1045:
4076:. CNTs intrinsic electronic properties lead them to form large aggregates in solution, precluding useful applications. Adding small chemical groups to the walls of CNT can eliminate this propensity and tune the response to the surrounding environment. The use of polymers instead of smaller molecules can modify CNT properties (and conversely, nanotubes can modify polymer mechanical and electronic properties). For example, researchers coated carbon nanotubes with polystyrene by first polymerizing polystyrene via chain radical polymerization and subsequently mixing it at 130 °C with carbon nanotubes to generate radicals and graft them onto the walls of carbon nanotubes (Figure 27). Chain growth polymerization ("grafting to") synthesizes a polymer with predetermined properties. Purification of the polymer can be used to obtain a more uniform length distribution before grafting. Conversely, âgrafting fromâ, with radical polymerization techniques such as
1836:: In this process, polymer chains are allowed to grow along template macromolecules for the greater part of their lifetime. A well-chosen template can affect the rate of polymerization as well as the molar mass and microstructure of the daughter polymer. The molar mass of a daughter polymer can be up to 70 times greater than those of polymers produced in the absence of the template and can be higher in molar mass than the templates themselves. This is because of retardation of the termination for template-associated radicals and by hopping of a radical to the neighboring template after reaching the end of a template polymer.
602:
1551:
1581:
1533:
1506:
1481:
3668:
1129:
1401:
1152:
956:
3642:
1463:
1417:
991:
686:
1440:
29:
1381:
918:
708:
1326:
1932:: used to synthesize linear or branched polymers with narrow molecular weight distributions and reactive end groups on each polymer chain. The process has also been used to create block co-polymers with unique properties. Conversion rates are about 100% using this process but require temperatures of about 135 °C. This process is most commonly used with acrylates, styrenes, and dienes. The reaction scheme in Figure 23 illustrates the SFRP process.
1315:
4126:
3638:=CXY. There are two ways that a monomer molecule can approach the terminal carbon: the mirror approach (with like substituents on the same side) or the non-mirror approach (like substituents on opposite sides). If free rotation does not occur before the next monomer adds, the mirror approach will always lead to an isotactic polymer and the non-mirror approach will always lead to a syndiotactic polymer (Figure 25).
1935:
1344:
598:. The relatively non-specific nature of free-radical chemical interactions makes this one of the most versatile forms of polymerization available and allows facile reactions of polymeric free-radical chain ends and other chemicals or substrates. In 2001, 40 billion of the 110 billion pounds of polymers produced in the United States were produced by free-radical polymerization.
1946:
3626:. Isotactic polypropene is a high-melting (165 °C), strong, crystalline polymer, which is used as both a plastic and fiber. Atactic polypropene is an amorphous material with an oily to waxy soft appearance that finds use in asphalt blends and formulations for lubricants, sealants, and adhesives, but the volumes are minuscule compared to that of isotactic polypropene.
1080:. Metallocenes in combination with initiators accelerate polymerization of poly(methyl methacrylate) and produce a polymer with a narrower molecular weight distribution. The example shown here consists of indenylzirconium (a metallocene) and benzoyl peroxide (an initiator). Also, initiating systems containing heteroaromatic diketo carboxylic acids, such as 3,6-bis(
1311:. The free radical uses one electron from the pi bond to form a more stable bond with the carbon atom. The other electron returns to the second carbon atom, turning the whole molecule into another radical. This begins the polymer chain. Figure 12 shows how the orbitals of an ethylene monomer interact with a radical initiator.
1867:: The polymerization is initiated by high-intensity ultrasound. Polymerization to high molecular weight polymer is observed but the conversions are low (<15%). The polymerization is self-limiting because of the high viscosity produced even at low conversion. High viscosity hinders cavitation and radical production.
1886:, controlled radical polymerization, reversible deactivation radical polymerization (RDRP) relies on completely pure reactions, preventing termination caused by impurities. Because these polymerizations stop only when there is no more monomer, polymerization can continue upon the addition of more monomer.
4084:
3176:
3616:
polymers consist of a random arrangement of stereochemistry and are amorphous (noncrystalline), soft materials with lower physical strength. The corresponding isotactic (like substituents all on the same side) and syndiotactic (like substituents of alternate repeating units on the same side) polymers
3602:
studied the stereoisomerism in chain polymerization of vinyl monomers in the late 1920s, and it took another two decades for people to fully appreciate the idea that each of the propagation steps in the polymer growth could give rise to stereoisomerism. The major milestone in the stereochemistry was
1573:
the radical of a polymer chain abstracts a hydrogen atom from somewhere on another polymer chain (Figure 22). This terminates the growth of one polymer chain, but allows the other to branch and resume growing. This reaction step changes neither the number of polymer chains nor the number of monomers
1515:
The effectiveness of chain transfer involving solvent molecules depends on the amount of solvent present (more solvent leads to greater probability of transfer), the strength of the bond involved in the abstraction step (weaker bond leads to greater probability of transfer), and the stability of the
1373:
two chain ends simply couple together to form one long chain (Figure 14). One can determine if this mode of termination is occurring by monitoring the molecular weight of the propagating species: combination will result in doubling of molecular weight. Also, combination will result in a polymer that
1033:
initiator is the combination of several types of initiators into one initiating system. The types of initiators are chosen based on the properties they are known to induce in the polymers they produce. For example, poly(methyl methacrylate) has been synthesized by the ternary system benzoyl peroxide
3629:
When a monomer adds to a radical chain end, there are two factors to consider regarding its stereochemistry: 1) the interaction between the terminal chain carbon and the approaching monomer molecule and 2) the configuration of the penultimate repeating unit in the polymer chain. The terminal carbon
2857:
If chain transfer is considered, the kinetic chain length is not affected by the transfer process because the growing free-radical center generated by the initiation step stays alive after any chain-transfer event, although multiple polymer chains are produced. However, the number average degree of
4121:
network polymer, with clay particles acting as branching points for multiple polymer chain segments. Free radical polymerization used in this context allows the synthesis of polymers from a wide variety of substrates (the chemistries of suitable clays vary). Termination reactions unique to chain
2494:
v is a measure of the average number of monomer units reacting with an active center during its lifetime and is related to the molecular weight through the mechanism of the termination. Without chain transfer, the kinetic chain length is only a function of propagation rate and initiation rate.
4651:
Kato, M; Kamigaito, M; Sawamoto, M; Higashimura, T (1995). "Polymerization of Methyl
Methacrylate with the Carbon Tetrachloride / Dichlorotris-(triphenylphosphine)ruthenium(II) / Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization".
1547:
a polymer chain reacts with an initiator, which terminates that polymer chain, but creates a new radical initiator (Figure 21). This initiator can then begin new polymer chains. Therefore, contrary to the other forms of chain transfer, chain transfer to the initiator does allow for further
1890:
can be made this way. RDRP allows for control of molecular weight and dispersity. However, this is very difficult to achieve and instead a pseudo-living polymerization occurs with only partial control of molecular weight and dispersity. ATRP and RAFT are the main types of complete radical
1856:
undergo polymerization to high molecular weight products under these conditions. The propagation mechanisms appear to involve both ionic and radical species. Plasma polymerization offers a potentially unique method of forming thin polymer films for uses such as thin-film capacitors,
1092:
of the polymer. The combination of all of these componentsâa metallocene, an initiator, and a heteroaromatic diketo carboxylic acidâyields a ternary initiating system that was shown to accelerate the polymerization and produce polymers with enhanced heat resistance and regular
1362:
is inevitable in radical polymerization due to the high reactivity of radicals. Termination can occur by several different mechanisms. If longer chains are desired, the initiator concentration should be kept low; otherwise, many shorter chains will result.
1023:(the formation and collapse of cavities in the liquid). The collapse of the cavities generates very high local temperatures and pressures. This results in the formation of excited electronic states, which in turn lead to bond breakage and radical formation.
3607:
to synthesize stereoregular polymers. The reason why the stereochemistry of the polymer is of particular interest is because the physical behavior of a polymer depends not only on the general chemical composition but also on the more subtle differences in
4532:
Pojman, John A.; Jason Willis; Dionne
Fortenberry; Victor Ilyashenko; Akhtar M. Khan (1995). "Factors affecting propagating fronts of addition polymerization: Velocity, front curvature, temperature profile, conversion, and molecular weight distribution".
2696:
1340:) or until termination occurs. There may be anywhere from a few to thousands of propagation steps depending on several factors such as radical and chain reactivity, the solvent, and temperature. The mechanism of chain propagation is as follows:
5020:
Richard, R. E.; M. Schwarz; S. Ranade; A. K. Chan; K. Matyjaszewski; B. Sumerlin (2005). "Evaluation of acrylate-based block copolymers prepared by atom transfer radical polymerization as matrices for paclitaxel delivery from coronary stents".
2258:, the concentration of the active growing chains remains constant, i.e. the rates of initiation and of termination are equal. The concentration of active chain can be derived and expressed in terms of the other known species in the system.
