CN116656008A - Preparation method, product and application of microcapsule type hollow mesoporous silica flame retardant - Google Patents
Preparation method, product and application of microcapsule type hollow mesoporous silica flame retardant Download PDFInfo
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- CN116656008A CN116656008A CN202310149238.XA CN202310149238A CN116656008A CN 116656008 A CN116656008 A CN 116656008A CN 202310149238 A CN202310149238 A CN 202310149238A CN 116656008 A CN116656008 A CN 116656008A
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- flame retardant
- hollow mesoporous
- mesoporous silica
- microcapsule type
- silane coupling
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003063 flame retardant Substances 0.000 title claims abstract description 89
- 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 83
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 60
- 239000003094 microcapsule Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 aldehyde compound Chemical class 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- 239000003822 epoxy resin Substances 0.000 claims description 35
- 229920000647 polyepoxide Polymers 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 claims description 2
- 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 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical class C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 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 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a preparation method, a product and application of a microcapsule type hollow mesoporous silica flame retardant, wherein the preparation method comprises the following steps: s1: mixing a silane coupling agent with an aldehyde compound for a coupling reaction to obtain a Schiff base structure compound, and then adding an aromatic compound containing P-H bonds for a nucleophilic addition reaction to obtain a phosphorus-containing silane coupling agent; s2: sequentially adding catalyst strong ammonia water, structural directing agent cetyl trimethyl ammonium bromide, silicon source tetraethyl orthosilicate and etchant hydrochloric acid ethanol solution into ethanol and water to react to generate hollow mesoporous silicon dioxide; s3: dissolving the hollow mesoporous silica and the phosphorus-containing silane coupling agent in an organic solvent, carrying out ultrasonic treatment and stirring, then carrying out centrifugal separation, and heating the solid obtained by the centrifugal separation at 100-130 ℃ to obtain the microcapsule type hollow mesoporous silica flame retardant. The flame retardant disclosed by the invention has excellent flame retardant property and durability, and also has good EP mechanical properties.
Description
Technical Field
The invention relates to the technical field of flame retardant materials, in particular to a preparation method, a product and application of a microcapsule type hollow mesoporous silica flame retardant.
Background
The epoxy resin molecular main chain contains a plurality of ether bonds, benzene ring structures, secondary hydroxyl groups and extremely high-reactivity epoxy end groups, so that the epoxy resin has the advantages of excellent adhesion, corrosion resistance, good dimensional stability and the like, and is widely applied to the fields of electronic packaging, civil construction, mechanical manufacturing, aerospace and the like. However, the three-dimensional network structure formed by the method limits the movement capability of a molecular chain segment, so that the cured product shows obvious brittleness, and the defects of crack extension resistance and poor external force impact resistance exist, so that the application of the cured product in the high-end technical field is limited to a great extent. In addition, epoxy resins are flammable materials with limiting oxygen index of about 23%, which are extremely easy to ignite and release a lot of heat and toxic gases during combustion. Therefore, the flame retardant property and the mechanical property of the epoxy resin are improved, and the epoxy resin has important application value and practical significance.
Flame retardants currently in common use for epoxy resin flame retardant applications include inorganic particles or organic phosphorus-containing compounds. And the inorganic particle flame retardant mainly comprises silicon dioxide, graphene, carbon nano tubes, layered double metal hydroxide, expanded graphite and the like. Although the addition of the inorganic flame retardant has a remarkable improvement effect on the thermal stability of the matrix, the flame retardant efficiency of the traditional unmodified inorganic flame retardant in the matrix material is relatively low. The addition of the inorganic flame retardant is increased, so that the viscosity of the system is too high to be beneficial to the molding processing of the epoxy resin, and the mechanical property of the material is reduced to a certain extent due to the large amount of aggregation of the inorganic flame retardant. Therefore, organic modification of inorganic particles has become an indispensable important means for improving their dispersibility in EP and flame retardant efficiency. The common organic phosphorus-containing flame retardant mainly comprises phosphaphenanthrene compounds, organic phosphonate derivatives and the like. Compared with inorganic particle flame retardants, the organic phosphorus compound flame retardants have good dispersibility in a base material and high flame retardant efficiency, but commonly use small molecular compounds which are easy to migrate and separate out in the base material, so that the flame retardant performance of the material is gradually reduced along with the increase of the service time, and the flame retardant durability is poor. The flame retardant containing the P/N/Si integrated with a series of macromolecular organic-inorganic hybrid is prepared in the earlier stage, the flame retardant has good flame retardant effect, but the mechanical property of the epoxy resin is still deteriorated due to the excessively high content of aliphatic chain segments, namely the problem of contradiction between EP high-efficiency flame retardance and mechanical high strength exists. Therefore, how to design and prepare a multi-component synergistic flame retardant, and on the basis of maintaining or even enhancing the mechanical properties of EP, simultaneously endowing a material with excellent flame retardant properties and durability is a current problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method, a product and application of a microcapsule type hollow mesoporous silica flame retardant, so as to at least achieve the effects of good flame retardant effect, good durability and strong mechanical property of the flame retardant.
