CN104891512B - A kind of phosphorous polymer modified Nano particle and preparation method thereof - Google Patents
A kind of phosphorous polymer modified Nano particle and preparation method thereof Download PDFInfo
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- CN104891512B CN104891512B CN201510306901.8A CN201510306901A CN104891512B CN 104891512 B CN104891512 B CN 104891512B CN 201510306901 A CN201510306901 A CN 201510306901A CN 104891512 B CN104891512 B CN 104891512B
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229920000642 polymer Polymers 0.000 title claims abstract description 85
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 230000004048 modification Effects 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 150000002118 epoxides Chemical group 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000010257 thawing Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims 2
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical class OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 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 description 4
- 239000004113 Sepiolite Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229910052624 sepiolite Inorganic materials 0.000 description 3
- 235000019355 sepiolite Nutrition 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZDMZLTIFXMREFI-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.OCCOC(=O)C=C ZDMZLTIFXMREFI-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 210000000720 eyelash Anatomy 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a kind of phosphorous polymer modified Nano particle and preparation method thereof, handled with silane couplerSiO prepared by method2Particle, obtains the SiO of surface modification epoxide group2Nano-particle；The controllable phosphorous polymer of synthesized polymer degree is polymerize by RAFT with phosphorous-containing monomers；Again by the SiO of surface modification epoxy radicals2Nano-particle and the phosphorus hydroxyl reaction in phosphorous polymer, SiO is grafted on by phosphorous polymer2Nanoparticle surface, obtains the phosphorous polymer modified Nano particle SiO with core shell structure2‑PMOEP.The present invention is by phosphorous homopolymer in nanoparticle surface, preparation condition is gentle, it is simple to operate, more stablize than conventional physical adsorption method, and two kinds of elements of P, Si have cooperative flame retardant effect, on surface, the field such as modification, nanoscale enhancing, halogen-free flameproof and raising wearability is respectively provided with good application prospect.
Description
Technical field
The invention belongs to hybrid multifunctional material field, being related to a kind of has containing for enhancing and flame retardant effect
A kind of phosphorus polymer modification nano-particle and preparation method thereof, and in particular to the SiO after surface modification epoxide group2Nanoparticle
Son, the SiO with enhancing and flame retardant effect is prepared by the controllable phosphorous polymer PMOEP of chemical graft size2- PMOEP receives
Rice corpuscles.
Background technology
It is well known that high polymer material belongs to inflammable, combustible material, fire spread is easily caused, can be discharged in burning
Substantial amounts of heat and smog poison gas aggravate the extent of injury of fire.Therefore, fire-retardant and suppression cigarette processing is carried out to high polymer material to compel
The eyebrows and eyelashes.
At present using the compound system that most fire retardants is phosphonium flame retardant, such as phosphorous-nitrogen compounds, phosphorus-silicon compound
Deng.In general good flame retardation effect, cheap, wide material sources, but hygroscopicity are big for wherein inorganic phosphorus flame retardant, ornamental
Difference；Expensive and though organic phosphorus flame retardant can overcome disadvantage mentioned above, smoke amount is big, using being subject to certain restrictions.
Therefore, attempt inorganic nano-particle and organic phosphorus flame retardant compounding use, imitated using the cooperative flame retardant of two kinds of elements of P, Si
Really, with extensive research and application prospect.Meso-porous titanium dioxide is prepared as disclosed one kind in Chinese patent CN 102766471A
The method of silicon composite nanometer flame retardant, uses silicon source for presoma first, and mesoporous dioxy is made in the presence of structure directing agent
SiClx；Then a certain amount of phosphorus system, phosphorus-nitrogen containing flame retardant are dissolved in solvent and form uniform solution, add above-mentioned meso-porous titanium dioxide
Silicon particle, stirs solvent flashing, that is, obtains mesoporous silicon dioxide nano composite flame-retardant agent.The composite flame-retardant agent good dispersion, tool
There are excellent cooperative flame retardant and suppression cigarette effect, can be widely applied to fire-retardant in multiple material, but the stability of the nano-particle
It is poor；And for example, row surface chemical modification is improved to nano-particle, high molecular polymer is grafted to by nano-particle by chemical bond
Surface, such as in document Polymers for Advanced Technologies, 2013,24:There is researcher will in 732-739
DOPO chemical grafts are in SiO2Added after nanoparticle surface in polypropylene, the heat endurance of PP/IFR composites is improved, combustion
SiO during burning2- DOPO nano-particles can also induce the formation of continuous layer of charcoal, effectively hinder the transport of gas and heat.China
A kind of preparation method of POSS modified Nanos particle, the first dioxy in 100nm or so are disclosed in patent CN 103755898A
The upper RAFT reagents of SiClx particle surface modification, then trigger MAPOSS to carry out RAFT polymerizations, the function of isolated core shell structure
Change nano-particle.A kind of preparation method of DOPO graft modifications sepiolite fibre is disclosed in Chinese patent CN 103980736A,
First by being purified to sepiolite fibre and acidification, and reacted with coupling agent, the DOPO on its surface chemistry is bonded,
A kind of sepiolite fibre of new DOPO surface graft modifications is obtained, can be blended with multiple polymers matrix, give full play to it
Phosphorus silicon fire retardation；But remain in the prior art polymer sizes be difficult to regulate and control, reaction condition requirement it is higher, nanoparticle
The defects such as sub- less stable.
