CN109422839A - Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material and preparation method - Google Patents

Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material and preparation method Download PDF

Info

Publication number
CN109422839A
CN109422839A CN201710763613.4A CN201710763613A CN109422839A CN 109422839 A CN109422839 A CN 109422839A CN 201710763613 A CN201710763613 A CN 201710763613A CN 109422839 A CN109422839 A CN 109422839A
Authority
CN
China
Prior art keywords
vdac
tio
emulsion
initiator
polystyrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710763613.4A
Other languages
Chinese (zh)
Other versions
CN109422839B (en
Inventor
郑俊萍
丁永
陈雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201710763613.4A priority Critical patent/CN109422839B/en
Publication of CN109422839A publication Critical patent/CN109422839A/en
Application granted granted Critical
Publication of CN109422839B publication Critical patent/CN109422839B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania materials and preparation method thereof, the following steps are included: step 1, using St and VDAC as comonomer, initiator is added, prepare pre-emulsion, wherein initiator and water form water phase, and VDAC, St are as oily phase；Step 2, using VDAC as dispersing agent, by nano-TiO2It is pre-dispersed in aqueous solution, to obtain TiO2Nanoparticle dispersion liquid adds VDAC and initiator, forms emulsion polymerization systems, wherein initiator, nano-TiO2Water phase is formed with water, VDAC, St are as oily phase；Step 3, emulsion polymerization systems are warming up to initiation temperature, and pre-emulsion is added dropwise into emulsion polymerization systems and stirs carry out emulsion polymerization, obtain P (St-co-VDAC)/TiO2Copolymer emulsion.In copolymer emulsion and copolymer microsphere powder, nano-titanium dioxide is nano-dispersion, and dispersity is uniformly and stable, solves the problems, such as the serious agglomeration of nanoparticle in polystyrene-composite titania material.

