant is not applied to flame retarded polymeric material and tests flame retardant effect by the invention.
The Chinese patent of Publication No. CN 104262682B discloses a kind of containing three phosphonitrile of ring and cup [4] aromatic ring structure
Phosphaphenanthrene fire retardant, preparation method and applications, in the fire retardant two kinds of elements of N, P can synergistic it is fire-retardant, can not only be used for reacting
Type fire retardant prepares halogen-free flame-retardant resin, and the halogen-free flame retardants of engineering plastics is used for but also as additive flame retardant.This is fire-retardant
Agent synthetic method is cumbersome, and production cost is higher.
Summary of the invention:
The technical problem to be solved in the invention be tri- kinds of N, P, S effective ignition-proof elements are assembled in single intramolecular, if
Count out synergistic intumescent flame retardant in a kind of novel molecular.
The present invention needs another key technical problem solved to be to provide new expansion type flame retardant preparation method.
The present invention provides a kind of expansion type flame retardants, as shown in Figure 1:
Wherein, R is organic amine or phenol containing sulfonate.
Specific structure is showed in Fig. 1 with molecular formula.
Preferred R is to methoxy benzenesulfonic acid salt.
Preferred R is sulfanilate.
Preferred R is taurate.
Wherein sulfonate is sodium salt or sylvite.
N-P-S expansion type flame retardant of the present invention the preparation method is as follows:
Hexachlorocyclotriph,sphazene is dissolved in acetone (1), organic amine, phenol or alcohol containing sulfonic acid are added dropwise to NaOH (or KOH)
In saturated solution (2), (1) is added dropwise in the latter (2), pH to 9-14 is adjusted with NaOH (or KOH), first reacts at room temperature 2h, so
After be warming up to 60-80 DEG C of reaction 48h.After reaction, it is adjusted to neutrality with dilute hydrochloric acid, cooling and standings, NaCl (or KCl) is big
Amount is precipitated, collected by suction filtrate.Filtrate is risen to 80 DEG C, neutral alumina absorption is added and falls foreign pigment, filtrate is collected by filtration,
Reverse phase precipitating reagent is added, product is precipitated, and decompression filters, and filter cake freeze-day with constant temperature is arrived expansion type flame retardant.
The hexachlorocyclotriph,sphazene described: organic amine, phenol or alcohol containing sulfonic acid: the ratio between amount of substance of NaOH is 1: 6.0
~7.2: 14.4~20；
The amount of acetone used in every mole of hexachlorocyclotriph,sphazene is 1500-2000mL；
Reverse phase precipitating reagent dosage is 5-7 times for reacting final volume；
Pass through in reaction process31P NMR monitors reaction process.
The present invention provides a kind of expansion type flame retardants and preparation method thereof, compared with existing expansion type flame retardant, this hair
The expansion type flame retardant of bright offer connects six effectively fire-retardant sulfonate groups using three phosphonitrile of ring as core simultaneously, combine N,
P, tri- kinds of ignition-proof elements of S, to be remarkably improved flame retarding efficiency.
Detailed description of the invention:
Fig. 1 is the molecular structure of expansion type flame retardant of the present invention；
Fig. 2 is the reaction equation of expansion type flame retardant synthesis in embodiment 1；
Fig. 3 is the reaction equation of expansion type flame retardant synthesis in embodiment 2；
Fig. 4 is the reaction equation of expansion type flame retardant synthesis in embodiment 3；
Fig. 5 is the reaction equation of expansion type flame retardant synthesis in embodiment 4；
Fig. 6 is the reaction equation of expansion type flame retardant synthesis in embodiment 5；
Fig. 7 is the reaction equation of expansion type flame retardant synthesis in embodiment 6.
Specific embodiment:
The following examples are further illustrations of the invention, however, the present invention is not limited to these examples.
