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Complex Amphiphilic Hyperbranched Fluoropolymers by Atom Transfer Radical

Complex Amphiphilic Hyperbranched Fluoropolymers by Atom Transfer Radical Self-Condensing Vinyl(Co)polymerization

Kenya T.Powell,Chong Cheng,and Karen L.Wooley*

Center for Materials Inno V ation,Department of Chemistry and Department of Radiology,Washington Uni V ersity,Saint Louis,Missouri63130-4899

Recei V ed December18,2006;Re V ised Manuscript Recei V ed April3,2007

ABSTRACT:Amphiphilic hyperbranched fluorohomopolymer(M n)9.06kDa,M w/M n)1.90)and fluoroco-polymer(M n)17.2kDa,M w/M n)2.50)with tri(ethylene glycol)units incorporated at the molecular level were synthesized by atom transfer radical self-condensing vinyl homopolymerization of an inimer,4-[oxy(tri(ethylene glycol))bromoisobutyryl]-2,3,5,6-tetrafluorostyrene,and copolymerization of the inimer with2,3,4,5,6-pentafluo-rostyrene(1:3,inimer:monomer),using2,2′-bipyridine together with CuCl/CuCl2as the ligand/catalyst/deactivator system.The structure and composition of the fluoropolymers were characterized by1H,13C,and19F NMR spectroscopies.As detected by thermogravimetric analyses,the homopolymer and the copolymer had thermal stability up to175and210°C,respectively.Differential scanning calorimetry revealed a glass transition temperature of-19°C for the homopolymer and20°C for the copolymer.Solubility tests indicated that both polymers were soluble in a broad range of organic solvents,and the presence of tri(ethylene glycol)units resulted in the formation of water-dispersible micelles from each of the polymers.

Introduction

Investigations of the theory,design,preparation,and applica-tions of highly branched macromolecules,including dendri-mers1-12and hyperbranched polymers(HBPs),13-23have been widespread over the past two decades due to the special architectures and properties of these polymers relative to linear polymers.24-28HBPs are highly branched polymers with lower structural regularity than dendrimers.Although many types of HBPs have been prepared by various synthetic pathways, polycondensation of AB x monomers(x g2)has remained as the traditional and most common methodology for the prepara-tion of HBPs.20,29

In1995,Fre′chet et al.reported self-condensing vinyl po-lymerization(SCVP)of bifunctional AB*monomers,called inimers.30,31Inimers were so named because they possessed both a monomer group(A)and an initiator functionality(B*).These seminal studies led to a new approach in the production of HBPs.Although only a handful of suitable inimers were used in early studies,32this methodology has been extended by constituting charge-transfer complexes(CTCs)as new inimers or by copolymerization of inimers with comonomers.In2003, Wang et al.reported a copolymerization of p-chloromethylsty-rene(CMS)and chlorotrifluoroethylene(CTFE)following the atom transfer radical-SCVP(ATR-SCVP)mechanism,to give a fluorinated HBP with controlled structures.33The electron-rich CMS was believed to assemble with electron-deficient CTFE to form a CTC that served as an inimer for the SCVP system.Self-condensing vinyl copolymerization(SCVCP)of AB*inimers with comonomers has also significantly expanded the synthetic methodologies for the preparation of HBPs and has provided a broad range of HBPs with diverse compo-sition.16,34-36HBPs by SCVCP possess stable-C-C-back-bones and have structural units that can be derived from commercially available monomers.Their structural features, such as degrees of branching(DBs),can be controlled through the structures of the comonomer(s)and inimer(s),their feed ratios,and the copolymerization conditions.

We have a long-standing interest in hyperbranched fluo-ropolymers(HBFPs),37based upon their unique properties, including low coefficient of friction,low surface energy,low viscosity,enhanced solubility,and their facile production as compared with the production of their linear fluoropolymer counterparts.38Initially,our studies involved the design,syn-thesis,characterization,and applications of our first type hyperbranched fluoropolymer,HBFP(I),prepared by the poly-condensation of a bis(pentafluorobenzyl)ether of3,5-dihy-droxybenzyl alcohol in the presence of elemental sodium.37,39,40 HBFP(I)had perfluoroaromatic rings and ether linkages through-out its structure,with pentafluorobenzyl chain ends that can undergo nucleophilic aromatic substitution reactions for post-modification and derivatization.Furthermore,amphiphilic cross-linked networks were prepared from HBFP(I)and diamine-terminated poly(ethylene glycol)(DA-PEG),and their surface characteristics could be mediated by the mass ratio of HBFP to DA-PEG.40,41The amphiphilic cross-linked networks possessed enhanced anti-biofouling ability,42unusual sequestration and release behavior for a variety of small molecule guests,43and atypical mechanical performance.44We also recently reported the synthesis of our second type hyperbranched fluorocopolymer material,HBFP(II),by the ATR-SCVCP of inimer CMS with 2,3,4,5,6-pentafluorostyrene(PFS).34In contrast to HBFP(I) obtained by multistep reactions under severe reaction conditions, HBFP(II)were prepared by a one-pot synthesis using com-mercially available reactants under mild reaction conditions.The ATR-SCVCP method also allowed for ready control of fluo-rocarbon content,molecular weights,and DBs for the resulting HBFP(II).Moreover,HBFP(II)-DA-PEG amphiphilic cross-linked networks were synthesized economically,and their surfaces possessed tunable structural features,with topographical,mor-phological,and compositional heterogeneities similar to the surfaces of HBFP(I)-DA-PEG.45As a result of the thermody-namically driven phase segregation of the hydrophobic HBFP and hydrophilic PEG segments,the3-fold complexity(topog-

