CN111253437A - P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof - Google Patents
P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- 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 43
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 7
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims abstract description 18
- LDCXABKMPZWWDJ-UHFFFAOYSA-N 2-ethenyl-1H-imidazole-4,5-diamine Chemical compound C(=C)C=1NC(=C(N=1)N)N LDCXABKMPZWWDJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUPABJWBMRETIM-UHFFFAOYSA-N 5-ethenyl-1,3-thiazole-2,4-diamine Chemical compound C(=C)C1=C(N=C(S1)N)N XUPABJWBMRETIM-UHFFFAOYSA-N 0.000 claims abstract description 10
- KGTZBTUOZOIOBJ-UHFFFAOYSA-N dichloro(ethenyl)silicon Chemical compound Cl[Si](Cl)C=C KGTZBTUOZOIOBJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006757 chemical reactions by type Methods 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 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 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 230000007123 defense Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- -1 methyl vinyl diaminothiazole Chemical compound 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a P/N/Si-containing multi-element reactive epoxy resin flame retardant and a preparation method thereof, wherein the flame retardant is prepared by a two-step method by using 2-aminothiazole or 2-aminoimidazole, vinyl dichlorosilane and DOPO as main raw materials. The first step is as follows: 2-aminothiazole or 2-aminoimidazole reacts with vinyl dichlorosilane to generate vinyl diaminothiazole or vinyl diaminoimidazole; the second step is that: the addition reaction of DOPO and vinyl diamino thiazole or vinyl diamino imidazole is utilized to synthesize the P/N/Si-containing multi-element reaction type epoxy resin flame retardant. The obtained flame retardant not only contains an NH-Si-NH structure, but also can cause the epoxy group of the epoxy resin to generate ring-opening reaction, belonging to a reactive flame retardant; and contains aromatic heterocyclic and phosphaphenanthrene structures, thereby realizing the synergistic flame-retardant effect of P/N/Si multi-elements. The flame retardant enables the modified epoxy resin condensate to have good flame retardant effect, mechanical property and thermal stability, thereby meeting the application requirements in the fields of national defense materials, electronics and electricity, building materials and the like.
Description
Technical Field
The invention belongs to the field of epoxy resin flame retardants, and particularly relates to a P/N/Si-containing multi-element reactive epoxy resin flame retardant and a preparation method thereof.
Background
The epoxy resin is a thermosetting polymer containing two or more epoxy groups and capable of forming a cross-linked network structure under proper conditions, has the characteristics of excellent adhesive property, electric insulation property, chemical stability, mechanical property and the like, and is widely applied to the fields of ships, oceans, automobiles, electronics and electricity and the like. However, epoxy resins have problems of easy combustion, large heat release amount during combustion, generation of a large amount of smoke and toxic gases, and the like, and pose serious threats to life and property safety, thereby limiting the application of the epoxy resins in many fields. Therefore, the flame-retardant modification of the epoxy resin is an effective method for improving the application range of the epoxy resin, and has important research value.
In general, flame retardancy of materials can be broadly divided into physical and chemical effects. The physical effects mainly comprise heat dissipation/absorption, dilution and barrier protection; the chemical action mainly includes radical capture, formation of barrier protective layer, etc. Although different flame retardants have different flame retardant mechanisms, they can retard or even stop the combustion of the material at a certain stage or stages, thereby inhibiting the combustion of the material. For example, the epoxy novolac resin containing DOPO groups is mixed with bisphenol A diglycidyl ether (DGEBA) to prepare the flame-retardant epoxy cured product which can pass the V-0 grade and has the tensile strength of 48.0MPa and the impact strength of 14.5kJ/m2. (Polym.Degrad.Stabil.2014,109, 218-225). It has also been reported that a phosphaphenanthrene-containing flame retardant (PFR) is synthesized by reacting a DOPO derivative with phenylphosphoryl dichloride, when the amount of phosphorus added is 2 wt%, the epoxy resin burns vertically through V-0 level, the oxygen index reaches 40.0%, but the addition of the flame retardant also reduces the modificationThermal stability of epoxy resins and affects the mechanical properties of the materials (j. mater. chem. a 2014,2, 16230-. Researches show that although many flame retardants can better solve the problem of flammability of epoxy resin at present, the problems of toughness, thermal stability and the like of the epoxy resin are not well considered.
Disclosure of Invention
Based on the research background, the invention aims to overcome the defects of the prior art and provide a P/N/Si-containing multi-element reactive epoxy resin flame retardant and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a P/N/Si-containing multi-element reactive epoxy resin flame retardant, which has the following structure:
wherein R is1Is methyl or phenyl; r2Is NH or S.
