CN110157041A - It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application - Google Patents
It is a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application Download PDFInfo
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/5399—Phosphorus bound to nitrogen
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a kind of containing double DOPO bases and the reactive flame retardant of nitrogen and its preparation method and application.It is described to utilize the synthetic method being simple and efficient containing the reactive flame retardant of double DOPO bases and nitrogen, it can be prepared in high yield by two-step reaction, it is reacted using the reactive group on its molecule with epoxy resin, effectively improve the flame retardant property of epoxy resin, and mechanical property also improves, after i.e. using reactive flame retardant of the present invention to epoxy resin modification, the flame retardant effect of epoxy resin, mechanical strength is improved simultaneously, and the fire retarding effect cooperateed with by phosphorus nitrogen, under very low flame retardant agent content, the flame retardant property of gained modified epoxy can be greatly improved, pass through limit oxygen index and UL-94 vertical burn test its anti-flammability, V-0 grades can be reached, limit oxygen index (LOI) reaches 30.9.Reactive flame retardant preparation method provided by the invention containing double DOPO bases and nitrogen is simple, and raw material is cheap and easy to get, is that one kind is expected to industrialized reactive flame retardant.
Description
Technical field
The invention belongs to fire proofing technical field, especially a kind of phosphorous response type macromolecular fire retardant and its preparation and
Using.
Background technique
Since epoxy resin in 1936 is by invention because have good physics, chemical property and traffic transport
Defeated, infrastructure construction, ship and ocean, nearly all field such as aerospace are widely used.But due to general type ring
The inflammable feature of oxygen resin is not available in some specific occasions, or in daily life, once anti-calamity of lighting a fire, to people
Life and safety belt threaten.As epoxy resin industry gradually refines, functionalization, and the environmental consciousness of people by
Cumulative strong, halogen flame a part is gradually prohibited from using, therefore developing new efficient halogen-free anti-inflaming agent is current scientist
The hot spot studied.
Fire Retardant of The Expoxy Resin is varied at present, is divided into phosphorus system according to fire-retardant element difference, nitrogen system, silicon systems and two kinds
Or the synergistic fire retardant of a variety of fire retardant collaborations.It is divided into addition type and response type according to the addition manner of fire retardant.Although phosphorus system
Fire retardant is more more environmentally friendly than halogen flame to a certain extent, but does not still meet the requirement of Green Chemistry, addition type
Fire retardant can migrate in the substrate, be precipitated, in contrast, the flame retardant effect of the macromolecular fire retardant of response type more accommodates
Long, and while improving the fire retardancy of epoxy resin, the mechanical performance of epoxy resin is maintained or even increased.(the Xie such as Xie
C,Zeng B,Gao H,et al.Improving thermal and flame-retardant properties of
epoxy resins by a novel reactive phosphorous-containing curing agent[J]
.Polymer Engineering&Science, 2014,54 (5): 1192-1200.) synthesize a kind of containing for single reaction functional group
Phosphorus monomer DOPO-PHM, then the fire retardant of different proportion is reacted with epoxy resin (E-51), obtains the epoxy of different phosphorus contents
Resin.When phosphorus content reaches 1.7%, limit oxygen index (LOI) is 33.5%.
