Synthesis of fluorinated hyperbranched polymers capable as highly hydrophobic and oleophobic coating materials
Weiyi Tang a ,Yangen Huang a ,Weidong Meng a ,Feng-Ling Qing a,b,*
a College of Chemistry,Chemical Engineering and Biotechnology,Donghua University,2999North Renmin Road,Shanghai 201620,China
b
Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,Chine Academy of Science,345Lingling Lu,Shanghai 200032,China
a r t i c l e i n f o Article history:
Received 21May 2009
来自于英语Received in revid form 13October 2009Accepted 1December 2009
Available online 5December 2009Keywords:
Hyperbranched polymers Fluoropolymers Coating
Surface free energy Wettability
a b s t r a c t
A ries of coating materials were prepared from two class of hyperbranched polymers containing short fluorocarbon chains (HPEFs/HPUFs ).The obtained hyperbranched poly-mers were characterized by FT-IR,1H NMR,13C NMR,19F NMR,GPC and TG analys.HPEFs/HPUFs exhibited very low surface free energies (13.67–24.49mJ/m 2)which almost are independent of their internal backbone but dependent on the terminal fluorocarbon chains.Highly hydrophobic and/or oleophobic surfaces of cotton woven fabric can be achieved from the polymers by solution-immersion coating method.The static and dynamic wettabilities of the HPEFs/HPUFs treated fabrics have been investigated.The sta-tic contact angles reached to 146°,122°and 102°for water,hexadecane and decane,respectively.The lowest contact angle hysteresis reached to 5.9°.
Ó2009Elvier Ltd.All rights rerved.
1.Introduction
The wetting behavior of solid surfaces by a liquid is a very important aspect of surface physics and chemistry,which are of great importance for both fundamental re-arch and practical applications [1,2].As an important property of a solid surface,the wettability is governed by both the surface free energy and surface geometrical struc-ture.Therefore,the surface wettability can be modulated by changing one or two of the factors [3,4].Some special surface wettabilities,such as strong hydrophobicity and/or oleophobicity can be achieved from the combination of rough surfaces with hierarchical micro-and/or nano-scaled structures and materials with low surface free en-ergy [5–7].Various approaches for obtaining highly hydrophobic or oleophobic surface have been prented,
such as template synthesis [8–10],pha paration [11,12],sol–gel methods [13,14],lf-asmbly [15,16],solution-immersion methods [17,18]and so on.Among the methods,the solution-immersion method has been found to be a simple and effective technique for depositing hydrophobic coatings onto substrates.The major advanta-ges of using this approach include large deposition areas,uniform deposits on the objects with desired shapes.
Previously,the studies and applications of macromolecule coating materials with low surface free energy (generally organic silicon compounds or organic fluoro-compounds)are mostly focud on the linear polymer.Hyperbranched polymers are highly branched macromolecules with unique featur
es such as three-dimensional globular architecture,low melting viscosity,good solubility,and large amount of terminal functional groups [19,20].Terminal groups of hyperbranched polymers are tunable by chemical modifica-tion to obtain desired properties for some particular applica-tions [21,22].In addition,hyperbranched polymers can be obtained by one-step or a pudo-one step procedure.The simplicity of the synthesis and commercial availability of the materials are very attractive from an industrial point of view as they can be provided in large-scale at a reasonable
0014-3057/$-e front matter Ó2009Elvier Ltd.All rights rerved.doi:10.1016/j.eurpolymj.2009.12.005
*Corresponding author.Address:Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,Chine Academy of Science,345Lingling Lu,Shanghai 200032,China.Tel.:+862154925187;fax:+862164166128.
E-mail address:flq@mail.sioc.ac, (F.-L.Qing).
European Polymer Journal 46(2010)506–518
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cost[23].Compounds containing long perfluoroalkyl chains (R fn,n P8)had excellent hydrophobic and oleophobic effects [2,18,24,25].However,environmentally benignfluorinated coating materials containing short perfluoroalkyl chains are highly desirable becau there are increasing evidences indi-cating that compounds containing long perfluoroalkyl chains (R fn,n P8)are toxic or can accumulate in environment,espe-cially for perfluorooctanoic acid(PFOA)[26–28].
