CN117486939A - Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin - Google Patents
Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin Download PDFInfo
- Publication number
- CN117486939A CN117486939A CN202311570289.6A CN202311570289A CN117486939A CN 117486939 A CN117486939 A CN 117486939A CN 202311570289 A CN202311570289 A CN 202311570289A CN 117486939 A CN117486939 A CN 117486939A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- epoxy resin
- reaction
- halogen
- free flame
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 239000012745 toughening agent Substances 0.000 title claims abstract description 46
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- -1 aldehyde compound Chemical class 0.000 claims abstract description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012965 benzophenone Substances 0.000 claims abstract description 10
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 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 6
- 238000000034 method Methods 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000543 intermediate Substances 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- FSWXOANXOQPCFF-UHFFFAOYSA-N 4'-aminopropiophenone Chemical compound CCC(=O)C1=CC=C(N)C=C1 FSWXOANXOQPCFF-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 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 abstract description 41
- 230000000694 effects Effects 0.000 abstract description 13
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 abstract description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 12
- 239000003607 modifier Substances 0.000 description 10
- 239000012467 final product Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001491 aromatic compounds Chemical class 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 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 5
- 229920002521 macromolecule Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 108010085672 beta-lactamase PSE-2 Proteins 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- HJXPGCTYMKCLTR-UHFFFAOYSA-N 2-bromo-9,9-diethylfluorene Chemical group C1=C(Br)C=C2C(CC)(CC)C3=CC=CC=C3C2=C1 HJXPGCTYMKCLTR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 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 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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 System
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- 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
- 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
- C08L2201/22—Halogen free composition
Abstract
The invention relates to the technical field of high molecular flame retardant toughening, and discloses a preparation method of an epoxy resin halogen-free flame retardant toughening agent, which comprises the following steps: s1, melting and mixing DOPO, a benzophenone or aldehyde compound, an aniline compound and p-toluenesulfonic acid in an oil bath at 100 ℃, and heating to 110 ℃ for reaction for 3 hours to obtain a reaction liquid I; s2, recrystallizing and purifying the reaction solution I by using methanol and chloroform to obtain a reaction intermediate product II; s3, dissolving DOPO and p-hydroxybenzaldehyde in an organic solvent to obtain a mixed solution III; s4, dissolving a reaction intermediate product II in the mixed solution III, and heating in an oil bath for reacting for a period of time to obtain a reaction solution IV; s5, purifying the reaction solution IV to obtain the halogen-free flame retardant toughening agent; the halogen-free flame retardant toughening agent disclosed by the invention contains a plurality of phosphorus-oxygen groups and reactive sites, and the phosphorus-oxygen groups and the reactive sites generate a synergistic effect, so that the halogen-free flame retardant toughening agent can be applied to an epoxy resin system to improve the flame retardant and toughening effects at the same time, and has the advantages of good thermal performance, low viscosity and good application prospect.
Description
Technical Field
The invention relates to the technical field of high molecular flame retardant toughening, in particular to a preparation method and application of an epoxy resin halogen-free flame retardant toughening agent.
Background
The epoxy resin is a polymer material with a cross-linked network structure, has high rigidity and high hardness, has excellent dielectric property, adhesive property, mechanical property and thermal property, and is widely applied to the fields of machinery, electronics, electrics, aerospace, civil engineering, marine vessels, wind power and the like in the forms of adhesive, coating, packaging materials, composite materials and the like. However, epoxy resins suffer from two major drawbacks: (1) the epoxy resin has extremely inflammability, the limit index (LOI) of the epoxy resin is about 20%, the epoxy resin can be burnt in the air, and a large amount of black dense smoke and toxic gas are accompanied during the burning; (2) impact toughness is low, i.e. it has a large hardness and rigidity, but is a brittle material. In recent years, with the importance of the country on fire hazard, the flammability of epoxy resins has limited their wide application to a great extent; at the same time, the defect of poor toughness greatly hinders the application of the alloy in many fields. Therefore, improving the flame retardant properties and impact toughness of epoxy resins is a critical problem that needs to be solved for epoxy resin applications.
