CN106699955A - Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material - Google Patents
Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material Download PDFInfo
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Abstract
The invention discloses an application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, a composite material of the methacryloyloxyethylhexyldimethyl ammonium bromide, and a preparation method of the composite material. According to the invention, based on the electrostatic adsorption action between positive charges of a cationic monomer and negative charges generated by ionization of nanometer SiO2 in water, and winding and wrapping effects of a hexylalkyl long chain of the cationic monomer to the surface of SiO2, the methacryloyloxyethylhexyldimethyl ammonium bromide with positive charges is used as the cationic monomer and copolymerized with MMA; positive charges are introduced into a PMMA substrate; meanwhile, in-situ addition of the nanometer SiO2 is performed; and the influences of the positive charges of the cationic monomer and the hexylalkyl long chain on dispersibility of the nanometer SiO2 in the PMMA substrate and interface bonding strength between the nanometer SiO2 and the PMMA substrate are researched. Compared with pure PMMA resin, the composite material provided by the invention is greatly improved in tensile strength, and solves problems of a PMMA material in the aspect of mechanical strength.
Description
Technical field
The invention belongs to field of compound material, more specifically to a kind of polymethyl methacrylate (PMMA) composite wood
Material, particularly with PMMA as matrix, by cationic monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide (MEHDAB)
With filler nano silicon (SiO2) between produce electrostatic adsorption, promote the dispersion of nano silicon, improve
The mechanical property of PMMA based nano composite materials.
Background technology
Polymethyl methacrylate (PMMA) has many premium properties, is macromolecule transparent material best so far
Material, light transmittance is up to 94%；The resistance to gas corrosivity of PMMA is very strong, and product does not need the protective layers such as paint brush, even if
Contacted with the corrosive gas such as sulfur dioxide, ozone for a long time, remain to holding surface bright and clean；The temperature flowing of PMMA is fine,
Itself can show good viscoplasticity, thus machinability is very strong, and processing cost is low, can using drilling, cutting,
The methods such as injection, extrusion, blowing are processed into panoramic product；Meanwhile, PMMA is nontoxic to human body and and biological tissue
Have good compatibility, therefore be widely used in biomedical sector, be mainly used in oral artificial tooth, dental base acrylic resin powder,
Articular prosthesis and screw etc..These characteristics cause that PMMA is obtained in the fields such as building, traffic, advertisement, medical treatment, industry
It is widely applied, wherein the annual PMMA for being used for building field of China is more than 5000 tons, for medical PMMA 300
It is more than ton.
But the shortcomings of PMMA, such as non-refractory, easily it is aging, not wear-resisting, limit its industry, medical treatment neck
The application in domain, it is therefore desirable to treatment is modified to PMMA.A kind of method of modifying be add Nano filling such as silica,
Galapectite, carbon fiber etc., with the mechanical strength of reinforced PMMA based composites.But nano-particle is in PMMA matrixes
It is easy to reunite, it is reached fine dispersion in the base generally needs to carry out surface organic modification, and this causes operating process
More complicated, the production cycle is long, thereby increases and it is possible to Overall Properties of Composites can be had a negative impact.These side effects for
For industrialized production, can largely increase financial cost.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, with polymethyl methacrylate (PMMA) as base material, use
The method of in-situ suspension polymerization prepares PMMA based nano composite materials, it is therefore an objective to Nano filling is not carried out it is organically-modified
Under the premise of, obtain the composite of excellent performance.Positive charge and Nano-meter SiO_2 based on cationic monomer institute band2The electricity in water
The hexyl long alkyl chain of electrostatic adsorption and cationic monomer between the negative electrical charge for producing is to SiO2The winding on surface,
Parcel effect, methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide (MEHDAB) with positive charge is used as cation mono
Body carries out copolymerization with MMA so that polymeric matrix carries positive charge, and the addition Nano-meter SiO_2 in situ while polymerization2,
By the positive charge and hexyl long alkyl chain of cationic monomer institute band to Nano-meter SiO_22It is in situ coordinate/it is compound, improve its
Dispersive property and the two interface binding power in matrix PMMA, and then the addition raising for passing through cationic monomer
PMMA/SiO2The influence of nano composite material performance.
The purpose of the present invention is achieved by following technical proposals.
Application of the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide in dispersed silicon dioxide, long chain cation monomer first
Base acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide surface carries positive charge, the positive charge based on long chain cation monomer institute band
Electrostatic adsorption and cationic monomer methacryloxypropyl between the negative electrical charge for ionizing generation in water with nano silicon
Winding and parcel effect of the hexyl long alkyl chain to silica surface in ethylhexyl ammonium bromide so that live on surface
Property monomer situ add nano silicon, the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide with positive charge is made
It is that cationic monomer and methyl methacrylate carry out copolymerization so that polymeric matrix carries positive charge so that nano-silica
SiClx is dispersed in polymeric matrix and strengthens the interface binding power of nano silicon and polymeric matrix.
Methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silicon dioxide composite material, passes through
The mode of cationic monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide and methyl methacrylate copolymer, to polymerization
Positive charge and alkyl side chain are introduced in thing matrix, two kinds of monomers carry out copolymerization, the methyl-prop by way of suspension polymerisation
E pioic acid methyl ester and methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide composition oil phase, the consumption of methyl methacrylate monomer
Be 92-95wt% of oil phase quality, the consumption of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide for oil phase quality 5-
8wt%, the consumption of nano silicon is 7-9wt% of oil phase quality.Nano silicon is realized in situ with copolymerization product
It is compound, it is then that product is hot-forming.
The preparation of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silicon dioxide composite material
Method, is carried out as steps described below：
Step 1, with methyl methacrylate and methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide as comonomer, leads to
Cross suspension polymerisation to be obtained, in suspension polymerization system, the oil phase is by methyl methacrylate and methylacryoyloxyethyl
Two kinds of monomer compositions of hexyl ditallowdimethyl ammonium bromide, the consumption of methyl methacrylate monomer is 92-95wt% of oil phase quality,
The consumption of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide is 5-8wt% of oil phase quality；The water is by water and divides
Powder is constituted, and the consumption of wherein dispersant is two kinds of 2.5-3wt% of monomer mass sum；
Step 2, adds the nano silicon of 7-9wt% of oil phase quality in water phase, and methyl is added after ultrasonic disperse
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide consumption half is (i.e. oily
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of phase quality 2.5-4%), continue ultrasonic disperse and obtain suspension；
The methylacryoyloxyethyl hexyl of methylacryoyloxyethyl Dodecydimethylammonium bronides consumption half is added in oil phase
Ditallowdimethyl ammonium bromide (i.e. the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of 2.5-4wt% of oil phase quality), will
The suspension and oil phase are added in reactor, and stirring is passed through inert gas to keep whole reaction system during the course of the reaction
In inert gas atmosphere, after being warming up to the initiation temperature of initiator, add initiator to trigger polymerization, obtain methyl
Acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silica copolymer
(P(MMA-co-MEHDAB)/SiO2), the consumption of the initiator is two kinds of 1-1.5wt% of monomer mass sum；
Step 3, copolymer prepared by step 2 is filtered and washed, and copolymer powder is obtained after drying, is designated as
P(MMA-co-MEHDAB)/SiO2。
In suspension polymerization system of the invention, the dispersant is basic magnesium carbonate, calcium hydroxy phosphate (HAP), ethoxy fibre
One kind in dimension plain (HEC) or tricalcium phosphate, preferably hydroxyethyl cellulose (HEC)；The volume ratio of the water phase and oil phase
It is 3-5, preferably 4；The initiator is azodiisobutyronitrile (AIBN), ABVN (ABVN), benzoyl peroxide
One kind in formyl (BPO) or the own ester (EHP) of peroxy dicarbonate two (2- ethyls), preferably benzoyl peroxide (BPO)；
The inert gas is the one kind in nitrogen, helium or argon gas, preferably nitrogen；It is being heated to the initiation temperature of initiator
After 72-78 DEG C, the time needed for how much selective polymerizations reaction according to reactant, to ensure that two kinds of monomers are realized in copolymerization
Conversion ratio higher, the reaction time is 5-10 hours.
The particle diameter of the nano silicon is 20-30nm, and consumption is 7.5-8wt% of oil phase quality.
The copolymer powder of step 3 gained is hot-forming with heat pressing forming machines, and hot pressing condition is：Pressure 5-15MPa,
170-230 DEG C of temperature, time 10-30min；
The hot-forming condition is preferably：Pressure 10MPa, 200 DEG C of temperature, time 15min.
In technical solution of the present invention, the volume ratio of suspension polymerization system reclaimed water phase and oil phase is 1-5.
In the inventive solutions with dimethylaminoethyl methacrylate and bromohexane as raw material, acetone as solvent,
Synthesizing methyl acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide under conditions of backflow (60-80 degrees Celsius), magnetic agitation,
Dimethylaminoethyl methacrylate and bromohexane are selected when being prepared carries out the reaction of equal quality ratio, terminates in reaction
After carry out separating-purifying.The methylacryoyloxyethyl hexyl two synthesized in the present invention is characterized using proton nmr spectra
The structure of methyl bromide ammonium, deuterochloroform (CDCl3) it is internal standard reagent, the nucleus magnetic hydrogen spectrum of cationic monomer is as shown in Figure 1.