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Herein,we described the synthes offluorinated hyperbranched polymers holding different surface free energies and their applications as coating materials to af-ford highly hydrophobic and/or oleophobic cotton fabrics by solution-immersion method.The unique features of hyperbranched polymers make the us of long perfluoro-alkyl chains unnecessary for achieving low surface energy.
2.Experimental
2.1.Materials
3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-1-octanol(ABCR Co.,98%).Hexamethylene diisocyanate(HDI)(Alfa Aesar, 98%).2,2-bis(hydroxymethyl)propionic acid(DMPA)(Flu-ka,97%).2,2,3,4,4,4-Hexafluorobutanol,trifluoroethanol (XEOGIA Co.,Harbin,China,96%).Para-toluene sulfonic acid(P-TSA),ethanol,pentaerythritol(PE,98%),dietha-nolamine(DEOA,98%),toluene,n-hexadecane,n-decane and N,N-dimethylformamide(DMF)were purchad from Shanghai Chemical Reagent Company(Shanghai,China). Toluene and DMF were treated by distillation with anhydrous MgSO4.All of other reagents were ud as received.
2.2.Characterization
1H NMR,and13C NMR spectra were recorded on a Bru-ker AV400spectrometer with Me4Si as an internal stan-dard.19F NMR spectra were recorded on a Bruker AV400 (376MHz)with CFCl3as an external standard.All chemical shifts(d)are expresd in ppm,the following abbreviations are ud to explain the multiplicities:s=singlet,d=dou-blet,t=triplet,q=quartet,m=multiplet.FT-IR spectra were recorded on a Nicolet AT-380(Thermo Electro Co. USA)spectrometer.Two instruments,Waters105C gel per-meation chromatograph with light scattering detector (GPC-LS)(Waters Corp.,Milford,MA)with THF as solvent (for HPEs)and Waters1515GPC with refractive index (GPC-RI)detector and DMF as solvent(for HPU2G)were ud to measure the molecular weight.Linear polystyrene was ud as standards.Thermogravimetric analys(TGA) of polymers was conducted on a Netzsch TG209F1instru-ments.The surface chemical composition of the treated fabrics was carried out by X-ray photoelectron spectros-copy(XPS,Thermo ESCALAB250,USA)with a power of 150W and a monochromatic Al K a X-ray source(1486.6 eV).The surface morphology of the untreated and treated cottonfibers were determined by scanning electron microscopy(SEM,JSM-5600LV,JEOL,Japan)as well as by atomic force microscopy(AFM,Nano Scope IV,Veeco,USA)with tapping mode.Contact angles and advancing/ receding contact angles were measured by an automatic video contact-angle testing apparatus(OCA40,Dataphys-ics Co.,Germany)at ambient temperature,and all the values were averages from measurements on at least five different positions
for each sample.The water repel-lency rating(spray test method)and oil repellency rating of the treated fabrics were measured according to AATCC test methods22-2001and118-2002[29],respec-tively.