The content of the invention
There is enhancing and the preparation side of the organic/inorganic nano-hybrid materials of anti-flaming function it is an object of the present invention to provide a kind of
Method, in SiO2Nanoparticle surface modified response type epoxide group, while polymerizeing controllable phosphorous poly- of synthesis size by RAFT
Compound, is then grafted on SiO2Surface, prepares the hybrid particle of surface grafting phosphorous polymer, in Halogen
Flame retardant area is with a wide range of applications.
To reach above-mentioned purpose, one of the technical solution adopted by the present invention is：A kind of phosphorous polymer modified Nano particle
Preparation method, comprise the following steps：
1) SiO of surface modification epoxide group2The synthesis of nano-particle：UtilizeMethod hydrolyzing tetraethoxy orthosilane is in temperature
Particle diameter 60nm or so SiO is synthesized with the conditions of2Nano-particle, then adds silane coupler, stirs 6h, then heats to 80
DEG C backflow 2h；Product is centrifuged, cleaning produces the SiO of described surface modification epoxide group2Nano-particle；
2) synthesis of phosphorous polymer：Phosphorous-containing monomers, RAFT reagents and initiator are dissolved in solvent, it is de- through continuous freeze thawing
After gas 3~5 times, in after 60~80 DEG C of polymerizations, 18~24h of reaction under inert gas shielding, reaction is stopped through liquid nitrogen quenching, with
15 times of volume precipitating reagent repeated precipitations 2 times, polymerizeing synthesized polymer degree by reversible addition-fragmentation chain transfer free radical (RAFT) can
The phosphorous polymer of control, it is preferable that the phosphorous polymer is phosphorous homopolymer；The phosphorous-containing monomers, RFAT reagents, initiator
Mol ratio be 80~110: 1: 0.2~0.3；And the degree of polymerization of phosphorous-containing monomers can be controlled by adjusting rate of charge, is adjusted
The whole reaction time controls the conversion ratio of phosphorous-containing monomers；
3) synthesis of phosphorous polymer modified Nano particle：Take step 2) in obtained phosphorous polymer be dissolved in solvent,
Add step 1) in the obtained SiO of surface modification epoxide group2Nano-particle, triethylamine is added under inert gas shielding
Afterwards, in 75 DEG C of 24~30h of stirring reaction, the SiO after surface modification epoxy radicals is passed through2It is anti-with phosphorus hydroxyl in phosphorous polymer
Should, by phosphorous polymer PMOEP chemical grafts in SiO2Surface, centrifuges product, a kind of core shell structure is obtained after cleaning
Phosphorous polymer modified Nano particle.
The step 1) in,Method hydrolyzing tetraethoxy orthosilane synthesizes SiO2Nano-particle is concretely comprised the following steps：
Temperature constant magnetic stirring 2h at 100mL ethanol, 5.5mL ammoniacal liquor (28wt%), 40 DEG C is added in 150mL three-necked flasks, then is quickly added
Enter and be quickly stirred overnight at 5.3mL tetraethyl orthosilicates (TEOS), 40 DEG C, produce described SiO2Nano-particle, its size exists
60nm or so, synthetic route can be found in document：Langmuir 2010,26(18),14806–14813.