4004:
1763:
3770:, which is a constant for a given monomer, and has the same value for the radical derived from that specific monomer. For addition of monomer 2 to a growing polymer chain whose active end is the radical of monomer 1, the rate constant,
1596:
The most obvious effect of chain transfer is a decrease in the polymer chain length. If the rate of transfer is much larger than the rate of propagation, then very small polymers are formed with chain lengths of 2-5 repeating units
2884:
3621:
leads to higher physical strength and increased solvent and chemical resistance as well as differences in other properties that depend on crystallinity. The prime example of the industrial utility of stereoregular polymers is
1273:
1824:
similar to suspension polymerization except that the initiator is soluble in the aqueous phase rather than in the monomer droplets (the monomer is hydrophobic, and the initiator is hydrophilic). An emulsifying agent is also
640:
process. During initiation, an active center is created from which a polymer chain is generated. Not all monomers are susceptible to all types of initiators. Radical initiation works best on the carbonâcarbon double bond of
2485:
2230:
2061:
1088:-isopropylcarbazole in this example, are known to catalyze the decomposition of benzoyl peroxide. Initiating systems with this particular heteroaromatic diket carboxylic acid are also known to have effects on the
884:
987:
to form a radical cation (Figure 6). The radical ions then initiate free radical (and/or ionic) polymerization. This type of initiation is especially useful for coating metal surfaces with polymer films.
2352:
1436:
is the common inhibitor. The growing chain will react with molecular oxygen, producing an oxygen radical, which is much less reactive (Figure 17). This significantly slows down the rate of propagation.
657:
are created from the initiating molecules. In the second step, radicals are transferred from the initiator molecules to the monomer units present. Several choices are available for these initiators.
1007:
A gaseous monomer is placed in an electric discharge at low pressures under conditions where a plasma (ionized gaseous molecules) is created. In some cases, the system is heated and/or placed in a
717:
Photoinitiation can also occur by bi-molecular H abstraction when the radical is in its lowest triplet excited state. An acceptable photoinitiator system should fulfill the following requirements:
3863:
3492:
3430:
3368:
3306:
3244:
2852:
1530:
a hydrogen atom is abstracted from a monomer. While this does create a radical on the affected monomer, resonance stabilization of this radical discourages further propagation (Figure 20).
4117:. Polymers grow off the initiators that are in turn bound to the clay. Due to recombination and disproportionation reactions, growing polymer chains bind to one another, forming a strong,
765:
Reduction of hydrogen peroxide or an alkyl hydrogen peroxide by iron (Figure 3). Other reductants such as Cr, V, Ti, Co, and Cu can be employed in place of ferrous ion in many instances.
1921:
2858:
polymerization decreases as the chain transfers, since the growing chains are terminated by the chain-transfer events. Taking into account the chain-transfer reaction towards solvent
1492:
results in the destruction of only one radical, but also the creation of another radical. Often, however, this newly created radical is not capable of further propagation. Similar to
2251:
are the constants for initiator dissociation, chain propagation and termination, respectively. and are the concentrations of the initiator, monomer and the active growing chain.
4373:
Islamova, R. M.; Puzin, Y. I.; Kraikin, V. A.; Fatykhov, A. A.; Dzhemilev, U. M. (2006). "Controlling the
Polymerization of Methyl Methacrylate with Ternary Initiating Systems".
2501:
3617:
are usually obtained as highly crystalline materials. It is easier for the stereoregular polymers to pack into a crystal lattice since they are more ordered and the resulting
1398:
a hydrogen atom from one chain end is abstracted to another, producing a polymer with a terminal unsaturated group and a polymer with a terminal saturated group (Figure 15).
3766:, respectively. The polar effects in the transition state, the supposed permanent electric charge carried by that entity (radical or molecule), is quantified by the factor
3576:
become less negative. At a certain temperature, the polymerization reaches equilibrium (rate of polymerization = rate of depolymerization). This temperature is called the
3557:
must then be sufficiently negative to compensate for the unfavorable entropic term. Only then will polymerization be thermodynamically favored by the resulting negative ÎG
3541:
that releases the ring tension in a cyclic monomer. Meanwhile, during polymerization, a large amount of small molecules are associated, losing rotation and translational
2789:
2125:
2747:
3729:
3596:
The stereochemistry of polymerization is concerned with the difference in atom connectivity and spatial orientation in polymers that has the same chemical composition.
1815:
reaction mixture contains an aqueous phase, water-insoluble monomer, and initiator soluble in the monomer droplets (both the monomer and the initiator are hydrophobic).
4689:
Wang, J-S; Matyjaszewski, K (1995). "Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes".
1959:
molecule (Figure 24), premature termination by coupling is reduced. As with all living polymerizations, the polymer chain grows until all of the monomer is consumed.
1503:
a hydrogen atom is abstracted from a solvent molecule, resulting in the formation of radical on the solvent molecules, which will not propagate further (Figure 19).
3874:
3756:
1611:
5060:; K. Matyjaszewski; J. P. Vairon (2000). "Amphiphilic block copolymers prepared via controlled radical polymerization as surfactants for emulsion polymerization".
3171:{\displaystyle {\frac {1}{x_{n}}}={\frac {2k_{t,d}+k_{t,c}}{{k_{p}}^{2}^{2}}}v_{p}+C_{M}+C_{S}{\frac {}{}}+C_{I}{\frac {}{}}+C_{P}{\frac {}{}}+C_{T}{\frac {}{}}}
1044:
705:
Radiation cleaves a bond homolytically, producing two radicals (Figure 2). This method is used most often with metal iodides, metal alkyls, and azo compounds.
1102:
Due to side reactions, not all radicals formed by the dissociation of initiator molecules actually add monomers to form polymer chains. The efficiency factor
4411:
Islamova, R. M.; Puzin, Y. I.; Fatykhov, A. A.; Monakov, Y. B. (2006). "A Ternary
Initiating System for Free Radical Polymerization of Methyl Methacrylate".
2713:
can be correlated with the kinetic chain length. In the case of termination by disproportionation, one polymer molecule is produced per every kinetic chain:
1019:
High-intensity ultrasound at frequencies beyond the range of human hearing (16 kHz) can be applied to a monomer. Initiation results from the effects of
3526:. According to the thermodynamic equation ÎG = ÎH â TÎS, a negative enthalpy and an increasing entropy will shift the equilibrium towards polymerization.
3674:: Penultimate unit interactions cause monomer to add in a way that minimizes steric hindrance between substituent groups. (P represents polymer chain.)
5200:"Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties"
2363:
5258:
4483:
2133:
1496:, all chain-transfer mechanisms also involve the abstraction of a hydrogen or other atom. There are several types of chain-transfer mechanisms.
4182:
3695:, was first proposed by Alfrey and Price in 1947. The scheme takes into account the intrinsic thermodynamic stability and polar effects in the
1877:
4717:
1974:
778:
3652:
However, if interactions between the substituents of the penultimate repeating unit and the terminal carbon atom are significant, then
3542:
542:
4167:
1968:
In typical chain growth polymerizations, the reaction rates for initiation, propagation and termination can be described as follows:
137:
5216:
5199:
3514:) of the polymerization is commonly used to quantify the tendency of a polymeric reaction. The polymerization will be favored if ÎG
1901:
based on the formation of a carbon-carbon bond by atom transfer radical addition. This method, independently discovered in 1995 by
4993:
Braunecker, W. A.; K. Matyjaszewski (2007). "Controlled/living radical polymerization: Features, developments, and perspectives".
2357:
In this case, the rate of chain propagation can be further described using a function of the initiator and monomer concentrations
2264:
5087:
Homenick, C. M.; G. Lawson; A. Adronov (2007). "Polymer grafting of carbon nanotubes using living free-radical polymerization".
4157:
1179:
5243:
5073:
4790:
4354:
4290:
4228:
1106:
is defined as the fraction of the original initiator which contributes to the polymerization reaction. The maximal value of
4077:
1896:
1779:
is the rate constant for propagation. The Mayo equation assumes that transfer to solvent is the major termination pathway.
80:
75:
3783:
3537:
change, since addition of a monomer to the growing polymer chain involves the conversion of Ď bonds into Ď bonds, or a
3435:
3373:
3311:
3249:
3187:
3502:
In chain growth polymerization, the position of the equilibrium between polymer and monomers can be determined by the
2806:
594:
Free-radical polymerization is a key synthesis route for obtaining a wide variety of different polymers and materials
5290:
4978:
4955:
4874:
4854:
4834:
4814:
4596:
4576:
4446:
4064:
and lubricants. Block copolymers are used for a wide variety of applications including adhesives, footwear and toys.
307:
122:
85:
3553:< 0 for nearly all polymerization processes. Since depolymerization is almost always entropically favored, the ÎH
1295:
During polymerization, a polymer spends most of its time in increasing its chain length, or propagating. After the
169:
5268:
4746:
4142:
4113:. Aqueous dispersions of clay are treated with an initiator and a catalyst and the organic monomer, generally an
1332:: An orbital drawing of the initiator attack on ethylene molecule, producing the start of the polyethylene chain.
614:
5233:
4458:
535:
292:
5285:
4080:(ATRP) or nitroxide-mediated polymerization (NMP), allows rapid growth of high molecular weight polymers.
2691:{\displaystyle \nu ={\frac {v_{p}}{v_{i}}}={\frac {k_{p}}{2fk_{d}}}={\frac {k_{p}}{2(fk_{d}k_{t})^{1/2}}}}
4147:
3538:
622:
610:
322:
117:
112:
90:
1456:, Figure 18) are a few other inhibitors. The latter is an especially effective inhibitor because of the
1135:: Primary recombination of BPO; brackets indicate that the reaction is happening within the solvent cage
4487:
4187:
3604:
2255:
1393:
317:
146:
5253:
4887:
4122:
growth polymerization produce a material with flexibility, mechanical strength and biocompatibility.