The other purpose of the invention is to provide a preparation method of the P/N/Si-containing multi-element reactive epoxy resin flame retardant, which is obtained by two-step reaction under the protection of inert gas and by taking 2-aminothiazole or 2-aminoimidazole, vinyl dichlorosilane and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as main raw materials.
The first step is as follows: under the protection of inert gas, triethylamine (Et)3N) is an acid-binding agent, and 2-aminothiazole or 2-aminoimidazole reacts with vinyl dichlorosilane to generate vinyl diaminothiazole or vinyl diaminoimidazole;
wherein R is1Is methyl or phenyl; r2Is NH or S.
The second step is that: under the protection of inert gas, Azodiisobutyronitrile (AIBN) is used as an initiator, DOPO reacts with the vinyl diamino thiazole or the vinyl diamino imidazole generated in the first step, and the P/N/Si-containing multi-element reaction type epoxy resin flame retardant is obtained after post-treatment.
Wherein R is1Is methyl or phenyl; r2Is NH or S.
Furthermore, in the first reaction, the molar ratio of the 2-aminothiazole or the 2-aminoimidazole to the vinyl dichlorosilane is 2 (1-1.1), the molar ratio of the vinyl dichlorosilane to the triethylamine is 1 (2-2.1), the reaction temperature is 20-40 ℃, and the reaction time is 3-6 hours.
Further, in the second reaction step, the molar ratio of vinyldiaminothiazole or vinyldiaminoimidazole to DOPO is 1: (1-1.4), the reaction temperature is 80-110 ℃, the reaction time is 12-23 h, and the dosage of AIBN is 0.2-0.7% of the molar number of DOPO.
The analysis shows that the P/N/Si-containing multi-element reactive epoxy resin flame retardant and the preparation method thereof have the advantages that:
① uses 2-aminothiazole or 2-aminoimidazole, vinyl dichlorosilane and DOPO as main raw materials, firstly uses Si-Cl and NH2The reaction of (1) synthesizing the vinyl diamino thiazole or the vinyl diamino imidazole, and then carrying out addition reaction on the vinyl diamino thiazole or the vinyl diamino imidazole and DOPO to synthesize the P/N/Si-containing multi-element reactive epoxy resin flame retardant.
② the obtained flame retardant not only contains NH-Si-NH structure, which can make the epoxy group of epoxy resin generate ring-opening reaction, belongs to reactive flame retardant, and is beneficial to improving the compatibility and bonding capability with epoxy resin, and further improving the performance of epoxy resin condensate, but also contains aromatic heterocycle and phosphaphenanthrene structure, which can realize P/N/Si multi-element synergistic flame retardant effect, and make the modified epoxy resin condensate have good flame retardant effect, mechanical property and thermal stability, thereby meeting the application requirements in the fields of national defense materials, electronic and electrical, building materials and the like.
Drawings
FIG. 1 is a TG curve of the cured product prepared in example 1 under nitrogen;
FIG. 2 is a TG curve of the cured product prepared in example 1 under nitrogen.
Detailed Description
The technical solution of the present invention is further explained below with reference to the accompanying drawings and specific embodiments.
Example 1
Under the protection of nitrogen, adding 2-aminothiazole (40mmol) and triethylamine (40mmol) into a three-neck flask, adjusting the temperature of a reaction system to be 30 ℃, adding a mixed solution of methyl vinyl dichlorosilane (20mmol) and tetrahydrofuran through a constant-pressure dropping funnel, continuing to react for 5 hours at the temperature after the dropwise addition is finished, after the reaction is finished, carrying out suction filtration to remove hydrochloride of the triethylamine, collecting filtrate, washing with anhydrous ether, carrying out rotary evaporation to remove a solvent, and carrying out vacuum drying to obtain the methyl vinyl diaminothiazole. Then, adding DOPO (16.5mmol), methylvinyldiaminothiazole (15mmol) and toluene into another 150ml three-neck flask provided with a magnetic stirrer and a reflux condenser tube in sequence, adding AIBN (0.075mmol) solution dissolved in the toluene through a constant pressure dropping funnel, carrying out reflux reaction at 80 ℃ for 20h after the dropwise addition is finished, and carrying out post-treatment after the reaction is finished to obtain the P/N/Si-containing reactive type epoxy resin flame retardant, wherein the structural formula of the flame retardant is as follows:
FT-IR:3348cm-1(-NH-),2986cm-1(-CH3),1263cm-1(Si-C),1210cm-1(P＝O),915cm-1(Si-N)。
1H-NMR:0.10ppm(Si-CH3),1.27ppm(Si-CH2-),2.36ppm(-CH2-P),3.76ppm(-NH-),6.47～7.29ppm(Ar-H)。
using 4, 4-diaminodiphenylmethane as curing agent, using synthetic flame retardant to modify bisphenol A type epoxy resin (E-44) so as to obtain the invented productCompounds of formula (I) in N2The thermogravimetry (heating rate of 10 ℃/min) curve (TG) in the atmosphere is shown in figure 1, the weight loss is 5% (T)d5) And maximum rate of thermal weight loss (T)dmax) The corresponding temperatures are 329.3 ℃ and 376.1 ℃ respectively, and the mass retention rate at 800 ℃ is 18.6 percent; the limiting oxygen index reaches 30.2 percent and passes the V-0 grade of UL-94; the bending strength, the tensile strength and the impact strength are respectively 104.5MPa, 65.6MPa and 24.2kJ/m2Has excellent flame retardance, thermal stability and mechanical property.