Described silane coupler is 3- glycidyloxypropyl trimethoxy silanes, and end is active, can be with
Silica surface is handled, is grafted on by the form of chemical bond on nano-particle.
Described phosphorous-containing monomers are the monomer that can occur RAFT polymerizations, can be selected from phosphoric acid ester monomer base acrylic acid -2-
Hydroxyethyl ester phosphate (MOEP), a kind of reactive phosphorous-containing monomers, containing polymerizable double bond, in the presence of RAFT reagents,
Living control polymerization can be carried out.
Described RFAT reagents are dithiobenzoic acid cumyl ester (CDB).
The initiator is azodiisobutyronitrile (AIBN).
The two of the technical solution adopted by the present invention are：A kind of phosphorous polymer modified Nano particle, its be particle diameter 65~
70nm, and surface grafting has one layer of phosphorous polymer such as PMOEP SiO2Nano-particle.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
(1) present invention uses the SiO of one pot process particle diameter 60nm or so surface grafting epoxide group2Nano-particle, behaviour
Make simple, reaction condition is gentle.
(2) the use of methacrylic acid -2- hydroxyethyl esters phosphate is monomer, under anaerobic, can be polymerize by RAFT,
Synthesize a series of controllable phosphorous polymer of sizes.
(3) present invention combines the method that RAFT polymerize first, one layer of controllable phosphorous polymer of size is grafted on inorganic
SiO2Nanoparticle surface, the size of phosphorous polymer can be adjusted as needed, and prepared by the method adsorbed than conventional physical
Core-shell type functional nanoparticles are more stablized, and by the cooperative flame retardant effect of two kinds of elements of P, Si, can improve inorganic nano-particle
The mechanical performance and fire resistance of son and matrix, expand the application field of nano-particle.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 (a) and (b) are respectively phosphorous polymer PMOEP in embodiment 180's1H NMR and31P NMR nuclear magnetic spectrograms；
Fig. 2 (a) and (b) are respectively SiO in embodiment 32- epoxy group and SiO2-PMOEP100ESEM
(SEM) figure；
Fig. 3 (a) and (b) are respectively SiO in embodiment 32- epoxy group and SiO2-PMOEP100Transmission electron microscope
(TEM) figure.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1：
1) SiO of surface modification epoxide group2Nano-particle SiO2- epoxy group synthesis：
UtilizeMethod hydrolyzing tetraethoxy orthosilane synthesizes SiO2Nano-particle：100mL is added in 150mL three-necked flasks
Ethanol, 5.5mL ammoniacal liquor (28wt%), temperature constant magnetic stirring 2h at 40 DEG C, then rapidly join and quickly stirred at 5.3mL TEOS, 40 DEG C
Mix overnight, produce size 60nm or so SiO2Nano-particle；Then 0.5mL silane coupler 3- glycidyl epoxides are added
6h is stirred under propyl trimethoxy silicane, moderate rate, 80 DEG C of backflow 2h are then heated to；Centrifuge product
(12000rpm), is cleaned for several times with ethanol, obtains the SiO of particle diameter 60nm or so surface modification epoxide group2Nano-particle
(SiO2- epoxy group), it is dispersed in standby in 10ml absolute methanols；
2) phosphorous polymer PMOEP80Synthesis：
By phosphorous-containing monomers methacrylic acid -2- hydroxyethyl esters phosphate (MOEP) 0.91g (4mmol), the sulphur of RAFT reagents two
For benzoic acid cumyl ester (CDB) 13.62mg (0.05mmol) and initiator azodiisobutyronitrile (AIBN) 1.64mg
(0.01mmol) is dissolved in 5ml solvent absolute methanols, through continuous freeze thawing deaerate 3~5 times after, under inert gas argon gas shielded in
After 65 DEG C of polymerizations, reaction 24h, stop reaction through liquid nitrogen quenching, be 75ml precipitating reagent ethanol repeated precipitation 2 times with 15 times of volumes,
Produce product phosphorous polymer PMOEP80；
3) phosphorous polymer modified Nano particle SiO2-PMOEP80Synthesis：
Take step 2) in obtained phosphorous homopolymer PMOEP801g is dissolved in after 4mL solvent absolute methanols, is added to 50mL's
In there-necked flask, add step 1) in obtained 6mL SiO2- epoxy group dispersion liquids, in inert gas N2Protection is lower to be added
After 1mL triethylamines (TEA), in 75 DEG C of moderate-speed mixer reaction 24h, product is centrifuged, with a large amount of absolute methanols to centrifugation product
Cleaning separation is carried out, is repeated 5 times, that is, obtains phosphorous polymer modified Nano particle (SiO2-PMOEP80), its particle diameter be 65~
70nm, and surface grafting has one layer of phosphorous polymer PMOEP80。
Target phosphorous polymer PMOEP has been obtained by polymerizeing in embodiment 180, Fig. 1 (a)1Change in H NMR nuclear magnetic spectrograms
Displacement study δ=4.695 are the methene proton peak being connected with the oxygen of ester group, and chemical shift δ=4.08 are to be connected with hydroxyethyl ester
Methene proton peak, chemical shift δ=0.5-2.0 be methacrylate-based monomer polymerize after diagnostic protons peak；Fig. 1
(b)31Unique unimodal, chemical shift δ=1.889 are shown as in P NMR nuclear magnetic spectrograms, the phosphorous polymer is further demonstrated
PMOEP80Successful synthesis.
