CN115850708A - Preparation method and application of N-P-Si-containing cage polysilsesquioxane flame retardant - Google Patents
Preparation method and application of N-P-Si-containing cage polysilsesquioxane flame retardant Download PDFInfo
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- CN115850708A CN115850708A CN202211695743.6A CN202211695743A CN115850708A CN 115850708 A CN115850708 A CN 115850708A CN 202211695743 A CN202211695743 A CN 202211695743A CN 115850708 A CN115850708 A CN 115850708A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 149
- 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 138
- 229920000734 polysilsesquioxane polymer Polymers 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910014299 N-Si Inorganic materials 0.000 claims abstract description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 aldehyde compound Chemical class 0.000 claims abstract description 8
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- 239000004417 polycarbonate Substances 0.000 claims description 65
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- 238000000034 method Methods 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- 238000000520 microinjection Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002262 Schiff base Substances 0.000 abstract description 10
- 150000004753 Schiff bases Chemical class 0.000 abstract description 10
- 238000007259 addition reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 5
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- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- 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 15
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
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- 230000002195 synergetic effect Effects 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
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- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a cage-shaped polysilsesquioxane flame retardant containing N-P-Si, which comprises the following steps: mixing an organic solvent, concentrated hydrochloric acid and a silane coupling agent precursor in a reaction container to obtain cage-shaped polysilsesquioxane; adding 4-aminoacetophenone, aniline, p-toluenesulfonic acid and DOPO into a reaction vessel, and reacting at the temperature of B under the protection of nitrogen to obtain NH through Schiff base reaction and addition reaction for the time of B 2 -DOPO; adding deionized water, absolute ethyl alcohol and N, N-dimethylformamide into a reaction container, and adding cage-shaped polysilsesquioxaneAlkylene oxide, aldehyde compound and NH 2 And (4) reacting the DOPO for C time at the temperature of C to obtain the P-N-Si-containing cage polysilsesquioxane flame retardant. The P-N-Si-containing cage-shaped polysilsesquioxane flame retardant prepared by the invention is applied to flame retardant research of polymer materials, and the flame retardant is proved to have excellent mechanical property and flame retardant property, and also have excellent effects of smoke suppression and toxicity reduction and good compatibility.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a preparation method and application of a N-P-Si-containing cage polysilsesquioxane flame retardant.
Background
The discovery and development history of the polymer is long, and from the natural high score discovered in ancient times to the wide application of the modern synthetic polymer in the plastic industry, china has become a big country for plastic production and consumption. Epoxy resin and polycarbonate are two types of high molecular materials with large dosage. However, plastics mainly comprise hydrocarbon and oxygen, have the defect of extremely easy combustion, and have fire hazard in the application process, so that the research on flame retardance of polymer-based composite materials is widely concerned.
The development of flame retardants has been rapidly advanced in the last century, and since about 60 years in the beginning of the 50 th century, especially since about 30 years in the beginning of the 80 th century, flame retardants and flame retardant polymer materials play an important role in reducing life and property losses caused by fire. The research course of China on the flame retardant is relatively late compared with that of China, the flame retardant is single in variety, but through decades of development, and with the development of synthetic material industry and the continuous expansion of application fields in China, the flame retardant is applied to various fields such as chemical building materials, electronic and electric appliances, transportation, aerospace, daily furniture, interior decoration, clothes and housing, and has huge development potential.
The flame retardant can be classified into an additive type flame retardant and a reactive type flame retardant according to the type of addition. The industrial common use is additive flame retardant which is simple to use and low in price, but the method can cause poor compatibility of the flame retardant and the base material and easy migration, thereby influencing the mechanical property of the base material; the reactive flame retardant introduces chemical elements with flame retardant effect into the synthetic raw materials of the base material through chemical reaction, so that the synthesized base material has certain flame retardancy, but the method usually needs very high addition amount to achieve certain flame retardant effect, and the high addition amount inevitably causes adverse effect on the mechanical property of the material.
