CN105669762B - A kind of preparation method of expansion type flame retardant - Google Patents
A kind of preparation method of expansion type flame retardant Download PDFInfo
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- CN105669762B CN105669762B CN201510982370.4A CN201510982370A CN105669762B CN 105669762 B CN105669762 B CN 105669762B CN 201510982370 A CN201510982370 A CN 201510982370A CN 105669762 B CN105669762 B CN 105669762B
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Abstract
The present invention relates to technical field of flame retardant agent preparation, refering in particular to a kind of phenolic containing steric hindrance has the preparation method of expansion type flame retardant of antioxygen function.The intermediate that nucleophilic substitution obtains target product is carried out using six chlorine atoms on o-allyl phenol and hexachlorocyclotriph,sphazene, using resulting midbody product and 2,6 DI-tert-butylphenol compounds form a kind of expansion type flame retardant containing steric hindrance phenolic with antioxygen function under catalyst action.There is prepared phenolic containing steric hindrance the fire retardant of antioxygen function to have taken into account the induction period of polymer combustion and the developing stage of burning, greatly improve the flame retarding efficiency of polymer, simultaneously, [the γ (3 of fire retardant six involved in the present invention, the hydroxyphenyl of 5 di-t-butyl 4) phenylpropyl] three phosphonitrile preparation technologies of ring are simple, easily operated and environment friendly and pollution-free, and industrialized production can be used on a large scale.
Description
Technical field
The present invention relates to technical field of flame retardant agent preparation, the intumescent that refering in particular to a kind of phenolic containing steric hindrance has antioxygen function hinders
Fire the preparation method of agent.
Background technology
In the induction period of polymer combustion, along with chemical bond and the cleavage reaction of strand.For antioxidant, its
Effect is mainly reflected in termination free chain reaction, that is, prevents or suppress chain initiation reaction and chain propagation reaction, promote chain whole
Only react；Main in plastic applications to make chain terminating agent using phenolic compound, its effect is：Capture is centered on oxygen atom
Free radical, such as ROO, HO and RO, the latter because activity it is very high, under excess oxygen quickly with O2Role transformation into
ROO, the active H atom that Hinered phenols antioxidant is provided can catch these free radicals, then cause with their combinations such
Free radical loses original activity, and then realizes chain termination, therefore, and the main function of hindered phenolic antioxidant is to fire in polymer
Burning terminates in induction period, so as to delay or postpone the early stage of polymer combustion.
Phosphazene compound is to replace the class inorganic compound that double bond is arranged as backbone structure with P, N, with ring-type or linear
Structure is present, and it is this product that phenoxy group is accessed on the phosphorus atom, and the introducing of phenoxy group makes phosphazene compound turn into inorganic compound
The product being combined with organic compound, is a kind of environment-friendly fire retardant of good Halogen；Phosphazene compound it is fire-retardant
Mechanism shows as the comprehensive function of four kinds of approach, and heat absorption is coolant mechanism when phosphonitrile is thermally decomposed；Its phosphoric acid thermally decomposed to generate,
Metaphosphoric acid and polyphosphoric acid, can form one layer of fixedness diaphragm on the surface of polymeric material, completely cut off air, and this is isolation
Film mechanism；The gases such as carbon dioxide, ammonia, nitrogen, water vapour are released after simultaneously heated, this is diluents mechanism；These do not burn
The gas occluding supply of oxygen, realize the purpose of fire-resistant synergistic and collaboration, and there are the PO groups to be formed during polymer combustion,
It can be combined with H, OH active group in flame region, play a part of suppressing flame, and this is to terminate chain mechanism.
Acted synergistically due to more than, system shows good fire resistance；Phosphazene flame retardant as environmentally friendly, efficient phosphorus-
Nitrogen combustion inhibitor product developed rapidly in the last few years, the existing relatively broad application in the polymeric material of it and it derivative,
It is fire-retardant that patent CN102603800A, CN101985455A and CN102250147A etc. individually disclose aldehyde radical phenoxy cyclotriphosphazene
The preparation method of agent, hexaphenoxy cyclotriphosphazene fire retardant and the siliceous phosphonitrile fire retardant of functional group's ring three.