The aim of the invention is realized by the following technical scheme:
the preparation method of the microcapsule type hollow mesoporous silica flame retardant comprises the following steps:
s1: mixing a silane coupling agent with an aldehyde compound for a coupling reaction to obtain a Schiff base structure compound, and then adding an aromatic compound containing P-H bonds for a nucleophilic addition reaction to obtain a phosphorus-containing silane coupling agent;
the reaction temperature of the coupling reaction is 50-60 ℃ and the reaction time is 6-8h; the reaction temperature of the nucleophilic addition reaction is 80-90 ℃ and the reaction time is 12-24h.
S2: sequentially adding concentrated ammonia water serving as a catalyst, cetyl trimethyl ammonium bromide serving as a structure guiding agent, tetraethyl orthosilicate serving as a silicon source and ethanol hydrochloride serving as an etchant into ethanol and water serving as solvents, and reacting to generate hollow mesoporous silica;
s3: dissolving the hollow mesoporous silica and the phosphorus-containing silane coupling agent in an organic solvent, carrying out ultrasonic treatment and stirring, then carrying out centrifugal separation, heating the solid obtained by the centrifugal treatment at 100-130 ℃, and promoting the phosphorus-containing silane coupling agent in the hollow mesoporous silica cavity to crosslink and solidify, thus obtaining the microcapsule type hollow mesoporous silica flame retardant.
Further, in step S1, the silane coupling agent has three ethoxy groups, including one of 3-aminopropyl triethoxysilane or aminomethyltriethoxysilane; 3-aminopropyl triethoxysilane is preferred.
Further, in step S1, the aldehyde compound includes one of parahydroxybenzaldehyde and paraformaldehyde.
Further, in step S1, the aromatic compound containing a p—h bond includes one of phenyl hypophosphorous acid, DOPO and diphenyl phosphorus oxide.
Further, in step S1, the molar ratio of the silane coupling agent, the aldehyde compound and the aromatic compound is 1:1:1.
Further, in step S2, the molar ratio of the structure directing agent, the silicon source and the etchant is 1:9-12:3000-4000.
Further, in step S2, the volume ratio of ethanol to water in the solvent is 7:10-14.
Further, in step S2, the volume ratio of hydrochloric acid to ethanol in the hydrochloric acid-ethanol solution is 1:400-1000.
Further, in the step S3, the mass ratio of the phosphorus-containing silane coupling agent to the hollow mesoporous silica is 2:1-5.
Further, in step S3, the organic solvent includes one of ethanol, chloroform and N, N-dimethylformamide.
The phosphorus-containing silane coupling agent comprises the following structural formula:
the microcapsule type hollow mesoporous silica flame retardant is used for flame retardance in epoxy resin composite materials.
The specific method for preparing the epoxy resin composite material comprises the following steps:
s4: mixing the microcapsule type hollow mesoporous silica flame retardant, epoxy resin and curing agent, and mechanically stirring under a vacuum condition to obtain an intermediate product;
s5: pouring the intermediate product into a mould, heating to perform a curing reaction, and cooling to room temperature after the reaction is finished to obtain the epoxy resin composite material.
The beneficial effects of the invention are as follows:
compared with halogen flame retardant, no halogen element is added, and the environment-friendly concept proposed by the nation is met; the phosphorus-containing silane flame retardant contains phosphorus element, nitrogen element and silicon element with flame retardant effect, the addition of the phosphorus element improves the flame retardant efficiency of the flame retardant, reduces the toxicity of the flame retardant, improves the capture of free radicals in the combustion process, can also play a role in diluting combustible gas and oxygen, and can also produce the synergistic flame retardant effect of phosphorus-nitrogen-silicon; the hollow mesoporous silica is used as a carrier, so that not only can the mechanical property, the thermal property and the heat barrier property of the composite material be improved, but also the flame-retardant durability of the composite material can be improved.
