1056:
4087:. 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
1847:: 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.
613:
1562:
1592:
1544:
1517:
1492:
3679:
1140:
1412:
1163:
967:
3653:
1474:
1002:
1428:
1943:: 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.
1451:
697:
40:
1392:
929:
719:
1337:
3649:=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).
1326:
4137:
609:. 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.
3637:. 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.
1091:. 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(
1946:
1355:
1957:
1322:. 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.
1878:: 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.
1897:, 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.
3187:
3627:
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
3613:
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
1584:
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
1526:
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
1384:
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
1044:
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
3640:
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
2868:
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
4132:
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
2505:
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.
4662:
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".
1558:
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
1901:
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
1867:
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,
1103:
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
4095:
1373:
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.
1034:(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.
3618:
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
4543:
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".
2707:
1351:) 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:
5031:
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".
2269:, 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.
4015:
1774:
3781:, 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,
1607:
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
2895:
3632:
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
1284:
1835:
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
651:
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
2496:
2241:
2072:
1099:-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
1932:
895:
1055:
998:
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.
2363:
1447:
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.
668:
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.
1018:
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
728:
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:
3874:
3503:
3441:
3379:
3317:
3255:
2863:
1541:
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).
4128:. 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,
776:
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.
2869:
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
1503:
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
2262:
are the constants for initiator dissociation, chain propagation and termination, respectively. and are the concentrations of the initiator, monomer and the active growing chain.
4384:
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".
2512:
3628:
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
1409:
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).
3777:, 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
3587:
become less negative. At a certain temperature, the polymerization reaches equilibrium (rate of polymerization = rate of depolymerization). This temperature is called the
3568:
must then be sufficiently negative to compensate for the unfavorable entropic term. Only then will polymerization be thermodynamically favored by the resulting negative ÎG
3552:
that releases the ring tension in a cyclic monomer. Meanwhile, during polymerization, a large amount of small molecules are associated, losing rotation and translational
2800:
2136:
2758:
3740:
3607:
The stereochemistry of polymerization is concerned with the difference in atom connectivity and spatial orientation in polymers that has the same chemical composition.
1826:
reaction mixture contains an aqueous phase, water-insoluble monomer, and initiator soluble in the monomer droplets (both the monomer and the initiator are hydrophobic).
4700:
Wang, J-S; Matyjaszewski, K (1995). "Controlled/"living" radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes".
1970:
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.
1514:
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).
3885:
3767:
1622:
5071:; K. Matyjaszewski; J. P. Vairon (2000). "Amphiphilic block copolymers prepared via controlled radical polymerization as surfactants for emulsion polymerization".
4193:
1888:
3182:{\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 {}{}}}
716:
Radiation cleaves a bond homolytically, producing two radicals (Figure 2). This method is used most often with metal iodides, metal alkyls, and azo compounds.
1113:
Due to side reactions, not all radicals formed by the dissociation of initiator molecules actually add monomers to form polymer chains. The efficiency factor
4422:
Islamova, R. M.; Puzin, Y. I.; Fatykhov, A. A.; Monakov, Y. B. (2006). "A Ternary
Initiating System for Free Radical Polymerization of Methyl Methacrylate".
2724:
can be correlated with the kinetic chain length. In the case of termination by disproportionation, one polymer molecule is produced per every kinetic chain:
1030:
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
3537:. According to the thermodynamic equation ÎG = ÎH â TÎS, a negative enthalpy and an increasing entropy will shift the equilibrium towards polymerization.
3553:
553:
3685:: Penultimate unit interactions cause monomer to add in a way that minimizes steric hindrance between substituent groups. (P represents polymer chain.)
4178:
148:
5211:"Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties"
2374:
5269:
4494:
2144:
1507:, all chain-transfer mechanisms also involve the abstraction of a hydrogen or other atom. There are several types of chain-transfer mechanisms.
4168:
3706:, was first proposed by Alfrey and Price in 1947. The scheme takes into account the intrinsic thermodynamic stability and polar effects in the
4728:
4801:
4365:
4301:
4239:
1985:
4088:
1907:
789:
91:
86:
3663:
However, if interactions between the substituents of the penultimate repeating unit and the terminal carbon atom are significant, then
1979:
In typical chain growth polymerizations, the reaction rates for initiation, propagation and termination can be described as follows:
96:
5301:
4989:
4966:
4885:
4865:
4845:
4825:
4607:
4587:
4457:
318:
133:
5227:
5210:
3525:) of the polymerization is commonly used to quantify the tendency of a polymeric reaction. The polymerization will be favored if ÎG
1912:
based on the formation of a carbon-carbon bond by atom transfer radical addition. This method, independently discovered in 1995 by
5004:
Braunecker, W. A.; K. Matyjaszewski (2007). "Controlled/living radical polymerization: Features, developments, and perspectives".
2368:
In this case, the rate of chain propagation can be further described using a function of the initiator and monomer concentrations
2275:
180:
5098:
Homenick, C. M.; G. Lawson; A. Adronov (2007). "Polymer grafting of carbon nanotubes using living free-radical polymerization".
4153:
1190:
625:
5254:
5084:
546:
1117:
is defined as the fraction of the original initiator which contributes to the polymerization reaction. The maximal value of
1790:
is the rate constant for propagation. The Mayo equation assumes that transfer to solvent is the major termination pathway.
303:
5296:
3794:
3548:
change, since addition of a monomer to the growing polymer chain involves the conversion of Ď bonds into Ď bonds, or a
3446:
3384:
3322:
3260:
3198:
101:
4158:
3549:
3513:
In chain growth polymerization, the position of the equilibrium between polymer and monomers can be determined by the
2817:
633:
621:
605:
Free-radical polymerization is a key synthesis route for obtaining a wide variety of different polymers and materials
333:
128:
123:
4075:
and lubricants. Block copolymers are used for a wide variety of applications including adhesives, footwear and toys.
3615:
3564:< 0 for nearly all polymerization processes. Since depolymerization is almost always entropically favored, the ÎH
4198:
2266:
1404:
1306:
During polymerization, a polymer spends most of its time in increasing its chain length, or propagating. After the
328:
157:
81:
5279:
4757:
4124:. Aqueous dispersions of clay are treated with an initiator and a catalyst and the organic monomer, generally an
1821:
1343:: An orbital drawing of the initiator attack on ethylene molecule, producing the start of the polyethylene chain.
539:
5244:
4469:
1561:
4665:
3664:
2717:
1586:
1440:
296:
4619:
3703:
1921:
1830:
1812:
1591:
1543:
1516:
919:
629:
398:
393:
167:
4091:(ATRP) or nitroxide-mediated polymerization (NMP), allows rapid growth of high molecular weight polymers.
2702:{\displaystyle \nu ={\frac {v_{p}}{v_{i}}}={\frac {k_{p}}{2fk_{d}}}={\frac {k_{p}}{2(fk_{d}k_{t})^{1/2}}}}
1869:
279:
4173:
1894:
1851:
1467:, Figure 18) are a few other inhibitors. The latter is an especially effective inhibitor because of the
1348:
1146:: Primary recombination of BPO; brackets indicate that the reaction is happening within the solvent cage
683:
677:
493:
313:
308:
4498:
3678:
1139:
5264:
4898:
5183:
4929:
4674:
4553:
4133:
growth polymerization produce a material with flexibility, mechanical strength and biocompatibility.
2502:
1332:: Phenyl initiator from benzoyl peroxide (BPO) attacks a styrene molecule to start the polymer chain.
162:
56:
1411:
1347:
Once a chain has been initiated, the chain propagates (Figure 13) until there are no more monomers (
1162:
1008:: (Top) Formation of radical anion at the cathode; (bottom) formation of radical cation at the anode
5068:
4732:
4044:). Values for each monomer can then be assigned relative to a reference monomer, usually chosen as
3588:
1803:
1573:
1314:(Figure 11). In an ethene monomer, one electron pair is held securely between the two carbons in a
966:
665:
503:
71:
5115:
4401:
3610:
2769:
2080:
1504:
940:
606:
466:
449:
408:
232:
5274:
4521:
3652:
2730:
1473:
4793:
4787:
3713:
1937:
requires a compound that can act as a reversible chain-transfer agent, such as dithio compound.
