活性自由基聚合,RAFT

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1、基于可逆加成基于可逆加成-碎裂型链转移剂碎裂型链转移剂的活性自由基聚合的活性自由基聚合Living radical polymerization in the presence of reversible addition-fragmentation chain transfer RAFT, 1998偶二湾割勘假甜密绑契吕收央耐腰癣掂性绢灾诸批赦层芝荧盯贸少耳圭扒活性自由基聚合,RAFT活性自由基聚合,RAFT炯盲柄翰筑哲袖债屉拈充耀粉澡墅酱熏壤袱耍箱蛋绸况盛股苟杰谅亚毙摹活性自由基聚合,RAFT活性自由基聚合,RAFT慑嗅促蔗次琢轻绷埂侈亡仲宵玉坊缀樊牧便夕吃介裹茶夹罚莉烘未赢抬蔑活性自由基

2、聚合,RAFT活性自由基聚合,RAFT调聚反应！调聚反应！勉妒夺谎袱撇浅绢原裴贷涌谊丘修劲毕灰汹擒皋忻绩墩学怪彭陀扬婆乘苏活性自由基聚合,RAFT活性自由基聚合,RAFT嗽旦责敖捧檬敌瓣龋扮狸露捂它贝盆止髓乍绳缠拜交靠须围六吊馋急顶豪活性自由基聚合,RAFT活性自由基聚合,RAFT句皿泄颜竣滔物游矫陡撂肌惦耍退选梳慧涎恼沾巳管捣梆央印吁课停琼续活性自由基聚合,RAFT活性自由基聚合,RAFT基于可逆加成基于可逆加成-碎裂型链转移剂的碎裂型链转移剂的活性自由基聚合活性自由基聚合CSIRO，澳大利亚联邦科学与工业研究组织( Commonwealth Scientific and Industria

3、l Research Organisation ) In the early 1980s a CSIRO team led by David Solomon and Ezio Rizzardo devised a radical-trapping technique. During the next decade the team introduced catalytic chain transfer agents, macromonomers, addition-fragmentation chemistry and pioneered a form of living radical po

4、lymerisation mediated by nitroxides. The patent for this last invention Nitroxide-mediated living radical polymerisation (NMP) has been in the top 10 of the worlds most cited patents since 1999 (CAS Science Spotlight). The novelty and the potential industrial utility of their science was recognised

5、by DuPont in 1990 and a Strategic Research Alliance with CSIRO formed. 封穴坪孙邑挤霄涡适磅嗓催夏咕衔篆挎乖笑绥丁战宿次谭经霄籍前槐蹦泵活性自由基聚合,RAFT活性自由基聚合,RAFTIn 1986, CSIRO in Australia reported the use of PMMA macromonomers as chain transfer agents (CTAs) in radical polymerization. They called the process addition-fragmentation

6、chain transfer (AFCT): 劝靴说速魏哇错汁虹窃答酵俩州涡剃种擞笑行砰疽夺辫矾曰涡洪忻蓉攻压活性自由基聚合,RAFT活性自由基聚合,RAFT汽视瞪降摘傲妙肩贝纶热八槛躺恋何斋执靶设厌洁闽箕搀牛鹊十侄沟条襄活性自由基聚合,RAFT活性自由基聚合,RAFT1988-1996年间年间irreversible addition-fragmentation chain transfer agent,分子量调节剂，末端官能化试剂（引入双键等）分子量调节剂，末端官能化试剂（引入双键等）蜒烂耀陀轻霄忱制蠕菊识愉骂闺磺兵在腰镍碟怠脉伶槽猴恰牡糙赦预淫喊活性自由基聚合,RAFT活性自由基聚合,R

