CN104961895A - Flame-retardant bismaleimide resin - Google Patents
Flame-retardant bismaleimide resin Download PDFInfo
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- CN104961895A CN104961895A CN201410681429.1A CN201410681429A CN104961895A CN 104961895 A CN104961895 A CN 104961895A CN 201410681429 A CN201410681429 A CN 201410681429A CN 104961895 A CN104961895 A CN 104961895A
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- NOHXDUCNZYVZOZ-UHFFFAOYSA-N O=C(C1Cc2ccc(Cc(cc3)ccc3N(C(C=C3)=O)C3=O)cc2)C=CC1=O Chemical compound O=C(C1Cc2ccc(Cc(cc3)ccc3N(C(C=C3)=O)C3=O)cc2)C=CC1=O NOHXDUCNZYVZOZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a flame-retardant bismaleimide resin. The resin is prepared by uniformly mixing bismaleimide, an allyl compound and phosphaphenanthrene-group-containing bismaleimide according to a mass ratio of 100: (1-100): (1-50) and then carrying out curing. The flame-retardant bismaleimide resin provided by the invention is prepared by blending and curing phosphaphenanthrene-group-containing bismaleimide, bismaleimide and the allyl compound, and has the advantages of heat resistance, electric insulation performance, weather resistance and excellent flame retardant property. The flame-retardant bismaleimide resin in the invention has a thermal weight loss temperature of greater than 410 DEG C and a limit oxygen index (LOI) of 32% to 40% and reaches the fire rating of UL94V-0.
Description
Technical field
The invention belongs to flame retarded polymeric material technical field, be specifically related to a kind of flame-retardant bismaleimide resin.
Background technology
Bimaleimide resin (BMI) is the bifunctional compound that a class has double bond active group, and it has excellent thermotolerance, electrical insulating property, wave, radiation hardness, flame retardant resistance, weather resisteant, good mechanical property and dimensional stability.Bimaleimide resin moulding process is similar to epoxy resin, is widely used in the resin matrix of advanced composite material in the industrial circles such as Aeronautics and Astronautics, machinery, electronics, high-temperature insulation material and tackiness agent etc.
Along with the development of modern science and technology, require more and more higher to the flame retardant resistance of polymer materials, self-extinguishing.The polymkeric substance of BMI can release CO when burning
2, there is certain self-extinguishing, but still difficulty meets flame-retardancy requirements.Therefore, people consider fire-retardant factor and the level of system when development of new BMI resin.
Adding fire retardant is the effective ways improving flame retardance of polymer.Conventional fire retardant has halogenated flame retardant, phosphorus flame retardant and inorganic combustion inhibitor.Wherein phosphorus flame retardant is because its low cigarette, nontoxic, flame retarding efficiency high are by people's extensive concern, has good development prospect.
Organic phosphorus flame retardant comprises phosphoric acid ester, phosphorous acid ester, phosphonic acid ester, organophosphorated salt, also has phosphorous heterocylic compound and polymkeric substance phosphorus (phosphine) acid esters etc.Wherein organophosphorus heterogeneous ring compound is organophosphorus chemistry study hotspot.Organophosphorus heterogeneous ring compound fire retardant mainly contains five-ring, six-ring and volution compound.Wherein phosphorous six-ring compound is occupied an leading position.In recent years, have been a great concern with the synthesis of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) fire retardant that is intermediate and application.DOPO and derivative thereof can be used as response type and additive flame retardant, the fire retardant Halogen of synthesis, smokeless, nontoxic, and do not move, flame retardant properties is lasting.Can be used for the multiple macromolecular material fire-retardant finish such as linear polyester, polymeric amide, epoxy resin, urethane.External being widely used in plastics for electronics, brass presses the fire-retardant of the material such as layer, circuit card.
Comprehensive above can to find out, DOPO to be introduced bismaleimide resin and prepare a kind of novel bimaleimide resin, with the needs of the modern science and technology adapting to develop rapidly, there is important theory significance and actual value.