Drawings
FIG. 1 is a scanning electron microscope image of hollow mesoporous silica and flame retardant in example 4 of the present invention;
FIG. 2 is a vertical burning test chart of application examples 1, 3, 5 of the present invention;
FIG. 3 is a graph of EDS energy spectrum of example 4 of the present invention;
FIG. 4 is a graph showing the tensile strength versus impact strength values of application example 1 and comparative example 1 according to the present invention;
FIG. 5 is a graph showing the comparison of flexural strength and flexural modulus values of application example 1 and comparative example 1 of the present invention;
FIG. 6 is a graph showing the specific surface area of the hollow mesoporous silica prepared in example 1 of the present invention;
FIG. 7 is a pore size diagram of the hollow mesoporous silica prepared in example 1 of the present invention.
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 microcapsule type hollow mesoporous silica flame retardant comprises the following specific steps:
s1, adding 11.05g of 3-aminopropyl triethoxysilane and 6.1g of p-hydroxybenzaldehyde into a three-neck flask, adding 50mL of ethanol, condensing and refluxing for magnetic stirring for 6 hours at 60 ℃, adding 100mL of ethanol dissolved with 7.1g of phenyl hypophosphorous acid, and magnetically stirring for 12 hours at 80-90 ℃ to finally obtain a phosphorus-containing silane flame retardant a;
s2, using ethanol and deionized water as solvents and strong ammonia water as a catalyst, mechanically stirring for 500rmp, keeping the temperature at 30-35 ℃, then dissolving a structure directing agent Cetyl Trimethyl Ammonium Bromide (CTAB) in the mixed solution, then adding tetraethyl orthosilicate (TEOS), rapidly stirring for 10min, and regulating the rotating speed to the original speed after white is generated, and reacting for 24h; after the reaction is finished, carrying out suction filtration and collection, washing with ethanol for three times, and transferring into a mixed solution of deionized water and ethanol, and carrying out hot bath at 90 ℃ for 24 hours; and (3) continuing to perform suction filtration and collection, washing with ethanol for three times, transferring into ethanol solution containing hydrochloric acid for etching, mechanically stirring at 60 ℃ for 3 hours, repeating for 3 times, and finally performing suction filtration, washing and drying to obtain the hollow mesoporous silica.
S3, dispersing 2g of hollow mesoporous silica in 50mL of organic solvent dissolved with phosphorus-containing silane flame retardant a, carrying out ultrasonic treatment for 1h, carrying out vacuum suction and magnetic stirring for 1h, centrifuging for multiple times, collecting solids, and carrying out heat treatment in a high-temperature oven at 100 ℃ to obtain a final product.
Example 2
The preparation method of the microcapsule type hollow mesoporous silica flame retardant comprises the following specific steps:
s1, adding 11.05g of 3-aminopropyl triethoxysilane and 1.5g of paraformaldehyde into a three-neck flask, then adding 50mL of chloroform, condensing and refluxing for magnetic stirring at 50 ℃ for 6 hours, then adding 100mL of chloroform dissolved with 7.1g of phenyl hypophosphorous acid, and magnetically stirring at 80 ℃ for 12 hours to finally obtain a phosphorus-containing silane flame retardant b;
s2, using ethanol and deionized water as solvents and strong ammonia water as a catalyst, mechanically stirring for 500rmp, keeping the temperature at 30 ℃, then dissolving a structure directing agent Cetyl Trimethyl Ammonium Bromide (CTAB) in the mixed solution, then adding tetraethyl orthosilicate (TEOS), rapidly stirring for 10min, and regulating the rotating speed to the original speed after white is generated, and reacting for 24h; after the reaction is finished, carrying out suction filtration and collection, washing with ethanol for three times, and transferring into a mixed solution of deionized water and ethanol, and carrying out hot bath at 90 ℃ for 24 hours; and (3) continuing to perform suction filtration and collection, washing with ethanol for three times, transferring into ethanol solution containing hydrochloric acid for etching, mechanically stirring at 60 ℃ for 3 hours, repeating for 3 times, and finally performing suction filtration, washing and drying to obtain the hollow mesoporous silica.