Among them, the halogen flame retardant has been developed earlier, has been industrially produced, and has low cost, excellent flame retardant property and wide application. However, in 1980, a great deal of research indicates that the halogen flame retardant releases a great amount of carcinogenic substances in the flame retardant process and is banned by various countries. In recent years, phosphorus flame retardants have excellent flame retardant properties and a wide range of sources, and can be classified into inorganic phosphorus flame retardants (including ammonium polyphosphate, melamine phosphate, and the like) and organic phosphorus flame retardants (including phosphonate ester, organic phosphinic acid, phosphazene, phenanthrene, and the like), and the phosphorus flame retardants can cooperate with other flame retardants to have good designability, flame retardancy, and low toxicity, and thus are widely researched and applied by people. In addition, phosphorus-nitrogen flame retardants also generate some inert gases, such as NH, when they are thermally cracked 3 And H 2 O, etc., thereby diluting the concentration of combustible gas and oxygen in the system, and finally terminating combustion. In the condensed phase, the phosphorus-containing flame retardant is decomposed by heating to generate phosphate or pyrophosphate, the phosphorus-silicon flame retardant also generates a carbon layer of silicon dioxide, and the incombustible solid substances are wrapped on the surface of the material and can isolate oxygen and heat from continuing to be transmitted to the interior of the material, so that the flame retardant effect is achieved.
At present, researches on flame retardance tend to combine phosphorus flame retardants and other flame retardants with flame retarding effects to improve the flame retardant performance of materials, and after all, the flame retardant effect of a single flame retardant system is limited.
In addition, studies on smoke suppression and attenuation have been focused on as an inseparable problem from the flame retardancy, and development of a green and highly effective smoke suppression and attenuation agent has become a subject of attention of various researchers.
Therefore, the development of a halogen-free multi-component synergistic flame retardant which can be hybridized by phosphorus and nitrogen elements and is synergistic with organic and inorganic components is urgently needed, the flame retardant performance of the composite material is improved in the application process, and other performances of the composite material are not obviously reduced.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing an N-P-Si-containing caged polysilsesquioxane flame retardant comprising the steps of:
s1, mixing an organic solvent, concentrated hydrochloric acid and a silane coupling agent precursor in a reaction container, and hydrolyzing the silane coupling agent for A time under the acidic condition of A temperature to obtain cage-shaped polysilsesquioxane;
s2, adding 4-aminoacetophenone, aniline, p-toluenesulfonic acid and DOPO into a reaction vessel, and reacting at the temperature of B under the protection of nitrogen to obtain NH through Schiff base reaction and addition reaction for the time of B 2 -DOPO；
S3, adding deionized water, absolute ethyl alcohol and N, N-dimethylformamide into a reaction container, and then adding cage-shaped polysilsesquioxane, aldehyde compounds and NH 2 And (4) reacting the DOPO for C time at the temperature of C to obtain the P-N-Si-containing cage polysilsesquioxane flame retardant.
Preferably, in S1, the silane coupling agent precursor includes one of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and gamma glycidoxypropyltrimethoxysilane; in the S3, the aldehyde compound includes one of carboxybenzaldehyde, terephthalaldehyde, and paraformaldehyde.
Preferably, in S1, the organic solvent includes one of methanol, toluene and acetonitrile.
Preferably, in S1, the volume ratio of the concentrated hydrochloric acid to the silane coupling agent precursor is 1 to 3mL, wherein the concentration of the concentrated hydrochloric acid is 36.0wt%, and the volume of the organic solvent is greater than 90mL.
Preferably, in the S2, the molar ratio of the 4-aminoacetophenone to the aniline to the DOPO to the p-toluenesulfonic acid is 1.
Preferably, among them, in the S3, the cage-like polysilsesquioxane, the aldehyde compound and NH 2 -DOPO molar ratio of 1.
Preferably, in S3, the volume ratio of the deionized water, the absolute ethyl alcohol and the N, N-dimethylformamide is 1.
Preferably, in the S1, the temperature A is 60-90 ℃, and the time A is 12-18 h;
in the S2, the temperature B is 100-130 ℃, and the time B is 12-24 h;
in the S3, the temperature of C is 40-80 ℃, and the time of C is 8-12 h.
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in the epoxy resin comprises the following steps:
step one, mixing 1-10 parts by weight of the P-N-Si cage-shaped polysilsesquioxane flame retardant, 80-100 parts by weight of epoxy resin and 20-25 parts by weight of curing agent, and mechanically stirring for 30min at 80 ℃ under a vacuum condition to obtain an intermediate product;
and step two, pouring the intermediate product into a mold, carrying out curing reaction according to a programmed heating mode of 100 ℃/3h +130 ℃/3h, and cooling to room temperature after the reaction is finished to obtain the flame-retardant modified epoxy resin composite material.