Summary of the invention
Technical problem to be solved by this invention is, for above-mentioned the deficiencies in the prior art, to provide a kind of flame-retardant bismaleimide resin.This flame-retardant bismaleimide resin is obtained after blended and solidification by the bismaleimides rolled into a ball containing phospha phenanthryl, bismaleimides and allylic cpd, there is thermotolerance, electrical insulating property, wave, radiation hardness, weather resisteant, there is excellent flame retardant properties simultaneously, its thermal weight loss temperature is greater than 410 DEG C, limiting oxygen index(LOI) (LOI) is 32% ~ 40%, and fire-protection rating reaches UL94V-0 standard.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of flame-retardant bismaleimide resin, it is characterized in that, by bismaleimides, allylic cpd and containing phospha phenanthryl roll into a ball bismaleimides according to 100:(1 ~ 100): the mass ratio of (1 ~ 50) mixes after fixing and makes;
The structural formula of the described bismaleimides containing phospha phenanthryl group is:
In formula ,-X-is:
-o-or-s-.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the temperature of described mixing is 90 DEG C ~ 160 DEG C.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the temperature of described solidification is 180 DEG C ~ 220 DEG C, and the time of solidification is 4h ~ 8h.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, described allylic cpd is one or more in diallyl bisphenol, diallyl bisphenol S, allyl group linear resol and N-allyl group aniline.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the structural formula of described bismaleimides is:
In formula ,-R-is:
-o-or-s-.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the preparation method of the described bismaleimides containing phospha phenanthryl group comprises the following steps:
Step one, DOPO is dissolved in non-protonic solvent, obtains DOPO solution; Described non-protonic solvent is one or more in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone;
Step 2, by bismaleimides and non-protonic solvent according to 1:(10 ~ 50) mol ratio add in reactor, under nitrogen protection, stir under 50 DEG C ~ 120 DEG C conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 90 DEG C ~ 160 DEG C, stirring reaction 1h ~ 5h; Described non-protonic solvent is one or more in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone; The molar weight of described bismaleimides is 1 ~ 1.5 times of DOPO molar weight;
Step 3, in the reaction system after stirring reaction in step 2, add organic solvent, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; Described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the drop rate of the solution of DOPO described in step 2 is 1mL/min ~ 5mL/min.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the volume of organic solvent described in step 3 is 1 ~ 5 times of the reaction system volume in step 2 after stirring reaction.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, the preparation method of the described bismaleimides containing phospha phenanthryl group comprises the following steps:
Step one, by DOPO and bismaleimides according to 1:(1 ~ 1.5) mixed in molar ratio, constant temperature stirring reaction 2h ~ 10h after mixture being heated to 140 DEG C ~ 230 DEG C under nitrogen protection;
Add organic solvent in step 2, reaction system in step one after constant temperature stirring reaction, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; Described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone.
Above-mentioned a kind of flame-retardant bismaleimide resin, is characterized in that, in the molar weight of organic solvent described in step 2 and step one, the ratio of the integral molar quantity of DOPO and bismaleimides is 1:(1 ~ 3).
The present invention compared with prior art has the following advantages:
1, flame-retardant bismaleimide resin of the present invention, obtained after blended and solidification by the bismaleimides rolled into a ball containing phospha phenanthryl, bismaleimides and allylic cpd, there is thermotolerance, electrical insulating property and weather resisteant, there is excellent flame retardant properties simultaneously.
2, the bismaleimides of single-side bonding phospho hetero phenanthrene group of the present invention, the active carbon-carbon double bond of bismaleimides is remained introduce phospho hetero phenanthrene group in bismaleimide structure while, make it can be cured reaction with allylic cpd, form the bimaleimide resin with phospho hetero phenanthrene group.
3, the thermal weight loss temperature of flame-retardant bismaleimide resin of the present invention is greater than 410 DEG C, and limiting oxygen index(LOI) (LOI) is 32% ~ 40%, and fire-protection rating reaches UL94V-0 standard.
Below in conjunction with drawings and Examples, technical solution of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the bismaleimides containing phospha phenanthryl group prepared by the embodiment of the present invention 1.
Fig. 2 is the infrared spectrogram of diphenyl methane dimaleimide.
Fig. 3 is the infrared spectrogram of DOPO.
Embodiment
Embodiment 1: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
diphenyl methane dimaleimide be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, 10.0g DOPO is dissolved in DMF, obtains 50mLDOPO solution;
Step 2, by 16.6g diphenyl methane dimaleimide and N, dinethylformamide adds in reactor according to the mol ratio of 1:10, under nitrogen protection, stir under 50 DEG C of conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 160 DEG C, stirring reaction 1h; The drop rate of described DOPO solution is 1mL/min;
Step 3, in the reaction system after stirring reaction in step 2, add the methyl alcohol equal with reaction system volume, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group.
