CN1580108A - Phosphorous compound - Google Patents
Phosphorous compound Download PDFInfo
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- CN1580108A CN1580108A CN 03153173 CN03153173A CN1580108A CN 1580108 A CN1580108 A CN 1580108A CN 03153173 CN03153173 CN 03153173 CN 03153173 A CN03153173 A CN 03153173A CN 1580108 A CN1580108 A CN 1580108A
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Abstract
This invention provides a kind of phosphorus-containing compound demonstrated by the figure (1)and its manufacturing method. All of the definitions of those symbols in the figure are explained in the specification. It includes the phosphorus-containing compound produced by the method after the addition reaction between the organic orbicular phosphorous compound and aromatic aldehyde compound and the condensation reaction between the aromatic compound with active hydrogen and the organic acid as the accelerant. The phosphorus-containing compound in this invention can be used as the hardener of rosin and also can be used to improve the fire performance and thermal endurance of this rosin combination when being used as hardener in the surrounding of fire resistance epoxy resin. It is especially adaptable to producing the printed circuit board of electronic or electric products and rosin combination of multi-layer circuit.
Description
Technical field
The invention relates to a kind of P contained compound and manufacture method thereof, this compound can directly react the formation phosphorous epoxy resin, or is used as the stiffening agent of composition epoxy resin.
Background technology
Resins, epoxy has characteristics such as solvent resistance, physical strength, electric insulation character and dimensional stability, and process easily, be widely used in coating, insulating material, printed wiring laminated plates and electronic package material, building and material of construction, solid and space industry etc.Yet the not good and easy burning of heat-resisting character is the main drawback that Resins, epoxy faces on using.In recent years, flourish along with electronics industry day by day raises to the difficulty combustion and the heat-stable requirement of Resins, epoxy, therefore, how to improve effectively the difficulty combustion of Resins, epoxy and heat-resisting character the target of making great efforts to develop for industry.
The known flame retardancy matter that has many methods to can be used to improve Resins, epoxy wherein more commonly imports incombustible agent in epoxy compounds or its stiffening agent structure; Yet; at present in the method that adopts; major part is that halogen-containing incombustible agent is imported in Resins, epoxy or its stiffening agent; though halogen has obvious effects to pressing down combustion; but can produce and have corrodibility and toxic hydrogen halide; under the consideration of difficulty combustion rules increasingly stringent and environment protection, halogen-containing incombustible agent is disabled gradually.Therefore, the new incombustible agent of exploitation is the important key of present technical development.
Have multinomial research to point out, phosphorus be incombustible agent have that toxicity is lower, processibility is good, addition is few, the amount of being fuming is low and with the compatible advantage such as good of resin, develop into the incombustible agent of a new generation gradually.Phosphorus be incombustible agent in combustion processes, on the one hand impel macromolecular material to carry out dehydration earlier, make the hydrogen of hydrocarbon polymer and airborne oxygen form water, reach difficult effect of firing so as to the temperature that reduces context; On the other hand; under heat, can decompose phosphoric acid; impel the carbonization of macromolecular compound; and formation uninflammability coke layer; simultaneously, the phosphoric acid esterification of at high temperature can further dewatering forms polyphosphoric acid, forms glassy molten mass and cover the combustionmaterial surface to form a protective layer; the release that stops oxygen to enter unburned internal layer of polymer and inhibition volatility lysate, and then stop flame transmission to reach the effect of difficult combustion.
At present the phosphorus containg substances that uses can be divided into the P contained compound that contains the functional group or the P contained compound of general non-response type; Wherein, the thermotolerance of the P contained compound of non-response type is relatively poor, be not suitable for being used for needing high heat-stable composition epoxy resin, and have reactive P contained compound owing to the reason of other molecular binding, and has higher heat-resistant quality, therefore, have reactive P contained compound and become following main flow gradually.
