CN101220153A - Production method for dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor - Google Patents
Production method for dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor Download PDFInfo
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- CN101220153A CN101220153A CNA2007101153199A CN200710115319A CN101220153A CN 101220153 A CN101220153 A CN 101220153A CN A2007101153199 A CNA2007101153199 A CN A2007101153199A CN 200710115319 A CN200710115319 A CN 200710115319A CN 101220153 A CN101220153 A CN 101220153A
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Abstract
The invention discloses a method for preparing diphenol type phosphor-containing high flameproofing benzene-oxaxine resin, which uses monoamine, phosphor-containing diphenol formaldehyde as raw reaction materials. A benzene-oxaxine midbody is introduced with a compound containing phosphor to synthesize a phosphor-containing flameproofing benzene-oxaxine midbody which is solidified and crosslinked to obtain thermalsetting phosphor-containing high flameproofing benzene-oxaxine resin. Other fire retardants are not required to be added into the flameproofing materials which adopt the phosphor-containing flameproofing benzene-oxaxine resin of the invention as the basic flameproofing material; the flameproofing material using the resin has excellent flameproofing capacity, the flameproofing level can reach V-0, the thermal capacity is rather good and the vitrification transforming temperature can reach 225 DEG C. The phosphor-containing flameproofing benzene-oxaxine midbody which is prepared by the method of the invention can be individually used or used by being mixed with other type benzene-oxaxine midbody or phenolic resin or epoxy resin; an obtained solidified product has higher thermal resistance, and the phosphor-containing flameproofing benzene-oxaxine midbody is applicable to the production of structural material, flameproofing material, electric insulation material, electronic encapsulation material, ablation resistance material or braking material with high capacities which are used at the temperature higher than 180 DEG C.
Description
Technical field
The invention belongs to the thermosetting resin preparing technical field, relate in particular to a kind of preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor.
Background technology
Benzoxazine be a class by phenolic compound, aminated compounds and formaldehyde by polycondensation synthetic 6-membered heterocyclic compound, in the Mannich reaction, find at first, ring-opening polymerization under heating or catalyst action generates the reticulated structure of nitrogenous and similar resol.Benzoxazine colophony is as a kind of novel resol, it not only has thermal characteristics, mechanical property, the electric property of traditional resol, and has excellent processing characteristics: in the shaping solidification process, do not discharge small molecules, volume shrinks near zero, therefore causes people's extensive studies interest.
Since the seventies, carried out preliminary research with regard to the ring-opening polymerization and the goods exploitation of Dui benzoxazine abroad.1973, fritz Schreiber in German Patent 2217099 " Phenolic resin as electric insulator " reported first the ring-opening polymerization of benzoxazine compound, and by benzoxazine compound and Resins, epoxy together the impregnate paper thermofixation prepared the electrical apparatus insulation material.Yet not the mechanism of Dui benzoxazine ring-opening reaction etc. is not more goed deep into systematic research in this piece patent of Schreiber.1985, Riess etc. were at " Advances in Polymer Synthesis, Polymer Science ﹠amp; Technology " studied the ring-opening polymerization of simple function group benzoxazine compound in the book, find only to obtain low-molecular-weight phenolic structure.After the nineties, both at home and abroad extensive studies has just been carried out in synthetic, the ring-opening polymerization of Dui benzoxazine intermediate and aspects such as structure and property relationship, applies for a patent several 80 remainders that reach.