1H-NMR(CDCl3):δ=5.651-6.117 (m, 2H), δ=4.634 (t, 2H), δ=4.148 (t, 2H), δ=3.618 (t, 2H),
δ=3.498 (s, 6H), δ=1.923 (s, 3H), δ=1.741 (m, 2H), δ=1.303 (m, 6H), δ=0.839 (t, 3H).From MEHDAB
's1H-NMR nuclear magnetic spectrograms can see：The absworption peak of chemical shift δ 7.265 is CDCl3Internal standard peak；Chemical shift
Two hydrogen in the C=C double bonds corresponding with the absworption peak of δ 5.651 of δ 6.117；It is direct with oxygen atom that the peak of δ 4.634 is corresponding
Two hydrogen on connected carbon atom；It is two be joined directly together with N atoms that two peaks of δ 4.148 and δ 3.618 are corresponding
Four hydrogen on methylene；It is six hydrogen on two methyl being joined directly together with N atoms that the peak of δ 3.498 is corresponding；
It is three hydrogen on the methyl being connected with vinyl that the peak of δ 1.923 is corresponding；δ 1.741 is corresponding with the absworption peak of δ 1.303
It is eight hydrogen on hexyl mid methylenes carbon atom；It is three hydrogen on hexyl tail end methyl that the peak of δ 0.839 is corresponding.
Understand that peak area is directly proportional to the proton number in molecule on nuclear-magnetism figure by analysis, it was demonstrated that synthesis target product methacryloxypropyl
Ethylhexyl ammonium bromide and products pure.
Nano-meter SiO_22Be present the hydroxyl of a large amount of unsaturation residual bonds and different bond styles due to surface in particle, easily reunite, and lead to
Often exist in the form of secondary agglomeration body, it is difficult to be homogeneously dispersed in aqueous systems.TEM is a kind of effective observation nanometer
The instrument of particle morphology and its particle diameter distribution.Fig. 2 (a) is original Nano-meter SiO_22TEM figure of the particle after ultrasonic disperse in water
Piece, Nano-meter SiO_2 in picture2Water-borne paint is very big, and color is deeper, illustrates the interaction of hydrogen bond of skin effect and hydroxyl
So that Nano-meter SiO_22Easily reunite in water, have impact on the performance of its advantageous effect.Fig. 2 (b) is a small amount of MEHDAB of addition
Nano-meter SiO_22TEM pictures after ultrasonic disperse, it can be seen that SiO from picture2Color is shallower, and discrete areas expand,
Water-borne paint is substantially reduced.This explanation add cationic monomer after, the positive charge of one side cationic monomer institute band with receive
Rice SiO2There is electrostatic interaction in the negative electrical charge on surface, reduce the hydroxyl of ionized state；Another aspect cationic monomer
The long alkyl chain of institute's band can effectively wind, be wrapped in Nano-meter SiO_22Surface, so as to increased SiO2The spacing of particle, drop
Low Nano-meter SiO_22Surface can, and reduce the interaction of hydrogen bond of surface hydroxyl.The collective effect of the two is obviously reduced
Nano-meter SiO_22Reunion, make Nano-meter SiO_22Disperse to be more uniformly distributed.
Infrared spectrum characterization is carried out to copolymer powder of the invention extracting resultant product, as shown in Figure 3.PMMA/SiO2
With P (MMA-co-MEHDAB)/SiO2The infrared spectrum of the extracting resultant product of complex microsphere is as shown in Figure 3.From spectrogram
In as can be seen that spectral line (a), (b) overall peak shape it is basically identical, wherein in 804cm-1And 1084cm-1The absworption peak at place
Corresponding respectively is SiO2The symmetrical and asymmetric stretching vibration absworption peak of middle O-Si-O, 954cm-1The absworption peak correspondence at place
Be Si-OH stretching vibration absworption peak, 464cm-1It is the flexural vibrations absworption peak of O-Si-O that the absworption peak at place is corresponding,
3433cm-1It is SiO that place is corresponding2The stretching vibration absworption peak of surface hydroxyl, 1630cm-1It is residual that the absworption peak at place is corresponding
Stay the H-O-H flexural vibrations absworption peaks of water.The presence of features above absworption peak proves that extracting resultant product is SiO2。1736
cm-1The absworption peak at place is the stretching vibration absworption peak of carbonyl, 2950cm-1And 2845cm-1The absworption peak difference at place is corresponding
It is the characteristic absorption peak of methyl and methylene, this proves to contain polymerization to some extent by resultant product after soxhlet type
Thing composition.Due to the SiO that this experiment is used2Raw material is pore type, and SiO2There is certain hydrogen bond between PMMA
Interact, therefore have a small amount of polymer residue, it is difficult to extracted, but SiO in spectrogram (a)2Characteristic absorption peak
It is relatively strong, and polymer features peak is weaker, although this explanation contains residual polyalcohol, content is few；And in spectrogram (b)
The intensity of the absworption peak of polymer is very high, illustrates that the polymer content of remnants is higher, and this is primarily due to cationic monomer institute
The positive charge and SiO of band2The negative electrical charge of institute's band produces electrostatic adsorption, enhances SiO2Tie at interface with polymeric matrix
With joint efforts, and there are more monomers in SiO2Surface aggregate, thus while by fully extracting, SiO2Particle surface still has
More polymer residue.Analysis understands that the electrostatic adsorption between cationic monomer and nano-particle can have according to more than
Interface binding power between effect ground enhancing nano-particle and polymeric matrix.