2.3.Synthesis offluorinated hyperbranched polyesters/
poly(urea-urethane)
2.3.1.Synthes of hyperbranched polyesters(HPEs)
HPEs were synthesized in a pudo one-step process as shown in Scheme1.To a four-neckedflask equipped with a mechanical stirrer,a nitrogen inlet,a Dean and Stark appa-ratus and a thermometer,PE(0.82g,6mmol),DMPA (3.22g,24mmol),and P-TSA(0.016g,0.5wt.%of DMPA) were added in one portion,toluene(30mL)was ud as solvent.The reaction mixture was heated to reflux and stir-red for10h,and then DMPA(6.43g,48mmol)and P-TSA (0.032g)were added together in an amount corresponding to the cond generation product.After stirring for12h, DMPA(12.86g,96mmol)and P-TSA(0.064g)were added for making the third generation product.The reaction mix-ture was stirred at reflux for further12h and toluene was then removed.The residue was stirred in vacuum at140°C (about5mm Hg)for further2h to give the third genera-tion product(HPE3G)
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as pale yellow solid.The fourth,fifth and sixth generation(called HPE4G,HPE5G and HPE6G, respectively)products were obtained by repeating the above process.HPE3G:IR m max(cmÀ1,KBr),3600–3200 (O–H),2980,2880,1735(C@O).1H NMR(ppm,DMSO-d6),4.92(s),4.65(d),4.11(q),3.46(q),1.08(t).13C NMR (ppm,DMSO-d6),174.2–172.9(group),63.7,50.2,48.2, 46.2,16.7.HPE4G:IR m max(cmÀ1,KBr),3600–3200(O–H), 2980,2887,1732(C@O).1H NMR(ppm,DMSO-d6),4.90 (s),4.75(d),4.10(q),3.42(q),1.06(t).13C NMR(ppm, DMSO-d6),174.2–172.8(group),63.7,50.1,48.2,46.1, 16.7.HPE5G:IR m max(cmÀ1,KBr),3600–3200(O–H), 2963,2890,1735(C@O).1H NMR(ppm,DMSO-d6),4.93 (s),4.77(d),4.11(q),3.46(q),1.08(t).13C NMR(ppm, DMSO-d6),174.2–173.0(group),63.7,50.2,48.2,46.2, 16.7.HPE6G:IR m max(cmÀ1,KBr),3600–3200(O–H), 2978,2887,1736(C@O).1H NMR(ppm,DMSO-d6),4.93 (s),4.60(d),4.10(d),3.46(t),1.08(t).13C NMR(ppm, DMSO-d6),174.2–172.9(group),63.6,50.1,48.2,46.1,16.6.鲨鱼的画法
2.3.2.Synthesis of HPEN by lf-polymerization of DMPA做网店怎么推广
DMPA(20.10g,150mmol),P-TSA(1.01g)and toluene (80mL)were charged in the reactor and reacted for24h at reflux,and then toluene was removed and the residue was stirred in vacuum at140°C in vacuum for2h to give the product as white solid.HPEN:IR m max(cmÀ1,KBr), 3600–3200(O–H),2977,
2887,1736(C@O).1H NMR (ppm,DMSO-d6),4.99(s),4.67(s),4.18(q),3.52(q),1.14 (t).13C NMR(ppm,DMSO-d6),174.2–172.9(group),63.6, 50.1,48.2,46.1,16.7.
W.Tang et al./European Polymer Journal46(2010)506–518507
2.3.3.Synthesis of hyperbranched poly(urea-urethane)(HPU )
To a solution of DEOA (2.52g,24mmol)in DMF (20mL),HDI (4.03g,24mmol)in DMF (8mL)was added slowly with vigorous stirring under nitrogen at À5–0°C.The mixture was stirred at À5–0°C for 12h,and then PE (0.27g,2mmol)was added.The reaction mixture was warmed to room tem-perature and stirred for 10h,and then 80°C for 24h to ob-tain the resulting solution of HPU2G .Pure HPU2G product was obtained by pouring the resulting solution into diethyl ether (200mL)and the precipitate was collected,washed with diethyl ether (200mL Â3)and dried in vacuum at 80°C for 24h to afford pure HPU2G product as a pale yellow solid in theory a perfect two generation (Scheme 1).IR m max (cm À1,KBr):3430–3230(O–H,N–H),1704(NH CO O),1629(NH CO N).1H NMR (ppm,DMSO-d 6):7.10(s),6.26(s),5.73(s),4.83(s),3.96(s),3.46(s),3.38(s),3.34(s),3.26(t),2.95(d),2.55(m),1.37(s),1.23(s).13C NMR (ppm,DMSO-d 6):161.1–158.7(m),64.9,62.9,62.0,60.1,53.0,42.4,41.5,32.8–32.2,
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Scheme 1.Synthesis of fluorinated hyperbranched polyester/poly(urea-urethane).
