CN1660917A - Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 - Google Patents

Modification method for graft polymerization of acrylic ester of silicane coupled to Nano SiO2 Download PDF

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CN1660917A
CN1660917A CN 200510045707 CN200510045707A CN1660917A CN 1660917 A CN1660917 A CN 1660917A CN 200510045707 CN200510045707 CN 200510045707 CN 200510045707 A CN200510045707 A CN 200510045707A CN 1660917 A CN1660917 A CN 1660917A
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coupled
silicane
sio
graft polymerization
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CN1323092C (en
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张蕾
张丹凤
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Liaoning University
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Abstract

A process for modifying the graft polymer of acrylate by silane coupled nano-SiO2 includes such steps as dispersing the silane coupled nano-SiO2 in toluene solution, stirring, adding azodiisobutanenitrile as trigger, reaction, cooling, filtering, extracting from filtered cake in toluene solution, and baking. It can be used for oily paint to improve its resistance to UV radiation, stability, thixotropy, adhesion, etc.

Description

Silicane coupled to Nano SiO 2Modification method for graft polymerization of acrylic ester
Technical field: the present invention relates to a kind of method of modifying of silicon compound, relate to a kind of nanometer SiO specifically 2Method of modifying.
Background technology: in recent years along with the continuous development of nanotechnology, nano inorganic particles is added to the nano composite material that obtains in some materials to be widely used with its particular performances, but nano particle diameter is little, specific surface energy is big, cohesive force is strong, easily reunite and reach and problems such as the organic matrix bonding force is lower, greatly the restriction of degree the application of inorganic nano-particle, therefore, the dispersion of research nano-powder in different liquid phase mediums, and the key that just becomes this bottleneck problem of solution by surface modification raising nano-powder and organic matrix bonding force.
Tsubokawa N in following document, Fujiki K, Sone Y Macromol Sci.Chem.[J] 1991, A28 (8): 715-718; Yukio Shirai, Kawatsura, Norio Tsubokawa.Progress inorganic coatings[J], 1999,36:217-224; Norio Tsubokawa, Shinji Hayashi, JunichiNishimura.Progress in organic coatings[J], 2002,44:69-74; Wei Wu, JianfengChen, Lei shao, et al.Journal of university of science and technology Beijing[J], 2002 (9), 6:426-430; Minzhi Rong, Mingqiu Zhang, Yongxiang Zheng, et al.Polymer [J], 2001.42:167-183; K Fujiki, N Tsubokawa, YSone, Polymer[J], 1990,22:661-670; N Tsubokawa, A Kogure, K Maruyama et.al.Polymer[J], 1990,22:827-833; Liu Peng, Tian Jun, Liu Weimin etc., chemistry circular [J], 2003,2:73-77; Be reported in carbon black, nano-TiO 2, nanometer SiO 2Monomeric surface grafting polymerizations such as methyl methacrylate, vinylbenzene, vinyl cyanide vinylcarbazole, 4-vinylpyridine vinylformic acid, vinyl acetate and methyl vinyl ketone are caused on the surface.Above-mentioned graft modification is improving the dispersiveness of inorganic nano in organic phase in varying degrees, but dispersed not ideal enough, and dispersion temperature requires below 32 ℃, so graftomer is restricted on using, and the present invention is at modified Nano SiO 2Carrying out graft polymerization of acrylic ester does not appear in the newspapers.
Summary of the invention: at nanometer SiO 2The low problem of dispersion stabilization in organic phase the invention provides a kind of raising nanometer SiO 2The modification method for graft polymerization of dispersion stabilization in organic phase; For reaching the concrete technical scheme that goal of the invention the present invention adopts: with a certain amount of silicane coupled to Nano SiO 2Be scattered in the toluene solution, stir, add the initiator Diisopropyl azodicarboxylate, logical N 2Protection is warming up to 70 ℃, drips the acrylate of removing stopper in advance, and temperature of reaction is controlled at 80～90 ℃, reacts 2.5～3.5 hours, after reaction finishes, and cooling, the toluene extracting of suction filtration, filter cake is then 95～105 ℃ of oven dry.
