CN108440726A - One kind preparing SiO by aqueous phase reactions2The method for being grafted polymethyl methacrylate hybrid particle - Google Patents
One kind preparing SiO by aqueous phase reactions2The method for being grafted polymethyl methacrylate hybrid particle Download PDFInfo
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- CN108440726A CN108440726A CN201810294339.5A CN201810294339A CN108440726A CN 108440726 A CN108440726 A CN 108440726A CN 201810294339 A CN201810294339 A CN 201810294339A CN 108440726 A CN108440726 A CN 108440726A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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Abstract
It preparing surface grafting the invention discloses a kind of with general radical emulsion polymerization and has the Nano-meter SiO_2 of polymethyl methacrylate2Particle (is denoted as SiO2PMMA) the straightforward procedure of hybrid material, includes the following steps：Surface is fixed with to the Nano-meter SiO_2 of molecule of primary amine layer2Particle (is denoted as SiO2‑NH2), methyl methacrylate (being denoted as MMA) be sufficiently mixed, gentle agitation, that is, form stable Pickering lotions；Using the copper of high oxidation state or cobalt salt as oxidant, 1h 12h are reacted at 80 DEG C and obtain SiO2PMMA hybrid materials.Gained SiO with optimal conditions2The grafting rate of PMMA is suitable with the prior art up to 30%.Reaction process is stablized, phenomena such as without being layered, flocculating, operating procedure of the present invention is simple, the use of raw material is all the cheap commercially available product that is easy to get, without deoxygenation or additional emulsifier, easy to operate, environmental pollution is small, reaction terminates simple rinse and removes unreacted residues object, therefore has wide industrial applications foreground.
Description
Technical field
The invention belongs to prepare organic-inorganic materials field, more particularly to one kind is in water phase with transition gold
Belong to salt oxidation and is fixed on Nano-meter SiO_22The primary amine of particle surface is that free radical initiation methyl methacrylate free radical emulsion is poly-
Close the method for obtaining hybrid particle.
Background technology
The nano inorganic granular materials of surface grafting organic high molecular compound, also referred to as hybrid material are a kind of tools
The matter that has specific characteristics and widely applied composite material, be widely used in optical material, electronic material, biomaterial, medical material,
Structural material etc., and expanding new application field (hybrid inorganic-organic materials are write in Wu Biyao, Zhang Chaocan, chapter text tribute etc.
And its apply Beijing：Chemical Industry Press, 2005.07；Xu Guocai, Zhang Lide write nanocomposite Beijing：Chemical work
Industry publishing house, 2002.03).
The method for preparing organic-inorganic materials at present can be divided into following several：
1. fixing azo or peroxide monolayer in nano grain surface, subsequent thermal induction azo or peroxide decompose, wherein
The limited free radical that particle surface is fixed on by covalent bond causes the graft polymerization of corresponding monomer, to obtain grafting on particle table
Polymer (N Tsubokawa, A Kogure, K Maruyama, Y Sone, M Shimomura, the Polymer Journal in face
1990,22,827–833；N Tsubokawa,H Ishida Polymer Journal 1992,24,809–816).The method
It does not require nothing more than and first passes through multistep reaction and could fix initiator azo or peroxide monolayer, and due to per molecule azo or mistake
Oxygen solution generates two primary group of free radicals, therefore the limited free radical for being only fixed in surface could cause polymerization and generate grafting
Polymer chain, and be conducive to the free radical polymerization in reaction medium and generate free copolymer such as needs to extract repeatedly at the steps
Suddenly it could remove.
