CN111592689A - Cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures, preparation process and application thereof - Google Patents
Cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures, preparation process and application thereof Download PDFInfo
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- CN111592689A CN111592689A CN202010501692.3A CN202010501692A CN111592689A CN 111592689 A CN111592689 A CN 111592689A CN 202010501692 A CN202010501692 A CN 202010501692A CN 111592689 A CN111592689 A CN 111592689A
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- flame retardant
- phosphaphenanthrene
- cyclotriphosphazene
- dopo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 117
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 109
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 title claims abstract description 62
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 title claims abstract description 61
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000004305 biphenyl Chemical group 0.000 title claims abstract description 24
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 26
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 39
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 35
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- 239000000463 material Substances 0.000 claims description 25
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
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- 239000012153 distilled water Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
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- 239000000843 powder Substances 0.000 claims description 9
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 150000007529 inorganic bases Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 abstract description 55
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002131 composite material Substances 0.000 abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
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- 230000015556 catabolic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
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- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
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- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a halogen-free flame retardant, and particularly relates to a cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures. The flame retardant is a cyclotriphosphazene flame retardant containing a phosphaphenanthrene group and a dihydroxybiphenyl structure, which is synthesized by reasonably assembling and modifying core structure segments of a dihydroxybiphenyl, DOPO and cyclotriphosphazene flame retardant. The flame retardant has high phosphorus content, nitrogen content, heat resistance and high-temperature char yield, is well compatible with polylactic acid, ABS and other matrixes, has good thermal stability, and the prepared composite material has excellent mechanical properties and good flame retardant effect.
Description
Technical Field
The invention belongs to the technical field of chemical industry, mainly relates to the technical field of flame retardants, and particularly relates to a cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures, a preparation process and application thereof in preparation of flame-retardant high polymer materials.
Background
The traditional halogen flame retardant is widely applied to flame retardant application of high polymer materials due to the advantages of high flame retardant efficiency, small addition amount, high cost performance and the like. With the promulgation of European Union laws and the increase of environmental awareness of people, the halogen flame retardant may release carcinogens such as dioxin and the like in the combustion process, thereby causing serious harm to the health of people; and the halogen flame retardant has large smoke generation amount in the combustion process and causes secondary damage to escape personnel on the fire scene, so that the halogen-free flame retardant with single molecule and multiple elements for synergistic flame retardance becomes an international research hotspot.
The cyclotriphosphazene is a planar hexacyclic inorganic compound consisting of N, P atoms alternately, and the cyclotriphosphazene derivative flame retardant with excellent flame retardance and heat resistance can be obtained by changing a substituent group connected with a phosphorus atom. However, the cyclotriphosphazene flame retardant has some problems in the application process, and the molecular weight of the cyclotriphosphazene flame retardant is small, so that the cyclotriphosphazene flame retardant is not good in compatibility with a polymer, and the mechanical property of the composite material is seriously reduced after the flame retardant is added. The phosphaphenanthrene flame retardant represented by DOPO has become a hotspot content of research on the halogen-free flame retardant due to the advantages of no halogen, no toxicity, difficult hydrolysis and volatilization, good compatibility with a polymer matrix and the like. However, the direct use of DOPO for flame retardancy of polymers still has some problems: on one hand, under high temperature, on the other hand, the thermal weight loss temperature of DOPO is about 180 ℃, degradation may be generated in the processing process of the polymer, and thus the flame retardant effect is influenced.
Disclosure of Invention
Aiming at the defects and problems that the conventional halogen-containing flame retardant generates carcinogenic substances, and halogen-free cyclotriphosphazene flame retardant has poor compatibility with polymers to cause serious reduction of mechanical properties of composite materials and is easy to degrade, the invention provides a cyclotriphosphazene flame retardant containing a phosphaphenanthrene group and a dihydroxybiphenyl structure, a preparation process and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures has the following molecular structure:
the synthetic route of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures is as follows:
the invention also provides a preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures, which comprises the following steps:
step one, dissolving dihydroxybiphenyl in acetone under an ice bath condition, adding an acid-binding agent, stirring uniformly, and then dropwise adding an acetone solution containing hexachlorocyclotriphosphazene, wherein the molar ratio of hexachlorocyclotriphosphazene to dihydroxybiphenyl is 1:1-1:1.4, and the molar ratio of hexachlorocyclotriphosphazene to the acid-binding agent is 1: 2-1: 2.8; reacting at room temperature for 15-20min, standing and filtering the solution, collecting filtrate, and washing a filter cake with a solvent for 3-5 times; dropwise adding distilled water into the filtrate to obtain a white precipitate, and vacuum drying the white precipitate at 80 ℃ for 10-30h to obtain an intermediate I;
step two, adding THF (tetrahydrofuran) as a solvent into a reaction container, adding an acid-binding agent and p-hydroxybenzaldehyde into the reaction container, and fully stirring until the acid-binding agent and the p-hydroxybenzaldehyde are completely dissolved; dissolving the intermediate I in THF, then dripping the intermediate I into a reaction container, wherein the molar ratio of the intermediate I to p-hydroxybenzaldehyde is 1:4.5-1:6, raising the temperature in the reaction container to a reflux state, reacting for 22-24h, then cooling the solution to room temperature, filtering, washing filter cakes for 2-5 times respectively with distilled water and absolute ethyl alcohol, drying for 4h after washing in a blast oven, and adding ethyl acetate for recrystallization to obtain a white acicular solid which is an intermediate II;
step three, adding DMF (dimethyl formamide) as a solvent into a reaction container, adding DOPO into the reaction container, heating to 120 ℃, and stirring until the DOPO is completely dissolved; adding an intermediate II, wherein the molar ratio of the intermediate II to the phosphaphenanthrene DOPO is 1: 4.8-1: 6, heating to 140 ℃, and continuing to react for 10 hours; filtering, adding a large amount of ice water into the filtrate to obtain white precipitate, filtering the white precipitate by using filter paper with the pore diameter of 50-80 mu m, washing the white precipitate for 3-5 times by using an absolute ethyl alcohol/toluene mixed solution, and drying the white precipitate for 24 hours in a vacuum oven to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure.
The preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures is characterized by comprising the following steps of: in the first step, the molar ratio of hexachlorocyclotriphosphazene to dihydroxybiphenyl is 1:1.2, and the molar ratio of hexachlorocyclotriphosphazene to acid-binding agent is 1: 2.5.
In the preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures, the acid-binding agent is inorganic base or organic base without active hydrogen, wherein the inorganic base is one or more of potassium carbonate, sodium carbonate or sodium hydroxide, and the organic base without active hydrogen is pyridine or triethylamine.
In the preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures, in the first step, the solvent used for washing the filter cake is one or more of tetrahydrofuran, N-dimethylformamide and acetone.
In the preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures, the molar ratio of the intermediate I to the p-hydroxybenzaldehyde in the step two is 1: 4.8.
In the preparation process of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures, the molar ratio of the intermediate II to the phosphaphenanthrene DOPO is 1:5 in the step III.
The invention relates to application of a cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures in preparation of flame retardant materials.
The invention has the beneficial effects that:
1. the flame retardant has good compatibility with polylactic acid, ABS matrix and the like, and can maintain the mechanical property of matrix materials; the dihydroxybiphenyl structure can provide higher heat resistance and high-temperature char formation rate; the DOPO structure can provide a carbon source for the composite material when it is burned; the cyclotriphosphazene structure can provide higher phosphorus and nitrogen content.
2. The flame retardant is prepared by introducing a dihydroxybiphenyl structure and a phosphaphenanthrene structure unit into a cyclotriphosphazene structure to achieve the purpose of phosphorus-nitrogen synergistic flame retardance, has high phosphorus content, nitrogen content, heat resistance and high-temperature char yield, and can be used as an additive halogen-free flame retardant for polylactic acid (PLA) and ABS.
3. The cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures is a white crystal, has a melting point of 188-190 ℃, has good thermal stability, and has the weight loss of 5% when the temperature reaches 360 ℃ and the char yield of 47% when the temperature reaches 800 ℃; the flame retardant can be dissolved in solvents such as dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and the like.
4. The cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure has the advantages of easily available raw materials, advanced process, simple operation, high yield and high purity of the obtained finished product; the product post-treatment is simple; the used solvent can be recycled, and is economical and practical.
Drawings
FIG. 1 is an FTIR spectrum of cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene group and dihydroxybiphenyl structure prepared by the invention.
FIG. 2 is a nuclear magnetic spectrum diagram of a cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene groups and dihydroxybiphenyl structures prepared by the invention.
FIG. 3 shows TG and DTG spectra of cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene group and dihydroxybiphenyl structure prepared by the present invention.
FIG. 4 is an FTIR spectrum of a blend material of cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene groups and dihydroxybiphenyl structures and polylactic acid prepared by the invention.
FIG. 5 is a Heat Release Rate (HRR) curve of a cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene groups and dihydroxybiphenyl structures and a polylactic acid blended material prepared by the invention.
FIG. 6 is the Total Heat Release (THR) curve of the blend material of the cyclotriphosphazene flame retardant (HABP-DOPO) containing the phosphaphenanthrene group and the dihydroxybiphenyl structure and the polylactic acid prepared by the invention.
FIG. 7 is TG and DTG curves of a blend material of a cyclotriphosphazene flame retardant (HABP-DOPO) containing a phosphaphenanthrene group and a dihydroxybiphenyl structure and polylactic acid prepared by the invention;
FIG. 8 is a graph showing the change of impact strength of a blend material of a cyclotriphosphazene flame retardant (HABP-DOPO) containing a phosphaphenanthrene group and a dihydroxybiphenyl structure and a polylactic acid prepared by the method.
