CN104891512A - Phosphorus-containing polymer modified nano-particles and preparation method thereof - Google Patents
Phosphorus-containing polymer modified nano-particles and preparation method thereof Download PDFInfo
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- CN104891512A CN104891512A CN201510306901.8A CN201510306901A CN104891512A CN 104891512 A CN104891512 A CN 104891512A CN 201510306901 A CN201510306901 A CN 201510306901A CN 104891512 A CN104891512 A CN 104891512A
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Abstract
The invention discloses phosphorus-containing polymer modified nano-particles and a preparation method thereof. The preparation method comprises the following steps: obtaining SiO2 nano-particles with epoxy groups modified on surfaces by using SiO2 particles prepared by a silane coupling agent treatment Stober method; synthesizing a phosphorus-containing polymer with a controllable polymerization degree by using a phosphorus-containing monomer by virtue of RAFT polymerization; and enabling the SiO2 nano-particles with the epoxy groups modified on the surfaces to react with phosphorus hydroxyl in the phosphorus-containing polymer, and grafting the phosphorus-containing polymer to the surfaces of the SiO2 nano-particles to obtain the phosphorus-containing polymer modified nano-particles SiO2-PMOEP with a core-shell structure. According to the preparation method disclosed by the invention, a phosphorus-containing homopolymer is grafted to the surfaces of the nano-particles, preparation conditions are mild, the operation is simple, and the preparation method is more stable compared with a conventional physical adsorption method; and the two elements of P and Si have a synergistic flame-retardant effect, so that the preparation method has very good application prospects in the fields of surface modification, nano scale enhancement, halogen-free flame retardance and wear resistance improvement.
Description
Technical field
The invention belongs to hybrid multifunctional material field, relate to a kind of phosphorous polymer modified Nano particle and preparation method thereof with enhancing and flame retardant effect, be specifically related to the SiO after a kind of finishing epoxide group
2nanoparticle, has the SiO of enhancing and flame retardant effect by the phosphorous polymer PMOEP preparation that chemical graft size is controlled
2-PMOEP nanoparticle.
Background technology
As everyone knows, macromolecular material belongs to inflammable, combustible matl, easily causes fire spread, can discharge the hazard rating of a large amount of heat and smog poison gas aggravation fire when burning.Therefore, to macromolecular material carry out fire-retardant and press down cigarette process extremely urgent.
The compound system that the maximum fire retardant of current use is phosphonium flame retardant, as phosphorous-nitrogen compounds, phosphorus-silicon compound etc.Wherein inorganic phosphorus flame retardant in general good flame retardation effect, low price, wide material sources, but water absorbability is large, ornamental difference; And though organic phosphorus flame retardant can overcome above shortcoming, price is more expensive, and the amount of being fuming is large, and application is subject to certain restrictions.Therefore, attempt, by inorganic nano-particle and the composite use of organic phosphorus flame retardant, utilizing the cooperative flame retardant effect of P, Si two kinds of elements, there is investigation and application prospect widely.As disclosed a kind of method preparing mesoporous silicon dioxide nano composite flame-retardant agent in Chinese patent CN 102766471A, first silicon source is adopted to be presoma, obtained mesoporous silicon oxide under the effect of structure directing agent; Then a certain amount of phosphorus system, phosphorus-nitrogen containing flame retardant are dissolved in solvent and form uniform solution, add above-mentioned mesoporous silicon oxide particle, stir solvent flashing, namely obtain mesoporous silicon dioxide nano composite flame-retardant agent.This composite flame-retardant agent good dispersity, has excellent cooperative flame retardant and presses down cigarette effect, can be widely used in multiple material fire-retardant, but the less stable of this nanoparticle; And for example, row surface chemical modification is improved to nanoparticle, by chemical bond, high molecular polymer is grafted to nanoparticle surface, as at document Polymers for Advanced Technologies, investigator is had by DOPO chemical graft at SiO in 2013,24:732 – 739
2add after nanoparticle surface in polypropylene, the thermostability of PP/IFR matrix material improves, SiO in combustion processes
2-DOPO nanoparticle can also bring out the formation of continuous layer of charcoal, effectively hinders the transport of gas and heat.A kind of preparation method of POSS modified Nano particle is disclosed in Chinese patent CN 103755898A, first RAFT reagent is modified in the silica particle surface of about 100nm, then cause MAPOSS and carry out RAFT polymerization, be separated the functional nanoparticle obtaining nucleocapsid structure.A kind of preparation method of DOPO graft modification sepiolite fibre is disclosed in Chinese patent CN 103980736A, first by carrying out purifying and acidification to sepiolite fibre, and react with coupling agent, DOPO on its surface chemistry keyed jointing, obtain a kind of sepiolite fibre of novel DOPO surface graft modification, can be blended with multiple polymers matrix, give full play to its phosphorus silicon fire retardation; But still also exist in prior art that polymer sizes is difficult to regulation and control, reaction conditions requirement is higher, the defects such as nanoparticle less stable.