Example 2
Under the protection of nitrogen, adding 2-aminoimidazole (40mmol) and triethylamine (42mmol) into a three-neck flask, adjusting the temperature of a reaction system to be 20 ℃, adding a mixed solution of methyl vinyl dichlorosilane (20mmol) and tetrahydrofuran through a constant-pressure dropping funnel, continuing to react for 6 hours at the temperature after the dropwise addition is finished, after the reaction is finished, performing suction filtration to remove hydrochloride of the triethylamine, collecting filtrate, washing with anhydrous ether, performing rotary evaporation to remove a solvent, and performing vacuum drying to obtain the methyl vinyl diaminoimidazole. Then, adding DOPO (20mmol), methylvinyldiaminoimidazole (15mmol) and toluene into another 150ml three-neck flask provided with a magnetic stirrer and a reflux condenser tube in sequence, adding AIBN (0.075mmol) solution dissolved in toluene through a constant pressure dropping funnel, carrying out reflux reaction at 110 ℃ for 12h after the dropwise addition is finished, and carrying out post-treatment after the reaction is finished to obtain the P/N/Si-containing multi-element reaction type epoxy resin flame retardant, wherein the structural formula of the flame retardant is as follows:
FT-IR:3356cm-1(-NH-),2995cm-1(-CH3),1258cm-1(Si-C),1202cm-1(P＝O),918cm-1(Si-N)。
1H-NMR:0.11ppm(Si-CH3),1.28ppm(Si-CH2-),2.33ppm(-CH2-P),3.75ppm(-NH-),6.51～7.57ppm(Ar-H)。
using 4, 4-diaminodiphenylmethane as curing agent, modifying bisphenol A type epoxy resin (E-44) with synthetic flame retardant, and obtaining the cured product in N2The thermogravimetry (heating rate of 10 ℃/min) curve (TG) in the atmosphere is shown in FIG. 2, the weight loss is 5% (T)d5) And maximum rate of thermal weight loss (T)dmax) The corresponding temperatures are 353.5 ℃ and 388.5 ℃ respectively, and the mass retention rate at 800 ℃ is 18.7%; the limiting oxygen index reaches 32.3 percent and passes the V-0 grade of UL-94; the bending strength, the tensile strength and the impact strength are respectively 110.5MPa, 78.3MPa and 29.1kJ/m2Has excellent flame retardance, thermal stability and mechanical property.
Claims (9)
1. A P/N/Si-containing multi-element reaction type epoxy resin flame retardant is characterized in that: the flame retardant has the following structure:
wherein R is1Is methyl or phenyl; r2Is NH or S.
2. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 1, wherein: which comprises the following steps:
the first step is as follows: under the protection of inert gas, triethylamine is used as an acid-binding agent, and 2-aminothiazole or 2-aminoimidazole and vinyl dichlorosilane react to generate vinyl diaminothiazole or vinyl diaminoimidazole;
the second step is that: under the protection of inert gas, AIBN is used as an initiator, and the P/N/Si multi-element reaction type epoxy resin flame retardant is generated through the addition reaction of DOPO and the vinyl diamino thiazole or the vinyl diamino imidazole generated in the first step reaction.
3. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the first step of reaction, the molar ratio of the 2-aminothiazole or the 2-aminoimidazole to the vinyl dichlorosilane is 2 (1-1.1).
4. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the first step of reaction, the reaction temperature is 20-40 ℃, and the reaction time is 3-6 h.
5. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the first step of reaction, the molar ratio of the vinyl dichlorosilane to the triethylamine is 1 (2-2.1).
6. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the second step of reaction, the molar ratio of the vinyldiaminothiazole or the vinyldiaminoimidazole to the DOPO is 1 (1-1.4).
7. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the second step of reaction, the reaction temperature is 80-110 ℃, and the reaction time is 12-23 h.
8. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: in the second step of reaction, the dosage of AIBN is 0.2 to 0.7 percent of the mol number of DOPO.
9. The method for preparing the P/N/Si-containing multi-element reactive epoxy resin flame retardant according to claim 2, wherein: the inert gas is nitrogen, helium or argon.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690171A (en) * | 2020-07-10 | 2020-09-22 | 宁波保税区君一汽配科技有限公司 | Flame retardant and flame-retardant PC plastic |
| CN114213807A (en) * | 2021-12-15 | 2022-03-22 | 天津大学 | High-thermal-stability intumescent compound flame retardant modified epoxy resin material and preparation method thereof |
| WO2022089459A1 (en) * | 2020-10-29 | 2022-05-05 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, preparation methods therefor and applications thereof |
| DE102023000325B3 (en) | 2023-02-03 | 2024-02-22 | lnstitut für Kunststofftechnologie und -recycling e.V. | Thiazole compounds as flame retardants containing phosphorus, nitrogen and sulfur and their use |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009040A (en) * | 2016-06-24 | 2016-10-12 | 福建师范大学 | Flame retardant containing phosphorus, nitrogen and sulfur and used for epoxy resin and preparation method of flame retardant |
| CN106749413A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
| CN107474223A (en) * | 2017-08-19 | 2017-12-15 | 福建师范大学泉港石化研究院 | A kind of siliceous nitrogen benzimidazole type epoxy curing agent and preparation method thereof |
| CN109354673A (en) * | 2018-10-15 | 2019-02-19 | 福建师范大学 | A kind of epoxy resin preparation method modified based on silicon thiazole DOPO type fire retardant |
| CN109438758A (en) * | 2018-10-15 | 2019-03-08 | 福建师范大学 | A kind of siliceous thiazole DOPO type fire retardant preparation method |
-
2020
- 2020-03-10 CN CN202010162933.6A patent/CN111253437A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009040A (en) * | 2016-06-24 | 2016-10-12 | 福建师范大学 | Flame retardant containing phosphorus, nitrogen and sulfur and used for epoxy resin and preparation method of flame retardant |
| CN106749413A (en) * | 2016-11-24 | 2017-05-31 | 福建师范大学 | Using the preparation method of the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy |
| CN107474223A (en) * | 2017-08-19 | 2017-12-15 | 福建师范大学泉港石化研究院 | A kind of siliceous nitrogen benzimidazole type epoxy curing agent and preparation method thereof |
| CN109354673A (en) * | 2018-10-15 | 2019-02-19 | 福建师范大学 | A kind of epoxy resin preparation method modified based on silicon thiazole DOPO type fire retardant |
| CN109438758A (en) * | 2018-10-15 | 2019-03-08 | 福建师范大学 | A kind of siliceous thiazole DOPO type fire retardant preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690171A (en) * | 2020-07-10 | 2020-09-22 | 宁波保税区君一汽配科技有限公司 | Flame retardant and flame-retardant PC plastic |
| CN111690171B (en) * | 2020-07-10 | 2022-07-05 | 广州森赛逖康化工科技有限公司 | Flame retardant and flame-retardant PC plastic |
| WO2022089459A1 (en) * | 2020-10-29 | 2022-05-05 | 广东广山新材料股份有限公司 | Reactive phosphorus-silicon synergistic flame retardant, polymeric phosphorus-silicon synergistic flame retardant, preparation methods therefor and applications thereof |
| CN114213807A (en) * | 2021-12-15 | 2022-03-22 | 天津大学 | High-thermal-stability intumescent compound flame retardant modified epoxy resin material and preparation method thereof |
| CN114213807B (en) * | 2021-12-15 | 2023-06-27 | 天津大学 | High-thermal-stability intumescent flame retardant modified epoxy resin material and preparation method thereof |
| DE102023000325B3 (en) | 2023-02-03 | 2024-02-22 | lnstitut für Kunststofftechnologie und -recycling e.V. | Thiazole compounds as flame retardants containing phosphorus, nitrogen and sulfur and their use |
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