FIG. 9 is a scanning electron microscope image of a blend material of cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene groups and dihydroxybiphenyl structures and polylactic acid prepared by the invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1: the embodiment provides a preparation method of cyclotriphosphazene flame retardant containing phosphaphenanthrene groups and dihydroxybiphenyl structures, which comprises the following steps:
step one, 4.0g (11.50mmol) of purified hexachlorocyclotriphosphazene and 40ml of acetone are added into a 250ml three-neck flask provided with magnetons and a drying tube. Starting a magnetic stirrer to dissolve hexachlorocyclotriphosphazene, and adding K2CO33.18g (23.0mmol) of powder and 2.14g (11.50mmol) of 2, 2' -biphenol using weak N2The flow flushes residual air from the bottle. The whole reaction system is in a room temperature environment and reacts for 15 min. And after the reaction is finished, carrying out suction filtration, washing a filter cake by using a small amount of acetone, taking filtrate in a bottle, dropwise adding distilled water and continuously stirring to generate a large amount of precipitates in the filtrate, filtering to obtain a white filter cake, washing the filter cake three times by using absolute ethyl alcohol and distilled water, and drying for 24 hours in a vacuum oven at 80 ℃ to obtain a white powdery product intermediate I.
Step two, sequentially adding K into a 500mL three-neck flask provided with magnetons and a drying tube2CO36.62g (0.048mol), p-hydroxybenzaldehyde 5.86g (0.048mol) and 200mL of anhydrous THF, stirring at room temperature for 1h under nitrogen protection; 4.6g (0.01mol) of intermediate I dissolved in 100ml of DMF are then added over 30min and stirred at reflux temperature for 22 h. And after the reaction is finished, filtering to remove residual solids, dripping the filtrate into a large amount of ice water and continuously stirring to generate white precipitate immediately, standing, filtering, washing the filter cake twice by using distilled water and absolute ethyl alcohol respectively, and drying for 4 hours in a forced air oven. Ethyl acetate was recrystallized to give intermediate ii as a white needle-like solid.
And step three, sequentially adding DOPO4.54g (0.021mol) and 100mL of DMF (dimethyl formamide) into a 500mL three-neck flask provided with magnetons, a condenser tube and a nitrogen device, heating to 120 ℃, stirring until the mixture is completely dissolved, introducing nitrogen, adding 3.3g (0.004mol) of an intermediate product II, heating to 140 ℃, and continuing to react for 10 hours. And cooling for half an hour after the reaction is finished, dropwise adding the reaction solution into a large amount of ice water, immediately separating out white precipitate, filtering, washing the reaction solution with distilled water for three times, performing suction filtration, washing the filter cake with an absolute ethyl alcohol/toluene mixed solution for three times, and drying the filter cake in a vacuum oven for 24 hours to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure, wherein the yield is 94.9%.
Example 2: the preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure comprises the following steps:
step one, 4.0g (11.50mmol) of purified hexachlorocyclotriphosphazene and 40ml of acetone are added into a 250ml three-neck flask provided with magnetons and a drying tube. Starting a magnetic stirrer to dissolve hexachlorocyclotriphosphazene, and adding Na2CO33.18g (30mmol) of powder and 2.23g (12.0mmol) of 2, 2' -biphenol using weak N2The flow flushes residual air from the bottle. The whole reaction system is in a room temperature environment and reacts for 15 min. And after the reaction is finished, carrying out suction filtration, washing a filter cake by using a small amount of acetone, taking filtrate in a bottle, dropwise adding distilled water and continuously stirring to generate a large amount of precipitates in the filtrate, filtering to obtain a white filter cake, washing the filter cake three times by using absolute ethyl alcohol and distilled water, and drying for 24 hours in a vacuum oven at 80 ℃ to obtain a white powdery product intermediate I.
Step two, sequentially adding Na into a 500mL three-neck flask provided with magnetons and a drying tube2CO35.09g (0.048mol), p-hydroxybenzaldehyde 6.1g (0.05mol) and 200mL of anhydrous THF, stirring for 1h at room temperature under the protection of nitrogen; 4.6g (0.01mol) of intermediate I dissolved in 100ml of DMF are then added over 30min and stirred at reflux temperature for 22 h. Filtering to remove residual solid after reaction, dripping the filtrate into a large amount of ice water, stirring continuously to generate white precipitate, standing, vacuum filtering, washing the filter cake with distilled water and anhydrous ethanol twice, and oven drying in a forced air ovenDrying for 4 h. Ethyl acetate was recrystallized to give intermediate ii as a white needle-like solid.
