CN105295092A - Cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements, and preparation method and application thereof - Google Patents
Cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements, and preparation method and application thereof Download PDFInfo
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- CN105295092A CN105295092A CN201410281776.5A CN201410281776A CN105295092A CN 105295092 A CN105295092 A CN 105295092A CN 201410281776 A CN201410281776 A CN 201410281776A CN 105295092 A CN105295092 A CN 105295092A
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Abstract
The invention discloses a cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements. The flame retardant has a structural general formula as shown in the description. The invention also discloses a preparation method of the cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements, and an application of the flame retardant when the flame retardant is added into a light-cured epoxy resin system. The cyclopentadienyl iron salt flame retardant preparation process is simple. According to the preparation process, a cyclopentadienyl iron salt containing a chlorobenzene ligand is adopted as a raw material; an imine intermediate is synthesized, such that a group containing the nitrogen element is introduced; the intermediate is subjected to a reaction with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, such that a phosphorus-containing flame-retarding group is introduced. With the cyclopentadienyl iron salt provided by the invention, the mobility of the aromatic hydrocarbon ligand removed during a photo-initiation process with the cyclopentadienyl iron salt as an initiator is solved. As an additive flame retardant, cyclopentadienyl iron metal and the ligand containing phosphorous and nitrogen elements provide synergistic flame-retarding effects. Resin added with the compound has a substantially improved flame-retarding property and increased residual char content.
Description
Technical field
The invention belongs to functional metallocene compound and applied technical field thereof, be specifically related to that a class is phosphorous, the luxuriant molysite of nitrogen element and preparation method thereof, and the purposes of fire retardant as epoxy resin.
Background technology
The application of macromolecular material in life is more and more extensive, but the hidden danger of the easy initiation fire of macromolecular material can not be ignored, and fire retardant can hinder flame, reduces the generation of toxic gas and smog.Though halogenated flame retardant good flame retardation effect, but produce the poisonous gas and limited use gradually of being corrosive such as hydrogen halide because high temperature can decompose.Organic phosphonium flame retardant flame retardant effect is excellent, and environmental protection is pollution-free, is the desirable selection of alternative halogenated flame retardant.
In existing compound flame-retardant system, expansion type flame retardant is the fire retardant being applied to a kind of environment-friendly high-efficiency of high molecular polymer of generally acknowledging at present, and the fire retardant containing phosphorus, nitrogen element is the expansion type flame retardant of a quasi-representative.Phosphorus, nitrogen element have cooperative flame retardant effect, phosphorus nitrogen synergistic fire retardant (Polym.Degrad.Stab., 2008,93:1037-1043 more excellent in independent organic phosphonium flame retardant flame retardant effect; Polym.Degrad.Stab., 2011,96:1118-1124).Phosphorus nitrogen systems is in the combustion of pyrolytic decomposition difficulty, and nontoxic gas can dilute oxygen and the inflammable gas of surrounding, and easily forms the high expansion carbon-coating of content under polyol exists, and isolated heat and oxygen, reach flame retardant effect.Applying more is have high phosphorus and the ammonium polyphosphate of nitrogen content, but the consistency of its water tolerance, thermostability and base material is bad, the important means solving consistency prepares the fire retardant of organic phosphorus-nitrogen containing element, but the problem that the fire retardant ubiquity usage quantity developed is large.
Metal fire retardant is as halogen-free flame retardants, have nontoxic, non-volatile, the advantages such as corrodibility is little (progress of halogen-free flame retardants. plastics industry, 2006,34:69-72.), but these inorganic combustion inhibitors need could obtain moderate flame retardant resistance when higher addition, but high add-on will affect processing characteristics and the mechanical property of base material, the compatibility of material also can reduce widely.Bibliographical information carries out LOI test to the polymkeric substance containing ferrocene structure, the LOI value that polymkeric substance containing ferrocene structure contrasts with the LOI value of the polymkeric substance not containing ferrocene structure the polymkeric substance found containing ferrocene building stone significantly improves, and LOI value can improve about 5.And test that the final carbon left of discovery system is the highest can reach 72%, residuals content very high (React.Funct.Polym., 2007,67,883 – 892) to carrying out TGA containing the polymkeric substance of ferrocene structure.Also have bibliographical information ferrocene-containing compound can reduce flame propagation velocity (FiresafetyJ., 2012,51,10 – 17; Prog.EnergyCombust.Sci.2008,34,288 – 329).