In the aspect of flame retardance of epoxy resin, the addition of the flame retardant is a method with low cost and simple operation. The phosphorus flame retardant is the flame retardant which is most widely applied after the halogen flame retardant, and the phosphorus-containing functional group has the advantages of various structures, easy preparation, low toxicity and small secondary pollution, and can be introduced into the epoxy resin structure to prepare the product with high-efficiency flame retardant property, excellent electrical property and environmental friendliness. For example, chinese patent document CN202310313247.8, filing date 20230328, entitled: a DOPO-based reactive flame retardant for flame-retardant epoxy resin and a preparation method thereof, discloses a reactive flame retardant with a side group structure, which can obviously improve the flame retardant property of the epoxy resin. As a reactive flame retardant, the effect on the mechanical properties of the composite material is small, and the light transmittance is not obviously reduced. Meanwhile, the existing flame retardant is added in a reaction mode, a small amount of flame retardant achieves an ideal flame retardant effect, but when the adding amount of the flame retardant is large, the mechanical property or the thermal property of the epoxy resin is obviously reduced, and the application of the flame retardant epoxy resin is limited.
In terms of toughening epoxy resins, the prior art and literature publications report that the epoxy resins are toughened in a variety of ways, and the toughening agents involved include thermoplastic resins, block copolymers, core-shell particles, hyperbranched polymers, rubber elastomers, nanofiller particles, carbon materials or modifications thereof, and the like. For example, chinese patent document CN201610202906.0, filing date 2016041, entitled: a toughening agent and modified epoxy resin are disclosed, which are one or more of polyether sulfone and its derivative, polyether polyol and its derivative, and polyether ketone and its derivative, and can obviously improve the toughness of epoxy resin. However, the thermal properties of the toughened epoxy resin are affected to some extent.
Therefore, there is a need for a reactive epoxy resin halogen-free flame retardant toughening agent that can maintain or enhance thermal properties while enhancing flame retardant and toughening effects.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects of the prior art and provide a halogen-free flame retardant toughening agent for epoxy resin, so as to at least achieve the effects of improving flame retardance and toughening effect, and simultaneously maintaining and even improving thermal performance and low viscosity.
The above object is achieved by the following technical scheme: an epoxy resin halogen-free flame retardant toughening agent has a structural formula shown in formula I and formula II:
wherein R is 1 Methyl, ethyl or propyl; r is R 2 And R is 3 Is hydroxyl, amino or carboxyl.
The second purpose of the invention is to overcome the defects of the prior art and provide a preparation method of the halogen-free flame retardant toughening agent for epoxy resin.
The above object is achieved by the following technical scheme: the preparation method of the halogen-free flame retardant toughening agent for the epoxy resin comprises the following steps:
s1, melting and mixing DOPO, a benzophenone or aldehyde compound, an aniline compound and p-toluenesulfonic acid in an oil bath at 100 ℃ and raising the temperature to 110 ℃ for reaction for 3 hours to obtain a reaction liquid I;
s2, recrystallizing and purifying the reaction solution I by using methanol and chloroform to obtain a reaction intermediate product II;
s3, dissolving DOPO and p-hydroxybenzaldehyde in an organic solvent to obtain a mixed solution III;
s4, dissolving a reaction intermediate product II in the mixed solution III, and heating in an oil bath for reacting for a period of time to obtain a reaction solution IV;
s5, purifying the reaction solution IV to obtain the organic halogen-free flame retardant toughening agent.
Term interpretation:
(1) the benzophenone or aldehyde compound refers to a compound with aldehyde or ketone functional groups on benzene rings.
(2) The aniline compound disclosed by the invention refers to an aromatic compound containing an amino group.
(3) The aldehyde compound refers to aromatic or hydrocarbon compounds containing aldehyde groups.
Further, the benzophenone or aldehyde compound comprises one of 4-amino acetophenone, 4-amino propiophenone and vanillin.