The content of the invention
It is an object of the invention to prepare a kind of phenolic containing steric hindrance to have the expansion type flame retardant of antioxygen function, system middle position
Resistance phenolic group group can effectively catch the living radical of polymer combustion generation at initial stage, delay or postpone the induction rank of polymer combustion
Section.In addition, the sterically hindered phenol in the prepared fire retardant of the present invention has preferable synergy with nitrogen phosphorus, polymer combustion can be promoted
During CO2、NH3Deng the release of inert gas, the concentration of fuel gas is diluted, the feedback of heat is effectively reduced, separately
Outside, sterically hindered phenol group condensed phase serve barrier cooling, catalytic esterification into charcoal, consolidate the effect of layer of charcoal, effectively increase biography
The flame retarding efficiency of system Intumescent Retardant System.
Present disclosure is：The phosphonitrile fire retardant of six [γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] ring three, with
Structure centered on its phosphonitrile of ring three, its molecular formula is as shown below, using six on o-allyl phenol and hexachlorocyclotriph,sphazene
Individual chlorine atom carries out the intermediate that nucleophilic substitution obtains target product, utilizes the resulting uncle of midbody product and 2,6- bis-
Butylphenol formed under catalyst action it is a kind of containing steric hindrance phenolic have antioxygen function expansion type flame retardant six [γ-(3,
5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] three phosphonitrile of ring, its structural formula such as Fig. 3.
A kind of phenolic containing steric hindrance has the preparation method of the expansion type flame retardant of antioxygen function, it is characterised in that according to following
Step is carried out：O-allyl phenol, acid binding agent and organic solvent A are sequentially added, stirring dissolves it under inert gas shielding,
First set reaction a few hours under certain temperature；Appropriate hexachlorocyclotriph,sphazene is weighed afterwards to be dissolved in same organic solvent A,
Be slowly dropped in above-mentioned reacted mixed system, second reaction a few hours after completion of dropping, by reaction solution suction filtration,
It is adjacent that concentration, washing, filtering, recrystallization are for several times, drying and other steps obtain the expansion type flame retardant intermediate six with antioxygen function
The phosphonitrile of allyl benzene basic ring three；Weigh appropriate 2,6- DI-tert-butylphenol compounds to melt into reaction bulb, and at a certain temperature, so
Proper catalyst is dissolved in organic solvent B under inert gas shielding afterwards, the catalyst after dissolving is added drop-wise to reaction bulb
In, the prepared phosphonitrile of six o-allyl basic ring of intermediate three is then weighed, and be dissolved in above-mentioned identical organic solvent B
In, be added drop-wise in above-mentioned reaction system, after completion of dropping at a certain temperature third time reaction a few hours, by reaction solution suction filtration,
Concentration, washing, filtering, recrystallize for several times, drying and other steps obtain the [γ-(the tertiary fourths of 3,5- bis- of fire retardant six with antioxygen function
Base -4- hydroxyphenyls) phenylpropyl] three phosphonitrile of ring.
Wherein described hexachlorocyclotriph,sphazene and the mol ratio of o-allyl phenol are 1:6~8；Hexachlorocyclotriph,sphazene is with tiing up
The mol ratio of sour agent is 1:8~10；Described acid binding agent is one kind in potassium carbonate, sodium hydroxide, sodium carbonate；Described is organic
Solvent orange 2 A is one kind in tetrahydrofuran, acetonitrile, pyridine, dimethylbenzene；The mass volume ratio of hexachlorocyclotriph,sphazene and organic solvent A
For 1g:The gross mass of 2~5ml, o-allyl phenol and acid binding agent and the mass volume ratio of organic solvent A are 1g:8~15ml；
Described inert gas is one kind in nitrogen, argon gas, helium；The temperature of the first set reaction is normal temperature, reacts 2h, second
The temperature of secondary response is 60~75 DEG C, and the time of the second secondary response is 24~36h.