Silicane coupled to Nano SiO of the present invention 2Be with To nanometer SiO 2Carry out modification, its structure is:
Described acrylate is a butyl methacrylate.
Silicane coupled to Nano SiO of the present invention 2Modification method for graft polymerization of acrylic ester is based on utilization through silane coupler modified nanometer SiO 2On unsaturated group C=C and acrylate carry out graft polymerization reaction, its main process is:
Be used for graft polymerization modified silane coupled to Nano SiO 2Mainly be to nanometer SiO by silane coupling agent 2Carry out modification, can be used for nanometer SiO 2The silane coupling agent of modification mainly contains commodity coupling agent A-151, and its chemical structure is CH 2=CH-Si (OCH 3) 3, coupling agent A-171 chemical structure is CH 2=CH 2-Si (OCH 2CH 3) 3, coupling agent JH-70 chemical structure is
Figure A20051004570700044
Through above-mentioned coupling agent modified nanometer SiO 2Its lipophilic degree is different with water-intake rate, and the present invention selects the nanometer SiO of coupling agent JH-70 modification for use 2Promptly
Figure A20051004570700051
Silicane coupled to Nano SiO of the present invention 2: acrylate: solvent: Diisopropyl azodicarboxylate=1: 8～10: 8～10: 0.2～0.25 (mass parts).
The acrylate monomer that is used for graft polymerization can be methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate etc., what the present invention selected for use is butyl methacrylate, its graft polymerization condition, with reference to esters of acrylic acid polymerization condition, mainly select the suitable monomer amount, quantity of solvent, initiator amount; Temperature of reaction is reacted since 70 ℃ by common esters of acrylic acid polymerization, reaction is thermopositive reaction, for preventing bumping and esters of acrylic acid autohemagglutination, temperature of reaction should be controlled at below 90 ℃, and reaction later stage thermal discharge is little, carry out to keep temperature of reaction fully for making reaction, up to reacting completely, lower the temperature, inclining reaction product, through suction filtration, obtain graft polymerization of acrylic ester modified silane coupled to Nano SiO after the extracting 2, hereinafter to be referred as graft modification nanometer SiO 2, its percentage of grafting can be calculated as follows:
And the inventor's theoretical according to the esters of acrylic acid graft polymerization reaction test, the influence factor of this graft polymerization mainly contains: 1. acrylate monomer amount: according to silicane coupled to Nano SiO 2Mass parts adds 8～10: 1 part of monomer for suitable, and amount of monomer is lower than 8 parts, and percentage of grafting is on the low side, is higher than 10 parts of percentage of grafting and does not improve, and increases monomer consumption, increases the aftertreatment time; 2. initiator amount: initiator is relevant with monomer acrylate consumption, when initiator concentration is crossed when low, initiator molecule is among monomer or solvent surround, after decomposition of initiator becomes elementary free radical, must diffuse out the polymerization of encirclement ability trigger monomer, as untimely diffusing out side reaction formation stable molecule just may take place, consume initiator, cause percentage of grafting lower, when initiator concentration is too high, can aggravate homopolymerization, and cause too much grafting site, thereby cause percentage of grafting to descend; 3. solvent load: solvent load influences percentage of grafting, when quantity of solvent is excessive, around initiator, exist monomer less, the elementary free radical that initiator produces is failed timely trigger monomer polymerization, and the living radical coupling takes place in self, thereby makes it lose activity, causes percentage of grafting on the low side, in reaction system, quantity of solvent is than silane-modified nanometer SiO 2Mass parts is 8～10: 1 for suitable.
Experimental example 1: silicane coupled to Nano SiO of the present invention 2Modification method for graft polymerization of acrylic ester carries out the control condition of graft modification and the inventor's laboratory test is carried out by the following method according to common propylene ester class in solution, and analyzes by FTIR, the generation of checking graft polymerization.