Non-protonic solvent N in the present embodiment, dinethylformamide all can adopt N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolinone, acetonitrile or acetone, or N, at least two kinds in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone substitute.Organic solvent methyl alcohol in the present embodiment can adopt ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
Fig. 1 is the infrared spectrogram of the bismaleimides containing phospha phenanthryl group prepared by the present embodiment.Fig. 2 is the infrared spectrogram of diphenyl methane dimaleimide.Fig. 3 is the infrared spectrogram of DOPO.Fig. 1, Fig. 2 and Fig. 3 are contrasted, 3400cm in product infared spectrum
-1left and right is υ
o-Habsorption peak; 3067cm
-1for υ on insatiable hunger carbon-carbon double bond
c-Habsorption peak; 2926cm
-1for υ on methyl
c-Habsorption peak; 1714cm
-1for υ on amide group
c=Oabsorption peak; 1664cm
-1for the υ with C=O key conjugation
c=Cabsorption peak; 1595cm
-1and 1513cm
-1for υ on aromatic ring
c=Cabsorption peak; 1388cm
-1for υ
p-Cabsorption peak; 1239cm
-1for υ on amide group
c-Nabsorption peak; 1193cm
-1for υ
p=Oabsorption peak.It can thus be appreciated that, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.
Embodiment 2: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
2,2-diphenyl propane bismaleimidess be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, 10.0g DOPO is dissolved in dimethyl sulfoxide (DMSO), obtains 50mL DOPO solution;
Step 2, by 21.3g 2,2-diphenyl propane bismaleimides and dimethyl sulfoxide (DMSO) add in reactor according to the mol ratio of 1:50, under nitrogen protection, stir under 90 DEG C of conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 90 DEG C, stirring reaction 5h; The drop rate of described DOPO solution is 3mL/min;
Step 3, in the reaction system after stirring reaction in step 2, add dimethylbenzene, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; The volume of described dimethylbenzene is 3 times of the reaction system volume in step 2 after stirring reaction.
Non-protonic solvent dimethyl sulfoxide (DMSO) in the present embodiment all can adopt N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1,3-dimethyl-2-imidazolinone, acetonitrile or acetone, or N, at least two kinds in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone substitute.Organic solvent dimethylbenzene in the present embodiment can adopt methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
To the raw material 2 that the present embodiment adopts, 2-diphenyl propane bismaleimides and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.
Embodiment 3: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
benzophenone bismaleimides be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, 10.0g DOPO is dissolved in acetone, obtains 50mL DOPO solution;
Step 2, by 25.67g benzophenone bismaleimides and 1,3-dimethyl-2-imidazolinone is according to 1:30) mol ratio add in reactor, under nitrogen protection, stir under 120 DEG C of conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 140 DEG C, stirring reaction 3h; The drop rate of described DOPO solution is 5mL/min;
Step 3, in the reaction system after stirring reaction in step 2, add acetonitrile, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; The volume of described acetonitrile is 5 times of the reaction system volume in step 2 after stirring reaction.
Non-protonic solvent acetone in the present embodiment can adopt N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolinone or acetonitrile, or N, at least two kinds in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone substitute; DMI can adopt DMF, N, N-N,N-DIMETHYLACETAMIDE, acetonitrile or acetone, or DMF, N, at least two kinds in N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone substitute.Organic solvent acetonitrile in the present embodiment can adopt methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
The raw material benzophenone bismaleimides that the present embodiment is adopted and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.
Embodiment 4: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
sulfobenzide bismaleimides be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, 10.0g DOPO is dissolved in DMI, obtains 80mLDOPO solution;
Step 2, by 18.77g sulfobenzide bismaleimides and 1,3-dimethyl-2-imidazolinone adds in reactor according to the mol ratio of 1:20, under nitrogen protection, stir under 60 DEG C of conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 90 DEG C, stirring reaction 5h; The drop rate of described DOPO solution is 4mL/min;
Step 3, in the reaction system after stirring reaction in step 2, add propyl carbinol, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; The volume of described propyl carbinol is 2 times of the reaction system volume in step 2 after stirring reaction.
