CN104277223B - Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant - Google Patents

Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant Download PDF

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CN104277223B
CN104277223B CN201310292269.7A CN201310292269A CN104277223B CN 104277223 B CN104277223 B CN 104277223B CN 201310292269 A CN201310292269 A CN 201310292269A CN 104277223 B CN104277223 B CN 104277223B
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flame retardant
nitrogen
silicon
elements
phosphorus
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CN104277223A (en
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王涛
李永杰
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and a synthesis method of the macromolecular flame retardant. The synthesis method is characterized in that an organic silicon polymer containing an amino group firstly reacts with an aldehyde type substance and then reacts with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare novel flame retardant molecules which simultaneously contain three flame retardant elements of phosphorus, nitrogen and silicon in the molecules. The flame retardant disclosed by the invention is simple in a preparation process and has good solubility with resin, and the three flame retardant elements of phosphorus, nitrogen and silicon are synergistic for realizing flame retardance, so that the flame retardant effect of resin added with the flame retardant is significantly improved, and the flame retardant can be used as the additive flame retardant for halogen-free flame retardance of epoxy resin, polyurethane, ABS (acrylonitrile butadiene styrene), nylon and other engineering plastics.

Description

One class is phosphorous, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon and its synthetic method and Purposes
Technical field
The present invention relates to not halogen-containing fire retardant of a class and preparation method thereof, belong to Minute Organic Synthesis technical field.
Background technology
With the progress of industrial technology, increasing organic synthesis macromolecular material enters into our daily life In, these materials have excellent properties, as good in hardness, and tensile strength is high, and water-fast, corrosion-resistant etc., range is very wide.But by It is all inflammable or combustible in epoxy resin, polyester and engineering plastics Polymer material great majority, and release when burning Substantial amounts of poisonous and corrosive gas, so the harmfulness that the fire being induced by produces is also more serious.Therefore prevent height The fire that molecular material burning causes has become as people needs the urgent problem solving.
At present, use halogenated flame retardant although halogenated flame retardant flame retardant effect is preferable in macromolecular material more, but such Fire retardant often decomposes generation toxic gas when meeting fire burning(As HBr), or even produce many bromos dibenzo two in burning The carcinogen such as English and PBDF is restricted so using.Organophosphorous fire retardant is considered as to replace The organic fire-retardant of halogen flame, this based flame retardant is mostly nontoxic, low cigarette and flame retardant effect substantially, wherein organophosphorus ester Class product is more, but organophosphorus ester based flame retardant heat endurance during preparation and use is low, volatility is big, easily migration Thus affecting material property.9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxides are that a kind of flame retarding efficiency is high, environmental friendliness The phosphorous reactive flame retardant of type, itself has anti-flammability.Due to containing active hydrogen in its structure, can carry out with multiple compounds React so warp prepares fire retardant frequently as intermediate, but, find the poor-performing of resistance to molten drop of sample in use.
Multielement synergistic fire retardant is considered as preferable fire retardant.Document report(Polym. Degr. Stab., 2009, 94:1693-1699;Ind. Eng. Chem. Res., 2011, 50: 1881-1892;Polym. Degr. Stab., 2011, 96: 1720-1724)Phosphorus-nitrogen containing flame retardant, with phosphorus, nitrogen as active component, can play during fire-retardant Significantly phosphorus nitrogen synergy, forms heat-insulated, oxygen barrier and the foamed char full of inert gas, and producing ratio individually contains phosphorus or nitrogen The more excellent flame retardant effect of fire retardant.
Silicon-containing compound can make the high silica of layer of charcoal surface distributed heat endurance, thus preventing under high temperature after decomposing The decomposition further of layer of charcoal, has certain anti-flammability by this silicon-containing compound.In addition silicon-containing compound has excellent heat surely Qualitative, surface energy is low, and oxidation resistance is strong, and moisture-proof is good, the features such as chain pliability is high.Document report(J. Polym. Sci. B Polym. Phys., 2010, 48: 693-705; Polym. Degrad. Stab., 2011, 96: 1508- 1515;J. Polym. Sci. B Polym. Phys., 2007, 45: 1542-1551)Phosphorus silicon-series five-retardant makes material Fire resistance improves, and compared with fire retardant phosphorous merely, phosphorus silicon-series five-retardant generally will not reduce modified resin Heat endurance, material heat release rate in thermal decomposition process substantially slows down, and the carbon left after decomposition also accordingly increases.