The small pearl polymethyl methacrylate being made through suspension polymerisation is the main component of medical composite material.The present invention
Technical scheme is from cationic monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide (MEHDAB) with positive charge
With MMA copolymerization, introducing can produce the positive charge and alkyl side chain of electrostatic adsorption in the base with nano silicon,
To realize the boundary of dispersed and enhancing nano silicon of the nano silicon in polymeric matrix and polymeric matrix
Face adhesion.Technical scheme meets medical compound by the small pearl copolymerized polymer prepared after suspension polymerisation
The basic demand of material, after toner is made into standard specimen, purer PMMA resins, tensile strength obtains larger amplitude
Degree is improved, and successfully improves Nano-meter SiO_22Dispersiveness in the base, enhances SiO2With the interface cohesion of polymeric matrix
Power, solves the problems, such as that PMMA based nano composite materials are particularly in terms of tensile strength in terms of mechanical strength.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism of the long chain cation monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide used in the present invention
Resonance1H-NMR spectrum；
Fig. 2 is TEM photo of the Nano particles of silicon dioxide ultrasonic disperse for preparing of the invention in water, wherein, (a)
It is original Nano-meter SiO_22Particle, (b) is the Nano-meter SiO_2 for adding a small amount of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide2
Particle；
Fig. 3 is copolymer powder P (MMA-co-MEHDAB)/SiO that the present invention is prepared2With poly-methyl methacrylate
Ester and Nano particles of silicon dioxide polymer P MMA/SiO2The infrared spectrogram of resultant product is extracted, wherein, (a) is
PMMA/SiO2, (b) is P (MMA-co-MEHDAB)/SiO2。
Specific embodiment
Technical scheme is further described below by specific embodiment.
The key instrument and medicine that embodiment is selected are as shown in the table：
The primary raw material of table 1
| Material name | Specification | Manufacturer |
| Methyl methacrylate (MMA) | Analysis is pure | Ke Miou chemical reagent Co., Ltd |
| Nano silicon (SiO2) | HN-sp600 particle diameters 20nm | Tangshan Cao Fei pastures are safe great bright up to new material Co., Ltd |
| Dimethylaminoethyl methacrylate (DM) | Analysis is pure | Sa En chemical technologies Co., Ltd |
| Bromohexane | Analysis is pure | Tianjin Yuan Li Co., Ltds |
| Benzoyl peroxide (BPO) | Analysis is pure | Ke Wei companies of University Of Tianjin |
| Hydroxyethyl cellulose (HEC) | It is medical | Heda Co., Ltd, Shandong |
| NaOH (NaOH) | Chemistry is pure | Ke Miou chemical reagent Co., Ltd |
| Anhydrous calcium chloride (CaCl2) | Analysis is pure | Tianjin sky over the river Chemical Engineering Technology Co., Ltd |
| Tetrahydrofuran (TMF) | Analysis is pure | Tianjin sky over the river Chemical Engineering Technology Co., Ltd |
| Acetone | Analysis is pure | Ke Miou chemical reagent Co., Ltd |
| Ether | Analysis is pure | Tianjin sky over the river Chemical Engineering Technology Co., Ltd |
The key instrument equipment of table 2
| Instrument title | Model | Manufacturer |
| Ultrasonic cell disruptor | JY92-II N | Ningbo Xin Zhi biotechnologies joint-stock company |
| Electric-heated thermostatic water bath | DZKW-4 | Zhong Xing great achievements Instrument Ltd. of Beijing |
| A ten thousandth electronic balance | AL104 | Plum Teller-support benefit Instrument Ltd. |
| Multiplex vavuum pump of circulating water type | SHB-III | Zhengzhou Greatwall Scientific Industrial ＆ Trading Co., Ltd. |
| Liquid NMR spectrometer | INOVA 500MHz | The U.S., Varian |
| Infrared spectrometer | Nicolet-5DX | The U.S., Nicolet |
| Heat pressing forming machines | YJ-450 | Yuyao City Hua Cheng hydraulic presses Co., Ltd |
| Omnipotent mechanics machine | M350-20KN | Britain, Testometric |
| Flied emission transmission electron microscope | JEM-2100F | Japanese JEOL |
The percentage that following embodiments are marked is mass percent, and carries out quality hundred according to the content that Summary is recorded
The determination of fraction basis, weighs MMA monomers and MEHDAB monomers first when actually weighing material, further according to two kinds of monomer matter
Amount sum carries out weighing for unclassified stores.
