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Preparation of Hyperbranched Polymers by Atom Transfer Radical

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Preparation of Hyperbranched Polymers by Atom Transfer Radical PreparationofHyperbranchedPolymersbyAtomTransfer RadicalPolymerization JIANGBIBIAO,1 YANGYANG,1 DENGJIAN,1 FUSHIYANG,1 ZHURONGQI,2 HAOJIANJUN,2 WANGWENYUN2 1 DepartmentofChemicalEngineering,JiangsuInstituteofPetrochemicalTechnology,Changzhou, People’sRepublicofChina,213016 2 DepartmentofPolymerMaterialScienceandEngineering,SichuanUniversity,Chengdu, People’sRepublicofChina,610065 Received24January2001;accepted6March2001 Publishedonline20December2001 ABSTRACT: AcheapacrylicAB*monomer,2-(2-chloroacetyloxy)-isopropylacrylate (CAIPA),waspreparedfrom2-hydroxyisopropylacrylatewithchloroacetylchloridein thepresenceoftriethylamine.Theself-condensingvinylpolymerizationbyatomtrans- ferradicalpolymerization(ATRP),a“living”/controlledradicalpolymerization,has yieldedhyperbranchedpolymers.Allthepolymerizationproductswerecharacterized byprotonnuclearmagneticresonancespectroscopy(1HNMR).CAIPAexhibiteddis- tinctivepolymerizationbehaviorthatissimilartoaclassicalstep-growthpolymeriza- tionintherelationshipofmolecularweighttopolymerizationtime,especiallyduring theinitialstageofthepolymerization.However,asignificantamountofmonomer remainedpresentthroughoutthepolymerization,whichisconsistentwithtypicalchain polymerization.Also,ifamuchlongerpolymerizationtimewasused,thepolymer becamegel.AsaresultoftheunequalreactivityofgroupA*andB*,thepolymerization isdifferentfromanidealself-condensingvinylpolymerization:thebranchstructuresof polymersprepareddependdramaticallyontheratioof2,2’-bipyridyltoCAIPA.Hyper- branchedpolymersexhibitimprovedsolubilityinorganicsolvent,however,theyhave lowerthermalstabilitythantheirlinearanalogs.©2002JohnWiley&Sons,Inc.JAppl PolymSci83:2114–2123,2002 Keywords:hyperbranchedpolymers;atomtransferradicalpolymerization;NMR; thermogravimetricanalysis;self-condensingvinylpolymerization INTRODUCTION ture.Dendriticpolymersprovidedramaticexam- plesoftheeffectofbranchingonpolymerstruc- Theaccuratecontrolofmacromoleculararchitec- tureandpropertiesbecausetheyhavebeen tureisanimportantthemeinmodernpolymer showntoexhibitphysicalpropertiesdistinctly science,withmanyadvancedmaterialsthatpos- differentfromlinearpolymers.3,4 However,be- 1,2 sessneworimprovedproperties. Amethod causethesynthesisofregularlybranchedden- commonlyusedtoachievethesegoalsisthein- drimersisnottrivialandrequiresmultistepsyn- troductionofbranchingintothepolymerstruc- thesis,theircommercialdevelopmenthasbeen limitedtoonlyafewstructures.Thesynthesisof Correspondenceto:J.Bibiao([email protected]). hyperbranchedpolymers,polymersthatpossess JournalofAppliedPolymerScience,Vol.83,2114–2123(2002) lessperfectbranchedstructures,hasbeenex- ©2002JohnWiley&Sons,Inc. DOI10.1002/app.10153 ploredtodevelopdendriticmoleculesinsingle 2114 HYPERBRANCHED POLYMERS MADE BY ATOM TRANSFER RADICAL POLYMERIZATION 2115 and one-pot reactions.5–8 These polymers are usu- EXPERIMENTAL ally obtained by the reaction of AB2 monomer, in which A and B are functional groups capable of Reagents reacting with each other to form stable bonds. 2-Hydroxyisopropyl acrylate, a commercial prod- Because of the unusual structure of the AB 2 uct from Wuxi Huayi Chemicals, was used as monomer, reaction between two monomers re- received. 2,2’-Bipyridyl (Bipy), an analytical re- sults in the formation of a dimer with one A group agent, was used as obtained from Shanghai No.1 and three B groups. This process repeats itself by chemical reagent factory. Chloroacetyl chloride, a reaction with monomer, dimer, trimer, etc., as in chemical reagent from Shanghai No.1 chemical classical step-growth polymerization. The result- reagent factory, was distilled under atmospheric ϩ ing macromolecules have one A group and n 1B pressure; the distillate between 105 and 107 °C groups, where n is the number of repeat units. In was collected and used. Copper (I) chloride (CuCl, addition to the step-growth polymerization used AR grade) was purified by stirring in acetic acid, in the preparation of hyperbranched polymers, washing with methanol, and then drying under the original idea and pioneer work should be that reduced pressure. AIBN, AR grade, was recrystal- proposed and carried out by Frechet and co-work- lized from ethanol. Acetone, tetrahydrofuran ers; they have described a new method, named (THF), ethanol, acetic acid, methanol, petroleum self-condensing vinyl polymerization, by which ether (30–60 °C), ether, triethylamine, activated AB* monomers can be used to synthesize hyper- charcoal, H2SO4, and NaHCO3 (AR grade) were branched polymers with a whole carbon backbone used without further purification. by cationic polymerization.9 This monomer satis- fies the AB* requirements for formation of hyper- Preparation of 2-(2-Chloroacetyloxy)-isopropyl