Embodiment 2：
1) SiO of surface modification epoxide group2Nano-particle SiO2- epoxy group synthesis：Step in be the same as Example 1
1)；
2) phosphorous polymer PMOEP80Synthesis：Step 2 in be the same as Example 1)；
3) phosphorous polymer modified Nano particle SiO2-PMOEP80Synthesis：
Take step 2) in obtained phosphorous polymer PMOEP801.5g is dissolved in after 4mL solvent absolute methanols, is added to 50mL
There-necked flask in, add step 1) in obtained 6mL SiO2- epoxy group dispersion liquids, in inert gas N2Protection is lower to be added
Enter after 1mL TEA, in 75 DEG C of moderate-speed mixer reaction 30h, centrifuge product, centrifugation product is carried out clearly with a large amount of absolute methanols
Separation is washed, is repeated 5 times, that is, obtains phosphorous polymer modified Nano particle (SiO2-PMOEP80), its particle diameter is 65~70nm, and
Surface grafting has one layer of phosphorous polymer PMOEP80。
Embodiment 3：
1) SiO of surface modification epoxide group2Nano-particle SiO2- epoxy group synthesis：Step in be the same as Example 1
1)；
2) phosphorous polymer PMOEP100Synthesis：
By phosphorous-containing monomers MOEP 1.14g (5mmol), RAFT reagent C DB 13.62mg (0.05mmol) and initiator A IBN
1.64mg (0.01mmol) is dissolved in 6ml solvent absolute methanols, after being deaerated 3~5 times through continuous freeze thawing, is protected in inert gas argon gas
In after 65 DEG C of polymerizations, reaction 24h under shield, stop reaction through liquid nitrogen quenching, be that 90ml precipitating reagent ethanol sinks repeatedly with 15 times of volumes
Form sediment 2 times, produce product phosphorous polymer PMOEP100；
3) phosphorous polymer modified Nano particle SiO2-PMOEP100Synthesis：
Take step 2) in obtained phosphorous polymer PMOEP1001.5g is dissolved in after 4mL solvent absolute methanols, is added to 50mL
There-necked flask in, add step 1) in obtained 6mL SiO2- epoxy group dispersion liquids, in inert gas N2Protection is lower to be added
Enter after 1mL TEA, in 75 DEG C of moderate-speed mixer reaction 30h, centrifuge product, centrifugation product is carried out clearly with a large amount of absolute methanols
Separation is washed, is repeated 5 times, that is, obtains phosphorous polymer modified Nano particle (SiO2-PMOEP100), its particle diameter is 65~70nm, and
Surface grafting has one layer of phosphorous polymer PMOEP100。
Target SiO has been obtained by the graft reaction in embodiment 32- epoxy group and SiO2-PMOEP100, Fig. 2 (a)
Difference SiO (b)2- epoxy group and SiO2-PMOEP100SEM figures, contrast is it can be seen that exposed SiO in (a)2Nanometer
Particle surface is relatively rough and particle between be separated from each other, and nanoparticle surface smoother in (b) after parcel polymer and
If dried particle interconnects；Fig. 3 (a) and (b) are respectively SiO2- epoxy group and SiO2-PMOEP100TEM figure,
Contrasting significantly to find out, surface grafting phosphorous polymer PMOEP100SiO afterwards2Nanoparticle surface has wrapped one layer of 5nm
The polymer of left and right, is formd with Nano-meter SiO_22For core, phosphorous polymer PMOEP100For the nano-core-shell structure of shell, illustrate mesh
Mark the successful preparation of phosphorous polymer modified Nano particle.