1427:
1001:
594:). Free radicals can be formed by a number of different mechanisms, usually involving separate
5049:
4985:
4962:
4881:
4861:
4841:
4821:
4797:
4702:
4603:
4583:
4453:
4361:
4297:
4235:
4020:
For the copolymerization of a given pair of monomers, the two experimental reactivity ratios r
4010:{\displaystyle r_{1}={\frac {k_{11}}{k_{12}}}={\frac {Q_{1}}{Q_{2}}}\exp(-e_{1}(e_{1}-e_{2}))}
3518:
1769:{\displaystyle {\frac {1}{x_{n}}}=\left({\frac {1}{x_{n}}}\right)_{o}+{\frac {k_{tr}}{k_{p}}}}
1450:
1370:
1307:
1078:
973:: The three steps involved in ionizing radiation: ejection, dissociation, and electron-capture
696:
595:
567:
459:
423:
242:
237:
4920:
Alfrey, Turner; Price, Charles C. (1947). "Relative reactivities in vinyl copolymerization".
3614:
established by
Ziegler and Natta and their coworkers in 1950s, as they developed metal based
1527:
solvent radical that is formed (greater stability leads to greater probability of transfer).
5222:
5191:
5154:
5146:
5107:
5080:
5041:
5013:
4937:
4710:
4682:
4644:
4561:
4431:
4393:
4329:
4084:
3879:
The monomer reactivity ratio for the addition of monomers 1 and 2 to this chain is given by
3707:
3534:
1898:
1041:
1013:
978:
961:
704:
413:
383:
323:
138:
3745:
1391:
918:
The dissociation of a persulfate in the aqueous phase (Figure 4). This method is useful in
17:
4121:
4064:
1913:
1088:
928:
486:
428:
378:
205:
1457:: Inhibition of polystyrene propagation due to reaction of polymer with molecular oxygen.
1177:
One radical is produced instead of the three radicals that could be produced (Figure 10).
5187:
4933:
4678:
4557:
4136:
1855:: The polymerization is initiated with plasma. A variety of organic molecules including
1378:
Combination of two active chain ends: one or both of the following processes may occur.
960:
cause ejection of an electron from the initiating species, followed by dissociation and
718:
686:
cleaved, producing two radicals (Figure 1). This method is used most often with organic
5017:
4188:
4163:
3668:
3620:
3514:
2713:
1609:
1500:
1100:
1019:
945:
648:
579:
520:
373:
116:
39:
4648:
1336:
1169:: Recombination of phenyl radicals from the initiation of BPO outside the solvent cage
5290:
4333:
4106:
4061:
3672:
3629:
1917:
1569:
949:
691:
418:
227:
222:
200:
5135:"Grafting of alkoxyamine end-capped (co)polymers onto multi-walled carbon nanotubes"
5119:
4405:
3694:
Traditionally, the reactivity of monomers and radicals are assessed by the means of
1131:
Two radicals recombine before initiating a chain (Figure 8). This occurs within the
4094:
3659:: (Top) formation of isotactic polymer; (bottom) formation of syndiotactic polymer.
1925:
1460:
1325:
1155:
1132:
983:
587:
510:
454:
403:
388:
212:
195:
5150:
3702:
scheme, the most widely used tool for the semi-quantitative prediction of monomer
994:
to become a radical anion, and a monomer molecule will give up an electron at the
5195:
4635:
Colombani, Daniel (1997). "Chain-Growth
Control in Free Radical Polymerization".
2763:
Termination by combination leads to one polymer molecule per two kinetic chains:
763:
The photoinitiator and any byproducts resulting from its use should be non-toxic.
4565:
4072:
4057:
4056:
Free radical polymerization has found applications including the manufacture of
3634:
1612:). The Mayo equation estimates the influence of chain transfer on chain length (
1082:
1074:
987:
923:
747:
653:
591:
525:
471:
259:
247:
4941:
1124:
The following types of reactions can decrease the efficiency of the initiator.
5249:
5111:
4435:
4397:
4129:
4125:
4101:: Grafting of a polystyrene free radical onto a single-walled carbon nanotube.
3667:
factors could cause the monomer to add to the polymer in a way that minimizes
3541:
1315:
1031:
1025:
913:
754:
736:
711:
368:
348:
190:
3192:
It is usual to define chain-transfer constants C for the different molecules
2811:, the contribution of disproportionation to the overall termination process:
2491:{\displaystyle v_{p}={k_{p}}\left({\frac {fk_{d}}{k_{t}}}\right)^{1/2}^{1/2}}
1559:
propagation. Peroxide initiators are especially sensitive to chain transfer.
4109:
3788:, is postulated to be related to the four relevant reactivity parameters by
3695:
3624:
1468:
1398:: Termination by the combination of two poly(vinyl chloride) (PVC) polymers.
953:
657:
343:
274:
264:
217:
61:
5133:
Lou, X. D.; C. Detrembleur; V. Sciannamea; C. Pagnoulle; R. Jerome (2004).
5053:
1154:
Two radical initiators recombine before initiating a chain, but not in the
5228:
10.1002/1521-4095(20020816)14:16<1120::AID-ADMA1120>3.0.CO;2-9
4320:
Hageman, H. J. (1985). "Photoinitiators for Free
Radical Polymerization".
3645:
hybridization and is planar. Consider the polymerization of the monomer CH
2236:{\displaystyle v_{t}={-\operatorname {d} /\operatorname {d} t}=2k_{t}^{2}}
1945:
1491:
1425:
Combination of an active chain end with an initiator radical (Figure 16).
612:
598:. Following its generation, the initiating free radical adds (nonradical)
5259:
5134:
4117:
3545:
2805:
Any mixture of both these mechanisms can be described by using the value
1598:: Chain transfer from polypropylene to backbone of another polypropylene.
1532:
687:
498:
476:
338:
4714:
4686:
1354:
4183:
4045:
3557:
1928:) and a transition metal halide catalyst (to activate dormant species).
1528:
1319:
1311:
991:
661:
599:
583:
76:
66:
5045:
4761:
2067:{\displaystyle v_{i}={\operatorname {d} /\operatorname {d} t}=2k_{d}f}
760:
Should not impart yellowing or unpleasant odors to the cured material.
5159:
4618:
The Mayo equation for chain transfer should not be confused with the
4068:
1864:
1860:
1856:
1444:
1085:
743:
515:
5085:
10.1002/1521-3900(200002)150:1<39::AID-MASY39>3.0.CO;2-D
1053:-isopropylcarbazole and di-Ρ-indenylzirconium dichloride (Figure 7).
890:{\displaystyle {\ce {{H2O2}+Fe^{2+}->{Fe^{3+}}+{HO^{-}}+HO^{.}}}}
4135:
4093:
3677:
3651:
1967:
1955:
1944:
1924:, requires reversible activation of a dormant species (such as an
1590:
1560:
1542:
1515:
1490:
1472:
1449:
1426:
1410:
1390:
1353:
1335:
1324:
1161:
1138:
1054:
1000:
995:
965:
957:
927:
770:
717:
695:
611:
1808:
reaction mixture contains only initiator and monomer, no solvent.
1418:: Termination by disproportionation of poly(methyl methacrylate).
27:
Polymerization process involving free radicals as repeating units
4113:
1956:
1464:
1135:, meaning that no solvent has yet come between the new radicals.
481:
269:
143:
3579:
is small. Depolymerization is favored at high temperatures: TÎS
3575:
In practice, polymerization is favored at low temperatures: TÎS
1933:
Reversible
Addition-Fragmentation Chain-Transfer Polymerization
1840:
Other methods of radical polymerization include the following:
1798:
There are four industrial methods of radical polymerization:
1361:: Propagation of polystyrene with a phenyl radical initiator.
4792:(2nd ed.). Blackie (USA: Chapman & Hall). pp.
4083:
Free radical polymerization allows the functionalization of
1463:, butylated hydroxyl toluene, and diphenyl picryl hydrazyl (
1291:: Reaction of polymer chain R with other species in reaction
38:
5067:
Burguiere, C.; S. Pascual; B. Coutin; A. Polton; M. Tardi;
4143:: General synthesis procedure for a nanocomposite hydrogel.
2358:{\displaystyle =\left({\frac {k_{d}f}{k_{t}}}\right)^{1/2}}
1817:
reaction mixture contains solvent, initiator, and monomer.
1279:{\displaystyle {\ce {{R.}+ {R'-O-O-R'}-> ROR' + R'O'}}}
742:
Efficient generation of radicals capable of attacking the
664:. Initiation has two steps. In the first step, one or two
818:
805:
1585:
which have been polymerized, so that the number-average
1434:: Termination of PVC by reaction with radical initiator.