Non-protonic solvent 1 in the present embodiment, 3-dimethyl-2-imidazolinone all can adopt N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, acetonitrile or acetone, or N, at least two kinds in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone substitute.Organic solvent propyl carbinol in the present embodiment can adopt methyl alcohol, ethanol, propyl alcohol, toluene, dimethylbenzene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
The raw material sulfobenzide bismaleimides that the present embodiment is adopted and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.
Embodiment 5: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
phenol benzoate bismaleimides be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, by DOPO and the Diphenyl Ether Bismaleimide mixed in molar ratio according to 1:1, constant temperature stirring reaction 2h after under nitrogen protection mixture being heated to 140 DEG C;
Add methyl alcohol in step 2, reaction system in step one after constant temperature stirring reaction, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; In the molar weight of described methyl alcohol and step one, the ratio of the integral molar quantity of DOPO and phenol benzoate bismaleimides is 1:1.
The starting benzoic acid phenyl ester bismaleimides that the present embodiment is adopted and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.Organic solvent methyl alcohol in the present embodiment can adopt ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
Embodiment 6: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
diphenyl Ether Bismaleimide be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, by DOPO and the Diphenyl Ether Bismaleimide mixed in molar ratio according to 1:1.5, constant temperature stirring reaction 5h after under nitrogen protection mixture being heated to 230 DEG C;
Add toluene in step 2, reaction system in step one after constant temperature stirring reaction, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; In the molar weight of described toluene and step one, the ratio of the integral molar quantity of DOPO and Diphenyl Ether Bismaleimide is 1:2.
The raw material Diphenyl Ether Bismaleimide that the present embodiment is adopted and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.Organic solvent toluene in the present embodiment can adopt methyl alcohol, ethanol, propyl alcohol, propyl carbinol, dimethylbenzene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
Embodiment 7: preparation is containing the bismaleimides of phospha phenanthryl group
The present embodiment employing structural formula is
diphenyl sulfide bismaleimides be the bismaleimides of raw material preparation containing phospha phenanthryl group, the structural formula of bismaleimides containing phospha phenanthryl group of preparation is:
The preparation method of the present embodiment comprises the following steps:
Step one, by DOPO and the diphenyl sulfide bismaleimides mixed in molar ratio according to 1:1.2, constant temperature stirring reaction 10h after under nitrogen protection mixture being heated to 190 DEG C;
Add methyl alcohol in step 2, reaction system in step one after constant temperature stirring reaction, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; In the molar weight of described methyl alcohol and step one, the ratio of the integral molar quantity of DOPO and diphenyl sulfide bismaleimides is 1:3.
The raw material diphenyl sulfide bismaleimides that the present embodiment is adopted and DOPO, and the bismaleimides containing phospha phenanthryl group of preparation carries out Infrared spectroscopy, there is in product the charateristic avsorption band of the charateristic avsorption band of unsaturated C=C double bond and the P-C key of DOPO and P=O key simultaneously, therefore can judge phospho hetero phenanthrene group by nucleophilic reaction single-side bonding to bismaleimide structure and the C=C double bond remained.Organic solvent methyl alcohol in the present embodiment can adopt ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile or acetone, or in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone at least two kinds substitute.
Flame-retardant bismaleimide resin of the present invention is described according to following examples 8 to embodiment 21, and the preparation method of flame-retardant bismaleimide resin of the present invention is: by bismaleimides, allylic cpd and containing phospha phenanthryl group bismaleimides according to 100:(1 ~ 100): the mass ratio of (1 ~ 50) mixes after fixing and makes; The temperature of described mixing is 90 DEG C ~ 160 DEG C; The temperature of described solidification is 180 DEG C ~ 220 DEG C, and the time of solidification is 4h ~ 8h.The parameter of embodiment 8 to embodiment 21 is specifically in table 1.
The raw material of the flame-retardant bismaleimide resin of table 1 embodiment 8 to embodiment 21 and preparation condition
The thermostability of the flame-retardant bismaleimide resin of embodiment 8 to embodiment 21, flame retardant properties and fire-protection rating are detected, result shows, the thermal weight loss temperature of the flame-retardant bismaleimide resin of embodiment 8 to embodiment 21 is all greater than 410 DEG C, fire-protection rating all reaches UL94V-0 standard, and flame retardant properties the results are shown in Table 2 and table 3.