Embodiment 4
1) SiO of surface modification epoxide group2Nano-particle SiO2- epoxy group synthesis：Step in be the same as Example 1
1)；
2) phosphorous polymer PMOEP110Synthesis：
By phosphorous-containing monomers MOEP 1.254g (5.5mmol), RAFT reagent C DB 13.62mg (0.05mmol) and initiator
AIBN 2.46mg (0.015mmol) are dissolved in 6ml solvent absolute methanols, after being deaerated 3~5 times through continuous freeze thawing, in inert gas
In after 60 DEG C of polymerizations, reaction 21h under argon gas protection, stop reaction through liquid nitrogen quenching, be 90ml precipitating reagent ethanol with 15 times of volumes
Repeated precipitation 2 times, produces product phosphorous polymer PMOEP110；
3) phosphorous polymer modified Nano particle SiO2-PMOEP110Synthesis：
Take step 2) in obtained phosphorous polymer PMOEP1101.5g is dissolved in after 4mL solvent absolute methanols, is added to 50mL
There-necked flask in, add step 1) in obtained 6mL SiO2- epoxy group dispersion liquids, in inert gas N2Protection is lower to be added
Enter after 1mL TEA, in 75 DEG C of moderate-speed mixer reaction 24h, centrifuge product, centrifugation product is carried out clearly with a large amount of absolute methanols
Separation is washed, is repeated 5 times, that is, obtains phosphorous polymer modified Nano particle (SiO2-PMOEP110), its particle diameter is 65~70nm, and
Surface grafting has one layer of phosphorous polymer PMOEP110。
Embodiment 5
1) SiO of surface modification epoxide group2Nano-particle SiO2- epoxy group synthesis：Step in be the same as Example 1
1)；
2) phosphorous polymer PMOEP100Synthesis：
By phosphorous-containing monomers MOEP 1.14g (5mmol), RAFT reagent C DB 13.62mg (0.05mmol) and initiator A IBN
2.46mg (0.015mmol) is dissolved in 6ml solvent absolute methanols, after being deaerated 3~5 times through continuous freeze thawing, in inert gas argon gas
Under protection in 80 DEG C polymerization, reaction 18h after, through liquid nitrogen quenching stop reaction, with 15 times of volumes be 90ml precipitating reagents ethanol repeatedly
Precipitation 2 times, produces product phosphorous polymer PMOEP100；
3) phosphorous polymer modified Nano particle SiO2-PMOEP100Synthesis：
Take step 2) in obtained phosphorous polymer PMOEP1001.5g is dissolved in after 4mL solvent absolute methanols, is added to 50mL
There-necked flask in, add step 1) in obtained 6mL SiO2- epoxy group dispersion liquids, in inert gas N2Protection is lower to be added
Enter after 1mL TEA, in 75 DEG C of moderate-speed mixer reaction 27h, centrifuge product, centrifugation product is carried out clearly with a large amount of absolute methanols
Separation is washed, is repeated 5 times, that is, obtains phosphorous polymer modified Nano particle (SiO2-PMOEP100), its particle diameter is 65~70nm, and
Surface grafting has one layer of phosphorous polymer PMOEP100。
The present invention combines the method that RAFT polymerize first, in controllable phosphorous of one layer of size of inorganic nano-particle surface grafting
Polymer P MOEP.Due to PMOEP reactivity and good flame-retardance, such a SiO2- PMOEP hybrid material futures will received
The fields such as meter Zeng Qiang, halogen-free flameproof are with a wide range of applications.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (8)
1. a kind of preparation method of phosphorous polymer modified Nano particle, it is characterised in that：Comprise the following steps：
1) SiO of surface modification epoxide group2The synthesis of nano-particle：UtilizeMethod hydrolyzing tetraethoxy orthosilane synthesizes SiO2
Nano-particle, then adds silane coupler, stirs 4~8h, then heats to 70~90 DEG C of 1~3h of backflow；Centrifuge production
Thing, cleaning, produces the SiO of surface modification epoxide group2Nano-particle；
2) synthesis of phosphorous polymer：Phosphorous-containing monomers, RAFT reagents and initiator are dissolved in solvent, through continuous freeze thawing degassing 2