4497:. Case Western Reserve University. 2009. Archived from
1963:: TEMPO molecule used to functionalize the chain ends.
1070:-isopropylcarbazole + di-Ρ-indenylzicronium dichloride
3888:
3797:
3748:
3716:
3449:
3387:
3325:
3263:
3201:
2898:
2820:
2772:
2733:
2515:
2377:
2278:
2147:
2083:
1988:
1625:
1193:
990:. A monomer molecule will receive an electron at the
792:
5176:
Current
Opinion in Solid State and Materials Science
4546:
Journal of
Polymer Science Part A: Polymer Chemistry
4112:. These gels are made of water-swellable nano-scale
4789:
Polymers: Chemistry and Physics of Modern Materials
4294:
Polymers: Chemistry and Physics of Modern Materials
4009:
3869:{\displaystyle k_{12}=P_{1}Q_{2}\exp(-e_{1}e_{2})}
3868:
3761:
3734:
3497:
3435:
3373:
3311:
3249:
3181:
2857:
2794:
2752:
2716:effect occurs in the reaction, the number average
2701:
2490:
2357:
2235:
2130:
2066:
1768:
1278:
889:
5174:Haraguchi, K. (2008). "Nanocomposite hydrogels".
3498:{\displaystyle C_{T}={\frac {k_{tr}^{T}}{k_{p}}}}
3436:{\displaystyle C_{P}={\frac {k_{tr}^{P}}{k_{p}}}}
3374:{\displaystyle C_{I}={\frac {k_{tr}^{I}}{k_{p}}}}
3312:{\displaystyle C_{S}={\frac {k_{tr}^{S}}{k_{p}}}}
3250:{\displaystyle C_{M}={\frac {k_{tr}^{M}}{k_{p}}}}
1966:Because the chain end is functionalized with the
4048:with the arbitrary values Q = 1.0 and e = â0.8.
2858:{\displaystyle x_{n}={\frac {2}{1+\delta }}\nu }
1121:is 1, but typical values range from 0.3 to 0.8.
4982:The Elements of Polymer Science and Engineering
4858:The Elements of Polymer Science and Engineering
4838:The Elements of Polymer Science and Engineering
4818:The Elements of Polymer Science and Engineering
4600:The Elements of Polymer Science and Engineering
4580:The Elements of Polymer Science and Engineering
3769:are considered to have intrinsic reactivities P
1550:: Chain transfer from polypropylene to monomer.
902:: Redox reaction of hydrogen peroxide and iron.
4234:(4th ed.). New York: Wiley-Interscience.
4194:Reversible-deactivation radical polymerization
4105:Radical polymerization also aids synthesis of
1889:Reversible-deactivation radical polymerization
1883:Reversible deactivation radical polymerization
1389:symmetric about the point of the combination.
656:monomers and the carbonâoxygen double bond in
5250:Free Radical Polymerization (video animation)
1523:: Chain transfer from polystyrene to solvent.
547:
8:
5255:Free Radical Polymerization - Chain Transfer
4961:(3rd ed., Pearson Prentice-Hall 2003) p.364
1783:is the rate constant for chain transfer and
1499:Contrary to the other modes of termination,
4976:
4974:
4379:
4377:
616:IUPAC definition for radical polymerization
4489:
4487:
4417:
4415:
4292:Cowie, J. M. G.; Arrighi, Valeria (2008).
3583:is large. As the temperature increases, ÎG
1480:: Inhibition of polymer chain, R, by DPPH.
1073:This type of initiating system contains a
986:of a solution containing both monomer and
753:Adequate solubility in the binder system (
602:units, thereby growing the polymer chain.
554:
540:
29:
5226:
5158:
4999:
4997:
4781:
4779:
4287:
4285:
4283:
4281:
4279:
4277:
4275:
4273:
4271:
4179:Nitroxide mediated radical polymerization
3995:
3982:
3969:
3945:
3935:
3929:
3918:
3908:
3902:
3893:
3887:
3857:
3847:
3825:
3815:
3802:
3796:
3753:
3747:
3726:
3721:
3715:
3487:
3477:
3469:
3463:
3454:
3448:
3425:
3415:
3407:
3401:
3392:
3386:
3363:
3353:
3345:
3339:
3330:
3324:
3301:
3291:
3283:
3277:
3268:
3262:
3239:
3229:
3221:
3215:
3206:
3200:
3153:
3147:
3114:
3108:
3075:
3069:
3036:
3030:
3017:
3004:
2991:
2975:
2968:
2963:
2948:
2929:
2919:
2908:
2899:
2897:
2834:
2825:
2819:
2777:
2771:
2738:
2732:
2686:
2682:
2663:
2653:
2623:
2616:
2595:
2556:
2549:
2538:
2528:
2522:
2514:
2469:
2465:
2445:
2441:
2429:
2418:
2408:
2396:
2391:
2382:
2376:
2345:
2341:
2329:
2306:
2299:
2277:
2227:
2208:
2183:
2161:
2152:
2146:
2101:
2088:
2082:
2046:
2021:
2002:
1993:
1987:
1941:Stable Free Radical Polymerization (SFRP)
1730:
1688:
1681:
1672:
1660:
1651:
1635:
1626:
1624:
1231:
1223:
1215:
1206:
1195:
1194:
1192:
880:
866:
861:
851:
847:
842:
833:
829:
817:
812:
804:
799:
794:
793:
791:
725:: Photolysis of azoisobutylnitrile (AIBN)
620:Free-radical polymerization is a type of
149:Nitroxide-mediated radical polymerization
4953:
4951:
4752:
4750:
4630:
4628:
4269:
4267:
4265:
4263:
4261:
4259:
4257:
4255:
4253:
4251:
2250:is the efficiency of the initiator and k
682:The initiator is heated until a bond is
4957:Allcock H.R., Lampe F.W. and Mark J.E.
4351:
4349:
4347:
4345:
4343:
4315:
4313:
4225:
4223:
4221:
4219:
4217:
4215:
4213:
4209:
1022:field to assist in creating the plasma.
922:, in which the radical diffuses into a
32:
4169:Cobalt-mediated radical polymerization
1872:, and various types of thin membranes.
1318:. The other is more loosely held in a
672:Types of initiation and the initiators
4360:. New York: Oxford University Press.
4296:(3rd ed.). Scotland: CRC Press.
3540:In general, the polymerization is an
935:: Thermal degradation of a persulfate
7:
4758:"Stable Free Radical Polymerization"
4472:. Materials World Modules. June 2009
4386:Russian Journal of Applied Chemistry
4089:atom transfer radical polymerization
1908:Atom transfer radical polymerization
647:Initiation is the first step of the
586:forms by the successive addition of
5209:Haraguchi, K.; Takehisa T. (2002).
4880:(2nd ed., Prentice-Hall 2003) p.39
4452:(2nd ed., Prentice-Hall 2003) p.36
1495:IUPAC definition for chain transfer
5280:Stable Free Radical Polymerization
5018:10.1016/j.progpolymsci.2006.11.002
4760:. Xerox Corp. 2010. Archived from
4729:"The 2011 Wolf Prize in Chemistry"
4358:Polymer Chemistry: An Introduction
2188:
2165:
2026:
2003:
25:
5260:Free Radical Vinyl Polymerization
3533:> 0, the polymer will undergo
2881:, and added chain-transfer agent
964:to produce a radical (Figure 5).
134:Controlled radical polymerization
4878:Polymer Science & Technology
4450:Polymer Science & Technology
4899:"The Polymerization of Alkenes"
4820:(Academic Press 1982) pp.195-9
4154:Anionic addition polymerization
1439:Interaction with impurities or
4959:Contemporary Polymer Chemistry
4004:
4001:
3975:
3959:
3863:
3837:
3173:
3167:
3162:
3156:
3134:
3128:
3123:
3117:
3095:
3089:
3084:
3078:
3056:
3050:
3045:
3039:
2988:
2981:
2679:
2675:
2669:
2643:
2635:
2629:
2607:
2601:
2580:
2571:
2568:
2562:
2485:
2479:
2462:
2455:
2318:
2312:
2288:
2279:
2224:
2214:
2180:
2171:
2125:
2116:
2113:
2107:
2061:
2055:
2018:
2009:
1760:
1736:
1721:
1697:
1471:stabilization of the radical.
1245:
839:
1:
5265:The Polymerization of Alkenes
5151:10.1016/j.polymer.2004.06.050
4649:10.1016/S0079-6700(97)00022-1
4116:(especially those classed as
2889:will be modified as follows:
1895:living radical polymerization
1062:: benzoyl peroxide + 3,6-bis(
739:in the 300â400 nm range.