*Corresponding author:Tel(314)935-7136,Fax(314)935-9844, e-mail:klwooley@https://www.wendangku.net/doc/b515213623.html,.4509

Macromolecules2007,40,4509-4515

10.1021/ma0628937CCC:$37.00?2007American Chemical Society

Published on Web05/26/2007

raphy,morphology,and composition)is hypothesized to be responsible for the significant anti-biofouling behavior of the amphiphilic cross-linked networks.Because we hypothesized that the small size of the heterogeneities is also an important factor to enhance the resistance of protein adsorption and marine organism adhesion,we have a keen interest in the synthesis of amphiphilic structures with smaller surface domain sizes.In our current efforts to develop new types of hyperbranched fluorocopolymer materials,our goals are to improve the anti-biofouling characteristics by increasing the PEG content while retaining nanoscale surface heterogeneities.However,increas-ingly larger surface domain sizes were observed in cross-linked networks of HBFP (II)-PEG with mass fractions of PEG greater than 50%.These findings necessitated the creation of a HBFP with improved PEG compatibility.Additionally,the successful production of HBFP (II)by ATR-SCVCP indicates that more types of hyperbranched fluoropolymers might be prepared using the same synthetic methodology.With these concepts in mind,we have developed our third type hyperbranched fluoropoly-mers,HBFP (III),by ATRR-SCVP or SCVCP using a tri(ethylene glycol)-functionalized amphiphilic fluorinated inimer.Results and Discussion

Syntheses.In order to synthesize hyperbranched fluoropoly-mers 1and 2,having oligo(ethylene glycol)(OEG)chains incorporated within their frameworks via the ATR-SCVCP methodology,an OEG-functionalized fluorinated inimer 3that possesses a polymerizable vinylic group and an initiator functionality for ATRP was prepared (Scheme 1).The formula-tion of such a molecule began with the nucleophilic aromatic substitution of 2,3,4,5,6-pentafluorostyrene (PFS)by tri(ethylene glycol)(TEG).In the presence of NaH in THF heated at reflux for 1.5h,the reaction of PFS with 7.5equiv of TEG afforded 4in 88%yield,after chromatographic purification.Both PFS and TEG were selected on the basis of their commercial availability and laboratory convenience,in addition to their well-characterized and well-understood properties.Relative to PFS,an excess of TEG was required in the preparation of 4to suppress the side product in which both of the hydroxyl groups of TEG were arylated by PFS.Additionally,TEG,instead of longer EG segments,was chosen to maintain simplicity.Transformation of 4into the inimer,3,was accomplished by allowing 4to undergo reaction with 2-bromoisobutyryl bromide in THF at room temperature for 20h,to give 3in 88%yield,after chromatographic purification.

Homopolymerization of 3was performed using CuCl/CuCl 2/2,2-bipyridine (BiPy)as the catalyst/deactivator/ligand system ([3]0/[CuCl]0/[CuCl 2]0/[BiPy]0) 1.0/0.1/0.01/0.22)in fluo-robenzene (PhF)at 60°C,and the polymerization process was monitored by 1H NMR spectroscopy.As measured by 1H NMR spectroscopy,comparison of the vinylic proton resonances at 5.62, 6.02,and 6.62ppm with the proton resonances of methylene units on the R -positions to the ester oxygen and the phenyl ether group at 4.20-4.35ppm found that these reaction conditions gave a 70%conversion of the vinylic groups at 10h,an 80%conversion at 20h.Conversions of the alkyl halide initiating site were also observed on the basis of decreased resonance intensities of the methyl protons of the alkyl halide initiating site of 3resonating at 2.05ppm in comparison to the TEG proton signals,giving 40%and 49%conversions at 10and 20h,respectively.The polymerization was quenched at 24h,and the polymerization mixture was diluted with THF and passed through an alumina column.Concentration of the solution and repeated precipitations into hexanes then gave hyper-branched fluorohomopolymer 1in 64%yield (80%yield based upon an estimated 80%conversion of 3).As determined by size exclusion chromatography (SEC)equipped with both a differential refractometer and a dynamic light scattering detector,1had an absolute M n of 9.06kDa with a M w /M n value of 1.90(Figure 1a).

Copolymerization of 3with PFS was performed to produce an amphiphilic hyperbranched fluorocopolymer that has struc-ture somewhat similar to HBFP (II)34but possesses TEG units that were absent from HBFP (II).The feed ratio of PFS to 3was 3:1to dramatically alter the composition and structure relative to the homopolymer 1.This ratio was also selected to mimic the feed ratio of [monomer]0:[inimer]0of 3:1,which resulted in the highest fluorocarbon content for HBFP (II)and for later comparisons of DA-PEG cross-linked networks and copolymer 2with HBFP (II)-DA-PEG cross-linked networks.45The reaction was conducted with the initial feed ratios of [PFS]0/[3]0/[CuCl]0/[CuCl 2]0/[BiPy]0of 3.0/1.0/0.1/0.01/0.22,in PhF at 60°C.The copolymerization process was monitored by 1H NMR spectros-copy.Because of structural similarity,3and PFS have

Scheme 1.Syntheses of Hyperbranched Fluorohomopolymer 1and Fluorocopolymer 2by Atom Transfer Radical Vinyl