DOPO chemical name is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and DOPO and its derivative can be made
It is the fire retardant Halogen of synthesis, smokeless, nontoxic for response type and additive flame retardant, it does not migrate, flame retardant property is lasting.It can be used for
A variety of high molecular material flame retardant treatments such as linear polyester, polyamide, epoxy resin, polyurethane.Foreign countries are widely used in electronics and set
The materials such as pressurized layer, circuit board is fire-retardant in spare plastics, brass.Hydroxyl, phenolic hydroxyl group, carboxyl, ammonia are introduced in DOPO derivative
Base etc. can promote the ring-opening polymerisation of epoxy bond, by Molecular Design, available different functional groups, and thermal stability, just
Property and solidification temperature require different curing agent and fire retardant containing DOPO, and the mutual collaboration of multiple element can be improved resistance
Fuel efficiency rate, thus reduction fire retardant addition as far as possible.Benzoxazine is a kind of novel hot setting resin, contains N and O six in structure
The compound of first oxazines ring is referred to as, and does not have that small molecule release, cure shrinkage is almost nil, modulus is high, strong in solidification process
Spend it is big, heat-resisting it is good, water absorption rate is low.Simultaneously benzoxazine monomer also have flexible design (Ghosh N N, Kiskan B,
Yagci Y.Polybenzoxazines—new high performance thermosetting resins:synthesis
And properties [J] .Progress in polymer Science, 2007,32 (11): 1344-1391.), it can be with structure
The compound of construction meter functional group containing different function.The solidification of benzoxazine monomer be benzoxazine ring heating condition under open loop
Reaction, solidification are prepared into intrinsically flame retarded benzoxazine resin, and according to its open-loop principles (Dunkers J, Ishida
H.Reaction of benzoxazine-based phenolic resins with strong and weak
carboxylic acids and phenols as catalysts[J].Journal of Polymer Science Part
A:Polymer Chemistry, 1999,37 (13): 1913-1921.) a large amount of phenolic hydroxyl group can be generated, therefore utilize oxazines ring
Characteristic, monomer just has very strong functional group's designability, therefore DOPO and benzoxazine ring with aldehyde radical is direct
Reaction designing synthesis has the new flame retardant of the response type of phenolic hydroxyl group and alcoholic extract hydroxyl group, compared to the additive flame retardant of small molecule
Agent, macromolecular reaction type fire retardant can prevent the migration of fire retardant, reduce the pollution to environment and keep material for a long time
Flame-retardant nature.
There are many researchs to the modification of DOPO and benzoxazine in the prior art, the still many technical problems of band urgently solve
Certainly.Chinese CN103012484 A discloses a kind of phosphorous benzoxazine resin, is with aromatic diamine and salicylaldhyde
Condensation reaction is carried out, then carries out addition reaction with DOPO, then react to obtain phosphorous benzoxazine resin with formaldehyde.But it is prepared
Method is complicated, and uses a large amount of organic solvents, and gained yield is not high, and being not that one kind is economically viable prepares response type DOPO
The method of fire retardant.CN104774343A discloses a kind of phenyl phosphate fire retardant containing DOPO, is with 4-aminophenol, 2-
Hydroxy benzaldehyde, DOPO, formaldehyde synthetic intermediate I, phenoxy group phosphinylidyne dichloro, resorcinol synthetic intermediate II, intermediate compound I and
Intermediate II reacts to obtain the phenyl phosphate fire retardant containing DOPO.Although the fire retardant flame retardant effect is fine, preparation process
It is excessively complicated, need first to be prepared two kinds of intermediates and synthesized again, yield is low, it is at high cost, be therefore also not suitable for it is extensive
Industrialized production.CN107033329A discloses a kind of halogen-free flameproof epoxy hardener, be by HPM and p-aminobenzoic acid and
Polyformaldehyde reaction, then react to obtain the curing agent of double DOPO structures with DOPO.The epoxy resin obtained using the curing agent,
LOI is 28.1, although in the scope of firing-difficult matter, but the value of LOI is still relatively low, uses fire-retardant material in current building materials and traffic
Material requires in the case where being increasingly stringenter flame retardant property, it may not be possible to meet the performance requirement of fire retardant, and its reactive group
Group is phenolic hydroxyl group and benzoic acid group, even if being also extremely easy hydrolysis so that flame retardant property variation, leads to it with after resin reaction
The field that can be applicable in is restricted.
Summary of the invention
The purpose of the present invention is to provide a kind of reactive flame retardant containing double DOPO bases and nitrogen, contain in molecular structure
Two DOPO groups, and also have two active reactive groups of phenolic hydroxyl group and alcoholic extract hydroxyl group.The present invention also provides described in one kind
The preparation method of double DOPO reaction-type flame-retardings is the designability using benzoxazine functional group, DOPO unit is passed through letter
Single reaction and benzoxazine reaction, are directly and efficiently made the phosphorous reactive flame retardant with phenolic hydroxyl group and alcoholic extract hydroxyl group, and
And the fire retardant is compounded with benzoxazine, can effectively increase the efficiency of fire retardant, so that phosphorus content is effectively reduced.