Further, the aniline compound comprises one of aniline, o-phenylenediamine and m-phenylenediamine.
Further, the aldehyde compound includes one of parahydroxybenzaldehyde, terephthalaldehyde, and paraformaldehyde.
Further, the molar ratio of DOPO, benzophenone or aldehyde compounds, aniline compounds and p-toluenesulfonic acid in S1 is 1-2:1:2-6:0.01-0.1, and the molar ratio of DOPO, p-hydroxybenzaldehyde and intermediate II in S2 and S3 is 1-2:2-4:1.
Further, the organic solvent includes one of methanol, ethanol and chloroform.
Further, in S5, the heating and the period of time of the oil bath are respectively: the temperature is 50-80 ℃ and the period of time is 3-8 h.
The invention further aims to provide an application of the organic halogen-free flame retardant toughening agent.
The above object is achieved by the following technical scheme: the application comprises the following steps:
s1, mixing the halogen-free flame retardant toughening agent, epoxy resin and a curing agent, and mechanically stirring under a vacuum condition to obtain an intermediate product;
s2, pouring the intermediate product into a mold, performing a curing reaction according to a temperature programming mode, and cooling to room temperature after the reaction is finished to obtain the epoxy resin composite material.
Further, the epoxy resin is E-51 epoxy resin; the curing agent is 2, 4-diaminodiphenyl methane (DDM) or methyltetrahydrophthalic anhydride (MeTHPA).
Further, S1 is specifically: 1 to 10 parts of the organic halogen-free flame retardant toughening agent, 75 to 100 parts of the E-51 epoxy resin and 20 to 25 parts of the 2, 4-diaminodiphenyl methane are weighed according to parts by weight, and mechanically stirred for 0.5 to 1.0 hour under the vacuum condition of 60 to 80 ℃ to obtain an intermediate product;
or, 1-10 parts of the organic halogen-free flame retardant toughening agent, 75-100 parts of the E-51 epoxy resin and 60-80 parts of the methyltetrahydrophthalic anhydride are weighed according to parts by weight, and mechanically stirred for 0.5-1.0 h under the vacuum condition of 60-80 ℃ to obtain an intermediate product.
Further, according to the temperature programming mode, the curing temperature of the curing reaction is 100 ℃/2h+130 ℃/2h or 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h.
It is worth noting that the DOPO has high phosphorus content, so that the DOPO has good flame retardant property, but can not be independently and directly applied to epoxy resin because the DOPO can not react with an epoxy curing system, has small molecular weight, has obvious plasticizing effect after being added, and has reduced mechanical property, thermal property, electrical property and the like; the aldehyde compound has a typical flexible long chain, so that the epoxy resin can be endowed with good toughness, when the aldehyde compound is added and contains more benzene rings, the molecular chain contains more benzene rings, so that the thermal performance is favorably maintained, but the toughness of a cured product is also caused by the reduction of the crosslinking density of the benzene rings due to the rigid structure of the benzene rings. Meanwhile, due to the reasonable design of the benzene ring structures of the DOPO and the aromatic compound, the thermal stability of the epoxy resin cured product can be improved, and meanwhile, the impact strength of the epoxy resin cured product can also be improved.
In the invention, firstly, nucleophilic dehydration reaction is carried out on the benzophenone or the aldehyde compound, the aniline compound and DOPO to prepare a macromolecular compound, then the aldehyde compound and DOPO are reacted on the macromolecular compound according to the Schiff base principle to obtain the halogen-free flame retardant toughening agent for epoxy resin, wherein the benzophenone and the aniline compound provide a reinforcing part, the phosphorus-oxygen group of the DOPO provides a flame retardant effect, the aldehyde group of the aldehyde compound is used as a reaction part, and the aniline compound is used as a group of an epoxy addition reaction to introduce the flame retardant toughening agent into a chain segment of the epoxy resin, so that the strength performance of macromolecules of a benzene ring structure can be fully exerted, and the three can generate a functional synergistic effect, thereby achieving the effects of improving flame retardant and toughening effects, maintaining even improving thermal performance and low viscosity.