The wherein described phosphonitrile of six o-allyl basic ring of intermediate three is 1 with 2,6 di t butyl phenol mol ratio:6~
8,2,6- DI-tert-butylphenol compounds are 1 with catalyst molar ratio:0.01~0.05；The melting temperature is 70 DEG C, described catalysis
Agent is one kind in sodium tert-butoxide, potassium tert-butoxide, tert-butyl alcohol lithium；Described organic solvent B is the tert-butyl alcohol, tetrahydrofuran, toluene
In one or more, the mass volume ratio of the phosphonitrile of six o-allyl basic ring three and organic solvent B is 0.1g:5~10ml, 2,
The mass volume ratio of the gross mass and organic solvent B of 6- DI-tert-butylphenol compounds and catalyst is 0.1g:10~20ml；Described is lazy
Property gas be nitrogen, argon gas, helium in one kind；The temperature of third time reaction is 90~110 DEG C, third time reaction when
Between be 6~8h.
A kind of phenolic containing steric hindrance has the phosphonitrile of six o-allyl basic ring of expansion type flame retardant intermediate three of antioxygen function,
Its structural formula such as Fig. 4.
Beneficial effect：
In the initial stage of polymer combustion, i.e. induction period, along with chemical bond and molecule chain break, this fracture
It is to increase fire retardant prepared in realization, the present invention with chain by the generation of free radical to contain substantial amounts of obstruction phenol structure,
It can provide the hydrogen with certain activity, can capture the free radical centered on oxygen atom, such as ROO, HO and RO；And
Due to big steric hindrance structure, so losing the active relatively low of the new free radical formed after hydrogen, it is not enough to trigger new macromolecular
Chain causes chain to increase, but can with the free radical coupling in system and realize chain termination, so as to reduce the thermal decomposition of polymer, drop
The concentration of low fuel gas, postpones the burning time of polymeric material and raises ignition temperature, therefore, containing prepared by the present invention
The expansion type flame retardant that steric hindrance phenolic has antioxygen function can delay or postpone the induction period of polymer combustion；Involved phosphorus
Nitrile fire retardant contains nitrogen P elements simultaneously, and nitrogen provides source of the gas for system during polymer combustion, can effectively dilute
Polymer produced imflammable gas in combustion；P elements form phosphoric acid in thermal histories, can serve as fire retardant
Acid source；Polymer forms the layer of charcoal of densification, the effectively thermal source and oxygen outside isolation during burning under phosphatizing
Gas, so as to reach preferable flame retardant effect, itself just has higher heat endurance and fire resistance with regard to fire retardant；Institute
There is the phenolic containing steric hindrance prepared the fire retardant of antioxygen function to have taken into account the induction period of polymer combustion and the development rank of burning
Section, greatly improves the flame retarding efficiency of polymer, meanwhile, [the γ-(3,5- di-t-butyl -4- hydroxyls of fire retardant six involved in the present invention
Phenyl) phenylpropyl] three phosphonitrile preparation technologies of ring are simple, easily operated and environment friendly and pollution-free, and industrial metaplasia can be used on a large scale
Production.
Brief description of the drawings
Fig. 1 is the FTIR spectrograms of raw material and product；(a) o-allyl phenol；(b) the o-allyl basic ring three of intermediate six
Phosphonitrile；(c) phosphonitrile of six [γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] ring three.
Fig. 2 is the partial enlargement FTIR spectrograms of raw material and product；(a) o-allyl phenol；(b) the adjacent pi-allyl of intermediate six
The phosphonitrile of benzyl ring three；(c) phosphonitrile of six [γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] ring three.
Fig. 3 is the phosphorus of expansion type flame retardant six of the present invention [γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] ring three
The structural formula of nitrile.
Fig. 4 is the structural formula of the phosphonitrile of six o-allyl basic ring of expansion type flame retardant intermediate three.
Embodiment
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Acid binding agent of the present invention is specially potassium carbonate.
Organic solvent specially tetrahydrofuran described in when the present invention prepares intermediate.
Catalyst of the present invention is potassium tert-butoxide.
Catalyst-solvent organic solvent of the present invention is the tert-butyl alcohol.
Inertia protection gas of the present invention is nitrogen.