Embodiment 1
(1) 95wt%MMA monomers and 2.5wt%MEHDAB are added in there-necked flask；In 240mL deionizations
9wt%SiO is added in water2, 2.5wt%MEHDAB, will after mixture ultrasonic disperse add 2.5wt% hydroxy ethyl fibers
Plain (HEC), is then added into there-necked flask, and with the rotating speed stirring at low speed of 400r/min.It is passed through N2Protection 40min
Afterwards, 75 DEG C are warming up to, and continue to keep inert atmosphere, add 1wt% initiator Bs PO to trigger polymerization, rotating speed is transferred to 700
r/min；Stop heating after reaction 6h, continue to stir；After 30min, rotating speed is down to 400r/min；It is anti-after 15min
Should terminate.By reaction system cold filtration, filtration product is washed with deionized repeatedly, perseverance is dried under vacuum at 60 DEG C
Determine weight, obtain P (MMA-co-MEHDAB)/SiO2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 10MPa, 200 DEG C of temperature, time 15min.
Embodiment 2
(1) 94wt%MMA monomers and 3wt%MEHDAB are added in there-necked flask；In 240mL deionized waters
Add 7wt%SiO2, 3wt%MEHDAB, will after mixture ultrasonic disperse add 3.0wt% basic magnesium carbonates, then
In adding it to there-necked flask, and with the rotating speed stirring at low speed of 400r/min.After being passed through argon gas protection 60min, it is warming up to
72 DEG C, and continue to keep inert atmosphere, add 1.5wt% initiator azodiisobutyronitriles (AIBN) to trigger polymerization, rotating speed is adjusted
To 700r/min；Stop heating after reaction 5h, continue to stir；After 40min, rotating speed is down to 400r/min；10min
Reaction afterwards terminates.By reaction system cold filtration, filtration product is washed with deionized repeatedly, is vacuum dried at 50 DEG C
To constant weight, P (MMA-co-MEHDAB)/SiO is obtained2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 5MPa, 230 DEG C of temperature, time 30min.
Embodiment 3
(1) 92wt%MMA monomers and 4wt%MEHDAB are added in there-necked flask；Add in 240mL deionized waters
Enter 7wt%SiO2, 4wt%MEHDAB, will after mixture ultrasonic disperse add 3.0wt% calcium hydroxy phosphates (HAP), then
In adding it to there-necked flask, and with the rotating speed stirring at low speed of 400r/min.After being passed through helium protection 30min, it is warming up to
78 DEG C, and continue to keep inert atmosphere, add 1.2wt% initiators ABVN (ABVN) to trigger polymerization, rotating speed is adjusted
To 700r/min；Stop heating after reaction 10h, continue to stir；After 15min, rotating speed is down to 400r/min；5min
Reaction afterwards terminates.By reaction system cold filtration, filtration product is washed with deionized repeatedly, is vacuum dried at 70 DEG C
To constant weight, P (MMA-co-MEHDAB)/SiO is obtained2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 15MPa, 170 DEG C of temperature, time 10min.
Embodiment 4
(1) 93wt%MMA monomers and 3.5wt%MEHDAB are added in there-necked flask；In 240mL deionized waters
Add 8wt%SiO2, 3.5wt%MEHDAB, will after mixture ultrasonic disperse add 2.5wt% tricalcium phosphates, then by it
It is added in there-necked flask, and with the rotating speed stirring at low speed of 400r/min.It is passed through N2After protection 40min, 75 DEG C are warming up to,
And continue to keep inert atmosphere, add the own ester (EHP) of 1.5wt% initiators peroxy dicarbonate two (2- ethyls) to trigger polymerization,
Rotating speed is transferred to 700r/min；Stop heating after reaction 8h, continue to stir；After 30min, rotating speed is down to 400r/min；
Reaction terminates after 15min.By reaction system cold filtration, filtration product is washed with deionized repeatedly, it is true at 65 DEG C
Sky is dried to constant weight, obtains P (MMA-co-MEHDAB)/SiO2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 9MPa, 200 DEG C of temperature, time 20min.
Embodiment 5
(1) 95wt%MMA monomers and 2.5wt%MEHDAB are added in there-necked flask；In 240mL deionized waters
Add 8.5wt%SiO2, 2.5wt%MEHDAB, will after mixture ultrasonic disperse add 2.8wt% hydroxyethyl celluloses (HEC),
It is then added into there-necked flask, and with the rotating speed stirring at low speed of 400r/min.After being passed through helium protection 40min, rise
Temperature continues to keep inert atmosphere to 75 DEG C, adds 1.5wt% initiator Bs PO to trigger polymerization, and rotating speed is transferred to 700r/min；
Stop heating after reaction 6h, continue to stir；After 30min, rotating speed is down to 400r/min；Reaction terminates after 15min.
By reaction system cold filtration, filtration product is washed with deionized repeatedly, constant weight is dried under vacuum at 60 DEG C,
Obtain P (MMA-co-MEHDAB)/SiO2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 10MPa, 200 DEG C of temperature, time 15min.Embodiment 6
(1) 94wt%MMA monomers and 3wt%MEHDAB are added in there-necked flask；Add in 240mL deionized waters
Enter 7.5wt%SiO2, 3wt%MEHDAB, will after mixture ultrasonic disperse add 2.8wt% hydroxyethyl celluloses (HEC),
It is then added into there-necked flask, and with the rotating speed stirring at low speed of 400r/min.After being passed through argon gas protection 40min, rise
Temperature continues to keep inert atmosphere to 77 DEG C, adds 1.2wt% initiator Bs PO to trigger polymerization, and rotating speed is transferred to 700r/min；
Stop heating after reaction 9h, continue to stir；After 30min, rotating speed is down to 400r/min；Reaction terminates after 15min.