1, starting material:
(1) silicane coupled to Nano SiO 2: structural formula is:
Figure A20051004570700061
The spherical purity 99.9% of particle diameter: 20～25nm
Lipophilic degree 60%, water-intake rate 2.38%
Liaoning University provides
(2) butyl methacrylate (BMA) AR
(3) Diisopropyl azodicarboxylate (AIBN) AR
(4) toluene AR
(5) tetrahydrofuran (THF) (THF) AR
(6) nitrogen: 99%
2, plant and instrument:
1) has the four-hole boiling flask of stirring, reflux condensing tube
2) water bath with thermostatic control
3) suction filtration device
4) baking oven
5) Magnu-IR560 type Fourier transformation infrared spectrometer
6) UV-1100 UV, visible light spectrophotometer
7) transmission electron microscope: NEC JEM-100SX
3, graft polymerization procedure:
(1) proportioning: mass parts
Silicane coupled to Nano SiO 2: BMA: toluene: AIBN=1: 8～10: 8～10: 0.2～0.25
(2) graft polymerization:
The 40-50ml solvent toluene is added in the four-hole boiling flask, add 5g silicane coupled to Nano SiO 2, magnetic agitation makes silicane coupled to Nano SiO 2Be scattered in the toluene, add 1.0-1.25gAIBN then, feed N 2Protection is warming up to 70 ℃ and begins to drip BMA40-50g, and 80～90 ℃ of control reaction temperature were reacted 2.5～3.5 hours, and reaction finishes, cooling, and suction filtration, filter cake after 8～9 hours, is put into baking oven 100 ℃ of oven dry with the toluene extracting, obtains graft modification nanometer SiO 2
Graft modification nanometer SiO 2Spherical lipophilic degree 61.00% water-intake rate of particle diameter: 30～40nm 2.38% percentage of grafting 40.71%
With nanometer SiO 2, silicane coupled to Nano SiO 2, graft modification nanometer SiO 2Carry out spectroscopic analysis, from Fig. 1 spectrogram, can find out nanometer SiO 2(a) charateristic avsorption band, 1096.58cm -1, 803.40cm -1And 470.80cm -1The peak at place is respectively the antisymmetric stretching vibration of Si-O-Si key, symmetrical stretching vibration and flexural vibration, 961.24cm -1Corresponding to the stretching vibration of Si-OH key, silicane coupled to Nano SiO 2(b) except SiO is arranged 2Charateristic avsorption band outside, at 1428.79cm -1And 1395.08cm -1The absorption peak that the place occurs is-CH 3With-CH 2-the flexural vibration of c h bond, 2850.99cm -1And 2960.63cm -1The absorption peak that the place occurs is-CH 3With-CH 2The stretching vibration of c h bond, 1654.03cm -1The place is the stretching vibration absorption peak of C=C, 1703.69cm -1The absorption peak that the place occurs is the charateristic avsorption band of C=O, graft modification nanometer SiO 2(c) the characteristic peak C=O peak of ester is at 1730cm -1With C-O-C at 1330cm -1Obviously occur, show at silicane coupled to Nano SiO 2Graft polymerization takes place in the surface.
Dispersion stabilization compares: as follows, respectively take by weighing 0.0100g nanometer SiO 2, silicane coupled to Nano SiO 2And graft modification nanometer SiO 2Place the 10ml colorimetric cylinder, add the 10ml tetrahydrofuran (THF), sonic oscillation 30min leaves standstill, and at 1 hour at interval, gets supernatant liquid its transmittance of UV-Vis spectrophotometric determination T.Draw dispersity D% by the following formula conversion.
D ( % ) = 100 - T 100 × 100
Nanometer SiO 2, silicane coupled to Nano SiO 2, graft modification nanometer SiO 2Its stability as shown in Figure 2.Nanometer SiO 2(a) because surface hydrophilicity is strong, a little less than the hydrophobicity, very fast sedimentation in organic medium is through the nanometer SiO of coupling modification 2(b), lipophilicity strengthens in organic medium, graft modification nanometer SiO 2(c) stability significantly improves in organic medium, can reach 80%.
Experimental example 2:
Starting material, plant and instrument, except that butyl methacrylate changed butyl acrylate, Jia Jibingxisuanyizhi, methyl acrylate into, other was with experimental example 1;
Graft polymerization procedure: press experimental example 1 method, at silicane coupled to Nano SiO 2Drip 4g butyl acrylate, Jia Jibingxisuanyizhi, methyl acrylate in the toluene solution respectively, reaction product is calculated percentage of grafting and the stability that is determined in the organic medium after treatment.
