CN103073746B - Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof - Google Patents
Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a reactive phosphorus flame retardant containing DOPO and an active double bond and a preparation method and application thereof. Dichloro replaces phosphate to react with polyhydric alcohols or polyhydric phenol acidifying with propylene or partial methyl propene and then with DOPO modified aryl-dihydric phenol and DOPO modified aryl-dihydric alcohol, and a reactive flame retardant monomer molecule capable of being cured and provided with active double bonds and a DOPO flame retardant group are obtained and can be used in various flame retardants of epoxyacrylates and unsaturated polyester resins and the like containing unsaturated double bond polymer resins. The flame retardant overcomes defects that the compatibility between an additive flame retardant and a matrix is poor, the additive flame retardant and the matrix are easy to lose, the water resistance is poor, and the like, and the LOI (limit oxygen index) value of resins can be improved remarkably and the flame-resistant effect is good when the flame retardant is used for flame retarding in the epoxyacrylates and the unsaturated polyester resins.
Description
Technical field
The invention belongs to fire retardant design field, be specifically related to a kind of response type phosphonium flame retardant containing DOPO and activity double key and preparation method thereof, and this fire retardant application in the polymeric matrixs such as epoxy resin, unsaturated polyester resin.
Background technology
Macromolecular material is because processing, wide in variety is enriched, is easy in its source, and superior performance, low price, be widely used in the numerous areas such as space flight and aviation, electronic information, household electrical appliance, automotive industry.But macromolecular material is inflammable material mostly, easily leads to fire, causes the heavy losses of human life's property.Therefore, the fire-retardant of macromolecular material is a problem demanding prompt solution.The fire-retardant method of macromolecular material extensively adopting is at present in polymkeric substance, in the course of processing, to add fire retardant to improve its flame retardant properties, and existing conventional flame retardants is generally organic or inorganic additive, conventionally add-on is very large, and need to be in construction time and base-material blend, cause the crosslinked difficulty of some macromolecule resins or severely degrade, therefore, can be directly fire-retardant group or element be directly introduced to reactive flame retardant in macromolecule matrix segment due to its good dispersiveness, higher flame retarding efficiency, obtained lot of domestic and foreign scholar's broad research.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) type fire retardant is organic phosphates heterogeneous ring compound.DOPO has higher thermostability, oxidation-resistance and good water tolerance, good response type and additive flame retardant, it is mainly used in the fire-retardant of trevira, urethane foam, heat curing-type resin and caking agent, due to its excellent flame retardant properties, its derived structure is the focus of fire retardant research and development always.At present, also less about the report that contains the DOPO reactive flame retardant that unsaturated double-bond and flame retarding efficiency are higher.
China Patent Publication No. CN101838538A has reported a kind of fire retardant of polyphosphate of DOPO side group structure, the intermediate that contains phosphoryl chloride structure that it is obtained by DOPO structure and phosphorus oxychloride reaction, with bisphenol compound melt polymerization, obtain the fire retardant of polyphosphate that contains DOPO side group structure.But this fire retardant has the general shortcoming of additive flame retardant, as the course of processing, to decompose, use procedure is run off, poor water resistance etc.
China Patent Publication No. CN101376665A has reported luxuriant and rich with fragrance flame retardant compound of assorted phosphine containing s-triazine structure and preparation method thereof, the Heat stability is good of this fire retardant, flame retarding efficiency is high, can be used as reactive flame retardant for resins such as epoxy resin, urethane, can be used as again fire-retardant for nylon, ABS engineering plastics of additive flame retardant.When but this fire retardant is used as reactive flame retardant, because the reactive behavior of the hydroxyl of fire retardant is poor, cause solidifying not exclusively of material, thereby can reduce other performances of material.
China Patent Publication No. CN1382739A has reported a kind of phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent and preparation method thereof, take phosphoric acid, react the phosphoric acid ester trivalent alcohol generating with epoxy compounds as response matrix, by " pre-polymerization method " or " single stage method ", add the monohydroxy end-caps of isocyanic ester and radiation-curable, the phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation obtaining can fast setting under ultraviolet light irradiation, thereby obtain transparent hard cured film, its body oxygen index is 27.But it is not high that its defect is flame retarding efficiency, and preparation process is numerous and diverse.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and the response type phosphonium flame retardant containing DOPO and activity double key that a kind of flame retarding efficiency is higher is provided.
Another object of the present invention is to provide the preparation method of the above-mentioned response type phosphonium flame retardant containing DOPO and activity double key.
The 3rd object of the present invention is that the above-mentioned response type phosphonium flame retardant containing DOPO and activity double key is applied in the polymeric matrixs such as epoxy resin, unsaturated polyester resin.
