CN104910327A - Phosphorus-nitrogen cooperative flame-retardant epoxy polymer and preparation method thereof - Google Patents
Phosphorus-nitrogen cooperative flame-retardant epoxy polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a phosphorus-nitrogen cooperative flame-retardant epoxy polymer and a preparation method thereof. The molecular weight of the phosphorus-nitrogen cooperative flame-retardant epoxy polymer is within the range of 7000-100000g/mol, and the structural formula of the polymer is as shown in the specification, wherein R1, R2 and R3 can be H or methyl; X is a benzene ring or a C2-6 linear alkyl; x: y: z=(10-50): (10-30): (50-10). The polymer contains epoxy groups having extremely high reaction activity, and the epoxy groups can be well dispersed and connected in the epoxy resin by virtue of chemical bonds, and therefore, the defects of poor compatibility, easy migration and the like of a non-reactive flame-retardant polymer are avoided. The polymer simultaneously contains two flame-retardant elements P and N and therefore is good in flame-retardant effect; the polymer can be used as a flame retardant or an intrinsically flame-retardant polymer; the polymer hardly affects the mechanical properties of a material substrate; the preparation method of the polymer is simple, good in repeatability and suitable for expanded production.
Description
Technical field
The invention belongs to flame retardance of polymer technical field, be specifically related to a kind of phosphorus nitrogen cooperative flame retardant epoxy polymer and preparation method thereof.
Background technology
Epoxy resin, as a kind of thermoset macromolecule material of excellent property, is widely used in the fields such as coating, tackiness agent, matrix material, so far existing more than 60 year history.Nearest research mainly concentrates on epoxy resin variation and performance application aspect, and the deficiency of flame retardant properties limits the development of epoxy resin in high-end fields such as electronic apparatuss.Therefore, most of epoxy resin has to pass through fire-retardant finish in actual applications, makes it reach the corresponding fire-retardant rank of national regulation.At present, the most frequently used method adopts to add the flammability problems that halogenated flame retardant, phosphorous fire retardant and inorganic combustion inhibitor solve polymer materials.But additive flame retardant causes the decline as polymer materials mechanical property and the transparency to resin matrix, the burning of halogen containing flame-retardant also can produce be corrosive gas not only contaminate environment also can harm humans healthy, simultaneously As time goes on can because of the migration of fire retardant, loss and reduce flame retardant effect.So the fire-retardant developing direction of future polymer should be the halogen-free flame retardants of response type.
CN101014650A discloses a kind of Halogenless fire retarded polymer foam materials, in polystyrene thaw process, is incorporated in polymeric matrix by fire retardant together with organic blowing agent, and halogen-free flame retardants used is a kind of phosphorous ring compound.But its phosphonium flame retardant adopted is small molecules, and this kind of flame retardant products still also exists the passing along with duration of service in use procedure, because fire retardant runs off, moves and make the shortcoming that the flame retardant properties of material reduces.
CN102391403 discloses a kind of high molecular fire retardant polymkeric substance, this polymkeric substance is formed by radical polymerization by the reactive monomer containing phosphorus nitrogen two kinds of ignition-proof elements, advantage can not only use as a kind of additive flame retardant, also can be used as intrinsically flame retarded macromolecular material simultaneously and use.But due to its still a kind of additive flame retardant in essence, be realize moving less object due to macromolecular chain and resin matrix physical crosslinking, still do not reach the effect be connected with resin matrix by chemical bond.
Summary of the invention
Object of the present invention is just the total shortcoming overcoming existing additive flame retardant, provides a kind of phosphorus nitrogen cooperative flame retardant epoxy polymer.
Another object of the present invention is exactly the preparation method being to provide above-mentioned phosphorus nitrogen cooperative flame retardant epoxy polymer.
Present invention employs following technical scheme:
A kind of phosphorus nitrogen cooperative flame retardant epoxy polymer, its molecular weight is 7000 ~ 100000g/mol, and its structural formula is as follows:
Wherein, R
1, R
2and R
3for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; X:y:z=10 ~ 50:10 ~ 30:50 ~ 10.