Iron arene complexes has the sandwich structure similar to ferrocene, is the simple luxuriant iron complex of a class synthetic method, can be used as the thermofixation of epoxy compounds and the initiator of photocuring.There is the luxuriant molysite of simple ligand structure in elicitation procedure, the part taken off can remain in resin, affect the performance of resin, one of direction solving this problem gives arene ligand in luxuriant molysite to have collaborative functional with luxuriant iron, and seldom have report about the research in this direction.
Summary of the invention
The invention provides the luxuriant molysite fire retardant and preparation method thereof of a class phosphorus, nitrogen element, and the purposes of fire retardant as epoxy resin, such luxuriant molysite preparation is simple, luxuriant iron and phosphorus, nitrogen element cooperative flame retardant, be not only and obtain high flame retardant and the flame retardant resin systems of excellent property provides new way and novel method, solve the impact of arene ligand on resin property of luxuriant molysite simultaneously.
Specifically, the present invention includes:
One class contains the luxuriant molysite fire retardant of phosphorus, nitrogen element, it is characterized in that this contain phosphorus, the luxuriant molysite general structure (I) of nitrogen element or (II) as follows:
Wherein R
1, R
2, R
3be selected from :-H ,-R ', phenyl, halogen ,-OH ,-OR ', the R ' of halo ,-R ' COO-or-R ' CONHR, wherein R ' be C1-12 alkyl or alkylidene group, R is the alkyl of C1-12;
Ar is selected from benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkyl anthracene, carbazole or N-alkyl carbazole.
The above-mentioned synthetic method with the luxuriant molysite fire retardant containing phosphorus, nitrogen element of structure formula I, this synthetic method is carried out according to the following steps: react with the luxuriant molysite of chlorobenzene with the phenol of amino, the luxuriant molysite of generating structure formula III; By the luxuriant molysite of the luxuriant molysite of structure formula III and aryl aldehyde reaction generating structure formula IV; The luxuriant molysite of structure formula IV and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are reacted the luxuriant molysite containing phosphorus, nitrogen element of generating structure formula I;
Wherein R
1, R
3described above with the definition of Ar.
The above-mentioned synthetic method with the luxuriant molysite fire retardant containing phosphorus, nitrogen element of structure formula II, synthetic method is carried out according to the following steps: with the luxuriant molysite of chlorobenzene and the aromatic yl acid reaction with aldehyde radical, the luxuriant molysite of generating structure formula (V); The luxuriant molysite of structural formula (V) and arylamines are reacted the luxuriant molysite of generating structure formula VI; The luxuriant molysite of structure formula VI and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are reacted the luxuriant molysite containing phosphorus, nitrogen element of generating structure formula II;
Wherein R
1, R
3described above with the definition of Ar.
The luxuriant molysite containing phosphorus, nitrogen element of structure formula I, (II) can as fire retardant in epoxy resin, acrylate resin and methacrylate resin.
There is a photo curable epoxy-resin systems for flame retardant resistance, it is characterized in that the composition by mass percentage of this epoxy-resin systems: the luxuriant molysite containing phosphorus, nitrogen element that structural formula is (I) or (II): 0.5%-10%; Cationic photoinitiator: 0%-5%; Epoxy resin: 70-95%; Reactive thinner: 4.5-30%.
The above-mentioned photo curable epoxy-resin systems with flame retardant resistance, is characterized in that epoxy resin used comprises alicyclic type epoxy resin, bisphenol A type epoxy resin and phenol aldehyde type epoxy resin; Reactive thinner used comprises alicyclic ring type epoxy monomer and lard type epoxy monomer; Cationic photoinitiator used comprises diaryl group iodized salt and triaryl sulfonium salts.