Have now in reactive P contained compound, the most normal user is the P contained compound of straight chain type, this kind have reactive straight chain type P contained compound usually because of on its main chain-the O-P-O-key, cause the general halogen-containing or not halogen-containing composition epoxy resin of its thermotolerance poor; On the other hand, no matter the phosphorated flame-retardant resin composition has straight chain type P contained compound or non-response type P contained compound, the poor in processability of its all more existing brominated composition epoxy resin on using.Therefore, difficult flame retardancy and the thermotolerance of taking into account this resin combination simultaneously.
For effectively improving the flame retardancy of composition epoxy resin, take into account the thermotolerance of this resin combination simultaneously, the inventor finds a kind of new P contained compound and manufacture method thereof after deliberation.This kind P contained compound has the side chain type structure that is different from general existing straight chain type P contained compound, except that forming the phosphorous epoxy resin via reactions such as various additions or epoxidations, also can be directly used in the composition epoxy resin as stiffening agent.Not only can improve the flame retardancy of this resin combination effectively, more can take into account the thermotolerance of this resin combination simultaneously, needing in the high heat-stable composition epoxy resin be particularly suitable for.
Summary of the invention
For overcoming the shortcoming of above-mentioned prior art, a purpose of the present invention provides the P contained compound shown in a kind of formula (I):
In the formula, each symbol definition is as follows.This compound forms the phosphorous resin of flame retardancy except that can be used for, and also can be used as the stiffening agent of difficult combustible epoxy resin composition.
Another object of the present invention provides a kind of method of making this P contained compound, comprise and make organic ring-type phosphorus compound and aromatic aldehyde compounds carry out addition reaction, carry out condensation reaction with organic acid as catalyst and aromatics again, and make P contained compound of the present invention with active hydrogen.
The invention provides a kind of suc as formula the P contained compound shown in (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that constitutes of group such as acid anhydrides, wherein R
4Be hydrogen or alkyl; And Ar
1With Ar
2Be independently selected from:
Wherein, R
2Be selected from the cohort that hydrogen, alkyl, alkoxyl group, nitro, halogen and aryl constitute; R
3For chemical bond or stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2The cohort of-formation; R
1With R
4As above definition; A and b independently are 0 to 6 integer and a+b≤6; C and d independently are 0 to 4 integer and c+d≤4; And z is 1 to 20 integer.
Above-mentioned R
2With R
4Shown alkyl is meant straight chain, side chain or cyclic alkyl, comprising: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, second butyl, tributyl, amyl group, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, isopentyl, second amyl group, 3-methyl-2-butyl, neo-pentyl, hexyl, 4-methyl-2-amyl group, cyclopentyl and cyclohexyl etc.R
3Shown in the alkyl of stretching comprise: stretch methyl, stretch ethyl, stretch propyl group, stretch butyl, stretch amyl group and stretch hexyl etc.R
2Shown in alkoxyl group comprise: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, second butoxy, the 3rd butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, hexyloxy and cyclohexyloxy etc.R
2Shown in aryl, comprising: phenyl, tolyl, xylyl, phenmethyl and naphthyl etc.
The present invention is to carry out addition reaction by reactive organic ring-type phosphorus compound and aromatic aldehyde compounds with monofunctional suc as formula the P contained compound shown in (I), formation has the P contained compound of alcohol radical, utilize organic acid as catalyst again, make have one-OH at least ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides and this P contained compound with alcohol radical carry out condensation reaction.
Above-mentioned example with reactive organic ring-type phosphorus compound of monofunctional is 9 shown in the formula (II), and the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compound:
The aromatic aldehyde compounds that is used to make P contained compound of the present invention has a substituting group at least, and be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Reach the cohorts that group constituted such as acid anhydrides, comprise the benzaldehyde compounds or the naphthaldehyde compounds that are substituted or are unsubstituted.This benzaldehyde compounds can be the phenyl aldehyde compounds shown in the formula (III):
In the formula, R
1, R
2With R
3Definition as above; M is 1 to 5 integer; And n is 0 to 4 integer, and its condition is m+n≤5.
