CN104448333A - Preparation method and product of dual-sensitive polymer hybrid nanoparticle - Google Patents
Preparation method and product of dual-sensitive polymer hybrid nanoparticle Download PDFInfo
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Abstract
The invention provides a preparation method of a dual-sensitive polymer hybrid nanoparticle. The preparation method comprises the following steps: dispersing a silicon nanoparticle and toluene diisocyanate in anhydrous toluene and putting under an ultrasonic bath for 10-15min, degassing the mixture at 95 DEG C and preserving the temperature at a constant temperature for 6h, and centrifuging to obtain a toluene diisocyanate functionalized silicon nanoparticle; dissolving the prepared toluene diisocyanate functionalized silicon nanoparticle, mercapto poly N-isopropylacrylamide (PNIPAAm-SH), mercapto poly (N,N'-diethylaminoethyl methacrylate) (PDEAEMA-SH) and trimethylamine in anhydrous toluene and carrying out circulating degassing under neon atmosphere via freezing-pumping-unfreezing; and precipitating and separating the product into n-hexane, washing by methanol and acetone, carrying out centrifugation and finally putting the product in vacuum to dry overnight so as to obtain a final product. The obtained nanometer silicon hybrid particle has favorable environment sensitivity and outstanding application property in biological medicine and chromatography matrix. The preparation method has the advantages of simple and easy process, environmental friendliness, low energy consumption and high target product grafting ratio.
Description
Technical field
The invention belongs to field of polymer composite material, relate to but be not limited to functionalized nano-silicon hybrid material of temperature-and pH-sensitivity and preparation method thereof.
Background technology
Environment sensitive material: environment sensitive material is also called intelligent material, agility material or stimuli responsive shaped material.The development of society and the raising of people's quality of life and level, show more urgent demand to novel material and it is also proposed higher requirement.Flourish along with Materials science, now various hi tech and new material be emerge in an endless stream with rapid changepl. never-ending changes and improvements.Wherein environment sensitive macromolecular material is because of its good environmental sensitivity and sensing susceptibility, and the advantages such as human body affinity, are seized of special and important one seat all the time in the R&D work of novel material.Environment sensitive material is that organic materials itself has the biological Premium Features given by the method for molecular designing and organic synthesis.The organism of environment sensitive good auxiliary to be combined with the silicon nano of using value with having in field of polymer technology, the environment sensitive macromolecular material with ecotopia sensitivity characteristic can be designed.Field involved by environment sensitive material ten/wide.The rich first-class of Tanaka of Massachusetts Institute of Technology in 1975 finds, when cooling polyacrylamide gel, gel can gradually become opaque by transparent, and under temperature impact, this kind of phenomenon reversible again.Polyacrylamide is placed in boiling solvent by further, finds that the subtle change of temperature and concentration can make gel that larger size deformation occurs.They find and open new research field thus.After this research of environment sensitive material is obtained to the concern of certain degree.Nowadays environmental sensitivity gel has obtained practical application to a certain degree.
Polymeric material field achievement in research is combined with environment sensitive investigation of materials achievement, an open Application Areas with tremendous potential.Using organic or inorganic high molecular polymer as environment sensitive factor vectors, in conjunction with each material and technology premium properties.But the preparation method of general temperature-and pH-sensitivity silicon hybridization nanoparticle for now, it is in cost of manufacture, and on process cycle and institute's product yield, one or more aspects have defect.The present invention: the method for doubling sensitivity hybridized nanometer particle is prepared in the reaction of a kind of single stage method click chemistry, solves current temperature-and pH-sensitivity silicon hybridization nanoparticle and prepares the poor problem with instability of brought product property.In addition, this method is one-step preppn process, has the simple and easy and less energy-consumption of technique, Green Chemistry and eco-friendly advantage.Prepared product, percentage of grafting is high, and the high and product performance of productive rate are stablized and had good temperature and pH environmental sensitivity.