There is a photo curable acrylate resin system for flame retardant resistance, it is characterized in that the composition by mass percentage of this acrylate resin system: the luxuriant molysite containing phosphorus, nitrogen element that structural formula is (I) or (II): 0.5%-10%; Acrylate resin: 70-95%; N-Methyl pyrrolidone: 0.5%-5%; Reactive thinner: 4.5-30%.
The above-mentioned acrylate resin system with flame retardant resistance, is characterized in that acrylate resin used comprises acrylate resin and methacrylate resin; Reactive thinner used comprises acrylate monomer and methacrylate monomer.
The present invention has the following advantages:
1, because fire retardant provided by the invention has iron, phosphorus and nitrogen element simultaneously, therefore there is cooperative flame retardant function, facilitate the increase of flame retardant resistance and carbon left, make addition less, good flame retardation effect;
2, because preparation method provided by the invention is ripe, simple to operation, thus suitability for industrialized production is convenient to;
3, luxuriant molysite provided by the invention is when for epoxy resin and acrylic resin fire-retardant, as fire retardant, also can not only can be used as initiator, can reduce costs, can reduce again the operation adding initiator, and flame retardant properties improves
4, luxuriant molysite provided by the invention solves luxuriant molysite arene ligand to the detrimentally affect of resin property.
Accompanying drawing explanation
Fig. 1 be (
η 6 -4-(1-phenylamino-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) nucleus magnetic hydrogen spectrum of iron hexafluorophosphate (FCP).
Fig. 2 be (
η 6 -4-(1-phenylamino-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) iron hexafluorophosphate (FCP) nuclear-magnetism phosphorus spectrum.
Fig. 3 be (
η 6 -4-(1-(4-hydroxyanilino)-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) nucleus magnetic hydrogen spectrum of iron hexafluorophosphate (FCPH).
Fig. 4 be (
η 6 -4-(1-(4-hydroxyanilino)-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) iron hexafluorophosphate (FCPH) nuclear-magnetism phosphorus spectrum.
Fig. 5 be (
η 6 -4-(N-(1-phenyl-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) nucleus magnetic hydrogen spectrum of iron hexafluorophosphate (FCOP).
Fig. 6 be (
η 6 -4-(N-(1-phenyl-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) iron hexafluorophosphate (FCOP) nuclear-magnetism phosphorus spectrum.
Fig. 7 be (
η 6 -4-(N-(1-p-hydroxybenzene-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) nucleus magnetic hydrogen spectrum of iron hexafluorophosphate (FCOPH).
Fig. 8 be (
η 6 -4-(N-(1-p-hydroxybenzene-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) iron hexafluorophosphate (FCOPH) nuclear-magnetism phosphorus spectrum.
synthetic example
embodiment 1fire retardant (
η 6 -4-(N-(1-p-hydroxybenzene-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) synthesis of iron hexafluorophosphate FCOPH
Building-up process is shown in following formula:
Add in 250ml round-bottomed flask (
η 6 -chlorobenzene) (
η 5-cyclopentadiene) iron hexafluorophosphate (Fc-Cl) 20g(0.026mol), 4-amino phenol 7g(0.032mol) and, salt of wormwood 10g(0.036mmol), DMF 120ml, (25 DEG C) lucifuge reaction under room temperature, thin-layer chromatography point plate monitoring reaction, until (
η 6 -chlorobenzene) (
η 5 -cyclopentadiene) iron hexafluorophosphate reacts completely.Reactant is poured in cold water, has yellow solid to separate out, leave standstill, filtration under diminished pressure, with ethanol rinse filter cake three times, obtain target compound (
η 6 -amino-diphenylethers) (
η 5 -cyclopentadiene) iron hexafluorophosphate, yellow solid, productive rate: 72%.
Prolong is being housed, is adding in the 250ml there-necked flask of thermometer
(η 6 – amino-diphenylethers) (
η 5 -cyclopentadiene) iron hexafluorophosphate 20g(0.044mol), p-Hydroxybenzaldehyde 5.4g(0.044mmol) and 100mlN, dinethylformamide, lucifuge, stir under 30 DEG C of conditions after 5 hours and add 9.6g(0.044mol) DOPO, thin-layer chromatography point plate monitoring reaction, reaction in 13 hours terminates.Pour in cold water by reaction solution after completion of the reaction, have yellow solid to separate out, leave standstill, decompress filter obtains product (productive rate: 79%).