S3, dispersing 2g of hollow mesoporous silica in 50mL of organic solvent dissolved with phosphorus-containing silane flame retardant b, carrying out ultrasonic treatment for 1h, carrying out vacuum suction and magnetic stirring for 1h, centrifuging for multiple times, collecting solids, and carrying out heat treatment in a high-temperature oven at 110 ℃ to obtain a final product.
Example 3
The preparation method of the microcapsule type hollow mesoporous silica flame retardant comprises the following specific steps:
s1, adding 11.05g of 3-aminopropyl triethoxysilane and 6.1g of p-hydroxybenzaldehyde into a three-neck flask, adding 50mL of ethanol, condensing and refluxing for magnetic stirring for 6 hours at 60 ℃, adding 100mL of ethanol dissolved with 10.8g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and magnetically stirring for 12 hours at 80 ℃ to finally obtain a phosphorus-containing silane flame retardant c;
s2, using ethanol and deionized water as solvents and strong ammonia water as a catalyst, mechanically stirring for 500rmp, keeping the temperature at 30-35 ℃, then dissolving a structure directing agent Cetyl Trimethyl Ammonium Bromide (CTAB) in the mixed solution, then adding tetraethyl orthosilicate (TEOS), rapidly stirring for 10min, and regulating the rotating speed to the original speed after white is generated, and reacting for 24h; after the reaction is finished, carrying out suction filtration and collection, washing with ethanol for three times, and transferring into a mixed solution of deionized water and ethanol, and carrying out hot bath at 90 ℃ for 24 hours; and (3) continuing to perform suction filtration and collection, washing with ethanol for three times, transferring into ethanol solution containing hydrochloric acid for etching, mechanically stirring at 60 ℃ for 3 hours, repeating for 3 times, and finally performing suction filtration, washing and drying to obtain the hollow mesoporous silica.
S3, dispersing 2g of hollow mesoporous silica in 50mL of organic solvent dissolved with phosphorus-containing silane flame retardant c, carrying out ultrasonic treatment for 1h, carrying out vacuum suction and magnetic stirring for 1h, centrifuging for multiple times, collecting solids, and carrying out heat treatment in a high-temperature oven at 120 ℃ to obtain a final product.
Example 4
The preparation method of the microcapsule type hollow mesoporous silica flame retardant comprises the following specific steps:
s1, adding 11.05g of 3-aminopropyl triethoxysilane and 6.1g of p-hydroxybenzaldehyde into a three-neck flask, adding 50mL of ethanol, condensing and refluxing for magnetic stirring for 6 hours at 60 ℃, adding 100mL of ethanol dissolved with 10.11g of diphenyl phosphorus oxide, and magnetically stirring for 12 hours at 80-90 ℃ to finally obtain a phosphorus-containing silane flame retardant d;
s2, using ethanol and deionized water as solvents and strong ammonia water as a catalyst, mechanically stirring for 500rmp, keeping the temperature at 30 ℃, then dissolving a structure directing agent Cetyl Trimethyl Ammonium Bromide (CTAB) in the mixed solution, then adding tetraethyl orthosilicate (TEOS), rapidly stirring for 10min, and regulating the rotating speed to the original speed after white is generated, and reacting for 24h; after the reaction is finished, carrying out suction filtration and collection, washing with ethanol for three times, and transferring into a mixed solution of deionized water and ethanol, and carrying out hot bath at 90 ℃ for 24 hours; and (3) continuing to perform suction filtration and collection, washing with ethanol for three times, transferring into ethanol solution containing hydrochloric acid for etching, mechanically stirring at 60 ℃ for 3 hours, repeating for 3 times, and finally performing suction filtration, washing and drying to obtain the hollow mesoporous silica.
S3, dispersing 2g of hollow mesoporous silica in 50mL of organic solvent dissolved with phosphorus-containing silane flame retardant e, carrying out ultrasonic treatment for 1h, carrying out vacuum suction and magnetic stirring for 1h, centrifuging for multiple times, collecting solids, and carrying out heat treatment in a high-temperature oven at 130 ℃ to obtain a final product.
Table 1 shows the EDS element statistics of the microcapsule type hollow mesoporous silica flame retardant of example 4.