Summary of the invention
The object of the present invention is to provide and a kind ofly solve the loaded down with trivial details simple and easy one-step preppn process of temperature-and pH-sensitivity silicon hybridization nanoparticle preparation technology, and the product performance of improvement related products and improve productive rate.The present invention has the simple and easy and environmental friendliness of technique and the low advantage that consumes energy.Prepared product, all has gratifying lifting in productive rate or product performance.Its application prospect is extensive, has outstanding application potential especially in the fields such as sensor, biological medicine and chromatography matrix.
For achieving the above object, the technical solution adopted in the present invention is: a kind of preparation method of doubling sensitivity polymer hybrid nanoparticle, comprises the following steps:
(1) silicon nano and tolylene diisocyanate are distributed in dry toluene, and are placed on 10-15 min in ultra sonic bath, gained mixture is placed in 95 DEG C of magnetics and stirs degassed and constant temperature is incubated 6 h, obtained reaction product A;
(2) by product A centrifugation, with the toluene cleaning unreacted of drying and the tolylene diisocyanate of physical adsorption, obtain product B, by product B vacuum-drying, obtain the silicon nano (SiO that tolylene diisocyanate is functionalized
2-NCO);
(3) sulfhydrylation poly N-isopropyl acrylamide (PNIPAAm-SH) and sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) (PDEAEMA-SH) is synthesized respectively.
(4) step (2) is obtained the functionalized silicon nano (SiO of tolylene diisocyanate
2-NCO) be dissolved in dry toluene with the sulfhydrylation poly N-isopropyl acrylamide of step (3) gained and sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) together with triethylamine, obtain mixture C;
(5) mixture C is after degassed precipitation and centrifugal separation, in a vacuum dried overnight, the obtained silicon hybridization nanoparticle with temperature-and pH-sensitivity.
In step (3), the method for described synthesis sulfhydrylation poly N-isopropyl acrylamide (PNIPAAm-SH) is:
A () uses Grignard reagent legal system for dithio benzyl benzoate, bromobenzene Grignard reagent is first prepared in the examination of bromobenzene grignard, then bromobenzene Grignard reagent and dithiocarbonic anhydride, benzyl bromine reaction obtains dithio benzyl benzoate (BDTB), and namely separating-purifying obtains pure product dithio benzyl benzoate (BDTB);
B () is by NIPA (NIPAAm), dithio benzyl benzoate (BDTB) and 2,2'-azo two (isopropyl cyanide) (AIBN) is dissolved in tetrahydrofuran (THF), mixture D is obtained with degassed 30 min of neon, with degassed 30 min of neon, products therefrom is reacted 24 h at 70 DEG C of temperature, obtains poly N-isopropyl acrylamide (PNIPAAm);
C gained poly N-isopropyl acrylamide in step (b) is dissolved in methanol solution by (), and add sodium borohydride wherein, gained mixture reacts 48 h under room temperature in neon atmosphere, after dialysis washed with de-ionized water, cooling drying obtains sulfhydrylation poly N-isopropyl acrylamide (PNIPAAm-SH).
In step (3), the method for described synthesis sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) (PDEAEMA-SH) is:
A () uses Grignard reagent legal system for dithio benzyl benzoate, bromobenzene Grignard reagent is first prepared in the examination of bromobenzene grignard, then bromobenzene Grignard reagent and dithiocarbonic anhydride, benzyl bromine reaction obtains dithio benzyl benzoate (BDTB), and namely separating-purifying obtains pure product dithio benzyl benzoate;
B () is by N, N'-diethylamide ethylmethyl acrylate (DEAEMA), dithio benzyl benzoate (BDTB) and 2,2'-azo two (isopropyl cyanide) (AIBN) is dissolved in tetrahydrofuran (THF), after degassed with neon, mixture is polymerized 24 h under 70 DEG C of degree, obtains poly-(N, N'-diethylamide ethylmethyl acrylate) (PDEAEMA)
C obtained poly-(N, N'-diethylamide ethylmethyl acrylate) (PDEAEMA) is carried out drying under reduced pressure with after dialysis methyl alcohol and normal hexane purification by (), be dissolved in methanol solution and also add sodium borohydride wherein;
D gained mixing solutions in (c) is reacted 48 h by () in neon atmosphere under room temperature, through the purification of dialysis normal hexane, can collect sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) (PDEAEMA-SH) under vacuum after drying.