Embodiment 1：
In with agitator, thermometer, the three-necked flask of reflux condenser, sequentially add 40.3g o-allyl phenols,
Acid binding agent potassium carbonate 55.4g, and be dissolved under nitrogen protection in 765ml tetrahydrofurans, stirring and dissolving reacts 2h at normal temperatures,
Then weigh 17.4g hexachlorocyclotriph,sphazenes to be dissolved in 35ml tetrahydrofurans, at normal temperatures using constant pressure funnel by the phosphorus of chlordene ring three
Nitrile is slowly dropped in above-mentioned reaction system, after time for adding is 1h, completion of dropping, and system temperature is increased into 65 DEG C, and
React 30h at this temperature, finally by reaction solution suction filtration, concentration, washing, filtering, recrystallize for several times, drying and other steps, obtain light
The phosphonitrile of six o-allyl basic ring of yellow liquid intermediate three.
67g 2 is added in agitator, thermometer, the three-necked flask of reflux condenser, 6- DI-tert-butylphenol compounds lead to
Enter nitrogen and drain air, system is melted at 70 DEG C, after treating that 2,6- DI-tert-butylphenol compounds solids are completely melt, use the tertiary fourths of 36ml
0.36g catalyst potassium tert-butoxide is completely dissolved by alcohol under nitrogen protection, is poured into constant pressure funnel and is slowly dropped into three-necked flask,
30min is added dropwise；Then the phosphonitrile of six o-allyl basic ring of 50g intermediates three is dissolved in the tert-butyl alcohol, instilled in three-necked flask,
Time for adding is that temperature of reaction system is increased into 110 DEG C after 1h, completion of dropping, reacts 6h；To reaction solution suction filtration, concentrate, wash
Wash, filter, recrystallize for several times, drying and other steps, obtain [the γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl alcohol of white powder six
Base] three phosphonitrile of ring.
It is the fire retardant prepared by 2%wt to weigh mass fraction (using polypropylene as standard), and fire retardant leads to matrix resin
The mode for crossing banburying blending forms flame-proof composite material, shaping, cuts out sample, with reference to GB/T2046.2-2009 standards, uses oxygen index (OI)
Instrument is tested the combustibility of material, and it is 27.9% to measure limited oxygen index, is carried on the basis of virgin pp oxygen index (OI)
Nearly 10 units are risen, its flame retardant effect is obviously improved.
According to Fig. 1 as can be seen that positioned at 3450cm in Fig. 1 (a)-1Place's phenolic hydroxyl group characteristic peak is wholly absent in Fig. 1 (b),
Because with the high activity P-Cl keys on hexachlorocyclotriph,sphazene nucleophilic substitution occurs for-the OH on o-allyl phenol；Phase
Than being located at 962cm in Fig. 2 (a), Fig. 2 (b)-1There is a new characteristic peak in place, and the peak belongs to P-O-C characteristic peak, said
Bright o-allyl phenol is successfully connected in hexachlorocyclotriph,sphazene structure, therefore successfully synthesizes flame retardant intermediate, in addition, Fig. 2
(a) with 1639cm in Fig. 2 (b)-1The characteristic absorption peak of place's end alkene is still had, and such as Fig. 1 (c) is understood, in 3637cm-1Place goes out
The characteristic peak of existing phenolic hydroxyl group, in addition, positioned at 1639cm-1The end alkene characteristic peak at place disappears, and can illustrate more than, 2,6- bis- uncles
Butylphenol is successfully grafted on intermediate structure, and target product is successfully synthesized.
Embodiment 2：
In with agitator, thermometer, the three-necked flask of reflux condenser, sequentially add 53.7g o-allyl phenols,
Acid binding agent potassium carbonate 69g, and be dissolved under nitrogen protection in 980ml tetrahydrofurans, stirring and dissolving, 2h is reacted at normal temperatures, so
After weigh 17.4g hexachlorocyclotriph,sphazenes and be dissolved in 35ml tetrahydrofurans, at normal temperatures using constant pressure funnel by hexachlorocyclotriph,sphazene
It is slowly dropped in above-mentioned reaction system, time for adding is that system temperature is increased into 60 DEG C after 1h, completion of dropping, and in the temperature
The lower reaction 36h of degree, finally by reaction solution suction filtration, concentration, washing, filtering, recrystallization for several times, drying and other steps, obtain faint yellow
The phosphonitrile of six o-allyl basic ring of liquid intermediate three.