The beneficial effects of the invention are as follows:
1. the invention designs the reactive halogen-free flame retardant toughening agent with a plurality of benzene ring structures and phosphorus-oxygen groups based on the relation of material structures and performances, and the reactive halogen-free flame retardant toughening agent has a functional synergistic effect, so that the flame retardant and toughening effects are improved, and the thermal performance is maintained and even improved.
2. According to the halogen-free flame retardant toughening agent, through the mutual synergistic effect of different functional components, the halogen-free flame retardant toughening agent is used in an amount ofUnder the condition of lower (3% -5%), the vertical burning test (UL-94) reaches V-0 grade, the LOI reaches about 30%, and the impact strength is more than 40kJ/m 2 。
3. According to the preparation method of the halogen-free flame retardant toughening agent for the epoxy resin, the molecular weight of a macromolecular compound can be adjusted by controlling the component proportion, so that the obtained reactive halogen-free flame retardant toughening agent has low viscosity, is favorable for fully and uniformly mixing with the epoxy resin, increases the fluidity of the mixed epoxy resin, can adapt to various processing technological processes, and has good processability and is favorable for application in multiple fields.
Drawings
FIG. 1 is an infrared spectrum of the final product obtained in example 1;
FIG. 2 shows the final product obtained in example 1 31 P-NMR chart;
FIG. 3 is a photograph of a UL-94 burn test of the epoxy resin composite material prepared in application example 1.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the accompanying drawings, but the scope of the present invention is not limited to the following description.
Example 1
The preparation method of the halogen-free flame retardant toughening agent comprises the following steps:
s1, adding 21.6g,0.1mol of 9, 10-diammine-9 oxa-10 phosphaphenanthrene-10-oxide (DOPO), 13.5g,0.1mol of 4-aminoacetophenone, 36.2ml,0.4mol of aniline and 2.038g,0.02mol of p-toluenesulfonic acid into a three-neck flask, placing the three-neck flask in an oil bath pot at 100 ℃ to be melted into liquid, and stirring and reacting for 10 hours to obtain a reaction liquid I;
s2, carrying out post-treatment such as suction filtration and drying on the reaction liquid I to obtain an intermediate product II;
s3, dissolving 53.2g,0.2mol of DOPO, 24.4g,0.2mol of p-hydroxybenzaldehyde and 22.3g,0.1mol of intermediate II in 300ml of ethanol, and condensing and refluxing for reaction for 5 hours to obtain a reaction solution III;
s4, carrying out suction filtration and washing on the reaction solution III to obtain a precipitate, and drying the precipitate in a 100 ℃ oven for 24 hours to obtain a final product.
Wherein the infrared spectrum of the final product is shown in figure 1: 921cm -1 The P-O-C bond absorption peak of DOPO is 1116cm -1 Where p=o bond of DOPO, 1203cm -1 The P=C bond at the junction of DOPO and 4-amino acetophenone is 1610cm -1 The three absorption peaks prove the existence and successful grafting of the phenylphosphoryl dichloride in the final product; 3446cm -1 The absorption peak of the-OH group of the phenolic hydroxyaldehydes is shown to demonstrate the presence of the phenolic hydroxyaldehydes.
The final product is 31 P-NMR is shown in FIG. 2: it can be seen that there are three distinct absorption peaks, respectively for three phosphorus absorption peaks at three DOPOs, which are shown to differ in intensity due to the problem of their chemical structure.