In sum, halogen flame environmental pollution is larger, and business-like environment-friendly type phosphorus flame retardant has anti-melting Dripping property and hydrolytic resistance are poor, and the defect that the heat endurance of addition ambassador's resin declines.When phosphorus is common with silicon or nitrogen Cooperative effect can be produced during same-action, not only make fire retardant have excellent fire resistance, flame-retardant system can also be improved Mechanical performance and heat endurance.But in document, the report of synergistic flame retardant is focused mostly on and phosphorus nitrogen and phosphorus silicon type fire retardant, and Structure and complicated process of preparation, have such problems as bad with resin compatible simultaneously.Do not see at present with regard to containing phosphorus, Nitrogen, the report of the macromolecular fire retardant of three kinds of elements of silicon.
Content of the invention
The present invention provides a class to contain phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon and preparation method thereof, and such is fire-retardant Agent preparation is simple, three kinds of element cooperative flame retardants, and the flame retardant resin systems for obtaining high flame retardant and function admirable provide new way And new method.
Specifically, the present invention includes:
One class contains the macromolecular fire retardant of phosphorus, nitrogen, three kinds of elements of silicon it is characterised in that structural formula(Ⅰ)As follows:
(Ⅰ)
Wherein, R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace C1-C12Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
R1, R2, R3, R4Identical or different, it preferably is selected from C1-C3Alkyl and C6-C12Aryl;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C11-C22's Alkyl-substituted naphthaline base, hydroxyl substituted naphthyl;
M preferably is selected from hydroxyl substituted-phenyl and hydroxyl substituted naphthyl;
n=0-50.
Containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method it is characterised in that make comprise following substance A Reacted with the mixture of aldehyde material:
Substance A is formula(Ⅱ)Organosilicon polymer:
(Ⅱ)
Aldehyde material for formula is(Ⅲ)Compound:
(Ⅲ)
Wherein R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace C1- C12Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C1-C12Alkane Base substituted naphthyl, hydroxyl substituted naphthyl;
n=0-50.
Preparation containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method, its reaction comprises following synthesis step:
By organosilicon polymer(Structure is as shown in formula II)With solvent be added to anti-with agitating device and temperature regulating device Answer in device, aldehyde material(Structure is as shown in formula III)According to aldehyde radical and amino mol ratio 1:1 amount is added in reactor, temperature Control and react 1 ~ 10 hour under the conditions of 0 ~ 50 DEG C, obtain imine intermediate after the completion of reaction, be directly used in the next step;
9,10- dihydro -9- oxa- -10- phospho hetero phenanthrene -10- oxide is pressed the mol ratio 1 of P-H and amino:1 addition To in the above-mentioned reaction system containing imine intermediate, temperature control is reacted 1 ~ 20 hour under the conditions of 0 ~ 50 DEG C, and reaction terminates Afterwards, cool down, remove solvent, through recrystallization or column chromatography purification, obtain solid.
Described solvent is that the combination of one or more of dichloromethane, chloroform, methyl alcohol, ethanol, ethylene glycol, dioxane is molten Agent.
A class according to claim 1 contain phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that: Such compound can be used as the halogen-free flameproof of the engineering plastics such as epoxy resin, polyurethane, ABS, nylon.
The effect of the present invention:Contain phosphorus, silicon, three kinds of nitrogen fire-retardant in the BACN molecular structure of designed synthesis simultaneously Element, fire resistance significantly improves;Due to introducing poly- silica chain in molecular structure, this based flame retardant is made to be added in resin system There is good compatibility;The resin adding this based flame retardant has preferable heat endurance;Containing phosphorus silicon nitrogen of the present invention fire-retardant Agent is not halogen-containing, is conducive to environmental protection;The fire-retardant FRW process is simple of containing phosphorus silicon nitrogen of the present invention, is suitable for large-scale production.
Synthetic example
The synthesis of embodiment 1 fire retardant DPP-Si-1
(Ⅳ)
The building-up process of fire retardant DPP-Si-1 is shown in above formula(Ⅳ).