Embodiment 1
Prepare the N-P-S expansion type flame retardant with Fig. 2 structure:
41.4g NaOH solid is added in 1000mL round-bottomed flask, 80mL deionized water is added and is made into aqueous solution, Yu Bing
The p-hydroxybenzenyl sulfonate aqueous solution that 138.8g mass fraction is 65% is added dropwise under water bath condition, the disodium of p-hydroxybenzenyl sulfonate is made
Saline solution.25.0g hexachlorocyclotriph,sphazene solid is weighed in the round-bottomed flask of 250mL, 150mL acetone is added and is allowed to completely molten
Solution, which is slowly added dropwise into the disodium saline solution of p-hydroxybenzenyl sulfonate, reacts at room temperature 2h.Reaction system is warming up to 80
DEG C reaction 72h, use31P NMR monitors end of reaction.5mL concentrated hydrochloric acid is diluted in 10mL deionized water, adjusts reaction system with it
PH to 7.0 or so, stands overnight, and a large amount of NaCl white needle-like crystals are precipitated, and depressurizes collected by suction filtrate.Filtrate is warming up to 80
DEG C, 24g neutral alumina is added in three times, adsorbs foreign pigment, filters out aluminium oxide and collects filtrate.Filtrate volume is concentrated into original
1/2 or so come, is added the reverse phase precipitating reagent dehydrated alcohol of 5 times of volumes, product is largely precipitated in the form of white precipitate.Decompression
It filters, is washed with dehydrated alcohol, obtain white filter cake, dried in 80 DEG C of constant temperature ovens to get one kind of the present invention is arrived
N-P-S expansion type flame retardant.
Embodiment 2
Prepare the N-P-S expansion type flame retardant with Fig. 3 structure:
21.3g KOH solid is added in the round-bottomed flask of 100mL, 30mL deionized water is added and is made into aqueous solution, Yu Bing
The aqueous solution for the p-hydroxybenzenyl sulfonate that 50.9g mass fraction is 65% is added dropwise under water bath condition, the two of p-hydroxybenzenyl sulfonate are made
Sylvite aqueous solution.10.0g hexachlorocyclotriph,sphazene solid is weighed in the round-bottomed flask of 50mL, 20mL acetone is added and is allowed to completely molten
Solution, which is slowly added dropwise into the dipotassium saline solution of p-hydroxybenzenyl sulfonate, reacts at room temperature 2h.Then raise temperature to 80 DEG C instead
48h is answered, is used31P NMR detects end of reaction.Dilute 2mL concentrated hydrochloric acid in 5mL deionized water, with its adjust reaction system pH to
7.0 or so, it stands overnight, a large amount of KCl white needle-like crystals are precipitated, and depressurize collected by suction filtrate.Filtrate is warming up to 80 DEG C, divides three
Secondary addition 10g neutral alumina adsorbs foreign pigment, filters out aluminium oxide and collects filtrate.Filtrate volume is concentrated into original 1/2
Left and right, is added the reverse phase precipitating reagent dehydrated alcohol of 5 times of volumes, product is largely precipitated in the form of white precipitate.Decompression filters, and uses
Dehydrated alcohol washing, obtains white filter cake, is dried in 80 DEG C of constant temperature ovens to get swollen to a kind of N-P-S of the present invention
Swollen type fire retardant.
Embodiment 3
Prepare the N-P-S expansion type flame retardant with Fig. 4 structure:
7.2g triethylamine, 10.4g p-aminobenzene sulfonic acid are added in the round-bottomed flask of 100mL, 150mL deionized water is added
It is made into aqueous solution；3.5g hexachlorocyclotriph,sphazene is dissolved in 10mL THF, and is instilled in the former aqueous solution.It then raises temperature to
75 DEG C of reaction 12h are used31P NMR monitors end of reaction.It is cooled to room temperature, vacuum filtration falls inorganic salts, collects filtrate, obtains
To sulfonic acid product.2.9g NaOH solid is added in the product while stirring to get a kind of N-P-S expansion of the present invention is arrived
Type fire retardant.