Self-Condensing Vinyl

(Co)polymerization

4510Powell et al.Macromolecules,Vol.40,No.13,2007

similar positions for the 1H NMR resonances of their vinylic protons.On the basis of quantitative 19F NMR analysis (vide infra),it was determined that the structural units of 3and PFS were present in the final copolymer 2in a ratio equivalent to that of the original feed.Thus,3and PFS possessed similar reactivity under the copolymerization conditions,and their percent conversions were equal to the total percent conversion of all vinyl groups.As detected by 1H NMR analysis,the conversion of the vinylic groups was 65%at 8h and 75%at 23h.The copolymerization was quenched at 24h,and the copolymerization mixture was diluted with THF and passed through an alumina column.Concentration of the solution and repeated precipitations into hexanes then gave hyperbranched fluorocopolymer 2in 56%yield (75%yield based upon 75%conversion of PFS and 3).As determined by SEC (Figure 1b),hyperbranched fluorocopolymer 2had an absolute M n of 17.2kDa with a M w /M n value of 2.50.As illustrated by the SEC traces of Figure 1,relative to homopolymerization of 3,copolymerization of 3with PFS actually gave polymers with higher molecular weights in a shorter polymerization time,presumably due to the higher polymerizable group-to-initiator site ratio for the copolymerization system.

NMR Spectroscopic Characterization.Both hyperbranched fluorohomopolymer 1and fluorocopolymer 2were characterized by 1H,13C,and 19F NMR spectroscopies.As shown in Figure 2,both of the polymers had similar 1H NMR spectra.Their backbone methylene and methine protons,resulting from the conversion of vinylic groups,resonated at 1.5-3.1ppm as broad resonances.Relative to homopolymer 1with only backbone protons from 3,copolymer 2exhibited stronger 1H NMR resonances in this region because it possessed backbone protons from both 3and PFS units.Before initiation,the methyl protons of the residual R -bromoisobutyrate groups from 3resonated at 1.9ppm as a sharp singlet;after initiation,the methyl protons resonated at 0.7-1.5ppm as broad signals.The methylene protons (C H 2O)of the TEG segment from 3resonated at 3.2-4.5ppm.Benzylic protons of the terminal benzylic chloride and benzylic bromide functionalities,which were formed by initia-tion from 3with or without halogen exchange,resonated at 4.6-5.4ppm as several broad peaks.Finally,the vinylic protons of the head groups,which resulted from units of 3whose vinylic group was not polymerized,resonated at 5.6,6.0,and 6.6ppm.The 13C NMR spectra for hyperbranched fluorohomopolymer 1and fluorocopolymer 2are shown in Figure 3.For both of the polymers,their carbons resonated in four primary regions.For the region from 20to 63ppm,the 13C NMR resonances are from all backbone carbons,methyl carbons,and all halogenated aliphatic carbons.The methylene carbons (C H 2O)of the TEG segments were observed from 63to 75ppm,and the aromatic and vinylic carbons resonated over 120-149ppm.The 13C NMR resonances from 171to 181ppm were assigned to the ester carbons of the isobutyrate groups.Homopolymer 1exhibited strong 13C NMR resonances at 31.0,55.7,and 171.5ppm for the methyl carbons,bromide carbons,and ester carbons of the residual R -bromoisobutyrate groups from inimer 3,which indicated that 1contained a significant portion of repeat units that had undergone vinylic group reaction for incorporation

into

Figure 1.SEC traces for (a)homopolymerization of 3at t )10h and (b)copolymerization of 3and PFS at t )8h,with SEC traces of the final purified polymers 1and 2(t )24h)included as

insets.

Figure 2.1H NMR (300MHz,CDCl 3)spectra for (a)hyperbranched fluorohomopolymer 1and (b)hyperbranched fluorocopolymer 2

Figure 3.13C NMR (150.8MHz,CDCl 3)spectra for (a)hyperbranched fluorohomopolymer 1and (b)hyperbranched fluorocopolymer 2

Figure 4.19F NMR (282MHz,CDCl 3)spectra for (a)hyperbranched fluorohomopolymer 1and (b)hyperbranched fluorocopolymer 2.

Macromolecules,Vol.40,No.13,2007Amphiphilic Hyperbranched Fluoropolymers 4511

the polymer but retained their noninitiated R-bromoisobutyrate groups.In the13C NMR spectrum of copolymer2,resonances at171.5ppm for the ester carbons of the residual R-bro-moisobutyrate groups from inimer3without initiation were much weaker than the resonances at176.6ppm for the ester carbons of extended chains,indicating that copolymer2had only an insignificant amount of remaining R-bromoisobutyrate groups.

The19F NMR spectra for hyperbranched fluorohomopolymer 1and fluorocopolymer2are shown in Figure4.The meta-fluorines and the ortho-fluorines of1exhibited resonances concentrated at-157.1and-144.6ppm,respectively(Figure 4a).The ratio of19F NMR resonance intensities from these two peaks were in excellent agreement with the expected fluorine number ratio of2:2.In the19F NMR spectrum of2(Figure 4b),the meta-fluorines of the PFS units of2showed resonances concentrated at-161.1ppm.Resonances of the para-fluorines of its PFS units and the meta-fluorines of its inimer3units overlap around156.6ppm.Resonances of the ortho-fluorines of its PFS and3units were observed at-143.0ppm. Integrations of the19F NMR resonance intensities from these three regions gave a ratio of6:5:8,indicating a3:1molar ratio of PFS units to units derived from inimer3,which was equal to the initial molar feed ratio of PFS to3in this copolymeri-zation.The results also suggested that PFS and3had similar reactivities under the copolymerization conditions. Elemental Analysis.Hyperbranched fluorohomopolymer1 and fluorocopolymer2were also characterized by elemental analysis.For both polymers,experimental elemental percentages of C,H,and F were close to the theoretical values,and such agreement for2also confirmed its composition of3:1molar ratio of PFS units to inimer3units.However,for both polymers, experimental elemental percentages of Br(9.85%for1;4.22% for2)were significantly lower than the theoretical values (16.90%for1;7.57%for2).Biradical coupling was considered as the major reason for the lower-than-expected bromine percentages in the polymers.Furthermore,because CuCl and CuCl2were used as catalyst/deactivator for their synthetic systems,the occurrences of halogen exchange during polymer-