The example of this phenyl aldehyde compounds comprises, but non-being limited to: through alkyl, alkoxyl group, nitro, the hydroxy benzaldehyde that halogen or aryl replace or be unsubstituted, the hydroxymethyl phenyl aldehyde, the hydroxyethyl phenyl aldehyde, hydroxyl isopropyl benzene formaldehyde, carboxyl benzaldehyde, the carboxyl tolyl aldehyde, the carboxy ethyl phenyl aldehyde, carboxyl isopropyl benzene formaldehyde, the amido phenyl aldehyde, the amine tolyl aldehyde, amine ethylbenzene formaldehyde, amido isopropyl benzene formaldehyde, phthalaldehyde, the hydroxybenzene dialdehyde, the carboxyl phthalaldehyde, the amido phthalaldehyde, and the thiophenol that on phenyl ring, has an aldehyde radical at least, hydroxythiophenol, the carboxyl thiophenol, the amido thiophenol, the benzyl thiophenol, hydroxyl benzyl thiophenol, carboxyl benzyl thiophenol, the aminocarbonyl phenylmethyl thiophenol, Phenylsulfonic acid, hydroxy benzenesulfonic acid, the carboxyl Phenylsulfonic acid, the amido Phenylsulfonic acid, benzamide, hydroxybenzamide, the carboxyl benzamide, the amido benzamide, the anilino methyl-formiate, the anilino ethyl formate, isopropyl N-phenyl carbamate, benzene methanamine base methyl-formiate, benzene methanamine base ethyl formate, phthalate anhydride, dihydroxy-benzene, benzene dicarboxylic acid, benzene disulfonic acid, benzene diamide etc.
Also can use the naphthaldehyde compounds to prepare P contained compound of the present invention, the example of this naphthaldehyde compounds comprises, but non-being limited to: through alkyl, alkoxyl group, nitro, the naphthaldehyde that halogen or aryl replace or be unsubstituted, the hydroxyl naphthaldehyde, the methylol naphthaldehyde, the hydroxyethyl naphthaldehyde, hydroxyl isopropyl naphthalene formaldehyde, the carboxyl naphthaldehyde, the carboxymethyl naphthaldehyde, the propyloic naphthaldehyde, carboxyl isopropyl naphthalene formaldehyde, the amido naphthaldehyde, amine methylnaphthalene formaldehyde, amine ethyl naphthalene formaldehyde, amido isopropyl naphthalene formaldehyde, the naphthalene dialdehyde, hydroxyl naphthalene dialdehyde, carboxyl naphthalene dialdehyde, amido naphthalene dialdehyde, and the thionaphthol that on naphthalene nucleus, has an aldehyde radical at least, the hydroxyl thionaphthol, the carboxyl thionaphthol, the amido thionaphthol, the naphthalene methylthio phenol, hydroxyl naphthalene methylthio phenol, carboxyl naphthalene methylthio phenol, amido naphthalene methylthio phenol, naphthene sulfonic acid, croceine acid, the carboxyl naphthene sulfonic acid, the amido naphthene sulfonic acid, naphthoamide, the hydroxyl naphthoamide, the carboxyl naphthoamide, the amido naphthoamide, the naphthylamine base methyl-formiate, the naphthylamine base ethyl formate, the naphthylamine base isopropyl formate, naphthalene methylamino methyl-formiate, the naphthalene methylurethane, naphthalic anhydride, naphthalenediol, naphthalene dicarboxylic acids, naphthalene disulfonic acid, naphthalene diamide etc.
Except that above-mentioned phenyl aldehyde compounds and naphthaldehyde compounds, other aromatic aldehyde compounds that on phenyl ring, has an aldehyde radical at least, also can be used for making P contained compound of the present invention, this examples for compounds comprises, but non-being limited to: biphenyl compound, phenylbenzene alkyl compound, diphenylether compound, diphenylmethyl ketone compounds, diphenylsulfide compounds, diphenyl sulfoxide compounds and the sulfobenzide compounds etc. that on phenyl ring, have an aldehyde radical at least.