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in polycarbonate comprises the following steps:
step one, mixing 1-10 parts by weight of the P-N-Si cage-shaped polysilsesquioxane flame retardant and 100-150 parts by weight of polycarbonate, and extruding and granulating in a double-screw extruder to obtain an intermediate product; wherein the temperature of the feeding section of the extruder is 200 ℃, the temperature of the compression section is 220 ℃, the temperature of the metering section is 240 ℃, the temperature of the machine neck is 260 ℃, and the temperature of the neck mold is 260 ℃; the rotating speed of the screw of the extruder is 15rmp;
pouring the intermediate product into a micro injection molding machine, and performing injection molding to obtain the flame-retardant modified polycarbonate composite material; wherein the temperature of the micro injection molding machine is 260 ℃, the injection molding pressure is 0.8MPa, and the residence time is 5s.
The invention at least comprises the following beneficial effects: compared with halogen flame retardants, the N-P-Si-containing cage-shaped polysilsesquioxane flame retardant prepared by the invention does not contain halogen elements, and accords with the green and environment-friendly concept proposed by the state; the phosphorus flame retardant is added, so that the flame retardant efficiency of the flame retardant is improved, the toxicity of the flame retardant is reduced, and the introduction of the phosphorus flame retardant can improve the capture of free radicals in the combustion process; and finally, the POSS containing the long-chain branch structure is introduced, so that the compatibility of the flame retardant and a base material can be improved, and the comprehensive properties of the composite material, such as mechanical property, heat resistance and the like, can be improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a graph showing the vertical burning times of 20s and 7s for the flame retardant modified epoxy resin composite prepared in application example 1;
FIG. 2 is a test chart of vertical burning 10s and 5s of the flame-retardant modified epoxy resin composite material prepared in application example 2;
FIG. 3 is a test chart of vertical combustions of 5s and 4s of the flame-retardant modified polycarbonate composite material prepared in application example 5;
FIG. 4 is a transparent test chart of pure epoxy resin and flame retardant modified epoxy resin and polycarbonate composite materials prepared in application example 1, application example 3, application example 4 and application example 6;
FIG. 5 is a photograph of a three-point bending test of the flame retardant modified polycarbonate composite prepared in application example 5.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or combinations thereof.
Example 1
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL3-aminopropyltriethoxysilane precursors in a three-neck flask, and hydrolyzing a silane coupling agent for 18 hours at 90 ℃ under an acidic condition to obtain cage-shaped Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 2
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of 3-aminopropylmethyldiethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18 hours at 90 ℃ under an acidic condition to obtain cage-shaped Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 3
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of gamma glycidyl ether oxypropyl trimethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18h at 90 ℃ under an acidic condition to obtain caged Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 4
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of 3-aminopropyltriethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18 hours at 90 ℃ under an acidic condition to obtain cage-shaped Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-di into a 250mL three-neck flaskMethyl formamide, then 1.0g POSS, 2.79g terephthalaldehyde and 8.85g NH were added 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 5
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of 3-aminopropylmethyldiethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18 hours at 90 ℃ under an acidic condition to obtain cage-shaped Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 6
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of gamma glycidyl ether oxypropyl trimethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18h at 90 ℃ under an acidic condition to obtain caged Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 -DOPO, at 60 ℃ for 12h to prepareObtaining the P-N-Si-containing cage polysilsesquioxane flame retardant.
Example 7
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of 3-aminopropyltriethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18 hours at 90 ℃ under an acidic condition to obtain cage-shaped Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Example 8
A preparation method of a P-N-Si-containing cage-shaped polysilsesquioxane flame retardant comprises the following steps:
s1, mixing 100mL of methanol, 15mL of concentrated hydrochloric acid and 15.2mL of gamma glycidyl ether oxypropyl trimethoxysilane precursor in a three-neck flask, and hydrolyzing a silane coupling agent for 18h at 90 ℃ under an acidic condition to obtain caged Polysilsesquioxane (POSS);
s2, adding 5.75g of 4-aminoacetophenone, 17mL of aniline, 0.32g of p-toluenesulfonic acid and 10g of DOPO into a three-neck flask, and carrying out Schiff base reaction and addition reaction for 16h under the condition of 130 ℃ nitrogen protection to obtain NH 2 -DOPO；
S3, adding 70mL of deionized water, 70mL of absolute ethyl alcohol and 70mL of N, N-dimethylformamide into a 250mL three-neck flask, and then adding 1.0g of POSS, 2.79g of terephthalaldehyde and 8.85g of NH 2 And (4) reacting the-DOPO for 12 hours at the temperature of 60 ℃ to prepare the P-N-Si containing cage polysilsesquioxane flame retardant.