izations were also confirmed by the presences of0.58%of Cl in1and0.78%of Cl in2,as detected by element analysis. Thermal Analysis.Thermogravimetric analyses were con-ducted to evaluate the thermal stabilities of hyperbranched fluorohomopolymer1and fluorocopolymer2(Figure5).Ho-mopolymer1showed an early mass loss at ca.100°C,which was most likely due to water evaporation,an indication of the homopolymer’s affinity for water swelling.For copolymer2, no thermal transition for water was observed,which suggests a diminished capacity for water swelling,with the presence of a high molar fraction of hydrophobic PFS units.Homopolymer 1exhibited an initial decomposition onset temperature(T d)at 175°C,followed by three distinct thermal decomposition ranges with midpoints at260,302,and385°C(Figure5a).Interest-ingly,copolymer sample2(Figure5b,solid)showed a less heterogeneous thermolytic profile with an initial T d onset at210°C,indicative of greater thermal stability,and only two major thermal transitions with midpoints at310and413°C(Figure 5b,dashed).The transition from175to275°C in homopolymer 1accounted for10mass%loss and was attributed to thermal degradation of terminal halide functionalities.The reduction of the intensity of this transition in copolymer2was expected due to the relative decrease in terminal halides with the incorporation of PFS units.Each of these results was in good agreement with the data from elemental analyses.The percentages of mass loss for the second and third transitions of1,from275to340°C and from340to425°C,were25%and48%,respectively.The two major thermal transitions of copolymer2ranged from210 to345°C with a mass loss of22%and from345to425°C with a mass loss of56%.

Differential scanning calorimetry(DSC)experiments were performed to evaluate the possible glass transition temperatures (T g)and melting transition temperatures(T m)of1and2(Figure 6).Homopolymer1displayed a low T g at-19°C,presumably due to its high OEG content(Figure6a).With a high fraction of PFS units,sample2exhibited a T g at20°C,significantly higher than that of sample1.However,this value is much lower than that observed at110°C for the HBFP(II)copolymer based upon PFS and CMS.Additionally,no melting endotherm was observed for1or2on heating up to150°C(not shown),a sign of the absence of PEG domains within the polymer materials,in contrast to the amphiphilic networks of HBFP(II) and DA-PEG that allowed for phase segregation and crystal-lization of the PEG component,giving a T m onset at30°C.45 Solubility.Similar to that observed for HBFP(II),solubility studies of hyperbranched fluorohomopolymer1and fluoroco-polymer2were performed at room temperature,and it was found that1and2were soluble in a broad range of organic solvents,including tetrahydrofuran,chloroform,

methylene Figure5.Thermolytic profiles for(a)hyperbranched fluorohomopoly-mer1and(b)hyperbranched fluorocopolymer2.Mass%is illustrated with solid lines and the first-derivative plots are shown as dashed

lines.

Figure6.DSC thermograms for(a)hyperbranched fluorohomopolymer 1and(b)hyperbranched fluorocopolymer2.

4512Powell et al.Macromolecules,Vol.40,No.13,2007

chloride,benzene,toluene,and acetone.Nonsolvents based upon direct precipitation for these polymers were hexanes,methanol, and water.Thus,the incorporation of TEG did not result in a significant improvement in the water solubility of either1or2, although both polymers showed evidence of water swelling.We attribute these results to the significant hydrophobic composi-tions in1and2.However,the presence of TEG did modify the characteristics of the polymers.For instance,upon the slow addition of nanopure water to a dilute solution of1or2in THF (10mg/mL),followed by dialysis of the THF against distilled water,water-dispersible micelles were formed.As detected by dynamic light scattering(DLS)measurements,the micelles of 1had a number-average hydrodynamic diameter(D h,n)of170 (20nm and a volume-average hydrodynamic diameter(D

h,v

) of190(10nm,and the micelles of2had a D h,n of210(20 nm and a D h,v of240(20nm.These encouraging results suggest that hyperbranched fluorocopolymers produced with inimers containing longer EG chains may display appreciably greater water solubility.Further evaluation of the aqueous solution-based assembly of these polymers,1and2and others having greater OEG content,are underway and will be reported elsewhere.

Conclusions

Amphiphilic hyperbranched fluorohomopolymer and fluoro-copolymer have been prepared by ATR-SCVP of an amphiphilic fluorinated inimer and SCVCP of the inimer with a comonomer. The presence of covalently attached TEG units was found to have a significant effect on the observed spectroscopic,thermal, and solution-state properties of the polymers.NMR spectro-scopic characterization confirmed the structure and composition of both polymers,while thermal analyses revealed a decrease in thermal stability for1but a similar thermal degradation profile for2relative to HBFP(II).Both1and2displayed a single glass transition temperature,each having a T g value that was lower than that expected for a styrenyl-based backbone,which was an indication of well-incorporated TEG units.Moreover,the T g for1was lower than that of2due in part to a lower molecular weight value as well as an increased TEG content.Polymers1 and2were both soluble in a broad range of organic solvents. Neither polymer possessed appreciable water solubility;how-ever,they underwent aggregation to afford nanoscale,intermo-lecular,complex micelles.The formation of1and2with increasingly larger ethylene glycol chains is currently under investigation,and these materials are being developed as potential19F MRI agents.Both1and2possess secondary and tertiary bromides and chlorides as well as a tetrafluorophenyl moiety,and2also has pentafluorophenyl groups that contain para-fluorine reactive sites.The secondary and tertiary bromides and para-fluorines are expected to be of great importance in future studies,as they may be utilized for polymer postmodi-fication through atom transfer radical,substitution,or nucleo-philic aromatic substitution reactions.Relative to HBFP(I)and HBFP(II),HBFP(III)is expected to have greater miscibility with DA-PEG to lead to decreased domain sizes for their resulting cross-linked networks.These materials are also expected to exhibit increased surface wettability and improved mechanical robustness,without the loss of fluorocarbon content,architectural advantages,3-fold complexity,or ease of production.Thus,we are also investigating the reaction of1and2with diamine-terminated poly(ethylene glycol)in the preparation of complex, amphiphilic networks for anti-biofouling applications,among others.Experimental Section