（KBr）νmax（cm
?1）：844（PF
6 -），921（P-O-C），1236（P=O），1456，1503，1608，1656（Arring），3107（Ar-H），3280（-N-H），3407（-OH）；
1 H-NMR（400MHz，DMSO-
d 6 ）δ：4.99（m，1H，P-C-H），5.08（s，5H，Cp-H），6.09（m，3H，Ar-H），6.24（t，2H，Ar-H），6.73（d，2H，Ar-H），6.81（d，2H，Ar-H），6.96（d，3H，Ar-H），7.09（d，1H，Ar-H），7.24（d，2H，Ar-H），7.35（t，1H，Ar-H），7.49（t，1H，Ar-H），7.61（t，1H，Ar-H），7.81（t，1H，Ar-H），8.04（t，1H，Ar-H），8.21（m，2H，Ar-H），9.47（s，1H，-OH）；
31 P-NMR（400MHz，DMSO-
d 6 ）δ
ppm：28.59；
MS：m/z=626（M+1）
+。
embodiment 2fire retardant (
η 6 -4-(N-(1-phenyl-1-DOPO) methyl) amino-benzene oxygen benzene) (
η 5 -cyclopentadiene) synthesis of iron hexafluorophosphate (FCOP)
Building-up process is shown in following formula:
Prolong is being housed, add in the 250ml there-necked flask of thermometer (
η 6 – amino-diphenylethers) (
η 5 -cyclopentadiene) iron hexafluorophosphate (Fc-NH
2) 20g(0.044mol), phenyl aldehyde 4.7g(0.044mol) and 100mlDMF, lucifuge, stirs under 30 DEG C of conditions after 5 hours and adds 9.6g(0.044mol) DOPO, thin-layer chromatography point plate monitoring reaction, reaction in 13 hours terminates.After completion of the reaction reaction solution is poured in cold water, have yellow solid to separate out, leave standstill, filter and obtain target product (productive rate: 82%).
（KBr）νmax（cm?1）:842（PF
6 -），929（P-O-C），1237（P=O），1456，1477，1503，1607（Arring），3090，（Ar-H）；
1 H-NMR（400MHz，DMSO-
d 6 ）δ：5.08（s，5H，CP-H），5.15（m，1H，P-C-H），6.10（m，3H，Ar-H），6.25（t，2H，Ar-H），6.65（m，1H，Ar-H），6.84（m，2H，Ar-H），6.95（m，2H，Ar-H），7.08（m，1H，Ar-H），7.36（m，4H，Ar-H），7.45（m，3H，Ar-H），7.63（m，1H，Ar-H），7.83（m，1H，Ar-H），8.05（m，1H，Ar-H），8.22（m，2H，Ar-H）；
31 P-NMR（400MHz，DMSO-
d 6 ）δ
ppm：33.32；
MS：m/z=610（M+1）
+。
embodiment 3fire retardant (
η 6 -4-(1-(4-hydroxyanilino)-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) synthesis of iron hexafluorophosphate (FCPH)
Building-up process is shown in following formula:
50g(0.13mol is added in 500ml round-bottomed flask) (
η 6 -chlorobenzene) (
η 5 -cyclopentadiene) iron hexafluorophosphate, 22.5g(0.15mol) 4-aldehyde radical phenylo boric acid, 2mol L ￣
1wet chemical 100ml, tetrahydrofuran (THF) 200ml, tetra-triphenylphosphine palladium 0.3g, nitrogen protection, reflux under the condition of lucifuge.Thin-layer chromatography monitoring reaction, 12h reaction is complete.After cooling, cross and filter insoluble impurity, wash organic phase with water three times, retain organic phase, concentrated, in the solvent after concentrated, add methyl tertiary butyl ether, have a large amount of yellow solid to separate out, filtration obtains product, (
η 6 – 4-aldehyde radical biphenyl) (
η 5 -cyclopentadiene) iron hexafluorophosphate (Fc-CHO), productive rate 87%.