TABLE 1
| Element(s) | wt％ | Atomic percent |
| C | 32.53 | 45.48 |
| N | 0.00 | 0.00 |
| O | 31.59 | 33.16 |
| Si | 34.24 | 20.47 |
| P | 1.64 | 0.89 |
| Total amount of | 100.00 | 100.00 |
Example 5
The preparation method of the microcapsule type hollow mesoporous silica flame retardant comprises the following specific steps:
s1, adding 11.05g of 3-aminopropyl triethoxysilane and 1.5g of paraformaldehyde into a three-neck flask, adding 50mL of chloroform, condensing and refluxing at 45-55 ℃ for magnetic stirring for 6 hours, adding 100mL of chloroform dissolved with 10.11g of diphenyl phosphorus oxide, and magnetically stirring at 70-80 ℃ for 12 hours to finally obtain a phosphorus-containing silane flame retardant e;
s2, using ethanol and deionized water as solvents and strong ammonia water as a catalyst, mechanically stirring for 500rmp, keeping the temperature at 30 ℃, then dissolving a structure directing agent Cetyl Trimethyl Ammonium Bromide (CTAB) in the mixed solution, then adding tetraethyl orthosilicate (TEOS), rapidly stirring for 10min, and regulating the rotating speed to the original speed after white is generated, and reacting for 24h; after the reaction is finished, carrying out suction filtration and collection, washing with ethanol for three times, and transferring into a mixed solution of deionized water and ethanol, and carrying out hot bath at 90 ℃ for 24 hours; and (3) continuing to perform suction filtration and collection, washing with ethanol for three times, transferring into ethanol solution containing hydrochloric acid for etching, mechanically stirring at 60 ℃ for 3 hours, repeating for 3 times, and finally performing suction filtration, washing and drying to obtain the hollow mesoporous silica.
S3, dispersing 2g of hollow mesoporous silica in 50mL of organic solvent dissolved with phosphorus-containing silane flame retardant f, carrying out ultrasonic treatment for 1h, carrying out vacuum suction and magnetic stirring for 1h, centrifuging for multiple times, collecting solids, and carrying out heat treatment in a high-temperature oven at 110 ℃ to obtain a final product.
Application example 1
80 parts of epoxy resin, 19 parts of DDM curing agent and 1 part of microcapsule type hollow mesoporous silica flame retardant prepared in example 1 are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant modified epoxy resin composite material with the flame retardant content of 1%.
Application example 2
78 parts of epoxy resin, 20 parts of DDM curing agent and 2 parts of microcapsule type hollow mesoporous silica flame retardant prepared in example 2 are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain the flame-retardant modified epoxy resin composite material with the flame retardant content of 2%.
Application example 3
76 parts of epoxy resin, 19 parts of DDM curing agent and 3 parts of microcapsule type hollow mesoporous silica flame retardant prepared in example 3 are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain the flame-retardant modified epoxy resin composite material with 3% of flame retardant content.
Application example 4
76 parts of epoxy resin, 19 parts of DDM curing agent and 4 parts of microcapsule type hollow mesoporous silica flame retardant prepared in example 4 are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain the flame retardant modified epoxy resin composite material with the flame retardant content of 4%.
Application example 5
76 parts of epoxy resin, 19 parts of DDM curing agent and 5 parts of microcapsule type hollow mesoporous silica flame retardant prepared in example 5 are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain the flame-retardant modified epoxy resin composite material with the flame retardant content of 5%.
Comparative example 1
80 parts of epoxy resin and 20 parts of DDM curing agent are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain pure epoxy resin bars.
Comparative example 2
80 parts of epoxy resin, 19 parts of DDM curing agent and 1 part of phosphorus-containing silane coupling agent are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured through a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h, so as to obtain pure epoxy resin bars. The phosphorus-containing silane coupling agent is phosphorus-containing silane flame retardant a in example 1.
Comparative example 3
80 parts of epoxy resin, 19 parts of DDM curing agent and 1 part of hollow mesoporous silica are weighed, mechanically stirred for 30min at 80 ℃, then poured into a mold, and cured by a temperature programming process of 80 ℃/2h+100 ℃/2h+130 ℃/2h to obtain a pure epoxy resin spline. The hollow mesoporous silica was the hollow mesoporous silica prepared in example 1.