For solving above technical problem, the technical scheme that the present invention takes is:
Containing a response type phosphonium flame retardant for DOPO and activity double key, its structure is as follows:
R
1-O-R
2-O-R
3-O-R
2-O-R
1
；
Wherein, R
1for the hydroxyl structure that goes of the polyvalent alcohol of acrylated or part methyl acrylated or polyphenol;
R
2for the one in lower array structure:
R
3for the one in lower array structure:
Preferably, the polyvalent alcohol of described acrylated or part methyl acrylated or polyphenol are methacrylic acid-beta-hydroxy ethyl ester or senecioate-hydroxyl ethyl ester or 2-hydroxyl dimethyl allene acid glyceride or 2-hydroxyl glycerol diacrylate or 1-methylol-3,5-dimethyl allene acid phenenyl ester or 1-methylol-3,5-diacrylate phenyl ester.
The preparation method of the response type phosphonium flame retardant containing DOPO and activity double key of the present invention, its process is: take dichloro, replace phenyl-phosphate as response matrix, under protection of inert gas condition, by 1:1 reaction mol ratio, add polyvalent alcohol or the polyphenol of acrylated or part methyl acrylated, add organic solvent and acid binding agent, under condition of ice bath, be stirred to and no longer include hydrogenchloride generation; Then by reaction mol ratio, add 9, the aromatic base dihydric phenol or 9 of mix-10-phospho hetero phenanthrene-10-oxide modifying of 10-dihydro-9-oxy, the aromatic base dibasic alcohol of mix-10-phospho hetero phenanthrene-10-oxide modifying of 10-dihydro-9-oxy, at 0 ~ 80 ℃, stir after 8-12 hour, decompress filter is removed acid binding agent salt, organic solvent is removed in underpressure distillation again, obtains thickness colourless transparent liquid, is the described response type phosphonium flame retardant containing DOPO and activity double key;
Concrete synthetic route is as follows:
Wherein, R
1for the hydroxyl structure that goes of the polyvalent alcohol of acrylated or part methyl acrylated or polyphenol;
R
2for the one in lower array structure:
R
3for the one in lower array structure:
Preferably, described solvent is selected from tetrahydrofuran (THF), methylene dichloride or chloroform.
Preferably, described rare gas element is selected from nitrogen, helium or argon gas.
Preferably, the temperature of described condition of ice bath is controlled at-5 ~ 5 ℃.
Preferably, described acid binding agent is selected from triethylamine or pyridine.
Response type phosphonium flame retardant containing DOPO and activity double key of the present invention can be applied in epoxy acrylic resin, unsaturated polyester resin.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention replaces phosphoric acid ester with dichloro and reacts with polyvalent alcohol or the polyphenol of acrylated or part methyl acrylated, and then with the aromatic base dihydric phenol of DOPO modification or the aromatic base diol reaction of DOPO modification, obtain having the curable reaction-type flame-retarding monomer molecule of activity double key and the fire-retardant group of DOPO simultaneously, be the response type phosphonium flame retardant containing DOPO and activity double key of the present invention, it can be used in the fire-retardant of the multiple fluoropolymer resins that contain unsaturated double-bond such as epoxy acrylic resin and unsaturated polyester resin.This fire retardant compared with existing additive flame retardant, the shortcoming such as overcome additive flame retardant and matrix phase capacitive is poor, and use procedure is easily run off, poor water resistance; With traditional containing compared with the reactive flame retardant of DOPO, the two keys of response type and the liquid characteristic of fire retardant of the present invention make itself and resin matrix have better consistency, and high phosphorus content makes it have again good flame retardant effect, when for epoxy acrylic resin and unsaturated polyester resin fire-retardant, use 30% fire retardant of the present invention, the limiting oxygen index(LOI) (LOI) that just can significantly improve epoxy acrylic resin and unsaturated polyester resin, flame retardant effect is very good.In addition, the preparation method of fire retardant of the present invention also have advantages of simple, reaction conditions is controlled, last handling process is easy.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but be not limited to these embodiment.