The aromatics that can carry out condensation reaction with above-mentioned P contained compound with alcohol radical is as shown in the formula (IV) or the compound (V):
In the formula, R
1, R
2With R
3As above definition; M is 1 to 5 integer; N is 0 to 4 integer, and its condition is m+n≤5; P is 1 to 7 integer; And q is 0 to 6 integer, and its condition is p+q≤7.
Except that formula (IV) with (V) shown in aromatics, also can use have one-OH at least ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent biphenyl compound of acid anhydrides, phenylbenzene alkyl compound, diphenylether compound, diphenylmethyl ketone compounds, diphenylsulfide compounds, diphenyl sulfoxide compounds or sulfobenzide compounds and above-mentioned P contained compound with alcohol radical carry out condensation reaction.
Can carry out the aromatics of condensation reaction to have hydroxyl with P contained compound with alcohol radical, carboxyl or amido person are preferable, the example comprises, but non-being limited to: phenol, phenylcarbinol, phenylethyl alcohol, phenylformic acid, toluylic acid, phthalandione, hydroxy-benzoic acid, aniline, benzene methanamine, amido phenol, the amido Phenylsulfonic acid, amido phenol sulfonic acid, hydroxymethyl aniline, Qiang Yijibenan, the amido phenylformic acid, naphthols, 2, the 6-dihydroxy naphthlene, naphthoic acid, naphthalic acid, naphthylamines, naphthylene diamine, the amido naphthols, the amido naphthene sulfonic acid, the amido sulfonaphthol, the methylol naphthylamines, the hydroxyethyl naphthylamines, the amido naphthoic acid.
Except that above-mentioned aromatics, the 4-xenol, 4,4 '-dihydroxybiphenyl, the 4-carboxyl biphenyl, 4,4 '-dicarboxylate biphenyl, 2, two (4-hydroxy phenyl) propane of 2-, 2-(3-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, two (4-hydroxy phenyl) methane, 2, two (4-carboxyl phenyl) propane of 2-, 2-(3-carboxyl phenyl)-2-(4 '-carboxyl phenyl) propane, two (4-carboxyl phenyl) methane, 4-hydroxyl phenylate, two (2-hydroxybenzene) ether, two (3-hydroxybenzene) ether, two (4-hydroxybenzene) ether, 4-carboxyl phenylate, two (2-carboxyl benzene) ether, two (3-carboxyl benzene) ether, two (4-carboxyl benzene) ether, the 4-dihydroxy benaophenonel, two (2-hydroxybenzene) ketone, two (3-hydroxybenzene) ketone, two (4-hydroxybenzene) ketone, the 4-carboxyl benzophenone, two (2-carboxyl benzene) ketone, two (3-carboxyl benzene) ketone, two (4-carboxyl benzene) ketone, 2-hydroxy-4-methyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethyl benzophenone, 4-carboxyl-2 methyl benzophenone, the 4-aminobenzophenone, 4-hydroxyl diphenyl sulfide, two (2-hydroxybenzene) thioether, two (3-hydroxybenzene) thioether, two (4-hydroxybenzene) thioether, 4-carboxyl diphenyl sulfide, two (2-carboxyl benzene) thioether, two (3-carboxyl benzene) thioether, two (4-carboxyl benzene) thioether, 2-hydroxy-4-methyl diphenyl sulfide, 2-hydroxyl-4-methoxyl group diphenyl sulfide, 2,2 '-dihydroxyl-4,4 '-dimethyl diphenyl sulfide, 4-carboxyl-2-methyldiphenyl thioether, 4-amido diphenyl sulfide, two (2-hydroxybenzene) sulfoxide, two (3-hydroxybenzene) sulfoxide, two (4-hydroxybenzene) sulfoxide, two (2-carboxyl benzene) sulfoxide, two (3-carboxyl benzene) sulfoxide, two (4-carboxyl benzene) sulfoxide, two (2, the 3-dihydroxy-benzene) sulfoxide, two (5-chloro-2, the 3-dihydroxy-benzene) sulfoxide, two (2, the 4-dihydroxy-benzene) sulfoxide, two (2,4-dihydroxyl-6-methylbenzene) sulfoxide, two (5-chloro-2, the 4-dihydroxy-benzene) sulfoxide, two (2, the 5-dihydroxy-benzene) sulfoxide, two (3, the 4-dihydroxy-benzene) sulfoxide, two (3, the 5-dihydroxy-benzene) sulfoxide, two (2,3, the 4-trihydroxybenzene) sulfoxide, two (2,3,4-trihydroxy--6-methylbenzene) sulfoxide, two (5-chloro-2,3, the 4-trihydroxybenzene) sulfoxide, two (2,4, the 6-trihydroxybenzene) sulfoxide, two (5-chloro-2,4, the 6-trihydroxybenzene) sulfoxide, two (2-hydroxybenzene) sulfone, two (3-hydroxybenzene) sulfone, two (4-hydroxybenzene) sulfone, two (2-carboxyl benzene) sulfone, two (3-carboxyl benzene) sulfone, two (4-carboxyl benzene) sulfone, two (2, the 4-dihydroxy-benzene) sulfone, two (3, the 4-dihydroxy-benzene) sulfone, two (3, the 5-dihydroxy-benzene) sulfone, two (3, the 6-dihydroxy-benzene) aromatics such as sulfone and two (3,5-dimethyl-4-hydroxybenzene) sulfone also is suitable for making P contained compound of the present invention.
The organic acid that is used as the catalyst of preparation P contained compound of the present invention can be carboxylic acid or the sulfonic acid that is substituted or is unsubstituted.This organic acid example comprises, but non-being limited to: formic acid, acetate, propionic acid, butyric acid, 2 Methylpropionic acid, valeric acid, 3 Methylbutanoic acid, 2-Methyl Butyric Acid, caproic acid, enanthic acid, sad, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, hydroxyethanoic acid, lactic acid, tartrate, citric acid, oxysuccinic acid, ethylenediamine tetraacetic acid (EDTA), the salicylic acid hexahydrobenzoic acid, 1, the 4-cyclohexane dicarboxylic acid, phenylformic acid, phthalandione, the benzene tricarbonic acid, trifluoromethayl sulfonic acid, ethane sulfonic acid, propane sulfonic acid, Phenylsulfonic acid, benzene disulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid, right-toluenesulphonic acids.
P contained compound of the present invention is to carry out addition reaction by organic ring-type phosphorus compound and the aromatic aldehyde compounds shown in the above-mentioned formula (II), formation has the P contained compound of alcohol radical, in the organic ring-type phosphorus compound shown in 1 mole of formula (II), the consumption of this aromatic aldehyde compounds is 0.7 to 1.3 mole, be preferably 0.8 to 1.2 mole, be more preferred from 0.9 to 1.1 mole; Wherein, there is no particular restriction to carry out the condition of this addition reaction, the temperature of carrying out this reaction generally be with 80 to 160 ℃ preferable, the reaction times is with preferable more than 0.5 hour, just carries out the condition of this addition reaction and can optionally adjust according to its experience by being familiar with this operator.Treat that this addition reaction finishes, form have the P contained compound of alcohol radical after, with organic acid as catalyst, make have one-OH at least ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides and the prepared P contained compound with alcohol radical of addition reaction carry out condensation reaction, can make the present invention suc as formula the P contained compound shown in (I); 1 mole of the P contained compound that makes in above-mentioned addition reaction with alcohol radical, the consumption that is used to carry out the aromatics of condensation reaction is more than 0.8 mole, is preferably more than the l mole, is more preferred from again more than 3.5 to 7 moles; Wherein, there is no particular restriction as the organic acid consumption of catalyst, 0.01 to 5 weight % with the total restatement of reactant is preferable, the condition of this condensation reaction does not have special restriction yet, the temperature of this reaction generally is with preferable more than 90 ℃, with better more than 100 ℃, the reaction times is with preferable more than 2 hours, but those skilled in the art can rule of thumb optionally adjust.