The present invention further an object is that provide a kind of double DOPO reactive flame retardant and its with benzoxazine compound ligand
The application of system.There are two the hydroxyls of reactivity for the reactive flame retardant band of double DOPO of the invention, are retaining original DOPO resistance
While combustion property, can and epoxy resin, remaining group react on phenolic resin, be in the form of chemical bond and resin
Connection, rather than in a manner of physical blending, there is more obvious promotion to the flame retardant property of resin material, it is more importantly, fire-retardant
Stability ensured, even if that is, reactive flame retardant treated resin is stored for a long time, or in some extreme feelings
(acid and alkali corrosion, humidity) also can guarantee with good flame retardant effect under condition.
Shown in the reactive flame retardant structure such as following formula (I) containing double DOPO bases and nitrogen:
Wherein, A1、A2、A3、A4It is hydroxyl with one in A5, the adjacent A group of hydroxyl isRemaining
For hydrogen.
Preferably, the reactive flame retardant structure such as following formula (II) of the invention containing double DOPO bases and nitrogen, formula (III) and formula
(IV) shown in:
The present invention also provides a kind of methods for preparing logical formula (I) compound, are with aniline, hydroxy benzaldehyde, poly
Formaldehyde reacts to obtain intermediate PHB (synthetic method reference Ran Q C, Gu Y.Concerted reactions of aldehyde
groups during polymerization of an aldehyde-functional benzoxazine[J].Journal
Of Polymer Science Part A:Polymer Chemistry, 2011,49 (7): 1671-1677.), then it is anti-with DOPO
The reactive flame retardant containing double DOPO bases and nitrogen should be made in high yield.The position of phenolic hydroxyl group is by hydroxy benzenes in products therefrom
Formaldehyde determines, for example with parahydroxyben-zaldehyde is raw material, and obtained product is i.e. A shown in formula (II)3For hydroxyl.If with neighbour
The phenolic hydroxyl group position of reactive flame retardant obtained by hydroxy benzaldehyde or m-hydroxybenzaldehyde finally containing double DOPO bases and nitrogen is
It is different.
By taking the compound of formula (II) structure as an example, the reactive flame retardant synthetic route containing double DOPO bases and nitrogen is such as
Under:
Specifically, the reactive flame retardant synthesis step containing double DOPO bases and nitrogen is as follows:
(1) specific step is as follows for -6 aldehyde radical -3,4- dihydro -2H-1,3- benzoxazine (referred to as PHB) of 3- phenyl: by benzene
After amine, parahydroxyben-zaldehyde and paraformaldehyde are dissolved in organic solvent, under agitation, 60-100 DEG C reaction 8-15 hours, instead
It depressurizes and filters after answering, obtain faint yellow solid PHB；
(2) DOPO is added, PHB is dissolved in organic solvent, under nitrogen protection, and under agitation, 120-140 DEG C of reaction 3-
6 hours, after the reaction was completed, filtering, vacuum drying oven drying.
The organic solvent in toluene, dimethylbenzene, DMF, DMSO, THF, dioxane, methylene chloride, chloroform extremely
Few one kind.
Wherein, the molar ratio of aniline, parahydroxyben-zaldehyde and paraformaldehyde is 1-2:1-1.5:2-4 in step (1)；Step
Suddenly the molar ratio of PHB in (2), DOPO are 1:2-4.
The present invention also provides the reactive flame retardants containing double DOPO bases and nitrogen described in one kind in fire proofing or coating
Purposes.
It is also another object of the present invention to provide a kind of reactive flame retardant modified epoxy resin or phenolic resin, are
So that epoxy resin or phenolic resin and the reaction-type flame-retarding system of any of claims 1 or 2 containing double DOPO bases and nitrogen are solid
Reaction obtains in the presence of agent.