After~6 times, in after 55~85 DEG C of polymerizations, 15~30h of reaction under inert gas shielding, stop reaction through liquid nitrogen quenching, with 12
~18 times of volume precipitating reagent repeated precipitations 1~3 time, produce phosphorous polymer；The phosphorous-containing monomers, RAFT reagents, initiator it
Mol ratio is 70~120: 0.8~1.2: 0.1~0.4；The phosphorous-containing monomers are methacrylic acid -2- hydroxyethyl ester phosphates；
3) synthesis of phosphorous polymer modified Nano particle：Take step 2) in obtained phosphorous polymer be dissolved in solvent, then add
Enter step 1) in the obtained SiO of surface modification epoxide group2Nano-particle, is added after triethylamine under inert gas shielding,
In 70~80 DEG C of 20~35h of stirring reaction, product is centrifuged, is cleaned 3~6 times, that is, obtains phosphorous polymer modified Nano grain
Son.
2. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1, it is characterised in that：Including
Following steps：
1) SiO of surface modification epoxide group2The synthesis of nano-particle：UtilizeMethod hydrolyzing tetraethoxy orthosilane synthesizes SiO2
Nano-particle, then adds silane coupler, stirs 5.5~6.5h, then heats to 79~81 DEG C of 1.5~2.5h of backflow；From
Heart separation product, cleaning produces the SiO of described surface modification epoxide group2Nano-particle；
2) synthesis of phosphorous polymer：Phosphorous-containing monomers, RAFT reagents and initiator are dissolved in solvent, through continuous freeze thawing degassing 3
After~5 times, in after 59~81 DEG C of polymerizations, 17~25h of reaction under inert gas shielding, stop reaction through liquid nitrogen quenching, with 14
~16 times of volume precipitating reagent repeated precipitations 2 times, produce described phosphorous polymer；The phosphorous-containing monomers, RAFT reagents, initiator
Mol ratio be 79~111: 0.9~1.1: 0.18~0.32；
3) synthesis of phosphorous polymer modified Nano particle：Take step 2) in obtained phosphorous polymer be dissolved in solvent, then add
Enter step 1) in the obtained SiO of surface modification epoxide group2Nano-particle, is added after triethylamine under inert gas shielding,
In 74~76 DEG C of 23~31h of stirring reaction, product is centrifuged, is cleaned 5 times, described phosphorous polymer modified Nano grain is produced
Son.
3. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1 or 2, it is characterised in that：
The step 1) in,Method hydrolyzing tetraethoxy orthosilane synthesizes SiO2Nano-particle is concretely comprised the following steps：By ethanol with
28wt% ammoniacal liquor is mixed, and constant temperature stirs 1.5~2.5h at 35~45 DEG C, adds tetraethyl orthosilicate, 35~45 DEG C stirred
At night, produce described SiO2Nano-particle；The ethanol, 28wt% ammoniacal liquor, the volume ratio of tetraethyl orthosilicate are 100:5.5:
5.3。
4. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1 or 2, it is characterised in that：
The step 1) in, SiO2The particle diameter of nano-particle is 55~65nm.
5. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1 or 2, it is characterised in that：
The step 1) in, silane coupler is 3- glycidyloxypropyl trimethoxy silanes.
6. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1 or 2, it is characterised in that：
The step 2) in, RAFT reagents are dithiobenzoic acid cumyl ester.
7. a kind of preparation method of phosphorous polymer modified Nano particle according to claim 1 or 2, it is characterised in that：
The step 2) in, initiator is azodiisobutyronitrile.
8. the phosphorous polymer modified Nano grain prepared by a kind of preparation method according to any one of claim 1 to 7
Son, it is characterised in that：The phosphorous polymer modified Nano particle is 65~70nm of particle diameter, and surface grafting have one layer it is phosphorous poly-
The SiO of compound2Nano-particle.
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