Butyl acrylate graft modification nanometer SiO 26.96g
Percentage of grafting 39.2%
Stability 62.1%
Jia Jibingxisuanyizhi graft modification nanometer SiO 26.99g
Percentage of grafting 39.8%
Stability 65.2%
Methyl acrylate modification: graft modification nanometer SiO 26.93g
Percentage of grafting 38.6%
Stability 58.5%
Can find out that from above-mentioned experimental example the acrylate except that butyl methacrylate can obtain the percentage of grafting close with butyl methacrylate, but its stability in organic medium all is lower than butyl methacrylate graft polymerization modified silane coupled to Nano SiO 2
Can find out that from the TEM photo wherein Fig. 3 is nanometer SiO 2Particulate, particulate is reunited together as can be seen, and particle diameter ratio is bigger; Fig. 4 is silicane coupled to Nano SiO 2The surface self assembled monolayer makes nanometer SiO 2Reunion make moderate progress; Fig. 5 is the nanometer SiO after BMA graft polymerization modification 2, as can be seen from Figure 5 particulate connects together with the form of molecule long-chain, owing to be at nanometer SiO 2The microparticle surfaces grafting makes nanometer SiO 2The particle diameter of particulate increases to some extent, is about 30～40nm.
Silicane coupled to Nano SiO of the present invention 2The beneficial effect of modification method for graft polymerization of acrylic ester: by to silicane coupled to Nano SiO 2Carry out the graft polymerization of acrylic ester modification, not only make lipophilic degree reach 61.00%, the water specific absorption drops to 2.3%, and has significantly improved nanometer SiO 2Therefore dispersion stabilization in organic medium has widened nanometer SiO 2Range of application, can be used for the manufacturing of oil paint, improve the radioprotective of coating, ageing-resistant and thixotroping suspension etc.
Description of drawings:
Fig. 1 is silicane coupled to Nano SiO of the present invention 2The experimental example 1FTIR of modification method for graft polymerization of acrylic ester analyzes spectrogram;
Fig. 2 is silicane coupled to Nano SiO of the present invention 2The experimental example 1 dispersion stabilization comparison diagram of modification method for graft polymerization of acrylic ester;
Fig. 3 is nanometer SiO 2The TEM photo;
Fig. 4 is silicane coupled to Nano SiO 2The TEM photo;
Fig. 5 is graft modification nanometer SiO 2The TEM photo.
Embodiment: the starting material that embodiment adopted, instrument, the same experimental example of equipment.
Embodiment 1: get the 45g solvent toluene, join and have stirring, in the four-hole boiling flask of reflux condensation mode, water bath with thermostatic control heating, take by weighing silicane coupled to Nano SiO 25g joins in the flask, and magnetic agitation makes silicane coupled to Nano SiO 2Be dispersed in the toluene, add 1.0g AIBN then, and feed N 2Protection; begin to be warming up to the BMA monomer 45g that stopper is removed in 70 ℃ of slow droppings of beginning in advance; temperature of reaction is controlled at 80 ℃; reaction was carried out 3 hours, and reaction finishes, then suction filtration; filter cake is used toluene extracting 8-9 hour; except that after desolvating, at 100 ℃ of dryings in baking oven, gained graft modification nanometer SiO 27.02g calculating percentage of grafting is 40.4% stability 78.4%
Embodiment 2: except that temperature of reaction is controlled at 70 ℃, other is with embodiment 1;
Gained graft modification nanometer SiO 25.86g,
Percentage of grafting is 1.72% stability 41%, can find out that from present embodiment temperature of reaction graft reaction below 70 ℃ carries out slowly.