2. due to peroxide or the heated easily decomposition of azo compound, place prepares, stores, will all divide successively in preprocessing process
Solution, continuously decreases so as to cause efficiency of initiation.To avoid thermal cracking type initiator from easily decomposing, poor repeatability the shortcomings that, can first exist
Inorganic particle surfaces fix heat-staple amine, mercaptan monolayer, are then aoxidized to it using peroxide cheap and easy to get,
To generate the limited free radical for being fixed on particle surface, generation grafted polymer (pacify by Du Ruikui Xu Chun chrysanthemums after causing polymerization
Rich and powerful high Li Yan Bin Wangrui Xin Shixue army's one kind of spoiling of protecting is in silica particle surface efficient graft polymerization methyl propenoic acid glycidyl
The method Chinese invention patent CN102675564B of ester；Pacify refined high protect of rich and powerful all roc Du Ruikuiliyan and tender utilizes aryl tertiary amine-BPO oxygen
Method Chinese invention patent of the change reduction initiating system realization styrene in silica particle surface efficient graft polymerization
CN102558461B).The advantages of such method, is that prepare amine, thio-alcohol monolayer simpler, and stores and relatively stablize, but by
One free free radical will also be generated to the oxidation of amine or mercaptan in per molecule peroxide, to ultimately form free copolymer
Chain.Such as with the surfaces 1g be fixed with amine, thio-alcohol monolayer SiO2Particle, containing having more than the organic molten of 10g monomers
In liquid, after the free radical polymerization that redox system causes the monomers such as styrene, methacrylate is constituted with peroxide,
Even if monomer conversion is more than 80%, but grafting rate only about 20%, show that most of monomer is all consumed in free free radical and draws
It sends out and forms free copolymer, and non-formation grafted polymer.
3. to improve the grafting efficiency of monomer, it should so that only particle surface just generates limited free radical, it so can be maximum
Amplitude avoids the generation of free copolymer.For example be fixed with high-activity carbon-halogen covalent bond monolayer on surface, then it can be in hypoxemia
Change and surface grafting polymerization object is formed with atom transfer radical polymerization mechanism under the catalysis of state transition metal salt, and without free polymerization
Object generates (M.Husseman, E.E.M.McNamara,M.Mate,D.Mecerreyes,D. G.Benoit,
J.L.Hedrick,P.Mansky,E.Huang,T.P.Russell,C.J.Hawker, Macromolecules 1999,32,
1424).Similarly, stabilized radical adjusting polymerization can then be carried out under thermal induction by fixing NO free radical monolayer on surface
(C.Bartholome,E.Beyou,E.Bourgeat-Lami,P. Chaumont,N.Zydowicz,Macromolecules
2003,36,7946), surface fix mercaptan monolayer cause mercaptan-lactamase activity free radical polymerization (H-S Hwang,
J-H Bae, H-G Kim, K-T Lim European Polymer Journal 2010,46 1654-1659).This Type of Collective
In the process, the free copolymer of generation is negligible, but polymerizing condition is often harsher, higher if you need to deoxygenation repeatedly, reaction temperature
Deng.
4. using the electromagnetic wave of certain wavelength, especially ultraviolet light (UV), the activation of certain organic matters can also be formed and
Only form the limited free radical positioned at material surface.For example two arone, xanthone, 9-Fluorenone etc. can be captured positioned at material surface
Reactive hydrogen atom, generate surface fix carbon radicals, cause free radical polymerization, and itself formed semipinacol base free radical
Almost without initiating power, therefore only form graft polymers, monomer grafting efficiency higher (W-T Yang, B
Macromolecules 1996,29,3308-3310).N, single point of N- diethylaminos dithiocarbonic acid benzyl ester are fixed on surface
Sublayer then can be by the N for the benzyl carbon radicals and low activity that UV light-induced cracking is high activity, and N- diethylaminos two are thio
Formyl Thiyl Radical, the latter's initiating power is poor, thus primarily form graft polymers (B.Boer, H.K.Simon,
M.P.L.Werts,E.W.Vegte,G.Hadziioannou, Macromolecules 2000,33,349).By three chloro second
Acyl-oxygen monolayer is fixed on after particle surface the Mn under UV inductions2(CO)10Oxidable three chloroacetyls oxygen is to be fixed in
The carbon radicals on grain surface cause polymerization, and only form grafted polymer, grafting efficiency higher (the Y Shirai, K of monomer
Shirai,N Tsubokawa Journal of Polymer Science:Part A:Polymer Chemistry,2001,
39,2157–2163).Due to being irradiated UV, this method is relatively suitable for the planar materials such as film, tablet, and to nano particle
Etc. non-planar materials then need each direction that additional measures make graft reaction equably be happened at particle.
5. using the active monolayer in high oxidation transition-metal cation complex compound oxidation material surface often also only
The primary group of free radicals for being fixed on material surface is formed, therefore only forms grafted polymer.Such as with Cu2+It can be incited somebody to action in aqueous solution
It is fixed on SiO2The primary amine on surface is oxidized to free radical, causes the free yl graft polymerization of water-soluble monomer, and without free polymerization
(Chen Xiao wins Zhai Guang groups of one kind of Zhou Yongsheng in Nano-meter SiO_2 for object formation2The method CN102731734B of surface grafting polymerization object).
