CN113337005A - Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof - Google Patents
Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof Download PDFInfo
- Publication number
- CN113337005A CN113337005A CN202110418755.3A CN202110418755A CN113337005A CN 113337005 A CN113337005 A CN 113337005A CN 202110418755 A CN202110418755 A CN 202110418755A CN 113337005 A CN113337005 A CN 113337005A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- dopo
- novel
- dopo flame
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 86
- 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 79
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 125000001544 thienyl group Chemical group 0.000 title claims abstract description 9
- 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 title claims 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims abstract description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- HVXCGIPRXBJIRK-UHFFFAOYSA-N 4-methylthiophene-2-carbaldehyde Chemical compound CC1=CSC(C=O)=C1 HVXCGIPRXBJIRK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229960004050 aminobenzoic acid Drugs 0.000 claims abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 46
- 229930192474 thiophene Natural products 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 238000005034 decoration Methods 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 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
- 239000000463 material Substances 0.000 description 3
- -1 phosphorus heterocyclic compound Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 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 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a novel thienyl-containing DOPO flame retardant, which has the following structural formula:
the novel thienyl DOPO flame retardant is prepared by taking 4-methylthiophene-2-formaldehyde, p-aminobenzoic acid, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as a raw material in a mixed solvent of DMF and THF and taking potassium hydroxide as an acid-binding agent in a nitrogen atmosphere by adopting a one-step synthesis method, and when the novel thienyl DOPO flame retardant is applied to flame retardance of epoxy resin, the limiting oxygen index LOI of the resin can be remarkably improved, the char yield is high, and UL-94 is vertically combusted: flame retardantReaches V-0 grade when the content is 5 percent (W percent) (the P content is 0.3360 percent), and has good flame retardant effect. The flame retardant is synthesized by adopting a one-step method, and has the advantages of simple method, convenient purification, higher yield and good repeatability; the modified epoxy resin has good heating stability and wide application prospect in the fields of aerospace, home decoration and construction, microelectronic packaging, ornaments and the like.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a novel thiophene-group-containing DOPO flame retardant, a synthesis method thereof and application of the flame retardant in an epoxy resin polymer matrix.
Background
The polymer material has the advantages of abundant product types, convenient molding and processing, and higher specific strength and cost performance than other types of materials, so that the polymer material is widely applied in the fields of industry, agriculture and life, such as aerospace, rail transit, automobiles, buildings, household appliances and the like. However, most of high polymer materials are easy to burn, so that the application of the high polymer materials in many fields is limited, and potential harm is also caused to the life and property safety of users, so that the flame retardant modification of the high polymer materials is a very urgent technical proposition which also has important significance.
Although some novel intrinsic flame-retardant polymer materials begin to appear in recent years, the price of the products is very high at present, and the search and development of various additive flame retardants are still the mainstream of the flame-retardant modification technology and application of the polymer. However, most of the conventional flame retardant modifiers are added in a large amount, so that other excellent properties of a high polymer base material are easily influenced, and the problems of environmental pollution caused by flame retardant precipitation and migration loss, rapid attenuation of later-stage flame retardance of products and the like exist.
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is used as an organic phosphorus heterocyclic compound, the phosphorus content is more than or equal to 14 percent, the compound has a certain flame retardant effect, more importantly, the P-H bond contained in the structure has activity on olefin, epoxy bond and carbonyl, the compound can react with various compounds such as aldehyde and Schiff base to generate a plurality of flame retardant derivatives with unique performance, and the compound can also play a stable flame retardant modification effect with a plurality of polymer resin substrates needing flame retardant modification such as epoxy resin and the like through chemical bonding, so the compound can be selected as an intermediate for preparing a novel flame retardant.