Description

Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-titanium dioxide is compound Material and preparation method
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of polystyrene (PS) composite material, especially Using PS as matrix, pass through cationic monomer vinylbenzyl dimethyl lauryl ammonium chloride (VDAC) and nano-titanium dioxide (TiO2) between generate electrostatic interaction and steric hindrance interaction, promote the dispersion of titanium dioxide, prepare PS base nanometer Composite material.
Background technique
Polymer based nanocomposites refer to that, using polymer as matrix, dispersed phase size is at least less than in one-dimensional direction The composite material of 100nm.Polymer based nanocomposites combine the advantages of polymer and nano material, realize performance On optimization it is complementary, have wide research and application prospect.However, since nano particle diameter is small, large specific surface area, surface Energy is big, surface action is strong, causes its easy to reunite, bad dispersibility.Nano particle surface modifying method reported at present is grasped mostly Make complexity, complex steps are made troubles to the preparation of polymer based nanocomposites.
Summary of the invention
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide a kind of polystyrene-ethylene bases Benzyldimethyldodecylammonium ammonium chloride-composite titania material and preparation method are used with polystyrene (PS) for substrate The method of emulsion polymerization prepares styryl nanocomposite, it is therefore an objective to use simple, efficient, environmental protection the method for one kind by TiO2 Nanoparticle is scattered in polymeric matrix, prepares high-dispersion nano composite material.The present invention synthesizes sun by quaternization reaction Ion monomer vinylbenzyl dimethyl lauryl ammonium chloride (VDAC).The cationic monomer can be used as dispersing agent, realize Nanoparticle is evenly dispersed in water phase and polymer phase, and can be used as polymerisable emulsifier, participates in emulsion polymerization process.One Aspect, cationic monomer is by electrostatic interaction and steric hindrance interaction dispersion and stablizes nanoparticle, the dispersion Journey carries out in water, easy to operate, and Nano grade can be realized without carrying out complicated interminable graft modification to nanoparticle Dispersion effect；On the other hand, cationic monomer can be reacted after polymerization, be avoided as polymerisable emulsifier in phase participation New ingredient is introduced into system, be can be obtained stable polymerizing microballoons lotion without demulsification after lotion reaction, is a kind of green The New-type emulsifier of environmental protection.This method can be used for preparing P (St-co-VDAC)/TiO of high dispersive2Nanocomposite.
The technical solution adopted to achieve the purpose of the present invention is:
Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material system of the invention Preparation Method, comprising the following steps:
Step 1, using St and VDAC as comonomer, initiator is added, prepares pre-emulsion, wherein initiator and water composition Water phase, VDAC, St are as oily phase；
Step 2, using VDAC as dispersing agent, by nano-TiO2It is pre-dispersed in aqueous solution, to obtain TiO2Nanoparticle dispersion Liquid adds St and initiator, forms emulsion polymerization systems, wherein initiator, nano-TiO2Water phase, VDAC, St are formed with water As oily phase；
Step 3, emulsion polymerization systems are warming up to initiation temperature, and pre-emulsion is added dropwise into emulsion polymerization systems and carries out Emulsion polymerization obtains P (St-co-VDAC)/TiO2Copolymer emulsion；Wherein:
The mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1 in step 1, and the dosage of St monomer is oily phase quality 90.0-99.9wt%, preferably 92-95wt%, the dosage of VDAC are the 0.1-10.0wt%, preferably 5- of oily phase quality 8wt%；Wherein the dosage of initiator is the 0.1-1.0wt%, preferably 0.2-0.5wt% of two kinds of monomer mass sums.
The mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1 in step 2, and the dosage of St monomer is oily phase quality 90.0-99.9wt%, the dosage of preferably 92-95wt%, VDAC are the 0.1-10.0wt%, preferably 5-8 of oily phase quality Wt%；Nano-titanium dioxide is the 0.1-5.0wt% of oily phase quality, and preferably 2-3wt%, the dosage of initiator is two kinds of monomers The 0.1-1.0wt% of quality sum, preferably 0.2-0.5wt%；
The mass ratio of St is (40-50): (50-60) in St and step 2 in step 1, in step 1 in VDAC and step 2 The mass ratio of VDAC is (40-50): (50-60)；
Wherein: St is styrene, and VDAC is vinylbenzyl dimethyl lauryl ammonium chloride, P (St-co-VDAC)/ TiO2For polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material.
Preferably, the St mass ratio in the step 1 and step 2 is 1:1, the VDAC mass in the step 1 and step 2 Than for 1:1, the time for adding of pre-emulsion is 1-1.5 hour in the step 3, and emulsion polymerisation time is 3-3.5 hours.
Preferably, P (the St-co-VDAC)/TiO step 3 obtained2Copolymer emulsion is filtered, washs and dries It is dry, obtain copolymer powder.
Preferably, in the step 1, first VDAC, initiator is dissolved in deionized water, add monomer styrene, Pre-emulsion is prepared, wherein VDAC and the mass volume ratio of deionized water are (8-12) g:1L, in the step 2, first by TiO2 Nanoparticle and cationic monomer VDAC are scattered in deionized water, with ultrasonic cell disruptor ultrasonic disperse, obtain ultrasound Dispersion liquid, wherein VDAC and the mass volume ratio of deionized water are (8-12) g:1L.
Preferably, VDAC and the mass volume ratio of deionized water are 10g:1L in the step 1 and step 2.
Preferably, the initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), benzoyl peroxide (BPO) or potassium peroxydisulfate (KPS).
Another aspect of the present invention further includes P (St-co-VDAC)/TiO that the preparation method obtains2Copolymer cream Liquid.
Preferably, P (the St-co-VDAC)/TiO2TiO in copolymer emulsion2Evenly dispersed, emulsification micellar particle size is 80-85nm, particle size distribution index 0.37-0.38, TiO2Average grain diameter is 4-6nm.
Another aspect of the present invention further includes P (St-co-VDAC)/TiO that the preparation method obtains2Copolymer powder End.
Preferably, P (the St-co-VDAC)/TiO2TiO in copolymer powder2It is evenly dispersed, TiO2Average grain diameter is 4- 6nm。
Another aspect of the present invention further includes VDAC evenly dispersed TiO in polystyrene based polymers2Nanoparticle Using.
Preferably, it using VDAC as comonomer and emulsifier, is copolymerized with styrene, while VDAC is as cation Monomer passes through electrostatic interaction and steric hindrance interaction dispersion and stabilized chlorine titanium nanoparticle.
Compared with prior art, the beneficial effects of the present invention are:
Technical solution of the present invention synthesis has the cationic monomer vinylbenzyl dimethyl ten of positive charge and long alkyl chain Dialkylammonium chloride realizes the evenly dispersed of nano-titanium dioxide first using cationic monomer as dispersing agent, then by sun from Sub- monomer realizes emulsion polymerization, after polymerisation the phase as emulsifier, cationic monomer with it is styrene copolymerized, obtain stable be total to Polymers multiple emulsion.The copolymer emulsion that technical solution of the present invention is prepared after emulsion polymerization meets the basic of antipollution coating It is required that the copolymer powder after dry substantially meets the requirement of photocatalysis film.In copolymer emulsion and copolymer microsphere powder In, nano-titanium dioxide is nano-dispersion, and dispersity is uniformly and stable, and it is compound to solve polystyrene-titanium dioxide The serious agglomeration problem of nanoparticle in material.
Detailed description of the invention
Fig. 1 show the nucleus magnetic hydrogen spectrum of cationic monomer VDAC.
Fig. 2 is dynamic light scattering (DLS) test chart that cationic monomer VDAC disperses TiO2 nanoparticle, and ordinate is water Close TiO 2 particles size (i.e. Hydrodynamic size of TiO2)。
Fig. 3 is polystyrene-composite titania material TEM photo.
Wherein: (a) P (St-SDS)/TiO2Lotion, (b) P (St-SDS)/TiO2Ultra-thin section.
(c)P(St-co-VDAC)/TiO2Lotion, (d) P (St-co-VDAC)/TiO2Ultra-thin section.
Specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.It should be appreciated that described herein Specific embodiment be only used to explain the present invention, be not intended to limit the present invention.
Raw material used in the present invention, equipment are as shown in the table:
1 primary raw material of table
2 key instrument equipment of table
The step of preparing VDAC:
26.22g Dodecyl Dimethyl Amine and 12.5g 4- chloromethylbenzene second are added in 100mL single necked round bottom flask Alkene adds appropriate ether and makees solvent, is stirred to react 72h under room temperature.Filtration product, with ether washed product until obtaining white Solid.It is dried in vacuo to obtain white powder product, i.e. cationic monomer VDAC.
For the structure of the cationic monomer VDAC of characterization synthesis, weighs about 15mg cationic monomer VDAC and be dissolved in deuterated chloroform (CDCl3) reagent, it is placed in sample preparation in nuclear magnetic tube, solvent liquid level is not less than 4cm, and benefit carries out nucleus magnetic hydrogen spectrum detection.Cationic monomer Nucleus magnetic hydrogen spectrum it is as shown in Figure 1.
1H-NMR(CDCl3): δ=5.38 (d, 1H), δ=5.84 (d, 1H), δ=6.70 (m, 1H), δ=7.59 (d, 1H), δ=7.46 (d, 1H), δ=5.01 (s, 2H), δ=3.30 (s, 1H), δ=3.45 (m, 2H), δ=1.70 (s, 2H), δ= 1.25 (m, 2H), δ=0.89 (t, 3H).It can be seen that the absorption of chemical shift δ 7.265 from the 1H-NMR nuclear magnetic spectrogram of VDAC Peak is CDCl3Internal standard peak；It is superolateral that the absorption peak of chemical shift δ 5.38 and δ 5.84 correspond to the C=C double bond on the left of phenyl ring Two hydrogen；It is hydrogen between C=C double bond and phenyl ring that the absorption peak of δ 6.70 is corresponding；Two absorption peaks of δ 7.59 and δ 7.46 Corresponding is two hydrogen of two positions on phenyl ring；It is between phenyl ring and nitrogen-atoms on methylene that the absorption peak of δ 5.01 is corresponding Two hydrogen；It is two hydrogen on the methylene being connected directly on chain alkyl with nitrogen-atoms that the absorption peak of δ 3.30 is corresponding；δ It is chain alkyl close to second of nitrogen-atoms side and four on third methylene that the absorption peak of 3.45 and δ 1.70 is corresponding A hydrogen；It is three hydrogen on chain alkyl tail end methyl that the absorption peak of δ 0.89 is corresponding.The peak area on nuclear-magnetism figure known to analysis It is directly proportional to the proton number in molecule, it was demonstrated that successfully synthesize target product VDAC and products pure.
Firstly, the VDAC for investigating various concentration disperses TiO2The effect of nanoparticle is surveyed with determining the optium concentration of VDAC For test result table as shown in table 1 and Fig. 2, experimental results reflect the increase with cationic monomer VDAC concentration, TiO2It receives The partial size of rice corpuscles and the variation of polydispersity.When nanoparticle is as filler, dispersion situation decides the property of composite material Can, it is even more important so just seeming to the research of the partial size of nanoparticle aggregate.The critical micelle concentration (cmc) of VDAC is 3.7mmol/L, i.e. 1.35g/L initially form micella when indicating that the concentration of VDAC in water is 1.35g/L.Cationic monomer exists It is positively charged in water, and TiO2Nanoparticle ionizes in water, and surface is negatively charged, passes through VDAC and TiO2Between nanoparticle Electrostatic interaction and VDAC chain alkyl steric hindrance interaction, make TiO2Nanoparticle is evenly dispersed.DLS test The results show that the TiO of VDAC is not added2Since skin effect keeps its surface action strong, agglomeration occurs, partial size is larger.It removes Except this, particle size distribution index (polydispersity index, PDI) can reflect the uniform degree of grain diameter, number Value is between 0 to 1, and the smaller monodispersity for indicating particle of numerical value is better, and particle diameter distribution is narrower, on the contrary then poorer.It is not added The TiO of VDAC2Particle size distribution index is larger, and monodispersity is poor, and grain diameter is inhomogenous.The addition of cationic monomer VDAC makes TiO2Nanoparticle better disperses in water, and partial size significantly reduces, and polydispersity is also decreased obviously.When the concentration of VDAC is When 10g/L, TiO2The partial size of nanoparticle reaches minimum value 61.7nm.Comprehensively consider amount, the grain of cationic monomer VDAC addition The factors such as diameter size and polydispersity are dispersion TiO when the final concentration for determining VDAC is 10g/L2Nanoparticle is most Good value.
1 cationic monomer VDAC of table disperses TiO2The DLS test result table of nanoparticle
Embodiment 1
(1) 0.5g VDAC is weighed, 0.057g initiator KPS is dissolved in 50mL deionized water, then weighs 10g monomer benzene Ethylene is added in 250mL four-hole boiling flask, is stirred pre-emulsification 2h with the revolving speed of 700rpm, pre-emulsion is obtained, by pre-emulsion It is added in constant pressure funnel stand-by；
(2) by 0.5g TiO2Nanoparticle and 0.5g cationic monomer VDAC are scattered in 50mL deionized water, are used JY92-II N-type ultrasonic cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound 30min under ice bath environment, obtains ultrasonic disperse liquid and is added in 250mL four-hole boiling flask；
(3) 10g styrene is added in the slave ultrasonic disperse liquid into 250mL four-hole boiling flask again, room temperature water-bath is emulsified 0.5 h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS, is dissolved in In a small amount of deionized water, it is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, after insulation reaction 0.5h, starts to four The pre-emulsion of a dropping step (1) preparation in mouthful flask, and the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started to warm up； Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, with the Buddhist nun of 300 mesh Imperial strainer filtering, and its pH value is adjusted to 7-8 with ammonium hydroxide, that is, polymer-based nano multiple emulsion is obtained, P (St-co- is denoted as VDAC)/TiO2。
(4)P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano combined Object powder； P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, temperature 190 DEG C, time 5min.
Embodiment 2
Preparation is using cationic monomer VDAC as the polystyrene of emulsifier-nano titania multiple emulsion: weighing 0.6g VDAC, 0.057g initiator KPS, are dissolved in 50mL deionized water, then weigh 10g monomer styrene, are added to 250mL tetra- In mouth flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel for use；Again will 0.5g TiO2Nanoparticle and 0.4g cationic monomer VDAC are scattered in 50mL deionized water, with JY92-II N-type ultrasonic wave Cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；10g styrene is weighed again, is added to 250mL four-hole boiling flask In, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, and heat preservation is anti- After answering 0.5h, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is dripped Finish, starts to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, It is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer-based nano multiple emulsion, be denoted as P(St-co-VDAC)/TiO2。P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, is received Rice composite powder；P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, time 5min.
Embodiment 3
Preparation is using cationic monomer VDAC as the polystyrene of emulsifier-nano titania multiple emulsion: weighing 0.4g VDAC, 0.057g initiator KPS, are dissolved in 50mL deionized water, then weigh 10g monomer styrene, are added to 250mL tetra- In mouth flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel for use；Again will 0.5g TiO2Nanoparticle and 0.6g cationic monomer VDAC are scattered in 50mL deionized water, with JY92-II N-type ultrasonic wave Cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；10g styrene is weighed again, is added to 250mL four-hole boiling flask In, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, and heat preservation is anti- After answering 0.5h, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is dripped Finish, starts to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, It is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer-based nano multiple emulsion, be denoted as P(St-co-VDAC)/TiO2。P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, is received Rice composite powder；P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, time 5min.
Embodiment 4
Preparation is using cationic monomer VDAC as the polystyrene of emulsifier-nano titania multiple emulsion: weighing 0.5g VDAC, 0.057g initiator KPS, are dissolved in 50mL deionized water, then weigh 5g monomer styrene, are added to tetra- mouthfuls of 250 mL In flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel for use；Again by 0.5g TiO2Nanoparticle and 0.5g cationic monomer VDAC are scattered in 50mL deionized water, with JY92-II N type supersonic cell Pulverizer ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound 30min under ice bath environment, Ultrasonic disperse liquid is added in 250mL four-hole boiling flask；15g styrene is weighed again, is added in 250mL four-hole boiling flask, room temperature Water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, insulation reaction 0.5h Afterwards, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is started Heating；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, with 300 mesh Nylon leaching net filtering, and its pH value is adjusted to 7-8 with ammonium hydroxide, i.e. acquisition polymer-based nano multiple emulsion, is denoted as P (St- co-VDAC)/TiO2。P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, and it is multiple to obtain nanometer Close object powder；P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, temperature 190 DEG C, time 5min.
Embodiment 5
Preparation is using cationic monomer VDAC as the polystyrene of emulsifier-nano titania multiple emulsion: weighing 0.5g VDAC, 0.057g initiator KPS, are dissolved in 50mL deionized water, then weigh 15g monomer styrene, are added to 250mL tetra- In mouth flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel for use；Again will 0.5g TiO2Nanoparticle and 0.5g cationic monomer VDAC are scattered in 50mL deionized water, with JY92-II N-type ultrasonic wave Cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；5g styrene is weighed again, is added in 250mL four-hole boiling flask, Room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, and heat preservation is anti- After answering 0.5h, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is dripped Finish, starts to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, It is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer-based nano multiple emulsion, be denoted as P(St-co-VDAC)/TiO2。P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, is received Rice composite powder；P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, time 5min.
Embodiment 6
Preparation is using cationic monomer VDAC as the polystyrene of emulsifier-nano titania multiple emulsion: weighing 0.5g VDAC, 0.057g initiator KPS, are dissolved in 50mL deionized water, then weigh 10g monomer styrene, are added to 250mL tetra- In mouth flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, pre-emulsion is added in constant pressure funnel for use；Again will 1.0g TiO2Nanoparticle and 0.5g cationic monomer VDAC are scattered in 50mL deionized water, with JY92-II N-type ultrasonic wave Cell disruptor ultrasonic disperse, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound under ice bath environment Ultrasonic disperse liquid is added in 250mL four-hole boiling flask by 30min；10g styrene is weighed again, is added to 250mL four-hole boiling flask In, room temperature water-bath pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, and heat preservation is anti- After answering 0.5h, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is dripped Finish, starts to warm up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, It is filtered with the nylon leaching net of 300 mesh, and its pH value is adjusted to 7-8 with ammonium hydroxide, is i.e. acquisition polymer-based nano multiple emulsion, be denoted as P(St-co-VDAC)/TiO2。P(St-co-VDAC)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, is received Rice composite powder；P(St-co-VDAC)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, time 5min.
Comparative example 1
Preparation is using traditional lauryl sodium sulfate SDS as the polystyrene of emulsifier-nano titania multiple emulsion: claiming 0.5 g SDS, 0.057g initiator KPS is taken, is dissolved in 50mL deionized water, then weigh 10g monomer styrene St, is added to In 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, by pre-emulsion be added in constant pressure funnel to With；Again by 0.5g TiO2Nanoparticle is scattered in 50mL deionized water, super with JY92-II N-type ultrasonic cell disruptor Sound dispersion, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound 30min under ice bath environment divide ultrasound Dispersion liquid is added in 250mL four-hole boiling flask；0.5g SDS and 10g styrene is weighed again, is added in 250mL four-hole boiling flask, often Tepidarium pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, insulation reaction 0.5h Afterwards, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is opened Begin to heat up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, with 300 The filtering of purpose nylon leaching net, and its pH value is adjusted to 7-8 with ammonium hydroxide, that is, polymer-based nano multiple emulsion is obtained, P (St- is denoted as SDS)/TiO2。P(St-SDS)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder； P(St-SDS)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time 5min。
Comparative example 2
Preparation is using traditional lauryl sodium sulfate SDS as the polystyrene of emulsifier-nano titania multiple emulsion: claiming 0.6 g SDS, 0.057g initiator KPS is taken, is dissolved in 50mL deionized water, then weigh 10g monomer styrene St, is added to In 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, by pre-emulsion be added in constant pressure funnel to With；Again by 0.5g TiO2Nanoparticle is scattered in 50mL deionized water, super with JY92-II N-type ultrasonic cell disruptor Sound dispersion, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound 30min under ice bath environment divide ultrasound Dispersion liquid is added in 250mL four-hole boiling flask；0.4g SDS and 10g styrene is weighed again, is added in 250mL four-hole boiling flask, often Tepidarium pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, insulation reaction 0.5h Afterwards, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is opened Begin to heat up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, with 300 The filtering of purpose nylon leaching net, and its pH value is adjusted to 7-8 with ammonium hydroxide, that is, polymer-based nano multiple emulsion is obtained, P (St- is denoted as SDS)/TiO2。P(St-SDS)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder； P(St-SDS)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time 5min。
Comparative example 3
Preparation is using traditional lauryl sodium sulfate SDS as the polystyrene of emulsifier-nano titania multiple emulsion: claiming 0.4 g SDS, 0.057g initiator KPS is taken, is dissolved in 50mL deionized water, then weigh 10g monomer styrene St, is added to In 250mL four-hole boiling flask, pre-emulsification 2h is stirred with the revolving speed of 700rpm, by pre-emulsion be added in constant pressure funnel to With；Again by 0.5g TiO2Nanoparticle is scattered in 50mL deionized water, super with JY92-II N-type ultrasonic cell disruptor Sound dispersion, setup parameter are as follows: power 600W, working time 3s, intermittent time 2s, ultrasound 30min under ice bath environment divide ultrasound Dispersion liquid is added in 250mL four-hole boiling flask；0.6g SDS and 10g styrene is weighed again, is added in 250mL four-hole boiling flask, often Tepidarium pre-emulsification 0.5h, setting mixing speed is 700rpm, after 0.5h, is started to warm up；Temperature reaches 70 DEG C, weighs 0.057g KPS is dissolved in a small amount of deionized water, is added in four-hole boiling flask, starts to warm up；Temperature reaches 75 DEG C, insulation reaction 0.5h Afterwards, start that above-mentioned stand-by pre-emulsion is added dropwise into four-hole boiling flask, and the reaction was continued 1h；After 1h, pre-emulsion is added dropwise, and is opened Begin to heat up；Temperature reaches 82 DEG C, insulation reaction 2h；After 2h, stops heating, do not stop stirring, be cooled to room temperature；Discharging, with 300 The filtering of purpose nylon leaching net, and its pH value is adjusted to 7-8 with ammonium hydroxide, that is, polymer-based nano multiple emulsion is obtained, P (St- is denoted as SDS)/TiO2。P(St-SDS)/TiO2Multiple emulsion is dried under vacuum to constant weight at 60 DEG C, obtains nano-complex powder； P(St-SDS)/TiO2Powder heat pressing forming machines are hot-forming.Hot pressing condition is: pressure 10MPa, 190 DEG C of temperature, the time 5min。
Pure PS lotion, the DLS test result of polymer-based nano multiple emulsion are as shown in table 2.Result can from table Out, compared with pure PS lotion, P (St-SDS)/TiO of nanoparticle is added2The partial size of lotion has a degree of increase, reason It is to answer polymer-based nano after the partial size that nanoparticle itself has ten a few nanometers to tens of nanometers, with polymer matrix bluk recombination The partial size for closing microballoon has to be increased by a small margin.Will use SDS be emulsifier synthesis polymer-based nano multiple emulsion partial size with The VDAC synthesized using this experiment is that the partial size of the polymer-based nano multiple emulsion of polymerisable emulsifier synthesis compares, can To find that the variation of microspherulite diameter in lotion slightly becomes larger.The experimental results showed that being closed in this experiment compared with conventional emulsifier SDS At novel polymerizable emulsifier VDAC can play good emulsifying effectiveness, and then it is multiple to prepare nanoscale polymer-based nano Lotion is closed, is a kind of emulsifier of function admirable.
The DLS test result table of 2 polymer-based nano multiple emulsion of table
To P (St-SDS)/TiO2、P(St-co-VDAC)/TiO2Transmission electron microscope analysis is carried out, as shown in figure 3, shining in TEM In piece, contrast is smaller and partial size it is biggish be PS, contrast is larger and partial size it is lesser be TiO2Nanoparticle.From TEM photo As can be seen that the use of SDS being polymer-based nano multiple emulsion prepared by emulsifier, TiO2Nanoparticle does not have and polymer matrix Body success is compound and obvious agglomeration occurs, aggregated particle size 200nm-250nm, and this serious reunion is very big The performance for affecting composite material of degree；It is P (the MMA-co-VDAC polymer matrix of polymerisable emulsifier preparation using VDAC Nano-composite emulsion, TiO2Nanoparticle and polymeric matrix success are compound, meanwhile, TiO2Nanoparticle is well dispersed, does not send out Raw agglomeration.Nano-titanium dioxide partial size is average up to 4-6nm.Due to the TiO of reunion2The quilt in high speed centrifugation operation mostly It removes, therefore can not observe TiO substantially in TEM photo2The biggish aggregate of nanoparticle, only only a few be not removed and When can be observed, thus can be explained using SDS as emulsifier in TEM photo, TiO2Nanoparticle and polymer matrix Bluk recombination is unsuccessful and agglomeration is serious；And using VDAC is the polymer-based nano multiple emulsion of polymerisable emulsifier preparation Particle is with the compound success of matrix and without nanoparticle agglomeration.After hot-forming, P (St-co-VDAC)/TiO2It is super The TEM of slice shows that the dispersity of titanium dioxide obtains good holding, well dispersed TiO2Partial size is average up to 4- 6nm。
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications Also it should be regarded as protection scope of the present invention.

Claims (10)

1. polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material preparation method, special Sign is, comprising the following steps:
Step 1, using St and VDAC as comonomer, initiator is added, prepares pre-emulsion, wherein initiator and water form water Phase, VDAC, St are as oily phase；
Step 2, using VDAC as dispersing agent, by nano-TiO2It is pre-dispersed in aqueous solution, to obtain TiO2Nanoparticle dispersion liquid, St and initiator are added, forms emulsion polymerization systems, wherein initiator, nano-TiO2Water phase, VDAC, St conduct are formed with water Oily phase；
Step 3, emulsion polymerization systems are warming up to initiation temperature, and into emulsion polymerization systems be added dropwise pre-emulsion and stir into Row emulsion polymerization obtains P (St-co-VDAC)/TiO2Copolymer emulsion；Wherein:
The mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1 in step 1, and the dosage of St monomer is oily phase quality 90.0-99.9wt%, preferably 92-95wt%, the dosage of VDAC are the 0.1-10.0wt%, preferably 5- of oily phase quality 8wt%；Wherein the dosage of initiator is the 0.1-1.0wt%, preferably 0.2-0.5wt% of two kinds of monomer mass sums；
The mass ratio of water phase and oily phase is (4-8): 1, preferably 5:1 in step 2, and the dosage of St monomer is oily phase quality 90.0-99.9wt%, the dosage of preferably 92-95wt%, VDAC are the 0.1-10.0wt%, preferably 5- of oily phase quality 8wt%；Nano-titanium dioxide is the 0.1-5.0wt% of oily phase quality, and preferably 2-3wt%, the dosage of initiator is two kinds of lists The 0.1-1.0wt% of weight sum, preferably 0.2-0.5wt%；
The mass ratio of St is (40-50): (50-60) in St and step 2 in step 1, VDAC in VDAC and step 2 in step 1 Mass ratio is (40-50): (50-60)；
Wherein: St is styrene, and VDAC is vinylbenzyl dimethyl lauryl ammonium chloride, P (St-co-VDAC)/TiO2For Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material.
2. polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-titanium dioxide composite wood as described in claim 1 The preparation method of material, which is characterized in that the St mass ratio in the step 1 and step 2 is 1:1, in the step 1 and step 2 VDAC mass ratio be 1:1, the time for adding of pre-emulsion is 1-1.5 hours in the step 3, emulsion polymerisation time 3- 3.5 hour.
3. polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-titanium dioxide composite wood as described in claim 1 The preparation method of material, which is characterized in that P (the St-co-VDAC)/TiO for obtaining the step 32Copolymer emulsion carried out Filter, washing and drying, obtain copolymer powder.
4. polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-titanium dioxide composite wood as described in claim 1 The preparation method of material, which is characterized in that in the step 1, first VDAC, initiator are dissolved in deionized water, add list Body styrene prepares pre-emulsion, and wherein VDAC and the mass volume ratio of deionized water are (8-12): 1, preferably 10:1, institute It states in step 2, first by TiO2Nanoparticle and cationic monomer VDAC are scattered in deionized water, use ultrasonic cell disruptor Ultrasonic disperse obtains ultrasonic disperse liquid, and wherein VDAC and the mass volume ratio of deionized water are (8-12): 1, preferably 10:1.
5. polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-titanium dioxide composite wood as described in claim 1 The preparation method of material, which is characterized in that the initiator be azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide or Potassium peroxydisulfate.
6. P (the St-co-VDAC)/TiO obtained such as any one of claim 1-5 preparation method2Copolymer emulsion.
7. P (St-co-VDAC)/TiO as claimed in claim 62Copolymer emulsion, it is characterised in that: the P (St-co- VDAC)/TiO2TiO in copolymer emulsion2Evenly dispersed, emulsification micellar particle size is 80-85nm, particle size distribution index 0.37- 0.38, TiO2Partial size average out to 4-6nm.
8. P (St-co-VDAC)/TiO that preparation method as claimed in claim 3 obtains2Copolymer powder, it is characterised in that: TiO2It is evenly dispersed, TiO2Partial size average out to 4-6nm.
9.VDAC evenly dispersed TiO in polystyrene based polymers2The application of nanoparticle.
10. VDAC as claimed in claim 9 evenly dispersed TiO in polystyrene based polymers2The application of nanoparticle, It is characterized in that, using VDAC as comonomer and emulsifier, is copolymerized with styrene, while VDAC is logical as cationic monomer Cross electrostatic interaction and steric hindrance interaction dispersion and stabilized chlorine titanium nanoparticle.
CN201710763613.4A 2017-08-30 2017-08-30 Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-titanium dioxide composite material and preparation method thereof Expired - Fee Related CN109422839B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710763613.4A CN109422839B (en) 2017-08-30 2017-08-30 Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-titanium dioxide composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710763613.4A CN109422839B (en) 2017-08-30 2017-08-30 Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-titanium dioxide composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109422839A true CN109422839A (en) 2019-03-05
CN109422839B CN109422839B (en) 2020-12-29

Family

ID=65502260

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710763613.4A Expired - Fee Related CN109422839B (en) 2017-08-30 2017-08-30 Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-titanium dioxide composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109422839B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860545A (en) * 1971-12-27 1975-01-14 Daniel F Herman Thermoplastic film forming composition containing titanium dioxide microvoids
EP1291370A1 (en) * 2001-08-29 2003-03-12 Pacific Corporation UV-scattering inorganic/polymer composite particles and a method for preparing the same
CN1834155A (en) * 2006-03-01 2006-09-20 武汉化工学院 Method of preparing 3-D ordered multiporous polymer with hole contg. nano photocatalyst
CN1891720A (en) * 2005-07-08 2007-01-10 中国科学院化学研究所 Polymer microsphere containing inorganic nano microparticles, and its preparing method and use
CN102414232A (en) * 2009-04-27 2012-04-11 巴斯夫欧洲公司 Organic-inorganic composite particles
CN106700372A (en) * 2015-11-17 2017-05-24 天津大学 Application of methacrylatoethyl dodecyl dimethyl ammonium bromide in disperse silicon dioxide as well as composite material and preparation method of composite material
CN106699955A (en) * 2015-11-17 2017-05-24 天津大学 Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860545A (en) * 1971-12-27 1975-01-14 Daniel F Herman Thermoplastic film forming composition containing titanium dioxide microvoids
EP1291370A1 (en) * 2001-08-29 2003-03-12 Pacific Corporation UV-scattering inorganic/polymer composite particles and a method for preparing the same
CN1891720A (en) * 2005-07-08 2007-01-10 中国科学院化学研究所 Polymer microsphere containing inorganic nano microparticles, and its preparing method and use
CN1834155A (en) * 2006-03-01 2006-09-20 武汉化工学院 Method of preparing 3-D ordered multiporous polymer with hole contg. nano photocatalyst
CN102414232A (en) * 2009-04-27 2012-04-11 巴斯夫欧洲公司 Organic-inorganic composite particles
CN106700372A (en) * 2015-11-17 2017-05-24 天津大学 Application of methacrylatoethyl dodecyl dimethyl ammonium bromide in disperse silicon dioxide as well as composite material and preparation method of composite material
CN106699955A (en) * 2015-11-17 2017-05-24 天津大学 Application for methacryloyloxyethylhexyldimethyl ammonium bromide in disperse silicon dioxide, composite material of methacryloyloxyethylhexyldimethyl ammonium bromide, and preparation method of composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
UGUR, SAZIYE等: "Study of Film Formation From PS Latex/TiO2 Nanocomposites; Effect of Latex Size and TiO2 Content", 《POLYMER COMPOSITES》 *
张方等: "二氧化钛纳米管稳定Pickering乳液制备PS/TiO2纳米管复合微球", 《化工学报》 *

Also Published As

Publication number Publication date
CN109422839B (en) 2020-12-29

Similar Documents

Publication Publication Date Title
Pham et al. Synthesis of polymeric janus nanoparticles and their application in surfactant-free emulsion polymerizations
JP2019070125A (en) Irregular shaped particle
CN105131309B (en) Nano combined latex particle dispersion liquid of lithium metasilicate magnesium of polymer/artificial synthesized and preparation method thereof
CN104910311A (en) Large-particle-size hollow polymer microsphere, and preparation method thereof
Crespy et al. Synthesis of polymer particles and nanocapsules stabilized with PEO/PPO containing polymerizable surfactants in miniemulsion
Eldin et al. Poly (acrylonitrile-co-methyl methacrylate) nanoparticles: I. Preparation and characterization
CN107417841A (en) A kind of method for preparing small particle functional polymer nano microballoon in high yield
CN104277171B (en) A kind of preparation method of nono calcium carbonate modified styrene-acrylic emulsion
CN109627370A (en) The preparation method of a kind of nitrogen-containing functional group polyalcohol stephanoporate microballoons
CN104194003A (en) Method for preparing black monodisperse polymer microspheres
EP3307792B1 (en) Method for producing vinyl acetate-ethylene copolymers by means of emulsion polymerization
CN103360529B (en) A kind of controllable synthesis method of micron-grade monodisperse polystyrene microspheres
CN104610686B (en) A kind of preparation method of strawberry type organo-mineral complexing particle
CN109422988A (en) Polymethyl methacrylate-vinylbenzyl dimethyl lauryl ammonium chloride-composite titania material and preparation method
Sarobe et al. Synthesis of core-shell type polystyrene monodisperse particles with chloromethyl groups
CN109422839A (en) Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-composite titania material and preparation method
CN104151463B (en) In a kind of miniemulsion, photoinduction active free radical polymerization prepares polymer and technique
CN106366263B (en) Linear block copolymers, dendritic nano-silver composite material and preparation method
EP3241542B1 (en) Co-emulsification composition containing various emulsification particle sizes and method for preparing same
CN109422841A (en) Polystyrene-ethylene base benzyldimethyldodecylammonium ammonium chloride-barium titanate composite material and preparation method
CN109422847A (en) Polymethyl methacrylate-maleic acid fatty alcohol ester sodium salt-aluminum oxide nanocomposite and preparation method thereof
Zhang et al. Preparation and properties of soapless poly (styrene–butyl acrylate–acrylic acid)/SiO 2 composite emulsion
CN109422989A (en) Polymethyl methacrylate-vinylbenzyl dimethyl lauryl ammonium chloride-barium titanate composite material and preparation method
EP2711378B1 (en) Saponification product of vinyl ester/ethylenic unsaturated carboxylic acid ester copolymer and method for producing same
CN109422840A (en) Polystyrene-maleic acid fatty alcohol ester sodium salt-aluminum oxide nanocomposite and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201229

Termination date: 20210830