Summary of the invention
The object of the invention is to provide a kind of preparation method with the organic/inorganic nano-hybrid materials of enhancing and anti-flaming function, at SiO
2nanoparticle surface modified response type epoxide group, simultaneously by the phosphorous polymer that RAFT polymerization synthesis size is controlled, is then grafted on SiO
2surface, prepares the hybrid particle of surface grafting phosphorous polymer, is with a wide range of applications in halogen-free flameproof field.
For achieving the above object, one of the technical solution used in the present invention is: a kind of preparation method of phosphorous polymer modified Nano particle, comprises the following steps:
1) SiO of finishing epoxide group
2the synthesis of nanoparticle: utilize
method hydrolyzing tetraethoxy orthosilane synthesizes the SiO of particle diameter about 60nm in a mild condition
2nanoparticle, then adds silane coupling agent, stirs 6h, is then warming up to 80 DEG C of backflow 2h; Centrifugation product, cleaning, obtains the SiO of described finishing epoxide group
2nanoparticle;
2) synthesis of phosphorous polymer: phosphorous-containing monomers, RAFT reagent and initiator are dissolved in solvent, after degassed 3 ~ 5 times of continuous freeze thawing, in 60 ~ 80 DEG C of polymerizations under protection of inert gas, after reaction 18 ~ 24h, through liquid nitrogen quenching stopped reaction, with 15 times of volume precipitation agent repeated precipitation 2 times, be polymerized the controlled phosphorous polymer of synthesized polymer degree by reversible addition-fragmentation chain transfer free radical (RAFT), preferably, described phosphorous polymer is phosphorous homopolymer; The mol ratio of described phosphorous-containing monomers, RFAT reagent, initiator is 80 ~ 110: 1: 0.2 ~ 0.3; And the polymerization degree of phosphorous-containing monomers can be controlled by adjustment feed ratio, adjust the transformation efficiency that the reaction times controls phosphorous-containing monomers;
3) synthesis of phosphorous polymer modified Nano particle: get step 2) in the phosphorous polymer that obtains be dissolved in solvent, then add step 1) in the SiO of finishing epoxide group that obtains
2nanoparticle, add triethylamine under protection of inert gas after, in 75 DEG C of stirring reaction 24 ~ 30h, by the SiO after finishing epoxy group(ing)
2with the phosphorus hydroxyl reaction in phosphorous polymer, by phosphorous polymer PMOEP chemical graft at SiO
2surface, centrifugation product, obtains a kind of phosphorous polymer modified Nano particle of nucleocapsid structure after cleaning.
Described step 1) in,
method hydrolyzing tetraethoxy orthosilane synthesis SiO
2the concrete steps of nanoparticle are: in 150mL there-necked flask, add 100mL ethanol, 5.5mL ammoniacal liquor (28wt%), temperature constant magnetic stirring 2h at 40 DEG C, add 5.3mL tetraethoxy (TEOS) more fast, at 40 DEG C, rapid stirring spends the night, and obtains described SiO
2nanoparticle, its size is at about 60nm, and synthetic route can see document: Langmuir 2010,26 (18), 14806 – 14813.
Described silane coupling agent is 3-glycidyloxypropyl Trimethoxy silane, and end has activity, can process silica sphere, is grafted on nanoparticle by the form of chemical bond.
Described phosphorous-containing monomers is the monomer that RAFT polymerization can occur, can be selected from phosphoric acid ester monomer base 2-hydroxyethyl acrylate phosphoric acid ester (MOEP), a kind of reactive phosphorous-containing monomers, containing polymerisable double bond, under the effect of RAFT reagent, living control polymerization can be carried out.
Described RFAT reagent is dithiobenzoic acid cumyl ester (CDB).
Described initiator is Diisopropyl azodicarboxylate (AIBN).
Two of the technical solution used in the present invention is: a kind of phosphorous polymer modified Nano particle, it is particle diameter 65 ~ 70nm, and surface grafting has the SiO of one deck phosphorous polymer such as PMOEP
2nanoparticle.