By reaction system cold filtration, filtration product is washed with deionized repeatedly, constant weight is dried under vacuum at 55 DEG C,
Obtain P (MMA-co-MEHDAB)/SiO2Nano-complex；
(2) by P (MMA-co-MEHDAB)/SiO2Copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing
Condition is：Pressure 12MPa, 210 DEG C of temperature, time 25min.Comparative example 1
(1) by MMA monomers add there-necked flask in, while in 240mL deionized waters add 2.5wt% hydroxy ethyl fibers
Plain (HEC), is poured into there-necked flask after preliminary stirring, and with the rotating speed stirring at low speed of 400r/min.It is passed through N2Protection
After 40min, 75 DEG C are warming up to, and continue to keep inert atmosphere, add 1.8wt% initiator Bs PO to trigger polymerization, turned
Velocity modulation is to 700r/min；Stop heating after reaction 6h, continue to stir；After 30min, rotating speed is down to 400r/min；
Reaction terminates after 15min.By reaction system cold filtration, filtration product is washed with deionized repeatedly, it is true at 60 DEG C
Sky is dried to constant weight, obtains PMMA toners；
(2) it is PMMA toners is hot-forming with heat pressing forming machines.Hot pressing condition is：Pressure 10MPa, temperature
200 DEG C, time 15min.
Comparative example 2
(1) by MMA monomers addition there-necked flask；8wt%SiO is added in 240mL deionized waters2, after ultrasonic disperse
Addition 2.5wt% hydroxyethyl celluloses (HEC), is then added into there-necked flask, and with the rotating speed low speed of 400r/min
Stirring.It is passed through N2After protection 40min, 75 DEG C are warming up to, and continue to keep inert atmosphere, add 1.8wt% initiators
BPO triggers polymerization, and rotating speed is transferred to 700r/min；Stop heating after reaction 6h, continue to stir；After 30min, will turn
Prompt drop is to 400r/min；Reaction terminates after 15min.By reaction system cold filtration, filtering is washed with deionized repeatedly
Product, constant weight is dried under vacuum at 60 DEG C, obtains PMMA toners；
(2) by PMMA/SiO2Toner is hot-forming with heat pressing forming machines.Hot pressing condition is：Pressure 10MPa, temperature
200 DEG C of degree, time 15min.
Comparative example 3
(1) 92.0wt%MMA monomers and 4.0wt%MEHDAB are added in there-necked flask；In 240mL deionized waters
Middle addition 4.0wt%MEHDAB, will add 2.5wt% hydroxyethyl celluloses (HEC) after mixture ultrasonic disperse, then will
It is added in there-necked flask, and with the rotating speed stirring at low speed of 400r/min.It is passed through N2After protection 40min, 75 DEG C are warming up to,
And continue to keep inert atmosphere, add 1.8wt% initiator Bs PO to trigger polymerization, rotating speed is transferred to 700r/min；Reaction 6h
Stop heating afterwards, continue to stir；After 30min, rotating speed is down to 400r/min；Reaction terminates after 15min.Will reaction
System cold filtration, is washed with deionized filtration product repeatedly, and constant weight is dried under vacuum at 60 DEG C, obtains
P (MMA-co-MEHDAB) copolymer；
(2) it is P (MMA-co-MEHDAB) copolymerization product (powder) is hot-forming with heat pressing forming machines.Hot pressing condition is：
Pressure 10MPa, 200 DEG C of temperature, time 15min.
Nano composite material carries out the test of mechanical performance in the following ways.
Standard specimen is prepared using hot pressing formation process, size of sample：Mechanics sample is cuboid, size 70mm × 10mm
×1.5mm.Hot pressing condition：Pressure 5-15MPa, 170-230 DEG C of temperature, time 10-30min.
Tensile property is tested：Extension test is carried out to obtained standard tensile mechanics sample using omnipotent mechanics machine, is drawn
Speed is stretched for 2mm/min.