And step three, sequentially adding DOPO4.75g (0.022mol) and 100mL DMF (dimethyl formamide) into a 500mL three-neck flask provided with magnetons, a condenser tube and a nitrogen device, heating to 120 ℃, stirring until the mixture is completely dissolved, introducing nitrogen, adding 3.3g (0.004mol) of an intermediate product II, heating to 140 ℃, and continuing to react for 10 hours. And cooling for half an hour after the reaction is finished, dropwise adding the reaction solution into a large amount of ice water, immediately separating out white precipitate, filtering, washing the reaction solution with distilled water for three times, performing suction filtration, washing the filter cake with an absolute ethyl alcohol/toluene mixed solution for three times, and drying the filter cake in a vacuum oven for 24 hours to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure, wherein the yield is 95.4%.
Example 3: the embodiment provides a preparation method of cyclotriphosphazene flame retardant containing phosphaphenanthrene groups and dihydroxybiphenyl structures, which comprises the following steps:
step one, 4.0g (11.50mmol) of purified hexachlorocyclotriphosphazene and 40ml of acetone are added into a 250ml three-neck flask provided with magnetons and a drying tube. After the hexachlorocyclotriphosphazene was dissolved by starting the magnetic stirrer, 2.274g (28.75mmol) of pyridine powder and 2.568g (13.8mmol) of 2, 2' -biphenol were added using weak N2The flow flushes residual air from the bottle. The whole reaction system is in a room temperature environment and reacts for 15 min. And after the reaction is finished, carrying out suction filtration, washing a filter cake by using a small amount of tetrahydrofuran, taking filtrate in a bottle, dropwise adding distilled water and continuously stirring to generate a large amount of precipitates in the filtrate, filtering to obtain a white filter cake, washing the filter cake three times by using absolute ethyl alcohol and distilled water, and drying for 24 hours in a vacuum oven at 80 ℃ to obtain a white powdery product intermediate I.
Step two, sequentially adding K into a 500mL three-neck flask provided with magnetons and a drying tube2CO36.62g (0.048mol), 5.49g (0.045mol) of p-hydroxybenzaldehyde and 200mL of anhydrous THF, stirring for 1h at room temperature under the protection of nitrogen; 4.6g (0.01mol) of intermediate I dissolved in 100ml of DMF are then added over 30min and stirred at reflux temperature for 22 h. Filtering to remove residual solid after reaction, dripping the filtrate into a large amount of ice water and stirring continuously to generate white precipitate immediatelyStanding, filtering, washing the filter cake twice with distilled water and absolute ethyl alcohol respectively, and drying in a blast oven for 4 h. Ethyl acetate was recrystallized to give intermediate ii as a white needle-like solid.
And step three, sequentially adding DOPO4.32g (0.02mol) and 100mL of DMF (dimethyl formamide) into a 500mL three-neck flask provided with magnetons, a condenser tube and a nitrogen device, heating to 120 ℃, stirring until the mixture is completely dissolved, introducing nitrogen, adding 3.3g (0.004mol) of the intermediate II, heating to 140 ℃, and continuing to react for 10 hours. And cooling for half an hour after the reaction is finished, dropwise adding the reaction solution into a large amount of ice water, immediately separating out white precipitate, filtering, washing with distilled water for three times, performing suction filtration, washing the filter cake with an absolute ethyl alcohol/toluene mixed solution for three times, and drying the filter cake in a vacuum oven for 24 hours to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure, wherein the yield is 95.2%.
Example 4: the preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure comprises the following steps:
step one, 4.0g (11.50mmol) of purified hexachlorocyclotriphosphazene and 40ml of acetone are added into a 250ml three-neck flask provided with magnetons and a drying tube. After the hexachlorocyclotriphosphazene was dissolved by starting the magnetic stirrer, 2.356g (32.2mmol) of diethylamine and 3.0g (11.50mmol) of 2, 2' -biphenol were added, using weak N2The flow flushes residual air from the bottle. The whole reaction system is in a room temperature environment and reacts for 15 min. And after the reaction is finished, carrying out suction filtration, flushing a filter cake by using a small amount of N, N-dimethylformamide, taking filtrate in a bottle, dropwise adding distilled water and continuously stirring to generate a large amount of precipitate in the filtrate, filtering to obtain a white filter cake, washing the filter cake three times by using absolute ethyl alcohol and distilled water, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain a white powdery product intermediate I.
Step two, sequentially adding K into a 500mL three-neck flask provided with magnetons and a drying tube2CO36.62g (0.048mol), 7.32g (0.06mol) of p-hydroxybenzaldehyde and 200mL of anhydrous THF, stirring for 1h at room temperature under the protection of nitrogen; 4.6g (0.01mol) of intermediate I dissolved in 100ml of DMF are then added over 30min and stirred at reflux temperature for 22 h. After the reaction is finished, filtering and removingAnd (3) dropping the filtrate into a large amount of ice water while continuously stirring to generate a white precipitate immediately, standing, performing suction filtration, washing the filter cake twice with distilled water and absolute ethyl alcohol respectively, and drying for 4 hours in a blast oven. Ethyl acetate was recrystallized to give intermediate ii as a white needle-like solid.