Preferably, the epoxy resin is selected from bisphenol A type epoxy resin, preferably is selected from E-44, E-54, E-51, E-42, E-
35, at least one of E-31, E-20, E-14, E-12, E-06, E-03；The phenolic resin is selected from F-51, F-48, F-44, F-
47, at least one of F-43；The curing agent is aromatic amine curing agent, preferably is selected from m-phenylene diamine (MPD) (m-PDA), m-xylene diamine
(MXDA), two aminodiphenylmethane (DDM), 4,4' diaminodiphenyl sulfone (DDS), 4- chlorine o-phenylenediamine (CPDA), double benzyl ammonia
At least one of base ether.The above-mentioned specific choice to epoxy resin, phenolic resin, curing agent should not be understood as protecting the present invention
Protect the limitation of range, reactive flame retardant band provided by the invention there are two hydroxyl reactive group, can be convenient with all kinds of rings
Oxygen resin, phenolic resin generate flame-retardant modified epoxy resin under the action of curing agent, there is the very extensive scope of application.
Shown in the synthesis signal of the modified epoxy resin of above-mentioned reactive flame retardant or phenolic resin is lower:
Compared with the existing technology, beneficial effect obtained by the present invention is:
One, containing the phospha ring structure there are two DOPO in reaction-type flame-retarding agent molecule provided by the invention, phosphorus content is high, and
And an alcoholic extract hydroxyl group and phenolic hydroxyl group are existed simultaneously, it can both be reacted with epoxy resin cure, and phenolic hydroxyl group activity can be used as by force
The curing agent of epoxy resin.Compared with common reactive flame retardant, degree of functionality is high, stronger in conjunction with epoxy matrix.
New molecule entirety will be constituted in phosphorus atoms insertion strand by then passing through chemical reaction, so epoxy resin can be significantly improved
Anti-flammability and thermal stability.In major part embodiment of the present invention, using the reactive flame retardant to epoxy resin modification after,
The UL-94 fire-protection rating of sample can reach V-0 rank, and LOI is 30% or more.
Two, inventor is it has been unexpectedly found that reactive flame retardant provided by the invention and PHB are compounded, to asphalt mixtures modified by epoxy resin
Rouge is modified, and carbon yield substantially reduces, and significantly improves the condensed phase flame retardant effect of material, excellent heat stability.By its with
The prepared reactive flame retardant compounding containing double DOPO bases is used for epoxy resin modification, reaches V-0 grades in vertical burn test
When other, required retardant load level can be effectively reduced, so that P content reduces in epoxy resin.
Three, reactive flame retardant provided by the invention synthesis is simple, by two-step reaction can high yield obtained product.
In the excessive situation of DOPO, the conversion ratio of PHB is almost 100%, and the target product after reaction is not dissolved in reaction dissolvent
In, direct filtration washing, without complicated separating-purifying step, preparation method is efficient, simply.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of 1 intermediate PHB of preparation example.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram comparison of preparation example 1 intermediate PHB, DOPO and fire retardant DOPO-PHB.
The infrared spectrum comparison that Fig. 3 is the DOPO and fire retardant DOPO-PHB of preparation example 1.
Specific embodiment
The reactive flame retardant of the present invention containing double DOPO bases and nitrogen is described further below by embodiment.It is aobvious
So, described embodiment is only section Example of the invention, rather than all.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
Preparation example
By 1.39g (0.015mol) aniline, 1.22g (0.01mol) parahydroxyben-zaldehyde and 1.51g (0.05mol) poly
After formaldehyde is dissolved in 50mL dioxane, under agitation, 80 DEG C are reacted 10 hours, and decompression filters after reaction, obtains yellowish
- 6 aldehyde radical -3,4- dihydro -2H-1,3- benzoxazine PHB of color solid 3- phenyl, yield 94%, nuclear magnetic resonance spectroscopy such as Fig. 1 institute
Show；Be separately added into that PHB is 2.39g (0.01mol) and DOPO is 6.48g (0.03mol) in three-necked flask, be added 20ml without
Water-toluene leads to nitrogen protection, is warming up to 130 DEG C, reacts 5 hours under magnetic agitation.After the reaction was completed, it is filtered to remove solvent, is obtained
To faint yellow solid, then faint yellow solid is poured into toluene and is washed, filtered.It is repeated 3 times, to remove excessive DOPO, obtains
To target fire retardant DB, i.e. formula (II) compound represented, product is through nuclear magnetic resonance spectroscopy (as shown in Figure 2) and INFRARED SPECTRUM illustrated handbook
Determine such as (shown in Fig. 3).