Because technique scheme is used, the present invention compared with prior art has following advantages:
(1) the present invention adopts the SiO of one pot process particle diameter about 60nm surface grafting epoxide group
2nanoparticle, simple to operate, reaction conditions is gentle.
(2) use methacrylic acid-2-hydroxyethyl ester phosphoric acid ester to be monomer, under anaerobic, by RAFT polymerization, synthesize the phosphorous polymer that a series of size is controlled.
(3) the present invention is first in conjunction with the method for RAFT polymerization, and phosphorous polymer controlled for one deck size is grafted on inorganic SiO
2nanoparticle surface, the size of phosphorous polymer can be regulated as required, and it is more stable to prepare core-shell type functional nanoparticles than the method for conventional physical absorption, by the cooperative flame retardant effect of P, Si two kinds of elements, mechanical property and the flame retardant properties of inorganic nano-particle and matrix can be improved, expand the Application Areas of nanoparticle.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 (a) and (b) are respectively phosphorous polymer PMOEP in embodiment 1
80's
1h NMR and
31p NMR nuclear magnetic spectrogram;
Fig. 2 (a) and (b) are respectively SiO in embodiment 3
2-epoxy group and SiO
2-PMOEP
100scanning electron microscope (SEM) figure;
Fig. 3 (a) and (b) are respectively SiO in embodiment 3
2-epoxy group and SiO
2-PMOEP
100transmission electron microscope (TEM) figure.
Embodiment
Content of the present invention is illustrated below by embodiment:
Embodiment 1:
1) SiO of finishing epoxide group
2nanoparticle SiO
2the synthesis of-epoxy group:
Utilize
method hydrolyzing tetraethoxy orthosilane synthesis SiO
2nanoparticle: add 100mL ethanol, 5.5mL ammoniacal liquor (28wt%) in 150mL there-necked flask, temperature constant magnetic stirring 2h at 40 DEG C, then add 5.3mL TEOS fast, at 40 DEG C, rapid stirring spends the night, and obtains the SiO of about size 60nm
2nanoparticle; Then add 0.5mL silane coupling agent 3-glycidyloxypropyl Trimethoxy silane, under moderate rate, stir 6h, be then warming up to 80 DEG C of backflow 2h; Centrifugation product (12000rpm), with ethanol purge several, obtains the SiO of the finishing epoxide group of particle diameter about 60nm
2nanoparticle (SiO
2-epoxy group), be dispersed in 10ml anhydrous methanol for subsequent use;
2) phosphorous polymer PMOEP
80synthesis:
By phosphorous-containing monomers methacrylic acid-2-hydroxyethyl ester phosphoric acid ester (MOEP) 0.91g (4mmol); RAFT reagent dithiobenzoic acid cumyl ester (CDB) 13.62mg (0.05mmol) and initiator Diisopropyl azodicarboxylate (AIBN) 1.64mg (0.01mmol) are dissolved in 5ml solvent anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing; in 65 DEG C of polymerizations under rare gas element argon shield; after reaction 24h; through liquid nitrogen quenching stopped reaction; with 15 times of volumes and 75ml precipitation agent ethanol repeated precipitation 2 times, obtain product phosphorous polymer PMOEP
80;
3) phosphorous polymer modified Nano particle SiO
2-PMOEP
80synthesis:
Get step 2) in the phosphorous homopolymer PMOEP that obtains
801g is added in the there-necked flask of 50mL, then adds step 1 after being dissolved in 4mL solvent anhydrous methanol) in the 6mL SiO that obtains
2-epoxy group dispersion liquid, at rare gas element N
2after adding 1mL triethylamine (TEA) under protection, in 75 DEG C of moderate-speed mixer reaction 24h, centrifugation product, carries out cleaning with a large amount of anhydrous methanol to centrifugal product and is separated, repeat 5 times, namely obtain phosphorous polymer modified Nano particle (SiO
2-PMOEP
80), its particle diameter is 65 ~ 70nm, and surface grafting has one deck phosphorous polymer PMOEP
80.
Target phosphorous polymer PMOEP is obtained by polymerization in embodiment 1
80, Fig. 1 (a)
1in H NMR nuclear magnetic spectrogram, chemical shift δ=4.695 are the methene proton peak be connected with the oxygen of ester group, chemical shift δ=4.08 are the methene proton peak be connected with hydroxyethyl ester, and chemical shift δ=0.5-2.0 is the diagnostic protons peak after methacrylate-based monomer polymerization; Fig. 1 (b)
31be shown as unique unimodal in P NMR nuclear magnetic spectrogram, chemical shift δ=1.889, further demonstrate this phosphorous polymer PMOEP
80successful synthesis.