97:FloryâHuggins solution theory
5196:10.1016/j.cossms.2008.05.001
4984:(Academic Press 1982) p.289
4860:(Academic Press 1982) p.214
4840:(Academic Press 1982) p.209
4602:(Academic Press 1982) p.212
4582:(Academic Press 1982) p.220
4356:Stevens, Malcolm P. (1999).
4334:10.1016/0033-0655(85)80021-2
4322:Progress in Organic Coatings
4232:Principles of Polymerization
1151:Other recombination pathways
926:monomer-containing droplet.
5006:Progress in Polymer Science
4731:. Wolf Fund. Archived from
4637:Progress in Polymer Science
4566:10.1002/pola.1995.080330406
4159:Chain-growth polymerisation
4067:elastomers, cardiovascular
4028:permit the evaluation of (Q
3560:decreases in the system, ÎS
3517:of the polymerization. The
2795:{\displaystyle x_{n}=2\nu }
2131:{\displaystyle v_{p}=k_{p}}
1952:: Reaction scheme for SFRP.
703:: Thermal decomposition of
634:coordination polymerization
622:chain-growth polymerization
572:free-radical polymerization
163:Condensation polymerization
129:Free-radical polymerization
124:Chain-growth polymerization
18:Free-radical polymerization
5318:
5275:Radical Reaction Chemistry
4942:10.1002/pol.1947.120020112
4922:Journal of Polymer Science
4199:Step-growth polymerization
2753:{\displaystyle x_{n}=\nu }
2267:steady-state approximation
1886:
1605:Effects of chain transfer:
1405:Radical disproportionation
158:Step-growth polymerization
5112:10.1080/15583720701271237
4470:"Addition Polymerization"
4436:10.1134/S156009040605006X
4424:Polymer Science, Series B
4398:10.1134/S1070427206090229
3735:{\displaystyle M_{i}^{o}}
3675:interaction (Figure 26).
1822:Suspension polymerization
1535:, are easily transferred.
5302:Polymerization reactions
4786:Cowie, J. M. G. (1991).
2718:degree of polymerization
1587:degree of polymerization
1310:is formed, it attacks a
920:emulsion polymerizations
5245:Addition Polymerization
5073:Macromolecular Symposia
3544:process, i.e. negative
1922:Krzysztof Matyjaszewski
1870:antireflection coatings
1845:Template polymerization
1831:Emulsion polymerization
1813:Solution polymerization
168:Addition polymerization
102:Coilâglobule transition
4230:Odian, George (2004).
4144:
4102:
4011:
3870:
3763:
3736:
3686:
3660:
3499:
3437:
3375:
3313:
3251:
3183:
2859:
2796:
2754:
2703:
2492:
2359:
2237:
2132:
2068:
1964:
1953:
1770:
1599:
1577:
1568:: Chain transfer from
1551:
1524:
1496:
1481:
1458:
1435:
1419:
1399:
1362:
1344:
1333:
1280:
1170:
1147:
1071:
1009:
974:
936:
891:
726:
707:
617:
280:Self-healing hydrogels
43:
4174:Living polymerization
4139:
4097:
4012:
3871:
3764:
3762:{\displaystyle M_{j}}
3737:
3681:
3655:
3550:ringâopening reaction
3500:
3438:
3376:
3314:
3252:
3184:
2860:
2797:
2755:
2704:
2493:
2360:
2238:
2133:
2069:
1959:
1948:
1852:Plasma polymerization
1771:
1594:
1564:
1546:
1519:
1494:
1476:
1453:
1430:
1414:
1394:
1357:
1349:living polymerization
1339:
1328:
1281:
1165:
1142:
1128:Primary recombination
1058:
1004:
969:
931:
892:
721:
699:
678:Thermal decomposition
615:
494:Cookware and bakeware
446:Industrial production
314:X-ray crystallography
42:
3886:
3795:
3746:
3714:
3447:
3385:
3323:
3261:
3199:
2896:
2818:
2770:
2731:
2513:
2503:kinetic chain length
2375:
2276:
2145:
2081:
1986:
1623:
1191:
1109:Initiator efficiency
790:
5297:Reaction mechanisms
5188:2007COSSM..11...47H
4934:1947JPoSc...2..101A
4897:Clark, Jim (2003).
4764:on 28 November 2003
4715:10.1021/ja00125a035
4687:10.1021/ma00109a056
4679:1995MaMol..28.1721K
4620:MayoâLewis equation
4558:1995JPoSA..33..643P
4522:"Radical Chemistry"
4495:"Polymer Synthesis"
3731:
3589:ceiling temperature
3556:. As a result, the
3482:
3420:
3358:
3296:
3234:
2885:. The equation of P
1804:Bulk polymerization
1574:di-t-butyl peroxide
820:
807:
596:initiator molecules
467:Protective Coatings
82:MarkâHouwink theory
5215:Advanced Materials
4501:on 7 February 2010
4145:
4103:
4007:
3866:
3759:
3732:
3717:
3710:. A given radical
3687:
3661:
3611:Hermann Staudinger
3554:degrees of freedom
3495:
3465:
3433:
3403:
3371:
3341:
3309:
3279:
3247:
3217:
3179:
2855:
2792:
2750:
2699:
2488:
2355:
2233:
2128:
2064:
1965:
1954:
1766:
1600:
1578:
1552:
1525:
1505:disproportionation
1497:
1482:
1459:
1436:
1420:
1400:
1363:
1345:
1334:
1276:
1171:
1148:
1072:
1037:Ternary initiators
1010:
975:
941:Ionizing radiation
937:
887:
808:
795:
727:
708:
618:
44:
5270:Polymer Synthesis
5221:(16): 1120â1123.
5145:(18): 6097â6102.
5046:10.1021/bm050464v
5034:Biomacromolecules
4803:978-0-216-92980-7
4709:(20): 5614â5615.
4703:J. Am. Chem. Soc.
4367:978-0-19-512444-6
4303:978-0-8493-9813-1
4241:978-0-471-27400-1
4120:) enveloped by a
4079:Academic research
3951:
3924:
3704:reactivity ratios
3519:Gibbs free energy
3493:
3431:
3369:
3307:
3245:
3177:
3138:
3099:
3060:
2998:
2914:
2850:
2697:
2611:
2544:
2435:
2335:
1764:
1666:
1641:
1371:Chain termination
1308:radical initiator
1299:
1298:
1270:
1262:
1251:
1239:
1230:
1222:
1210:
1198:
1095:-carboxybenzoyl)-
1066:-carboxybenzoyl)-
1049:-carboxybenzoyl)-
910:
909:
879:
865:
846:
828:
811:
798:
590:building blocks (
578:) is a method of
568:polymer chemistry
564:
563:
477:Consumer products
16:(Redirected from
5309:
5233:
5232:
5230:
5206:
5200:
5199:
5171:
5165:
5164:
5162:
5130:
5124:
5123:
5095:
5089:
5088:
5064:
5058:
5057:
5040:(6): 3410â3418.
5028:
5022:
5021:
5001:
4992:
4978:
4969:
4955:
4946:
4945:
4917:
4911:
4910:
4908:
4906:
4894:
4888:
4874:
4868:
4854:
4848:
4834:
4828:
4814:
4808:
4807:
4783:
4774:
4773:
4771:
4769:
4754:
4745:
4744:
4742:
4740:
4725:
4719:
4718:
4697:
4691:
4690:
4673:(5): 1721â1723.
4659:
4653:
4652:
4643:(8): 1649â1720.
4632:
4623:
4616:
4610:
4596:
4590:
4576:
4570:
4569:
4540:
4534:
4533:
4531:
4529:
4517:
4511:
4510:
4508:
4506:
4491:
4482:
4481:
4479:
4477:
4466:
4460:
4446:
4440:
4439:
4419:
4410:
4409:
4392:(9): 1509â1513.