Example 2
The preparation method of the halogen-free flame retardant toughening agent comprises the following steps:
s1, adding 21.6g,0.1mol of 9, 10-diammine-9 oxa-10 phosphaphenanthrene-10-oxide (DOPO), 12.1g,0.1mol of 4-aminobenzaldehyde, 36.2ml,0.4mol of aniline and 2.038g,0.02mol of p-toluenesulfonic acid into a three-neck flask, placing the three-neck flask in an oil bath pot at 100 ℃ to be melted to liquid, and stirring and reacting for 10 hours to obtain a reaction liquid I;
s2, carrying out post-treatment such as suction filtration and drying on the reaction liquid I to obtain an intermediate product II;
s3, dissolving 53.2g,0.2mol of DOPO, 24.4g,0.2mol of p-hydroxybenzaldehyde and 22.3g,0.1mol of intermediate II in 300ml of ethanol, and condensing and refluxing for reaction for 5 hours to obtain a reaction solution III;
s4, carrying out suction filtration and washing on the reaction solution III to obtain a precipitate, and drying the precipitate in a 100 ℃ oven for 24 hours to obtain a final product.
Example 3
The preparation method of the halogen-free flame retardant toughening agent comprises the following steps:
s1, adding 21.6g,0.1mol of 9, 10-diammine-9 oxa-10 phosphaphenanthrene-10-oxide (DOPO), 13.5g,0.1mol of 4-aminoacetophenone, 10.8g,0.4mol of 1, 2-phenylenediamine and 2.038g,0.02mol of p-toluenesulfonic acid into a three-neck flask, placing the three-neck flask in an oil bath pot at 100 ℃ to be melted into liquid, and stirring and reacting for 10 hours to obtain a reaction liquid I;
s2, carrying out post-treatment such as suction filtration and drying on the reaction liquid I to obtain an intermediate product II;
s3, dissolving 53.2g,0.2mol of DOPO, 24.4g,0.2mol of p-hydroxybenzaldehyde and 22.3g,0.1mol of intermediate II in 300ml of ethanol, and condensing and refluxing for reaction for 5 hours to obtain a reaction solution III;
s4, carrying out suction filtration and washing on the reaction solution III to obtain a precipitate, and drying the precipitate in a 100 ℃ oven for 24 hours to obtain a final product.
Example 4
The preparation method of the halogen-free flame retardant toughening agent comprises the following steps:
s1, adding 21.6g,0.1mol of 9, 10-diammine-9 oxa-10 phosphaphenanthrene-10-oxide (DOPO), 12.1g,0.1mol of 4-aminobenzaldehyde, 10.8g,0.4mol of 1, 2-phenylenediamine and 2.038g,0.02mol of p-toluenesulfonic acid into a three-neck flask, placing the three-neck flask in an oil bath pot at 100 ℃ to be melted into liquid, and stirring and reacting for 10 hours to obtain a reaction liquid I;
s2, carrying out post-treatment such as suction filtration and drying on the reaction liquid I to obtain an intermediate product II;
s3, dissolving 53.2g,0.2mol of DOPO, 24.4g,0.2mol of p-hydroxybenzaldehyde and 22.3g,0.1mol of intermediate I in 300ml of ethanol, and condensing and refluxing for reaction for 5 hours to obtain a reaction solution III;
s5, carrying out suction filtration and washing on the reaction solution III to obtain a precipitate, and drying the precipitate in a 100 ℃ oven for 24 hours to obtain a final product.
Application example 1
85 parts of epoxy resin, 25 parts of DDM curing agent and 6 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 1 are weighed, mechanically stirred for 10min at 60 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant toughening modified epoxy resin composite material.
Application example 2
85 parts of epoxy resin, 25 parts of DDM curing agent and 7 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 2 are weighed, mechanically stirred for 10min at 60 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant toughening modified epoxy resin composite material.
Application example 3
85 parts of epoxy resin, 25 parts of DDM curing agent and 6 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 3 are weighed, mechanically stirred for 10min at 60 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant toughening modified epoxy resin composite material.
Application example 4
85 parts of epoxy resin, 25 parts of DDM curing agent and 7 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 4 are weighed, mechanically stirred for 10min at 60 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant toughening modified epoxy resin composite material.
Application example 5
100 parts of epoxy resin, 85 parts of MeTHPA curing agent and 10 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 1 are weighed, mechanically stirred for 30min at 50 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h, so as to obtain the flame retardant toughened modified epoxy resin composite material.