Equipped with condenser pipe, in 100 mL there-necked flasks of thermometer and magnetic agitation, add amido silicon oil(SiONH2, 20.0 g, 0.023 mol), parahydroxyben-zaldehyde(5.1 g, 0.041 mol)With 30 mL dichloromethane, under nitrogen protective condition Reaction room temperature reaction, after 3 hours, is dividedly in some parts DOPO(8.9 g, 0.041 mol), continue reaction, by a plate(Solvent is Chloroform/methanol=4:1)Detection reaction is carried out, and reacts 6 hours about, and DOPO reaction is complete, after revolving removes solvent, by silica gel Post carries out column chromatography purification(Eluent:Chloroform/methanol=10:1), after removing solvent, obtain yellow blocks of solid DPP-Si-1 24.8g(Yield:79.5 % ).IR(KBr)νmax(cm−1) :3305 (-OH); 2954~2846 (CH3and CH2); 1606,1523,1452 (Ar ring); 1187 (P=O); 1267(Si-CH3); 1040~1092 (Si-O-Si); 921 (P-O-C).1H-NMR(CDCl3, 400MHz) δppm: -0.14~0.21(-Si-CH3), 0.25~0.35(m, Si-CH2), 1.25~1.39(m, Si-CH2-CH 2 -), 2.21~2.58(m, -NH-+-NH-CH 2 -), 4.01~4.22(d, -P-CH-), 6.57~8.06(m, Ar-H), 9.83(s, -OH).31P-NMR (CDCl3, 400MHz)δppm: 20~25.
The synthesis of embodiment 2 fire retardant DPP-Si-2
(Ⅴ)
The building-up process of fire retardant DPP-Si-2 is shown in above formula(Ⅴ).
By amido silicon oil(SiONH2)(20.0g, 0.023mol), benzaldehyde(4.3g, 0.041mol)With 30mL dichloromethane Alkane adds equipped with condenser pipe, in the 100mL there-necked flask of thermometer and magnetic agitation, reacts room temperature reaction under nitrogen protective condition After 3 hours, add DOPO(8.9g, 0.041mol), by a plate(Solvent:Chloroform/methanol=5:1)Detection reaction is carried out, about After 8 hours, completely, revolving removes solvent, carries out column chromatography purification by silicagel column for DOPO reaction(Eluent:Chloroform/methanol= 12:1), after removing solvent, obtain faint yellow dope DPP-Si-2 23.8g(Yield:77.9 % ).IR(KBr)νmax(cm−1) :3071(Ar-H); 2964~2894 (CH3and CH2); 1599,1460 (Ar ring); 1193 (P=O); 1257(Si-CH3); 1043~1097 (Si-O-Si); 921 (P-O-C).1H- NMR (CDCl3, 400MHz): δppm= - 0.04~0.30 (-Si-CH3), 0.39~0.49 (Si-CH2), 1.13~1.59 (Si-CH2-CH 2 -), 2.14~2.84 (m, -NH-+-NH-CH 2 -), 4.10~4.32 (-P-CH-), 6.49~8.12 (Ar-H).31P-NMR (CDCl3, 400MHz)δppm: 16~24.
Application Example
The test bars being used for anti-flammability in the present invention are in high-pressure sodium lamp(λmax= 365 nm, I = 1 mW∙cm-2) Carry out preparation under heat cure again after irradiating the lower initiation photocuring by light trigger.Light trigger be cyclopentadienyl group-iron- (N- ethyl) carbazole hexafluorophosphate(In-Fe, is shown in formula(Ⅵ)), epoxy monomer used is a kind of alicyclic ring type of bifunctionality Epoxide(ERL4221, is shown in formula(Ⅶ)).
(Ⅵ)
(Ⅶ)
Oxygen index (OI)(LOI)Mensure use instrument be JF-3 type oxygen index instrument, content according to GB/T 2406-1993 Tested, the size of batten is 100 mm × 6.5 mm × 3 mm;
Before sample preparation first by epoxy monomer ERL4221 in 25 mmHg, vacuum distillation 3 hours under the conditions of 120 DEG C, remove resin Middle remaining moisture.
Embodiment 1
The fire retardant DPP-Si-1 of 5wt%, 10wt% and 15wt% is separately added in ERL4221, makes three groups of samples, plus After heat is thoroughly mixed uniformly to 110 DEG C, it is cooled to 80 DEG C, maintains this temperature to stir under the conditions of lucifuge whole to light trigger Dissolving.The liquid mixture of gained is poured into from molding jig, after high voltage mercury lamp radiation 10min, takes out, in an oven Under the conditions of 120 DEG C, heating 30min carries out solidify afterwards process, solidfied material is obtained required batten size after polishing, respectively obtains Sample EPDS1-5, EPDS1-10 and EPDS1-15 after the solidification of three different flame retardant additions.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, data is listed in table 1.
Sample after obtained solidification is carried out oxygen index (OI) test, data is listed in table 2.
As can be seen from Table 1 and Table 2, for sample EPDS1-15, system oxygen index (OI) reaches 27.2, corresponding weightlessness The heat decomposition temperature of 10wt% is 368 DEG C.Show the good flame retardant effect that prepared fire retardant plays to system, simultaneously solid Change resin and there is very high heat decomposition temperature.
Embodiment 2
The fire retardant DPP-Si-2 of 5wt%, 10wt% and 15wt% is separately added in ERL4221, makes three groups of samples, plus After heat is thoroughly mixed uniformly to 110 DEG C, it is cooled to 80 DEG C, maintains this temperature to stir under the conditions of lucifuge whole to light trigger Dissolving.The liquid mixture of gained is poured into from molding jig, after high voltage mercury lamp radiation 10min, takes out, in an oven Under the conditions of 120 DEG C, heating 30min carries out solidify afterwards process, solidfied material is obtained required batten size after polishing, respectively obtains Sample EPDS2-5, EPDS2-10 and EPDS2-15 after the solidification of three different flame retardant additions.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, data is listed in table 1.
Sample after obtained solidification is carried out oxygen index (OI) test, data is listed in table 3.
As can be seen that for sample EPDS2-15, system oxygen index (OI) reaches 24.2, corresponding weightlessness from table 1 and table 3 The heat decomposition temperature of 10wt% is 358 DEG C.