4381:
4372:
4371:
4353:
4338:
4337:
4317:
4308:
4307:
4289:
4246:
4245:
4227:
4085:carbon nanotubes
4016:
4014:
4013:
4008:
4000:
3999:
3987:
3986:
3974:
3973:
3952:
3950:
3949:
3940:
3939:
3930:
3925:
3923:
3922:
3913:
3912:
3903:
3898:
3897:
3875:
3873:
3872:
3867:
3862:
3861:
3852:
3851:
3830:
3829:
3820:
3819:
3807:
3806:
3768:
3766:
3765:
3760:
3758:
3757:
3741:
3739:
3738:
3733:
3730:
3725:
3708:transition state
3696:copolymerization
3535:depolymerization
3504:
3502:
3501:
3496:
3494:
3492:
3491:
3481:
3476:
3464:
3459:
3458:
3442:
3440:
3439:
3434:
3432:
3430:
3429:
3419:
3414:
3402:
3397:
3396:
3380:
3378:
3377:
3372:
3370:
3368:
3367:
3357:
3352:
3340:
3335:
3334:
3318:
3316:
3315:
3310:
3308:
3306:
3305:
3295:
3290:
3278:
3273:
3272:
3256:
3254:
3253:
3248:
3246:
3244:
3243:
3233:
3228:
3216:
3211:
3210:
3188:
3186:
3185:
3180:
3178:
3176:
3165:
3154:
3152:
3151:
3139:
3137:
3126:
3115:
3113:
3112:
3100:
3098:
3087:
3076:
3074:
3073:
3061:
3059:
3048:
3037:
3035:
3034:
3022:
3021:
3009:
3008:
2999:
2997:
2996:
2995:
2980:
2979:
2974:
2973:
2972:
2960:
2959:
2958:
2940:
2939:
2920:
2915:
2913:
2912:
2900:
2864:
2862:
2861:
2856:
2851:
2849:
2835:
2830:
2829:
2810:
2801:
2799:
2798:
2793:
2782:
2781:
2759:
2757:
2756:
2751:
2743:
2742:
2708:
2706:
2705:
2700:
2698:
2696:
2695:
2694:
2690:
2668:
2667:
2658:
2657:
2638:
2628:
2627:
2617:
2612:
2610:
2600:
2599:
2583:
2561:
2560:
2550:
2545:
2543:
2542:
2533:
2532:
2523:
2497:
2495:
2494:
2489:
2478:
2477:
2473:
2454:
2453:
2449:
2440:
2436:
2434:
2433:
2424:
2423:
2422:
2409:
2402:
2401:
2400:
2387:
2386:
2364:
2362:
2361:
2356:
2354:
2353:
2349:
2340:
2336:
2334:
2333:
2324:
2311:
2310:
2300:
2242:
2240:
2239:
2234:
2232:
2231:
2213:
2212:
2197:
2187:
2157:
2156:
2137:
2135:
2134:
2129:
2106:
2105:
2093:
2092:
2073:
2071:
2070:
2065:
2051:
2050:
2035:
2025:
1998:
1997:
1902:polymerization.
1899:Block copolymers
1775:
1773:
1772:
1767:
1765:
1763:
1735:
1734:
1724:
1696:
1695:
1682:
1677:
1676:
1671:
1667:
1665:
1664:
1652:
1642:
1640:
1639:
1627:
1285:
1283:
1282:
1277:
1275:
1274:
1268:
1266:
1260:
1255:
1249:
1244:
1243:
1237:
1235:
1228:
1227:
1220:
1219:
1214:
1208:
1202:
1196:
1181:
1180:
962:electron capture
896:
894:
893:
888:
886:
885:
884:
877:
872:
871:
870:
863:
857:
856:
855:
844:
838:
837:
826:
821:
819:
816:
809:
806:
803:
796:
780:
779:
705:dicumyl peroxide
556:
549:
542:
460:Applied coatings
297:Characterization
30:
21:
5317:
5316:
5312:
5311:
5310:
5308:
5307:
5306:
5287:
5286:
5241:
5236:
5208:
5207:
5203:
5173:
5172:
5168:
5132:
5131:
5127:
5100:Polymer Reviews
5097:
5096:
5092:
5066:
5065:
5061:
5030:
5029:
5025:
5003:
5002:
4995:
4979:
4972:
4956:
4949:
4919:
4918:
4914:
4904:
4902:
4896:
4895:
4891:
4876:Fried, Joel R.
4875:
4871:
4855:
4851:
4835:
4831:
4815:
4811:
4804:
4785:
4784:
4777:
4767:
4765:
4756:
4755:
4748:
4738:
4736:
4727:
4726:
4722:
4699:
4698:
4694:
4661:
4660:
4656:
4634:
4633:
4626:
4622:for copolymers.
4617:
4613:
4597:
4593:
4577:
4573:
4542:
4541:
4537:
4527:
4525:
4520:Leach, Mark R.
4519:
4518:
4514:
4504:
4502:
4493:
4492:
4485:
4475:
4473:
4468:
4467:
4463:
4448:Fried, Joel R.
4447:
4443:
4421:
4420:
4413:
4383:
4382:
4375:
4368:
4355:
4354:
4341:
4319:
4318:
4311:
4304:
4291:
4290:
4249:
4242:
4229:
4228:
4211:
4207:
4150:
4122:network polymer
4081:
4065:block copolymer
4054:
4043:
4039:
4035:
4031:
4027:
4023:
3991:
3978:
3965:
3941:
3931:
3914:
3904:
3889:
3884:
3883:
3853:
3843:
3821:
3811:
3798:
3793:
3792:
3787:
3776:
3772:
3749:
3744:
3743:
3712:
3711:
3692:
3648:
3605:
3603:Stereochemistry
3598:
3594:
3586:
3582:
3578:
3571:
3567:
3563:
3532:
3528:
3524:
3511:
3483:
3450:
3445:
3444:
3421:
3388:
3383:
3382:
3359:
3326:
3321:
3320:
3297:
3264:
3259:
3258:
3235:
3202:
3197:
3196:
3166:
3155:
3143:
3127:
3116:
3104:
3088:
3077:
3065:
3049:
3038:
3026:
3013:
3000:
2987:
2964:
2962:
2961:
2944:
2925:
2921:
2904:
2894:
2893:
2888:
2839:
2821:
2816:
2815:
2809:
2806:
2773:
2768:
2767:
2734:
2729:
2728:
2723:
2678:
2659:
2649:
2639:
2619:
2618:
2591:
2584:
2552:
2551:
2534:
2524:
2511:
2510:
2461:
2425:
2414:
2410:
2404:
2403:
2392:
2378:
2373:
2372:
2325:
2302:
2301:
2295:
2294:
2274:
2273:
2261:
2257:
2253:
2223:
2204:
2148:
2143:
2142:
2097:
2084:
2079:
2078:
2042:
1989:
1984:
1983:
1977:
1914:Mitsuo Sawamoto
1891:
1885:
1796:
1788:
1781:
1726:
1725:
1684:
1683:
1656:
1647:
1646:
1631:
1621:
1620:
1617:
1489:
1388:
1368:
1304:
1295:
1294:
1293:
1292:
1286:
1267:
1259:
1248:
1236:
1207:
1189:
1188:
1111:
1104:microstructure.
1089:carboxylic acid
979:Electrochemical
906:
905:
904:
903:
897:
876:
862:
843:
825:
788:
787:
746:double bond of
674:
645:
639:
560:
531:
530:
442:
434:
433:
364:
356:
355:
299:
289:
288:
206:Polyisobutylene
187:Functional type
183:
173:
172:
119:
109:
108:
52:
33:Polymer science
28:
23:
22:
15:
12:
11:
5:
5315:
5313:
5305:
5304:
5299:
5289:
5288:
5283:
5282:
5277:
5272:
5267:
5262:
5257:
5252:
5247:
5240:
5239:External links
5237:
5235:
5234:
5201:
5182:(3â4): 47â54.
5166:
5125:
5106:(2): 265â270.
5090:
5059:
5023:
4993:
4980:Rudin, Alfred
4970:
4947:
4928:(1): 101â106.
4912:
4889:
4869:
4856:Rudin, Alfred
4849:
4836:Rudin, Alfred
4829:
4816:Rudin, Alfred
4809:
4802:
4775:
4746:
4735:on 17 May 2007
4720:
4692:
4666:Macromolecules
4654:
4624:
4611:
4598:Rudin, Alfred
4591:
4578:Rudin, Alfred
4571:
4552:(4): 643â652.
4535:
4524:. Chemogenesis
4512:
4483:
4461:
4441:
4430:(3): 130â133.
4411:
4373:
4366:
4339:
4328:(2): 123â150.