Materials.2,3,4,5,6-Pentafluorostyrene(PFS)was distilled over

CaH2and stored under argon at4.0°C.All other chemicals and

reagents were purchased from Aldrich Chemical Co.and used as

received.

Characterization Methods.1H NMR spectra were recorded at

300MHz on solutions in CDCl3on a Varian Mercury300

spectrometer,with the solvent proton signal as standard.13C NMR

spectra were recorded at150.8MHz on solutions in CDCl3on a

Varian Unity600spectrometer with the solvent carbon signal as

standard.19F NMR spectra were recorded at282.2MHz on solutions

in CDCl3on a Varian Mercury300spectrometer with external

CFCl3as standard.IR spectra were recorded on a Perkin-Elmer

Spectrum BX FT-IR system as thin films on KBr disks and were

analyzed using FT-IR Spectrum v2.00software(Perkin-Elmer

Corp.,Beaconsfield,Bucks,England).

Size exclusion chromatography(SEC)was conducted on a

Waters1515HPLC(Waters Chromatography,Inc.)equipped with

a Waters2414differential refractometer,a PD2026dual-angle(15°

and90°)light scattering detector(Precision Detectors,Inc.),and a

three-column series PL gel5μm Mixed C,500?,and104?,300×7.5mm columns(Polymer Laboratories,Inc.).The system was equilibrated at35°C in anhydrous THF,which served as the

polymer solvent and eluent with a flow rate of1.0mL/min.Polymer

solutions were prepared at a known concentration(ca.3mg/mL),

and an injection volume of200μL was used.Data collection and

analysis were performed respectively with Precision Acquire

software and Discovery32software(Precision Detectors,Inc.).

Interdetector delay volume and the light scattering detector calibra-

tion constant were determined by calibration using a nearly

monodispersed polystyrene standard(Pressure Chemical Co.,M p )90kDa,M

/M n<1.04).The differential refractometer was

calibrated with standard polystyrene reference material(SRM706

NIST),of known specific refractive index increment d n/d c(0.184

mL/g).The d n/d c values of the analyzed polymers were then

determined from the differential refractometer response. Thermogravimetric analysis(TGA)was performed on a TGA/ SDTA851e instrument(Mettler-Toledo,Inc.)measuring the total mass loss on～5mg samples from25to550°C at a heating rate of10°C/min in a nitrogen flow of50mL/min.Glass transition temperature(T g)and/or melting transition temperature(T m)deter-minations were measured by differential scanning calorimetry (DSC)on a DSC822e instrument(Mettler-Toledo,Inc.)in a temperature range of-75to150°C with a heating rate of10°C/ min under nitrogen.For both TGA and DSC,data were acquired and analyzed with STAR e software(Mettler-Toledo,Inc.).The T g values were taken at the midpoint of the inflection tangent and T m values were taken as the onset,upon the third heating scans. Hydrodynamic diameters(D z,D n)and size distributions for the micellar aggregates in aqueous solutions were determined by dynamic light scattering(DLS).The DLS instrumentation consisted of a Brookhaven Instruments Limited(Holtsville,NY)system, 90Plus.Measurements were made at room temperature.Scattered light was collected at a fixed angle of90°.Only measurements in which the measured and calculated baselines of the intensity autocorrelation function agreed to within0.1%were used to calculate particle size.The calculations of the particle size distribu-tions and distribution averages were performed with the ISDA software package(Brookhaven Instruments Co.),which employed CONTIN analysis,and non-negatively constrained least-squares particle size distribution analysis routines.

Elemental analysis was performed by Galbraith Laboratories,

Inc.,Knoxville,TN.

Synthesis of4-[Oxy(tri(ethylene glycol))]-2,3,5,6-tetrafluo-

rostyrene(4).2,3,4,5,6-Pentafluorostyrene(1.96g,10.0mmol),

tri(ethylene glycol)(11.3g,75mmol),and NaH(0.380g,15.0

mmol)were allowed to react in the presence of THF(80.0mL)at

reflux for1.5h.The residue was partitioned between CH2Cl2and

saturated ammonium chloride solution.The combined organic layers

were concentrated,and the product was isolated by silica gel column

Macromolecules,Vol.40,No.13,2007Amphiphilic Hyperbranched Fluoropolymers4513

chromatography with hexane:CH2Cl2(1:1)as eluent and increasing

polarity to3%MeOH in CH2Cl2.Yield)88%.IR:3600-3200,

3050-2820,1660-1620,1530-1400,1350,1290,1250,1180-

1060,980-960,940,890,860,670cm-1.1H NMR(CDCl3):δ

2.32(t,J)6.0Hz,1H,O H),

3.59(t,J)

4.5Hz,2H,HOC H2),

3.63-3.75(m,6H,OC H2),3.83(t,J)

4.5Hz,2H,OC H2),4.38

(t,J)4.5Hz,2H,OC H2),5.62(d,J)12.0Hz,1H,cis C H H d

CHAr),6.02(d,J)18.0Hz,1H,trans CH H d CHAr),6.62ppm

(dd,J)12.0and18.0Hz,1H,CH2d C H Ar).13C NMR(CDCl3):δ61.9,70.3,70.5,71.1,72.6,74.3,111.1,122.2,122.3,122.4,

122.5,136.2,139.6,143.0,143.5,146.9ppm.19F NMR(CDCl3):

δ-158.5(m,2F,meta-F),-145.5ppm(m,2F,ortho-F).Anal.