Fire retardancy test of the present invention carries out according to following standard:
The testing standard that limiting oxygen index(LOI) LOI measures institute's foundation is: GB2406-80
The structure of raw material that the present invention uses and abbreviation thereof are as follows:
（1）、PDCP：
（2）、PPDC：
（3）、DOPO-HQ:
（4）、2DOPO-PhOH：
（5）、DOPO-HB：
（6）、2DOPO-TDCA：
Embodiment 1
In the 250ml there-necked flask that mechanical stirrer and constant pressure funnel are housed; add 21.1g(0.1mol) PhosphorodichloridicAcid Acid Phenyl Ester (being PPDC) and 80ml tetrahydrofuran (THF); under ice bath and nitrogen protection; stir 10 minutes; then add 21.2g(0.2mol) triethylamine; continuing in 3 hours, slowly to drip Hydroxyethyl acrylate 11.6g(0.1mol under stirring state) with the mixed solution of 30ml tetrahydrofuran (THF); sustained reaction 5 hours again; then by DOPO-HQ10.8g(0.05mol) join in above-mentioned reaction system, continue reaction 12 hours.Decompress filter afterwards, removes triethylamine salt, and solvents tetrahydrofurane is removed in underpressure distillation, and the colourless thickness transparent liquid obtaining is product of the present invention.Productive rate is 90%.
Synthetic route is as follows:
Get the present embodiment products therefrom and carry out infrared analysis, 584-541cm in PhosphorodichloridicAcid Acid Phenyl Ester
-1the P-Cl of place key disappears, 929cm
-1, 1193cm
-1the P-O-Ph of place characteristic peak, 1442cm
-1the P-Ph of place characteristic peak, 1735cm
-1the C=C of place characteristic peak occurs.Get products therefrom and carry out nuclear magnetic resonance spectroscopy, chemical shift disappears in the hydroxyl peak of the DOPO-HQ at 9.44ppm and 9.16ppm place.Provable thus, the colourless thickness transparent liquid of the present embodiment gained product is the phosphonium flame retardant of the present invention containing DOPO and activity double key.
Get phosphonium flame retardant 3g, epoxy acrylic resin 7g and light trigger α containing DOPO and activity double key that the present embodiment prepares, alpha-alpha-dimethyl-alpha-hydroxyacetophenone 0.1g stirs at 60 ℃; Then this hybrid resin liquid is poured in the grinding tool of long 8cm, wide 3cm, thick 3cm, under room temperature condition, on uv cure machine, solidifies, be 10s set time, is cooled to room temperature, and the demoulding obtains flame retardant epoxy acrylic resin sample.The limiting oxygen index(LOI) LOI that measures this sample with oxygen index instrument, reach 31.5, and the limiting oxygen index(LOI) of not fire-retardant pure epoxy acrylic resin is only generally 21.0.Thus, by this oxygen index measuring, can find out that the phosphonium flame retardant containing DOPO and activity double key prepared by the present embodiment has good fire retardation to epoxy acrylic resin.
In the present embodiment, DOPO-HQ can use equimolar 2DOPO-TDCA, and DOPO-HB or 2DOPO-PhOH substitute, and makes the corresponding response type phosphonium flame retardant containing DOPO and activity double key.
Embodiment 2
Being equipped with in the 250ml there-necked flask of mechanical stirrer and constant voltage dropping liquid leak; add 19.5g(0.1mol) benzene phosphinylidyne dichloro (being PDCP) and 80ml methylene dichloride; under ice bath and nitrogen protection; stir 10 minutes; then add 15.8g(0.2mol) pyridine; under lasting stirring state, in 1 hour, slowly drip Hydroxyethyl acrylate 11.6g(0.1mol) and 30ml methylene dichloride mixed solution; continue reaction 2 hours; again by DOPO-HQ10.8g(0.05mol) join in above-mentioned reaction system, continue reaction 8 hours.Decompress filter afterwards, removes pyridine, and methylene chloride is removed in underpressure distillation, and the colourless thickness transparent liquid obtaining is product of the present invention.Productive rate is 88%.
Synthetic route is as follows:
Get the present embodiment products therefrom and carry out infrared analysis, 584-541cm in benzene phosphinylidyne dichloro
-1place's P-Cl key disappears, and 929,1193cm
-1the P-O-Ph of place characteristic peak, 1442cm
-1the P-Ph of place, 1735cm
-1the C=C of place characteristic peak occurs.In addition, products therefrom is through nuclear magnetic resonance spectroscopy, chemical shift 9.44 and the hydroxyl peak of the DOPO-HQ at 9.16ppm place disappear.Provable thus, the colourless thickness transparent liquid of the present embodiment gained product is the phosphonium flame retardant of the present invention containing DOPO and activity double key.