4309:
4302:
4247:
4240:
4208:
4206:
4203:
4202:
4201:
4196:
4191:
4189:Polymerization
4186:
4181:
4176:
4171:
4166:
4164:Chain transfer
4161:
4156:
4149:
4146:
4080:
4077:
4053:
4050:
4041:
4037:
4033:
4029:
4025:
4021:
4018:
4017:
4006:
4003:
3998:
3994:
3990:
3985:
3981:
3977:
3972:
3968:
3964:
3961:
3958:
3955:
3948:
3944:
3938:
3934:
3928:
3921:
3917:
3911:
3907:
3901:
3896:
3892:
3877:
3876:
3865:
3860:
3856:
3850:
3846:
3842:
3839:
3836:
3833:
3828:
3824:
3818:
3814:
3810:
3805:
3801:
3785:
3774:
3770:
3756:
3752:
3742:and a monomer
3729:
3724:
3720:
3691:
3688:
3665:conformational
3646:
3621:microstructure
3604:
3601:
3596:
3592:
3584:
3580:
3576:
3569:
3565:
3561:
3530:
3526:
3522:
3515:thermodynamics
3510:
3509:Thermodynamics
3507:
3506:
3505:
3490:
3486:
3480:
3475:
3472:
3468:
3462:
3457:
3453:
3428:
3424:
3418:
3413:
3410:
3406:
3400:
3395:
3391:
3366:
3362:
3356:
3351:
3348:
3344:
3338:
3333:
3329:
3304:
3300:
3294:
3289:
3286:
3282:
3276:
3271:
3267:
3242:
3238:
3232:
3227:
3224:
3220:
3214:
3209:
3205:
3190:
3189:
3175:
3172:
3169:
3164:
3161:
3158:
3150:
3146:
3142:
3136:
3133:
3130:
3125:
3122:
3119:
3111:
3107:
3103:
3097:
3094:
3091:
3086:
3083:
3080:
3072:
3068:
3064:
3058:
3055:
3052:
3047:
3044:
3041:
3033:
3029:
3025:
3020:
3016:
3012:
3007:
3003:
2994:
2990:
2986:
2983:
2978:
2971:
2967:
2957:
2954:
2951:
2947:
2943:
2938:
2935:
2932:
2928:
2924:
2918:
2911:
2907:
2903:
2886:
2866:
2865:
2854:
2848:
2845:
2842:
2838:
2833:
2828:
2824:
2807:
2803:
2802:
2791:
2788:
2785:
2780:
2776:
2761:
2760:
2749:
2746:
2741:
2737:
2721:
2714:chain-transfer
2710:
2709:
2693:
2689:
2685:
2681:
2677:
2674:
2671:
2666:
2662:
2656:
2652:
2648:
2645:
2642:
2637:
2634:
2631:
2626:
2622:
2615:
2609:
2606:
2603:
2598:
2594:
2590:
2587:
2582:
2579:
2576:
2573:
2570:
2567:
2564:
2559:
2555:
2548:
2541:
2537:
2531:
2527:
2521:
2518:
2499:
2498:
2487:
2484:
2481:
2476:
2472:
2468:
2464:
2460:
2457:
2452:
2448:
2444:
2439:
2432:
2428:
2421:
2417:
2413:
2407:
2399:
2395:
2390:
2385:
2381:
2366:
2365:
2352:
2348:
2344:
2339:
2332:
2328:
2323:
2320:
2317:
2314:
2309:
2305:
2298:
2293:
2290:
2287:
2284:
2281:
2259:
2255:
2251:
2244:
2243:
2230:
2226:
2222:
2219:
2216:
2211:
2207:
2203:
2200:
2196:
2193:
2190:
2186:
2182:
2179:
2176:
2173:
2170:
2167:
2164:
2160:
2155:
2151:
2139:
2138:
2127:
2124:
2121:
2118:
2115:
2112:
2109:
2104:
2100:
2096:
2091:
2087:
2075:
2074:
2063:
2060:
2057:
2054:
2049:
2045:
2041:
2038:
2034:
2031:
2028:
2024:
2020:
2017:
2014:
2011:
2008:
2005:
2001:
1996:
1992:
1976:
1973:
1972:
1971:
1938:
1929:
1893:Also known as
1887:Main article:
1884:
1881:
1880:
1879:
1873:
1848:
1838:
1837:
1827:
1818:
1809:
1795:
1792:
1786:
1779:
1762:
1759:
1756:
1753:
1750:
1747:
1744:
1741:
1738:
1733:
1729:
1723:
1720:
1717:
1714:
1711:
1708:
1705:
1702:
1699:
1694:
1691:
1687:
1680:
1675:
1670:
1663:
1659:
1655:
1650:
1645:
1638:
1634:
1630:
1615:
1610:telomerization
1602:
1601:
1589:is unaffected.
1579:
1553:
1536:
1501:chain transfer
1488:
1487:Chain transfer
1485:
1484:
1483:
1437:
1423:
1422:
1421:
1401:
1386:
1367:
1364:
1303:
1300:
1297:
1296:
1287:
1273:
1265:
1258:
1254:
1247:
1242:
1234:
1226:
1218:
1213:
1205:
1201:
1187:
1186:
1185:
1184:
1179:
1178:
1175:
1174:Side reactions
1160:
1159:
1152:
1137:
1136:
1129:
1110:
1107:
1106:
1105:
1101:microstructure
1083:heteroaromatic
1038:
1035:
1028:
1023:
1020:radiofrequency
1016:
1011:
981:
976:
943:
938:
916:
908:
907:
898:
883:
875:
869:
860:
854:
850:
841:
836:
832:
824:
815:
802:
786:
785:
784:
783:
778:
777:
774:
767:
766:
765:
764:
761:
758:
751:
740:
730:
729:
714:
709:
680:
673:
670:
649:polymerization
644:
641:
580:polymerization
562:
561:
559:
558:
551:
544:
536:
533:
532:
529:
528:
523:
521:Plastic bottle
518:
513:
508:
507:
506:
504:Food Container
501:
491:
490:
489:
479:
474:
469:
464:
463:
462:
457:
447:
443:
440:
439:
436:
435:
432:
431:
426:
421:
416:
411:
406:
401:
396:
391:
386:
381:
376:
371:
365:
362:
361:
358:
357:
354:
353:
352:
351:
346:
336:
331:
326:
321:
316:
311:
306:
300:
295:
294:
291:
290:
287:
286:
285:
284:
283:
282:
267:
262:
257:
253:
252:
251:
250:
245:
240:
235:
228:Vinyl polymers
225:
220:
215:
210:
209:
208:
203:
198:
188:
184:
181:Classification
179:
178:
175:
174:
171:
170:
165:
160:
154:
153:
152:
151:
146:
141:
131:
126:
120:
115:
114:
111:
110:
107:
106:
105:
104:
99:
94:
89:
84:
77:Phase behavior
74:
69:
64:
59:
53:
50:
49:
46:
45:
35:
34:
26:
24:
14:
13:
10:
9:
6:
4:
3:
2:
5314:
5303:
5300:
5298:
5295:
5294:
5292:
5285:
5281:
5278:
5276:
5273:
5271:
5268:
5266:
5263:
5261:
5258:
5256:
5253:
5251:
5248:
5246:
5243:
5242:
5238:
5229:
5224:
5220:
5216:
5212:
5205:
5202:
5197:
5193:
5189:
5185:
5181:
5177:
5170:
5167:
5161:
5156:
5152:
5148:
5144:
5140:
5136:
5129:
5126:
5121:
5117:
5113:
5109:
5105:
5101:
5094:
5091:
5086:
5082:
5078:
5074:
5070:
5063:
5060:
5055:
5051:
5047:
5043:
5039:
5035:
5027:
5024:
5019:
5015:
5012:(1): 93â146.