To embodiment and the omnipotent mechanics machine of M350-20KN types of Testometric companies of comparative example product utilization Britain
Carry out tensile property test as follows：Mechanical stretch specimen size 70mm × 10mm × 1.5mm, rate of extension is 2
mm/min.Test result is as shown in table 3：
The pure PMMA of table 3, copolymer and composite materials property
| Material type | Tensile strength (MPa) | Young's modulus (GPa) | Breaking strain (%) |
| PMMA (comparative example 1) | 45.73±2.25 | 1.62±0.07 | 3.56±0.36 |
| PMMA/SiO2(comparative example 2) | 45.27±2.91 | 1.72±0.05 | 3.40±0.29 |
| P (MMA-co-MEHDAB) (comparative example 3) | 57.60±1.94 | 1.59±0.12 | 5.69±0.47 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 1) | 63.32±1.67 | 1.78±0.18 | 5.70±0.31 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 2) | 69.20±2.66 | 1.84±0.11 | 5.91±0.32 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 3) | 65.07±2.11 | 1.80±0.07 | 5.16±0.27 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 4) | 63.21±2.34 | 1.79±0.13 | 5.36±0.23 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 5) | 64.91±1.97 | 1.81±0.14 | 5.11±0.28 |
| P(MMA-co-MEHDAB)/SiO2(embodiment 6) | 65.81±2.37 | 1.82±0.17 | 5.54±0.33 |
Exemplary description is done to the present invention above, it should explanation, in the case where core of the invention is not departed from, appointed
What simple deformation, modification or other skilled in the art can not spend the equivalent of creative work to each fall within
Protection scope of the present invention.
Claims (10)
1. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silicon dioxide composite material, its
It is characterised by：Long chain cation monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide carries positive charge, based on long-chain
The positive charge and Nano-meter SiO_2 of cationic monomer institute band2Electrostatic adsorption and sun between the negative electrical charge for ionizing generation in water
The hexyl long alkyl chain of ion monomer is to SiO2The winding on surface, parcel effect, the methacryloxypropyl second with positive charge
Base hexyl ditallowdimethyl ammonium bromide (MEHDAB) carries out copolymerization as cationic monomer and methyl methacrylate so that polymer
Matrix carries positive charge, and the addition Nano-meter SiO_2 in situ while polymerization2So that nano silicon is in polymeric matrix
In interface binding power that is dispersed and strengthening nano silicon and polymeric matrix；Methylacryoyloxyethyl hexyl
Ditallowdimethyl ammonium bromide-polymethyl methacrylate-silicon dioxide composite material, by cationic monomer methacryloxypropyl second
The mode of base hexyl ditallowdimethyl ammonium bromide and methyl methacrylate copolymer, to introducing positive charge and alkyl in polymeric matrix
Side chain, two kinds of monomers carry out copolymerization, the methyl methacrylate and methacryloxypropyl second by way of suspension polymerisation
Base hexyl ditallowdimethyl ammonium bromide constitutes oil phase, and the consumption of methyl methacrylate monomer is 92-95wt% of oil phase quality,
The consumption of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide is 5-8wt% of oil phase quality, the use of nano silicon
It is 7-9wt% of oil phase quality to measure, and nano silicon realizes In-situ reaction with copolymerization product, is then hot pressed into product
Type；Carry out as steps described below：
Step 1, with methyl methacrylate and methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide as comonomer, leads to
Cross suspension polymerisation to be obtained, in suspension polymerization system, the oil phase is by methyl methacrylate and methylacryoyloxyethyl
Two kinds of monomer compositions of hexyl ditallowdimethyl ammonium bromide, the consumption of methyl methacrylate monomer is 92-95wt% of oil phase quality,
The consumption of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide is 5-8wt% of oil phase quality；The water is by water and divides
Powder is constituted, and the consumption of wherein dispersant is two kinds of 2.5-3wt% of monomer mass sum；
Step 2, adds the nano silicon of 7-9wt% of oil phase quality in water phase, and methyl is added after ultrasonic disperse
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide consumption half is (i.e. oily
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of phase quality 2.5-4%), continue ultrasonic disperse and obtain suspension；
The methylacryoyloxyethyl hexyl of methylacryoyloxyethyl Dodecydimethylammonium bronides consumption half is added in oil phase
Ditallowdimethyl ammonium bromide (i.e. the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of 2.5-4wt% of oil phase quality), will
The suspension and oil phase are added in reactor, and stirring is passed through inert gas to keep whole reaction system during the course of the reaction
In inert gas atmosphere, after being warming up to the initiation temperature of initiator, add initiator to trigger polymerization, obtain methyl
Acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silica copolymer
(P(MMA-co-MEHDAB)/SiO2), the consumption of the initiator is two kinds of 1-1.5wt% of monomer mass sum；
Step 3, copolymer prepared by step 2 is filtered and washed, and copolymer powder is obtained after drying, is designated as
P(MMA-co-MEHDAB)/SiO2。
2. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 1
SiClx composite, it is characterised in that：The dispersant is basic magnesium carbonate, calcium hydroxy phosphate (HAP), hydroxy ethyl fiber
One kind in plain (HEC) or tricalcium phosphate, preferably hydroxyethyl cellulose (HEC)；The water phase is with the volume ratio of oil phase
3-5, preferably 4；The initiator is azodiisobutyronitrile (AIBN), ABVN (ABVN), benzoyl peroxide first
One kind in acyl (BPO) or the own ester (EHP) of peroxy dicarbonate two (2- ethyls), preferably benzoyl peroxide (BPO)；Institute
It is the one kind in nitrogen, helium or argon gas, preferably nitrogen to state inert gas.
3. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 1
SiClx composite, it is characterised in that：The particle diameter of the nano silicon is 20-30nm, and consumption is oil phase quality
7.5-8wt%；The volume ratio of suspension polymerization system reclaimed water phase and oil phase is 1-5.
4. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 1
SiClx composite, it is characterised in that：After 72-78 DEG C of initiation temperature for being heated to initiator, according to the number of reactant
Time needed for selective polymerization reaction, to ensure that two kinds of monomers realize conversion ratio higher in copolymerization, the reaction time is 5-10
Hour.
5. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silicon dioxide composite material is prepared
Method, it is characterised in that：Carry out as steps described below：
Step 1, with methyl methacrylate and methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide as comonomer, leads to
Cross suspension polymerisation to be obtained, in suspension polymerization system, the oil phase is by methyl methacrylate and methylacryoyloxyethyl
Two kinds of monomer compositions of hexyl ditallowdimethyl ammonium bromide, the consumption of methyl methacrylate monomer is 92-95wt% of oil phase quality,
The consumption of methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide is 5-8wt% of oil phase quality；The water is by water and divides
Powder is constituted, and the consumption of wherein dispersant is two kinds of 2.5-3wt% of monomer mass sum；
Step 2, adds the nano silicon of 7-9wt% of oil phase quality in water phase, and methyl is added after ultrasonic disperse
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide consumption half is (i.e. oily
The methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of phase quality 2.5-4%), continue ultrasonic disperse and obtain suspension；
The methylacryoyloxyethyl hexyl of methylacryoyloxyethyl Dodecydimethylammonium bronides consumption half is added in oil phase
Ditallowdimethyl ammonium bromide (i.e. the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide of 2.5-4wt% of oil phase quality), will
The suspension and oil phase are added in reactor, and stirring is passed through inert gas to keep whole reaction system during the course of the reaction
In inert gas atmosphere, after being warming up to the initiation temperature of initiator, add initiator to trigger polymerization, obtain methyl
Acrylyl oxy-ethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-silica copolymer
(P(MMA-co-MEHDAB)/SiO2), the consumption of the initiator is two kinds of 1-1.5wt% of monomer mass sum；
Step 3, copolymer prepared by step 2 is filtered and washed, and copolymer powder is obtained after drying, is designated as
P(MMA-co-MEHDAB)/SiO2。
6. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 5
The preparation method of SiClx composite, it is characterised in that：The dispersant be basic magnesium carbonate, calcium hydroxy phosphate (HAP),
One kind in hydroxyethyl cellulose (HEC) or tricalcium phosphate, preferably hydroxyethyl cellulose (HEC)；The water phase and oil phase
Volume ratio be 3-5, preferably 4；The initiator be azodiisobutyronitrile (AIBN), ABVN (ABVN),
One kind in benzoyl peroxide (BPO) or the own ester (EHP) of peroxy dicarbonate two (2- ethyls), preferably benzoyl peroxide first
Acyl (BPO)；The inert gas is the one kind in nitrogen, helium or argon gas, preferably nitrogen.
7. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 5
The preparation method of SiClx composite, it is characterised in that：The particle diameter of the nano silicon is 20-30nm, and consumption is
7.5-8wt% of oil phase quality；The volume ratio of suspension polymerization system reclaimed water phase and oil phase is 1-5.
8. methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-polymethyl methacrylate-dioxy according to claim 5
The preparation method of SiClx composite, it is characterised in that：After 72-78 DEG C of initiation temperature for being heated to initiator, according to anti-
Time needed for answering how much selective polymerizations of thing to react, to ensure that two kinds of monomers realize conversion ratio higher in copolymerization, instead
It is 5-10 hours between seasonable.
9. the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide-poly-methyl methacrylate as described in Claims 1-4 is any
The application method of ester-silicon dioxide composite material, it is characterised in that：The copolymer powder hot pressing that the step 4 is obtained
Forming machine is hot-forming, and hot pressing condition is：Pressure 5-15MPa, 170-230 DEG C of temperature, time 10-30min；It is preferred that
For：Pressure 10MPa, 200 DEG C of temperature, time 15min.
10. application of the methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide in dispersed silicon dioxide, it is characterised in that：Long-chain sun
Ion monomer methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide surface carries positive charge, based on long chain cation monomer institute
In electrostatic adsorption and cationic monomer between the negative electrical charge that the positive charge and nano silicon of band ionize generation in water
Winding, parcel effect of the hexyl long alkyl chain to silica surface so that surface active monomer situ adds nanometer two
Silica, methylacryoyloxyethyl hexyl ditallowdimethyl ammonium bromide (MEHDAB) with positive charge as cationic monomer with
Methyl methacrylate carries out copolymerization so that polymeric matrix carries positive charge so that nano silicon is in polymer matrix
Interface binding power that is dispersed and strengthening nano silicon and polymeric matrix in body.
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