1810:
1321:: Phenyl initiator from benzoyl peroxide (BPO) attacks a styrene molecule to start the polymer chain.
528:
70:
1336:
Once a chain has been initiated, the chain propagates (Figure 13) until there are no more monomers (
997:: (Top) Formation of radical anion at the cathode; (bottom) formation of radical cation at the anode
4721:
4654:
4033:). Values for each monomer can then be assigned relative to a reference monomer, usually chosen as
3653:
2706:
1575:
1429:
1303:(Figure 11). In an ethene monomer, one electron pair is held securely between the two carbons in a
285:
4608:
3692:
2758:
2069:
1910:
1819:
1801:
908:
618:
387:
382:
156:
5263:
4510:
2719:
4782:
4776:
3702:
1926:
requires a compound that can act as a reversible chain-transfer agent, such as dithio compound.
1858:
583:). Free radicals can be formed by a number of different mechanisms, usually involving separate
268:
4009:
For the copolymerization of a given pair of monomers, the two experimental reactivity ratios r
3999:{\displaystyle r_{1}={\frac {k_{11}}{k_{12}}}={\frac {Q_{1}}{Q_{2}}}\exp(-e_{1}(e_{1}-e_{2}))}
1758:{\displaystyle {\frac {1}{x_{n}}}=\left({\frac {1}{x_{n}}}\right)_{o}+{\frac {k_{tr}}{k_{p}}}}
962:: The three steps involved in ionizing radiation: ejection, dissociation, and electron-capture
4909:
Alfrey, Turner; Price, Charles C. (1947). "Relative reactivities in vinyl copolymerization".
4162:
3603:
established by
Ziegler and Natta and their coworkers in 1950s, as they developed metal based
1883:
1840:
1516:
solvent radical that is formed (greater stability leads to greater probability of transfer).
1337:
672:
666:
482:
302:
297:
3868:
The monomer reactivity ratio for the addition of monomers 1 and 2 to this chain is given by
1550:
5172:
4918:
4663:
4542:
3734:
2491:
907:
The dissociation of a persulfate in the aqueous phase (Figure 4). This method is useful in
151:
45:
8:
5057:
3577:
1792:
1580:
1562:
1532:
1505:
1446:: Inhibition of polystyrene propagation due to reaction of polymer with molecular oxygen.
1166:
One radical is produced instead of the three radicals that could be produced (Figure 10).
654:
492:
60:
5176:
4922:
4667:
4546:
1844:: The polymerization is initiated with plasma. A variety of organic molecules including
1367:
Combination of two active chain ends: one or both of the following processes may occur.
949:
cause ejection of an electron from the initiating species, followed by dissociation and
675:
cleaved, producing two radicals (Figure 1). This method is used most often with organic
5104:
5006:
4390:
3599:
1493:
929:
595:
455:
438:
397:
221:
4637:
1158:: Recombination of phenyl radicals from the initiation of BPO outside the solvent cage
5038:
4974:
4951:
4870:
4850:
4830:
4810:
4786:
4691:
4592:
4572:
4531:
4442:
4350:
4322:
4286:
4224:
3667:
3507:
1359:
1296:
1128:
1067:
584:
556:
448:
412:
231:
226:
5124:"Grafting of alkoxyamine end-capped (co)polymers onto multi-walled carbon nanotubes"
5108:
4394:
3683:
Traditionally, the reactivity of monomers and radicals are assessed by the means of
1120:
Two radicals recombine before initiating a chain (Figure 8). This occurs within the
55:
5211:
5180:
5143:
5135:
5096:
5069:
5030:
5002:
4926:
4699:
4671:
4633:
4550:
4420:
4382:
4318:
4073:
3696:
3648:: (Top) formation of isotactic polymer; (bottom) formation of syndiotactic polymer.
3523:
1887:
1400:
1151:
1030:
1002:
967:
950:
693:
402:
372:
312:
127:
5139:
3691:
scheme, the most widely used tool for the semi-quantitative prediction of monomer
983:
to become a radical anion, and a monomer molecule will give up an electron at the
955:
5184:
4624:
Colombani, Daniel (1997). "Chain-Growth
Control in Free Radical Polymerization".
4410:
4372:
4110:
4053:
2752:
Termination by combination leads to one polymer molecule per two kinetic chains:
1902:
1077:
752:
The photoinitiator and any byproducts resulting from its use should be non-toxic.
475:
417:
367:
194:
4554:
4045:
Free radical polymerization has found applications including the manufacture of
3641:
1601:). The Mayo equation estimates the influence of chain transfer on chain length (
1462:
65:
4930:
4177:
4152:
3657:
3609:
3503:
2702:
1598:
1489:
1416:
1113:
The following types of reactions can decrease the efficiency of the initiator.
1089:
1008:
990:
934:
637:
568:
509:
362:
105:
5238:
5100:
4424:
4386:
4090:: Grafting of a polystyrene free radical onto a single-walled carbon nanotube.
3656:
factors could cause the monomer to add to the polymer in a way that minimizes
1439:
685:
5279:
4095:
4050:
3661:
3618:
3181:
It is usual to define chain-transfer constants C for the different molecules
2800:, the contribution of disproportionation to the overall termination process:
2480:{\displaystyle v_{p}={k_{p}}\left({\frac {fk_{d}}{k_{t}}}\right)^{1/2}^{1/2}}
1906:
1558:
1548:
propagation. Peroxide initiators are especially sensitive to chain transfer.
938:
680:
407:
216:
211:
189:
4650:
3777:, is postulated to be related to the four relevant reactivity parameters by
1387:: Termination by the combination of two poly(vinyl chloride) (PVC) polymers.
1380:
5122:
Lou, X. D.; C. Detrembleur; V. Sciannamea; C. Pagnoulle; R. Jerome (2004).
5042:
1914:
1449:
1144:
1143:
Two radical initiators recombine before initiating a chain, but not in the
1121:
972:
917:
576:
499:
443:
392:
377:
201:
184:
5217:
10.1002/1521-4095(20020816)14:16<1120::AID-ADMA1120>3.0.CO;2-9
5121:
4309:
Hageman, H. J. (1985). "Photoinitiators for Free
Radical Polymerization".
4125:
3634:
hybridization and is planar. Consider the polymerization of the monomer CH
2225:{\displaystyle v_{t}={-\operatorname {d} /\operatorname {d} t}=2k_{t}^{2}}
1480:
1414:
Combination of an active chain end with an initiator radical (Figure 16).
707:
601:
587:. Following its generation, the initiating free radical adds (nonradical)
5248:
5123:
4061:
4046:
3623:
2794:
Any mixture of both these mechanisms can be described by using the value
1587:: Chain transfer from polypropylene to backbone of another polypropylene.
1071:
1063:
976:
912:
736:
642:
580:
514:
460:
248:
236:
28:
4703:
4675:
1325:
4118:
4114:
3530:
1917:) and a transition metal halide catalyst (to activate dormant species).
1304:
1020:
1014:
902:
743:
725:
700:
357:
337:
179:
5034:
4750:
4083:
2056:{\displaystyle v_{i}={\operatorname {d} /\operatorname {d} t}=2k_{d}f}
1314:
749:
Should not impart yellowing or unpleasant odors to the cured material.
5148:
5055:
4607:
The Mayo equation for chain transfer should not be confused with the
4098:
3684:
3613:
1457:
942:
646:
332:
263:
253:
206:
50:
5074:
10.1002/1521-3900(200002)150:1<39::AID-MASY39>3.0.CO;2-D
5019:
1042:-isopropylcarbazole and di-Ρ-indenylzirconium dichloride (Figure 7).
879:{\displaystyle {\ce {{H2O2}+Fe^{2+}->{Fe^{3+}}+{HO^{-}}+HO^{.}}}}
4106:
3534:
1521:
676:
487:
465:
327:
1913:, requires reversible activation of a dormant species (such as an
4172:
4034:
3546:
1871:
1797:
reaction mixture contains only initiator and monomer, no solvent.
1517:
1407:: Termination by disproportionation of poly(methyl methacrylate).
1308:
1300:
980:
650:
588:
572:
16:
Polymerization process involving free radicals as repeating units
1124:, meaning that no solvent has yet come between the new radicals.
4057:
3568:
is small. Depolymerization is favored at high temperatures: TÎS
3564:
In practice, polymerization is favored at low temperatures: TÎS
1934:
1922:
Reversible
Addition-Fragmentation Chain-Transfer Polymerization
1853:
1849:
1845:
1829:
Other methods of radical polymerization include the following:
1433:
1074:
732:
504:
1343:
1956:
1787:
There are four industrial methods of radical polymerization:
1350:: Propagation of polystyrene with a phenyl radical initiator.
984:
946:
759:
4781:(2nd ed.). Blackie (USA: Chapman & Hall). pp.
4644:
4072:
Free radical polymerization allows the functionalization of
1452:, butylated hydroxyl toluene, and diphenyl picryl hydrazyl (
1280:: Reaction of polymer chain R with other species in reaction
5086:
5056:
Burguiere, C.; S. Pascual; B. Coutin; A. Polton; M. Tardi;
4132:: General synthesis procedure for a nanocomposite hydrogel.