5011:
5007:
5000:
4998:
4994:
4991:
4990:0-12-601680-1
4987:
4983:
4977:
4975:
4971:
4968:
4967:0-13-065056-0
4964:
4960:
4954:
4952:
4948:
4943:
4939:
4935:
4931:
4927:
4923:
4916:
4913:
4900:
4893:
4890:
4887:
4886:0-13-018168-4
4883:
4879:
4873:
4870:
4867:
4866:0-12-601680-1
4863:
4859:
4853:
4850:
4847:
4846:0-12-601680-1
4843:
4839:
4833:
4830:
4827:
4826:0-12-601680-1
4823:
4819:
4813:
4810:
4805:
4799:
4795:
4791:
4790:
4782:
4780:
4776:
4763:
4759:
4753:
4751:
4747:
4734:
4730:
4724:
4721:
4716:
4712:
4708:
4705:
4704:
4696:
4693:
4688:
4684:
4680:
4676:
4672:
4668:
4667:
4658:
4655:
4650:
4646:
4642:
4638:
4631:
4629:
4625:
4621:
4615:
4612:
4609:
4608:0-12-601680-1
4605:
4601:
4595:
4592:
4589:
4588:0-12-601680-1
4585:
4581:
4575:
4572:
4567:
4563:
4559:
4555:
4551:
4547:
4539:
4536:
4523:
4516:
4513:
4500:
4496:
4490:
4488:
4484:
4471:
4465:
4462:
4459:
4458:0-13-018168-4
4455:
4451:
4445:
4442:
4437:
4433:
4429:
4425:
4418:
4416:
4412:
4407:
4403:
4399:
4395:
4391:
4387:
4380:
4378:
4374:
4369:
4363:
4359:
4352:
4350:
4348:
4346:
4344:
4340:
4335:
4331:
4327:
4323:
4316:
4314:
4310:
4305:
4299:
4295:
4288:
4286:
4284:
4282:
4280:
4278:
4276:
4274:
4272:
4270:
4268:
4266:
4264:
4262:
4260:
4258:
4256:
4254:
4252:
4248:
4243:
4237:
4233:
4226:
4224:
4222:
4220:
4218:
4216:
4214:
4210:
4204:
4200:
4197:
4195:
4192:
4190:
4187:
4185:
4182:
4180:
4177:
4175:
4172:
4170:
4167:
4165:
4162:
4160:
4157:
4155:
4152:
4151:
4147:
4142:
4138:
4134:
4131:
4127:
4123:
4119:
4115:
4111:
4108:
4107:nanocomposite
4100:
4096:
4092:
4090:
4086:
4078:
4076:
4074:
4070:
4066:
4063:
4062:thermoplastic
4059:
4051:
4049:
4047:
3996:
3992:
3988:
3983:
3979:
3970:
3966:
3962:
3956:
3953:
3946:
3942:
3936:
3932:
3926:
3919:
3915:
3909:
3905:
3899:
3894:
3890:
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3803:
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3701:
3697:
3689:
3684:
3680:
3676:
3674:
3673:electrostatic
3670:
3666:
3658:
3654:
3650:
3644:
3638:
3636:
3631:
3630:crystallinity
3626:
3622:
3617:
3612:
3608:
3602:
3600:
3590:
3573:
3559:
3555:
3551:
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3536:
3529:< 0; if ÎG
3520:
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3422:
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3364:
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3269:
3265:
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3230:
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3218:
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3195:
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2969:
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2458:
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2326:
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2307:
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2039:
2036:
2032:
2029:
2022:
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2012:
2006:
1999:
1994:
1990:
1982:
1981:
1980:
1974:
1969:
1962:
1958:
1951:
1947:
1942:
1939:
1936:
1934:
1930:
1927:
1923:
1919:
1918:Jin-Shan Wang
1915:
1911:
1909:
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1904:
1903:
1900:
1896:
1890:
1882:
1877:
1874:
1871:
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1800:
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1611:
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1597:
1593:
1588:
1583:
1580:
1575:
1571:
1570:polypropylene
1567:
1563:
1557:
1556:To initiator:
1554:
1549:
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1540:
1537:
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1530:
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720:
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713:
710:
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702:
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693:
692:azo compounds
689:
685:
684:homolytically
681:
679:
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675:
671:
669:
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663:
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650:
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623:
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410:
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385:
382:
380:
377:
375:
372:
370:
367:
366:
360:
359:
350:
347:
345:
342:
341:
340:
337:
335:
332:
330:
327:
325:
322:
320:
317:
315:
312:
310:
307:
305:
302:
301:
298:
293:
292:
281:
278:
277:
276:
273:
272:
271:
268:
266:
263:
261:
258:
255:
254:
249:
246:
244:
241:
239:
236:
234:
231:
230:
229:
226:
224:
223:Polycarbonate
221:
219:
216:
214:
211:
207:
204:
202:
201:Polypropylene
199:
197:
194:
193:
192:
189:
186:
185:
182:
177:
176:
169:
166:
164:
161:
159:
156:
155:
150:
147:
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140:
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132:
130:
127:
125:
122:
121:
118:
113:
112:
103:
100:
98:
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93:
90:
88:
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83:
80:
79:
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4892:
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4766:. Retrieved
4762:the original
4737:. Retrieved
4733:the original
4723:
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4695:
4670:
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4499:the original
4474:. Retrieved
4464:
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4389:
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4357:
4325:
4321:
4293:
4231:
4140:
4130:cross-linked
4104:
4098:
4082:
4055:
4052:Applications
4019:
3878:
3782:
3778:
3699:
3693:
3682:
3662:
3656:
3642:
3639:
3609:
3606:
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3539:
3512:
3191:
2882:
2878:
2874:
2873:, initiator
2870:
2867:
2804:
2762:
2712:Assuming no
2711:
2500:
2367:
2264:
2247:
2245:
1978:
1960:
1949:
1940:
1931:
1926:alkyl halide
1906:
1892:
1875:
1850:
1844:
1839:
1829:
1820:
1811:
1802:
1797:
1784:
1777:
1613:
1604:
1603:
1595:
1581:
1565:
1555:
1547:
1538:
1520:
1511:
1498:
1477:
1461:Nitrobenzene
1454:
1431:
1415:
1403:
1395:
1382:Combination:
1381:
1369:
1358:
1346:
1340:
1329:
1305:
1288:
1166:
1156:solvent cage
1143:
1133:solvent cage
1123:
1118:
1114:
1112:
1096:
1092:
1067:
1063:
1059:
1050:
1046:
1045:and 3,6-bis(
1005:
984:Electrolysis
970:
932:
899:
737:absorptivity
722:
700:
646:
638:
619:
604:
592:repeat units
588:free-radical
575:
571:
565:
511:Vinyl record
455:Blow molding
441:Applications
213:Polyurethane
196:Polyethylene
57:Architecture
5069:B. Charleux
4901:. ChemGuide
4739:21 February
4073:surfactants
4071:, chemical
4058:polystyrene
3635:polypropene
1582:To polymer:
1539:To monomer:
1512:To solvent:
1366:Termination
1302:Propagation
1158:(Figure 9).
1075:metallocene
988:electrolyte
924:hydrophobic
914:Persulfates
757:+ monomer).
582:by which a
526:Plastic bag
472:3D printing
260:Homopolymer
248:Polystyrene
72:Degradation
5291:Categories
4205:References
4126:acrylamide
3698:data. The
3690:Reactivity
3542:exothermic
2877:, polymer
2265:Under the
1876:Sonication
1576:initiator.
1441:inhibitors
1316:sigma bond
1032:cavitation
1026:Sonication
755:prepolymer
712:Photolysis
643:Initiation
607:composites
487:Whitewalls
409:Staudinger
379:MacDiarmid
363:Scientists
349:Viscometry
191:Polyolefin
67:Morphology
51:Properties
5160:2268/8255
5079:: 39â44.
4141:Figure 28
4118:smectites
4110:hydrogels
4099:Figure 27
3989:−
3963:−
3957:
3841:−
3835:
3683:Figure 26
3657:Figure 25
3641:atom has
2853:ν
2847:δ
2790:ν
2748:ν
2578:⋅
2517:ν
2286:⋅
2221:⋅
2192:
2178:⋅
2169:
2163:−
2123:⋅
2030:
2016:⋅
2007:
1961:Figure 24
1950:Figure 23
1596:Figure 22
1566:Figure 21
1548:Figure 20
1531:, except
1521:Figure 19
1478:Figure 18
1469:resonance
1455:Figure 17
1432:Figure 16
1416:Figure 15
1396:Figure 14
1359:Figure 13
1341:Figure 12
1330:Figure 11
1289:Figure 10
1246:⟶
1233:−
1225:−
1217:−
1200:⋅
1079:initiator
882:⋅
868:−
840:⟶
773:reactions
750:monomers.