Thiophene, also known as thiacyclopentadiene, is a heterocyclic compound that is aromatic, similar to benzene, and more susceptible to electrophilic substitution than benzene. 4-methylthiophene-2-formaldehyde is a thiophene compound, has the activity of thiophene and aldehyde, has the characteristic of heterocycle, can be fused with an aromatic ring on a polymer main chain to form an expanded ladder-shaped structure, and the ladder-shaped structure becomes a constructed efficient p-type conjugated polymer, has good photophysical properties and electrochemical properties, but the research of applying the compound to a flame retardant of a high-molecular material in the prior art is not reported.
In view of the above, the present invention aims to provide a novel thiophene-based DOPO flame retardant.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel thiophene-group-containing DOPO flame retardant which has good compatibility with a matrix and good long-acting flame retardant effect.
In order to solve the problems, the technical scheme of the invention is as follows:
a novel thienyl group-containing DOPO flame retardant has a structure shown as the following formula (I):
a method for synthesizing a novel thiophene-group-containing DOPO flame retardant comprises the following steps:
4-methylthiophene-2-formaldehyde, p-aminobenzoic acid and DOPO are mixed according to a molar ratio of (1-2): (1-3): (1-4) adding the mixture into a reaction container, adding a certain amount of mixed solvent and acid-binding agent to make the reaction system alkaline, and controlling the reaction temperature to be 50-110 ℃;
and introducing inert gas, stirring, reacting for 3-8 hours, generating a large amount of light yellow precipitates, performing suction filtration after complete reaction, and recrystallizing by using a mixed solvent to obtain the pure thiophene-group-containing DOPO flame retardant.
Further, the acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole.
Further, the mixed solvent and the recrystallization solvent include at least two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF, and DMAC.
Further, the mixed solvent and the recrystallization solvent comprise two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the two solvents are mixed according to the volume ratio of 1-3: 1-4.
Further, the inert gas is one of nitrogen, argon and helium.
The invention also provides application of the novel thiophene-group-containing DOPO flame retardant in the preparation process of epoxy resin.
Furthermore, when the addition of the novel thiophene-group-containing DOPO flame retardant in the preparation process of the epoxy resin is 1-7% of the total amount of the epoxy resin, the UL-94 can reach V-0 level by vertical combustion.
Furthermore, the thermal decomposition temperature of the novel thiophene-group-containing DOPO flame retardant applied to the epoxy resin after modification is increased from 334 ℃ to 380 ℃.
Compared with the prior art, the novel thiophene-group-containing DOPO flame retardant, and the synthesis method and the application thereof have the beneficial effects that:
the novel thiophene-based DOPO flame retardant provided by the invention is prepared by using 4-methylthiophene-2-formaldehyde, p-aminobenzoic acid and DOPO as raw materials and synthesizing the novel thiophene-based DOPO flame retardant by a one-step method, and the novel thiophene-based DOPO flame retardant is applied to epoxy resin and can obviously improve the flame retardant effect of the resin.
The novel thiophene-group-containing DOPO flame retardant and the synthesis method thereof have the advantages of simple synthesis method, convenience in purification and high yield; the modified epoxy resin has good heating stability and wide application prospect in the fields of aerospace, home decoration and construction, microelectronic packaging, ornaments and the like.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an infrared spectrum of a novel thiophene-based DOPO flame retardant synthesized in accordance with the present invention;
FIG. 2 shows that the novel thiophene-based DOPO flame retardant synthesized by the invention1H-NMR chart.
FIG. 3 is a TG diagram of the application of the novel thiophene-group-containing DOPO flame retardant in epoxy resin and blank epoxy resin.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a synthesis method of a novel thiophene-group-containing DOPO flame retardant, which has the following reaction formula:
specifically, the synthesis method comprises the following steps:
4-methylthiophene-2-formaldehyde, p-aminobenzoic acid and DOPO are mixed according to a molar ratio of (1-2): (1-3): (1-4) adding the mixture into a reaction container, adding a certain amount of mixed solvent and acid-binding agent to make the reaction system alkaline, and controlling the reaction temperature to be 50-110 ℃;
and introducing inert gas, stirring, reacting for 3-8 hours, allowing a large amount of light yellow precipitates to appear, performing suction filtration after the spot plate raw materials completely react, and recrystallizing by using a mixed solvent to obtain the pure thiophene-group-containing DOPO flame retardant.