Phosphonium flame retardant 15g and the 35g unsaturated polyester resin (model is 147#) containing DOPO and activity double key of getting above-mentioned preparation stir at normal temperatures, then add 0.1g initiator benzoyl peroxide, after mixing, resin liquid is poured in the grinding tool of long 10cm, wide 10cm, thick 3cm, first at 60 ℃, solidify 2 hours, at 120 ℃, solidify 2 hours again, then naturally cool to room temperature, the demoulding, obtains flame-retarded unsaturated polyester resin sample.The limiting oxygen index(LOI) LOI that measures this flame-retarded unsaturated polyester resin sample with oxygen index instrument, reach 33, and the limiting oxygen index(LOI) LOI of fire-retardant pure unsaturated polyester resin is not only 18.Thus, by this oxygen index measuring, can find out that the phosphonium flame retardant containing DOPO and activity double key prepared by the present embodiment also has good fire retardation to unsaturated polyester resin.
In the present embodiment, DOPO-HQ can use equimolar 2DOPO-TDCA, and DOPO-HB or 2DOPO-PhOH substitute, and makes the corresponding response type phosphonium flame retardant containing DOPO and activity double key.
Embodiment 3
Being equipped with in the 250ml there-necked flask of mechanical stirrer and constant voltage dropping liquid leak; add 19.5g(0.1mol) benzene phosphinylidyne dichloro (being PDCP) and 80ml tetrahydrofuran (THF); under ice bath and nitrogen protection; stir 10 minutes; add 21.2g(0.2mol) triethylamine; under lasting stirring, in 1 hour, slowly drip Hydroxyethyl acrylate 11.6g(0.1mol) and 30ml tetrahydrofuran (THF) mixed solution; react again 2 hours; then by DOPO-HB11.5g(0.05mol) join in above-mentioned reaction system, continue reaction 12 hours.Decompress filter afterwards, removes triethylamine salt, and solvents tetrahydrofurane is removed in underpressure distillation, and the colourless thickness transparent liquid obtaining is product of the present invention.Productive rate is 87%.
Synthetic route is as follows:
Get the present embodiment products therefrom and carry out infrared analysis, 584-541cm in benzene phosphinylidyne dichloro
-1place's P-Cl key disappears, and 929,1193cm
-1the P-O-Ph of place characteristic peak, 1442cm
-1the P-Ph of place, 1735cm
-1the C=C of place characteristic peak occurs.In addition, products therefrom is through nuclear magnetic resonance spectroscopy, chemical shift 9.44 and the hydroxyl peak of the DOPO-HB at 9.16ppm place disappear.Provable thus, the colourless thickness transparent liquid of the present embodiment gained product is the phosphonium flame retardant of the present invention containing DOPO and activity double key.
Phosphonium flame retardant 15g and the 35g unsaturated polyester resin (model is 147#) containing DOPO and activity double key of getting above-mentioned preparation stir at normal temperatures, then add 0.1g initiator benzoyl peroxide, after mixing, resin liquid is poured in the grinding tool of long 10cm, wide 10cm, thick 3cm, first at 60 ℃, solidify 2 hours, at 120 ℃, solidify 2 hours again, then naturally cool to room temperature, the demoulding, obtains flame-retarded unsaturated polyester resin sample.The limiting oxygen index(LOI) LOI that measures this flame-retarded unsaturated polyester resin sample with oxygen index instrument, reaches 32, is only 18 with the limiting oxygen index(LOI) LOI(of fire-retardant pure unsaturated polyester resin not) compared with greatly improve.By this oxygen index measuring, can find out that the phosphonium flame retardant containing DOPO and activity double key prepared by the present embodiment has good fire retardation to unsaturated polyester resin.
In the present embodiment, DOPO-HB can use equimolar 2DOPO-TDCA, and DOPO-HQ or 2DOPO-PhOH substitute, and makes the corresponding response type phosphonium flame retardant containing DOPO and activity double key.
Embodiment 4
Being equipped with in the 250ml there-necked flask of mechanical stirrer and constant voltage dropping liquid leak; add 21.1g(0.1mol) PhosphorodichloridicAcid Acid Phenyl Ester (being PPDC) and 80ml tetrahydrofuran (THF); under ice bath and nitrogen protection; stir 10 minutes; add 21.2g triethylamine; continuing in 1 hour, slowly to drip hydroxyethyl methylacrylate 13.0g(0.1mol under stirring state) with the mixed solution of 30ml tetrahydrofuran (THF); sustained reaction 2 hours; then by DOPO-HQ10.8g(0.05mol) join in above-mentioned reaction system, continue reaction 12 hours.Decompress filter, removes triethylamine salt, and underpressure distillation is except desolventizing, and the colourless thickness transparent liquid obtaining is product of the present invention.Productive rate is 89%.