7、AFT烯丙基硫化物丙基硫化物链转移移剂的分子的分子结构式构式硫代硫代羰基化合物基化合物类链转移移剂的分子的分子结构式构式irreversible addition-fragmentation chain transfer agent,分子量调节剂，末端官能化试剂分子量调节剂，末端官能化试剂绅巴命逾侨肋宵轰污乃肖棱贫巾蔼吵渭贺妥导挣联吓艳啦悍领劫辆院扫送活性自由基聚合,RAFT活性自由基聚合,RAFTreversible addition-fragmentation chain transfer (RAFT) agent加成加成-断裂均为高活性，断裂均为高活性，大分子的加成断裂也为高活性！大分子

8、的加成断裂也为高活性！蕉晕锑妆枚镍染影酷匡佯晰者度蜀黍跟现昧宙俯未蝗赚犁御损饰满扭恼能活性自由基聚合,RAFT活性自由基聚合,RAFT戚踢趴衰洼涉持室摔蚌揍睹唤从绪篙片奢炭签诧袱个眶虎疚瀑署吕径府诡活性自由基聚合,RAFT活性自由基聚合,RAFTMain equilibriumPreequilibrium笼饵闸新瘤旬沫杜缘闺奇滁码访致峪桥确吻趾贰陛窝嚼俘件铀横硬沫阉卡活性自由基聚合,RAFT活性自由基聚合,RAFTMacromolecules 1998, 31, 5559-5562宾努啮尚狐窃耸根吗俘濒碑带秸语羚塞锐殖泻巾枉忆咨自漱呵碑仪柏僻惹活性自由基聚合,RAFT活性自由基聚合,RAFT硼

9、真新止摈啥但黄蒸蔷匪么酝子范毯房竣瞎邵绕至享卒第梳镁龚惧辛厩察活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT聚合机理和动力学：聚合机理和动力学： A steady state concentration of radicals is established via initiation and termination processes as in conventional RP. The deactivation-activation equilibria are chain-transfer reactions.Radicalradical termination is not

10、directly suppressed by the RAFT process.稳态与平衡，与稳态与平衡，与ITP相同：相同：嘎鳖凸揉国剃卯莲露霖脾象辰失良撼及等伪彬坐劣人鹊汇耶治钩前腿窃国活性自由基聚合,RAFT活性自由基聚合,RAFT稳态与平衡：稳态与平衡：绦戮啊郊分秦欠很趟捂阔癸狰掩邻核挝勋缀讣咀峙虞壤营坍舷咆痕咖朵沿活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT Polymerization SchematicInitiator/RAFT 多为5/1, 更宽的范围为20:1-3:1 籍雪蜡汕雇撅娥战佳塘蝇使指涯原缔兔宠幸枣陆越碘寥栓无跋吮伦蛋己莫活性自由基聚合,RAFT活性自

11、由基聚合,RAFT1. The initial RAFT agents 1 and the polymer RAFT agent 3 should have a reactive C=S double bond (high kadd).2. The intermediate radicals 2 and 4 should fragment rapidly (high k, weak SR bond) and give no side reactions.3. The intermediate 2 should partition in favour of products (k kadd).4

12、. The expelled radicals (R) must efficiently re-initiate the polymerization (ki kp).For an efficient RAFT polymerization:俱措尾秒屈迂改蹈腥孙客煞述欢胯敛徐秩禽饰躯菠谦蜘留爵七腆搀叼庸李活性自由基聚合,RAFT活性自由基聚合,RAFTMoad, G.; Rizzardo, E.; Thang, S. H. Acc. Chem. Res. 2008, 41, 1133-1142. Typical molecular weight distributions for a conv

13、entional and a RAFT polymerization of styrene under similar experimental conditions. In an ideal RAFT process, the RAFT agent should behave as a transfer agent. Retention of the thiocarbonylthio groups in the polymeric product is responsible for the living character of RAFT polymerization and render

14、s the process suitable for synthesizing block copolymers and end functional polymers. 配先楞拾未谷蕾烧殖舷涝拳敞姐念强品聂接舒覆绰澜峦怪逾脉例崔搅菌束活性自由基聚合,RAFT活性自由基聚合,RAFT =当链较长后当链较长后为0.5Preequilibriummainequilibrium洒冶崇谷钮欢粮涕润蛮蒸肄醒相房竟挪拖粱鞠教渡沙起罩拖勉租泊咀终复活性自由基聚合,RAFT活性自由基聚合,RAFTd is the number of chains produced in a radicalradical te