And step three, sequentially adding DOPO5.18g (0.024mol) and 100mL of DMF (dimethyl formamide) into a 500mL three-neck flask provided with a magneton, a condenser tube and a nitrogen device, heating to 120 ℃, stirring until the mixture is completely dissolved, introducing nitrogen, adding 3.3g (0.004mol) of the intermediate II, heating to 140 ℃, and continuing to react for 10 hours. And cooling for half an hour after the reaction is finished, dropwise adding the reaction solution into a large amount of ice water, immediately separating out white precipitate, filtering, washing with distilled water for three times, performing suction filtration, washing the filter cake with an absolute ethyl alcohol/toluene mixed solution for three times, and drying the filter cake in a vacuum oven for 24 hours to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure, wherein the yield is 94.7%.
Test example 1, Performance test
(1) Infrared spectroscopy (FTIR spectrogram)
The functional groups of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure prepared by the method are analyzed by Fourier infrared spectroscopy, and the specific figure is 1.
From the results of the infrared spectroscopic analysis FTIR (KBr) of FIG. 1, it can be seen that: 1438.46cm-1、1477.09cm-1、1502.04cm-1Is the oscillation peak of the benzene ring skeleton of H-1, 756.40cm-1Representing a 1, 2 ortho substitution on the phenyl ring, 858.27cm-1Represents 1, 4 substitution on a benzene ring, proves that a spiro ring has been successfully grafted on a cyclophosphazene molecule, 1704.01cm-1Is the vibrational peak of the C ═ O bond of-CHO, 2741.55cm-1、2844.26cm-1Is the C-H stretching vibration peak of-CHO, 1388.65cm-1Is the CH in-plane bending vibration peak of-CHO, 1178.56cm-1Is the C-C vibration peak of aromatic aldehyde, which indicates that the para-hydroxybenzaldehyde has been successfully substituted; 3424.54cm-1Is the oscillatory peak of-OH, 756.24cm-1、946.96cm-1Is the oscillation peak of P-O-Ph, 1209.64cm-1As P ═ N oscillation peak, evidenceDOPO was successfully incorporated into the flame retardant.
(2) Nuclear magnetic resonance analysis
Nuclear magnetic resonance is carried out on the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure, and the nuclear magnetic spectrum is shown in figure 2 (a)1HNMR；(b)31PNMR。
It can be seen from the nuclear magnetic hydrogen spectrum of HABP-DOPO of FIG. 2 that: in the nuclear magnetic hydrogen spectrum of HABP-DOPO, the absorption peak of C-H is 5.13-5.43ppm, and the absorption peak of-OH is 6.40-6.79 ppm. 6.93-8.23ppm are absorption peaks for DOPO groups and hydrogen on the carbon-attached benzene ring, with an integral ratio of about 1: 1: 14, in line with the expected results. Of H-331The peak at 8.83ppm, 9.40ppm in PNMR is the chemical shift of P with biphenyl, 25.06ppm, the chemical shift of the bimodal P-O-Ph-DOPO at 31.50ppm, from which it can be seen that three P have two chemical environments and the integrated area ratio is about 1:2, the product was confirmed to be the target compound.
(3) Analysis of elemental content
The element content analysis of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure prepared by the method is that C: 12.7 percent; h: 4.3 percent; 2.5% of N, which substantially corresponds to the elemental content of the desired product.
(4) Thermogravimetric analysis (TG)
The change in sample mass and the chemical properties of the components with increasing temperature were analyzed using a thermogravimetric analyzer, and the results are shown in fig. 3.
As can be seen from the TGA results of FIG. 3, the initial decomposition temperature of HABP-DOPO is about 359.4 deg.C (based on 5% weight loss); the main peak of thermal degradation was at about 472.4 ℃ and the residual mass at 800 ℃ was 47.7%.
Test example 2 shows that the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure provided by the invention is respectively used as a phosphorus-nitrogen synergistic flame retardant for polylactic acid and ABS.
(1) Performance test of flame retardant and polylactic acid blending material prepared by the invention
The composite material is prepared by controlling the content ratio of the flame retardant and the polylactic acid (PLA), standard sample bars are prepared according to GB/T2406-93 and GB/T2508-1996 test standards respectively, a limit oxygen index test and a vertical combustion test are carried out, a combustion performance test is carried out by JF-2 and FZ-5401 equipment, the flame retardant performance of the pure PLA and the blended material is researched by LOI and UL-94 tests, and the test result and the dripping performance are listed in Table 1.
TABLE 1 flame retarding Effect of the flame retardants of the present invention on polylactic acid
As can be seen from the data in Table 1, the LOI of pure PLA is 19%, it is a highly flammable polymer, and it is not possible to obtain a rating in the UL-94 test. Pure PLA can produce a large amount of drips during combustion, resulting in combustion that does not form an effective encapsulated carbon layer. With the gradual increase of the flame retardant HABP-DOPO, the limiting oxygen index and the vertical burning performance of the PLA composite material are also greatly improved. The LOI value of PLA/15% HABP-DOPO compound was 23% with burning dripping. As the HABP-DOPO content increased from 15% to 25%, the LOI increased rapidly from 23% to 29%, and the vertical burn performance also passed the V-0 test rating. This shows that the flame retardant properties of the PLA/HABP-DOPO blends are gradually enhanced with increasing HABP-DOPO content.