As optimization, in step (1), gained mixture is that magnetic agitation is degassed, and its constant temperature soaking time is 6 h temperature is 95 DEG C;
As optimization, in step (2), vacuum-drying temperature 80 DEG C, time 24 h.
As optimization, in step (4), mixture C carries out freezing for three times under neon atmosphere-and pump-thaw cycles is degassed, and at room temperature stir 24 h subsequently.
As optimization, in step (5), product centrifugation speed is 14000 rpm, and the centrifugal time length is 10-15 min.
The present invention also provides a kind of doubling sensitivity polymer hybrid nanoparticle obtained as aforesaid method, and it has good temperature and the dual environmental sensitivity of pH.
The present invention is with single stage method click-reaction preparation temperature and pH doubling sensitivity silicon hybridization nanoparticle.Reacted by the click chemistry between the sulfydryl of PNIPAAm-SH or PDEAEMA-SH cardinal extremity and cyanate ester based (-the NCO) of the functionalized silicon Nanosurface of tolylene diisocyanate, the high molecule nano material that obtained environmental sensitivity is good.A kind of " click chemistry reaction " without metal superlattice, as the click chemistry between sulfydryl isocyanic ester and mercaptan-alkene reacts, can make inorganic nano-particle that polymer is functionalized, thus the obtained hybrid particle with ideal performance.Obtained hybrid particle, in preparation method, the reagent of environment for use close friend and technique, have the advantage of obvious Green Chemistry, and in addition, products therefrom has outstanding environment sensitive performance and does well in the sensing of temperature and pH especially.Its application prospect is extensive, can be used as sensor, the potential application choice material of environment sensitive carrier.
The present invention is single stage method preparation, has manufacture craft simple and easy, environmental friendliness, the advantages such as Green Chemistry.Without the need to adding harmful catalyzer in making processes, and process byproducts is easy to treatment and purification.To production unit and production environment without excessive demand, low energy, is suitable for industrial applications.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is original nano silicon (a) and the infrared spectrogram through the functionalized silicon nano (b) of tolylene diisocyanate.
Fig. 2 is PNIPAAm-SH(A), PDEAEMA-SH(B) building-up reactions schematic diagram.
Fig. 3 is the silicon nano (SiO that poly N-isopropyl acrylamide is modified
2-g-P1) silicon nano (SiO that modifies of (a), poly N-isopropyl acrylamide and poly-(N, N'-diethylamide ethylmethyl acrylate)
2-g-P1/P2) (b) and poly-(N, N'-diethylamide ethylmethyl acrylate) silicon nano (SiO of modifying
2-g-P2) infrared spectrogram of (c).
Fig. 4 be under different poly N-isopropyl acrylamide content hybrid silicon nanoparticle at pH=11(a) and the pH=3(b) particle diameter of hybrid particle under condition.