In the research of Dui benzoxazine, the high performance of benzoxazine colophony is the focus of research always.For example, in molecule, introduce thermostability and the second-order transition temperature that rigidity functional group or other polymerizable groups can improve cured resin.Calendar year 2001, Tarek Agag etc. are at " Novel Benzoxazine Monomers Containing p-Phenyl Propargyl Ether:Polymerization of Monomers and properties of Polybenzoxazines " [Macromoleculars, 34,7257-7263 (2001)] synthesized the benzoxazine monomer that contains propargyl ether in the article, solidify and obtained benzoxazine colophony.Compare with traditional benzoxazine colophony that does not contain propargyl ether, the cross-linking density of this resinoid and hardness increase, and second-order transition temperature (251-318 ℃) has improved 100-140 ℃, and 5% weightless temperature has improved 20-40 ℃, and carbon yield has improved 22-29%.In addition, by forming the thermal characteristics that polymkeric substance, high polymer alloy or benzoxazinyl organic-inorganic nano composite material etc. also can significantly improve benzoxazine colophony with other polymer.2005, Yuan-Jyh Lee etc. are at " Synthesis and Characterizations of a Vinyl-Terminated Benzoxazine Monomer and lts BlendingWith polyhedral Oligomeric Silsesquioxane (POSS) " [Polymer, 46,2320-2330 (2005)] successfully prepared Polybenzoxazine/polyhedral oligomeric silsesquioxane (POSS) Organic in the article.Studies show that, introduce the second-order transition temperature (333 ℃) that POSS can significantly improve resin, and thermal degradation temperature (T
D5=355 ℃) and carbon yield (52%) also obviously be improved.
The research of previous Dui benzoxazine colophony mainly concentrates on syntheticly has the resin of high Tg to pursue resistance toheat, in recent years because the development of electronic industry, arithmetic speed is more and more faster, more and more higher to the IC printed board performance demands, press for the resin that not only has high heat resistance but also need have high flame retardant.Therefore the research of flame retardant type Polybenzoxazine resin causes people's very big attention.Halide-containing is effective fire retardant, but halide-containing can produce toxic gas in combustion processes.Contain the halogenation fire retardant for fear of use, people have been developed in macromolecular material and to have been introduced P contained compound to improve the method for flame retardant resistance.2004, M.A.Espinosa etc. are at " Development of Novel Flame-Retardant Thermosets Basedon Benzoxazine-Pjenolic Resins and a Glycidyl Phosphinate " [Journal of Polymer Science Part A:Polymer Chemistry, 42,279-289, (2004)] middle with phenolic resin modified benzoxazine colophony and the copolymerization of phosphorated epoxy compounds glycidyl phosphite, the multipolymer that obtains has high glass-transition temperature and thermostability, but also is the good flame material.Subsequently, M.A.Espinosa etc. are again at " Novel Phosphorilated Flame Retardant Thermosets:Epoxy-Benzoxazine-Novolac Systems " [Polymer, 45,6103-6109,2004) with phenolic resin modified Polybenzoxazine resin and isobutyl-two (Racemic glycidol n-butyl ether) phosphorous oxides copolymerization (Scheme 1), the gained cured product also has very high thermal characteristics and flame retardant properties in the article].2006, " Synthesis and Properties ofFlame-Retardant Benzoxazines by Three Approaches " [Journal of Polymer Science Part A:PolymerChemistry such as Ching Hsuan Lin, 44,3454-3468, (2006)] adopt benzoxazine monomer and P contained compound copolymerization (Scheme 2) to prepare the benzoxazine colophony of high flame resistance.
Above-mentioned fire-retardant benzoxazine colophony all obtains by adopting P contained compound Dui benzoxazine colophony to carry out chemical modification.Yet, the benzoxazine colophony that does not appear in the newspapers so far and self contain phosphorus and do not need to carry out modification, our design is a reaction raw materials with monoamine, phosphorous dihydric phenol and formaldehyde, synthetic high benzoxazine intermediate and the high fire-retardancy benzoxazine resin of phosphorus content.