Calcd C14H16O4F4(324.27Da):C,51.86;H,4.97;F,23.44%.

Found:C,51.28;H,4.97;F,22.10%.

Synthesis of4-[Oxy(tri(ethylene glycol))bromoisobutyryl]-

2,3,5,6-tetrafluorostyrene(3).To a reaction flask containing4

(11.8g,36.3mmol),pyridine(11.5g,145mmol),and THF(80.0

mL)was added2-bromoisobutyryl bromide(25.1g,109mmol)

dropwise.The mixture was allowed to react at room temperature

for20h.The residue was partitioned between CH2Cl2and H2O,

and the aqueous layer was extracted with CH2Cl2(×3).The organic

layers were combined,dried over MgSO4,and filtered,and the

solvent was evaporated in vacuo.The product was isolated by silica

gel column chromatography with hexane:CH2Cl2(1:1)as eluent

and increasing polarity to3%MeOH in CH2Cl2.Yield)88%.

IR:3050-2820,1750-1720,1660-1620,1530-1400,1390,

1370,1355,1280,1180-1060,1030,980-960,940,860,760,645

cm-1.1H NMR(CDCl3):δ1.93(s,6H,CC H3),3.63-3.76(m,

6H,OC H2),3.83(t,J)4.5Hz,2H,OC H2);4.32(br t,J)4.5

Hz,2H,OC H2);4.37(br t,J)4.5Hz,2H,OC H2);5.62(d,J)

12.0Hz,1H,cis C H H d CHAr),6.02(d,J)18.0Hz,1H,trans

CH H d CHAr),6.62ppm(dd,J)12.0and18.0Hz,1H,CH2d

C H Ar).13C NMR(CDCl3):δ30.5,55.6,64.9,70.1,70.6,74.1,

77.0,77.3,77.5,110.6,121.8,122.0,136.4,140.2,141.8,144.0,

145.7,171.3ppm.19F NMR(CDCl3):δ-158.7(m,2F,meta-F),

-145.9ppm(m,2F,ortho-F).Anal.Calcd for C

18H21O5F4Br

(473.26Da):C,45.69;H,4.47;F,16.06;Br,16.90%.Found:C,

44.63;H,4.35;F,15.56;Br,19.07%.

Synthesis of Hyperbranched Fluorohomopolymer(1).To a

reaction flask with a magnetic stirring bar,3(1.42g,1.0equiv),

BiPy(0.103g,0.22equiv),CuCl(0.0296g,0.1equiv),CuCl2

(0.004g,0.01equiv),and PhF(4.0mL,80vol%)were added.

The reaction mixture was degassed by at least three cycles of

freeze-pump-thaw and then heated with an oil bath at60°C.

During polymerization,small aliquots of polymerization were

withdrawn with syringe and were analyzed by1H NMR spectros-

copy for the determination of conversion of vinylic bonds based

on the remaining vinylic proton resonances at5.62,6.02,and6.62

ppm.Finally,the polymerization was quenched,by being allowed

to cool to room temperature,and then opening of the flask to air

and dilution of the reaction mixture by addition of THF,at a

polymerization time of24h,with an estimated conversion of vinylic

bonds of80%.The polymerization solution was passed through an

alumina column,eluted with THF,precipitated three times into

hexanes,and dried in vacuo to give0.91g of viscous,pale yellow

oil.Yield)64%.M n,SEC)9.06kDa,M w/M n)1.99;T g)-19

°C.TGA in N2:175-275°C,10%mass loss,275-340°C,25% mass loss,340-425°C,48%mass loss.IR:3010-2850,1745-

1725,1650,1510-1410,1390,1370,1353,1280,1180-1065,

1040,980-950,885,765,645cm-1.1H NMR(CDCl3):δ0.70-

1.50(br m,CC H3),1.50-3.10(br m,aliphatic backbone protons),

1.92(s,CC H3),3.20-4.40(br m,C H2O protons of OEG units),

4.60-

5.40(br m,ArC H Br and ArC H Cl),5.65(cis C H H d CHAr),

6.02(trans CH H d CHAr),6.60ppm(CH2d C H Ar).13C NMR (CDCl3):δ22.9-28.3,31.0,35.7-4

7.9,55.7,63.1-63.8,65.1, 6

8.7,70.1-71.1,74.2,110.7-116.5,122.0,137.2,141.0,144.6, 171.5,176.0-177.6,181.1ppm.19F NMR(CDCl3):δ-157(m, meta-F),-144ppm(m,ortho-F).Anal.Calcd for C18H21O5F4Br-(473.26Da):C,45.69;H,4.47;F,16.06;Br,16.90%.Found:C, 46.80;H,4.73;F,15.52;Br,

9.85;Cl,0.58%.