Synthetic route is as follows:
Get the present embodiment products therefrom and carry out infrared analysis, 584-541cm in PhosphorodichloridicAcid Acid Phenyl Ester
-1the P-Cl of place key disappears, 929cm
-1, 1193cm
-1the P-O-Ph of place characteristic peak, 1442cm
-1the P-Ph of place characteristic peak, 1735cm
-1the C=C of place characteristic peak occurs.Get products therefrom and carry out nuclear magnetic resonance spectroscopy, chemical shift disappears in the hydroxyl peak of the DOPO-HQ at 9.44ppm and 9.16ppm place.Provable thus, the colourless thickness transparent liquid of the present embodiment gained product is the phosphonium flame retardant of the present invention containing DOPO and activity double key.
Get phosphonium flame retardant 3g, epoxy acrylic resin 7g and light trigger α containing DOPO and activity double key that aforesaid method prepares, alpha-alpha-dimethyl-alpha-hydroxyacetophenone 0.1g stirs at 60 ℃; Then this hybrid resin liquid is poured in the grinding tool of long 8cm, wide 3cm, thick 3cm, under room temperature condition, on uv cure machine, solidifies, be 10s set time, is cooled to room temperature, and the demoulding obtains flame retardant epoxy acrylic resin sample.The limiting oxygen index(LOI) LOI that measures this sample with oxygen index instrument, reach 32.5, and the limiting oxygen index(LOI) of not fire-retardant pure epoxy acrylic resin is only generally 21.0.Thus, by this oxygen index measuring, can find out that the phosphonium flame retardant containing DOPO and activity double key prepared by the present embodiment has good fire retardation to epoxy acrylic resin.
In the present embodiment, DOPO-HQ can use equimolar 2DOPO-TDCA, and DOPO-HB or 2DOPO-PhOH substitute, and makes the corresponding response type phosphonium flame retardant containing DOPO and activity double key.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (7)
1. containing a response type phosphonium flame retardant for DOPO and activity double key, it is characterized in that: the structure of the described response type phosphonium flame retardant containing DOPO and activity double key is as follows:
R
1-O-R
2-O-R
3-O-R
2-O-R
1；
Wherein, R
1for the hydroxyl structure that goes of the polyvalent alcohol of acrylated or part methyl acrylated or polyphenol;
R
2for the one in lower array structure:
R
3for the one in lower array structure:
The polyvalent alcohol of described acrylated or part methyl acrylated or polyphenol are selected from methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl ethyl ester, 2-hydroxyl dimethyl allene acid glyceride, 2-hydroxyl glycerol diacrylate, 1-methylol-3,5-dimethyl allene acid phenenyl ester or 1-methylol-3,5-diacrylate phenyl ester.
2. the preparation method of the response type phosphonium flame retardant containing DOPO and activity double key claimed in claim 1, it is characterized in that: this preparation method's process is: take dichloro, replace phenyl-phosphate as response matrix, under protection of inert gas condition, by 1:1 reaction mol ratio, add polyvalent alcohol or the polyphenol of acrylated or part methyl acrylated, add organic solvent and acid binding agent, under condition of ice bath, be stirred to and no longer include hydrogenchloride generation; Then by reaction mol ratio, add 9, the aromatic base dihydric phenol or 9 of mix-10-phospho hetero phenanthrene-10-oxide modifying of 10-dihydro-9-oxy, the aromatic base dibasic alcohol of mix-10-phospho hetero phenanthrene-10-oxide modifying of 10-dihydro-9-oxy, at 0-80 ℃, stir after 8-12 hour, decompress filter is removed acid binding agent salt, organic solvent is removed in underpressure distillation again, obtains thickness colourless transparent liquid, is the described response type phosphonium flame retardant containing DOPO and activity double key;
Concrete synthetic route is as follows:
Wherein, R
1for the hydroxyl structure that goes of the polyvalent alcohol of acrylated or part methyl acrylated or polyphenol;
R
2for the one in lower array structure:
R
3for the one in lower array structure:
3. the preparation method of the response type phosphonium flame retardant containing DOPO and activity double key according to claim 2, is characterized in that: described solvent is selected from tetrahydrofuran (THF), methylene dichloride or chloroform.
4. the preparation method of the response type phosphonium flame retardant containing DOPO and activity double key according to claim 2, is characterized in that: described rare gas element is selected from nitrogen, helium or argon gas.
5. the preparation method of the response type phosphonium flame retardant containing DOPO and activity double key according to claim 2, is characterized in that: the temperature of described condition of ice bath is controlled at-5～5 ℃.
6. the preparation method of the response type phosphonium flame retardant containing DOPO and activity double key according to claim 2, is characterized in that: described acid binding agent is selected from triethylamine or pyridine.
7. the application of the response type phosphonium flame retardant containing DOPO and activity double key claimed in claim 1 in epoxy acrylic resin, unsaturated polyester resin.
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