Application example 1
The application of the P-N-Si cage-shaped polysilsesquioxane flame retardant in the epoxy resin comprises the following steps:
80.0g of epoxy resin, 20.0g of DDM curing agent and 1.01g of the halogen-free P-N-Si cage-shaped polysilsesquioxane flame retardant prepared in the embodiment 1 are weighed, mechanically stirred for 30min at 80 ℃ in vacuum, poured into a mold, and subjected to curing reaction through the temperature programming process of 100 ℃/3h +130 ℃/3h to obtain the flame-retardant modified epoxy resin composite material, which is named as a sample band EP-1.
Application example 2
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in the epoxy resin comprises the following steps:
80.0g of epoxy resin, 20.0g of DDM curing agent and 3.10g of the halogen-free P-N-Si cage-shaped polysilsesquioxane flame retardant prepared in the embodiment 1 are weighed, mechanically stirred for 30min at 80 ℃ in vacuum, poured into a mold, and subjected to curing reaction through the temperature programming process of 100 ℃/3h +130 ℃/3h to obtain the flame-retardant modified epoxy resin composite material, which is named as a sample band EP-3.
Application example 3
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in the epoxy resin comprises the following steps:
80.0g of epoxy resin, 20.0g of DDM curing agent and 5.26g of cage-shaped polysilsesquioxane flame retardant containing P-N-Si prepared in example 1 are weighed, mechanically stirred for 30min at 80 ℃ in vacuum, poured into a mold, and subjected to curing reaction through the temperature programming process of 100 ℃/3h +130 ℃/3h to obtain the flame-retardant modified epoxy resin composite material, which is named as a sample band EP-5.
Application example 4
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in polycarbonate comprises the following steps:
100.0g of polycarbonate and 1.01g of the cage polysilsesquioxane flame retardant containing P-N-Si prepared in example 1 are weighed, extruded and granulated in a double-screw extruder to obtain flame-retardant PC plastic, and then the flame-retardant PC plastic is poured into a micro injection molding machine for injection molding to obtain a flame-retardant PC sample strip, which is named as sample strip PC-1. Wherein the temperature of the feeding section of the extruder is 200 ℃, the temperature of the compression section is 220 ℃, the temperature of the metering section is 240 ℃, the temperature of the machine neck is 260 ℃, and the temperature of the neck mold is 260 ℃; the rotating speed of the screw of the extruder is 15rmp; the temperature of the micro injection molding machine is 260 ℃, the injection molding pressure is 0.8MPa, and the residence time is 5s.
Application example 5
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in polycarbonate comprises the following steps:
100.0g of polycarbonate and 3.10g of the cage polysilsesquioxane flame retardant containing P-N-Si prepared in example 1 are weighed, extruded and granulated in a double-screw extruder to obtain flame-retardant PC plastic, and then the flame-retardant PC plastic is poured into a micro injection molding machine for injection molding to obtain a flame-retardant PC sample strip, which is named as sample strip PC-3. Wherein the temperature of the feeding section of the extruder is 200 ℃, the temperature of the compression section is 220 ℃, the temperature of the metering section is 240 ℃, the temperature of the machine neck is 260 ℃, and the temperature of the neck mold is 260 ℃; the rotating speed of the screw of the extruder is 15rmp; the temperature of the micro-injection molding machine is 260 ℃, the injection pressure is 0.8MPa, and the residence time is 5s.
Application example 6
The application of the P-N-Si-containing cage polysilsesquioxane flame retardant in polycarbonate comprises the following steps:
100.0g of polycarbonate and 5.26g of the cage polysilsesquioxane flame retardant containing P-N-Si prepared in example 1 are weighed, extruded and granulated in a double-screw extruder to obtain flame-retardant PC plastic, and then the flame-retardant PC plastic is poured into a micro injection molding machine for injection molding to obtain a flame-retardant PC sample strip, which is named as sample strip PC-5. Wherein the temperature of the feeding section of the extruder is 200 ℃, the temperature of the compression section is 220 ℃, the temperature of the metering section is 240 ℃, the temperature of the machine neck is 260 ℃, and the temperature of the neck mold is 260 ℃; the rotating speed of the screw of the extruder is 15rmp; the temperature of the micro-injection molding machine is 260 ℃, the injection pressure is 0.8MPa, and the residence time is 5s.