Polybenzoxazine resin and isobutyl-two (Racemic glycidol n-butyl ether) phosphorous oxides copolyreaction that Scheme 1 is phenolic resin modified
Scheme 2 benzoxazine monomers and P contained compound copolyreaction
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of preparation method of novel dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor, do not need to add fire retardant in addition based on the fire retardant material of this resin, have good flame retardant resistance and thermal characteristics.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor is characterized in that: its processing step is,
The formalin or Paraformaldehyde 96 and the phosphorous monoamine compound of 2-20 weight part that in the solvent of 50-90 weight part, add the 35%-40% of 20-30 weight part, control reaction temperature is no more than 30 ℃, and to regulate pH value with triethylamine be 7-8, generates N-dihydroxymethyl compound and also keep it to stablize in solution;
The phosphorous dihydric phenolic compounds that adds the 10-50 weight part then, be warmed up to backflow, mixing solutions reacts 5h-6h down in reflux temperature, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups;
Gained solution is precipitated with fat-soluble solvent, cross the NaHCO of filtered product with 1N
3Solution washing 3-5 time, underpressure distillation removes and desolvates, and vacuum-drying gets phosphor-containing flame-proof benzoxazine intermediate; Pour the benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The preparation method of above-mentioned benzoxazine colophony, preferred processing step is:
The formalin or Paraformaldehyde 96 and the 4-17 weight part monoamine compound that in the solvent of 65-80 weight part, add the 35%-40% of 23-27 weight part, control reaction temperature is no more than 30 ℃, and to regulate pH value with triethylamine be 7.2-7.8, generates N-dihydroxymethyl compound and also keep it to stablize in solution; The phosphorous dihydric phenolic compounds that adds the 20-40 weight part then, be warmed up to backflow, mixing solutions reacts 5h down in reflux temperature, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups; Gained solution is precipitated with fat-soluble solvent, cross the NaHCO of filtered product with 1N
3Solution washing 3-4 time, underpressure distillation removes and desolvates, and vacuum-drying must contain the benzoxazine intermediate of active function groups; Pour the benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The chemical equation of above-mentioned phosphor-containing flame-proof benzoxazine intermediate preparation is as follows:
Wherein:
Among the preparation method of above-mentioned phosphor-containing flame-proof benzoxazine colophony: described solvent is at least a in dioxane, ethanol, chloroform, toluene and the dimethylbenzene.
Wherein: a kind of in the preferred dioxane of described solvent, the chloroform.
Among the preparation method of above-mentioned phosphor-containing flame-proof benzoxazine colophony: described dihydric phenol be 2 (4-hydroxy phenyl) phosphorous oxides, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound and 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10 oxide compound any.
Among the preparation method of above-mentioned phosphor-containing flame-proof benzoxazine colophony: described fat-soluble solvent is methyl alcohol or ethanol.
Table 1 is with regard to high fire-retardancy benzoxazine resin containing phosphor of the present invention and the thermal characteristics and the flame retardant resistance of phosphorated diamin type Polybenzoxazine resin do not compare.Compare with phosphorated benzoxazine colophony not, high fire-retardancy benzoxazine resin containing phosphor of the present invention has excellent second-order transition temperature, carbon yield and oxygen index.Especially oxygen index is greater than 35, and fire-retardant rank reaches the V-0 level.
The phosphorous benzoxazine colophony of table 1 is not with the thermal characteristics and the oxygen index of phosphorous benzoxazine colophony compare
| Sample | T g (℃) | 5% thermal weight loss temperature (℃) | Carbon yield (800 ℃ of %at) | Oxygen index | ||
| N 2 | Air | N 2 | Air | |||
| The not phosphorous benzoxazine colophony of phosphorous benzoxazine colophony | 225 195 | 287 329 | 293 366 | 47 47 | 24 0(at 626℃) | 37.9 27.5 |
The preparation method of phosphor-containing flame-proof benzoxazine colophony of the present invention has following effect or advantage:
(1) contains phosphorus compound in the novel flame-retardant benzoxazine intermediate of the present invention, do not need to add in addition fire retardant and just have good flame retardancy.
(2) the phosphor-containing flame-proof benzoxazine colophony of the inventive method preparation not only has good flame retardancy, but also has good thermal characteristics.
The phosphor-containing flame-proof benzoxazine intermediate of the inventive method preparation can use separately or mix use with the benzoxazine intermediate of other types or resol or Resins, epoxy, resulting cured article has higher thermotolerance, is applicable to make high performance structures material, fire retardant material, electrically insulating material, electronic package material, ablation resistant material or the brake material that uses more than 180 ℃.
Embodiment
Below by embodiment the present invention is specifically described, be necessary to be pointed out that at this: present embodiment only is used for the present invention is further specified, but does not limit to its scope.This area professional is conspicuous in the various improvement of having done without prejudice to essence of the present invention after reading the present invention, all belongs to the claimed scope of the present invention.