90g 2 is added in agitator, thermometer, the three-necked flask of reflux condenser, 6- DI-tert-butylphenol compounds lead to
Enter nitrogen and drain air, system is melted at 70 DEG C, after treating that 2,6- DI-tert-butylphenol compounds solids are completely melt, use the tertiary fourths of 50ml
0.49g catalyst potassium tert-butoxide is completely dissolved by alcohol under nitrogen protection, is poured into constant pressure funnel and is slowly dropped into three-necked flask,
30min is added dropwise；Then the phosphonitrile of six o-allyl basic ring of 50g intermediates three is dissolved in the tert-butyl alcohol, instilled in three-necked flask,
Time for adding is that temperature of reaction system is increased into 90 DEG C after 1h, completion of dropping, reacts 8h；To reaction solution suction filtration, concentrate, wash
Wash, filter, recrystallize for several times, drying and other steps, obtain [the γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl alcohol of white powder six
Base] three phosphonitrile of ring.
It is the fire retardant prepared by 2%wt to weigh mass fraction (using polypropylene as standard), and fire retardant leads to matrix resin
The mode for crossing banburying blending forms flame-proof composite material, shaping, cuts out sample, with reference to GB/T2046.2-2009 standards, uses oxygen index (OI)
Instrument is tested the combustibility of material, and it is 28.5% to measure limited oxygen index, is carried on the basis of virgin pp oxygen index (OI)
10.5 units are risen.
Embodiment 3：
In with agitator, thermometer, the three-necked flask of reflux condenser, sequentially add 40.3g o-allyl phenols,
Acid binding agent potassium carbonate 55.4g, and be dissolved under nitrogen protection in 765ml tetrahydrofurans, stirring and dissolving reacts 2h at normal temperatures,
Then weigh 17.4g hexachlorocyclotriph,sphazenes to be dissolved in 35ml tetrahydrofurans, at normal temperatures using constant pressure funnel by the phosphorus of chlordene ring three
Nitrile is slowly dropped in above-mentioned reaction system, and time for adding is that system temperature is increased into 75 DEG C after 1h, completion of dropping, and at this
At a temperature of react 24h, finally by reaction solution suction filtration, concentration, washing, filtering, recrystallize for several times, drying and other steps, obtain yellowish
The phosphonitrile of six o-allyl basic ring of color liquid intermediate three.
90g 2 is added in agitator, thermometer, the three-necked flask of reflux condenser, 6- DI-tert-butylphenol compounds lead to
Enter nitrogen and drain air, system is melted at 70 DEG C, after treating that 2,6- DI-tert-butylphenol compounds solids are completely melt, use the tertiary fourths of 50ml
0.49g catalyst potassium tert-butoxide is completely dissolved by alcohol under nitrogen protection, is poured into constant pressure funnel and is slowly dropped into three-necked flask,
30min is added dropwise；Then the phosphonitrile of six o-allyl basic ring of 50g intermediates three is dissolved in the tert-butyl alcohol, instilled in three-necked flask,
Time for adding is that temperature of reaction system is increased into 100 DEG C after 1h, completion of dropping, reacts 7h；To reaction solution suction filtration, concentrate, wash
Wash, filter, recrystallize for several times, drying and other steps, obtain [the γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl alcohol of white powder six
Base] three phosphonitrile of ring.
It is the fire retardant prepared by 2%wt to weigh mass fraction (using polypropylene as standard), and fire retardant leads to matrix resin
The mode for crossing banburying blending forms flame-proof composite material, shaping, cuts out sample, with reference to GB/T2046.2-2009 standards, uses oxygen index (OI)
Instrument is tested the combustibility of material, and it is 26.2% to measure limited oxygen index, is carried on the basis of virgin pp oxygen index (OI)
8.2 units are risen.
Embodiment 4：
In with agitator, thermometer, the three-necked flask of reflux condenser, sequentially add 53.7g o-allyl phenols,
Acid binding agent potassium carbonate 69g, and be dissolved under nitrogen protection in 980ml tetrahydrofurans, stirring and dissolving, 2h is reacted at normal temperatures, so
After weigh 17.4g hexachlorocyclotriph,sphazenes and be dissolved in 87ml tetrahydrofurans, at normal temperatures using constant pressure funnel by hexachlorocyclotriph,sphazene
It is slowly dropped in above-mentioned reaction system, time for adding is that system temperature is increased into 65 DEG C after 1h, completion of dropping, and in the temperature
The lower reaction 36h of degree, finally by reaction solution suction filtration, concentration, washing, filtering, recrystallization for several times, drying and other steps, obtain faint yellow
The phosphonitrile of six o-allyl basic ring of liquid intermediate three.