Comparative application example 1
The comparative application example provides a method for adding SO into epoxy resin 2 A method of preparing particles, which replaces 1.01g of halogen-free P-N-Si cage polysilsesquioxane flame retardant in application example 1 with 1.01g of SO 2 The particles, the remaining process was the same as in application example 1, and the obtained material was scored as 1wt% SiO 2 /EP。
Comparative application example 2
The comparative application example provides a method for adding SO into epoxy resin 2 Particle method replacing 3.10g of halogen-free P-N-Si caged polysilsesquioxane flame retardant of application example 2 with 3.10g of SO 2 The particles, the remaining process being the same as in application example 2, produced a material which was scored as 3wt% SiO 2 /EP。
Comparative application example 3
The comparative application example provides a method for adding SO into epoxy resin 2 Method of particle replacement of 5.26g of halogen-free P-N-Si caged polysilsesquioxane flame retardant of application example 3 with 5.26g SO 2 Particles, the remaining procedure was the same as in application example 1, and the obtained material was 5wt% SiO 2 /EP。
Comparative application example 4
The comparative application example provides a method for adding SO to polycarbonate 2 Method of particle replacement of 1.01g of halogen-free P-N-Si caged polysilsesquioxane flame retardant of application example 4 with 1.01g SO 2 The particles, the remaining process was the same as in application example 4, and the obtained material was scored as 1wt% SiO 2 /PC。
Comparative application example 5
This comparative application example provides an addition of SO to polycarbonate 2 Particle method replacing 3.10g of halogen-free P-N-Si caged polysilsesquioxane flame retardant of application example 5 with 3.10g of SO 2 The particles, the remaining process being the same as in application example 5, produced a material as 3wt% SiO 2 /PC。
Comparative application example 6
This comparative application example provides an addition of SO to polycarbonate 2 Method of particle replacement of 5.26g of halogen-free P-N-Si caged polysilsesquioxane flame retardant of application example 6 with5.26g SO 2 The particles, the remaining process was the same as in application example 6, and the obtained material was 5wt% SiO 2 /PC。
Effect of the experiment
In order to verify the flame retardant effect of the epoxy resin and polycarbonate composite material prepared by the halogen-free phosphorus-nitrogen-silicon synergistic flame retardant, the experiment is carried out. The experiments tested LOI and UL-94 for neat epoxy as well as EP-1, EP-3, EP-5, neat Polycarbonate (PC), PC-1, PC-3, and PC-5. The results are shown in the following table:
TABLE 1 results of vertical burn and LOI tests in the application examples
As can be seen from the above table, compared with EP and PC which are not added with P-N-Si cage polysilsesquioxane flame retardant, the flame retardant property and the mechanical property are obviously improved by introducing the halogen-free phosphorus-nitrogen compound and the POSS flame retardant into an epoxy resin curing system and polycarbonate according to a certain proportion.
Wherein, the UL-94 burning test photo of the epoxy resin composite material prepared in the application example 1 and the application example 2 is shown in figure 1 and figure 2, and the UL-94 burning test photo of the polycarbonate composite material prepared in the application example 5 is shown in figure 3, and it can be seen that when 3wt% of flame retardant is added, the epoxy resin and the polycarbonate composite material pass the V-0 level test, and the excellent flame retardant property is proved.