4102:
2347:{\displaystyle =\left({\frac {k_{d}f}{k_{t}}}\right)^{1/2}}
1453:
470:
258:
132:
4992:
1806:
reaction mixture contains solvent, initiator, and monomer.
1268:{\displaystyle {\ce {{R.}+ {R'-O-O-R'}-> ROR' + R'O'}}}
731:
Efficient generation of radicals capable of attacking the
653:. Initiation has two steps. In the first step, one or two
4688:
807:
794:
660:
1945:
1574:
which have been polymerized, so that the number-average
1423:: Termination of PVC by reaction with radical initiator.
4486:. Case Western Reserve University. 2009. Archived from
1952:: TEMPO molecule used to functionalize the chain ends.
1059:-isopropylcarbazole + di-Ρ-indenylzicronium dichloride
4682:
4280:
3877:
3786:
3737:
3705:
3438:
3376:
3314:
3252:
3190:
2887:
2809:
2761:
2722:
2504:
2366:
2267:
2136:
2072:
1977:
1614:
1182:
979:. A monomer molecule will receive an electron at the
781:
5197:
5165:
Current
Opinion in Solid State and Materials Science
4535:
Journal of
Polymer Science Part A: Polymer Chemistry
4101:. These gels are made of water-swellable nano-scale
4778:
Polymers: Chemistry and Physics of Modern Materials
4283:
Polymers: Chemistry and Physics of Modern Materials
3998:
3858:{\displaystyle k_{12}=P_{1}Q_{2}\exp(-e_{1}e_{2})}
3857:
3750:
3723:
3486:
3424:
3362:
3300:
3238:
3170:
2846:
2783:
2741:
2705:effect occurs in the reaction, the number average
2690:
2479:
2346:
2224:
2119:
2055:
1757:
1267:
878:
5163:Haraguchi, K. (2008). "Nanocomposite hydrogels".
3487:{\displaystyle C_{T}={\frac {k_{tr}^{T}}{k_{p}}}}
3425:{\displaystyle C_{P}={\frac {k_{tr}^{P}}{k_{p}}}}
3363:{\displaystyle C_{I}={\frac {k_{tr}^{I}}{k_{p}}}}
3301:{\displaystyle C_{S}={\frac {k_{tr}^{S}}{k_{p}}}}
3239:{\displaystyle C_{M}={\frac {k_{tr}^{M}}{k_{p}}}}
1955:Because the chain end is functionalized with the
5277:
4037:with the arbitrary values Q = 1.0 and e = â0.8.
2847:{\displaystyle x_{n}={\frac {2}{1+\delta }}\nu }
1110:is 1, but typical values range from 0.3 to 0.8.
4971:The Elements of Polymer Science and Engineering
4847:The Elements of Polymer Science and Engineering
4827:The Elements of Polymer Science and Engineering
4807:The Elements of Polymer Science and Engineering
4589:The Elements of Polymer Science and Engineering
4569:The Elements of Polymer Science and Engineering
3758:are considered to have intrinsic reactivities P
1539:: Chain transfer from polypropylene to monomer.
891:: Redox reaction of hydrogen peroxide and iron.
4223:(4th ed.). New York: Wiley-Interscience.
4183:Reversible-deactivation radical polymerization
4094:Radical polymerization also aids synthesis of
1878:Reversible-deactivation radical polymerization
1872:Reversible deactivation radical polymerization
1378:symmetric about the point of the combination.
645:monomers and the carbonâoxygen double bond in
5239:Free Radical Polymerization (video animation)
1512:: Chain transfer from polystyrene to solvent.
536:
5244:Free Radical Polymerization - Chain Transfer
4950:(3rd ed., Pearson Prentice-Hall 2003) p.364
1772:is the rate constant for chain transfer and
1488:Contrary to the other modes of termination,
5049:
4965:
4963:
4908:
4368:
4366:
605:IUPAC definition for radical polymerization
5013:
4478:
4476:
4406:
4404:
4281:Cowie, J. M. G.; Arrighi, Valeria (2008).
3572:is large. As the temperature increases, ÎG
1469:: Inhibition of polymer chain, R, by DPPH.
1062:This type of initiating system contains a
975:of a solution containing both monomer and
742:Adequate solubility in the binder system (
591:units, thereby growing the polymer chain.
543:
529:
5215:
5162:
5147:
5115:
4988:
4986:
4770:
4768:
4623:
4276:
4274:
4272:
4270:
4268:
4266:
4264:
4262:
4260:
4168:Nitroxide mediated radical polymerization
1930:Stable Free Radical Polymerization (SFRP)
840:
822:
714:: Photolysis of azoisobutylnitrile (AIBN)
609:Free-radical polymerization is a type of
138:Nitroxide-mediated radical polymerization
4960:
4942:
4940:
4741:
4739:
4619:
4617:
4363:
4258:
4256:
4254:
4252:
4250:
4248:
4246:
4244:
4242:
4240:
4124:
4082:
3666:
3640:
2239:is the efficiency of the initiator and k
1944:
1933:
1579:
1549:
1531:
1504:
1479:
1461:
1438:
1415:
1399:
1379:
1342:
1324:
1313:
1150:
1127:
1043:
989:
954:
916:
706:
684:
671:The initiator is heated until a bond is
600:
5080:
4946:Allcock H.R., Lampe F.W. and Mark J.E.
4473:
4401:
4344:
4340:
4338:
4336:
4334:
4332:
4308:
4304:
4302:
4214:
4212:
4210:
4208:
4206:
4204:
4202:
1097:
1011:field to assist in creating the plasma.
911:, in which the radical diffuses into a
5278:
5191:
4983:
4765:
4451:
4158:Cobalt-mediated radical polymerization
1861:, and various types of thin membranes.
1307:. The other is more loosely held in a
661:Types of initiation and the initiators
5156:
4937:
4885:
4879:
4774:
4736:
4614:
4525:
4502:
4349:. New York: Oxford University Press.
4285:(3rd ed.). Scotland: CRC Press.
4237:
4218:
3529:In general, the polymerization is an
924:: Thermal degradation of a persulfate
4747:"Stable Free Radical Polymerization"
4710:
4461:. Materials World Modules. June 2009
4375:Russian Journal of Applied Chemistry
4329:
4299:
4199:
4078:atom transfer radical polymerization
4067:
1897:Atom transfer radical polymerization
636:Initiation is the first step of the
575:forms by the successive addition of
5198:Haraguchi, K.; Takehisa T. (2002).
4869:(2nd ed., Prentice-Hall 2003) p.39
4441:(2nd ed., Prentice-Hall 2003) p.36
1484:IUPAC definition for chain transfer
13:
5269:Stable Free Radical Polymerization
5007:10.1016/j.progpolymsci.2006.11.002
4749:. Xerox Corp. 2010. Archived from
4718:"The 2011 Wolf Prize in Chemistry"
4347:Polymer Chemistry: An Introduction
3591:
2177:
2154:
2015:
1992:
27:
14:
5302:
5249:Free Radical Vinyl Polymerization
5227:
4508:
3522:> 0, the polymer will undergo
3497:
2870:, and added chain-transfer agent
1475:
953:to produce a radical (Figure 5).
123:Controlled radical polymerization
4867:Polymer Science & Technology
4439:Polymer Science & Technology
4902:
4888:"The Polymerization of Alkenes"
4859:
4839:
4819:
4809:(Academic Press 1982) pp.195-9
4799:
4601:
4581:
4561:
4143:Anionic addition polymerization
4040:
1428:Interaction with impurities or
4948:Contemporary Polymer Chemistry
4431:
3993:
3990:
3964:
3948:
3852:
3826:
3162:
3156:
3151:
3145:
3123:
3117:
3112:
3106:
3084:
3078:
3073:
3067:
3045:
3039:
3034:
3028:
2977:
2970:
2668:
2664:
2658:
2632:
2624:
2618:
2596:
2590:
2569:
2560:
2557:
2551:
2474:
2468:
2451:
2444:
2307:
2301:
2277:
2268:
2213:
2203:
2169:
2160:
2114:
2105:
2102:
2096:
2050:
2044:
2007:
1998:
1749:
1725:
1710:
1686:
1460:stabilization of the radical.
1354:
1290:
1234:
828:
1:
5254:The Polymerization of Alkenes
5140:10.1016/j.polymer.2004.06.050
4638:10.1016/S0079-6700(97)00022-1
4193:
4105:(especially those classed as
3678:
2878:will be modified as follows:
1884:living radical polymerization
1051:: benzoyl peroxide + 3,6-bis(
728:in the 300â400 nm range.
631:
86:FloryâHuggins solution theory
5185:10.1016/j.cossms.2008.05.001
4973:(Academic Press 1982) p.289
4849:(Academic Press 1982) p.214
4829:(Academic Press 1982) p.209
4591:(Academic Press 1982) p.212
4571:(Academic Press 1982) p.220
4345:Stevens, Malcolm P. (1999).
4323:10.1016/0033-0655(85)80021-2
4311:Progress in Organic Coatings
4221:Principles of Polymerization
1140:Other recombination pathways
915:monomer-containing droplet.