Application example 6
100 parts of epoxy resin, 85 parts of MeTHPA curing agent and 10 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 2 are weighed, mechanically stirred for 30min at 50 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h, so as to obtain the flame retardant toughened modified epoxy resin composite material.
Application example 7
100 parts of epoxy resin, 85 parts of MeTHPA curing agent and 10 parts of the organic halogen-free flame retardant toughening agent prepared in the embodiment 3 are weighed, mechanically stirred for 30min at 50 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h, so as to obtain the flame retardant toughened modified epoxy resin composite material.
Application example 8
100 parts of epoxy resin, 80 parts of MeTHPA curing agent and 8 parts of halogen-free flame retardant toughening agent prepared in example 4 are weighed, mechanically stirred for 30min at 50 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h, thus obtaining the flame retardant toughened modified epoxy resin composite material.
Comparative example 1 (without modifier, the curative was DDM)
Weighing 85 parts of epoxy resin and 25 parts of DDM curing agent, mechanically stirring for 10min at 60 ℃ in vacuum, pouring the mixture into a die, and performing curing reaction through a temperature programming process of 100 ℃/2h+130 ℃/2h to obtain the flame-retardant toughened modified epoxy resin composite material.
Comparative example 2 (no modifier added, curing agent MeTHPA)
100 parts of epoxy resin and 80 parts of MeTHPA curing agent are weighed, mechanically stirred for 30min at 50 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h, thus obtaining the flame-retardant toughened modified epoxy resin cured product.
Comparative example 3 (Aniline as modifier and DDM as curing agent)
80 parts of epoxy resin, 20 parts of DDM curing agent and 6 parts of aniline are weighed, mechanically stirred for 30min at 70 ℃, then poured into a mold, and cured through a temperature programming process of 100 ℃/2h+130 ℃/2h to obtain the flame-retardant toughened modified epoxy resin composite material.
Comparative example 4 (Aniline as modifier and MeTHPA as curing agent)
100 parts of epoxy resin, 80 parts of MeTHPA curing agent and 6 parts of aniline are weighed, mechanically stirred for 30min at 70 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/1h+100 ℃/2h+130 ℃/2h+150 ℃/4h to obtain the flame-retardant toughened modified epoxy resin cured product.
Comparative example 5 (reaction product of DOPO and 4-aminobenzaldehyde as modifier, curing agent DDM)
In the preparation process, when ammonia aromatic compounds are not added and only DOPO is reacted with 4-aminobenzaldehyde, an aromatic compound containing phosphorus and oxygen can be prepared, and the compound is used as a modifier for a comparison experiment;
80 parts of epoxy resin, 20 parts of DDM curing agent and 6 parts of aromatic compound modifier containing phosphorus and oxygen are weighed, mechanically stirred for 30min at 70 ℃, then poured into a mold, and cured and reacted through a temperature programming process of 100 ℃/2h+130 ℃/2h, thus obtaining the flame-retardant toughened and modified epoxy resin composite material.
Comparative example 6 (reaction product of DOPO and 4-aminobenzaldehyde as modifier, curing agent is MeTHPA)
In the preparation process, when ammonia aromatic compounds are not added and only DOPO is reacted with 4-aminobenzaldehyde, an aromatic compound containing phosphorus and oxygen can be prepared, and the compound is used as a modifier for a comparison experiment;
100 parts of epoxy resin, 80 parts of MeTHPA curing agent and 6 parts of aromatic compound modifier containing phosphorus and oxygen are weighed, mechanically stirred for 30min at 70 ℃, then poured into a mold, and cured by a temperature programming process of 80 ℃/1h+100 ℃/1h+130 ℃/2h+150 ℃/4h to obtain the flame-retardant toughened modified epoxy resin cured product.