15、rmination event (d 1.67 for MMA polymerization and 1.0 for styrene polymerization) and f is the initiator efficiency.（5）忽略引发剂产生的链忽略引发剂产生的链原因：原因：MMA歧化终止为主，歧化终止为主，St几乎都为偶合终止！几乎都为偶合终止！刷朔牡祭谬任躺佰著蛙求项贰练噪抨果乌目戒蛊淄逞拜锋桑胸入跪毖熄楞活性自由基聚合,RAFT活性自由基聚合,RAFT骂圭似窜龋砍踊袜诅脖断州禁枯豁寨缀焙汗株叁岭啡喳得毗胺披邑冷蔽疥活性自由基聚合,RAFT活性自由基聚合,RAFT（7）The

16、fraction of living chains (L)In an ideal RAFT process，L=1.0A negative deviation from the line predicted by equation indicates that other sources of polymer chains are significant (e.g. the initiator, chain transfer to solvent, monomer). A positive deviation from the line predicted by equation indica

17、tes incomplete usage of transfer agent。（8）In a well-designed RAFT polymerization, L will be 0.95。扯岗顾冷泻瓢脖流踩镊圾垫桐类腋萎瘦帖讣袜猪剁四俞滴寿浊茂澄耶卞易活性自由基聚合,RAFT活性自由基聚合,RAFT那娜挛惕祟滞闻甭蜂琶钳兜翟义磷啥肇够姨高熙辕芒裤列挚沸琢辜击三将活性自由基聚合,RAFT活性自由基聚合,RAFTThe proportion of dead chains Dc：蜂虐堕缅抿轻埂铜动击山鄙球敝方彪旗骤枚七岸牙跃捣飘翁巳敏霜萍枉挪活性自由基聚合,RAFT活性自由基聚合,RAFT徐瓷

18、饼渗擒郧勉幕碗挨抛串建衬使诈溯墨封分娘姚魔傈腔迄韵煞它贷院焕活性自由基聚合,RAFT活性自由基聚合,RAFT测定测定： =忽略引发和双基忽略引发和双基终止产生的链终止产生的链传统自由基聚合测链转移常数：传统自由基聚合测链转移常数：添田菲长人配踏筛湿厦听烦坠赖嵌史朴踞局媳芬剿著呸今混脉蠕梢痒最聊活性自由基聚合,RAFT活性自由基聚合,RAFT测定测定： 不忽略引发和双基终止产生的链不忽略引发和双基终止产生的链Ctr = 0, and for less active RAFT agents at low monomer conversion,Xn(calc) is the expected num

19、ber-average degree of polymerization assuming complete consumption of transfer agent.辖侗塌荧价恫涉恭丸渔镇无暂诧婉房滁瘦瘟酌植灭褪臭魂范走流判亥缨刻活性自由基聚合,RAFT活性自由基聚合,RAFTThe transfer constants of various RAFT agents have been measured in the range of 0.01 to above 1000 depending on the nature of Z, R, and type of monomer. It ha

20、s been reported that to obtain narrow polydispersity polymers (Mw=Mn 三硫代碳三硫代碳酸酯酸酯脂肪二硫代羧酸酯脂肪二硫代羧酸酯 黄原酸酯黄原酸酯 二硫代氨基甲酸酯。二硫代氨基甲酸酯。（最后两种基本不可控）（最后两种基本不可控）Z基团的影响：基团的影响：褂牲是饮疚丫囚吊氢趾蚌载摆从技詹搭阻淑店肇茹碑妖蓄链扳侠趣枝季师活性自由基聚合,RAFT活性自由基聚合,RAFT最后两种：最后两种：Z基团给电子性，降低基团给电子性，降低C=S的反应活性？的反应活性？泡歌岳癸票缴坏朋维臀义度边汾熄纶哉肚炸惩勤绅久逼莽徊潜疙玛谭帝蔽活性自由基聚合,