Claims (5)

1. a class contains the macromolecular fire retardant of phosphorus, nitrogen, three kinds of elements of silicon it is characterised in that structural formula (I) is as follows:
Wherein, R1, R2, R3, R4Identical or different, and independently selected from C1-C12Alkyl, N, O, S hetero atom replace C1-C12's Alkyl, C6-C22Aryl, C1-C12Alkoxyl, or a combination thereof;
M is selected from C1-C12Alkyl, phenyl, hydroxyl substituted-phenyl, C1-C12Alkyl-substituted phenyl, naphthyl, C1-C12Alkyl take For naphthyl, hydroxyl substituted naphthyl;
N=0-50.
2. according to claim 1 containing phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that:By such Compound is used for the halogen-free flameproof of engineering plastics.
3. according to claim 1 containing phosphorus, nitrogen, three kinds of elements of silicon macromolecular fire retardant it is characterised in that:By such Compound is used for epoxy resin, polyurethane, ABS, the halogen-free flameproof of nylon.
4. a kind of prepare claim 1 containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon method, its reaction comprises Following synthesis step:
Organosilicon polymer (structure is as shown in formula II) and solvent are added to the reactor with agitating device and temperature regulating device In, aldehyde material (structure is as shown in formula III) is according to aldehyde radical and amino mol ratio 1:1 amount is added in reactor, temperature control React 1~10 hour under the conditions of 0~50 DEG C, obtain imine intermediate after the completion of reaction, be directly used in the next step;
Wherein R1, R2, R3, R4Definition as claimed in claim 1;
The definition of n is as claimed in claim 1;
M-CHO
(Ⅲ)
The wherein definition of M is as claimed in claim 1;
Miscellaneous for 9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxide is pressed the mol ratio 1 of P-H and amino:1 is added to above-mentioned containing Have in the reaction system of imine intermediate, temperature control is reacted 1~20 hour under the conditions of 0~50 DEG C, after reaction terminates, cold But, remove solvent, through recrystallization or column chromatography purification, obtain solid.
5. preparation claim 1 according to claim 4 containing phosphorus, nitrogen, the macromolecular fire retardant of three kinds of elements of silicon Method is it is characterised in that described solvent is one of dichloromethane, chloroform, methyl alcohol, ethanol, ethylene glycol, dioxane or many The combination solvent planted.
CN201310292269.7A 2013-07-12 2013-07-12 Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant Expired - Fee Related CN104277223B (en)

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