508W.Tang et al./European Polymer Journal 46(2010)506–518
2.3.4.General procedure for the synthes of HPEFs/HPUFs
HPEFs/HPUFs were synthesized according to the same procedure as described for HPE3GF3as below(Scheme
1).Under nitrogen atmosphere,to a solution of HDI
(2.52g,15mmol)in DMF(17mL),trifluoroethanol (1.50g,15mmol)was added with stirring at0°C.The reac-tion mixture was stirred at35°C for2h and then the tem-perature was raid to80°C and stirred for15h to give a solution of M2.To this solution,HPE3G(1.59g)in DMF (7mL)(or proper quantity of resulting solution of HPU2G) was added.The reaction mixture was stirred at82°C until the absorption band of–NCO group in infrared spectrum (2273cmÀ1)disappeared.After cooling to room tempera-ture,ethanol(42mL)was added,and then the mixture was stirred for veral minutes to give the clear solution of HPE3GF3(85g/L bad on the complete conversion of reactant,not emulsion).The pure pr
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oduct will precipitate by adding deionized water(300mL)into this solution and which was collected byfiltration,washed with deionized water and diethyl ether(500and300mL, respectively)and dried under vacuum at80°C for24h to afford pure HPE3GF3product as white solid.When trifluo-roethanol was substituted by2,2,3,4,4,-hexafluorobutanol, HPE3GF6was obtained.HPEFs prepared from HPE3G/ HPE4G/HPE5G/HPE6G/HPEN and CF3(CF2)5(CH2)2OH were called HPE3GF13,HPE4GF13,HPE5GF13,HPE6GF13and HPENF13,respectively.HPUFs prepared from HPU2G and CF3CH2OH/CF3CFHCF2CH2OH/CF3(CF2)5(CH2)2OH were called HPU2GF3,HPU2GF6,HPU2GF13,respectively.19F NMR(ppm, DMSO),HPE3GF3:À72.18(d,3F).HPE3GF6:À72.81(s,3F),À116.72toÀ118.96(q,2F),À213.88(d,1F).HPE3GF13:À79.78(d,3F),À112.19(s,2F),À121.28(s,2F),À122.21 (s,2F),À122.78(s,2F),À125.30(s,2F).HPE4GF13:À79.72 (s,3F),À112.12(s,2F),À121.18(s,2F),À122.13(s,2F),À122.69(s,2F),À125.24(s,2F).HPE5GF13:À79.64(s,3F),À112.03(s,2F),À121.13(s,2F),À122.06(s,2F),À122.64(s,2F),À125.17(s,2F).HPE6GF13:À79.65(s,3F),À112.09 (s,2F),À121.16(s,2F),À122.09(s,2F),À123.42(s,2F),À125.42(s,2F).HPENF13:À79.67(s,3F),À112.12(s,2F),À121.18(s,2F),À122.12(s,2F),À122.67(s,2F),À125.22(s, 2F).HPU2GF3:À72.40(t,3F).HPU2GF6:À72.83(s,3F),À115.99toÀ118.96(q,2F),À213.93(d,1F).HPU2GF13:À79.91(s,3F),À112.29(s,2F),À121.34(s,2F),À122.28(s, 2F),À122.64(s,2F),À125.40(s,2F).
2.4.Fabrics treatment and smooth castfilms on glass slides
Clean,plain weave20Â20cm cotton fabric weighing 146g/m2was ud.Fabric samples werefirst imm
erd in the resulting clear solution of HPEFs/HPUFs(85g/L) for4–5min and then padded through two dips and two nips to reach a wet pickup of80–85%.The samples were dried at80°C for3min and baked at170°C for3min. The resulting clear solution of HPEFs/HPUFs(85g/L)was spread equably on the glass slide and dried at70°C for 30min then105°C for30min to afford the smooth cast films of HPEFs/HPUFs.
3.Results and discussion
3.1.Synthes and characterization of HPEs/HPU and HPEFs/HPUFs
3.1.1.Synthes and determination of degree of branching (DB)of HPEs/HPU
HPEs were synthesized from DMPA by esterification in the prence of P-TSA with PE as the core moiety through a pudo one-step process as shown in scheme1[30].HPEN was obtained through a one-step reaction.In order to achieve a high conversion and molecular weight,the water formed during the reaction must be removed continuously by nitrogenflowing and azeotropic distillation with
tolu-Fig.1.1H NMR spectra of HPEs in DMSO-d6.