Embodiment
Embodiment 1:
3.0 g silicon nanos and 3.12 g tolylene diisocyanates to be dispersed in the dry toluene of 50 mL and as 10-15 min under ultra sonic bath.Then mixture is stirred degassed at 95 DEG C of temperature lower magnetic forces, and be incubated 6 h with thermostatted.Subsequently, by powdery product centrifugation, carefully wash away unreacted and tolylene diisocyanate that is physical absorption with the toluene of drying.By products obtained therefrom, the silicon nano (SiO that namely tolylene diisocyanate is functionalized
2-NCO), vacuum-drying 24 h at 80 DEG C of temperature.By silicon nano (SiO functionalized for made tolylene diisocyanate
2-NCO) 50 mg, PNIPAAm-SH and PDEAEMA-SH(PNIPAAm-SH and PDEAEMA-SH mol ratio be 75:25, totally 500 mg) be dissolved in the dry toluene of 100 mL together with triethylamine (6.07 mg), and mixture is frozen for three times under neon atmosphere-pump-thaw cycles is degassed.Reaction mixture is magnetic agitation 24 h at room temperature, obtains the silicon nano (SiO that poly N-isopropyl acrylamide is modified with poly-(N, N'-diethylamide ethylmethyl acrylate)
2-g-P
1/ P
2), in the normal hexane of products therefrom by precipitate and separate to 50 mL, with after methyl alcohol and washing with acetone under 14000 rpm centrifugation 10-15 min.In supernatant liquor, unreacted PDEAEMA-SH and PNIPAAm-SH ethanol dialysis purifies.Finally, the silicon hybridization nanoparticle of the functionalization of polymers through having temperature and PH doubling sensitivity of gained being placed in vacuum dried overnight, obtaining the silicon hybridization nanoparticle of temperature-and pH-sensitivity.Test to product, be under the environment of 20 DEG C in pH=11 temperature, silicon nano diameter is 180 nm, is 110 nm when 40 DEG C.Be under the environment of 20 DEG C in pH=3 temperature, silicon nano diameter is 200 nm, is 120 nm when 40 DEG C.Products therefrom occurs obviously to change with the varying dimensions of temperature and pH.Result shows: successfully obtained temperature-and pH-sensitivity silicon hybridization nanoparticle target product.
Embodiment 2:
3.0 g silicon nanos and 3.12 g tolylene diisocyanates to be dispersed in the dry toluene of 50 ml and as 10-15 min under ultra sonic bath, mixture to be stirred degassed at 95 DEG C of temperature magnetics, and is incubated 6 h with thermostatted.After separated product, vacuum-drying 24 h at 80 DEG C of temperature.By silicon nano (SiO functionalized for made tolylene diisocyanate
2-NCO) 50 mg, PNIPAAm-SH and PDEAEMA-SH(PNIPAAm-SH and PDEAEMA-SH mol ratio be 50:50, totally 500 mg) be dissolved in the dry toluene of 100 mL together with triethylamine (6.07 mg), and mixture is frozen for three times under neon atmosphere-pump-thaw cycles is degassed.Reaction mixture is magnetic stirring 24 h at room temperature, obtains the silicon nano (SiO that poly N-isopropyl acrylamide is modified with poly-(N, N'-diethylamide ethylmethyl acrylate)
2-g-P
1/ P
2) product.In the normal hexane of products therefrom by precipitate and separate to 50 mL, with after methyl alcohol and washing with acetone under 14000 rpm centrifugation 10-15 min.Finally, the silicon hybridization nanoparticle of the functionalization of polymers through having temperature-and pH-sensitivity of gained is placed in vacuum dried overnight.To final product inspection, be under the environment of 20 DEG C in pH=11 temperature, silicon nano diameter is 175 nm, is 115 nm when 40 DEG C.Be under the environment of 20 DEG C in pH=3 temperature, silicon nano diameter is 195 nm, is 125 nm when 40 DEG C.Products therefrom occurs obviously to change with the varying dimensions of temperature and pH.Success obtains expection product.