6. if grafted monomers are immiscible with reaction medium, need that surfactant composition emulsion polymerization systems are added.Than
Such as styrene or methyl methacrylate are stably dispersed in water using cation or anion surfactant, constitute breast
Liquid, and with Ce4+/ nitric acid is that SiO is fixed in oxidation2The molecule of primary amine layer on surface can cause free radical surface grafting polymerization, instead
Cleaning removes surfactant, strong acid oxidant etc. and is fixed with polystyrene or poly- methyl to get to surface repeatedly after answering
The hydridization SiO of methyl acrylate strand2Particle.(M.Peng,Z.J.Liao,H.L.Guo,J. Mater.Sci.2009,44,
6286) major defect of this method is to need to remove emulsion breaker, and oxidant Ce used repeatedly after reaction4+The oxidisability of/nitric acid with
It is acid too strong, water or monomer etc. can be not only oxidized to free radical, initiation polymerization forms free copolymer, but also is easy to operation
The person and stainless steel cauldron of personnel causes to corrode.
7. using be fixed on the molecule of primary amine layer on surface with short of electricity subclass double bond Michael additions can level altitude it is hydrophilic
Property organic molecule is in surface, and these nano-particles can make hydrophobic monomer form Pickering lotions in water.For example,
SiO2The molecule of primary amine layer on surface first forms highly hydrophilic polyethylene glycol point with acrylic acid glycol ester by Michael additions
Sublayer, methyl methacrylate is added in water to form stable emulsion in no applying surface activating agent, by Ce4+/ nitric acid
Oxidized surface peg molecule layer must arrive the modified Nano SiO that surface is fixed with polymethyl methacrylate2Particle.
(H.J.Wang,M.Peng,J.Zheng,P.Li,J.Colloid Interface Sci.2008,326, 151-157).The party
The major defect of method is still to use Ce4+/ nitric acid is oxidant.
It can be seen that at present in Nano-meter SiO_22For surface grafting hydrophobic monomer is to prepare hybrid particle, it is difficult to
Not outer plus emulsifier, without using strong acid/strong oxidizer when polymerisation is carried out in water phase.In order to solve the above problem, this hair
The bright Nano-meter SiO_2 that molecule of primary amine layer is fixed with surface2Particle (is denoted as SiO2-NH2) in water phase by methyl methacrylate
(MMA) dispersion forms stable Pickering lotions.Immediately with mild Cu2+Or Co2+Complex compound aoxidizes fixation in water phase
In Nano-meter SiO_22The amine molecule layer on surface causes free yl graft polymerization, has polymethylacrylic acid to obtain surface grafting
The Nano-meter SiO_2 of methyl esters (PMMA)2Particle.Due to Nano-meter SiO_22Particle can stable emulsion, there is no need to additional emulsifiers；And it uses
Mild oxidizing agent can avoid the corrosion to operating personnel or reaction kettle.
Invention content
Present disclosure is that the Nano-meter SiO_2 of molecule of primary amine layer is fixed with surface2Particle (is denoted as SiO2-NH2) in water
Disperse MMA to form stable Pickering lotions in phase, and with Cu2+Complex compound amino-oxide group is that free radical causes MMA freedom
Nano-meter SiO_2 is fixed in emulsion polymerization, formation2The PMMA chains of particle surface；After reaction by simple cleaning, drying
The Nano-meter SiO_2 of PMMA is fixed with to surface2Hybrid particle.The reaction process is shown in attached drawing 1.
The beneficial effects of the present invention are：The present invention using commercially available cheap and to the common raw material that air moisture content is stablized,
In air atmosphere, water phase free radical polymerization is carried out, not additional emulsifier can be obtained the Nano-meter SiO_2 that surface is fixed with PMMA2It is miscellaneous
Change particle and (is denoted as SiO2-PMMA).Compared with other free radical polymerisation process being reported, the method is simple and efficient, operation
Simply, of less demanding to reaction condition, the reaction time is short, and environmental pollution is small.
Description of the drawings：
Fig. 1 is Cu2+Oxidation nanometer SiO2-NH2Particle causes the emulsion free-radical polymerization of MMA, forms Nano-meter SiO_22- PMMA
The procedure chart of grain；
Specific implementation method
The present invention is elaborated further with reference to specific embodiment, the experiment condition of following embodiment should by regarding
For the materialization to invention content, and it is non-limiting or reduce the scope.