W.Tang et al./European Polymer Journal46(2010)506–518509
ene at early stage of the polymerization and under reduced pressure when the condensation polymerization reached completion.
The1H NMR spectra of HPEs in DMSO-d6are shown in Fig.1.Resonance assignments(d ppm)are as follows: 1.02–1.22(–C H3),3.25–3.55(–C H2OH),3.9–4.2(–C H2OCO), 4.61(–O H),and4.92(–O H)[31].Methyl group protons of DMPA in the terminal repeat units(T),linear repeat units (L),and dendritic repeat units(D)resonate is at 1.02, 1.08,and1.17ppm,respectively.The13C NMR spectra of HPEs in DMSO-d6are shown in Fig.2.Signal assignments
(d ppm)are as follows:16.6–17.0(methyl carbons),46.1–
50.1(quaternary carbons),63.6–65.4(methylene groups), and171.6–175.3(carbonyl groups)[32].The top of Fig.2 is the expansion of the quaternary carbon region of differ-ent repeating units of HPE3G which are easily distin-guished from each other:d50.2ppm(T),d48.2ppm(L), and d46.2ppm(D).关于眼睛的作文
Degree of branching(DB)is one of the most important molecular parameters for hyperbranched polymers.It ex-erts a tremendous influence on the physical and chemical properties of the materials.I
n this paper,DB of hyper-branched polymers is given by the following equation[33] DB¼ðN DþN TÞ=ðN DþN TþN LÞð1Þ
N D,N T,and N L reprent the numbers of dendritic units, terminal units,and linear units,respectively.The relative amount of each type of monomer unit was determined by comparing the integrals of different peaks.There are two approaches for determine the DB of HPEs from1H NMR spectra.As shown in Fig.1,one method is bad on the methylene(C H2)and the ratio of(–O H)T and(–O H)L, the other is bad on the methyl group.DB of HPEs also can be calculated from the13C NMR by the inte-gration of corresponding quaternary carbon peaks(Fig.2). As shown in Table1,the values of DB(0.47–0.57)are gen-erally in agreement with each other for different calculat-ing methods and approached to the theoretical value (DB=0.5or0.67)[34,35]for the hyperbranched polymer made from AB2type monomer by one-step or pudo-one step procedure.
Polyureas are now widely ud in thefields of rubber, plastics,fiber,coating and so on.Herein,a hyperbranched polymer with alternating ureido and urethano units was prepared as shown in scheme1.The cond generation of hyperbranched poly(urea-urethane)(HPU2G)was syn-thesized from HDI and DEOA with PE as the core moiety. Equimolar amounts of HDI and DEOA and the temperature controlling are the keys for the synthesis;otherwi,gela-tion will occur during the reacti
on.The reaction must be kept atÀ5–0°C during the initial period in order to com-pletely form the AB2type monomer M1.HPU2G was also ud for a comparison of the structure–property relation-ship with HPEs.DB of HPU2G calculated from the integra-tion of corresponding13C NMR peaks of–C H2OH[36]was also shown in Table1.
3.1.2.GPC analysis
GPC or SEC is one of the most widely ud techniques for the determination of the molecular weight and polydis-persity index(PDI)of the polymers(including hyper-branched polymers)at prent.GPC with light scatter/ refraction index detector were ud to measure the
molec-Fig.2.13C NMR spectra of HPEs in DMSO-d6.
Table1
Characterization of HPEs and HPU.
Samples DB%(–C H3)DB%(–O H,–C H2–)DB%(C)M t a GPC M w/M n(PDI)b
M n M w HPE3G49.949.048.9338451005300 1.04 HPE4G50.151.248.9709676007700 1.01 HPE5G53.457.150.814,52013,30013,400 1.01 HPE6G54.457.250.529,36822,30022,600 1.01 HPEN50.647.349.4–15,10015,700 1.04 HPU2G––43.2341232,500171,400 5.27
a Theoretical molecular weight.
b Polydispersity index.
510W.Tang et al./European Polymer Journal46(2010)506–518