Embodiment fire retardant modified epoxy resin preparation and its performance test:
Analysis operating method and process in the present invention are routine techniques, wherein analysis instrument and parameter are as follows:
Nuclear Magnetic Resonance: instrument is the 600 liquid NMR spectrometer with superconducting magnet of AVANCEIII of Bruker company, solvent for use
For DMSO,1H-NMR experimental temperature is 299.0K, relaxation time 1.0sec, pulse width 6.5u sec.
Thermogravimetic analysis (TGA): instrument is 209 F1 type thermogravimetric analyzer of NETZSCH TG, and test temperature is 40-600 DEG C, is risen
Warm rate 10K/min, carries out in a nitrogen atmosphere, gas flow rate 5 0ml/min, amount of samples 3-5mg.
Limit oxygen index test: instrument is FTAII (1600) type limit oxygen index instrument of Britain RS company, test mark
Quasi- GB/T2406.2-2009, batten specification 100mm × 6mm × 3mm, one group of 5-10 item, test before by batten be placed in temperature 23 ±
2 DEG C, 88h or more is adjusted under 50 ± 5% environment of humidity.
UL-94 vertical burn test: instrument is the CZF-5A horizontal vertical burning analyzer of Jiangning analysis instrument factory
UL-94 vertical burn test is carried out, batten specification is 125mm × 13mm × 3.2mm, and one group of 5-10 item, testing standard is UL
94ISBN O-7629-0082-2.Batten is placed in 23 ± 2 DEG C of temperature before test, adjusted under 50 ± 5% environment of humidity 48h with
On.
The present invention passes through limit oxygen index and UL-94 vertical burn test to the reactive flame retardant modified epoxy tree of preparation
Rouge burns to it and flame retardant property is evaluated.
The preparation of the modified epoxy resin of 1 reactive flame retardant of embodiment (DB)
The fire retardant DB grind into powder that first preparation example 1 is synthesized.100g epoxy resin E-44 is weighed, is warming up to 140 DEG C,
5g fire retardant DB is added, adds 30g curing agent 4,4'- diaminodiphenylsulfone (DDS) pours into poly- the four of preheating after mixing evenly
Vinyl fluoride mold, 180 DEG C keep the temperature 4 hours, obtain the modified epoxy resin of fire retardant, referred to as PEa1.
The modified epoxy resin samples of fire retardant are prepared in the same manner, and difference is the additive amount of fire retardant DB not
Same: the additive amount of DB is 10g, and the modified epoxy resin of obtained flame-retardant agent is known as PEa2；The additive amount of DB is 15g, obtained flame-retardant
The modified epoxy resin of agent is known as PEa3；And the additive amount of DB is 20g, the modified epoxy resin of obtained flame-retardant agent is known as
PEa4。
The sample material composition of gained DB modified epoxy is listed in shown in table 1:
Table 1: different content DOPO-PHB modified epoxy resin
| Serial number | E44(g) | DB(g) | P content wt% |
| PEa1 | 100 | 5 | 0.34 |
| PEa2 | 100 | 10 | 0.64 |
| PEa3 | 100 | 15 | 0.95 |
| PEa4 | 100 | 20 | 1.23 |
The preparation of 2 reactive flame retardant of embodiment (DB) and benzoxazine (PHB) compound system modified epoxy:
The fire retardant DB grind into powder that first preparation example 1 is synthesized.100g epoxy resin E-44 is weighed, is warming up to 140 DEG C,
It is added without fire retardant DB, adds 30g curing agent 4, the aldehyde radical benzoxazine (PHB) of 4'- diaminodiphenylsulfone (DDS), 5g stirs
The Teflon mould of preheating is poured into after mixing uniformly, 180 DEG C keep the temperature 4 hours, and obtained epoxy resin is known as PEb1.