A preparation method for above-mentioned phosphorus nitrogen cooperative flame retardant epoxy polymer, comprises the steps:
(1) by 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO), p-aminophenol and paraformaldehyde react 4 ~ 8 hours in the first solvent at 30 ~ 80 DEG C, phenols intermediate is obtained after product with methylalcohol washing, this phenols intermediate and methacrylic chloride or acrylate chloride are reacted 4 ~ 8h under the second solvent and acid binding agent existent condition at 0 ~ 50 DEG C, cross and filter acid binding agent salt, steam and drying by washing, revolving again, obtain the first polymerization single polymerization monomer MAdiDOPO after purifying to crude product, its structural formula is as follows:
Wherein R
1for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; Described 9, the mix mol ratio of-10-phospho hetero phenanthrene-10-oxide compound, p-aminophenol and paraformaldehyde of 10-dihydro-9-oxy is 1:2.0 ~ 3.0:2.0 ~ 2.5, mol ratio 1:1.5 ~ 2.0:1.2 ~ 2.0 of described phenols intermediate, methacrylic chloride or acrylate chloride, acid binding agent;
(2) 2-amino-4-hydroxy-6-methylisocytosine (MIS) is dissolved in the 3rd solvent completely, then antipyretic to 90 ~ 170 DEG C, stop heating, add rapidly methacrylic acid-2-isocyanatoethyl ester (ICEMA) subsequently, after stirring 1 ~ 60min, use water cooling, to prevent the generation of polyreaction, by the first precipitation agent precipitation, vacuum-drying, obtains white powder, i.e. the second polymerization single polymerization monomer, its structural formula is as follows:
The mol ratio of described 2-amino-4-hydroxy-6-methylisocytosine and methacrylic acid-2-isocyanatoethyl ester is 1:0.8 ~ 2.0;
(3) by the first polymerization single polymerization monomer prepared by step (1), second polymerization single polymerization monomer prepared by step (2) and methacrylic acid (vinylformic acid) glycidyl ester (GMA) are dissolved in the 4th solvent, and add initiator, after logical oxide gas bubbling removes the oxygen in solvent, at 45 ~ 95 DEG C, stirring reaction 12 ~ 48h, after reaction terminates, concentration of reaction solution, by the second precipitation agent precipitation, obtain described phosphorus nitrogen cooperative flame retardant epoxy polymer, wherein the first polymerization single polymerization monomer, the total mole number of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester (GMA) is 100:0.2 ~ 3 with the ratio of the mole number of initiator, above-mentioned first polymerization single polymerization monomer, the mol ratio of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester (GMA) is 10 ~ 60:10 ~ 30:10 ~ 60.
In a preferred embodiment of the invention, described first solvent is ethanol, methyl alcohol, tetrahydrofuran (THF), acetone or acetonitrile, and described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the first solvent load are than being 1g:1 ~ 20mL.
In a preferred embodiment of the invention, described second solvent is toluene, ethyl acetate, tetrahydrofuran (THF), N, dinethylformamide, methylene dichloride or dimethyl sulfoxide (DMSO), the amount ratio of described methacrylic chloride or acrylate chloride and the second solvent is 1g:1 ~ 20mL.
In a preferred embodiment of the invention, described acid binding agent pyridine, triethylamine, sodium bicarbonate, sodium carbonate or sodium hydroxide.
In a preferred embodiment of the invention, described 3rd solvent is DMSO, DMF, ethylene dichloride or tetrachloroethane.
In a preferred embodiment of the invention, described first precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
In a preferred embodiment of the invention, described 4th solvent is toluene, tetrahydrofuran (THF), chloroform, tetrachloroethane or ethylene dichloride.
In a preferred embodiment of the invention, described initiator is ABVN, AIBN, BPO, DTBP or TBCP.
In a preferred embodiment of the invention, described second precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
The invention has the beneficial effects as follows:
1, the present invention is by regulating mole when reaction times of monomer and chain-transfer agent, effectively adjusts the content of phosphorus, nitrogen element, realizes the controlled design of multipolymer;
2, polymkeric substance of the present invention has the very high epoxide group of reactive behavior, can be good at the solidification disperseing also to be participated in epoxy resin by the epoxide group of GMA on polymer segment, thus be connected in resin matrix by chemical bond-linking by ignition-proof element, thus improve the shortcoming that current additive flame retardant easily moves, runs off;
3, polymkeric substance of the present invention contains P and N two kinds of ignition-proof elements simultaneously, good flame retardation effect, not only can do fire retardant and use, and also can do intrinsically flame retarded polymkeric substance and use, little to the mechanical impact of material matrix;
4, the reaction conditions of preparation method of the present invention is gentle, and prepare easy, transformation efficiency is high, and product purity is high, is applicable to expanding production.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra spectrogram of this flame-retardant polymer in the embodiment of the present invention 1, and in FIG, X-coordinate is chemical shift chemical shift (ppm);
Fig. 2 is the nucleus magnetic resonance phosphorus spectrum spectrogram of this flame-retardant polymer in the embodiment of the present invention 1, and in fig. 2, X-coordinate is chemical shift chemical shift (ppm).