20g(0.044mol is added in 250ml round-bottomed flask) (
η 6 – 4-aldehyde radical biphenyl) (
η 5 -cyclopentadiene) iron hexafluorophosphate (Fc-CHO); 4.8g(0.044mol) 4-amino phenol; add 150ml dissolve with methanol, nitrogen protection, 50 DEG C of lucifuge reactions; 9.6g(0.044mol is added after reaction 5h) DOPO; thin-layer chromatography point plate monitoring reaction, react completely after 8h, product is precipitated out from solution; filter, obtain target product (productive rate: 86%).
（KBr）νmax（cm
?1）：843（PF
6 -），928（P-O-C），1232（P=O），1458，1477，1512，1651（Arring），3103（Ar-H），3419（-OH）；
1 H-NMR（400MHz，DMSO-
d 6 ）δ：5.05（s，5H，CP-H），5.68（m，1H，P-C-H），6.44（d，3H），6.54（t，2H），6.62（d，2H），6.81（d，2H），7.22（d，1H）7.35（t，1H），7.47（m，2H），7.70（d，2H），7.78（t，1H），7.91（d，3H），8.24（m，2H），8.50（s，1H，-O-H）；
31 P-NMR（400MHz，DMSO-
d 6 ）δ
ppm：31.68；
MS：m/z=610（M+1）
+。
embodiment 4fire retardant (
η 6 -4-(1-phenylamino-1-DOPO) methyl diphenyl) (
η 5 -cyclopentadiene) synthesis of iron hexafluorophosphate (FCP)
Building-up process is shown in following formula:
20g(0.044mol is added in 250ml round-bottomed flask) (
η 6 -4-aldehyde radical biphenyl) (
η 5 -cyclopentadiene) iron hexafluorophosphate (Fc-CHO); 4.1g(0.044mol) aniline; add 150ml dissolve with methanol, nitrogen protection, 50 DEG C of lucifuge reactions; 9.6g(0.044mol is added after reaction 5h) DOPO; thin-layer chromatography point plate monitoring reaction, react completely after 8h, product is precipitated out from solution; filter, obtain target product (productive rate: 83%).
（KBr）νmax（cm
?1）：842（PF
6 -），927（P-O-C），1229（P=O），1458，1478，1499，1600（Arring），3103（Ar-H）；
1 H-NMR（400MHz，DMSO-
d 6 ）δ：5.06（s，5H，Cp-H），5.33（m，1H，P-C-H），6.45（d，2H），6.54（t，3H），6.76（d，2H），6.81（d，2H），6.96（m，3H），7.11（m，1H），7.36（m，1H），7.50（m，1H），7.62（d，2H），7.82（m，1H），7.91（d，2H），8.09（m，1H），8.23（m，2H）；
31 P-NMR（400MHz，DMSO-
d 6 ）δ
ppm：28.40；
MS：m/z=594（M+1）
+。
embodiment 5the flame retardant resistance of epoxy acrylic resin system
At high voltage mercury lamp (λ for the test bars of flame retardant resistance in the present invention
max=365nm, I=1mW cm
-2) under irradiation by prepare under carrying out thermofixation after light-initiated solidification again.Light trigger is luxuriant molysite (Fc-P) FCOPH, FCOP, FCPH, FCP containing phosphorus, nitrogen element that four kinds of above-mentioned preparation have flame retardant properties.Selected resin system is epoxy FRP pipe, and the structural formula of epoxy FRP pipe is as follows:
The mensuration of oxygen index (LOI) uses instrument to be JF-3 type oxygen index instrument, and according to GB/T2406-1993, content is tested, and batten is of a size of 100mm × 6.5mm × 3mm.