Therefore, the present invention also provides the method for the P contained compound shown in a kind of manufacturing formula (I), this method comprises: (1) makes the organic ring-type phosphorus compound shown in aromatic aldehyde compounds and the formula (II) carry out addition reaction, formation has the P contained compound of alcohol radical, wherein, in the organic ring-type phosphorus compound shown in 1 mole of formula (II), employed this aromatic aldehyde compounds is 0.7 to 1.3 mole; And (2) with organic acid as catalyst, make have one-OH at least ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides and addition reaction make the P contained compound that prosperity has alcohol radical and carry out condensation reaction, wherein, 1 mole of the P contained compound with alcohol radical that makes in above-mentioned addition reaction, employed aromatics is more than 0.8 mole.
Compared with prior art, provided by the invention have the side chain type structure that is different from general existing straight chain type P contained compound suc as formula P contained compound shown in (I) and manufacture method thereof, except that forming the phosphorous epoxy resin, also can be directly used in the composition epoxy resin as stiffening agent via reactions such as various additions or epoxidations.Not only can improve the flame retardancy of this resin combination effectively, more can take into account the thermotolerance of this resin combination simultaneously, needing in the high heat-stable composition epoxy resin be particularly suitable for.
Embodiment
Embodiment 1
With 9 of 216 grams, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compound and 216 gram toluene heating for dissolving and stirring in the glass reaction still, when treating that temperature reaches 110 ℃, add the 4-hydroxy benzaldehyde of 112 grams, reaction lasted more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain having organic ring-type phosphorus compound (9 of alcohol radical, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compound-10-yl)-(4-hydroxy phenyl) methyl alcohol (being designated hereinafter simply as HCAB), fusing point is 212 ℃.
Organic ring-type phosphorus compound HCAB of 338 grams and toluene heating for dissolving in the glass reaction still of 338 grams are also stirred, when treating that temperature reaches 110 ℃, add the phenol of 94 grams and the right-toluenesulphonic acids of 1.6 grams, react and last more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain P contained compound of the present invention (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compound-10-yl)-two (4-hydroxy phenyl) methane (being designated hereinafter simply as HPP), fusing point is 291 ℃.The ultimate analysis of this P contained compound HPP is as follows:
C％ H％ P％
Measured value 72.7% 4.6% 7.4%
Calculated value 72.46% 4.59% 7.49%
(C
25H
19O
4P formula weight=414)
Embodiment 2
With 9 of 216 grams, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 216 gram toluene heating for dissolving and stirring in the glass reaction still, when treating that temperature reaches 110 ℃, adds the 112 4-hydroxy benzaldehydes that restrain, and reaction is more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain having organic ring-type phosphorus compound (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-10-yl)-(4-hydroxy phenyl) methyl alcohol (hereinafter to be referred as HCAB) of alcohol radical, fusing point is 212 ℃.
Organic ring-type phosphorus compound HCAB of 338 grams and toluene heating for dissolving in the glass reaction still of 338 grams are also stirred, when treating that temperature reaches 110 ℃, add the phenol of 94 grams and the oxalic acid of 3.4 grams, react and last more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain P contained compound of the present invention (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compound-10-yl)-two (4-hydroxy phenyl) methane (being designated hereinafter simply as HPP), fusing point is 291 ℃.The ultimate analysis of this P contained compound HPP is as follows:
C％ H％ P％
Measured value 72.7% 4.6% 7.4%
Calculated value 72.46% 4.59% 7.49%
(C
25H
19O
4P formula weight=414)
Embodiment 3
With 216 grams 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound and 216 gram toluene heating for dissolving and stirring in the glass reaction still, when treating that temperature reaches 110 ℃, adds the 112 4-hydroxy benzaldehydes that restrain, and reaction lasted more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain having organic ring-type phosphorus compound HCAB of alcohol radical, fusing point is 212 ℃.