The modified epoxy resin samples of fire retardant are prepared in the same manner, and difference is the additive amount of fire retardant DB not
Same: the additive amount of DB is 5g, and the modified epoxy resin of obtained flame-retardant agent is known as PEb2；The additive amount of DB is 10g, obtained flame-retardant agent
Modified epoxy resin is known as PEb3；The additive amount of DB is 15g, and the modified epoxy resin of obtained flame-retardant agent is known as PEb4；DB's
Additive amount is 20g, and the modified epoxy resin of obtained flame-retardant agent is known as PEb5；
The sample material composition of the epoxy resin of gained DB and PHB compounding reaction modifying is listed in shown in table 2:
Table 2: different content DB and PHB modified epoxy resin
The preparation of the non-modified epoxy resin of comparative example 1
It weighs 100g epoxy resin E-44 and is warming up to 140 DEG C, be added 30g curing agent 4,4'- diaminodiphenylsulfone (DDS),
Mold is poured into after mixing evenly, keeps the temperature 4 hours at 180 DEG C, gained is known as E without the modified epoxy resin of fire retardant.
The test of 1 flame retardant effect of application examples
According to " the flammable test of plastic material, UL94 " (Tests for Flammability of Plastic
Materials, UL94) program carry out flammable test.Measuring instrument is the burning examination of LK-6604UL94 specification horizontal vertical
Test machine.Based on burn rate, the fall time, anti-dripping melt ability and fall drop whether just burning, if material combustibility is divided into
Dry grade.Based on test result, V-0, V-1, V-2 three grades are divided under flame vertical burn test conditions, flame retardant rating is pressed
Successively decrease step by step according to V-0, V-1, V-2.
The meaning of each grade is described as follows:
V-2: after carrying out 10 seconds combustion testings twice to sample, flame extinguishes in 30 seconds, 5 total burning times
It is 250 seconds or less, the absorbent cotton below the 30cm that can ignite.
V-1: after carrying out 10 seconds combustion testings twice to sample, flame extinguishes in 30 seconds, 5 total burning times
For the absorbent cotton below 250 seconds or less the 30cm that cannot ignite.
V-0: after carrying out 10 seconds combustion testings twice to sample, flame extinguishes in 10 seconds, 5 total burning times
It is 50 seconds or less, there cannot be comburant to fall down.
By its limit oxygen index of gained sample test, it the results are shown in Table 3:
The flame test result of 3 different content DB of table modified epoxy resin
The test of 2 carbon yield of application examples
Table 4 is to compare at 800 DEG C to the carbon yield of E, PEb1, PEa2, PEa4 and PEb3:
| Sample | 800 DEG C of carbon yield (N2) |
| E | 12.33 |
| PEb1 | 13.68 |
| PEa3 | 19.61 |
| PEa4 | 26.8 |
| PEb3 | 24.47 |
Therefore both it is fire-retardant to have effectively promoted condensed phase for DOPO derivative flame retardant and benzoxazine, and use DB
It is compounded with PHB, produces synergistic effect, obtained composite modified epoxy resin condensed phase flame retardant effect is more preferable.
Application examples 3
To resulting with its mechanical property of the sample test of obvious flame retardant effect, as a result it is listed in shown in table 5:
Crooked test: being tested according to GB/T 9341-2008 standard, and specimen size is 100mm length × 15mm width
× 4mm thickness, pressing to speed is 2mm/min；
The mechanical experimental results of the modified epoxy resin of 5 part DB flame-retardant system of table
From the data of application examples 1-3 it is found that the reactive flame retardant provided by the invention containing double DOPO bases and nitrogen is to epoxy
After resin is modified, flame retardant property is increased substantially, and limit oxygen index reaches 30% or more, when P content is 0.95wt%
When, the UL-94 fire-protection rating of sample can reach V-0 rank.The fire retardant and benzoxazine analog derivative (PHB) is multiple
Match, when P content only has 0.64wt%, fire-protection rating can reach V-0 rank.As it can be seen that reactive flame retardant provided by the present application
It is a kind of reaction-type flame-retarding system of reliable and effective phosphorus nitrogen synergistic effect, and benzoxazine has and can flexibly design very much
Property, to introduce some other functional groups, it can assign epoxy resin some other performances.Fire retardant of the present invention it is rigid
Property structure, the mechanical property of epoxy resin is not deteriorated not only, there are also a degree of promotion.But it is excessive fire-retardant when being added
When agent and benzoxazine compound system, the bending strength of material can be made to be declined, but bending modulus still increased, it is multiple
The content that DOPO can be effectively reduced with system reduces the content of P in system, therefore can select according to different needs
Select suitable flame-retardant system.Reactive flame retardant of the present invention containing double DOPO bases and nitrogen and its compound system preparation method letter
Single, raw material is cheap and easy to get, is that one kind is expected to industrialized reaction-type flame-retarding system, just can effectively promote benzoxazine in this way
The application of resin, to assign other excellent performances.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of reactive flame retardant containing double DOPO bases and nitrogen, shown in structure such as following formula (I):
Wherein, A1、A2、A3、A4It is hydroxyl with one in A5, the adjacent A group of hydroxyl isRemaining is
Hydrogen.