Wherein the acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole;
the mixed solvent and the recrystallization solvent comprise at least two of methanol, ethanol, trichloromethane, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC; preferably, two solvents are selected from the group, and the two solvents are mixed in a volume ratio of 1-3: 1-4;
the inert gas is one of nitrogen, argon and helium.
The novel thiophene-group-containing DOPO flame retardant and the synthesis method thereof provided by the invention are explained in detail according to specific examples below.
Example 1
The synthesis of the novel thiophene-group-containing DOPO flame retardant comprises the following reaction steps:
adding 0.1mol (12.6g) of 4-methylthiophene-2-formaldehyde, 0.1mol (13.6g) of p-aminobenzoic acid and 0.2mol (43.2g) of DOPO into a 150mL three-neck flask, adding 80mL of mixed solvents of Tetrahydrofuran (THF) and DMF (volume ratio is 1: 2), adding 0.2mol (11.2g) of potassium hydroxide as an acid binding agent, controlling the reaction temperature to be about 65 ℃, electrically stirring, reacting for 5 hours to generate a large amount of light yellow precipitates, almost completely reacting one raw material of a point plate, performing suction filtration, and recrystallizing by using trichloromethane to obtain 40.5g of a relatively pure thienyl group-containing DOPO flame retardant, wherein the yield is 87.85%.
Referring to fig. 1 and 2 in combination, fig. 1 is a graph showing an infrared spectrum of a novel thiophene-based DOPO flame retardant synthesized according to the present invention; FIG. 2 shows that the novel thiophene-based DOPO flame retardant synthesized by the invention1H-NMR chart.
The main absorption peaks of infrared absorption spectroscopy (IR) are: 3267(vs),2972(w), 1655(vs),1587(vs),1580(vs),1413(m),1285(vs),1223(vs),1177(vs), 1066(m), 941(m), 748(vs),632(m),526 (m).
The results of the nuclear magnetic tests are as follows:1H-NMR:δ2.28(3CH)，3.9(1CH)，6.41(1CH)，6.66(1CH)，6.88(2CH)，7.84(2CH)，7.29(1CH)，7.36(1CH)，7.41(1CH)，7.43(1CH)，7.47(1CH)，7.50(1CH)，7.75(1CH)，8.00(1CH)，8.04(NH)，12.71(OH)。
example 2
The synthesis of the novel thiophene-group-containing DOPO flame retardant comprises the following reaction steps:
adding 0.1mol (12.6g) of 4-methylthiophene-2-formaldehyde, 0.2mol (37.2g) of p-aminobenzoic acid and 0.2mol (43.2g) of DOPO into a 150mL three-neck flask, adding 80mL of mixed solvent THF and methanol (volume ratio is 1:1), adding 0.2mol (11.2g) of potassium hydroxide as an acid binding agent, controlling the reaction temperature to be about 60 ℃, electrically stirring, reacting for 7 hours to generate a large amount of light yellow precipitates, filtering after the reaction is completed, recrystallizing by using ethyl acetate and petroleum ether (volume ratio is 1:1) to obtain 42.3g of pure thiophene-containing DOPO flame retardant, wherein the yield is 91.7%.
Example 3
The synthesis of the novel thienyl DOPO thienyl flame retardant comprises the following reaction steps:
adding 0.1mol (12.6g) of 4-methylthiophene-2-formaldehyde, 0.1mol (13.6g) of p-aminobenzoic acid and 0.2mol (43.2g) of DOPO into a 150mL three-neck flask, adding 80mL of mixed solvent MDF and acetonitrile (volume ratio is 1:1), adding 0.2mol (8.0g) of sodium hydroxide as an acid binding agent, controlling the reaction temperature to be about 75 ℃, electrically stirring, reacting for 6 hours to generate a large amount of light yellow precipitates, performing suction filtration after the reaction is completed, and recrystallizing by using ethyl acetate and petroleum ether (volume ratio is 3:1) to obtain 41.0g of pure thiophene-containing DOPO flame retardant with the yield of 89.0%.