branched polymers because the vinyl group acts Acrylate as the difunctional group A and an additional 2-Hydroxyisopropyl acrylate (8 mL; 0.125 mol), alkyl halide functional group acts as the B* triethylamine (21 mL; 0.15 mol), 100 mL ether, group. By activation of the B* group with a Lewis and a little CuCl were added into a three-necked acid, polymerization through the double bond oc- flask equipped with a thermometer and a stirrer. curs cationically. After this original idea and pio- Chloroacetyl chloride (10 mL, 0.125 mol) dis- neer work, Hawker, Scott, Weimer, Matyjasze- solved in 25 mL of ether was added in a dropwise wski, and Frechet have extended this method into manner into the flask and the solution was stirred the living radical polymerization field; the mono- for1hat0–4 °C. After the addition of chloro- mers employed were 4-(chloromethyl) styrene, acetyl chloride, the reaction was continued at 35 self-made styrene type and acrylic AB* mono- °C for 6 h. The reaction mixture was washed three 10–15 mers. However, the cost of the monomers times with diluted H2SO4 (10% by weight) at first, used is very expensive and preparation of the and then three times each with concentrated 10–16 monomers is difficult. Matyjaszewski and co- NaHCO3 solution and distilled water. An orange workers have reported on the polymerization of transparent ether solution was obtained following AB* monomer with mismatched reactivities.17 In these purification processes. Anhydrous sodium summary, the commercial development of poly- sulfate and activated charcoal were added into mers from these AB* monomers may be limited. the solution, and the solution was allowed to We report here studies on the preparation of hy- stand overnight. The solution was filtered. Vola- perbranched polymer from a very inexpensive tilization of ether left a slightly yellow transpar- ent oil liquid in a yield of 72% and with the proton acrylic AB* monomer by atom transfer radical 1 polymerization (ATRP), a “living”/controlled rad- nuclear magnetic resonance ( H NMR) spectrum ical polymerization system that has been demon- shown in Figure 1A. strated to successfully polymerize styrene,18–22 (meth)acrylates,18,223–26 and acrylontrile.27 There Typical Polymerization Procedure of CAIPA are some comprehensive reviews in the literature In a typical polymerization, Bipy (0.624 g; 4.0 on ATRP.28–30 As will be later demonstrated, hy- mmol; 0.4 equiv), CuCl (0.2 g; 2.0 mmol; 0.2 perbranched polymers can be prepared from this equiv), CAIPA (2.06 g; 10 mmol; 1.0 equiv), and a inexpensive acrylic AB* monomer when a high stirrer bar made of PTFE were added to a dry concentration of catalyst is employed. flask. The flask was cycled between vacuum and 2116 BIBIAO ET AL. were the same as that stated in the polymeriza- tion of CAEA. After polymerization, ϳ25 mL of acetone was added, and the mixture was stirred to complete the dissolution of the polymer. Then, the solution was poured into a large amount of petroleum ether with rapid stirring to precipitate the products. The precipitated polymer was col- lected and washed three times with methanol, then purified by reprecipitation from the acetone solution into excess petroleum ether. Drying at room temperature for several hours allowed vol- atilization of the solvent, and then the sample was heated in a vacuum oven at 50 °C for at least 24 h. The monomer conversion or polymer yield was calculated gravimetrically. Figure 1 (A) 1H NMR spectrum of CAIPA. (B) 1H NMR spectrum of linear poly(CAIPA). (C) 1H NMR spectrum of hyperbranched polymer sample 15 from Preparation of Linear Polymer of CAIPA and CAIPA. Copolymer of CAIPA with Styrene Linear poly(CAIPA) was prepared as follows: CAIPA (7.68 g, 0.04 mol) and AIBN (0.0384 g, nitrogen Ͼ10 times to remove the oxygen. Then, 0.5% CAIPA by wt) were added into a round- the flask was sealed and placed in a preheated, bottomed flask and the flask was placed into an thermally regulated oil bath at 125 Ϯ 1 °C. After oil bath at 50 °C. After 45 min of polymerization, a certain period of polymerization, the flask was THF was added to dilute the polymerization mix- removed from the oil bath and allowed to cool for ture. The solid polymer was precipitated into a few minutes. Then, 12 mL of acetone was added methanol twice and dried at 40 °C for 24 h in to the flask, and the mixture was stirred at room vacuo to yield 17%. temperature to complete the dissolution of the Linear poly(CAIPA-co-styrene) was prepared polymer. Then, petroleum ether (5 times the ace- as follows: CAIPA (7.68 g, 0.04 mol), styrene (4.56 tone in volume) was added to precipitate the re- g, 0.04 mol), and AIBN (0.0612 g, 0.5% of mono- sulting polymer. After repeating these dissolution mer by wt) were added to a round-bottomed flask and precipitation processes another time, the and the flask was placed in an oil bath
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