Embodiment 1：
40mL deionized waters, 5g SiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g five be hydrated
Copper sulphate (CuSO4·5H2O), 1h is reacted respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, reaction process is without layering, demulsification etc.
Phenomenon occurs.After reaction, drying is centrifuged under supercentrifuge.Gained SiO is measured with thermogravimetric analysis (TGA)2-PMMA
Grafting rate be 6.72%.
Embodiment 2：
40mL deionized waters, 5g SiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g
CuSO4·5H2O, reacts 2h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is sent out without phenomena such as layering, demulsification
It is raw.After reaction, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 8.64%.
Embodiment 3：
40mL deionized waters, 5gSiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g CuSO4·
5H2Phenomena such as O reacts 4h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is without being layered, being demulsified.Reaction
After, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 23.42%.
Embodiment 4：
40mL deionized waters, 5gSiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g CuSO4·
5H2Phenomena such as O reacts 8h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is without being layered, being demulsified.Reaction
After, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 34.28%.
Embodiment 5：
40mL deionized waters, 5gSiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g CuSO4·
5H2Phenomena such as O reacts 12h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is without being layered, being demulsified.Reaction
After, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 32.32%.
Embodiment 6：
40mL deionized waters, 5gSiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.01g CuSO4·
5H2Phenomena such as O reacts 12h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is without being layered, being demulsified.Reaction
After, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 31.43%.
Embodiment 7：
40mL deionized waters, 5gSiO are sequentially added in 50mL round-bottomed flasks2-NH2, 5g MMA and 0.005g tetra- be hydrated second
Phenomena such as sour Asia cobalt, reacts 12h respectively under 80 DEG C of oil baths of constant temperature and magnetic agitation, and reaction process is without being layered, being demulsified.Instead
After answering, drying is centrifuged under supercentrifuge.Gained SiO2The grafting rate of-PMMA is 11.94%.
Claims (3)
1. the present invention relates to the Nano-meter SiO_2s that a kind of surface is fixed with polymethyl methacrylate chain2Hybrid particle (is denoted as SiO2-
PMMA method), it is characterised in that：
(1) Nano-meter SiO_2 of molecule of primary amine layer is fixed with by surface by stirring without additional emulsifier2Hybrid particle is in water
Methyl methacrylate (MMA) is separated into stable Pickering lotions；
(2) using bivalent cupric ion or cobalt ions as oxidant, oxidation primary amine is that free radical causes MMA surface grafting polymerizations, to
Nano-meter SiO_2 is fixed in formation2The PMMA chains of particle surface；
(3) free radical polymerization of the present invention carries out under air conditions, is not necessarily to deoxygenation；
(4) free radical polymerization of the present invention, reaction temperature are 80 DEG C；
(5) free radical polymerization of the present invention, reaction time are no less than 60min.
2. in the method taken such as claim 1, free copolymer chain is not formed in reaction process.
3. such as the obtained Nano-meter SiO_2 of claim 12The grafting rate of-PMMA hybrid particulates is 6%-35%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929093A (en) * | 2019-04-16 | 2019-06-25 | 江南大学 | A kind of microcapsule-type On The Latent Accelerator For Epoxy Resin and its methods for making and using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731734A (en) * | 2012-04-23 | 2012-10-17 | 常州大学 | Method for grafting polymer on nano-grade SiO2 surface |
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- 2018-03-30 CN CN201810294339.5A patent/CN108440726A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731734A (en) * | 2012-04-23 | 2012-10-17 | 常州大学 | Method for grafting polymer on nano-grade SiO2 surface |
Non-Patent Citations (1)
| Title |
|---|
| THANIDA ARPORNWICHANOP ET AL: "《Enhanced antibacterial activity of NR latex gloves with raspberry-like PMMA-N,N,N-trimethyl chitosan particles》", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929093A (en) * | 2019-04-16 | 2019-06-25 | 江南大学 | A kind of microcapsule-type On The Latent Accelerator For Epoxy Resin and its methods for making and using same |
| CN109929093B (en) * | 2019-04-16 | 2021-04-27 | 江南大学 | Microcapsule type epoxy resin latent curing accelerator and preparation and application methods thereof |
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Application publication date: 20180824 |