Embodiment 1
Synthesizing of 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester.
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 75ml chloroform, 0.7g triethylamine and 24ml35% formalin successively, stir miscible.Slowly add 13.4g aniline, control reaction temperature is no more than 30 ℃, is 7 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 25.7g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 87%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 2
Synthesizing of 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester.
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 90ml chloroform, 0.84g triethylamine and 28.8ml40% formalin successively, stir miscible.Slowly add 16.1g aniline, control reaction temperature is no more than 30 ℃, is 8 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 30.8g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing four times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 85%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 3
Synthesizing of 6,6 '-2 (3-methyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester.
With methylamine, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 75ml chloroform, 0.7g triethylamine and 24ml36% formalin successively, stir miscible.Slowly add the 4.5g methylamine, control reaction temperature is no more than 30 ℃, is 7.5 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 25.7g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing five times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-methyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 78%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 4
6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyls)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound synthetic.
With aniline, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound and formaldehyde are the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
The formalin that adds 75ml chloroform, 0.7g triethylamine and 24ml37% in having the 250ml there-necked flask of agitator and prolong successively stirs miscible.Slowly add 13.4g aniline, control reaction temperature is no more than 30 ℃, is 7.6 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Reaction add again behind the 15min 22.7g10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the orange-yellow oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1, the 3-benzoxazinyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, productive rate 76%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 5
6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyls)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound synthetic.
With aniline, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound and formaldehyde are the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 90ml chloroform, 0.84g triethylamine and 28.8ml38% formalin successively, stir miscible.Slowly add 16.1g aniline, control reaction temperature is no more than 30 ℃, is 7.6 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Reaction add again behind the 15min 27.2g10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the orange-yellow oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1, the 3-benzoxazinyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, productive rate 78%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 6
6,6 '-2 (3-methyl-3,4-dihydro-2H-1,3-benzoxazinyls)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound synthetic.
With aniline, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10 oxide compound and formaldehyde are the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 75ml chloroform, 0.7g triethylamine and 24ml40% formalin successively, stir miscible.Slowly add the 4.5g methylamine, control reaction temperature is no more than 30 ℃, is 7.8 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Reaction add again behind the 15min 22.7g10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the orange-yellow oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times obtains i.e. 6,6 '-2 (3-methyl-3,4-dihydro-2H-1, the 3-benzoxazinyls)-9 of white powder after underpressure distillation and the vacuum-drying, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound, productive rate 78%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 7
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 50ml chloroform, 0.7g triethylamine and 24ml35% formalin successively, stir miscible.Slowly add 2g aniline, control reaction temperature is no more than 30 ℃, is 7 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 10g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 5h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 87%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Embodiment 8
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 90ml chloroform, 0.7g triethylamine and 24ml40% formalin successively, stir miscible.Slowly add 20g aniline, control reaction temperature is no more than 30 ℃, is 8 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 50g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 6h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 87%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
Embodiment 9:
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 65ml chloroform, 0.7g triethylamine and 23ml35% formalin successively, stir miscible.Slowly add 4g aniline, control reaction temperature is no more than 30 ℃, is 7.2 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 20g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 6h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing three times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 87%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
Embodiment 10:
With aniline, 2 (4-hydroxy phenyl) phosphorous oxides and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof,
In having the 250ml there-necked flask of agitator and prolong, add 80ml chloroform, 0.7g triethylamine and 27ml40% formalin successively, stir miscible.Slowly add 17g aniline, control reaction temperature is no more than 30 ℃, is 7.8 by triethylamine control pH value, generates N-dihydroxymethyl compound and keeps it stable in solution;
Add 40g2 (4-hydroxy phenyl) phosphorous oxides again behind the reaction 15min, be warmed up to backflow, mixing solutions is stopped reaction after reflux temperature reacts 6h down, make generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups, it is the lurid oil phase of lower floor, the branch phase system of upper strata water white transparency water.