Example 4
The novel thiophene-group-containing DOPO flame retardant prepared in the embodiments 1-3 is applied to epoxy resin.
And (3) testing the combustion performance: weighing 25g of 4, 4-diaminodiphenylmethane in a 100mL beaker, heating and melting, cooling to about 100 ℃, adding 1%, 3%, 5% and 7% of flame retardants P1, P2 and P3 prepared in examples 1-3 with different mass contents, stirring and mixing uniformly, pouring 100g of epoxy resin which is weighed in a 75 ℃ water bath in advance into the beaker containing the curing agent and the flame retardants, stirring uniformly, quickly casting into a 130 x 6.5 x 3 national standard oxygen index sample strip and a 120 x 13 x 3.2 national standard vertical combustion sample strip mold, curing for 20 hours at room temperature, then curing for 3 hours at 100 ℃, then placing in a 160 ℃ vacuum drying oven for curing for 1 hour, naturally cooling to room temperature, and demolding to obtain a flame-retardant epoxy resin sample to be tested. The limit oxygen index was measured by JF 3-oxygen index meter, and UL-94 vertical burning performance test was carried out by FZ-5401 vertical burning meter, and the results are summarized in Table 1:
table 1: performance testing of flame-retardant epoxy resins
Wherein the weight percentages refer to the percentage of the additive relative to the total weight of the (epoxy resin Ep-51+ curing agent).
The determination of the limit oxygen index is based on the national standard method GB/T2406.2-2009, and the GB/T2408-2008 standard is adopted in the UL-94 vertical combustion test.
The epoxy resin (EP-51) is selected from epoxy resins CYD-128 (EP-51) of Baling, China petrochemical Co., Ltd.).
As can be seen from Table 1, the flame-retardant effect is markedly enhanced with an increase in the content of the flame retardant in EP, as compared with the blank EP (LOI:28.0, T:28 s; not extinguished on burning).
Compared with other flame retardants of the same type (in the Chinese patent CN201310008589 technology, the LOI of blank EP is 21, 7 percent, 10 percent and 12 percent of flame retardants with different contents (w percent) are added, the LOI values of the flame-retardant modified epoxy resin measured by the method are respectively 27, 28.5 and 29), the LOI value is high, and the flame-retardant effect is enhanced; compared with the technology of Chinese patent CN201610304553 (the content of the flame retardant is 18.1%, and the content of P reaches V-0 grade when being 2.5%), the content of the epoxy resin flame retardant is 5%, and the content of P reaches V-0 grade when being only 0.3360% (W%) through UL-94 test, which shows that the flame retardant effect is good, and the addition amount of the flame retardant is small.
Example 5
The novel thiophene-group-containing DOPO flame retardant prepared in example 1 is applied to epoxy resin for TG test, and the test method is as follows:
the flame retardant of example 1 was applied to a TG test in EP-51 (flame retardant used in an amount of 3% of the epoxy resin) using a thermogravimetric analyzer TGA (Q5000IR, TA instruments USA): in the air atmosphere, the temperature is raised within the range of 0-900 ℃ at the speed of 20 ℃/min, and finally no polymer remains. Please refer to fig. 3, which is a TG diagram of the application of the novel thiophene-based DOPO flame retardant in epoxy resin and blank epoxy resin. As can be seen in FIG. 3, the decomposition temperature of the blank EP is about 334 deg.C, while the decomposition temperature of the epoxy resin corresponding to the flame retardant of example 1 is 380 deg.C, indicating that the addition of the flame retardant provides a significant improvement in the thermal decomposition of the modified epoxy resin.