Organic ring-type phosphorus compound HCAB of 338 grams and toluene heating for dissolving in the glass reaction still of 338 grams are also stirred, when treating that temperature reaches 110 ℃, add the neighbour-cresols of 108 grams and the right-toluenesulphonic acids of 1.6 grams, react and last more than 3 hours.After treating that temperature is cooled to room temperature, filter and drying, obtain P contained compound of the present invention (9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound-10-yl)-(4-hydroxy phenyl)-(4-hydroxyl-2-tolyl) methane (being designated hereinafter simply as HPC), fusing point is 245 ℃.
Claims (21)
1. the P contained compound shown in the formula (I):
In the formula, R
1Be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Reach the cohorts that group constituted such as acid anhydrides, wherein R
4Be hydrogen or alkyl; And Ar
1With Ar
2Be independently selected from:
It is characterized in that R
2Be selected from the cohort that hydrogen, alkyl, alkoxyl group, nitro, halogen and aryl constitute; R
3For chemical bond or stretch alkyl; R
5Be selected from chemical bond ,-CR
2R
4-,-O-,-CO-,-S-,-SO-and-SO
2-the cohort that constituted; R
1With R
4As above definition; A and b independently are 0 to 6 integer and a+b≤6; C and d independently are 0 to 4 integer and c+d≤4; And z is 1 to 20 integer.
2. P contained compound as claimed in claim 1 is characterized in that Ar
1With Ar
2For stretching phenyl.
3. P contained compound as claimed in claim 1 is characterized in that R
1Be selected from-OH ,-COOH and-NH
2The cohort that is constituted.
4. P contained compound as claimed in claim 1, it is characterized in that, this compound is to carry out addition reaction by organic ring-type phosphorus compound and aromatic aldehyde compounds, carrying out condensation reaction with aromatics again makes, this aromatics has a substituting group at least, and be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the cohort that acid anhydrides constituted.
5. P contained compound as claimed in claim 4 is characterized in that, this organic ring-type phosphorus compound is 9, and the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound.
6. P contained compound as claimed in claim 4 is characterized in that, this aromatic aldehyde compounds is suc as formula the phenyl aldehyde compounds shown in (III):
In the formula, R
1, R
2, R
3, m and n definition as above.
7. P contained compound as claimed in claim 6, it is characterized in that this phenyl aldehyde compounds is selected from the cohort that hydroxy benzaldehyde, carboxyl benzaldehyde, carboxyl tolyl aldehyde, carboxy ethyl phenyl aldehyde, dicarboxyl phenyl aldehyde, amido phenyl aldehyde, aminomethyl phenyl aldehyde and amido ethylbenzene formaldehyde are constituted.
8. P contained compound as claimed in claim 6 is characterized in that, this phenyl aldehyde compounds is the 4-hydroxy benzaldehyde.
9. P contained compound as claimed in claim 4 is characterized in that, carry out condensation reaction and have a substituting group at least, and be selected from-OH ,-COOH ,-NH
2,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4And the aromatics of the cohort that acid anhydrides constituted is suc as formula the compound shown in (IV):
In the formula, R
1, R
2, R
3, m and n as above define.
10. P contained compound as claimed in claim 9 is characterized in that, in the aromatics shown in the formula (IV), and R
1Be selected from-OH ,-COOH and-NH
2The cohort that is constituted.
11. P contained compound as claimed in claim 10 is characterized in that, this aromatics is selected from the cohort that phenol, ortho-cresol, phenylformic acid, toluylic acid, aniline, benzene methanamine and phenylethylamine constitute.