7:
4995:Progress in Polymer Science
4720:. Wolf Fund. Archived from
4626:Progress in Polymer Science
4555:10.1002/pola.1995.080330406
4148:Chain-growth polymerisation
4136:
4056:elastomers, cardiovascular
4017:permit the evaluation of (Q
3549:decreases in the system, ÎS
3506:of the polymerization. The
2784:{\displaystyle x_{n}=2\nu }
2120:{\displaystyle v_{p}=k_{p}}
1963:
1941:: Reaction scheme for SFRP.
692:: Thermal decomposition of
623:coordination polymerization
611:chain-growth polymerization
561:free-radical polymerization
152:Condensation polymerization
118:Free-radical polymerization
113:Chain-growth polymerization
10:
5307:
5264:Radical Reaction Chemistry
4931:10.1002/pol.1947.120020112
4911:Journal of Polymer Science
4188:Step-growth polymerization
2742:{\displaystyle x_{n}=\nu }
2256:steady-state approximation
1875:
1782:
1594:Effects of chain transfer:
1394:Radical disproportionation
147:Step-growth polymerization
5101:10.1080/15583720701271237
4459:"Addition Polymerization"
4425:10.1134/S156009040605006X
4413:Polymer Science, Series B
4387:10.1134/S1070427206090229
3724:{\displaystyle M_{i}^{o}}
3664:interaction (Figure 26).
1811:Suspension polymerization
1524:, are easily transferred.
5291:Polymerization reactions
4775:Cowie, J. M. G. (1991).
2707:degree of polymerization
1576:degree of polymerization
1299:is formed, it attacks a
909:emulsion polymerizations
5234:Addition Polymerization
5062:Macromolecular Symposia
3533:process, i.e. negative
1911:Krzysztof Matyjaszewski
1859:antireflection coatings
1834:Template polymerization
1820:Emulsion polymerization
1802:Solution polymerization
157:Addition polymerization
91:Coilâglobule transition
4219:Odian, George (2004).
4133:
4091:
4000:
3859:
3752:
3725:
3675:
3649:
3488:
3426:
3364:
3302:
3240:
3172:
2848:
2785:
2743:
2692:
2481:
2348:
2226:
2121:
2057:
1953:
1942:
1759:
1588:
1566:
1557:: Chain transfer from
1540:
1513:
1485:
1470:
1447:
1424:
1408:
1388:
1351:
1333:
1322:
1269:
1159:
1136:
1060:
998:
963:
925:
880:
715:
696:
606:
269:Self-healing hydrogels
32:
4163:Living polymerization
4128:
4086:
4001:
3860:
3753:
3751:{\displaystyle M_{j}}
3726:
3670:
3644:
3539:ringâopening reaction
3489:
3427:
3365:
3303:
3241:
3173:
2849:
2786:
2744:
2693:
2482:
2349:
2227:
2122:
2058:
1948:
1937:
1841:Plasma polymerization
1760:
1583:
1553:
1535:
1508:
1483:
1465:
1442:
1419:
1403:
1383:
1346:
1338:living polymerization
1328:
1317:
1270:
1154:
1131:
1117:Primary recombination
1047:
993:
958:
920:
881:
710:
688:
667:Thermal decomposition
604:
483:Cookware and bakeware
435:Industrial production
303:X-ray crystallography
31:
3875:
3784:
3735:
3703:
3436:
3374:
3312:
3250:
3188:
2885:
2807:
2759:
2720:
2502:
2492:kinetic chain length
2364:
2265:
2134:
2070:
1975:
1612:
1180:
1098:Initiator efficiency
779:
5286:Reaction mechanisms
5177:2007COSSM..11...47H
4923:1947JPoSc...2..101A
4886:Clark, Jim (2003).
4753:on 28 November 2003
4704:10.1021/ja00125a035
4676:10.1021/ma00109a056
4668:1995MaMol..28.1721K
4609:MayoâLewis equation
4547:1995JPoSA..33..643P
4511:"Radical Chemistry"
4484:"Polymer Synthesis"
3720:
3578:ceiling temperature
3545:. As a result, the
3471:
3409:
3347:
3285:
3223:
2874:. The equation of P
1793:Bulk polymerization
1563:di-t-butyl peroxide
809:
796:
585:initiator molecules
456:Protective Coatings
71:MarkâHouwink theory
5204:Advanced Materials
4490:on 7 February 2010
4134:
4092:
3996:
3855:
3748:
3721:
3706:
3699:. A given radical
3676:
3650:
3600:Hermann Staudinger
3543:degrees of freedom
3484:
3454:
3422:
3392:
3360:
3330:
3298:
3268:
3236:
3206:
3168:
2844:
2781:
2739:
2688:
2477:
2344:
2222:
2117:
2053:
1954:
1943:
1755:
1589:
1567:
1541:
1514:
1494:disproportionation
1486:
1471:
1448:
1425:
1409:
1389:
1352:
1334:
1323:
1265:
1160:
1137:
1061:
1026:Ternary initiators
999:
964:
930:Ionizing radiation
926:
876:
797:
784:
716:
697:
607:
33:
5259:Polymer Synthesis
5210:(16): 1120â1123.
5134:(18): 6097â6102.
5035:10.1021/bm050464v
5023:Biomacromolecules
4792:978-0-216-92980-7
4698:(20): 5614â5615.
4692:J. Am. Chem. Soc.
4356:978-0-19-512444-6
4292:978-0-8493-9813-1
4230:978-0-471-27400-1
4109:) enveloped by a
4068:Academic research
3940:
3913:
3693:reactivity ratios
3508:Gibbs free energy
3482:
3420:
3358:
3296:
3234:
3166:
3127:
3088:
3049:
2987:
2903:
2839:
2686:
2600:
2533:
2424:
2324:
1753:
1655:
1630:
1360:Chain termination
1297:radical initiator
1288:
1287:
1259:
1251:
1240:
1228:
1219:
1211:
1199:
1187:
1084:-carboxybenzoyl)-
1055:-carboxybenzoyl)-
1038:-carboxybenzoyl)-
899:
898:
868:
854:
835:
817:
800:
787:
579:building blocks (
567:) is a method of
557:polymer chemistry
553:
552:
466:Consumer products
5298:
5222:
5221:
5219:
5195:
5189:
5188:
5160:
5154:
5153:
5151:
5119:
5113:
5112:
5084:
5078:
5077:
5053:
5047:
5046:
5029:(6): 3410â3418.
5017:
5011:
5010:
4990:
4981:
4967:
4958:
4944:
4935:
4934:
4906:
4900:
4899:
4897:
4895:
4883:
4877:
4863:
4857:
4843:
4837:
4823:
4817:
4803:
4797:
4796:
4772:
4763:
4762:
4760:
4758:
4743:
4734:
4733:
4731:
4729:
4714:
4708:
4707:
4686:
4680:
4679:
4662:(5): 1721â1723.
4648:
4642:
4641:
4632:(8): 1649â1720.
4621:
4612:
4605:
4599:
4585:
4579:
4565:
4559:
4558:
4529:
4523:
4522:
4520:
4518:
4506:
4500:
4499:
4497:
4495:
4480:
4471:
4470:
4468:
4466:
4455:
4449:
4435:
4429:
4428:
4408:
4399:
4398:
4381:(9): 1509â1513.
4370:
4361:
4360:
4342:
4327:
4326:
4306:
4297:
4296:
4278:
4235:
4234:
4216:
4074:carbon nanotubes
4005:
4003:
4002:
3997:
3989:
3988:
3976:
3975:
3963:
3962:
3941:
3939:
3938:
3929:
3928:
3919:
3914:
3912:
3911:
3902:
3901:
3892:
3887:
3886:
3864:
3862:
3861:
3856:
3851:
3850:
3841:
3840:
3819:
3818:
3809:
3808:
3796:
3795:
3757:
3755:
3754:
3749:
3747:
3746:
3730:
3728:
3727:
3722:
3719:
3714:
3697:transition state
3685:copolymerization
3524:depolymerization
3493:
3491:
3490:
3485:
3483:
3481:
3480:
3470:
3465:
3453:
3448:
3447:
3431:
3429:
3428:
3423:
3421:
3419:
3418:
3408:
3403:
3391:
3386:
3385:
3369:
3367:
3366:
3361:
3359:
3357:
3356:
3346:
3341:
3329:
3324:
3323:
3307:
3305:
3304:
3299:
3297:
3295:
3294:
3284:
3279:
3267:
3262:
3261:
3245:
3243:
3242:
3237:
3235:
3233:
3232:
3222:
3217:
3205:
3200:
3199:
3177:
3175:
3174:
3169:
3167:
3165:
3154:
3143:
3141:
3140:
3128:
3126:
3115:
3104:
3102:
3101:
3089:
3087:
3076:
3065:
3063:
3062:
3050:
3048:
3037:
3026:
3024:
3023:
3011:
3010:
2998:
2997:
2988:
2986:
2985:
2984:
2969:
2968:
2963:
2962:
2961:
2949:
2948:
2947:
2929:
2928:
2909:
2904:
2902:
2901:
2889:
2853:
2851:
2850:
2845:
2840:
2838:
2824:
2819:
2818:
2799:
2790:
2788:
2787:
2782:
2771:
2770:
2748:
2746:
2745:
2740:
2732:
2731:
2697:
2695:
2694:
2689:
2687:
2685:
2684:
2683:
2679:
2657:
2656:
2647:
2646:
2627:
2617:
2616:
2606:
2601:
2599:
2589:
2588:
2572:
2550:
2549:
2539:
2534:
2532:
2531:
2522:
2521:
2512:
2486:
2484:
2483:
2478:
2467:
2466:
2462:
2443:
2442:
2438:
2429:
2425:
2423:
2422:
2413:
2412:
2411:
2398:
2391:
2390:
2389:
2376:
2375:
2353:
2351:
2350:
2345:
2343:
2342:
2338:
2329:
2325:
2323:
2322:
2313:
2300:
2299:
2289:
2231:
2229:
2228:
2223:
2221:
2220:
2202:
2201:
2186:
2176:
2146:
2145:
2126:
2124:
2123:
2118:
2095:
2094:
2082:
2081:
2062:
2060:
2059:
2054:
2040:
2039:
2024:
2014:
1987:
1986:
1891:polymerization.