Embodiment 3:
3.0 g silicon nanos and 3.12 g tolylene diisocyanates to be dispersed in the dry toluene of 50 mL and as 10-15 min under ultra sonic bath, mixture to be stirred degassed at 95 DEG C of temperature magnetics, and is incubated 6 h with thermostatted.After separated product, vacuum-drying 24 h at 80 DEG C of temperature.By silicon nano (SiO functionalized for made tolylene diisocyanate
2-NCO) 50 mg, PNIPAAm-SH and PDEAEMA-SH(PNIPAAm-SH and PDEAEMA-SH mol ratio be 25:75, totally 500 mg) be dissolved in the dry toluene of 100 ml together with triethylamine (6.07 mg), and mixture is frozen for three times under neon atmosphere-pump-thaw cycles is degassed.Reaction mixture is magnetic stirring 24 h at room temperature, obtains the silicon nano (SiO that poly N-isopropyl acrylamide is modified with poly-(N, N'-diethylamide ethylmethyl acrylate)
2-g-P
1/ P
2) product.In the normal hexane of products therefrom by precipitate and separate to 50 mL, with after methyl alcohol and washing with acetone under 14000 rpm centrifugation 10-15 min.Finally, the silicon hybridization nanoparticle of the functionalization of polymers through having temperature-and pH-sensitivity of gained is placed in vacuum dried overnight.To final product inspection, be under the environment of 20 DEG C in pH=11 temperature, silicon nano diameter is 170 nm, is 120 nm when 40 DEG C.Be under the environment of 20 DEG C in pH=3 temperature, silicon nano diameter is 190 nm, is 140 nm when 40 DEG C.Products therefrom occurs obviously to change with the varying dimensions of temperature and pH.Product property meets expection experimental result.
Embodiment 4:
3.0 g silicon nanos and 3.12 g tolylene diisocyanates to be dispersed in the dry toluene of 50 ml and as 10-15 min under ultra sonic bath, mixture to be stirred degassed at 95 DEG C of temperature lower magnetic forces, and is incubated 6 h with thermostatted.After separated product, vacuum-drying 24 h at 80 DEG C of temperature.By silicon nano (SiO functionalized for made tolylene diisocyanate
2-NCO) 50 mg, PNIPAAm-SH and PDEAEMA-SH(PNIPAAm-SH and PDEAEMA-SH mol ratio be 100:0, totally 500 mg) together with triethylamine (6.07 mg,) be dissolved in the dry toluene of 100 mL, and mixture is frozen for three times under neon atmosphere-pump-thaw cycles is degassed.Reaction mixture is magnetic stirring 24 h at room temperature, obtains the silicon nano (SiO that poly N-isopropyl acrylamide is modified with poly-(N, N'-diethylamide ethylmethyl acrylate)
2-g-P
1/ P
2) product.In the normal hexane of products therefrom by precipitate and separate to 50 mL, with after methyl alcohol and washing with acetone under 14000 rpm centrifugation 10-15 min.Finally, the silicon hybridization nanoparticle of the functionalization of polymers through having temperature-and pH-sensitivity of gained is placed in vacuum dried overnight.To final product inspection, be under the environment of 20 DEG C in pH=11 temperature, silicon nano diameter is 185 nm, is 100 nm when 40 DEG C.Be under the environment of 20 DEG C in pH=3 temperature, silicon nano diameter is 205 nm, is 105 nm when 40 DEG C.Products therefrom occurs obviously to change with the varying dimensions of temperature and pH.Reach object of experiment.
Above-mentioned embodiment is implemented under premised on technical solution of the present invention, given detailed embodiment and process, is to further illustrate of the present invention, instead of limits the scope of the invention.