67g 2 is added in agitator, thermometer, the three-necked flask of reflux condenser, 6- DI-tert-butylphenol compounds lead to
Enter nitrogen and drain air, system is melted at 70 DEG C, after treating that 2,6- DI-tert-butylphenol compounds solids are completely melt, use the tertiary fourths of 35ml
0.36g catalyst potassium tert-butoxide is completely dissolved by alcohol under nitrogen protection, is poured into constant pressure funnel and is slowly dropped into three-necked flask,
30min is added dropwise；Then the phosphonitrile of six o-allyl basic ring of 65g intermediates three is dissolved in the tert-butyl alcohol, instilled in three-necked flask,
Time for adding is that system temperature is increased into 110 DEG C after 1h, completion of dropping, reacts 8h；To reaction solution suction filtration, concentration, washing, mistake
Filter, recrystallize for several times, drying and other steps, obtain white powder six [γ-(3,5- di-t-butyl -4- hydroxyphenyls) phenylpropyl] ring three
Phosphonitrile.
It is the fire retardant prepared by 2%wt to weigh mass fraction (using polypropylene as standard), and fire retardant leads to matrix resin
The mode for crossing banburying blending forms flame-proof composite material, shaping, cuts out sample, with reference to GB/T2046.2-2009 standards, uses oxygen index (OI)
Instrument is tested the combustibility of material, and it is 27.6% to measure limited oxygen index, is carried on the basis of virgin pp oxygen index (OI)
Nearly 9 units are risen.
Comparative example 5 is implemented with reference to Chinese patent CN102250147 B：
14.60g aminopropyl triethoxysilanes and 8.11g triethylamines are added in 20ml tetrahydrofuran solvents, stirred
Uniformly, argon gas is passed through, 60 DEG C are slowly heated to；3.48g hexachlorocyclotriph,sphazenes are dissolved in 10ml tetrahydrofuran solvents, magnetic force is stirred
Mixing makes it fully dissolve, and is then added dropwise in the solution in step 1, increasingly generates white precipitate, 30min is added dropwise, anti-at 67 DEG C
Answer 10h；Post-processed, product is blended into PP and is prepared into standard batten, material is carried out with reference to GB/T2046.2-2009 standards
The combustibility test of material, it is 21.5% to measure limited oxygen index.
Comparative example 6 is implemented with reference to Chinese patent CN102250147 B：
15.49g aminopropyl triethoxysilanes and 7.28g triethylamines are added in 20ml tetrahydrofuran solvents, stirred
Uniformly, argon gas is passed through, 60 DEG C are slowly heated to；3.47g hexachlorocyclotriph,sphazenes are dissolved in 10ml tetrahydrofuran solvents, magnetic force is stirred
Mixing makes it fully dissolve, and is then added dropwise in the solution in step 1, increasingly generates white precipitate, 30min is added dropwise, anti-at 67 DEG C
Answer 10h；Post-processed, product is blended into PP and is prepared into standard batten, material is carried out with reference to GB/T2046.2-2009 standards
The combustibility test of material, it is 23.9% to measure limited oxygen index.
Analyzed by the limited oxygen index of above example and comparative example, in the application of the fire retardant of same phosphazene backbone
In, phenolic containing steric hindrance prepared by this patent has in the unimolecular fire retardant of antioxygen function, sterically hindered phenol group collaboration phosphonitrile bone
Frame, cooperative flame retardant effect is played in the gas phase and condensed phase of base material, and its flame retardant effect is higher than the fire-retardant of traditional phosphazene flame retardant
Effect, therefore, the fire retardant prepared by this patent are applied in polypropylene matrix have higher limited oxygen index.