1888:Block copolymers
1764:
1762:
1761:
1756:
1754:
1752:
1724:
1723:
1713:
1685:
1684:
1671:
1666:
1665:
1660:
1656:
1654:
1653:
1641:
1631:
1629:
1628:
1616:
1274:
1272:
1271:
1266:
1264:
1263:
1257:
1255:
1249:
1244:
1238:
1233:
1232:
1226:
1224:
1217:
1216:
1209:
1208:
1203:
1197:
1191:
1185:
1170:
1169:
951:electron capture
885:
883:
882:
877:
875:
874:
873:
866:
861:
860:
859:
852:
846:
845:
844:
833:
827:
826:
815:
810:
808:
805:
798:
795:
792:
785:
769:
768:
694:dicumyl peroxide
545:
538:
531:
449:Applied coatings
286:Characterization
19:
18:
5306:
5305:
5301:
5300:
5299:
5297:
5296:
5295:
5276:
5275:
5230:
5225:
5196:
5192:
5161:
5157:
5120:
5116:
5089:Polymer Reviews
5085:
5081:
5054:
5050:
5018:
5014:
4991:
4984:
4968:
4961:
4945:
4938:
4907:
4903:
4893:
4891:
4884:
4880:
4865:Fried, Joel R.
4864:
4860:
4844:
4840:
4824:
4820:
4804:
4800:
4793:
4773:
4766:
4756:
4754:
4745:
4744:
4737:
4727:
4725:
4716:
4715:
4711:
4687:
4683:
4649:
4645:
4622:
4615:
4611:for copolymers.
4606:
4602:
4586:
4582:
4566:
4562:
4530:
4526:
4516:
4514:
4509:Leach, Mark R.
4507:
4503:
4493:
4491:
4482:
4481:
4474:
4464:
4462:
4457:
4456:
4452:
4437:Fried, Joel R.
4436:
4432:
4409:
4402:
4371:
4364:
4357:
4343:
4330:
4307:
4300:
4293:
4279:
4238:
4231:
4217:
4200:
4196:
4139:
4111:network polymer
4070:
4054:block copolymer
4043:
4032:
4028:
4024:
4020:
4016:
4012:
3984:
3980:
3971:
3967:
3958:
3954:
3934:
3930:
3924:
3920:
3918:
3907:
3903:
3897:
3893:
3891:
3882:
3878:
3876:
3873:
3872:
3846:
3842:
3836:
3832:
3814:
3810:
3804:
3800:
3791:
3787:
3785:
3782:
3781:
3776:
3765:
3761:
3742:
3738:
3736:
3733:
3732:
3715:
3710:
3704:
3701:
3700:
3681:
3637:
3594:
3592:Stereochemistry
3587:
3583:
3575:
3571:
3567:
3560:
3556:
3552:
3521:
3517:
3513:
3500:
3476:
3472:
3466:
3458:
3452:
3443:
3439:
3437:
3434:
3433:
3414:
3410:
3404:
3396:
3390:
3381:
3377:
3375:
3372:
3371:
3352:
3348:
3342:
3334:
3328:
3319:
3315:
3313:
3310:
3309:
3290:
3286:
3280:
3272:
3266:
3257:
3253:
3251:
3248:
3247:
3228:
3224:
3218:
3210:
3204:
3195:
3191:
3189:
3186:
3185:
3155:
3144:
3142:
3136:
3132:
3116:
3105:
3103:
3097:
3093:
3077:
3066:
3064:
3058:
3054:
3038:
3027:
3025:
3019:
3015:
3006:
3002:
2993:
2989:
2980:
2976:
2964:
2957:
2953:
2952:
2951:
2950:
2937:
2933:
2918:
2914:
2910:
2908:
2897:
2893:
2888:
2886:
2883:
2882:
2877:
2828:
2823:
2814:
2810:
2808:
2805:
2804:
2798:
2795:
2766:
2762:
2760:
2757:
2756:
2727:
2723:
2721:
2718:
2717:
2712:
2675:
2671:
2667:
2652:
2648:
2642:
2638:
2628:
2612:
2608:
2607:
2605:
2584:
2580:
2573:
2545:
2541:
2540:
2538:
2527:
2523:
2517:
2513:
2511:
2503:
2500:
2499:
2458:
2454:
2450:
2434:
2430:
2418:
2414:
2407:
2403:
2399:
2397:
2393:
2392:
2385:
2381:
2380:
2371:
2367:
2365:
2362:
2361:
2334:
2330:
2318:
2314:
2295:
2291:
2290:
2288:
2284:
2283:
2266:
2263:
2262:
2250:
2246:
2242:
2216:
2212:
2197:
2193:
2172:
2150:
2141:
2137:
2135:
2132:
2131:
2090:
2086:
2077:
2073:
2071:
2068:
2067:
2035:
2031:
2010:
1991:
1982:
1978:
1976:
1973:
1972:
1966:
1903:Mitsuo Sawamoto
1880:
1874:
1785:
1777:
1770:
1719:
1715:
1714:
1677:
1673:
1672:
1670:
1661:
1649:
1645:
1640:
1636:
1635:
1624:
1620:
1615:
1613:
1610:
1609:
1606:
1478:
1377:
1357:
1293:
1284:
1283:
1282:
1281:
1275:
1256:
1248:
1237:
1225:
1220:
1212:
1204:
1196:
1195:
1184:
1183:
1181:
1178:
1177:
1100:
1093:microstructure.
1078:carboxylic acid
968:Electrochemical
895:
894:
893:
892:
886:
869:
865:
855:
851:
850:
836:
832:
831:
818:
814:
806:
801:
793:
788:
783:
782:
780:
777:
776:
735:double bond of
663:
634:
628:
549:
520:
519:
431:
423:
422:
353:
345:
344:
288:
278:
277:
195:Polyisobutylene
176:Functional type
172:
162:
161:
108:
98:
97:
41:
22:Polymer science
17:
12:
11:
5:
5304:
5294:
5293:
5288:
5272:
5271:
5266:
5261:
5256:
5251:
5246:
5241:
5236:
5229:
5228:External links
5226:
5224:
5223:
5190:
5171:(3â4): 47â54.
5155:
5114:
5095:(2): 265â270.
5079:
5048:
5012:
4982:
4969:Rudin, Alfred
4959:
4936:
4917:(1): 101â106.
4901:
4878:
4858:
4845:Rudin, Alfred
4838:
4825:Rudin, Alfred
4818:
4805:Rudin, Alfred
4798:
4791:
4764:
4735:
4724:on 17 May 2007
4709:
4681:
4655:Macromolecules
4643:
4613:
4600:
4587:Rudin, Alfred
4580:
4567:Rudin, Alfred
4560:
4541:(4): 643â652.
4524:
4513:. Chemogenesis
4501:
4472:
4450:
4430:
4419:(3): 130â133.
4400:
4362:
4355:
4328:
4317:(2): 123â150.