In order to verify the transparency of the epoxy resin and polycarbonate composite material prepared by the halogen-free phosphorus-nitrogen-silicon synergistic flame retardant, the test is carried out. Tests carried out with pure epoxy resins (EP), EP-1, EP-3, EP-5, pure Polycarbonates (PC), PC-1, PC-3, PC-5 and with addition of inorganic SO 2 The permeability of the epoxy resin and polycarbonate of the particles. The results are shown in the following table:
TABLE 2 transmittance of 500nm and 700nm light for composite flame retardant materials prepared in application examples 1-6 and comparative application examples 1-6
| Name (R) | 500nm | 700nm | Name(s) | 500nm | 700nm |
| Pure EP | 76.3 | 86.1 | Pure PC | 85.9 | 95.8 |
| 1wt％APOP/EP | 70.2 | 81.0 | 1wt％APOP/PC | 80.4 | 90.7 |
| 3wt％APOP/EP | 67.6 | 78.5 | 3wt％APOP/PC | 74.6 | 85.1 |
| 5wt％APOP/EP | 63.4 | 75.1 | 5wt％APOP/PC | 69.8 | 83.5 |
| 1wt％SiO 2 /EP | 34.8 | 49.3 | 1wt％SiO 2 /PC | 36.1 | 52.4 |
| 3wt％SiO 2 /EP | 27.6 | 37.2 | 3wt％SiO 2 /PC | 30.8 | 47.3 |
| 5wt％SiO 2 /EP | 14.5 | 29.4 | 5wt％SiO 2 /PC | 22.4 | 35.0 |
As can be seen from the above table, the halogen-free phosphorus-nitrogen compound and POSS flame retardant of the invention are introduced into epoxy resin and polycarbonate, and the flame retardant is applied to the epoxy resin and polycarbonateThe ester transparency was less affected, and the 5.0wt% flame retardant added epoxy and polycarbonate had 63.4% and 69.8% transmittance at 500nm, respectively, which was only 16.9% and 18.7% lower than the pure epoxy and polycarbonate, respectively. Adding inorganic SiO into epoxy resin and polycarbonate 2 Then, the transparency is greatly reduced, and mainly the compatibility between the inorganic particles and the polymer-based material is poor, so that the transparency of the material is influenced.
Among them, the photographs of transparency test of the epoxy resin composites and polycarbonate composites prepared in application examples 1, 3 and 4 and application example 6 are shown in fig. 4, and it is apparent that when 5 parts of APOP is added, the pattern of the bottom of the resin can be clearly seen. Thus, the APOP flame retardant has higher compatibility with EP and PC. In the figure, PC and EP are pure polycarbonate and epoxy resin, EP-1 is the epoxy resin composite material prepared in application example 1, EP-5 is the epoxy resin composite material prepared in application example 3, PC-1 is the polycarbonate composite material prepared in application example 4, and PC-5 is the polycarbonate composite material prepared in application example 6.
In order to verify the mechanical properties of the epoxy resin and polycarbonate composite material prepared by the halogen-free phosphorus-nitrogen-silicon synergistic flame retardant, the experiment is carried out. Tests were carried out on impact strength of pure epoxy resins and EP-1, EP-3, EP-5, pure polycarbonate, PC-1, PC-3 and PC-5. The results are shown in the following table:
TABLE 3 results of impact strength test in application examples
| Name (R) | Pure EP | EP-1 | EP-3 | EP-5 | Pure PC | PC-1 | PC-3 | PC-5 |
| Impact Strength (KJ/m) 2 ) | 28 | 43 | 50 | 49 | 57 | 71 | 78 | 65 |
As can be seen from the above table, when the halogen-free phosphorus-nitrogen compound and POSS flame retardant are introduced into epoxy resin and polycarbonate, the impact resistance of the flame retardant to the epoxy resin and the polycarbonate is improved, and the impact strength of the epoxy resin and the polycarbonate added with 3.0wt% of the flame retardant is 60KJ/m 2 And 78KJ/m 2 The improvement is 78.6% and 36.8% compared to pure epoxy resin and polycarbonate, respectively.
The photograph of the three-point bending test of the polycarbonate composite material prepared in application example 5 is shown in fig. 5, and it is apparent that the polycarbonate composite material also has better bending property when 3 parts of APOP is added. The APOP flame retardant can effectively improve the mechanical property of PC.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, described and illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed, and to such extent that such modifications are readily available to those skilled in the art, and it is not intended to be limited to the details shown and described herein without departing from the general concept as defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of a cage-shaped polysilsesquioxane flame retardant containing N-P-Si is characterized by comprising the following steps:
s1, mixing an organic solvent, concentrated hydrochloric acid and a silane coupling agent precursor in a reaction container, and hydrolyzing the silane coupling agent for A time under the acidic condition of A temperature to obtain cage-shaped polysilsesquioxane;
s2, adding 4-aminoacetophenone, aniline, p-toluenesulfonic acid and DOPO into a reaction vessel, and reacting at the temperature of B under the protection of nitrogen for B time to obtain NH 2 -DOPO；
S3, adding deionized water, absolute ethyl alcohol and N, N-dimethylformamide into a reaction container, and then adding cage-shaped polysilsesquioxane, aldehyde compounds and NH 2 And (4) reacting the DOPO for C time at the temperature of C to obtain the P-N-Si-containing cage polysilsesquioxane flame retardant.