12. a method of making P contained compound as claimed in claim 1, comprising: (1) makes the organic ring-type phosphorus compound shown in aromatic aldehyde compounds and the formula (II) carry out addition reaction, forms the P contained compound with alcohol radical; And (2) with organic acid as catalyst, make have one-OH at least ,-COOH ,-NH2 ,-CHO ,-SH ,-SO
3H ,-CONH
2,-NHCOOR
4Or the substituent aromatics of acid anhydrides and the prepared P contained compound with alcohol radical of addition reaction carry out condensation reaction.
13. the method as claim 12 is characterized in that, this aromatic aldehyde compounds is the phenyl aldehyde compounds shown in the formula (III):
In the formula, R
1, R
2, R
3, m and n be as defined above.
14. method as claimed in claim 13, it is characterized in that this phenyl aldehyde compounds is to be selected from the cohort that hydroxy benzaldehyde, carboxyl benzaldehyde, carboxyl tolyl aldehyde, carboxy ethyl phenyl aldehyde, dicarboxyl phenyl aldehyde, amido phenyl aldehyde, aminomethyl phenyl aldehyde and amido ethylbenzene formaldehyde are constituted.
15. method as claimed in claim 12 is characterized in that, in 1 mole of this organic ring-type phosphorus compound, the consumption of this aldehyde compound is 0.7 to 1.3 mole.
16. method as claimed in claim 12 is characterized in that, the aromatics that carries out condensation reaction with the P contained compound with alcohol radical is a compound shown in the formula (IV):
In the formula, R
1, R
2, R
3, m and n as above define.
17. method as claimed in claim 16 is characterized in that, this aromatics is selected from the cohort that phenol, ortho-cresol, phenylformic acid, toluylic acid, aniline, benzene methanamine and phenylethylamine constitute.
18. method as claimed in claim 12 is characterized in that, in 1 mole of P contained compound with alcohol radical, the consumption that carries out the aromatics of condensation reaction is more than 0.8 mole.
19. method as claimed in claim 12 is characterized in that, this organic acid is selected from carboxylic acid or sulfonic acid.
20. method as claimed in claim 19 is characterized in that, this organic acid is right-toluenesulphonic acids.
21. method as claimed in claim 19 is characterized in that, this organic acid is an oxalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153173 CN1580108A (en) | 2003-08-08 | 2003-08-08 | Phosphorous compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153173 CN1580108A (en) | 2003-08-08 | 2003-08-08 | Phosphorous compound |
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| Publication Number | Publication Date |
|---|---|
| CN1580108A true CN1580108A (en) | 2005-02-16 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03153173 Pending CN1580108A (en) | 2003-08-08 | 2003-08-08 | Phosphorous compound |
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| Country | Link |
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| CN (1) | CN1580108A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880395A (en) * | 2010-06-21 | 2010-11-10 | 中国科学技术大学 | Polymer type phosphorous flame retardant containing DOPO and preparation method thereof |
| CN101723981B (en) * | 2008-11-04 | 2012-07-25 | 长春人造树脂厂股份有限公司 | Phosphorus compound and preparation method thereof |
| CN105254678A (en) * | 2015-11-23 | 2016-01-20 | 兰州理工大学 | Preparation method for fire retardant high in phosphorus content |
-
2003
- 2003-08-08 CN CN 03153173 patent/CN1580108A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723981B (en) * | 2008-11-04 | 2012-07-25 | 长春人造树脂厂股份有限公司 | Phosphorus compound and preparation method thereof |
| CN101880395A (en) * | 2010-06-21 | 2010-11-10 | 中国科学技术大学 | Polymer type phosphorous flame retardant containing DOPO and preparation method thereof |
| CN101880395B (en) * | 2010-06-21 | 2012-07-04 | 中国科学技术大学 | Polymer type phosphorous flame retardant containing DOPO and preparation method thereof |
| CN105254678A (en) * | 2015-11-23 | 2016-01-20 | 兰州理工大学 | Preparation method for fire retardant high in phosphorus content |
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