The luxuriant molysite fire retardant (Fc-P) containing phosphorus, nitrogen element of 1wt% and excessive N-Methyl pyrrolidone are joined in epoxy FRP pipe, after mixing, the liquid mixture of gained is poured in molding jig, after using high voltage mercury lamp radiation 10min, take out, cured article is obtained required batten size after polishing, obtains four kinds of solidifying products EA-FCOPH, EA-FCOP, EA-FCPH, EA-FCP respectively.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, and data list in table 1.Sample after obtained solidification is carried out oxygen index test, and data list in table 2.
simultaneous test: in epoxy FRP pipe, add conventional free radical photo-initiation 2,4,6-trimethylbenzoy-dipheny phosphine oxide (TPO) 1wt%, test as a comparison.According to the batten of the fixed measure of the method in embodiment 5, obtaining content is solidifying product EA-TPO.Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, and data list in table 1.Sample after obtained solidification is carried out oxygen index test, and data list in table 2.
As can be seen from Table 1 and Table 2, for sample EA-FCPH, system oxygen index reaches 25.2, and the heat decomposition temperature of corresponding weightless 10wt% is 408 DEG C, and carbon left is 16.59%.Indices is apparently higher than simultaneous test gained solidifying product EA-TPO.
Table 1EA-FCOPH, EA-FCOP, EA-FCPH and EA-FCP system Thermal Decomposition Data
Table 2EA-FCOPH, EA-FCOP, EA-FCPH and EA-FCP system flame retardant properties test result
embodiment 6the flame retardant resistance of epoxy-resin systems
Selected resin system is respectively epoxy FRP pipe and epoxy prepolymer E-51.The structural formula of epoxy FRP pipe and epoxy prepolymer E-51 is as follows:
The luxuriant molysite fire retardant Fc-P containing phosphorus, nitrogen element of 1wt% and diaryl group iodized salt are added in epoxy prepolymer E-51, Fc-P is respectively above-mentioned obtained FCOPH, FCOP, FCPH, FCP, after heating is fully uniformly mixed, maintains this temperature under lucifuge condition and be stirred to light trigger and all dissolve.The liquid mixture of gained is poured in molding jig, after using high voltage mercury lamp radiation 30min, take out, be heated to 120 DEG C of post curing treatment in an oven, cured article is polished into batten size, obtains respectively solidifying rear resin EP-FCOPH, EP-FCOP, EP-FCPH, EP-FCP.
Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, and data list in table 3.Sample after obtained solidification is carried out oxygen index test, and data list in table 4.
simultaneous test: add 4 of 3wt% in the epoxy, 4 ˊ-3,5-dimethylphenyl salt compounded of iodine hexafluorophosphate (IMO) and add 4 of 3wt% in the epoxy, the I-261 two groups experiment of 4 ˊ-3,5-dimethylphenyl salt compounded of iodine hexafluorophosphate (IMO) and 1wt% is tested as a comparison, prepare batten according to the method for embodiment 6, obtain solidifying product EP-IMO and EP-I-261.Sample after obtained solidification is measured heat decomposition temperature and remaining carbon by thermal analyzer, and data list in table 3.Sample after obtained solidification is carried out oxygen index test, and data list in table 4.
As can be seen from table 3 and table 4, for sample EP-FCPH, system oxygen index reaches 21.5, and the heat decomposition temperature of corresponding weightless 10wt% is 390 DEG C, and carbon left is 18.31%.Indices is better than simultaneous test gained solidifying product EP-IMO and EP-I-261.
The Thermal Decomposition Data of table 3EP-FCOPH, EP-FCOP, EP-FCPH and FP-FCP system
Table 4EP-FCOPH, EP-FCOP, EP-FCPH and EP-FCP system flame retardant properties test result
Claims (8)
1. a class contains the luxuriant molysite of phosphorus, nitrogen element, it is characterized in that this contain phosphorus, the luxuriant molysite general structure (I) of nitrogen element or (II) as follows:
Wherein R
1, R
2, R
3be selected from :-H ,-R ', phenyl, halogen ,-OH ,-OR ', the R ' of halo ,-R ' COO-or-R ' CONHR, wherein R ' be C1-12 alkyl or alkylidene group, R is the alkyl of C1-12;
Ar is selected from benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, alkyl anthracene, carbazole or N-alkyl carbazole.