Experimental example
In order to verify the flame retardant effect of the epoxy resin composite material prepared from the microcapsule type hollow mesoporous silica flame retardant of the present invention, experiments were performed. The experiments tested LOI and UL-94 of application examples 1-5 and comparative examples 1-3. The results are shown in the following table:
TABLE 2
| Group of | LOI(％) | UL-94 |
| Application example 1 | 30.8 | V-1 |
| Application example 2 | 31.3 | V-1 |
| Application example 3 | 32.0 | V-1 |
| Application example 4 | 32.6 | V-0 |
| Application example 5 | 33.4 | V-0 |
| Comparative example 1 | 23.8 | NO |
| Comparative example 2 | 30.3 | V-1 |
| Comparative example 3 | 25.2 | NO |
Compared with the blank comparison example 1, the microcapsule type hollow mesoporous silica flame retardant is introduced into an epoxy resin curing system according to a certain proportion, and the flame retardant property is obviously improved.
The UL-94 burning test photographs of the epoxy resin composite materials prepared in application examples 1, 3 and 5 are shown in figure 2, and it can be seen that the epoxy resin composite material passes the V-0 level test when 5wt% of flame retardant is added, and has excellent flame retardant property.
As is apparent from FIG. 3, the EDS test patterns of the microcapsule type hollow mesoporous silica flame retardant show distinct characteristic peaks of P, N and Si elements, and the contents of P and Si elements on the sample surface are found to be 0.89wt% and 20.47wt%, respectively, in Table 2. The method shows that most of silane flame retardants are successfully loaded into the hollow mesoporous silica, and a small amount of silane flame retardants are attached to the surface of the silica, so that the microcapsule type hollow mesoporous silica flame retardants are successfully prepared.
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 preparation method of the microcapsule type hollow mesoporous silica flame retardant is characterized by comprising the following steps of:
s1: mixing a silane coupling agent and an aldehyde compound for a coupling reaction to obtain a Schiff base structure compound, and then adding an aromatic compound containing P-H bonds for a nucleophilic addition reaction to obtain a phosphorus-containing silane coupling agent;
s2: sequentially adding catalyst strong ammonia water, structural directing agent cetyl trimethyl ammonium bromide, silicon source tetraethyl orthosilicate and etchant hydrochloric acid ethanol solution into ethanol and water to react to generate hollow mesoporous silicon dioxide;
s3: dissolving the hollow mesoporous silica and the phosphorus-containing silane coupling agent in an organic solvent, carrying out ultrasonic treatment and stirring, then carrying out centrifugal separation, and heating the solid obtained by the centrifugal separation at 100-130 ℃ to obtain the microcapsule type hollow mesoporous silica flame retardant.
2. The method of manufacturing according to claim 1, characterized in that: in step S1, the silane coupling agent has three ethoxy groups, including one of 3-aminopropyl triethoxysilane or aminomethyltriethoxysilane;
and/or, the aldehyde compound comprises one of parahydroxyben-zaldehyde and paraformaldehyde;
and/or the aromatic compound containing P-H bond comprises one of phenylphosphinic acid, DOPO and diphenylphosphorus oxide.
3. The method of manufacturing according to claim 1, characterized in that: in the step S1, the molar ratio of the silane coupling agent, the aldehyde compound and the aromatic compound is 1:1:1.
4. The method of manufacturing according to claim 1, characterized in that: in step S2, the molar ratio of the structure directing agent, the silicon source and the etchant is 1:9-12:3000-4000.
5. The method of manufacturing according to claim 1, characterized in that: in the step S3, the mass ratio of the phosphorus-containing silane coupling agent to the hollow mesoporous silica is 2:1-5.
6. The method of manufacturing according to claim 1, characterized in that: in step S3, the organic solvent includes one of ethanol, chloroform and N, N-dimethylformamide.
7. The method of manufacturing according to claim 1, characterized in that: the phosphorus-containing silane coupling agent comprises the following structural formula:
8. a microcapsule type hollow mesoporous silica flame retardant prepared by the preparation method of any one of claims 1 to 7.
9. Use of the microcapsule type hollow mesoporous silica flame retardant prepared by the preparation method of any one of claims 1 to 7, characterized in that: the microcapsule type hollow mesoporous silica flame retardant is used for preparing an epoxy resin composite material with high flame retardance.
10. The use according to claim 9, wherein the method of preparation comprises the steps of:
s4: mixing the microcapsule type hollow mesoporous silica flame retardant, epoxy resin and curing agent, and mechanically stirring under a vacuum condition to obtain an intermediate product;
s5: pouring the intermediate product into a mould, heating to perform a curing reaction, and cooling to room temperature after the reaction is finished to obtain the epoxy resin composite material.
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