Embodiment 4
Prepare the N-P-S expansion type flame retardant with Fig. 5 structure:
7.2g triethylamine, 10.4g p-aminobenzene sulfonic acid are added in the round-bottomed flask of 100mL, 150mL deionized water is added
It is made into aqueous solution；3.5g hexachlorocyclotriph,sphazene is dissolved in 10mL THF, and is instilled in the former aqueous solution.It then raises temperature to
75 DEG C of reaction 12h are used31P NMR detects end of reaction.It is cooled to room temperature, vacuum filtration falls inorganic salts and collects filtrate, obtains
Sulfonic acid product.4.0g KOH solid is added in the product while stirring to get a kind of N-P-S intumescent resistance of the present invention is arrived
Fire agent.
Embodiment 5
Prepare the N-P-S expansion type flame retardant with Fig. 6 structure:
7.2g triethylamine, 9.0g tarine are added in the round-bottomed flask of 100mL, 150mL deionized water is added and matches
At aqueous solution；3.5g hexachlorocyclotriph,sphazene is dissolved in 10mL THF, and is instilled in the former aqueous solution.Then raise temperature to 75
DEG C reaction 12h, use31P NMR monitors end of reaction.It is cooled to room temperature, vacuum filtration falls inorganic salts, collects filtrate, obtains
Sulfonic acid product.2.9g NaOH solid is added in the product while stirring to get a kind of N-P-S intumescent of the present invention is arrived
Fire retardant.
Embodiment 6
Prepare the N-P-S expansion type flame retardant with Fig. 7 structure:
7.2g triethylamine, 9.0g tarine are added in the round-bottomed flask of 100mL, 150mL deionized water is added and matches
At aqueous solution；3.5g hexachlorocyclotriph,sphazene is dissolved in 10mL THF, and is instilled in the former aqueous solution.Then raise temperature to 75
DEG C reaction 12h, use31P NMR monitors end of reaction.It is cooled to room temperature, vacuum filtration falls inorganic salts, collects filtrate, obtains
Sulfonic acid product.4.0g KOH solid is added in the product while stirring to get a kind of N-P-S intumescent of the present invention is arrived
Fire retardant.
Claims (5)
1. compound shown in novel N-P-S expansion type phosphor flame retardant formula 1.
2. the preparation method of novel N-P-S expansion type phosphor flame retardant, it is characterised in that according to the following steps:
1) first the substances such as the organic amine containing sulfonic acid or phenol are added dropwise in aqueous slkali, hexachlorocyclotriph,sphazene are dissolved in solvent,
And be added dropwise in the aqueous solution of sulfonate, it is down to room temperature after back flow reaction 48h, pH is adjusted to neutrality with dilute hydrochloric acid, stands
Inorganic salts are precipitated largely overnight；2) inorganic salts are filtered out, neutral alumina absorption is added in filtrate and falls foreign pigment, filtering is received
Collect filtrate；3) reverse phase precipitating reagent is added in filtrate, product is precipitated, decompression filters, and filter cake freeze-day with constant temperature is hindered to get to intumescent
Fire agent.
3. the novel N-P-S expansion type flame retardant preparation method described according to claim 2, it is characterised in that step (1) six
Three phosphonitrile of chlorine ring: organic amine, phenol or alcohol containing sulfonic acid: the ratio between amount of substance of NaOH is 1: 6.0~7.2: 14.4~20.
4. the novel N-P-S expansion type flame retardant preparation method described according to claim 2, it is characterised in that step (2) six
Three phosphonitrile solvent for use of chlorine ring is acetone.
5. the novel N-P-S expansion type flame retardant preparation method described according to claim 2, it is characterised in that step (3) is anti-
Phase precipitating reagent is dehydrated alcohol, and dosage is 5-7 times for reacting final volume.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483796A (en) * | 2019-08-26 | 2019-11-22 | 北京理工大学 | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof |
| CN113969037A (en) * | 2021-12-01 | 2022-01-25 | 湖南省新基源新材料科技有限公司 | Flame-retardant ABS material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483796A (en) * | 2019-08-26 | 2019-11-22 | 北京理工大学 | ZIF-67 adulterates six p-hydroxy benzenyl sulfonate sodium rings, three phosphonitrile fire retardant and preparation method thereof |
| CN113969037A (en) * | 2021-12-01 | 2022-01-25 | 湖南省新基源新材料科技有限公司 | Flame-retardant ABS material and preparation method thereof |
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Application publication date: 20190524 |