The flame retardant properties of the flame-retardant bismaleimide resin of table 2 embodiment 8 to embodiment 14
| Embodiment | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| Limiting oxygen index(LOI) (LOI) | 38％ | 32％ | 36％ | 40％ | 39％ | 34％ | 36％ |
The flame retardant properties of the flame-retardant bismaleimide resin of table 3 embodiment 15 to embodiment 21
| Embodiment | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
| Limiting oxygen index(LOI) (LOI) | 39％ | 34％ | 35％ | 38％ | 40％ | 33％ | 37％ |
The above; it is only preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. a flame-retardant bismaleimide resin, it is characterized in that, by bismaleimides, allylic cpd and containing phospha phenanthryl roll into a ball bismaleimides according to 100:(1 ~ 100): the mass ratio of (1 ~ 50) mixes after fixing and makes;
The structural formula of the described bismaleimides containing phospha phenanthryl group is:
In formula ,-X-is:
-o-or-s-.
2. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, the temperature of described mixing is 90 DEG C ~ 160 DEG C.
3. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, the temperature of described solidification is 180 DEG C ~ 220 DEG C, and the time of solidification is 4h ~ 8h.
4. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, described allylic cpd is one or more in diallyl bisphenol, diallyl bisphenol S, allyl group linear resol and N-allyl group aniline.
5. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, the structural formula of described bismaleimides is:
In formula ,-R-is:
-o-or-s-.
6. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, the preparation method of the described bismaleimides containing phospha phenanthryl group comprises the following steps:
Step one, DOPO is dissolved in non-protonic solvent, obtains DOPO solution; Described non-protonic solvent is one or more in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone;
Step 2, by bismaleimides and non-protonic solvent according to 1:(10 ~ 50) mol ratio add in reactor, under nitrogen protection, stir under 50 DEG C ~ 120 DEG C conditions, then under constant temperature, in described reactor, DOPO solution described in step one is dripped, the temperature dropwising rear maintenance reaction system is 90 DEG C ~ 160 DEG C, stirring reaction 1h ~ 5h; Described non-protonic solvent is one or more in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), DMI, acetonitrile and acetone; The molar weight of described bismaleimides is 1 ~ 1.5 times of DOPO molar weight;
Step 3, in the reaction system after stirring reaction in step 2, add organic solvent, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; Described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone.
7. a kind of flame-retardant bismaleimide resin according to claim 6, is characterized in that, the drop rate of the solution of DOPO described in step 2 is 1mL/min ~ 5mL/min.
8. a kind of flame-retardant bismaleimide resin according to claim 6, is characterized in that, the volume of organic solvent described in step 3 is 1 ~ 5 times of the reaction system volume in step 2 after stirring reaction.
9. a kind of flame-retardant bismaleimide resin according to claim 1, is characterized in that, the preparation method of the described bismaleimides containing phospha phenanthryl group comprises the following steps:
Step one, by DOPO and bismaleimides according to 1:(1 ~ 1.5) mixed in molar ratio, constant temperature stirring reaction 2h ~ 10h after mixture being heated to 140 DEG C ~ 230 DEG C under nitrogen protection;
Add organic solvent in step 2, reaction system in step one after constant temperature stirring reaction, filter after stirring, the filter residue after filtration, through washing post-drying, obtains the bismaleimides containing phospha phenanthryl group; Described organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, propyl carbinol, toluene, dimethylbenzene, acetonitrile and acetone.
10. a kind of flame-retardant bismaleimide resin according to claim 9, is characterized in that, in the molar weight of organic solvent described in step 2 and step one, the ratio of the integral molar quantity of DOPO and bismaleimides is 1:(1 ~ 3).
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| WO2019019483A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Intrinsic flame-retardant resin with low polarity, and preparation method therefor and use thereof |
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| CN105385105B (en) * | 2015-11-17 | 2017-12-12 | 西安元创化工科技股份有限公司 | A kind of purposes of the bi-maleimide modified epoxy resin and preparation method thereof with it |
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| KR102292464B1 (en) | 2017-07-26 | 2021-08-23 | 셍기 테크놀로지 코. 엘티디. | Low polarity intrinsic flame retardant resin and its manufacturing method and application |
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| CN109535628B (en) * | 2018-11-28 | 2020-11-24 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same |
| CN110964320A (en) * | 2019-12-25 | 2020-04-07 | 艾蒙特成都新材料科技有限公司 | Flame-retardant maleimide composition and preparation method of copper-clad plate thereof |
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