Embodiment 2:
1) SiO of finishing epoxide group
2nanoparticle SiO
2the synthesis of-epoxy group: with step 1 in embodiment 1);
2) phosphorous polymer PMOEP
80synthesis: with step 2 in embodiment 1);
3) phosphorous polymer modified Nano particle SiO
2-PMOEP
80synthesis:
Get step 2) in the phosphorous polymer PMOEP that obtains
801.5g is added in the there-necked flask of 50mL, then adds step 1 after being dissolved in 4mL solvent anhydrous methanol) in the 6mL SiO that obtains
2-epoxy group dispersion liquid, at rare gas element N
2after adding 1mL TEA under protection, in 75 DEG C of moderate-speed mixer reaction 30h, centrifugation product, carries out cleaning with a large amount of anhydrous methanol to centrifugal product and is separated, repeat 5 times, namely obtain phosphorous polymer modified Nano particle (SiO
2-PMOEP
80), its particle diameter is 65 ~ 70nm, and surface grafting has one deck phosphorous polymer PMOEP
80.
Embodiment 3:
1) SiO of finishing epoxide group
2nanoparticle SiO
2the synthesis of-epoxy group: with step 1 in embodiment 1);
2) phosphorous polymer PMOEP
100synthesis:
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 anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing; in 65 DEG C of polymerizations under rare gas element argon shield; after reaction 24h; through liquid nitrogen quenching stopped reaction, with 15 times of volumes and 90ml precipitation agent ethanol repeated precipitation 2 times, obtain product phosphorous polymer PMOEP
100;
3) phosphorous polymer modified Nano particle SiO
2-PMOEP
100synthesis:
Get step 2) in the phosphorous polymer PMOEP that obtains
1001.5g is added in the there-necked flask of 50mL, then adds step 1 after being dissolved in 4mL solvent anhydrous methanol) in the 6mL SiO that obtains
2-epoxy group dispersion liquid, at rare gas element N
2after adding 1mL TEA under protection, in 75 DEG C of moderate-speed mixer reaction 30h, centrifugation product, carries out cleaning with a large amount of anhydrous methanol to centrifugal product and is separated, repeat 5 times, namely obtain phosphorous polymer modified Nano particle (SiO
2-PMOEP
100), its particle diameter is 65 ~ 70nm, and surface grafting has one deck phosphorous polymer PMOEP
100.
Target SiO is obtained by the graft reaction in embodiment 3
2-epoxy group and SiO
2-PMOEP
100, Fig. 2 (a) and (b) SiO respectively
2-epoxy group and SiO
2-PMOEP
100sEM figure, contrast can find out SiO exposed in (a)
2nanoparticle surface is more coarse and be separated from each other between particle, and nanoparticle surface smoother in (b) after parcel polymkeric substance and some particles interconnect; Fig. 3 (a) and (b) are respectively SiO
2-epoxy group and SiO
2-PMOEP
100tEM figure, contrast can significantly be found out, surface grafting phosphorous polymer PMOEP
100after SiO
2nanoparticle surface has wrapped the polymkeric substance of one deck about 5nm, defines with Nano-meter SiO_2
2for core, phosphorous polymer PMOEP
100for the nano-core-shell structure of shell, the successful preparation of target phosphorous polymer modified Nano particle is described.
Embodiment 4
1) SiO of finishing epoxide group
2nanoparticle SiO
2the synthesis of-epoxy group: with step 1 in embodiment 1);
2) phosphorous polymer PMOEP
110synthesis:
By phosphorous-containing monomers MOEP 1.254g (5.5mmol); RAFT reagent C DB 13.62mg (0.05mmol) and initiator A IBN 2.46mg (0.015mmol) is dissolved in 6ml solvent anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing; in 60 DEG C of polymerizations under rare gas element argon shield; after reaction 21h; through liquid nitrogen quenching stopped reaction, with 15 times of volumes and 90ml precipitation agent ethanol repeated precipitation 2 times, obtain product phosphorous polymer PMOEP
110;
3) phosphorous polymer modified Nano particle SiO
2-PMOEP
110synthesis:
Get step 2) in the phosphorous polymer PMOEP that obtains
1101.5g is added in the there-necked flask of 50mL, then adds step 1 after being dissolved in 4mL solvent anhydrous methanol) in the 6mL SiO that obtains
2-epoxy group dispersion liquid, at rare gas element N
2after adding 1mL TEA under protection, in 75 DEG C of moderate-speed mixer reaction 24h, centrifugation product, carries out cleaning with a large amount of anhydrous methanol to centrifugal product and is separated, repeat 5 times, namely obtain phosphorous polymer modified Nano particle (SiO
2-PMOEP
110), its particle diameter is 65 ~ 70nm, and surface grafting has one deck phosphorous polymer PMOEP
110.