The epoxy resin (EP-51) in this example was also selected from epoxy resins CYD-128 (EP-51) of Baling, China petrochemical Co., Ltd.).
Compared with the prior art, the novel thiophene-group-containing DOPO flame retardant, and the synthesis method and the application thereof have the beneficial effects that:
the novel thiophene-based DOPO flame retardant provided by the invention is prepared by using 4-methylthiophene-2-formaldehyde, p-aminobenzoic acid and DOPO as raw materials and synthesizing the novel thiophene-based DOPO flame retardant by a one-step method, and the novel thiophene-based DOPO flame retardant is applied to epoxy resin and can obviously improve the flame retardant effect of the resin.
The novel thiophene-group-containing DOPO flame retardant and the synthesis method thereof have the advantages of simple synthesis method, convenience in purification and high yield; the modified epoxy resin has good heating stability and wide application prospect in the fields of aerospace, home decoration and construction, microelectronic packaging, ornaments and the like.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (9)
1. A novel thienyl group-containing DOPO flame retardant is characterized by having a structure shown as the following formula (I):
2. a synthesis method of a novel thiophene-group-containing DOPO flame retardant is characterized by comprising the following steps:
4-methylthiophene-2-formaldehyde, p-aminobenzoic acid and DOPO are mixed according to a molar ratio of (1-2): (1-3): (1-4) adding the mixture into a reaction container, adding a certain amount of mixed solvent and acid-binding agent to make the reaction system alkaline, and controlling the reaction temperature to be 50-110 ℃;
and introducing inert gas, stirring, reacting for 3-8 hours, generating a large amount of light yellow precipitates, performing suction filtration after complete reaction, and recrystallizing by using a mixed solvent to obtain the pure thiophene-group-containing DOPO flame retardant.
3. The method for synthesizing the novel thiophene-based DOPO flame retardant according to claim 2, wherein the acid-binding agent comprises at least one of sodium hydroxide, potassium hydroxide, triethylamine, potassium tert-butoxide, sodium methoxide, pyridine, sodium ethoxide and imidazole.
4. The method of claim 2, wherein the solvent mixture and recrystallization solvent comprise at least two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF, and DMAC.
5. The method for synthesizing a novel thiophene-based DOPO flame retardant according to claim 4, wherein the mixed solvent and the recrystallization solvent comprise two of methanol, ethanol, chloroform, tetrahydrofuran, dichloromethane, acetonitrile, dimethyl sulfoxide, 1, 4-dioxane, carbon tetrachloride, DMF and DMAC, and the two solvents are mixed in a volume ratio of 1-3: 1-4.
6. The method for synthesizing novel thiophene-based DOPO flame retardant according to claim 2, wherein the inert gas is one of nitrogen, argon and helium.
7. Use of a novel thiophene-based DOPO flame retardant according to claim 1 in an epoxy resin preparation process.
8. The use according to claim 7, wherein the addition of the novel thiophene-based DOPO flame retardant is 1-7% of the total amount of the epoxy resin, and the UL-94 for vertical burning reaches V-0 level.