Test effect
1. In order to verify the fireproof effect of the epoxy resin composite material prepared from the organic halogen-free flame retardant toughening agent disclosed by the invention, a test is carried out. The test was conducted to test the LOI, UL-94, impact strength and heat distortion temperature of comparative examples 1 to 6 and application examples 1 to 8. The results are shown in the following table:
application example | Curing agent | LOI% | UL-94 | Impact strength kJ/m 2 | Heat distortion temperature (DEG C) |
Comparative example 1 | DDM | 23 | NR | 21.9±3.1 | 145 |
Comparative example 2 | MeTHPA | 21 | NR | 26.6±3.7 | 110 |
Comparative example 3 | DDM | 22 | NR | 28.5±4.6 | 138 |
Comparative example 4 | MeTHPA | 21 | NR | 31.6±5.5 | 107 |
Comparative example 5 | DDM | 30.5 | V-1 | 33.2±3.8 | 145 |
Comparative example 6 | MeTHPA | 31.5 | V-1 | 34.3±4.1 | 107 |
Application example 1 | DDM | 31.5 | V-0 | 47.7±2.9 | 155 |
Application example 2 | DDM | 30.6 | V-0 | 43.2±3.5 | 161 |
Application example 3 | DDM | 31.3 | V-0 | 39.6±4.0 | 160 |
Application example 4 | DDM | 31 | V-0 | 42.1±3.8 | 162 |
Application example 5 | MeTHPA | 30 | V-1 | 45.0±3.0 | 118 |
Application example 6 | MeTHPA | 30 | V-1 | 40.3±2.6 | 117 |
Application example 7 | MeTHPA | 31 | V-1 | 42.1±4.8 | 118 |
Application example 8 | MeTHPA | 32.1 | V-1 | 42.2±4.5 | 119 |
Compared with comparative examples 1-6, the organic halogen-free flame retardant toughening agent is introduced into an epoxy resin curing system according to a certain proportion, so that the flame retardant property is obviously improved; moreover, the impact strength of the epoxy resin cured product is obviously improved as shown by the impact performance test; meanwhile, the heat distortion temperature is also improved; the main reason is that the macromolecular compounds formed by the two compounds form a functional synergistic effect, so that the comprehensive performance of the epoxy resin is obviously improved.
The UL-94 burning test photo of the epoxy resin composite material prepared in application example 1 is shown in fig. 3, and it can be seen that the epoxy resin composite material passes the V-0 level test, and has excellent flame retardant property.
The foregoing is merely a preferred embodiment of the invention, and it is to be understood that the invention is not limited to the form disclosed herein but is not to be construed as excluding other embodiments, but is capable of numerous other combinations, modifications and environments and is capable of modifications within the scope of the inventive concept, either as taught or as a matter of routine skill or knowledge in the relevant art. And that modifications and variations which do not depart from the spirit and scope of the invention are intended to be within the scope of the appended claims.
Claims (10)
1. The halogen-free flame retardant toughening agent for the epoxy resin is characterized by having a structural formula shown in a formula I and a formula II:
wherein R is 1 Methyl, ethyl or propyl; r is R 2 And R is 3 Is hydroxyl, amino or carboxyl.
2. A method for preparing the halogen-free flame retardant toughening agent of the epoxy resin according to claim 1, which is characterized by comprising the following steps:
s1, melting and mixing DOPO, a benzophenone or aldehyde compound, an aniline compound and p-toluenesulfonic acid in an oil bath at 100 ℃ and raising the temperature to 110 ℃ for reaction for 3 hours to obtain a reaction liquid I;
s2, recrystallizing and purifying the reaction solution I by using methanol and chloroform to obtain a reaction intermediate product II;
s3, dissolving DOPO and p-hydroxybenzaldehyde in an organic solvent to obtain a mixed solution III;
s4, dissolving a reaction intermediate product II in the mixed solution III, and heating in an oil bath for reacting for a period of time to obtain a reaction solution IV;
s5, purifying the reaction solution IV to obtain the halogen-free flame retardant toughening agent for the epoxy resin.
3. The method according to claim 2, wherein the benzophenone or aldehyde compound comprises one of 4-amino acetophenone, 4-amino propiophenone and vanillin.