The phosphazene structure in the flame retardant on the one hand generates a flame-retardant gas such as NH during pyrolysis3On the other hand, PO formed during decomposition of the phosphaphenanthrene groups can capture active free radicals H & OH & released during combustion of the polymer, and chain reaction in the combustion process is interrupted, thereby leading to a higher LOI value.
The phosphaphenanthrene group contained in the flame retardant is an excellent char-forming agent in the combustion process, a carbon layer formed by the flame retardant can wrap a PLA matrix during combustion, the heat exchange between the material and the external environment in the combustion process is weakened, the further combustion of the material is prevented, meanwhile, the dripping of the composite material in the combustion process is also prevented, the vertical combustion performance of the PLA composite material can pass a V-0 test, and the same explanation can be obtained from the residual form of the composite material after combustion.
(2) The flame retardant prepared by the invention has flame retardant effect on ABS
Controlling the content ratio of the flame retardant and the ABS to prepare the composite material, respectively preparing a standard sample strip according to GB/T2406-93 and GB/T2508-1996 test standards, carrying out a limit oxygen index test and a vertical combustion test, and carrying out a combustion performance test by JF-2 and FZ-5401 equipment; the flame retardant properties of the pure ABS and the blended materials were investigated by the LOI and UL-94 tests, the results of which and the dripping properties are given in Table 2.
TABLE 2 flame-retardant Effect of the flame retardants of the present invention on ABS
As can be seen from the data in Table 2, pure ABS has an LOI of 18%, is a highly flammable polymer, and does not achieve a rating in the UL-94 test. Pure ABS can generate a large amount of black smoke in the combustion process, so that the escape personnel are secondarily injured in the fire. With the gradual increase of the flame retardant HABP-DOPO, the limiting oxygen index and the vertical burning performance of the ABS composite material are also greatly improved. The LOI value of ABS/15% HABP-DOPO compound was 22%, with the LOI increasing rapidly from 22% to 28% as the HABP-DOPO content increased from 15% to 25%, and the vertical burn performance also passed the V-0 test rating. This shows that the flame retardant properties of the ABS/HABP-DOPO blends are gradually enhanced with increasing HABP-DOPO content.
(3) Infrared spectroscopic analysis was performed on the cyclotriphosphazene flame retardant (HABP-DOPO) containing phosphaphenanthrene groups and dihydroxybiphenyl structures prepared in the present invention and the polylactic acid blended material, and the results are shown in FIG. 4.
As can be seen from FIG. 4, the presence of a large number of-OH groups in the flame retardant leads to strong intermolecular hydrogen bonds O-H.cndot.O with the O atoms in the PLA, thereby reducing the energy of the system. Due to in-plane bending, i.e. pure PLA at 1360.7cm-1The peak at (A) is divided into 1360.7cm-1And 1382.1cm-1. As shown, a narrow symmetrical peak (at 1757 cm) characterized by C ═ O stretching of the ester in PLA-1Centered) becomes wider and eventually splits into two bands. This is achieved byThis is because the amide peak shows a strong weak cleavage after the flame retardant is added to the PLA matrix, and a new weak peak is gradually formed at a low wave number of the amide peak, because the hydrogen bond weakens the force constant of the C ═ O double bond. This demonstrates the presence of hydrogen bonding between the flame retardant and the PLA matrix.
(4) The heat release rate and the total heat release rate of the cyclotriphosphazene flame retardant (HABP-DOPO) containing the phosphaphenanthrene group and the dihydroxybiphenyl structure and the polylactic acid blended composite material prepared by the invention are tested, and the results are respectively shown in the figure 5 and the figure 6.
As can be seen from fig. 5, the addition of the flame retardant can effectively reduce the Heat Release Rate (HRR) of the PLA flame retardant material. When the amount of HABP-DOPO increased from 0% to 25%, the HRR peaked from 336.86kW/m2Reduced to 271.38kW/m2The reduction is 19.4%. As can be seen from the figure, the pure PLA is rapidly combusted after being ignited, only one peak appears in the combustion process, and the peak value reaches 336.86kW/m2This indicates that pure PLA is extremely flammable. The PLA/HABP-DOPO composite material has two peaks in the combustion process, the two peaks appear earlier than the pure PLA material, but the peak value is greatly reduced compared with the pure PLA material. The first peak appears in 80-100s, which is a peak generated by the rapid temperature rise of the surface of the composite material and the release of a large amount of heat due to the degradation of the material caused by the decomposition of the flame retardant. The second peak appears around 150s, caused by the burning of the material.