Embodiment 5
1) SiO of finishing epoxide group
2nanoparticle SiO
2the synthesis of-epoxy group: with step 1 in embodiment 1);
2) phosphorous polymer PMOEP
100synthesis:
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 anhydrous methanol; after degassed 3 ~ 5 times of continuous freeze thawing; in 80 DEG C of polymerizations under rare gas element argon shield; after reaction 18h; through liquid nitrogen quenching stopped reaction, with 15 times of volumes and 90ml precipitation agent ethanol repeated precipitation 2 times, obtain product phosphorous polymer PMOEP
100;
3) phosphorous polymer modified Nano particle SiO
2-PMOEP
100synthesis:
Get step 2) in the phosphorous polymer PMOEP that obtains
1001.5g is added in the there-necked flask of 50mL, then adds step 1 after being dissolved in 4mL solvent anhydrous methanol) in the 6mL SiO that obtains
2-epoxy group dispersion liquid, at rare gas element N
2after adding 1mL TEA under protection, in 75 DEG C of moderate-speed mixer reaction 27h, centrifugation product, carries out cleaning with a large amount of anhydrous methanol to centrifugal product and is separated, repeat 5 times, namely obtain phosphorous polymer modified Nano particle (SiO
2-PMOEP
100), its particle diameter is 65 ~ 70nm, and surface grafting has one deck phosphorous polymer PMOEP
100.
The present invention first in conjunction with RAFT polymerization method, at the phosphorous polymer PMOEP that inorganic nano-particle surface grafting one deck size is controlled.Due to reactive behavior and the good flame-retardance of PMOEP, this kind of SiO
2the fields such as-PMOEP hybrid material will strengthen in nanometer future, halogen-free flameproof are with a wide range of applications.
The above, be only present pre-ferred embodiments, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (10)
1. a preparation method for phosphorous polymer modified Nano particle, is characterized in that: comprise the following steps:
1) SiO of finishing epoxide group
2the synthesis of nanoparticle: utilize
method hydrolyzing tetraethoxy orthosilane synthesis SiO
2nanoparticle, then adds silane coupling agent, stirs 4 ~ 8h, is then warming up to 70 ~ 90 DEG C of backflow 1 ~ 3h; Centrifugation product, cleaning, obtains the SiO of finishing epoxide group
2nanoparticle;
2) synthesis of phosphorous polymer: phosphorous-containing monomers, RFAT reagent and initiator are dissolved in solvent, after degassed 2 ~ 6 times of continuous freeze thawing, in 55 ~ 85 DEG C of polymerizations under protection of inert gas, after reaction 15 ~ 30h, through liquid nitrogen quenching stopped reaction, with 12 ~ 18 times of volume precipitation agent repeated precipitation 1 ~ 3 time, obtain phosphorous polymer; The mol ratio of described phosphorous-containing monomers, RFAT reagent, initiator is 70 ~ 120: 0.8 ~ 1.2: 0.1 ~ 0.4;
3) synthesis of phosphorous polymer modified Nano particle: get step 2) in the phosphorous polymer that obtains be dissolved in solvent, then add step 1) in the SiO of finishing epoxide group that obtains
2nanoparticle, add triethylamine under protection of inert gas after, in 70 ~ 80 DEG C of stirring reaction 20 ~ 35h, centrifugation product, cleans 3 ~ 6 times, namely obtains phosphorous polymer modified Nano particle.
2. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1, is characterized in that: comprise the following steps:
1) SiO of finishing epoxide group
2the synthesis of nanoparticle: utilize
method hydrolyzing tetraethoxy orthosilane synthesis SiO
2nanoparticle, then adds silane coupling agent, stirs 5.5 ~ 6.5h, is then warming up to 79 ~ 81 DEG C of backflow 1.5 ~ 2.5h; Centrifugation product, cleaning, obtains the SiO of described finishing epoxide group
2nanoparticle;
2) synthesis of phosphorous polymer: phosphorous-containing monomers, RFAT reagent and initiator are dissolved in solvent, after degassed 3 ~ 5 times of continuous freeze thawing, in 59 ~ 81 DEG C of polymerizations under protection of inert gas, after reaction 17 ~ 25h, through liquid nitrogen quenching stopped reaction, with 14 ~ 16 times of volume precipitation agent repeated precipitation 2 times, obtain described phosphorous polymer; The mol ratio of described phosphorous-containing monomers, RFAT reagent, initiator is 79 ~ 111: 0.9 ~ 1.1: 0.18 ~ 0.32;
3) synthesis of phosphorous polymer modified Nano particle: get step 2) in the phosphorous polymer that obtains be dissolved in solvent, then add step 1) in the SiO of finishing epoxide group that obtains
2nanoparticle, add triethylamine under protection of inert gas after, in 74 ~ 76 DEG C of stirring reaction 23 ~ 31h, centrifugation product, cleans 5 times, obtains described phosphorous polymer modified Nano particle.
3. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 1) in,
method hydrolyzing tetraethoxy orthosilane synthesis SiO
2the concrete steps of nanoparticle are: mixed with the ammoniacal liquor of 28wt% by ethanol, and at 35 ~ 45 DEG C, constant temperature stirs 1.5 ~ 2.5h, then adds tetraethoxy, and 35 ~ 45 DEG C of stirrings are spent the night, and obtain described SiO
2nanoparticle; The ammoniacal liquor of described ethanol, 28wt%, the volume ratio of tetraethoxy are 100:5.5:5.3.
4. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 1) in, SiO
2the particle diameter of nanoparticle is 55 ~ 65nm.
5. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 1) in, silane coupling agent is 3-glycidyloxypropyl Trimethoxy silane.
6. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 2) in, phosphorous-containing monomers is the monomer that RAFT polymerization can occur.
7. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 or 2 or 6, is characterized in that: described step 2) in, phosphorous-containing monomers is methacrylic acid-2-hydroxyethyl ester phosphoric acid ester.
8. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 2) in, RFAT reagent is dithiobenzoic acid cumyl ester.
9. the preparation method of a kind of phosphorous polymer modified Nano particle according to claim 1 and 2, is characterized in that: described step 2) in, initiator is Diisopropyl azodicarboxylate.
10. a phosphorous polymer modified Nano particle, is characterized in that: described phosphorous polymer modified Nano particle is particle diameter 65 ~ 70nm, and surface grafting has the SiO of one deck phosphorous polymer
2nanoparticle.
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| CN107601452A (en) * | 2017-10-13 | 2018-01-19 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| CN110818949A (en) * | 2019-11-30 | 2020-02-21 | 苏州和塑美科技有限公司 | Hydrolysis-resistant efficient flame retardant and preparation method thereof |
| WO2020142857A1 (en) * | 2019-01-08 | 2020-07-16 | Comercial E Industrial Chile Chemicals Spa | Fire-resistant composition that provides active and passive protection against fires |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832413A (en) * | 2017-03-13 | 2017-06-13 | 厦门大学 | A kind of phosphorus-nitrogen containing polymer modification Nano particles of silicon dioxide and its preparation method and application |
| WO2018166440A1 (en) * | 2017-03-13 | 2018-09-20 | 厦门大学 | Phosphorus-nitrogen-containing polymer-modified silica nanoparticles, preparation method therefor and use thereof |
| CN106832413B (en) * | 2017-03-13 | 2019-03-29 | 厦门大学 | A kind of phosphorus-nitrogen containing polymer modification Nano particles of silicon dioxide and its preparation method and application |
| US11046832B2 (en) * | 2017-03-13 | 2021-06-29 | Xiamen University | Method of manufacturing modified silicon dioxide nanoparticles |
| CN107601452A (en) * | 2017-10-13 | 2018-01-19 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| CN107601452B (en) * | 2017-10-13 | 2019-07-23 | 厦门大学 | A kind of preparation method of phosphorous porous nano carbon ball |
| WO2020142857A1 (en) * | 2019-01-08 | 2020-07-16 | Comercial E Industrial Chile Chemicals Spa | Fire-resistant composition that provides active and passive protection against fires |
| CN110818949A (en) * | 2019-11-30 | 2020-02-21 | 苏州和塑美科技有限公司 | Hydrolysis-resistant efficient flame retardant and preparation method thereof |
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