2. The method for preparing N-P-Si containing caged polysilsesquioxane flame retardant of claim 1, wherein in S1, said silane coupling agent precursor comprises one of 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and gamma glycidoxypropyltrimethoxysilane; in the S3, the aldehyde compound includes one of carboxybenzaldehyde, terephthalaldehyde, and paraformaldehyde.
3. The method for preparing N-P-Si containing cage-shaped polysilsesquioxane flame retardant according to claim 1 or 2, wherein in S1, the organic solvent comprises one of methanol, toluene and acetonitrile.
4. The method for preparing the N-P-Si-containing caged polysilsesquioxane flame retardant according to claim 1 or 2, wherein in S1, the volume ratio of the concentrated hydrochloric acid to the silane coupling agent precursor is 1-3 mL, wherein the concentration of the concentrated hydrochloric acid is 36.0wt%, and the volume of the organic solvent is more than 90mL.
5. The method for preparing N-P-Si containing cage-like polysilsesquioxane flame retardant according to claim 1 or 2, wherein the molar ratio of 4-aminoacetophenone, aniline, DOPO and P-toluenesulfonic acid in S2 is 1.
6. The method for preparing N-P-Si-containing cage polysilsesquioxane flame retardant according to claim 1 or 2, wherein in S3, the cage polysilsesquioxane, the aldehyde compound, and NH 2 -DOPO molar ratio of 1.
7. The method for preparing the N-P-Si containing cage-shaped polysilsesquioxane flame retardant according to claim 1, wherein in S3, the volume ratio of the deionized water to the absolute ethyl alcohol to the N, N-dimethylformamide is 1.
8. The preparation method of the N-P-Si containing cage-shaped polysilsesquioxane flame retardant according to claim 1, wherein in S1, the temperature A is 60-90 ℃, and the time A is 12-18 h;
in the S2, the temperature B is 100-130 ℃, and the time B is 12-24 h;
in the S3, the temperature of C is 40-80 ℃, and the time of C is 8-12 h.
9. The application of the N-P-Si containing cage polysilsesquioxane flame retardant prepared by the preparation method of the N-P-Si containing cage polysilsesquioxane flame retardant disclosed by any one of claims 1 to 8 is characterized in that the application of the P-N-Si containing cage polysilsesquioxane flame retardant in epoxy resin comprises the following steps:
step one, mixing 1-10 parts by weight of the P-N-Si cage-shaped polysilsesquioxane flame retardant, 80-100 parts by weight of epoxy resin and 20-25 parts by weight of curing agent, and mechanically stirring for 30min at 80 ℃ under a vacuum condition to obtain an intermediate product;
and step two, pouring the intermediate product into a mold, carrying out curing reaction according to a programmed heating mode of 100 ℃/3h +130 ℃/3h, and cooling to room temperature after the reaction is finished to obtain the flame-retardant modified epoxy resin composite material.
10. The application of the N-P-Si containing cage polysilsesquioxane flame retardant prepared by the preparation method of the N-P-Si containing cage polysilsesquioxane flame retardant disclosed by any one of claims 1 to 8 is characterized in that the application of the P-N-Si containing cage polysilsesquioxane flame retardant in polycarbonate comprises the following steps:
step one, mixing 1-10 parts by weight of the P-N-Si cage-shaped polysilsesquioxane flame retardant and 100-150 parts by weight of polycarbonate, and extruding and granulating in a double-screw extruder to obtain an intermediate product; wherein the temperature of the feeding section of the extruder is 200 ℃, the temperature of the compression section is 220 ℃, the temperature of the metering section is 240 ℃, the temperature of the machine neck is 260 ℃, and the temperature of the neck mold is 260 ℃; the rotating speed of the screw of the extruder is 15rmp;
pouring the intermediate product into a micro injection molding machine, and performing injection molding to obtain the flame-retardant modified polycarbonate composite material; wherein the temperature of the micro injection molding machine is 260 ℃, the injection pressure is 0.8MPa, and the residence time is 5s.
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| CN117510860A (en) * | 2023-12-04 | 2024-02-06 | 四川启科新材料有限责任公司 | Silicon resin with high temperature resistance and excellent char formation and preparation method thereof |
| CN117510860B (en) * | 2023-12-04 | 2024-05-14 | 四川启科新材料有限责任公司 | Silicon resin with high temperature resistance and excellent char formation and preparation method thereof |
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