As can be seen from FIG. 6, the total heat release rate (THR) of the pure PLA material was 72.15MJ/m2When the content of HABP-DOPO was 15%, 20% and 25%, respectively, the THR of the composite material was reduced to 60.85MJ/m, respectively2、59.43MJ/m2And 43.07MJ/m2. The slope of the THR curve represents the flame diffusion rate of the material. In the graph, as the HABP-DOPO content increases, the slope gradually decreases, and combustion of the flame starts to slow down. The slope of the THR curve for the PLA/25% HABP-DOPO sample was the lowest, indicating that the flame was the slowest to propagate during combustion.
(5) The thermal weight loss of the cyclotriphosphazene flame retardant (HABP-DOPO) containing the phosphaphenanthrene group and the dihydroxybiphenyl structure and the polylactic acid blending material prepared by the invention is tested.
The change in the blended material and the chemical properties of the components with increasing temperature were analyzed using a thermogravimetric analyzer and the results are shown in fig. 7.
It can be seen from the combination of the graphs that the addition of flame retardant significantly changes the initial decomposition temperature of the PLA composite, as compared to neat PLA, the T of which5％From 326.7 ℃ down to 307.6 ℃ because the addition of the flame retardant promotes PLA degradation during combustion, which in turn lowers the initial decomposition temperature of the composite.
The carbon residue of pure PLA at 400 ℃ is only 0.026%, which can be almost ignored, while the carbon residue of the composite material added with 25% HABP-DOPO at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ is 17.4 wt%, 15.4 wt%, 15.0 wt% and 14.4 wt%, respectively. The results show that at temperatures above 360 ℃, the PLA/HABP-DOPO composite material shows better thermal stability, and forms more carbon residue than pure PLA, and the benzene ring and the carbon forming agent DOPO in the flame retardant structure are probably the main reasons for the increase of the carbon residue.
As can be seen from the DTG curve of the composite, the thermal degradation process of the PLA/HABP-DOPO composite at 800 ℃ goes through two stages, the first stage is that the PLA matrix starts to decompose under the action of the flame retardant and heat when the composite is between 330 ℃ and 350 ℃, and the second stage is that the HABP-DOPO starts to decompose when the temperature continues to rise. Pre-degradation of PLA results in a faster carbonization rate of the composite because the degradation products participate in the coke formation process, thereby imparting anti-drip properties to the composite. In addition, the protective layer consisting of the sample at the early stage of heating also acts to delay the degradation of the PLA sample as the temperature continues to rise. Thus, pre-degradation products of PLA participate in the coke formation process, thereby increasing the carbon residue content.
(6) The impact resistance of the cyclotriphosphazene flame retardant (HABP-DOPO) containing the phosphaphenanthrene group and the dihydroxybiphenyl structure and the polylactic acid blended material prepared by the invention is tested, and the result is shown in figure 8; and scanning the prepared blended material by an electron microscope, wherein the scanning electron microscope picture is shown in figure 9.
As can be seen from FIG. 8, the notched impact strength of pure PLA was highThe degree is 4.51KJ/m2When the content of HABP-DOPO was 15%, 20% and 25%, the corresponding notched impact strength was 4.37KJ/m2、4.3KJ/m2And 4.17KJ/m2. Generally, the introduction of flame retardants into polymers inevitably leads to a decrease in mechanical properties, most likely due to poor compatibility resulting from large differences in molecular weight. The notched impact strength of the composite material remained at a higher level, with only a slight decrease, than that of pure PLA, even with the addition of a certain amount of HABP-DOPO to PLA. Hydrogen bonding between flame retardants containing a high number of hydroxyl groups and the PLA matrix may be an important reason for good compatibility and improved impact properties. Meanwhile, the small molecular flame retardant can play a plasticizing role in the mixture.
As can be seen from fig. 9, there was no significant agglomeration of HABP-DOPO particles in the SEM micrograph, which means that the flame retardant particles were uniformly distributed in the PLA matrix. In addition, the flame retardant and the PLA matrix are not obviously separated and have good dispersibility, and the good compatibility between the flame retardant and the PLA matrix can be inferred by combining the change of the mechanical property of the composite material; when the HABP-DOPO filled PLA composite is subjected to an impact force, the HABP-DOPO will cause cracks in the matrix due to stress concentration and will increase the surface area to absorb the impact fracture energy, thereby increasing the impact strength of the composite.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and scope of the present invention are intended to be covered thereby.
Claims (9)
1. A cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures is characterized in that: the molecular structure is as follows:
2. the synthetic route of the cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures according to claim 1 is as follows:
3. a method for preparing a cyclotriphosphazene flame retardant containing phosphaphenanthrene and biphenyl structures according to any one of claims 1 or 2, characterized in that: the method comprises the following steps:
step one, dissolving dihydroxybiphenyl in acetone under an ice bath condition, adding an acid-binding agent, stirring uniformly, and then dropwise adding an acetone solution containing hexachlorocyclotriphosphazene, wherein the molar ratio of hexachlorocyclotriphosphazene to dihydroxybiphenyl is 1:1-1:1.4, and the molar ratio of hexachlorocyclotriphosphazene to the acid-binding agent is 1: 2-1: 2.8; reacting at room temperature for 15-20min, standing and filtering the solution, collecting filtrate, and washing a filter cake with a solvent for 3-5 times; dropwise adding distilled water into the filtrate to obtain a white precipitate, and vacuum drying the white precipitate at 80 ℃ for 10-30h to obtain an intermediate I;
step two, adding THF (tetrahydrofuran) as a solvent into a reaction container, adding an acid-binding agent and p-hydroxybenzaldehyde into the reaction container, and fully stirring until the acid-binding agent and the p-hydroxybenzaldehyde are completely dissolved; dissolving the intermediate I in THF, dripping into a reaction vessel, wherein the molar ratio of the intermediate I to p-hydroxybenzaldehyde is 1:4.5-1:6, heating the reaction vessel to a reflux state, reacting for 22-24h, cooling the solution to room temperature, filtering, washing the filter cake twice with distilled water and absolute ethyl alcohol respectively, drying for 4h in a blast oven after washing, adding ethyl acetate, and recrystallizing to obtain a white needle-like solid which is an intermediate II;
step three, adding DMF (dimethyl formamide) as a solvent into a reaction container, adding DOPO into the reaction container, heating to 120 ℃, and stirring until the DOPO is completely dissolved; adding an intermediate II, wherein the molar ratio of the intermediate II to the phosphaphenanthrene DOPO is 1:4.8-1.6, heating to 140 ℃, and continuing to react for 10 hours; filtering, adding a large amount of ice water into the filtrate to obtain white precipitate, filtering the white precipitate by using filter paper with the pore diameter of 50-80 mu m, washing the white precipitate for 3-5 times by using an absolute ethyl alcohol/toluene mixed solution, and drying the white precipitate for 24 hours in a vacuum oven to obtain white powder, namely the cyclotriphosphazene flame retardant containing the phosphaphenanthrene group and the dihydroxybiphenyl structure.
4. The preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structure according to claim 3, wherein the preparation method comprises the following steps: in the first step, the molar ratio of hexachlorocyclotriphosphazene to dihydroxybiphenyl is 1:1.2, and the molar ratio of hexachlorocyclotriphosphazene to acid-binding agent is 1: 2.5.
5. The preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structures according to claim 3 or 4, characterized in that: the acid-binding agent is inorganic base or organic base without active hydrogen, wherein the inorganic base is one or more of potassium carbonate, sodium carbonate or sodium hydroxide, and the organic base without active hydrogen is pyridine or triethylamine.
6. The preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structure according to claim 3, wherein the preparation method comprises the following steps: and in the first step, the solvent used for washing the filter cake is one or more of tetrahydrofuran, N-dimethylformamide and acetone.
7. The preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structure according to claim 3, wherein the preparation method comprises the following steps: in the second step, the molar ratio of the intermediate I to the p-hydroxybenzaldehyde is 1: 4.8.
8. The preparation method of the cyclotriphosphazene flame retardant containing the phosphaphenanthrene and biphenyl structure according to claim 3, wherein the preparation method comprises the following steps: in the third step, the molar ratio of the intermediate II to the phosphaphenanthrene DOPO is 1: 5.
9. Use of a cyclotriphosphazene flame retardant comprising phosphaphenanthrene and biphenyl structures according to any of claims 1-8 in the preparation of a flame retardant material.
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| CN113652002A (en) * | 2021-08-20 | 2021-11-16 | 贵州民族大学 | Flame retardant containing DOPS/phosphazene structure and preparation method and application thereof |
| CN114716759A (en) * | 2022-05-16 | 2022-07-08 | 广东九彩新材料有限公司 | Carbon black coloring ethylene-vinyl acetate copolymer color master batch and preparation method thereof |
| CN114957794A (en) * | 2022-06-01 | 2022-08-30 | 山东甲子湖畔新材料科技有限公司 | Halogen-free flame retardant and preparation method thereof |
| CN117551338A (en) * | 2024-01-12 | 2024-02-13 | 北京慕湖新材料技术有限公司 | Flame-retardant cold-resistant and damp-heat-resistant polyester composition and preparation method thereof |
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| CN114716759A (en) * | 2022-05-16 | 2022-07-08 | 广东九彩新材料有限公司 | Carbon black coloring ethylene-vinyl acetate copolymer color master batch and preparation method thereof |
| CN114957794A (en) * | 2022-06-01 | 2022-08-30 | 山东甲子湖畔新材料科技有限公司 | Halogen-free flame retardant and preparation method thereof |
| CN117551338A (en) * | 2024-01-12 | 2024-02-13 | 北京慕湖新材料技术有限公司 | Flame-retardant cold-resistant and damp-heat-resistant polyester composition and preparation method thereof |
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