Embodiment
By reference to the accompanying drawings below by way of embodiment technical scheme of the present invention is further detailed and is described.
Embodiment 1
The synthesis of step 1, described the first polymerization single polymerization monomer (MAdiDOPO):
First, DOPO, 10.9g (0.1mol) p-aminophenol of 43.2g (0.2mol) and 6.0g (0.1mol) paraformaldehyde and 200mL ethanol are joined in the three-necked flask of 500mL, stirring reaction 5h at 50 DEG C, obtains phenols midbody compound after product with methylalcohol washing.Then, by the triethylamine of phenols intermediate 10.1g (0.10mol) prepared by 33.2g (0.05mol) and the methylene dichloride of 100mL, under being placed in the condition of 0 DEG C, slow instillation 10.5g (0.10mol) methacrylic chloride, after dropwising rear continuation stirring reaction 8h, cross and filter triethylamine hydrochloride, by washing, revolve the phosphorus-nitrogen containing flame retardant MAdiDOPO (reference: CN104262398A) obtained after steaming and drying are purified to crude product containing activity double key.
The synthesis of step 2, described the second polymerization single polymerization monomer (UPyMA):
5g MIS is dissolved in appropriate 20mL DMSO completely, is heated to 150 DEG C, then reaction flask is taken out from oil bath.Add rapidly 6.2mL ICEMA subsequently, after stirring 20min, use water cooling.Reaction mixture normal hexane precipitates, and vacuum-drying obtains white powder, i.e. UPyMA (reference: the people Macromolecules such as Yamauchi, 2003,36,1083-1088 and Macromolecules, 2002,35,8745-8750).
The preparation of step 3, described flame-retardant polymer:
First, 1.7g (6mmol) UPyMA, 2.56g (18mmol) GMA, 22.7g (36mmol) MAdiDOPO (i.e. x:y:z=10:30:60) and 0.08g AIBN is in reaction flask, after logical oxide gas bubbling removes the oxygen in solvent, at 70 DEG C, stirring reaction 24h.After reaction terminates, concentration of reaction solution, with methanol extraction 2 ~ 3 times, obtains white powdery solids.The sign of polymkeric substance is as depicted in figs. 1 and 2: wherein chemical shift is the characteristic peak of UPy at three parcel peaks of 10ppm to 13ppm, 6ppm to 8ppm is the characteristic peak of DiDOPO, about 3.5ppm is the characteristic peak of GMA, in addition phosphorus spectrum demonstrates single peak, and target compound has correctly been synthesized in this explanation.
Embodiment 2 ~ 8
Experimental procedure 1 and 2 is with embodiment 1.The preparation method of step 3 is similar to Example 1, and the value just by adjusting x:y:z adjusts the ratio of different monomers, is that the phosphorus-nitrogen ratio in polymkeric substance changes.The ingredient proportion of concrete UPyMA, GMA, MAdiDOPO is concrete as table 1:
Table 1
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| UPyMA | 20 | 30 | 40 | 50 | 60 | 70 | 0 |
| GMA | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| MAdiDOPO | 50 | 40 | 30 | 20 | 10 | 0 | 70 |
Those of ordinary skill in the art are known, when technical parameter of the present invention changes in following ranges, can estimate to obtain same as the previously described embodiments or close technique effect:
A kind of phosphorus nitrogen cooperative flame retardant epoxy polymer, its molecular weight is 7000 ~ 100000g/mol, and its structural formula is as follows:
Wherein, R
1, R
2and R
3for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; X:y:z=10 ~ 50:10 ~ 30:50 ~ 10.