688:peroxides
658:aldehydes
450:Extrusion
429:Braconnot
419:Baekeland
399:de Gennes
384:Shirakawa
344:Rheometry
275:Hydrogels
265:Copolymer
256:Structure
218:Polyester
117:Synthesis
62:Tacticity
5120:96213227
5054:16283773
4768:10 March
4505:10 March
4406:94433190
4148:See also
4036:) and (e
3616:catalyst
3546:enthalpy
1975:Kinetics
1776:. Where
1533:fluorine
1529:Halogens
1272:′
1264:′
1253:′
1241:′
1212:′
1167:Figure 9
1144:Figure 8
1081:, and a
1060:Figure 7
1006:Figure 6
971:Figure 5
933:Figure 4
900:Figure 3
723:Figure 2
701:Figure 1
666:radicals
630:cationic
499:Bakelite
414:Goodyear
339:Rheology
5184:Bibcode
5139:Polymer
4930:Bibcode
4905:1 April
4675:Bibcode
4554:Bibcode
4528:2 April
4476:1 April
4184:Polymer
4046:styrene
3625:Atactic
3558:entropy
2258:, and k
1935:(RAFT):
1916:and by
1910:(ATRP):
1865:alkanes
1861:alkynes
1857:alkenes
1836:needed.
1794:Methods
1320:pi bond
1312:monomer
1042:ternary
992:cathode
662:ketones
626:anionic
600:monomer
584:polymer
424:Hayward
404:Ziegler
394:Edwards
5118:
5052:
4988:
4965:
4884:
4864:
4844:
4824:
4800:
4606:
4586:
4456:
4404:
4364:
4300:
4238:
4069:stents
3669:steric
2808:δ
2246:where
1863:, and
1445:Oxygen
1086:diketo
1014:Plasma
958:x-rays
744:alkene
516:Kevlar
374:Heeger
5116:S2CID
4794:58â60
4402:S2CID
4024:and r
3773:and Q
3599:= 0.
3595:). ÎG
1968:TEMPO
1077:, an
996:anode
956:, or
771:Redox
748:vinyl
735:High
654:vinyl
482:Tires
389:Natta
369:Flory
5050:PMID
4986:ISBN
4963:ISBN
4907:2010
4882:ISBN
4862:ISBN
4842:ISBN
4822:ISBN
4798:ISBN
4770:2010
4741:2011
4604:ISBN
4584:ISBN
4530:2010
4507:2010
4478:2010
4454:ISBN
4362:ISBN
4298:ISBN
4236:ISBN
4114:clay
2501:The
1920:and
1465:DPPH
1385:is C
660:and
632:and
309:FTIR
270:Gels
243:PVAc
144:RAFT
139:ATRP
92:LCST
87:UCST
5223:doi
5192:doi
5155:hdl
5147:doi
5108:doi
5081:doi
5077:150
5042:doi
5014:doi
4938:doi
4711:doi
4707:117
4683:doi
4645:doi
4562:doi
4432:doi
4394:doi
4330:doi
4040:â e
3954:exp
3832:exp
3700:Qâe
3671:or
3521:(ÎG
2254:, k
1619:):
1572:to
1250:ROR
690:or
576:FRP
566:In
334:DMA
329:TGA
324:NMR
319:DSC
304:GPC
238:PVA
233:PVC
5293::
5219:14
5217:.
5213:.
5190:.
5180:11
5178:.
5153:.
5143:45
5141:.
5137:.
5114:.
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5102:.
5075:.
5048:.
5036:.
5010:32
5008:.
4996:^
4973:^
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4936:.
4924:.
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4778:^
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4681:.
4671:28
4669:.
4641:22
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4627:^
4560:.
4550:33
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4428:48
4426:.
4414:^
4400:.
4390:79
4388:.
4376:^
4342:^
4326:13
4324:.
4312:^
4250:^
4212:^
4060:,
4032:/Q
3920:12
3910:11
3804:12
3786:12
3643:sp
3623:.
3591:(T
3572:.
3443:,
3381:,
3319:,
3257:,
1859:,
1780:tr
1443:.
1040:A
954:Îł-
952:,
950:β-
948:,
946:Îą-
878:HO
864:HO
845:Fe
827:Fe
694:.
636:.
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570:,
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5110::
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4532:.
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3993:e
3984:1
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3976:(
3971:1
3967:e
3960:(
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3937:1
3933:Q
3927:=
3916:k
3906:k
3900:=
3895:1
3891:r
3864:)
3859:2
3855:e
3849:1
3845:e
3838:(
3827:2
3823:Q
3817:1
3813:P
3809:=
3800:k
3783:k
3779:e
3775:j
3771:i
3755:j
3751:M
3728:o
3723:i
3719:M
3647:2
3597:p
3593:c
3585:p
3581:p
3577:p
3570:p
3566:p
3562:p
3531:p
3527:p
3523:p
3489:p
3485:k
3479:T
3474:r
3471:t
3467:k
3461:=
3456:T
3452:C
3427:p
3423:k
3417:P
3412:r
3409:t
3405:k
3399:=
3394:P
3390:C
3365:p
3361:k
3355:I
3350:r
3347:t
3343:k
3337:=
3332:I
3328:C
3303:p
3299:k
3293:S
3288:r
3285:t
3281:k
3275:=
3270:S
3266:C
3241:p
3237:k
3231:M
3226:r
3223:t
3219:k
3213:=
3208:M
3204:C
3174:]
3171:M
3168:[
3163:]
3160:T
3157:[
3149:T
3145:C
3141:+
3135:]
3132:M
3129:[
3124:]
3121:P
3118:[
3110:P
3106:C
3102:+
3096:]
3093:M
3090:[
3085:]
3082:I
3079:[
3071:I
3067:C
3063:+
3057:]
3054:M
3051:[
3046:]
3043:S
3040:[
3032:S
3028:C
3024:+
3019:M
3015:C
3011:+
3006:p
3002:v
2993:2
2989:]
2985:M
2982:[
2977:2
2970:p
2966:k
2956:c
2953:,
2950:t
2946:k
2942:+
2937:d
2934:,
2931:t
2927:k
2923:2
2917:=
2910:n
2906:x
2902:1
2887:n
2883:T
2879:P
2875:I
2871:S
2844:+
2841:1
2837:2
2832:=
2827:n
2823:x
2787:2
2784:=
2779:n
2775:x
2745:=
2740:n
2736:x
2722:n
2720:P
2692:2
2688:/
2684:1
2680:)
2676:]
2673:I
2670:[
2665:t
2661:k
2655:d
2651:k
2647:f
2644:(
2641:2
2636:]
2633:M
2630:[
2625:p
2621:k
2614:=
2608:]
2605:I
2602:[
2597:d
2593:k
2589:f
2586:2
2581:]
2575:M
2572:[
2569:]
2566:M
2563:[
2558:p
2554:k
2547:=
2540:i
2536:v
2530:p
2526:v
2520:=
2486:]
2483:M
2480:[
2475:2
2471:/
2467:1
2463:]
2459:I
2456:[
2451:2
2447:/
2443:1
2438:)
2431:t
2427:k
2420:d
2416:k
2412:f
2406:(
2398:p
2394:k
2389:=
2384:p
2380:v
2351:2
2347:/
2343:1
2338:)
2331:t
2327:k
2322:f
2319:]
2316:I
2313:[
2308:d
2304:k
2297:(
2292:=
2289:]
2283:M
2280:[
2260:t
2256:p
2252:d
2248:f
2229:2
2225:]
2218:M
2215:[
2210:t
2206:k
2202:2
2199:=
2195:t
2189:d
2185:/
2181:]
2175:M
2172:[
2166:d
2159:=
2154:t
2150:v
2126:]
2120:M
2117:[
2114:]
2111:M
2108:[
2103:p
2099:k
2095:=
2090:p
2086:v
2062:]
2059:I
2056:[
2053:f
2048:d
2044:k
2040:2
2037:=
2033:t
2027:d
2023:/
2019:]
2013:M
2010:[
2004:d
2000:=
1995:i
1991:v
1833::
1824::
1815::
1806::
1787:p
1785:k
1778:k
1761:]
1758:r
1755:e
1752:m
1749:o
1746:n
1743:o
1740:m
1737:[
1732:p
1728:k
1722:]
1719:t
1716:n
1713:e
1710:v
1707:l
1704:o
1701:s
1698:[
1693:r
1690:t
1686:k
1679:+
1674:o
1669:)
1662:n
1658:x
1654:1
1649:(
1644:=
1637:n
1633:x
1629:1
1616:n
1614:x
1608:(
1407::
1387:2
1269:O
1261:R
1257:+
1238:R
1229:O
1221:O
1209:R
1204:+
1197:R
1119:f
1115:f
1097:N
1093:o
1068:N
1064:o
1051:N
1047:o
874:+
859:+
853:+
849:3
835:+
831:2
823:+
814:2
810:O
801:2
797:H
574:(
555:e
548:t
541:v
20:)
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