Claims (8)
1. a preparation method for doubling sensitivity polymer hybrid nanoparticle, is characterized in that, comprises the following steps:
(1) silicon nano and tolylene diisocyanate are distributed in dry toluene, and are placed on 10-15 min in ultra sonic bath, gained mixture is placed in 95 DEG C of magnetics and stirs degassed and constant temperature is incubated 6 h, obtained reaction product A;
(2) by product A centrifugation, with the toluene cleaning unreacted of drying and the tolylene diisocyanate of physical adsorption, product B is obtained, will
product Bvacuum-drying, obtains the silicon nano (SiO that tolylene diisocyanate is functionalized
2-NCO);
(3) sulfhydrylation poly N-isopropyl acrylamide and sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) is synthesized respectively;
(4) step (2) is obtained the functionalized silicon nano of tolylene diisocyanate and the sulfhydrylation poly N-isopropyl acrylamide of step (3) gained and the poly-(N of sulfhydrylation, N'-diethylamide ethylmethyl acrylate) be dissolved in dry toluene together with triethylamine, obtain mixture C;
(5) mixture C is after degassed precipitation and centrifugal separation, in a vacuum dried overnight, the obtained silicon hybridization nanoparticle with temperature-and pH-sensitivity.
2. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, is characterized in that, in step (3), the method for described synthesis sulfhydrylation poly N-isopropyl acrylamide is:
A () uses Grignard reagent legal system for dithio benzyl benzoate, bromobenzene Grignard reagent is first prepared in the examination of bromobenzene grignard, then bromobenzene Grignard reagent and dithiocarbonic anhydride, benzyl bromine reaction obtains dithio benzyl benzoate, and namely separating-purifying obtains pure product dithio benzyl benzoate;
B () is by NIPA, dithio benzyl benzoate and 2,2'-azo two (isopropyl cyanide) is dissolved in tetrahydrofuran (THF), mixture D is obtained with degassed 30 min of neon, with degassed 30 min of neon, products therefrom is reacted 24 h at 70 DEG C of temperature, obtains poly N-isopropyl acrylamide;
C gained poly N-isopropyl acrylamide in step (b) is dissolved in methanol solution by (), and add sodium borohydride wherein, gained mixture reacts 48 h under room temperature in neon atmosphere, and after dialysis washed with de-ionized water, cooling drying obtains sulfhydrylation poly N-isopropyl acrylamide.
3. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, is characterized in that, in step (3), the method for described synthesis sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) is:
A () uses Grignard reagent legal system for dithio benzyl benzoate, bromobenzene Grignard reagent is first prepared in the examination of bromobenzene grignard, then bromobenzene Grignard reagent and dithiocarbonic anhydride, benzyl bromine reaction obtains dithio benzyl benzoate, and namely separating-purifying obtains pure product dithio benzyl benzoate;
B () is by N, N'-diethylamide ethylmethyl acrylate, dithio benzyl benzoate and 2,2'-azo two (isopropyl cyanide) is dissolved in tetrahydrofuran (THF), after degassed with neon, mixture is polymerized 24 h under 70 DEG C of degree, is gathered (N, N'-diethylamide ethylmethyl acrylate);
C obtained poly-(N, N'-diethylamide ethylmethyl acrylate) is carried out drying under reduced pressure with after dialysis methyl alcohol and normal hexane purification by (), be dissolved in methanol solution and also add sodium borohydride wherein;
D gained mixing solutions in (c) is reacted 48 h by () in neon atmosphere under room temperature, through the purification of dialysis normal hexane, can collect sulfhydrylation poly-(N, N'-diethylamide ethylmethyl acrylate) under vacuum after drying.
4. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, is characterized in that, as optimization, in step (1), gained mixture is that magnetic agitation is degassed, and its constant temperature soaking time is 6 h temperature is 95 DEG C.
5. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, is characterized in that, as optimization, in step (2), and vacuum-drying temperature 80 DEG C, time 24 h.
6. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, it is characterized in that, as optimization, in step (4), mixture C carries out freezing for three times under neon atmosphere-and pump-thaw cycles is degassed, and at room temperature stir 24 h subsequently.
7. the preparation method of doubling sensitivity polymer hybrid nanoparticle according to claim 1, is characterized in that, in step (5), product centrifugation speed is 14000 rpm, and the centrifugal time length is 10-15 min.
8. the doubling sensitivity polymer hybrid nanoparticle prepared of the method as described in claim 1-7.
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