4298:
4291:
4236:
4229:
4197:
4195:
4192:
4191:
4190:
4185:
4180:
4178:Polymerization
4175:
4170:
4165:
4160:
4155:
4153:Chain transfer
4150:
4145:
4138:
4135:
4069:
4066:
4042:
4039:
4030:
4026:
4022:
4018:
4014:
4010:
4007:
4006:
3995:
3992:
3987:
3983:
3979:
3974:
3970:
3966:
3961:
3957:
3953:
3950:
3947:
3944:
3937:
3933:
3927:
3923:
3917:
3910:
3906:
3900:
3896:
3890:
3885:
3881:
3866:
3865:
3854:
3849:
3845:
3839:
3835:
3831:
3828:
3825:
3822:
3817:
3813:
3807:
3803:
3799:
3794:
3790:
3774:
3763:
3759:
3745:
3741:
3731:and a monomer
3718:
3713:
3709:
3680:
3677:
3654:conformational
3635:
3610:microstructure
3593:
3590:
3585:
3581:
3573:
3569:
3565:
3558:
3554:
3550:
3519:
3515:
3511:
3504:thermodynamics
3499:
3498:Thermodynamics
3496:
3495:
3494:
3479:
3475:
3469:
3464:
3461:
3457:
3451:
3446:
3442:
3417:
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3407:
3402:
3399:
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3389:
3384:
3380:
3355:
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3333:
3327:
3322:
3318:
3293:
3289:
3283:
3278:
3275:
3271:
3265:
3260:
3256:
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3216:
3213:
3209:
3203:
3198:
3194:
3179:
3178:
3164:
3161:
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3153:
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3139:
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3119:
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3096:
3092:
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3075:
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3047:
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3036:
3033:
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3022:
3018:
3014:
3009:
3005:
3001:
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2983:
2979:
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2967:
2960:
2956:
2946:
2943:
2940:
2936:
2932:
2927:
2924:
2921:
2917:
2913:
2907:
2900:
2896:
2892:
2875:
2855:
2854:
2843:
2837:
2834:
2831:
2827:
2822:
2817:
2813:
2796:
2792:
2791:
2780:
2777:
2774:
2769:
2765:
2750:
2749:
2738:
2735:
2730:
2726:
2710:
2703:chain-transfer
2699:
2698:
2682:
2678:
2674:
2670:
2666:
2663:
2660:
2655:
2651:
2645:
2641:
2637:
2634:
2631:
2626:
2623:
2620:
2615:
2611:
2604:
2598:
2595:
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2587:
2583:
2579:
2576:
2571:
2568:
2565:
2562:
2559:
2556:
2553:
2548:
2544:
2537:
2530:
2526:
2520:
2516:
2510:
2507:
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2476:
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2465:
2461:
2457:
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2449:
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2396:
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2298:
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2287:
2282:
2279:
2276:
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2240:
2233:
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2211:
2208:
2205:
2200:
2196:
2192:
2189:
2185:
2182:
2179:
2175:
2171:
2168:
2165:
2162:
2159:
2156:
2153:
2149:
2144:
2140:
2128:
2127:
2116:
2113:
2110:
2107:
2104:
2101:
2098:
2093:
2089:
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2080:
2076:
2064:
2063:
2052:
2049:
2046:
2043:
2038:
2034:
2030:
2027:
2023:
2020:
2017:
2013:
2009:
2006:
2003:
2000:
1997:
1994:
1990:
1985:
1981:
1965:
1962:
1961:
1960:
1927:
1918:
1882:Also known as
1876:Main article:
1873:
1870:
1869:
1868:
1862:
1837:
1827:
1826:
1816:
1807:
1798:
1784:
1781:
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1730:
1727:
1722:
1718:
1712:
1709:
1706:
1703:
1700:
1697:
1694:
1691:
1688:
1683:
1680:
1676:
1669:
1664:
1659:
1652:
1648:
1644:
1639:
1634:
1627:
1623:
1619:
1604:
1599:telomerization
1591:
1590:
1578:is unaffected.
1568:
1542:
1525:
1490:chain transfer
1477:
1476:Chain transfer
1474:
1473:
1472:
1426:
1412:
1411:
1410:
1390:
1375:
1356:
1353:
1292:
1289:
1286:
1285:
1276:
1262:
1254:
1247:
1243:
1236:
1231:
1223:
1215:
1207:
1202:
1194:
1190:
1176:
1175:
1174:
1173:
1168:
1167:
1164:
1163:Side reactions
1149:
1148:
1141:
1126:
1125:
1118:
1099:
1096:
1095:
1094:
1090:microstructure
1072:heteroaromatic
1027:
1024:
1017:
1012:
1009:radiofrequency
1005:
1000:
970:
965:
932:
927:
905:
897:
896:
887:
872:
864:
858:
849:
843:
839:
830:
825:
821:
813:
804:
791:
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773:
772:
767:
766:
763:
756:
755:
754:
753:
750:
747:
740:
729:
719:
718:
703:
698:
669:
662:
659:
638:polymerization
633:
630:
569:polymerization
551:
550:
548:
547:
540:
533:
525:
522:
521:
518:
517:
512:
510:Plastic bottle
507:
502:
497:
496:
495:
493:Food Container
490:
480:
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478:
468:
463:
458:
453:
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234:
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217:Vinyl polymers
214:
209:
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199:
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192:
187:
177:
173:
170:Classification
168:
167:
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66:Phase behavior
63:
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48:
42:
39:
38:
35:
34:
24:
23:
15:
9:
6:
4:
3:
2:
5303:
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5270:
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5260:
5257:
5255:
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5245:
5242:
5240:
5237:
5235:
5232:
5231:
5218:
5213:
5209:
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5201:
5194:
5186:
5182:
5178:
5174:
5170:
5166:
5159:
5150:
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5141:
5137:
5133:
5129:
5125:
5118:
5110:
5106:
5102:
5098:
5094:
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5075:
5071:
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5063:
5059:
5052:
5044:
5040:
5036:
5032:
5028:
5024:
5016:
5008:
5004:
5001:(1): 93â146.
5000:
4996:
4989:
4987:
4980:
4979:0-12-601680-1
4976:
4972:
4966:
4964:
4957:
4956:0-13-065056-0
4953:
4949:
4943:
4941:
4932:
4928:
4924:
4920:
4916:
4912:
4905:
4889:
4882:
4876:
4875:0-13-018168-4
4872:
4868:
4862:
4856:
4855:0-12-601680-1
4852:
4848:
4842:
4836:
4835:0-12-601680-1
4832:
4828:
4822:
4816:
4815:0-12-601680-1
4812:
4808:
4802:
4794:
4788:
4784:
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4779:
4771:
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4604:
4598:
4597:0-12-601680-1
4594:
4590:
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4577:0-12-601680-1
4574:
4570:
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4454:
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4447:0-13-018168-4
4444:
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4131:
4127:
4123:
4120:
4116:
4112:
4108:
4104:
4100:
4097:
4096:nanocomposite
4089:
4085:
4081:
4079:
4075:
4065:
4063:
4059:
4055:
4052:
4051:thermoplastic
4048:
4038:
4036:
3985:
3981:
3977:
3972:
3968:
3959:
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3879:
3871:
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3663:
3662:electrostatic
3659:
3655:
3647:
3643:
3639:
3633:
3627:
3625:
3620:
3619:crystallinity
3615:
3611:
3606:
3601:
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3509:
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1940:
1936:
1931:
1928:
1925:
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1904:
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1560:
1559:polypropylene
1556:
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1543:
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681:azo compounds
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670:
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612:
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381:
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339:
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334:
331:
330:
329:
326:
324:
321:
319:
316:
314:
311:
309:
306:
304:
301:
299:
296:
294:
291:
290:
287:
282:
281:
270:
267:
266:
265:
262:
261:
260:
257:
255:
252:
250:
247:
244:
243:
238:
235:
233:
230:
228:
225:
223:
220:
219:
218:
215:
213:
212:Polycarbonate
210:
208:
205:
203:
200:
196:
193:
191:
190:Polypropylene
188:
186:
183:
182:
181:
178:
175:
174:
171:
166:
165:
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155:
153:
150:
148:
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4881:
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4755:. Retrieved
4751:the original
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4722:the original
4712:
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4690:
4684:
4659:
4653:
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4488:the original
4463:. Retrieved
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4314:
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4220:
4129:
4119:cross-linked
4093:
4087:
4071:
4044:
4041:Applications
4008:
3867:
3771:
3767:
3688:
3682:
3671:
3651:
3645:
3631:
3628:
3598:
3595:
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2871:
2867:
2863:
2862:, initiator
2859:
2856:
2793:
2751:
2701:Assuming no
2700:
2489:
2356:
2253:
2236:
2234:
1967:
1949:
1938:
1929:
1920:
1915:alkyl halide
1895:
1881:
1864:
1839:
1833:
1828:
1818:
1809:
1800:
1791:
1786:
1773:
1766:
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1527:
1509:
1500:
1487:
1466:
1450:Nitrobenzene
1443:
1420:
1404:
1392:
1384:
1371:Combination:
1370:
1358:
1347:
1335:
1329:
1318:
1294:
1277:
1155:
1145:solvent cage
1132:
1122:solvent cage
1112:
1107:
1103:
1101:
1085:
1081:
1056:
1052:
1048:
1039:
1035:
1034:and 3,6-bis(
994:
973:Electrolysis
959:
921:
888:
726:absorptivity
711:
689:
635:
627:
608:
593:
581:repeat units
577:free-radical
564:
560:
554:
500:Vinyl record
444:Blow molding
430:Applications
202:Polyurethane
185:Polyethylene
46:Architecture
5058:B. Charleux
4890:. ChemGuide
4728:21 February
4062:surfactants
4060:, chemical
4047:polystyrene
3624:polypropene
1571:To polymer:
1528:To monomer:
1501:To solvent:
1355:Termination
1291:Propagation
1147:(Figure 9).
1064:metallocene
977:electrolyte
913:hydrophobic
903:Persulfates
746:+ monomer).
571:by which a
515:Plastic bag
461:3D printing
249:Homopolymer
237:Polystyrene
61:Degradation
5280:Categories
4194:References
4115:acrylamide
3687:data. The
3679:Reactivity
3531:exothermic
2866:, polymer
2254:Under the
1865:Sonication
1565:initiator.
1430:inhibitors
1305:sigma bond
1021:cavitation
1015:Sonication
744:prepolymer
701:Photolysis
632:Initiation
596:composites
476:Whitewalls
398:Staudinger
368:MacDiarmid
352:Scientists
338:Viscometry
180:Polyolefin
56:Morphology
40:Properties
5149:2268/8255
5068:: 39â44.