9. The use according to claim 7, wherein the novel thiophene-based DOPO flame retardants after application to the epoxy resin modification have a thermal decomposition temperature which is increased from 334 ℃ to 380 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110418755.3A CN113337005A (en) | 2021-04-19 | 2021-04-19 | Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110418755.3A CN113337005A (en) | 2021-04-19 | 2021-04-19 | Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113337005A true CN113337005A (en) | 2021-09-03 |
Family
ID=77468138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110418755.3A Pending CN113337005A (en) | 2021-04-19 | 2021-04-19 | Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113337005A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116355284A (en) * | 2023-03-28 | 2023-06-30 | 福州大学 | DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405369A (en) * | 2006-01-20 | 2009-04-08 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant resin composition |
| US20120055705A1 (en) * | 2009-05-19 | 2012-03-08 | Albemarle Corporation | Dopo-derived flame retardant and epoxy resin composition |
| CN110981912A (en) * | 2019-12-16 | 2020-04-10 | 寿光卫东化工有限公司 | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof |
-
2021
- 2021-04-19 CN CN202110418755.3A patent/CN113337005A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405369A (en) * | 2006-01-20 | 2009-04-08 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant resin composition |
| US20120055705A1 (en) * | 2009-05-19 | 2012-03-08 | Albemarle Corporation | Dopo-derived flame retardant and epoxy resin composition |
| CN110981912A (en) * | 2019-12-16 | 2020-04-10 | 寿光卫东化工有限公司 | Phosphoric acid triester DOPO derivative flame retardant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| AI, LIANGHUI等: "Synergistic Flame Retardant Effect of Organic Phosphorus-Nitrogen and Inorganic Boron Flame Retardant on Polyethylene", 《POLYMER ENGINEERING AND SCIENCE》 * |
| HAJIBEYGI, MOHSEN等: "Fabrication and study of thermal and combustion resistance of DOPO-functionalized polyamide reinforced with organo-modified Mg(OH)(2) nanoparticles", 《POLYMER INTERNATIONAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116355284A (en) * | 2023-03-28 | 2023-06-30 | 福州大学 | DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof |
| CN116355284B (en) * | 2023-03-28 | 2024-06-07 | 福州大学 | DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651595B (en) | Halogen-free flame-retardant bio-based epoxy resin precursor and preparation method and application thereof | |
| CN107090083B (en) | Nitrogen-phosphorus-silicon copolymer with double-layer silsesquioxane as main chain and preparation method and application thereof | |
| CN108440598B (en) | Preparation method and application of sulfur-nitrogen-phosphorus composite flame retardant | |
| CN109467674B (en) | Resveratrol-based flame-retardant epoxy resin and preparation method thereof | |
| CN113429627B (en) | P-aminobenzoic acid-condensed p-hydroxyl Schiff base/DOPO flame retardant, preparation method thereof and modified epoxy resin | |
| CN107652468B (en) | Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO | |
| CN102850622B (en) | Organic halogen-free flame-retardant silane cross-linked polyethylene and its preparation method and composition | |
| CN104277223A (en) | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant | |
| CN110183727B (en) | Benzothiazole nitrogen phosphorus sulfur ternary synergistic flame retardant containing double DOPO units, and preparation method and application thereof | |
| CN113264961A (en) | Novel phosphorus-nitrogen-containing DOPO flame retardant and preparation method and application thereof | |
| CN113337004A (en) | Novel phosphorus-nitrogen DOPO derivative flame retardant and synthetic method and application thereof | |
| CN113583047A (en) | Porphyrin phosphate compound, preparation method and application of porphyrin phosphate compound as flame retardant | |
| CN114015051A (en) | Preparation method and application of DOPO-POSS flame retardant | |
| CN110467747B (en) | Metal ion flame-retardant complex with Schiff base structure and preparation method thereof | |
| CN113337005A (en) | Novel thienyl-containing DOPO flame retardant and synthesis method and application thereof | |
| CN110643066B (en) | Phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN113337006A (en) | Novel Schiff base DOPO phosphorus-nitrogen-containing flame retardant and preparation method and application thereof | |
| CN113461734A (en) | Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof | |
| CN110128702A (en) | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications | |
| CN110128474B (en) | Preparation method and application of nitrogen-phosphorus-sulfur ternary synergistic flame retardant bis-DOPO thiazole compound | |
| CN114409827B (en) | Synthesis and performance of transparent epoxy resin material with high flame retardant performance based on chitosan derivative | |
| CN113512233A (en) | Novel nitrogen-phosphorus flame retardant containing furyl DOPO and preparation method and application thereof | |
| CN113264960A (en) | Novel phosphorus-nitrogen flame retardant containing Schiff base DOPO derivative and preparation method and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN113429629B (en) | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |