CN106496604A - The preparation method of polymer Janus nanometer sheets PtBMA/PAM - Google Patents

The preparation method of polymer Janus nanometer sheets PtBMA/PAM Download PDF

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CN106496604A
CN106496604A CN201610915749.8A CN201610915749A CN106496604A CN 106496604 A CN106496604 A CN 106496604A CN 201610915749 A CN201610915749 A CN 201610915749A CN 106496604 A CN106496604 A CN 106496604A
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ptbma
snp
pam
nanometer sheets
preparation
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张国林
邱红芳
吴秋华
刘学
矣杰
宋溪明
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Liaoning University
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Liaoning University
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract

The present invention relates to the preparation method of polymer Janus nanometer sheets PtBMA/PAM.With SNP as template, its surface carry out amination modified and bromination modified SNP Br；With SNP Br as initiator, CuBr is catalyst, Me6TREN is part, and EGDMA is crosslinking agent, causes the polymerization of Tert-butyl Methacrylate, obtains SNP g PtBMA Br；Again with SNP g PtBMA Br as initiator, acrylamide is monomer, and pentamethyl-diethylenetriamine is part, and cuprous bromide is catalyst, by ATRP living polymerizations, obtains SNP g PtBMA b PAM.Finally performed etching with hydrofluoric acid, obtain polymer sacculus, then crushed with cell disruptor, obtain Janus nanometer sheets.Polymer Janus nanometer sheets obtained in of the invention, with good emulsifiability.

Description

The preparation method of polymer Janus nanometer sheets PtBMA/PAM
Technical field
The invention belongs to the field of chemical synthesis, more particularly to a kind of preparation of polymer Janus nanometer sheets PtBMA/PAM Method.
Background technology
Janus materials refer to material while having the anisotropic material of two kinds of different structures and chemical composition.This not Asymmetry on symmetric property, such as hydrophilic-hydrophobic, positive charge-negative electrical charge, polar-nonpolar and pattern etc., all gives Janus materials special features, can meet the needs under complicated environmental condition.
On the basis of Janus particles, people begin to focus on Janus flaky materials.Because relative to spheric granules Itself, anisotropic Janus flaky materials have the phase behavior for more enriching, for Janus flaky materials, not only chemical group Into being non-centrosymmetrical, its pattern is also non-centrosymmetrical.Compared with the inorganic Janus nanometer sheets of rigidity, flexible polymer Thing Janus nanometer sheets have the Assembling Behavior for more enriching, and have more preferable toughness, and are easier to make for functionalization.Existing The method for preparing Janus flaky materials is complicated, and condition is harsh, without universality.
Content of the invention
It is an object of the invention to provide a kind of method is simple, and mild condition, the polymer Janus nanometer sheets with universality The preparation method of PtBMA/PAM.
To achieve these goals, the technical solution used in the present invention is：Polymer Janus nanometer sheets PtBMA/PAM Preparation method, comprises the steps：
1) with Nano-meter SiO_22Microballoon is template, carries out amination modified on its surface, obtains SNP-NH2, recycle 2- bromos Isobutyl acylbromide and SNP-NH2Reaction, carries out bromination modification on its surface, obtains SNP-Br；
2) with SNP-Br as initiator, CuBr is catalyst, three (2- dimethylaminoethyls) amine (Me6TREN) it is part, GDMA (EGDMA) is crosslinking agent, and polymeric layer is crosslinked, and causes Tert-butyl Methacrylate (tBMA) it is polymerized, obtains SNP-g-PtBMA-Br；
3) with SNP-g-PtBMA-Br as initiator, acrylamide (AM) be monomer, pentamethyl-diethylenetriamine (PMDETA) it is part, cuprous bromide (CuBr) is catalyst, by ATRP living polymerizations, obtains SNP-g-PtBMA-b-PAM；
4) by SNP-g-PtBMA-b-PAM hf etchings, polymer sacculus is obtained；
5) under ice-water bath, crushed with cell disruptor, obtained target product.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, described step 1) comprise the steps：
1.1) ethanol in proper amount, ammoniacal liquor and deionized water is taken, is stirred, then dropwise instill tetraethyl orthosilicate (TEOS) Ethanol solution, under magnetic agitation 30-40 DEG C reaction 10-15 hours after, be centrifuged off supernatant liquor, wash, dry, received Rice SiO2Microballoon (SNPs)；
1.2) by the Nano-meter SiO_2 for obtaining2Microballoon is distributed in toluene, and ultrasonic disperse is uniform, adds three ethoxy of 3- aminopropyls Base silane, reacts 15-20 hours under 60-80 DEG C of magnetic agitation, reactant is centrifuged, removes supernatant liquor, collected solid, obtain Amination modified Nano-meter SiO_2 is carried out to surface2Microballoon (SNP-NH2)；
1.3) by SNP-NH2Ultrasonic disperse is in CH2Cl2In, appropriate Et is added under the conditions of ice-water bath3N and 2- bromos are different Butyryl bromide, magnetic agitation 20-30h under normal temperature, uses CH2Cl2Reactant is washed, is centrifuged, solid is dried, obtaining surface is carried out The modified Nano-meter SiO_2 of bromination2Microballoon SNP-Br.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, Nano-meter SiO_22Microballoon and three second of 3- aminopropyls The mass ratio of TMOS is 1.5:0.8-1.0, preferably 1.5:0.8.Per 1mg SNP-NH2Add 15-20ml 2- bromo isobutyls Acylbromide, preferably solid-to-liquid ratio are 1:15.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, the step 2) comprise the steps：Will SNP-Br ultrasonic disperses are transferred in polymerization pipe after DMF, add the appropriate monomer methacrylic acid tert-butyl ester (tBMA), are handed over Connection agent GDMA (EGDMA), part three (2- dimethylaminoethyls) amine (Me6TREN), it is well mixed, uses Liquid nitrogen frozen, vacuumizes, and melts；Circulating liquid nitrogen freezes, vacuumizes, melt three times after, add catalyst in nitrogen atmosphere CuBr, then carry out liquid nitrogen frozen, vacuumize, after thaw cycle, tube sealing under vacuum condition is little in 70-80 DEG C of reaction 12-18 When, terminating reaction after ingress of air, centrifugation, washing remove supernatant, solid are dried, SNP-g-PtBMA-Br is obtained.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, SNP-Br and Tert-butyl Methacrylate Mass ratio is 1:7-15, preferably 1:10.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, the step 3) comprise the steps：Will SNP-g-PtBMA-Br ultrasonic disperses are transferred in polymerization pipe after DMF, add appropriate monomeric acrylamide (AM), part Pentamethyl-diethylenetriamine (PMDETA), is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, circulating liquid nitrogen freezes, vacuumizes, After melting three times, add catalyst CuBr in nitrogen atmosphere, then carry out liquid nitrogen frozen, vacuumize, after thaw cycle, very Tube sealing under empty condition, reacts 12-18 hours, terminating reaction after ingress of air at 70-80 DEG C.Centrifugation, washing remove supernatant, Solid is dried, SNP-g-PtBMA-b-PAM is obtained.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, SNP-g-PtBMA-Br and acrylamide Mass ratio is 1:6-15, preferably 1:10.
The preparation method of above-mentioned polymer Janus nanometer sheets PtBMA/PAM, the step 4) in, the volume of hydrofluoric acid Percentage concentration is 10%-50%.
The target product prepared using the method for the present invention has polymer Janus nanometer sheets PtBMA/PAM, and side is thin Aqueous polymethyl tert-butyl acrylate, opposite side are hydrophilic acrylamide.
The invention has the beneficial effects as follows：The present invention, from the point of view of building-up process, with silica as template, through amino, bromination Modified two steps ATRP method is obtained polymer sacculus, through cell disruptor Ultrasonic Pulverization, obtains Janus nanometer sheets.Scanning Electronic Speculum and transmission electron microscope show that this method can obtain Janus hollow nanospheres and Janus nanometer sheets, illustrate the method Feasibility.This Janus nanometer sheets being made up of PtBMA/PAM, as side is hydrophobic, opposite side is hydrophilic, with good breast Change performance, have good application prospect in oil-water emulsion field.
Description of the drawings
Fig. 1 is (a) SNPs, (b) SNP-NH prepared by embodiment 12、(c)SNP-Br、(d)SNP-g-PtBMA-Br1、(e) The infrared spectrogram of SNP-g-PtBMA-b-PAM1.
Fig. 2 be embodiment 1 prepare (a) SNPs, (b) SNP-g-PtBMA-Br1, (c) SNP-g-PtBMA-b-PAM1 Thermal gravimetric analysis curve figure.
Fig. 3 be embodiment 1 prepare (a) SNPs, (b) SNP-g-PtBMA-Br1, (c) SNP-g-PtBMA-b-PAM1, (d) nanometer sacculus PtBMA/PAM 1, the scanning electron microscope (SEM) photograph of (e) polymer Janus nanometer sheets PtBMA/PAM1.
Fig. 4 be embodiment 1 prepare (a) SNPs, (b) SNP-g-PtBMA-Br1, (c) SNP-g-PtBMA-b-PAM1, (d) nanometer sacculus PtBMA/PAM 1, the transmission electron microscope picture of (e) polymer Janus nanometer sheets PtBMA/PAM1.
Fig. 5 is the microscope photograph of polymer Janus nanometer sheets PtBMA/PAM1 emulsification toluene prepared by embodiment 1 and water Piece.
Fig. 6 is the microphotograph that different proportion polymer Janus nanometer sheets emulsify toluene and water：(a)PtBMA/PAM1、 (b) PtBMA/PAM2 and (c) PtBMA/PAM3
Specific embodiment
The preparation of 1 polymer Janus nanometer sheets PtBMA/PAM1 of embodiment
(1) synthesis of SNP-Br
1st, Nano-meter SiO_22The preparation of microballoon (SNPs)
42.6g ethanol is weighed respectively, and 25% ammoniacal liquor of 25g, 9.75g water are put in 250mL round-bottomed flasks, stir. 7.7g TEOS and 30g ethanol is uniformly mixed, is placed in dropping funel, dropwise instilled in round-bottomed flask, magnetic agitation is lower 35 DEG C Reaction 12 hours.After reaction terminates, reactant mixture is centrifuged, removes supernatant, white solid ethanol with water volume ratio is 9:1 mixed solution is washed three times, obtains Nano-meter SiO_22Microballoon (SNPs).It is standby that product is put into vacuum drying chamber.Synthetic route is such as Shown in lower：
2nd, Nano-meter SiO_22Microballoon (SNPs) surface amino groups modification (SNP-NH2)：
1.5g SNPs are added in 50mL dry toluenes, and ultrasound is until dispersion is complete.Take three ethoxy of 0.8g 3- aminopropyls Base silane (APTES) is added in the mixed solution of SNPs and toluene, and 60 DEG C of magnetic agitations are reacted 18 hours.After the completion of reaction, Supernatant liquor is centrifuged off, then solid is disperseed with toluene, then be centrifuged, repeated this operation three times, obtain SNP-NH2.By product It is put into vacuum drying chamber standby.Synthetic route is as follows：
3rd, Nano-meter SiO_22Microballoon (SNPs) surface bromination modification (SNP-Br)
Weigh the SNP-NH of 0.1g2The CH that ultrasonic disperse is dried in 40mL2Cl2In, add under the conditions of ice-water bath 6mLEt3The 2- bromo isobutyl acylbromides of N and 1.5mL, magnetic agitation reaction 24h under normal temperature.Use CH2Cl2By reactant washing centrifugation For several times, solid is dried, you can obtain intermediate (SNP-Br).Synthetic route is as follows：
(2) synthesis of SNP-g-PtBMA-Br1
By the SNP-Br ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds 1.0g tBMA, 0.15g EGDMA, the Me of 36 μ L6TREN, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen is freezed-taken out very Empty-melt three times after, add catalyst 30mg CuBr in nitrogen atmosphere, then carry out liquid nitrogen frozen-vacuumize-melt After circulation, tube sealing under vacuum condition.React 15 hours at 73 DEG C.Terminating reaction after ingress of air.Centrifuge washing, removes supernatant Liquid, solid is dried, that is, obtain SNP-g-PtBMA-Br1.Synthetic route is as follows：
(3) synthesis of SNP-g-PtBMA-b-PAM1
By the SNP-g-PtBMA-Br1 ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds The PMDETA of 1.0g AM, 48mg, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen freezes-vacuumizes-melts After three times, catalyst 30mg CuBr are added in nitrogen atmosphere, then after carrying out liquid nitrogen frozen-vacuumize-thaw cycle, Tube sealing under vacuum condition.React 24 hours at 70 DEG C.Terminating reaction after ingress of air.Centrifuge washing, removes supernatant, by solid Dry, that is, obtain SNP-g-PtBMA-b-PAM1.Synthetic route is as follows：
(4) synthesis of nanometer sacculus PtBMA/PAM 1
0.1g SNP-g-PtBMA-b-PAM1 are weighed in 100mL centrifuge tubes, ultrasound to being thoroughly dispersed in ultra-pure water, Appropriate 40%HF is added, is etched 24 hours at room temperature.Reactant mixture is centrifuged, removes supernatant, solid is again with anhydrous Ethanol is washed three times, obtains a nanometer sacculus PtBMA/PAM 1.Synthetic route is as follows：
(5) synthesis of polymer Janus nanometer sheets PtBMA/PAM1
Nanometer sacculus PtBMA/PAM 1 is disperseed in ethanol, ultrasonic mixing is uniform.Cell disruptor powder is used under frozen water Broken for several times, obtain polymer Janus nanometer sheets PtBMA/PAM1.
(6) testing result
Fig. 1 is (a) SNPs, (b) SNP-NH2、(c)SNP-Br、(d)SNP-g-PtBMA-Br1、(e)SNP-g-PtBMA- The infrared spectrogram of b-PAM1.Wherein (a) is SiO2The infrared spectrum of nano-particle, 1100cm-1And 800cm-1Place belongs to Si- The antisymmetric stretching vibration of O-Si keys and symmetrical stretching vibration, 471cm-1Place belongs to the flexural vibrations of Si-O-Si keys, and above three Characteristic absorption peak of place's absworption peak for Nano particles of silicon dioxide.B) be amino modified and hydroxyl modification after SiO2Nano-particle Infrared spectrum, 3000-2800cm-1Locate primary amine characteristic peak from scratch, successfully modification SiO is described2Nano-particle.(c)、(d)、 E () is in 1730cm-1Place is absorbed as carbonyl absorption on 2- bromine isobutyl acylbromides and PtBMA and PAM chains, shows to react successfully using ATRP Cause the polymerization of tBMA and AM, obtain SNP-g-PtBMA-b-PAM1 polymer.
Fig. 2 is the thermal gravimetric analysis curve of (a) SNPs, (b) SNP-g-PtBMA-Br1 and (c) SNP-g-PtBMA-b-PAM1 Figure.Curve (a) is SiO2The thermogravimetric curve of nano-particle (SNPs), when temperature rises to 800 DEG C from room temperature, which loses weight For 16.72%, the dehydration of the predominantly water of silicon ball surface absorption.Curve (b) is that cross-linked polymer coats SNP-Br nano-particles (SNP-g-PtBMA-Br1) thermogravimetric curve, relative to the weight that curve (a) loses 16.53% more, shows tBMA successfully It is grafted to SiO2Nanoparticle surface.Curve (c) is the SiO of two layers of polymers cladding2Nano-particle (SNP-g-PtBMA-b- PAM1 thermogravimetric curve), relative to the weight that curve (b) loses 19.14% more, shows the SNP-g- for successfully synthesizing PtBMA-b-PAM1 polymer.
Fig. 3 be (a) SNPs, (b) SNP-g-PtBMA-Br1, (c) SNP-g-PtBMA-b-PAM1, (d) nanometer sacculus PtBMA/PAM 1, (e) scanning electron microscope (SEM) photograph of polymer Janus nanometer sheets PtBMA/PAM1.As seen from the figure, (a) be SiO2 Nano-particle, passes throughThe Nano particles of silicon dioxide size of method synthesis is homogeneous, smooth surface.B () is the PtBMA of crosslinking The SiO of grafting2Nano-particle (SNP-g-PtBMA-Br1), can significantly be found out by (b), silicon ball surface becomes coarse, shows PtBMA is successfully grafted to its surface.C () is the SiO of two layers of polymers cladding2Nano-particle (SNP-g-PtBMA-b-PAM1), Silicon ball surface is more coarse, and than more uniform, shows two layers of polymers has been grafted to silicon successfully by the reaction of two steps ATRP On ball.(d) be SNP-g-PtBMA-b-PAM1 after hf etching, the nanometer sacculus PtBMA/PAM 1 that obtains can see After going out through hf etching, the hollow ball partial collapse of formation has certain thickness, still assumes hollow cavity body structure.E) it is Through polymer Janus nanometer sheets PtBMA/PAM1 of low temperature ultrasonic cell pulverization, it can be seen that most sacculus has been crushed, Become Janus nanometer sheets.
Fig. 4 be (a) SNPs, (b) SNP-g-PtBMA-Br1, (c) SNP-g-PtBMA-b-PAM1, (d) nanometer sacculus PtBMA/PAM 1, (e) transmission electron microscope picture of polymer Janus nanometer sheets PtBMA/PAM1.A () is SiO2Nano-particle, size Homogeneous, the smooth of the edge, (b) be crosslinking PtBMA grafting SiO2Nano-particle (SNP-g-PtBMA-Br1), can be with bright by (b) Aobvious finds out, silicon ball surface becomes coarse, shows that PtBMA is successfully grafted to its surface.C () is the SiO of two layers of polymers cladding2 Nano-particle (SNP-g-PtBMA-b-PAM1), silicon ball surface is more coarse, and than more uniform, shows to react by two steps ATRP Successfully two layers of polymers has been grafted in silicon ball.(d) be SNP-g-PtBMA-b-PAM1 after hf etching, obtain Nanometer sacculus PtBMA/PAM1, it can be seen that after through hf etching, the hollow ball partial collapse of formation has certain thickness Degree, still assumes hollow cavity body structure.E) it is polymer Janus nanometer sheets PtBMA/PAM1 through low temperature ultrasonic cell pulverization, It can be seen that most sacculus has been crushed, become Janus nanometer sheets.
Fig. 5 is the microphotograph that polymer Janus nanometer sheets PtBMA/PAM1 emulsify toluene and water.Can be seen by Fig. 5 Go out, toluene and water blend together a phase.Microscopy has uniform drop to occur, and the polymer Janus nanometer sheets for synthesizing are described PtBMA/PAM1 can be good at stable emulsion interface.Demonstrating Janus nanometer sheets can be fine as Solid particle emulsifying agents Stable emulsion interface.
The preparation of 2 polymer Janus nanometer sheets PtBMA/PAM2 of embodiment
(1) synthesis of SNP-Br：With embodiment 1
(2) synthesis of SNP-g-PtBMA-Br2
By the SNP-Br ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds 0.75g tBMA, 0.15g EGDMA, the Me of 36 μ L6TREN, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen is freezed-taken out very Empty-melt three times after, add catalyst 30mg CuBr in nitrogen atmosphere, then carry out liquid nitrogen frozen-vacuumize-melt After circulation, tube sealing under vacuum condition.React 12 hours at 73 DEG C.Terminating reaction after ingress of air.Centrifuge washing, removes supernatant Liquid, solid is dried, that is, obtain SNP-g-PtBMA-Br2.
(3) synthesis of SNP-g-PtBMA-b-PAM2
By the SNP-g-PtBMA-Br2 ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds The PMDETA of 0.6g AM, 24mg, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen freezes-vacuumizes-melts After three times, catalyst 15mg CuBr are added in nitrogen atmosphere, then after carrying out liquid nitrogen frozen-vacuumize-thaw cycle, Tube sealing under vacuum condition.React 24 hours at 70 DEG C.Terminating reaction after ingress of air.Centrifuge washing, removes supernatant, by solid Dry, that is, obtain SNP-g-PtBMA-b-PAM2.
(4) synthesis of nanometer sacculus PtBMA/PAM 2：With embodiment 1
(5) synthesis of polymer Janus nanometer sheets PtBMA/PAM2：With embodiment 1
The preparation of 3 polymer Janus nanometer sheets PtBMA/PAM3 of embodiment
(1) synthesis of SNP-Br：With embodiment 1
(2) synthesis of SNP-g-PtBMA-Br3
By the SNP-Br ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds 1.5g tBMA, 0.12g EGDMA, the Me of 36 μ L6TREN, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen is freezed-taken out very Empty-melt three times after, add catalyst 30mg CuBr in nitrogen atmosphere, then carry out liquid nitrogen frozen-vacuumize-melt After circulation, tube sealing under vacuum condition.React 24 hours at 73 DEG C.Terminating reaction after ingress of air.Centrifuge washing, removes supernatant Liquid, solid is dried, that is, obtain SNP-g-PtBMA-Br3.
(3) synthesis of SNP-g-PtBMA-b-PAM3
By the SNP-g-PtBMA3 ultrasonic disperses of 0.1g after the DMF that 8mL is dried, it is transferred in polymerization pipe, adds 1.5g The PMDETA of AM, 48mg, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen freezes-vacuumizes-melt three times Afterwards, catalyst 30mg CuBr are added in nitrogen atmosphere, then after carrying out liquid nitrogen frozen-vacuumize-thaw cycle, vacuum Under the conditions of tube sealing.React 24 hours at 70 DEG C.Terminating reaction after ingress of air.Centrifuge washing, supernatant of going out, solid is dried SNP-g-PtBMA-b-PAM3 is obtained.
(4) synthesis of nanometer sacculus PtBMA/PAM 3：With embodiment 1
(5) synthesis of polymer Janus nanometer sheets PtBMA/PAM3：With embodiment 1.
The emulsifiability of 4 different proportion polymer Janus nanometer sheets PtBMA/PAM of embodiment
Different proportion polymer Janus nanometer sheets PtBMA/PAM1, PtBMA/PAM2 and PtBMA/PAM3 are emulsified The contrast experiment of performance.
Method：Weigh 10mg difference polymer Janus nanometer sheets PtBMA/PAM respectively, be put into by 1mL toluene and 1mL first In the mixed liquor of the aqueous solution composition of base orange dyeing, fully shaking obtains emulsion.Examine under a microscope different polymer Janus Emulsifying effectiveness of nanometer sheet PtBMA/PAM to toluene-aqueous solution.
As a result as shown in fig. 6, as seen from Figure 6, the emulsifying effectiveness of polymer Janus nanometer sheets PtBMA/PAM2 is remote not Such as polymer Janus nanometer sheets PtBMA/PAM1 and PtBMA/PAM3.Reason is possibly due to the Janus nanometer sheets two ends to be formed Hydrophilic, oleophilic layer is fewer, and emulsifying capacity is poorer, and emulsifying effectiveness is got over unobvious.

Claims (10)

1. the preparation method of polymer Janus nanometer sheets PtBMA/PAM, it is characterised in that comprise the steps：
1) with Nano-meter SiO_22Microballoon is template, carries out amination modified on its surface, obtains SNP-NH2, recycle 2- bromo isobutyls Acylbromide and SNP-NH2Reaction, carries out bromination modification on its surface, obtains SNP-Br；
2) with SNP-Br as initiator, CuBr is catalyst, and three (2- dimethylaminoethyls) amine is part, dimethacrylate second Diol ester is crosslinking agent, and polymeric layer is crosslinked, and causes Tert-butyl Methacrylate polymerization, obtains SNP-g-PtBMA- Br；
3) with SNP-g-PtBMA-Br as initiator, acrylamide is monomer, and pentamethyl-diethylenetriamine is part, cuprous bromide For catalyst, by ATRP living polymerizations, SNP-g-PtBMA-b-PAM is obtained；
4) by SNP-g-PtBMA-b-PAM hf etchings, polymer sacculus is obtained；
5) under ice-water bath, crushed with cell disruptor, obtained target product.
2. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 1, it is characterised in that：Described The step of 1) comprise the steps:
1.1) ethanol in proper amount, ammoniacal liquor and deionized water is taken, is stirred, the ethanol for then dropwise instilling tetraethyl orthosilicate is molten Liquid, under magnetic agitation after 30-40 DEG C of reaction 10-15 hour, is centrifuged off supernatant liquor, washs, dry, obtain Nano-meter SiO_22Micro- Ball；
1.2) by the Nano-meter SiO_2 for obtaining2Microballoon is distributed in toluene, and ultrasonic disperse is uniform, adds 3- aminopropyl-triethoxy silicon Alkane, reacts 15-20 hours under 60-80 DEG C of magnetic agitation, reactant is centrifuged, removes supernatant liquor, collected solid, obtain table Face carries out amination modified Nano-meter SiO_22Microballoon SNP-NH2；
1.3) by SNP-NH2Ultrasonic disperse is in CH2Cl2In, appropriate Et is added under the conditions of ice-water bath3N and 2- bromo isobutyryls Bromine, magnetic agitation 20-30h under normal temperature, uses CH2Cl2Reactant is washed, is centrifuged, solid is dried, obtaining surface carries out bromination Modified Nano-meter SiO_22Microballoon SNP-Br.
3. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 2, it is characterised in that：Nanometer SiO2Microballoon is 1.5 with the mass ratio of 3- aminopropyl triethoxysilanes:0.8-1.0；Per 1mg SNP-NH2Add 15-20ml2- Bromo isobutyl acylbromide.
4. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 1, it is characterised in that：Described Step 2) comprise the steps：By SNP-Br ultrasonic disperses after DMF, it is transferred in polymerization pipe, adds appropriate monomer methyl Tert-butyl acrylate, crosslinking agent GDMA, part three (2- dimethylaminoethyls) amine are well mixed, and use Liquid nitrogen frozen, vacuumizes, and melts；Circulating liquid nitrogen freezes, vacuumizes, melt three times after, add catalyst in nitrogen atmosphere CuBr, then carry out liquid nitrogen frozen, vacuumize, after thaw cycle, tube sealing under vacuum condition is little in 70-80 DEG C of reaction 12-18 When, terminating reaction after ingress of air, centrifugation, washing remove supernatant, solid are dried, SNP-g-PtBMA-Br is obtained.
5. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 4, it is characterised in that：SNP- Br is 1 with the mass ratio of Tert-butyl Methacrylate:7-15.
6. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 1, it is characterised in that：Described Step 3) comprise the steps：By SNP-g-PtBMA-Br ultrasonic disperses after DMF, it is transferred in polymerization pipe, adds appropriate Monomeric acrylamide, part pentamethyl-diethylenetriamine, is well mixed, and with liquid nitrogen frozen, vacuumizes, and melts, and circulating liquid nitrogen is cold After freezing, vacuumize, melting three times, catalyst CuBr is added in nitrogen atmosphere, then carry out liquid nitrogen frozen, vacuumize, melt After changing circulation, tube sealing under vacuum condition reacts 12-18 hours at 70-80 DEG C, and terminating reaction after ingress of air, centrifugation are washed, Supernatant is removed, solid is dried, SNP-g-PtBMA-b-PAM is obtained.
7. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 6, it is characterised in that：SNP- G-PtBMA-Br is 1 with the mass ratio of acrylamide:6-15.
8. according to the preparation method of polymer Janus nanometer sheets PtBMA/PAM described in claim 1, it is characterised in that：Described Step 4) in, the concentration expressed in percentage by volume of hydrofluoric acid is 10%-50%.
9., according to the preparation method of arbitrary described polymer Janus nanometer sheets PtBMA/PAM of claim 1-8, its feature exists In：Target product polymer Janus nanometer sheets PtBMA/PAM of preparation are flaky nanometer structure, and side has hydrophobic poly- Methacrylic acid tertiary butyl ester, opposite side have hydrophilic polyacrylamide.
10. polymer Janus nanometer sheets PtBMA/PAM according to the arbitrary described method preparation of claim 1-8 are in profit breast Application in change field.
CN201610915749.8A 2016-10-20 2016-10-20 The preparation method of polymer Janus nanometer sheets PtBMA/PAM Pending CN106496604A (en)

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