2. reactive flame retardant as described in claim 1, which is characterized in that structure such as following formula (II), formula (III) and formula (IV)
It is shown:
3. the preparation method of the reactive flame retardant of formula described in claim 1 (I) structure, includes the following steps, with aniline, hydroxyl
Benzaldehyde, polyformaldehyde reaction obtain intermediate PHB, then the reaction-type flame-retarding containing double DOPO bases and nitrogen is made with DOPO reaction
Agent.
4. the preparation method of the reactive flame retardant of formula described in claim 2 (II) structure, synthetic route are as follows:
5. the preparation method of the reactive flame retardant of formula (II) structure as claimed in claim 4, which is characterized in that including following step
It is rapid:
(1) synthesis of -6 aldehyde radical -3,4- dihydro -2H-1,3- benzoxazine (PHB) of 3- phenyl: by aniline, parahydroxyben-zaldehyde and
After paraformaldehyde is dissolved in organic solvent, under agitation, 60-100 DEG C reaction 8-15 hours, after reaction decompression filter,
Obtain faint yellow solid PHB；
(2) DOPO is added, PHB is dissolved in organic solvent, and under nitrogen protection, under agitation, 120-140 DEG C of reaction 3-6 is small
When, after the reaction was completed, filtering, vacuum drying oven drying；Obtain reactive flame retardant.
6. the preparation method of the reactive flame retardant of formula (II) structure as claimed in claim 5, which is characterized in that in step (1)
The molar ratio of aniline, parahydroxyben-zaldehyde and paraformaldehyde is 1-2:1-1.5:2-4；PHB in step (2), mole of DOPO
Than for 1:2-4.
7. the preparation method of the reactive flame retardant of formula (II) structure as claimed in claim 5, which is characterized in that described organic molten
Agent is selected from least one of toluene, dimethylbenzene, DMF, DMSO, THF, dioxane, methylene chloride, chloroform.
8. purposes of the reactive flame retardant of any of claims 1 or 2 containing double DOPO bases and nitrogen in fire proofing or coating.
9. a kind of reactive flame retardant modified epoxy resin or phenolic resin, are by epoxy resin or phenolic resin and right
It is required that the reactive flame retardant containing double DOPO bases and nitrogen described in 1 or 2 reacts obtain in the presence of a curing agent, optionally, may be used also
Benzoxazine derivative PHB is added.
10. reactive flame retardant as claimed in claim 9 modified epoxy resin or phenolic resin, which is characterized in that described
Epoxy resin is selected from bisphenol A type epoxy resin, preferably is selected from E-44, E-54, E-51, E-42, E-35, E-31, E-20, E-14, E-
12, at least one of E-06, E-03；The phenolic resin is selected from at least one of F-51, F-48, F-44, F-47, F-43；Institute
Stating curing agent is aromatic amine curing agent, preferably is selected from m-phenylene diamine (MPD) (m-PDA), m-xylene diamine (MXDA), two amido diphenyl
Methane (DDM), 4,4'- diaminodiphenylsulfone (DDS), at least one of 4- chlorine o-phenylenediamine (CPDA), double benzyl amino ethers, it is described
Benzoxazine derivative PHB is -6 aldehyde radical -3,4- dihydro -2H-1,3- benzoxazine of 3- phenyl.
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