A preparation method for above-mentioned phosphorus nitrogen cooperative flame retardant epoxy polymer, comprises the steps:
(1) by 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO), p-aminophenol and paraformaldehyde react 4 ~ 8 hours in the first solvent at 30 ~ 80 DEG C, phenols intermediate is obtained after product with methylalcohol washing, this phenols intermediate and methacrylic chloride or acrylate chloride are reacted 4 ~ 8h under the second solvent and acid binding agent existent condition at 0 ~ 50 DEG C, cross and filter acid binding agent salt, steam and drying by washing, revolving again, obtain the first polymerization single polymerization monomer MAdiDOPO after purifying to crude product, its structural formula is as follows:
Wherein R
1for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; Described 9, the mix mol ratio of-10-phospho hetero phenanthrene-10-oxide compound, p-aminophenol and paraformaldehyde of 10-dihydro-9-oxy is 1:2.0 ~ 3.0:2.0 ~ 2.5, mol ratio 1:1.5 ~ 2.0:1.2 ~ 2.0 of described phenols intermediate, methacrylic chloride or acrylate chloride, acid binding agent;
(2) 2-amino-4-hydroxy-6-methylisocytosine (MIS) is dissolved in the 3rd solvent completely, then antipyretic to 90 ~ 170 DEG C, stop heating, add rapidly methacrylic acid-2-isocyanatoethyl ester (ICEMA) subsequently, after stirring 1 ~ 60min, use water cooling, to prevent the generation of polyreaction, by the first precipitation agent precipitation, vacuum-drying, obtains white powder, i.e. the second polymerization single polymerization monomer, its structural formula is as follows:
The mol ratio of described 2-amino-4-hydroxy-6-methylisocytosine and methacrylic acid-2-isocyanatoethyl ester is 1:0.8 ~ 2.0;
(3) by the first polymerization single polymerization monomer prepared by step (1), second polymerization single polymerization monomer prepared by step (2) and methacrylic acid (vinylformic acid) glycidyl ester (GMA) are dissolved in the 4th solvent, and add initiator, after logical oxide gas bubbling removes the oxygen in solvent, at 45 ~ 95 DEG C, stirring reaction 12 ~ 48h, after reaction terminates, concentration of reaction solution, by the second precipitation agent precipitation, obtain described phosphorus nitrogen cooperative flame retardant epoxy polymer, wherein the first polymerization single polymerization monomer, the total mole number of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester (GMA) is 100:0.2 ~ 3 with the ratio of the mole number of initiator, above-mentioned first polymerization single polymerization monomer, the mol ratio of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester (GMA) is 10 ~ 60:10 ~ 30:10 ~ 60.
Described first solvent is ethanol, methyl alcohol, tetrahydrofuran (THF), acetone or acetonitrile, and described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the first solvent load are than being 1g:1 ~ 20mL.
Described second solvent is toluene, ethyl acetate, tetrahydrofuran (THF), DMF, methylene dichloride or dimethyl sulfoxide (DMSO), and the amount ratio of described methacrylic chloride or acrylate chloride and the second solvent is 1g:1 ~ 20mL.
Described acid binding agent pyridine, triethylamine, sodium bicarbonate, sodium carbonate or sodium hydroxide.
Described 3rd solvent is DMSO, DMF, ethylene dichloride or tetrachloroethane.
Described first precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
Described 4th solvent is toluene, tetrahydrofuran (THF), chloroform, tetrachloroethane or ethylene dichloride.
Described initiator is ABVN, AIBN, BPO, DTBP or TBCP.
Described second precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (10)
1. a phosphorus nitrogen cooperative flame retardant epoxy polymer, is characterized in that: its molecular weight is 7000 ~ 100000g/mol, and its structural formula is as follows:
Wherein, R
1, R
2and R
3for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; X:y:z=10 ~ 50:10 ~ 30:50 ~ 10.