Reaction product poured in excessive fat-soluble solvent methyl alcohol or the ethanol precipitate, cross the NaHCO of filtered product with 1N
3Solution washing four times, the benzoxazine intermediate white powder that obtains containing active function groups after underpressure distillation and the vacuum-drying i.e. 6,6 '-2 (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) phenyl phosphate ester, productive rate 87%.
Pour above-mentioned benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
The also available methylamine of aniline among the present invention or other monoamine substitute, the also available 10-of 2 (4-hydroxy phenyl) phosphorous oxides (2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound or 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10 oxide compound or other phosphorous dihydric phenol substitute.Chloroform also can adopt a kind of the substituting in dioxane, ethanol, toluene and the dimethylbenzene.
Claims (6)
1. the preparation method of a dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor is characterized in that: its processing step is,
With monoamine, phosphorous dihydric phenol and formaldehyde is the preparation technology of synthetic benzoxazine intermediate of raw material and resin thereof:
The formalin or Paraformaldehyde 96 and the 2-20 weight part monoamine compound that in the solvent of 50-90 weight part, add the 35%-40% of 20-30 weight part, control reaction temperature is no more than 30 ℃, and to regulate pH value with triethylamine be 7-8, generates N-dihydroxymethyl compound and also keep it to stablize in solution;
The phosphorous dihydric phenolic compounds that adds the 10-50 weight part then, be warmed up to backflow, mixing solutions reacts 5h-6h down in reflux temperature, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups;
Gained solution is precipitated with fat-soluble solvent, cross the NaHCO of filtered product with 1N
3Solution washing 3-5 time, underpressure distillation removes and desolvates, and vacuum-drying gets phosphor-containing flame-proof benzoxazine intermediate; Pour the benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
2. the preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor according to claim 1, it is characterized in that: its processing step is:
The formalin or Paraformaldehyde 96 and the 4-17 weight part monoamine compound that in the solvent of 65-80 weight part, add the 35%-40% of 23-27 weight part, control reaction temperature is no more than 30 ℃, and to regulate pH value with triethylamine be 7.2-7.8, generates N-dihydroxymethyl compound and also keep it to stablize in solution;
The phosphorous dihydric phenolic compounds that adds the 20-40 weight part then, be warmed up to backflow, mixing solutions reacts 5h down in reflux temperature, makes generation condensation reaction in ortho position on N-dihydroxymethyl compound and phenolic hydroxyl group and the phenyl ring thereof, and dehydration closed-loop generates the benzoxazine midbody solution that contains active function groups;
Gained solution is precipitated with fat-soluble solvent, cross the NaHCO of filtered product with 1N
3Solution washing 3-4 time, underpressure distillation removes and desolvates, and vacuum-drying must contain the benzoxazine intermediate of active function groups; Pour the benzoxazine intermediate into the rectangular aluminum mould, segmentation curing obtains heat cured phosphor-containing flame-proof benzoxazine colophony in Constant Temp. Oven; Solidifying temperature-rise period is: 100 ℃/2h, and 140 ℃/2h, 180 ℃/2h, 220 ℃/2h, 260 ℃/2h.
3. according to the preparation method of claim 1 or 2 described dihydric phenol type high fire-retardancy benzoxazine resin containing phosphors, it is characterized in that: described solvent is a kind of in dioxane, ethanol, chloroform, toluene and the dimethylbenzene.
4. the preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor according to claim 3 is characterized in that: described solvent is a kind of in dioxane, the chloroform.
5. the preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor according to claim 1 and 2, it is characterized in that: described dihydric phenol be 2 (4-hydroxy phenyl) phosphorous oxides, 10-(2 ', 5 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10 oxide compound and 10,10 '-2 (4 ', 4 '-dihydroxy phenyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10 oxide compound any.
6. the preparation method of dihydric phenol type high fire-retardancy benzoxazine resin containing phosphor according to claim 1 and 2, it is characterized in that: described fat-soluble solvent is methyl alcohol or ethanol.
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| CN115612165B (en) * | 2022-10-19 | 2023-08-22 | 西南石油大学 | Flame-retardant benzoxazine aerogel and preparation method thereof |
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