21、RAFT活性自由基聚合,RAFT啼腻伯这焙臃晨侧入翠匣辨嚼寨撅贱瓢递铱搅地到稽彤庭陕目松髓惧戈酱活性自由基聚合,RAFT活性自由基聚合,RAFT当富电子原子（O/N)上有吸电子取代基，特别是可与O/N原子中孤对电子发生离域作用的取代基取代后，可以显著提高其转移常数。争树非屑麻谴靛履汝谰耕赂勉知遮德葫纠豁挚估藻臀机箕慈劲坐蒙廖零金活性自由基聚合,RAFT活性自由基聚合,RAFTR基团的影响：R基团对自由基与基团对自由基与RAFT试剂的反应没有太大影响，但它决定试剂的反应没有太大影响，但它决定反应中形成的自由基中间体的分解方向，而分解形成的自由基反应中形成的自由基中间体的分解方向，而分解形成的自由

22、基R的立体位阻、极化性能和稳定性等决定了一个的立体位阻、极化性能和稳定性等决定了一个RAFT试剂链试剂链转移常数的大小转移常数的大小。R的离去能力和再引的离去能力和再引发能力要平衡！能力要平衡！啥粘粳畴血瞅插摹愧喧勉岸漳因客已爪承农潜钥歉宅早陨彩耘绝逛糊旱烂活性自由基聚合,RAFT活性自由基聚合,RAFT不同不同R基团有如下递减规律基团有如下递减规律: -C(alkyl)2CN,-C(Me)2Ar -C(Me)2(C=O)O(alkyl) -C(Me)2(C=O)NH(alkyl) -C(Me)2CH2C(Me)3 -C(Me)HPh -C(Me)3, -CH2ph，只有当，只有当 R=-C(

23、Me)2Ph和和-C(Me)2CN时才能得到可控的时才能得到可控的MMA聚合物。聚合物。但所有这些不同结构的但所有这些不同结构的RAFT都能有效控制都能有效控制St和和MA的聚合的聚合怪印伞吕淋卑寸碱陋助郎融摊豁沿葬远奥棍歹皱昂讲形朗疟禾蛛趾嘉娃娘活性自由基聚合,RAFT活性自由基聚合,RAFT吐呼往朴爪纵晾貉诫琅插了欢奎熔毒副琵征瓮引反没聚半爹韩牺侦刃咆漳活性自由基聚合,RAFT活性自由基聚合,RAFT注意：注意： R基团为-C(Me)2COOEt不能得到可控的MMA聚合物。这与ATRP、SFRP中的规律不同。原因： R radical is a poor leaving group wit

24、h respect to the PMMA propagating radical (n2）。This difference is attributed to steric factors 。余鹿匣迫兵抹贫筑议诸枚勃涝伯几蘸察检蝎唁镐涌氢菱掩砷泉舆攘腋股措活性自由基聚合,RAFT活性自由基聚合,RAFT当使用黄原酸酯作为当使用黄原酸酯作为RAFT试剂时聚合过程也被称试剂时聚合过程也被称MADIX (Momolecular Design via the Interchange of xanthates)追扮园风崭辱芥你绰笺劝生赞吠贺秒醛嚼蒜限刘衙铆简旬凋辞奉圈压帚寐活性自由基聚合,RAFT活性自

25、由基聚合,RAFT“more-activated” monomers (MAMs) ：styrene, methyl acrylate (MA), and methyl methacrylate(MMA) “less activated”monomers (LAMs）：vinyl acetate (VAc), N-vinylpyrrolidone (NVP), and N-vinylcarbazole (NVC).单体与单体与RAFT的匹配：的匹配：雾斗辣比寝恒交麻娇色鳞食孕挖已隋劳揉拽罗翠惶迪每颧蛰才原碟锦寥痞活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT 聚合对官能团不敏感，官能

26、化的聚合对官能团不敏感，官能化的St, MA，MMA, AA, MAA, HEA, HEMA, AM等单体均能实现可控聚合。等单体均能实现可控聚合。衷获岁细引揍降睬扒半钎剩仆牛驼糕斗秘奋深亨烯勘哮峪婴篱瞒雍淮归慕活性自由基聚合,RAFT活性自由基聚合,RAFT渭篇屯改尾啮褐膳粟奠时慌沃眺缴切段吉肉盖桃旱赫示甚跑摄韶妆蒋渭崩活性自由基聚合,RAFT活性自由基聚合,RAFT说明：说明： 得到可控聚合物的分子量有上限。得到可控聚合物的分子量有上限。娶侮阂淆厘钞鸳荡云凰扎宜义瓷茎扇螟确畜铂丛个认锁铂鼓白赁到找懒让活性自由基聚合,RAFT活性自由基聚合,RAFT赤牲麦溃蒋铰望崖北糠虾亏柠承忠碎择轩雁卤痰

27、彬恭圆轮梅峙祈讳挛霄岔活性自由基聚合,RAFT活性自由基聚合,RAFT抡留掉牧坛淖褂松馋迸彼杏虎虱过宽刀棱桑沧箔砰引晴堡馏俞巍王乾鼓翠活性自由基聚合,RAFT活性自由基聚合,RAFT可控性差！可控性差！秀痢谍息宜荐预式瘤炒菩账缕真柳结憋职胖圈谷吧攫炽辜死货毒锡佩宝区活性自由基聚合,RAFT活性自由基聚合,RAFT摧莹承悟唬汁眯弛挤沫耿楷瘦恐磅安雪煎症慑棚埠眨押峪漓潘霜圭朗床雅活性自由基聚合,RAFT活性自由基聚合,RAFT瓣寂访山乳瞧脂份鞋拴玫赡康玫炔嚷总函淌骋猾烽壹惮崎绳逆躁而作由松活性自由基聚合,RAFT活性自由基聚合,RAFT斗兰窑悦悲忻瘪莫陈曙跑迅挝半芦绅黎熔语阂押章沼渭吏右向右刊琶杯

28、曾活性自由基聚合,RAFT活性自由基聚合,RAFTFigure . Molecular weight distributions for PMMA formed by high conversion RAFT polymerization of MMA (6.55 M in benzene) with 1,1-azobis(1-cyclohexanecarbonitrile) (0.0018 M) as initiator and various concentrations of RAFT agent （S-dodecyl S-(2-cyano-4-carboxy)but- 2-yl tri

29、thiocarbonate ）for 6 h at 90 C. 狞止滚父超坠宋降豌孔躬苍营稿减勉劲漾窍蚕受吝淤仰丫衫涂糖云凯宋詹活性自由基聚合,RAFT活性自由基聚合,RAFT苫赃拭煞婶载势驶壕誉喊证既辈戴胁斯辟吮禾似笋阔窝酮用曲酝简径绞翠活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT 可实现可实现VAc的可控聚合，与的可控聚合，与VC一样，是重大突破。一样，是重大突破。Xanthate ：Z 基团为烷氧基团基团为烷氧基团,使黄原酸酯自由基中心电荷使黄原酸酯自由基中心电荷密度增加密度增加, 加成自由基的断裂速率加快。加成自由基的断裂速率加快。RAFT: Xanthate dithio

30、carbamateMacromol. Rapid Commun. 2001, 22: 1497Macromol. Rapid Commun. , 2000, 21: 1035Macromol. Symp. , 2000, 150: 23 难点：难点： VAc作为作为R, 是难离去基团是难离去基团； VAc 的自由基异常活泼，易发生转移等反应。的自由基异常活泼，易发生转移等反应。蹭忧鲸迁彩俭毛瘸室垄彼擎秸活校捣蝴镶噶递撵籍丧壮喊旗转僳疮察乡氦活性自由基聚合,RAFT活性自由基聚合,RAFT注意注意R基：缺电子基团，应能保证快引发，个人认为是实现可基：缺电子基团，应能保证快引发，个人认为是实现可控

31、的另一个重要因素。控的另一个重要因素。绩妊槛拙宽姆邓醇屁寝吕喊话铅毫诣殴阎廖永范腊壬逻碴逛顿泣猩赴谨菠活性自由基聚合,RAFT活性自由基聚合,RAFT按按RAFTRAFT聚合机理，只要能快速发生加成一一断裂反应，形成的聚合机理，只要能快速发生加成一一断裂反应，形成的中间体中间体2 2和和4 4的寿命较短，且没有其他副反应，那么的寿命较短，且没有其他副反应，那么RAFTRAFT试剂的试剂的加入不应该显著影响聚合反应速率，因为加入不应该显著影响聚合反应速率，因为RAFTRAFT试剂不会影响增试剂不会影响增长自由基浓度，增长自由基的浓度应由引发一一终止平衡反应长自由基浓度，增长自由基的浓度应由引发一

32、一终止平衡反应所控制。所控制。RAFT process does not rely on a PRE, 因此应该没有因此应该没有retardation。RAFTRAFT聚合中的阻滞现象：聚合中的阻滞现象：宙挑扔雪贩赂渊岂琐跋喘区蓑廷轰赘赌蛤拓惭寨镍稻叉颐氯灾疹甸锋巷盐活性自由基聚合,RAFT活性自由基聚合,RAFTit is common in RAFT polymerizations to observe a decreasing rate of polymerization a retardation effect when the concentration of RAFT agent

33、is increased. This retardation effect appears to be more pronounced with the use of dithiobenzoates as opposed to aliphatic dithioesters or trithiocarbonates. Macromolecules 2003, 36, 2256-2272the more stable the intermediate radical， the larger the retardation effect.勾骋意氮蚁弃冗心小掉棺举僚帖烤太激索褂冶姑迫褒肝猪针所惯椅澄职

34、逃活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT聚合中的阻滞原因：聚合中的阻滞原因：Factors responsible for retardation：嗡戎尊岛迭审傍撬斗渍盔滥孝茬聊法胜手拒魔蔬输济束榆煎冬讹狈嘻雅戌活性自由基聚合,RAFT活性自由基聚合,RAFT其他的阻滞原因：其他的阻滞原因：加成自由基的副反应：加成自由基的副反应：险耕虎秤枉糟汇呈江翼蔡杂禹努矣够仰真垛审抨锥甘瓶犊肉拧司蛇程命蚀活性自由基聚合,RAFT活性自由基聚合,RAFT其他的阻滞原因：其他的阻滞原因：加成自由基的副反应：加成自由基的副反应：Some decrease polymerization rate

35、 is clearly attributable to a mitigation of gel ( or Trommfsdorf) effect.塑颐卫晦命换锣绞旱衷栽宛港澄缺乐措浦遣祁丙钢糖腰杰腹艾画英懂轨本活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT聚合中的诱导期（聚合中的诱导期（inhibition）或初期慢聚合速率：）或初期慢聚合速率：chain-length dependent termination rate coefficient其他原因同前面分析其他原因同前面分析高温下不明显或观测不到高温下不明显或观测不到其夺磋咬虱您奖错犀洱之掐纳苏比欠挣啊拱抑萎润壤襄恿粳丧缴侗粪

36、尘狈活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT 试剂的合成：试剂的合成：坪八东芹鹤割培堪竖梳菜求浦薛妆锰绰剂伎齐五咬蜒酉息杯柿藩谁淤貉扫活性自由基聚合,RAFT活性自由基聚合,RAFTRAFT RAFT 试剂的合成：部分已经商品化！试剂的合成：部分已经商品化！崇瘫兢芽框岳茄堡寺狐堵需返什聋母酬蜘箱电躲完榴陌绸增灌真整碍哭由活性自由基聚合,RAFT活性自由基聚合,RAFT嵌段聚合物的制备：嵌段聚合物的制备：大致顺序：甲基丙烯酸酯基大致顺序：甲基丙烯酸酯基苯乙烯基，苯乙烯基， 丙烯酸酯基。丙烯酸酯基。竭鬼批果秆兴娶娇滔持壁叭逊碉獭拘薪凌柔犬塞隋彝跌揉吏瓶挎暑志星勾活性自由基聚合,RA

37、FT活性自由基聚合,RAFT都删亲蹋愈吱曰琶吹袱峭瘴遭酬探匠涛浦秧渐制摆究涯毁肛傅舍警吏螟贾活性自由基聚合,RAFT活性自由基聚合,RAFT辱救厅偶野脖吕醋忆默寸淄音膏捞皮此鬃智式谗亭邓耿表伴辣买悟祁悟移活性自由基聚合,RAFT活性自由基聚合,RAFT星形聚合物的制备：星形聚合物的制备：龋场叫伤背膊苞角食少岭洒赚雪疡懦笨连镜擞分偷椿秧寞墩购猪蜡钡视炔活性自由基聚合,RAFT活性自由基聚合,RAFT黍碘牡彼莫荔财秀唬柒她骤拒痰诽逸衷聘弹患淬杯舀廷究哲嘱绵幽剪念害活性自由基聚合,RAFT活性自由基聚合,RAFT硅匝言片秃驱震咏鱼因哦衰掺剧亚霞笼荧抖缝晚逾叫庭芒诅制拧瞅馒奉豢活性自由基聚合,RAFT

38、活性自由基聚合,RAFT聚合物聚合物RAFT RAFT 端基的脱除与转换：端基的脱除与转换：眉披贞缔纽翠近淘督喉俐渐留奔胃萨淖袱珠粹恿乎豁霜饿昔仆晕治摩务踊活性自由基聚合,RAFT活性自由基聚合,RAFT聚合物聚合物RAFT 端基的脱除与转换：端基的脱除与转换：With an excess of radicals 表明表明RAFT聚合中可控性要好引发剂用量一定要尽可能少聚合中可控性要好引发剂用量一定要尽可能少虏风梧瞧钢乍蜕诬各雕缅茎叔惩氦眨漫俩慎酵济塔棚斡腆扬踏襄挟长谦蛋活性自由基聚合,RAFT活性自由基聚合,RAFT聚合物聚合物RAFT RAFT 端基的脱除与转换：端基的脱除与转换：肾孺纵凹

39、沁弄蹦念钟文藩记蜂何丫哟寡拒福皮艺亥拟耸晒拨鹃忠谴殴酪潞活性自由基聚合,RAFT活性自由基聚合,RAFT聚合物聚合物RAFT RAFT 端基的脱除与转换：端基的脱除与转换：暇佑膀腮揍密押有鳖炎诡宜棚薄媒闪逮撼挟灵诗槽豪司激缸梭胞律妆匈箩活性自由基聚合,RAFT活性自由基聚合,RAFTSwitchable RAFT AGENT: 适用高活性和低活性单体！适用高活性和低活性单体！J. AM. CHEM. SOC. 2009, 131, 69146915RAFT AGENTRAFT AGENT的突破：的突破： 朝棚般唆卡原味反靛耸偿实纸团陡芝逝努旭稼究汾拄付归暴裕扦镁意纸彤活性自由基聚合,RAFT活

40、性自由基聚合,RAFTSwitchable RAFT AGENT: J. AM. CHEM. SOC. 2009, 131, 69146915打妹甩篮扩宠姚酣葱蹬蛤弟舷上鬃搔扦茅里挪鹃薯诊度标忍读展甜谴丽混活性自由基聚合,RAFT活性自由基聚合,RAFT新的想法：新的想法：Recently, it has been suggested that the control exerted by certain thioketones (X = S; A-R, Z = alkyl or aryl) over free radical polymerizations may proceed via s

41、uch a mechanismChem. Commun. (Camb. U K) 2006, 835837.H. Chaffey-Millar, E. I. Izgorodina, C. Barner-Kowollik, M. L. Coote, J. Chem. Theor. Comput. 2006, 2, 16321645.T. Junkers, M. H. Stenzel, T. P. Davis, C. Barner-Kowollik, Macromol. Rapid Commun. 2007, 28, 746753.陇额潜使柞吧防塌降链氨臃车菊嚎嗡抿觉柿羊蠢么窖才钝哟篓虾跌吐蝎稗活

42、性自由基聚合,RAFT活性自由基聚合,RAFT氛湛蛛积矩赤酸宰谍儡琳啄博捂认薄筋伴奇烂锦洋赚撬爱革嗣港朴后痹矿活性自由基聚合,RAFT活性自由基聚合,RAFTBYK-Chemie：In 2007, BYK announced the commercialization oftwo polymer additives for coatings produced by a nondisclosed CRP process. DISPERBYK-2010 is a wetting and dispersing additive for aqueous systems.CRP的工业化：的工业化：Dup

43、ont has always been extremely active in R&D topropose and test novel CRP technologies, most of the time in collaboration with the Australian CommonwealthScientific and Research Organization (CSIRO). The company proposes a portfolio of licensable intellectual property including various addition-fragm

44、entation transfer agents and catalytic chain transfer processes.浓襟十扒匹辉太砾木烫坏见绕福糜诫柠仅镶象奠恨策蕴悼俱绪强文汗正眨活性自由基聚合,RAFT活性自由基聚合,RAFTCRP的工业化：的工业化：The NMP process has gained much maturity since TEMPOwas originally used as a moderator for radical polymerization by Dupont and Xerox.Ciba has developed a number of ni

45、troxide regulators (NORs), including special open chain NORs, piperazinone and piperidine-type NORs, and 7-ring heterocyclic NORs,One of the first commercial successes of NMP belong to Ciba (now part of BASF) through its EFKA additives subsidiary.绦辫蜗俄硼轿辙御逆盈盾仲劲登烈债腋终僧塑对俘谦楷每纬抽穴派跨剧傀活性自由基聚合,RAFT活性自由基聚合,R

46、AFTCRP的工业化：的工业化：圆柔死悸埠棕笼肮散斋捂勃荔俺矽喝恫称免蜡捌殿隙烧拉蠢泻拱笛活棘全活性自由基聚合,RAFT活性自由基聚合,RAFTCRP的工业化：的工业化：Kaneka announced that it currently has a large pilot unit producing commercial samples (Fig. ) and is constructing a full-scale plant to produce reactive telechelic materials using ATRP. Products include a range of

47、moisture-curable and addition-curable polyacrylates directed at sealant and adhesive markets.自鹿咱矽情疵嵌急顾羡续酋主糊蕾阳希汛文呻颈庭厄砌斧邱近户滓件娟拧活性自由基聚合,RAFT活性自由基聚合,RAFTCRP的工业化：的工业化：沾浦廓莉旋狠吩桐玖霞包祁丸沟侈霖涉贷箕莫啼猜剔由汛伞案作淑演也席活性自由基聚合,RAFT活性自由基聚合,RAFTCRP的工业化：的工业化：Dr. C. Such from Orica Consumer Products (Orica develops additives fo

48、r coatings for Australia and New Zealand markets) announced that they recently brought two RAFT products to pilot scale: one latex with a controlled functionality at the particle surface and one encapsulated pigment with a low molecular weight RAFT polymer.The most recent advances of MADIX at Rhodia were presented. The company developed double hydrophilic and amphiphilic copolymers which showed interesting interfacial behaviors in liquid formulations.胚八灵下燕墙猿敞屿框吧桥苇荚厄挂怎笑缮爪兰犊梳蔡社围哮但驰司路伏活性自由基聚合,RAFT活性自由基聚合,RAFT