2. a preparation method for phosphorus nitrogen cooperative flame retardant epoxy polymer according to claim 1, is characterized in that: comprise the steps:
(1) by 9,10-dihydro-9-oxy assorted-10-phospho hetero phenanthrene-10-oxide compound, p-aminophenol and paraformaldehyde react 4 ~ 8 hours in the first solvent at 30 ~ 80 DEG C, phenols intermediate is obtained after product with methylalcohol washing, this phenols intermediate and methacrylic chloride or acrylate chloride are reacted 4 ~ 8h under the second solvent and acid binding agent existent condition at 0 ~ 50 DEG C, cross and filter acid binding agent salt, steam and drying by washing, revolving again, obtain the first polymerization single polymerization monomer MAdiDOPO after purifying to crude product, its structural formula is as follows:
Wherein R
1for H or methyl; X is the straight chained alkyl of phenyl ring or 2 ~ 6 carbon; Described 9, the mix mol ratio of-10-phospho hetero phenanthrene-10-oxide compound, p-aminophenol and paraformaldehyde of 10-dihydro-9-oxy is 1:2.0 ~ 3.0:2.0 ~ 2.5, mol ratio 1:1.5 ~ 2.0:1.2 ~ 2.0 of described phenols intermediate, methacrylic chloride or acrylate chloride, acid binding agent;
(2) 2-amino-4-hydroxy-6-methylisocytosine is dissolved in the 3rd solvent completely, then antipyretic to 90 ~ 170 DEG C, stop heating, add rapidly methacrylic acid-2-isocyanatoethyl ester subsequently, after stirring 1 ~ 60min, use water cooling, to prevent the generation of polyreaction, by the first precipitation agent precipitation, vacuum-drying, obtains white powder, i.e. the second polymerization single polymerization monomer, its structural formula is as follows:
The mol ratio of described 2-amino-4-hydroxy-6-methylisocytosine and methacrylic acid-2-isocyanatoethyl ester is 1:0.8 ~ 2.0;
(3) by the first polymerization single polymerization monomer prepared by step (1), second polymerization single polymerization monomer prepared by step (2) and methacrylic acid (vinylformic acid) glycidyl ester are dissolved in the 4th solvent, and add initiator, after logical oxide gas bubbling removes the oxygen in solvent, at 45 ~ 95 DEG C, stirring reaction 12 ~ 48h, after reaction terminates, concentration of reaction solution, by the second precipitation agent precipitation, obtain described phosphorus nitrogen cooperative flame retardant epoxy polymer, wherein the first polymerization single polymerization monomer, the total mole number of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester is 100:0.2 ~ 3 with the ratio of the mole number of initiator, above-mentioned first polymerization single polymerization monomer, the mol ratio of the second polymerization single polymerization monomer and methacrylic acid (vinylformic acid) glycidyl ester is 10 ~ 60:10 ~ 30:10 ~ 60.
3. preparation method as claimed in claim 2, is characterized in that: described first solvent is ethanol, methyl alcohol, tetrahydrofuran (THF), acetone or acetonitrile, and described 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the first solvent load are than being 1g:1 ~ 20mL.
4. preparation method as claimed in claim 2, it is characterized in that: described second solvent is toluene, ethyl acetate, tetrahydrofuran (THF), N, dinethylformamide, methylene dichloride or dimethyl sulfoxide (DMSO), the amount ratio of described methacrylic chloride or acrylate chloride and the second solvent is 1g:1 ~ 20mL.
5. preparation method as claimed in claim 2, is characterized in that: described acid binding agent pyridine, triethylamine, sodium bicarbonate, sodium carbonate or sodium hydroxide.
6. preparation method as claimed in claim 2, is characterized in that: described 3rd solvent is DMSO, DMF, ethylene dichloride or tetrachloroethane.
7. preparation method as claimed in claim 2, is characterized in that: described first precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
8. preparation method as claimed in claim 2, is characterized in that: described 4th solvent is toluene, tetrahydrofuran (THF), chloroform, tetrachloroethane or ethylene dichloride.
9. preparation method as claimed in claim 2, is characterized in that: described initiator is ABVN, AIBN, BPO, DTBP or TBCP.
10. preparation method as claimed in claim 2, is characterized in that: described second precipitation agent is ethanol, methyl alcohol, normal hexane, Skellysolve A or normal heptane.
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| CN109415541A (en) * | 2016-06-16 | 2019-03-01 | 株式会社普利司通 | Rubber additive |
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| WO2019019465A1 (en) * | 2017-07-26 | 2019-01-31 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board |
| CN108329804B (en) * | 2018-02-12 | 2020-02-11 | 莆田学院 | Preparation method of nitrogen-containing silica sol and phosphorus synergistic flame-retardant epoxy acrylate coating |
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| CN109467574A (en) * | 2018-11-13 | 2019-03-15 | 岭南师范学院 | It is a kind of novel based on vanillic aldehyde reactive flame retardant and its preparation, application |
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| CN114957547A (en) * | 2021-02-25 | 2022-08-30 | 中国石油化工股份有限公司 | Phosphorus flame retardant, preparation method thereof and flame-retardant compound |
| CN114957547B (en) * | 2021-02-25 | 2024-02-09 | 中国石油化工股份有限公司 | Phosphorus flame retardant, preparation method thereof and flame retardant compound |
| CN114907618A (en) * | 2021-12-13 | 2022-08-16 | 井冈山大学 | MXenes-based flame retardant, flame retardant compound for preparing MXenes-based flame retardant and application of flame retardant compound |
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| CN104910327B (en) | 2018-02-27 |
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