4. The method of claim 2, wherein the aniline compound comprises one of aniline, o-phenylenediamine, and m-phenylenediamine.
5. The method of claim 2, wherein the aldehyde compound comprises one of parahydroxybenzaldehyde, terephthalaldehyde, and paraformaldehyde.
6. The method according to claim 2, wherein the molar ratio of DOPO, benzophenone or aldehyde compounds, aniline compounds and p-toluenesulfonic acid in S1 is 1-2:1:2-6:0.01-0.1, and the molar ratio of DOPO, p-hydroxybenzaldehyde and intermediate II in S2 and S3 is 1-2:2-4:1.
7. The method of claim 2, wherein the organic solvent comprises one of methanol, ethanol, and chloroform.
8. The method according to claim 2, wherein the oil bath heating and reaction time in S4 are respectively: the temperature is 50-80 ℃ and the period of time is 3-8 h.
9. The method of claim 2, wherein the epoxy resin halogen-free flame retardant toughening agent is prepared and applied to modified epoxy resin.
10. The use according to claim 9, characterized by the steps of:
s1, mixing the halogen-free flame retardant toughening agent, epoxy resin and a curing agent, and mechanically stirring under a vacuum condition to obtain an intermediate product;
s2, pouring the intermediate product into a mold, performing a curing reaction according to a temperature programming mode, and cooling to room temperature after the reaction is finished to obtain the epoxy resin composite material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311570289.6A CN117486939A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311570289.6A CN117486939A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117486939A true CN117486939A (en) | 2024-02-02 |
Family
ID=89670682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311570289.6A Pending CN117486939A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117486939A (en) |
-
2023
- 2023-11-23 CN CN202311570289.6A patent/CN117486939A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5720085B2 (en) | Novel phosphorus-containing compounds and their preparation and use | |
CN1754913A (en) | Flame retardant compositions | |
CN112048042A (en) | Reactive nitrogen phosphorus-graphene composite flame retardant modified acrylate and preparation method thereof | |
CN111635618A (en) | Phosphazene-based organic metal complex flame-retardant epoxy resin and preparation method thereof | |
CN111961198B (en) | Halogen-free flame-retardant toughening agent and preparation method and application thereof | |
CN113234228B (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
Wang et al. | Synthesis and thermal degradation behaviors of hyperbranched polyphosphate | |
CN112442073A (en) | Phosphorus-containing reactive flame retardant and preparation method and application thereof | |
CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
CN115894860B (en) | Hyperbranched flame-retardant epoxy resin and epoxy resin composition prepared from same | |
CN117486939A (en) | Preparation method and application of halogen-free flame retardant toughening agent for epoxy resin | |
CN112250712A (en) | DOPO-containing bisphthalonitrile flame retardant and preparation method and application method thereof | |
CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
CN116656008A (en) | Preparation method, product and application of microcapsule type hollow mesoporous silica flame retardant | |
CN114262554A (en) | Nitrogen-phosphorus-containing epoxy resin fireproof coating and preparation method thereof | |
CN113248865A (en) | Benzoxazine resin system capable of being rapidly cured and composite material | |
CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
TWI417298B (en) | Multifunctional phosphorus-containing compounds as flame-retardancy curing agent and their preparing process and use | |
CN115678330B (en) | Flame-retardant solvent-free bio-based environment-friendly coating | |
RU2756360C1 (en) | Fire retardant catalyst for production of polymeric materials based on polybenzoxazines, compositions with its use | |
CN113582939B (en) | Secondary amino benzoxazine monomer and application thereof | |
CN113896850B (en) | Flame-retardant high-heat-resistance low-dielectric benzoxazine resin and preparation method thereof | |
CN109942807B (en) | Cable material containing DOPO and cross-linked alkenyl polyaryletherketone and preparation method thereof | |
CN115232470A (en) | Nylon glass fiber material for automobile parts and preparation method and application thereof | |
CN117659615A (en) | Epoxy resin composition, preparation method, prepreg and composite material thereof |
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 |