Synthesis of Hyperbranched Fluorocopolymer(2).To a reaction flask with a magnetic stirring bar,2,3,4,5,6-pentafluo-rostyrene(1.23g,3.0equiv),3(1.00g,1.0equiv),BiPy(0.217g, 0.66equiv),CuCl(0.0627g,0.3equiv),CuCl2(0.009g,0.03 equiv),and PhF(5.0mL,70v%)were added.The reaction mixture was degassed by at least three cycles of freeze-pump-thaw and then heated with an oil bath at60°C.During polymerization,small aliquots of polymerization were withdrawn with syringe and were analyzed by1H NMR spectroscopy for the determination of conversion of vinylic bonds based on the remaining vinylic proton resonances at5.62,6.02,and6.62ppm.Finally,the polymerization was quenched,by being allowed to cool to room temperature,and then opening of the flask to air and dilution of the reaction mixture by addition of THF,at a polymerization time of24h,with an estimated conversion of vinylic bonds of75%.The polymerization solution was passed through an alumina column,eluted with THF, precipitated three times into hexanes,and dried in vacuo to give 1.24g of crystalline,white solid.Yield)56%.M n,SEC)17.2kDa, M w/M n)2.48;T g)20.4°C.TGA in N2:210-345°C,22%mass loss,345-425°C,56%mass loss.IR:3010-2850,1740-1720, 1650,1540-1410,1390,1370,1300,1215,1175-1065,1085, 1000-930,880,760cm-1.1H NMR(CDCl3):δ0.70-1.50(br m,CC H3),1.50-3.10(br m,aliphatic backbone protons),1.92(s, CC H3),3.20-4.40(br m,C H2O protons of OEG units),4.60-5.40(br m,ArC H Br and ArC H Cl),5.65(cis C H H d CHAr),6.02 (trans CH H d CHAr), 6.60ppm(CH2d C H Ar).13C NMR (CDCl3):δ24.7,29.7-30.7,32.1-41.7,63.6,68.8,70.0-70.8, 74.3,114.7,122.2,137.6,140.7,144.7,176.6ppm.19F NMR (CDCl3):δ-162(m,meta-F(PFS)),-157(m,para-F(PFS)and meta-F(TFS)),-143ppm(m,ortho-F(PFS and TFS).Anal.Calcd for C42H30O5F19Br(3:1PFS:3):C,47.79;H,2.86;F,34.20;Br, 7.57%.Found:C,48.97;H,3.04;F,33.06;Br,4.22%;Cl,0.78%. Acknowledgment.Financial support from the Office of

Naval Research(N00014-05-1-0057)is gratefully acknowl-

edged.This material is also based upon work supported by the

National Heart Lung and Blood Institute of the National

Institutes of Health as a Program of Excellence in Nanotech-

nology(HL080729)and the McDonnell Pediatric Cancer Center

of the Children’s Discovery Institute at Washington University.

We also thank the Washington University Dean’s Fellowship

Program(KTP)and Unilever Corporation(CC)for Ph.D.student

and postdoctoral fellowship support,respectively. References and Notes

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那些冷门却让你心力交瘁的短篇文超级好看啊

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情感专家教你：情感专家教你： 2015/04/15 每个人都会被优秀的人所吸引，因为一个优秀的人身上必定会有出众的优点。而搞清楚女人心中优秀的男人是什么，并向着这个方向努力，才能有机会虏获女人的心。那么该如何成为一个女人喜爱的男人呢？一起来看本册内容。

目录情感专家教你：学习如何做一个体贴男人 ·如何成为女人喜爱的男人 ·体贴的男人要做到哪几点 ·幽默是男人征服女人的魔力 ·成熟的男人，对女人最有吸引力 ·如何塑造出成熟男人的魅力 ·如何才能成功吸引心仪的女生

·如何成为女人喜爱的男人每个人都会被优秀的人所吸引，因为一个优秀的人身上必定会有出众的优点。而搞清楚女人心中优秀的男人是什么，并向着这个方向努力，才能有机会虏获女人的心。那么该如何成为一个女人喜爱的男人呢？以下提几点方向作为建议： 1.塑造负责任的形象男人天生就具备更刚强有力的形象，这是生理所决定的。女人天生就比男人弱势，因此绝大部分女人都需要男人的保护。这种保护不仅是身体上的保护，在心理上男人也要给予女人充分的安全感。假如一个男人在女人遇到重大决定的时候能给出有效的建议，晚上约会总会坚持亲自送女人回家，遇到问题总是第一时间反省并承认自己的错误，那这个男人必定会得到女人的信任和依赖。一个男人负责任的态度会为女人带来安全感，且这种男人往往会显得更大度，更有能力，更受女人青睐。 2.提高自身的经济能力女人在选择男人（尤其是长期选择的对象）的时候也会看中对方的经济能力。无论你身上还有什么其他的才能，但女人一旦选择与你确立关系，都是要落到每天的生活上。没有经济实力就无法保证生活的质量，生活质量差往往会降低幸福感。因此，很实际的一个方法就是提升你的经济实力吧。在工作上更出色地表现，争取更高的职位和薪酬；学会理财和投资，增加额外收入；学习提升自身的技能，增加自身附加价值。假如现阶段的你还无法将你的经济实力立马提升起来，起码你也要表现出你赚钱的潜力。那么当女人感受到你是潜力股的时候也会在心里为你加分。 3.适当引导对方增加投入量女人对一个男人爱的程度很大部分取决于她对这段感情的投入量。情感大师康纳曾提到：