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 5 | Comparative example 6 |
| LOI/% | 27.9 | 28.5 | 26.2 | 27.6 | 21.5 | 23.9 |
Claims (6)
1. a kind of expansion type flame retardant, it is characterised in that：The expansion type flame retardant is six [γ-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propyl benzene epoxide] three phosphonitrile of ring, its structural formula is as follows,
2. a kind of preparation method of expansion type flame retardant as claimed in claim 1, it is characterised in that：Using o-allyl phenol
Nucleophilic substitution is carried out with six chlorine atoms on hexachlorocyclotriph,sphazene and obtains the intermediate of target product, using resulting
Midbody product and 2,6 di t butyl phenol are formed under catalyst action a kind of has antioxygen function containing steric hindrance phenolic
Expansion type flame retardant；Catalyst used is potassium tert-butoxide.
3. a kind of preparation method of expansion type flame retardant as claimed in claim 2, it is characterised in that：The molecule of the intermediate
Formula is as follows：
4. a kind of preparation method of expansion type flame retardant as claimed in claim 2, it is characterised in that carry out as steps described below：
O-allyl phenol, acid binding agent and organic solvent A are sequentially added, stirring dissolves it under inert gas shielding, certain temperature
Lower first set reaction a few hours；Appropriate hexachlorocyclotriph,sphazene is weighed afterwards to be dissolved in same organic solvent A, its is slow
It is added drop-wise in above-mentioned reacted mixed system, second reaction a few hours after completion of dropping, by reaction solution suction filtration, concentrates, washes
Wash, filter, recrystallize for several times, drying steps obtain the o-allyl base of expansion type flame retardant intermediate six with antioxygen function
The phosphonitrile of ring three；Weigh appropriate 2,6- DI-tert-butylphenol compounds to melt into reaction bulb, and at a certain temperature, then will urge in right amount
Agent is dissolved in organic solvent B under inert gas shielding, and the catalyst after dissolving is added drop-wise in reaction bulb, then weighed
The prepared phosphonitrile of six o-allyl basic ring of intermediate three, and be dissolved in above-mentioned identical organic solvent B, it is added drop-wise to above-mentioned
In reaction system, third time reacts a few hours at a certain temperature after completion of dropping, by reaction solution suction filtration, concentration, washing, mistake
Filter, recrystallize for several times, drying steps obtain the [γ-(3,5- di-t-butyl -4- hydroxyphenyls) benzene of fire retardant six with antioxygen function
Propyl group] three phosphonitrile of ring.
5. a kind of preparation method of expansion type flame retardant as claimed in claim 4, it is characterised in that：The described phosphorus of chlordene ring three
The mol ratio of nitrile and o-allyl phenol is 1:6~8；The mol ratio of hexachlorocyclotriph,sphazene and acid binding agent is 1:8~10；Described
Acid binding agent is one kind in potassium carbonate, sodium hydroxide, sodium carbonate；Described organic solvent A is tetrahydrofuran, acetonitrile, pyridine, two
One kind in toluene；Hexachlorocyclotriph,sphazene and the mass volume ratio of organic solvent A are 1g:2~5ml, o-allyl phenol and is tied up
The gross mass of sour agent and the mass volume ratio of organic solvent A are 1g:8~15ml；Described inert gas is nitrogen, argon gas, helium
One kind in gas；The temperature of the first set reaction is normal temperature, reacts 2h, the temperature of the second secondary response is 60~75 DEG C, second
The time of secondary response is 24~36h.
6. a kind of preparation method of expansion type flame retardant as claimed in claim 4, it is characterised in that：Described intermediate six is adjacent
The phosphonitrile of allyl benzene basic ring three is 1 with 2,6 di t butyl phenol mol ratio:6~8,2,6- DI-tert-butylphenol compounds rub with catalyst
You are than being 1:0.01~0.05；The melting temperature is 70 DEG C, and described catalyst is sodium tert-butoxide, potassium tert-butoxide, the tert-butyl alcohol
One kind in lithium；Described organic solvent B is the one or more in the tert-butyl alcohol, tetrahydrofuran, toluene, six o-allyl bases
The phosphonitrile of ring three and the mass volume ratio of organic solvent B are 0.1g:5~10ml, 2,6 di t butyl phenol and catalyst total matter
The mass volume ratio of amount and organic solvent B is 0.1g:10~20ml；Described inert gas is one in nitrogen, argon gas, helium
Kind；The temperature of the third time reaction is 90~110 DEG C, and the time of third time reaction is 6~8h.
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