Embodiment 3: except that temperature of reaction is controlled at 90 ℃, other is with embodiment 1;
Gained graft modification nanometer SiO 27.04g
Percentage of grafting is 40.80% stability 79.1%
Embodiment 4: except that the reaction times is 2.0 hours, other is with embodiment 3;
Gained graft modification nanometer SiO 25.43g
Percentage of grafting is 8.60% stability 46.2%
Embodiment 5: except that the reaction times is 4.0 hours, other is with embodiment 3;
Gained graft modification nanometer SiO 26.89g
Percentage of grafting is 37.78% stability 75.60%
Embodiment 6: except that the AIBN add-on was 0.75g, other was with embodiment 3;
Gained graft modification nanometer SiO 2
Percentage of grafting is 31.78% stability 60.30%
Embodiment 7: except that the AIBN add-on was 1.25g, other was with embodiment 3; Gained graft modification SiO 26.92g, percentage of grafting: 38.4% stability: 77.50%
Embodiment 8: except that the AIBN add-on was 1.75g, other was with embodiment 3;
Gained graft modification nanometer SiO 26.35g,
Percentage of grafting is 27.00% stability 50.40%
Embodiment 9: except that the BMA add-on was 40g, other was with embodiment 3;
Gained graft modification nanometer SiO 26.7g,
Percentage of grafting is 35.8% stability 70.30%
Embodiment 10: except that the BMA add-on was 50g, other was with embodiment 1;
Gained graft modification nanometer SiO 26.91g,
Percentage of grafting is 38.20% stability 74.50%
Embodiment 11: except that toluene add-on 40g, other is with embodiment 3;
Gained graft modification nanometer SiO 27.03g,
Percentage of grafting is 40.60% stability 78.10%
Embodiment 12: except that the toluene add-on was 50g, other was with embodiment 3;
Gained graft modification nanometer SiO 26.94g,
Percentage of grafting is 16.80% stability 77.70%
Can find out in the processing condition that the present invention proposes the graft modification nanometer SiO that produces from the foregoing description 2, its percentage of grafting be 37～40% in organic medium stability be 75～80%, its in organic medium stability than not doubling before the grafting.
This graft modification nanometer SiO 2In organic medium, have good dispersiveness, can be used for the modification of materials such as oil paint, nano composite material.Because nanometer SiO 2Small-size effect, surface interface effect, quantum size effect and macro quanta tunnel effect and unusual characteristic such as special light electrical characteristic, high magnetic resistance phenomenon, nonlinear resistance phenomenon and high-strength, the high-ductility that at high temperature still has, good stability, nanometer SiO 2But the widespread use every field has broad application prospects.The nanometer SiO of aforesaid method modification will be adopted 2Be added in the coating,, can well be scattered in the oil paint because its surperficial lipophilicity and the dispersiveness in organic medium improve greatly, and because nanometer SiO 2Be a kind of ultra-violet radiation resisting (promptly anti-aging) material, particle is little in addition, specific surface area is big, can be when coating be dry very fast formation network structure, add nanometer SiO 2Can improve shortcomings such as common coating such as suspension stability is poor, thixotropy is poor, weathering resistance is poor, abrasion resistance difference, film and the body of wall bonding strength significantly improves, hardness of film significantly increases, and the clean surfaces ability also is improved.Modified Nano SiO 2Have good heat-resistant stability, be not subjected to temperature limitation when being scattered in organic medium, so, nanometer SiO 2A kind of as nano material has important and practical meanings to its Application and Development.

Claims (4)

1, a kind of silicane coupled to Nano SiO 2Modification method for graft polymerization of acrylic ester, it is characterized in that: with a certain amount of silicane coupled to Nano SiO 2Be scattered in the toluene solution, stir, add the initiator Diisopropyl azodicarboxylate, logical N 2Protection is warming up to 70 ℃, drips the acrylate of removing stopper in advance, and temperature of reaction is controlled at 80～90 ℃, reacts 2.5～3.5 hours, after reaction finishes, and cooling, the toluene extracting of suction filtration, filter cake is then 95～105 ℃ of oven dry.
2, silicane coupled to Nano SiO according to claim 1 2Modification method for graft polymerization of acrylic ester, it is characterized in that: described silicane coupled to Nano SiO 2Structure is:
3, silicane coupled to Nano SiO according to claim 1 2Modification method for graft polymerization of acrylic ester, it is characterized in that: described acrylate is a butyl methacrylate.
4, silicane coupled to Nano SiO according to claim 1 2Modification method for graft polymerization of acrylic ester, it is characterized in that: described silicane coupled to Nano SiO 2Mass parts: acrylate: solvent: initiator Diisopropyl azodicarboxylate=1: 8～10: 8～10: 0.2～0.25.
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