2. the synthetic method with the luxuriant molysite fire retardant containing phosphorus, nitrogen element of structure formula I according to claims 1, it is characterized in that this synthetic method is carried out according to the following steps: react with the luxuriant molysite of chlorobenzene with the phenol of amino, the luxuriant molysite of generating structure formula III; By the luxuriant molysite of the luxuriant molysite of structure formula III and aryl aldehyde reaction generating structure formula IV; The luxuriant molysite of structure formula IV and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are reacted the luxuriant molysite containing phosphorus, nitrogen element of generating structure formula I;
Wherein R
1, R
3with the definition of Ar as claimed in claim 1.
3. there is the synthetic method of the luxuriant molysite fire retardant containing phosphorus, nitrogen element of structure formula II as claimed in claim 1, it is characterized in that this synthetic method is carried out according to the following steps: with the luxuriant molysite of chlorobenzene and the aromatic yl acid reaction with aldehyde radical, the luxuriant molysite of generating structure formula (V); The luxuriant molysite of structural formula (V) and arylamines are reacted the luxuriant molysite of generating structure formula VI; The luxuriant molysite of structure formula VI and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are reacted the luxuriant molysite containing phosphorus, nitrogen element of generating structure formula II;
Wherein R
1, R
3with the definition of Ar as claimed in claim 1.
4. according to claim 1 containing phosphorus, nitrogen element luxuriant molysite in epoxy resin, acrylate resin and methacrylate resin as the purposes of fire retardant.
5. there is a photo curable epoxy-resin systems for flame retardant resistance, it is characterized in that the luxuriant molysite containing phosphorus, nitrogen element used in this epoxy-resin systems described in claim 1, and mass percentage be composed as follows:
Luxuriant molysite containing phosphorus, nitrogen element: 0.5%-10%;
Cationic photoinitiator: 0%-5%;
Epoxy resin: 70-95%;
Reactive thinner: 4.5-30%.
6. the photo curable epoxy-resin systems with flame retardant resistance according to claim 5, is characterized in that epoxy resin used comprises alicyclic type epoxy resin, bisphenol A type epoxy resin and phenol aldehyde type epoxy resin; Reactive thinner used comprises alicyclic ring type epoxy monomer and lard type epoxy monomer; Cationic photoinitiator used comprises diaryl group iodized salt and triaryl sulfonium salts.
7. there is a photo curable acrylate resin system for flame retardant resistance, it is characterized in that this acrylate resin system uses the luxuriant molysite containing phosphorus, nitrogen element described in claim 1, and mass percentage be composed as follows:
Luxuriant molysite containing phosphorus, nitrogen element: 0.5%-10%;
Acrylate resin: 70-95%;
N-Methyl pyrrolidone: 0.5%-5%;
Reactive thinner: 4.5-30%.
8. the acrylate resin system with flame retardant resistance according to claim 7, is characterized in that acrylate resin used comprises acrylate resin and methacrylate resin; Reactive thinner used comprises acrylate monomer and methacrylate monomer.
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| CN106832416A (en) * | 2016-12-20 | 2017-06-13 | 衢州普信新材料有限公司 | A kind of preparation method of siliceous APP |
| CN107573799A (en) * | 2017-09-22 | 2018-01-12 | 陈晨特 | A kind of phosphorus nitrogen cooperates with self-flame-retardant environment friendly wood coatings |
| CN110511247A (en) * | 2019-08-05 | 2019-11-29 | 厦门大学 | A kind of phosphorous, hydridization activated monomer in transition metal ions synthetic method |
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| CN106832416A (en) * | 2016-12-20 | 2017-06-13 | 衢州普信新材料有限公司 | A kind of preparation method of siliceous APP |
| CN107573799A (en) * | 2017-09-22 | 2018-01-12 | 陈晨特 | A kind of phosphorus nitrogen cooperates with self-flame-retardant environment friendly wood coatings |
| CN110511247A (en) * | 2019-08-05 | 2019-11-29 | 厦门大学 | A kind of phosphorous, hydridization activated monomer in transition metal ions synthetic method |
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| CN105295092B (en) | 2018-06-26 |
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