4130:Figure 28
4107:smectites
4099:hydrogels
4088:Figure 27
3978:−
3952:−
3946:
3830:−
3824:
3672:Figure 26
3646:Figure 25
3630:atom has
2842:ν
2836:δ
2779:ν
2737:ν
2567:⋅
2506:ν
2275:⋅
2210:⋅
2181:
2167:⋅
2158:
2152:−
2112:⋅
2019:
2005:⋅
1996:
1950:Figure 24
1939:Figure 23
1585:Figure 22
1555:Figure 21
1537:Figure 20
1520:, except
1510:Figure 19
1467:Figure 18
1458:resonance
1444:Figure 17
1421:Figure 16
1405:Figure 15
1385:Figure 14
1348:Figure 13
1330:Figure 12
1319:Figure 11
1278:Figure 10
1235:⟶
1222:−
1214:−
1206:−
1189:⋅
1068:initiator
871:⋅
857:−
829:⟶
762:reactions
739:monomers.
677:peroxides
647:aldehydes
439:Extrusion
418:Braconnot
408:Baekeland
388:de Gennes
373:Shirakawa
333:Rheometry
264:Hydrogels
254:Copolymer
245:Structure
207:Polyester
106:Synthesis
51:Tacticity
5109:96213227
5043:16283773
4757:10 March
4494:10 March
4395:94433190
4137:See also
4025:) and (e
3605:catalyst
3535:enthalpy
1964:Kinetics
1765:. Where
1522:fluorine
1518:Halogens
1261:′
1253:′
1242:′
1230:′
1201:′
1156:Figure 9
1133:Figure 8
1070:, and a
1049:Figure 7
995:Figure 6
960:Figure 5
922:Figure 4
889:Figure 3
712:Figure 2
690:Figure 1
655:radicals
619:cationic
488:Bakelite
403:Goodyear
328:Rheology
5173:Bibcode
5128:Polymer
4919:Bibcode
4894:1 April
4664:Bibcode
4543:Bibcode
4517:2 April
4465:1 April
4173:Polymer
4035:styrene
3614:Atactic
3547:entropy
2247:, and k
1924:(RAFT):
1905:and by
1899:(ATRP):
1854:alkanes
1850:alkynes
1846:alkenes
1825:needed.
1783:Methods
1309:pi bond
1301:monomer
1031:ternary
981:cathode
651:ketones
615:anionic
589:monomer
573:polymer
413:Hayward
393:Ziegler
383:Edwards
5107:
5041:
4977:
4954:
4873:
4853:
4833:
4813:
4789:
4595:
4575:
4445:
4393:
4353:
4289:
4227:
4058:stents
3658:steric
2797:δ
2235:where
1852:, and
1434:Oxygen
1075:diketo
1003:Plasma
947:x-rays
733:alkene
505:Kevlar
363:Heeger
5105:S2CID
4783:58â60
4391:S2CID
4013:and r
3762:and Q
3588:= 0.
3584:). ÎG
1957:TEMPO
1066:, an
985:anode
945:, or
760:Redox
737:vinyl
724:High
643:vinyl
471:Tires
378:Natta
358:Flory
5039:PMID
4975:ISBN
4952:ISBN
4896:2010
4871:ISBN
4851:ISBN
4831:ISBN
4811:ISBN
4787:ISBN
4759:2010
4730:2011
4593:ISBN
4573:ISBN
4519:2010
4496:2010
4467:2010
4443:ISBN
4351:ISBN
4287:ISBN
4225:ISBN
4103:clay
2490:The
1909:and
1454:DPPH
1374:is C
649:and
621:and
298:FTIR
259:Gels
232:PVAc
133:RAFT
128:ATRP
81:LCST
76:UCST
5212:doi
5181:doi
5144:hdl
5136:doi
5097:doi
5070:doi
5066:150
5031:doi
5003:doi
4927:doi
4700:doi
4696:117
4672:doi
4634:doi
4551:doi
4421:doi
4383:doi
4319:doi
4029:â e
3943:exp
3821:exp
3689:Qâe
3660:or
3510:(ÎG
2243:, k
1608:):
1561:to
1239:ROR
679:or
565:FRP
555:In
323:DMA
318:TGA
313:NMR
308:DSC
293:GPC
227:PVA
222:PVC
5282::
5208:14
5206:.
5202:.
5179:.
5169:11
5167:.
5142:.
5132:45
5130:.
5126:.
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5037:.
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4997:.
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4670:.
4660:28
4658:.
4630:22
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4539:33
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4475:^
4417:48
4415:.
4403:^
4389:.
4379:79
4377:.
4365:^
4331:^
4315:13
4313:.
4301:^
4239:^
4201:^
4049:,
4021:/Q
3909:12
3899:11
3793:12
3775:12
3632:sp
3612:.
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3561:.
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3370:,
3308:,
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1848:,
1769:tr
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939:β-
937:,
935:Îą-
867:HO
853:HO
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816:Fe
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3905:k
3895:k
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3884:1
3880:r
3853:)
3848:2
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3838:1
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3827:(
3816:2
3812:Q
3806:1
3802:P
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3789:k
3772:k
3768:e
3764:j
3760:i
3744:j
3740:M
3717:o
3712:i
3708:M
3636:2
3586:p
3582:c
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3570:p
3566:p
3559:p
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3520:p
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3478:p
3474:k
3468:T
3463:r
3460:t
3456:k
3450:=
3445:T
3441:C
3416:p
3412:k
3406:P
3401:r
3398:t
3394:k
3388:=
3383:P
3379:C
3354:p
3350:k
3344:I
3339:r
3336:t
3332:k
3326:=
3321:I
3317:C
3292:p
3288:k
3282:S
3277:r
3274:t
3270:k
3264:=
3259:S
3255:C
3230:p
3226:k
3220:M
3215:r
3212:t
3208:k
3202:=
3197:M
3193:C
3163:]
3160:M
3157:[
3152:]
3149:T
3146:[
3138:T
3134:C
3130:+
3124:]
3121:M
3118:[
3113:]
3110:P
3107:[
3099:P
3095:C
3091:+
3085:]
3082:M
3079:[
3074:]
3071:I
3068:[
3060:I
3056:C
3052:+
3046:]
3043:M
3040:[
3035:]
3032:S
3029:[
3021:S
3017:C
3013:+
3008:M
3004:C
3000:+
2995:p
2991:v
2982:2
2978:]
2974:M
2971:[
2966:2
2959:p
2955:k
2945:c
2942:,
2939:t
2935:k
2931:+
2926:d
2923:,
2920:t
2916:k
2912:2
2906:=
2899:n
2895:x
2891:1
2876:n
2872:T
2868:P
2864:I
2860:S
2833:+
2830:1
2826:2
2821:=
2816:n
2812:x
2776:2
2773:=
2768:n
2764:x
2734:=
2729:n
2725:x
2711:n
2709:P
2681:2
2677:/
2673:1
2669:)
2665:]
2662:I
2659:[
2654:t
2650:k
2644:d
2640:k
2636:f
2633:(
2630:2
2625:]
2622:M
2619:[
2614:p
2610:k
2603:=
2597:]
2594:I
2591:[
2586:d
2582:k
2578:f
2575:2
2570:]
2564:M
2561:[
2558:]
2555:M
2552:[
2547:p
2543:k
2536:=
2529:i
2525:v
2519:p
2515:v
2509:=
2475:]
2472:M
2469:[
2464:2
2460:/
2456:1
2452:]
2448:I
2445:[
2440:2
2436:/
2432:1
2427:)
2420:t
2416:k
2409:d
2405:k
2401:f
2395:(
2387:p
2383:k
2378:=
2373:p
2369:v
2340:2
2336:/
2332:1
2327:)
2320:t
2316:k
2311:f
2308:]
2305:I
2302:[
2297:d
2293:k
2286:(
2281:=
2278:]
2272:M
2269:[
2249:t
2245:p
2241:d
2237:f
2218:2
2214:]
2207:M
2204:[
2199:t
2195:k
2191:2
2188:=
2184:t
2178:d
2174:/
2170:]
2164:M
2161:[
2155:d
2148:=
2143:t
2139:v
2115:]
2109:M
2106:[
2103:]
2100:M
2097:[
2092:p
2088:k
2084:=
2079:p
2075:v
2051:]
2048:I
2045:[
2042:f
2037:d
2033:k
2029:2
2026:=
2022:t
2016:d
2012:/
2008:]
2002:M
1999:[
1993:d
1989:=
1984:i
1980:v
1822::
1813::
1804::
1795::
1776:p
1774:k
1767:k
1750:]
1747:r
1744:e
1741:m
1738:o
1735:n
1732:o
1729:m
1726:[
1721:p
1717:k
1711:]
1708:t
1705:n
1702:e
1699:v
1696:l
1693:o
1690:s
1687:[
1682:r
1679:t
1675:k
1668:+
1663:o
1658:)
1651:n
1647:x
1643:1
1638:(
1633:=
1626:n
1622:x
1618:1
1605:n
1603:x
1597:(
1396::
1376:2
1258:O
1250:R
1246:+
1227:R
1218:O
1210:O
1198:R
1193:+
1186:R
1108:f
1104:f
1086:N
1082:o
1057:N
1053:o
1040:N
1036:o
863:+
848:+
842:+
838:3
824:+
820:2
812:+
803:2
799:O
790:2
786:H
563:(
544:e
537:t
530:v
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