动漫

TV版：就是在电视上放的动画版本 OVA：Original Video Anime（原创影象动画），一般能够作为OVA的作品一定是在首次推出时是未曾在电视或戏院上映过的，如果在电视或戏院上映过的作品再推出的录影带（或LD/VCD）等等就不能称作OVA了。剧场版：动画的电影版本。动漫体裁： SF=SCIENCE FICTION科幻类的作品，如EVA，高达，凉宫春日的忧郁动漫作品的缩写：动漫发烧友之间常常用缩写代表自己熟悉的作品，缩写通常是能理解的，但也有些对于新人来说不是很熟悉，在此略举一二，以后逐渐补充。 FF：大家最熟悉的大概就是FF(FINAL FANTASY)系列了，FF系列本来是SQUARE公司的一个著名游戏，因为非常受欢迎所以有很多周边，比如游戏动画，OVA，电影等。但是最近使用FF的缩写则需要辨别一下了，因为《黑客帝国》系列也出品了一部动画短片名叫FINAL FLIGHT OF THE OSIRIS(欧西里司最后的飞翔)，缩写同样是FF。该片导演和《FINAL FANTASY》的电影版是同一个人(安迪*琼斯)，怪不得连名字都一样了。 M0=MACROSS ZERO(ZERO是零的意思，所以用“0”表示) ROD系列：目前出品的有两个作品，一个是READ OR DIE(OVA)，中文名为“死亡的思考”；另一个是正在制作放映中的READ OR DREAM(TV)，目前国内还没有D版。它们的缩写均为ROD [编辑本段]☆制作动画片人员解释：监督：导演原作：原漫画或小说的作者脚本：依据原作进行创作剧本人员 CAST：声优，配音演员 STAFF：参与制作动画的人员制作：指负责制作该动画的公司或部门（在日本，要制作一部动画通常是要数个部门或公司共同合作完成的，分工明确，流水线操作。一部动画的制作水准往往会受到制作单位的影响。所以在一些情况下，知道制作某部动画的公司或部门就知道该动画的水准。） [编辑本段]部分日本动漫术语： BL: 原英文为Boy's Love，特指男同性恋,又称耽美. GL：原英文为Girl's Love，特指女同性恋，又称百合，蕾丝边。（如《神无月的巫女》） BG：原英文为Boy and Girl，特指男女之间的配对。 CP: 指的是配对。 SM：sadomasochism的简写，统指与施虐、受虐相关的性意识与行为，多见于H动画或游戏中（日本称为鬼畜）。残念：日语音译，遗憾的意思，引申词语有“碎碎念” 。幼齿：年龄在8岁以下的小女孩。

2018-2018年中国男女婚恋观调研报告

2018-2018年中国男女婚恋观调研报告近日，国家人口计生委培训交流中心与世纪佳缘交友网联合发布的《2018-2018年中国男女婚恋观调研报告》显示，18岁-25岁女性有70%是“大叔控”，其中“气质大叔”、“事业型大叔”、“细腻体贴大叔”是“大叔控”们的最爱。所谓“大叔”，通常指30岁-50岁的中年男士，倾向于选择中年男士作为配偶的青年女性被称作“大叔控”。近日，中国青年报社会调查中心通过民意中国网和搜狐网，对2371人进行的一项调查显示，40.1%的受访者直言自己身边“大叔控”多。44.3%的受访者感觉很多女性抱有“要现货”的心理，不愿与伴侣共同奋斗。受访者中，70后占41.4%，80后占24.4%，90后占4.8%。 67.2%的人认为中年男士受青睐是因为大多已具备一定物质基础 1990年出生的张兰(化名)来北京打工一年多了。前不久，她在换房时结识了房东的朋友——一个70后的“大叔”。初次见面，“大叔”就开车帮她搬来了所有行李。之后两人经常一起吃饭聊天儿。“我经常向他倾诉生活和工作中的各种不快，他不但不会不耐烦，还会给出很多实用建议。作为一个独自在北京打拼的女孩子，‘大叔’的成熟体贴让我感到很舒心。” “女朋友常指责我自私、不考虑她的感受，夸赞‘大叔’有魅力。”山东小伙李守伟说，他女朋友是日漫迷、韩剧迷，最喜欢收集动漫和韩剧里的美型“大叔”图片，还把“大叔”定为他以后的发展方向。“我感觉这种心态太幼稚了。” 为什么一些年轻女性更青睐中年男士?调查中，67.2%的

人认为是中年男士大多已具备一定物质基础;55.5%的人认为是中年男士更稳重，有魅力;40.5%的人表示是中年男士更能体贴女性;39.3%的人觉得是作为独生子女的年轻人更愿意被照顾，而不懂得照顾别人。世纪佳缘婚恋专家张佳芮告诉记者，“大叔控”大多集中于年轻女性。初入社会的年轻女性缺少社会经验，而这正是成熟中年男性所具有的，他们能给予女性安全感。此外，现在不少家庭是“421”模式，四个老人、两个大人围绕一个孩子转，很可能导致独生子女长大后缺乏耐性和包容力，在恋爱和婚姻中表现得以自我为中心。 “时代不同，适婚年龄人群择偶需求也不同。”张佳芮说，70年代生人崇尚与知识分子结合，80年代生人更注重对方物质基础，90年代生人择偶不但务实，而且更注重自我感受。所以不管从物质还是感情出发，不少女性都愿意选择已具备一定条件的男士。稳定的感情需要男女双方耐心磨合，一同成长调查显示，52.6%的受访者对年轻女性当“大叔控”持认同态度，17.0%的人持反对态度，30.4%的人表示不好说。张兰认为，年轻女性与“大叔”结合是恋爱自由，没什么不可以。“单方面要求女性理解自己伴侣，等待其成长，也是不公平的。” “不少年轻女性有攀比心理，看到同龄人因为嫁得好，享受了更好的物质条件，就可能在感情中动摇。”李守伟认为，认同年轻女性当“大叔控”，是认同了男女双方只考虑自己的做法，抹杀了爱情相伴相守的美好，可能导致更多女性把恋爱和婚