Core-first

LCB polymers can be formed by chemically linking preformed polymers (arm first or polymer first method) or by growing polymer chains from a multifunctional initiatior (core first method). In both cases living polymerization techniques are preferred because they provide better control over MW, MW distribution and the final branching architecture. However, highly selective coupling reactions e.g. with multifunctional isocyanates, or dicyclohexylcar-bodiimide (DCC) coupling, have also been successful. 

The core first method starts from multifunctional initiators and simultaneously grows all the polymer arms from the central core. The method is not useful in the preparation of model star polymers by anionic polymerization. This is due to the difficulties in preparing pure multifunctional organometallic compounds and because of their limited solubility. Nevertheless, considerable effort has been expended in the preparation of controlled divinyl- and diisopropenylbenzene living cores for anionic initiation. The core first method has recently been used successfully in both cationic and living radical polymerization reactions. Also, multiple initiation sites can be easily created along linear and branched polymers, where site isolation avoids many problems. 

The core first method has been applied to prepare four-arm star PMMA. In this case selective degradation of the core allowed unambiguous proof of the star structure. However, the MWD is a little too large to claim that only four-arm star polymers are present [81], Comb PMMAs with randomly placed branches have been prepared by anionic copolymerization of MMA and monodisperse PMMA macromonomers [82], A thorough dilute solution characterization revealed monodisperse samples with 2 to 13 branches. A certain polydispersity of the number of branches has to be expected. This was not detected because the branch length was very short relative to the length of the backbone [83]. Recently, PMMA stars (with 6 and 12 arms) have been prepared from dendritic... 

The core-first approach is based on the initiation of polymerization by a multifunctional initiator. The number of arms is then defined by the number of functional units present on the core. In order to have a good control of the molecular structure of star-shaped polyesters, the initiation must be quantitative and fast. It is also mandatory to avoid possible side-reactions between the initiating species on the core. 

Although the core-first method is the simplest, success depends on initiator preparation and quantitative initiation under living conditions. This method is of limited use in anionic polymerization because of the generally poor solubility of multifunctional initiators in hydrocarbon solvents [12]. Solubilities of multifunctional initiators are less of an issue in cationic polymerizations, and tri- and tetrafunctional initiators have been used to prepare well-defined three- and four-arm star polymers by this method [7] Except for two reports on the synthesis of hexa-arm polystyrene [27] and hexa-arm polyoxazoHne [26], there is a dearth of information in regard to well-defined multifunctional initiators for the preparation of higher functionality stars. 

In summary, a core-first method was used to prepare allyl-end functionalized octa-arm PIB stars by end quenching the living PIB stars by the use of allyltri-methylsilane. Characterizations by NMR and GPC are consistent with the expected structure and show close to quantitative end-functionalization. 

Star polymers may be synthesized in several ways. The arm-first method joins preformed arms together using a linking agent, and the core-first method utilizes a multifunctional initiator to grow the... 

Sachets. These are usually a laminate with aluminum as the center core. First the carrying pouch is formed, then dosed with product, then sealed so that contamination is reduced to a minimum. 

Boonyatumanond, R., Wattayakorn, G., Aamano, A., Inouchi, Y., Takada, H., 2007. Reconstruction of pollution history of organic contaminants in the upper Gulf of Thailand by using sediment cores First Report from Tropical Asia Core (TACO) Project. Mar. Pollut. Bull., in press. 

Depending on the target structure and on the availability of initiators and linkers, three main methods can be applied for the synthesis core-first techniques, core-last techniques, and mixed techniques. 

Six arm star polystyrenes were prepared by the core-first method using initiator 13 with six phenylethylchloride-type functions emanating from a central hexa-substituted benzene ring [24]. 

Synthesis of star-shaped copolymers by the core-first method. 868... 

Two general strategies are possible for the synthesis of star-shaped copolymers The arm-first method is based on the reaction of living chains with plurifunctional electrophiles carrying at least three reacting groups alternatively, polymerization can be initiated by a multifunctional initiator according to the core-first method. 

The core-first method, which uses an active multifimctional core to initiate growth of polymer chains, was apphcable to make hybrid POSS-core star-shaped polyoxazohnes that showed an increase in Tg, compared to that of polyoxazohne initiated by methyl p-toluenesulfonate (MeOTs) with poly(2-methyl-2-oxazohne) (POZO) [76]. Other hybrid star-shaped polyoxazohnes initiated by cube-OTs or cube-benzyl revealed the same phenomenon. This was attributed to the reduction of segmental mobifity of POZO in starshaped polyoxazolines, which was caused by the incorporation of hard, compact POSS moiety to the core of star polymer with the core-first technique. The conclusions were drawn that the thermal stabilities of star-shaped polymers increased as the POSS wt % was increased, and this was used as a measure of the effect of the inorganic POSS unit on polymer thermal properties. 

From a coordination viewpoint, there are two views that support the idea of an inner-sphere coordinated cyano bridge on the Cr(VI) core. First, four-coordinated Cr(VI) or Cr(V) changes to six-coordinate Cr(IV) so that there is room for coordination sphere expansion. Second, it has been shown (118) that, in spite of the high negative charge on octa-and hexacyano complexes, they can be used as nucleophiles in substitution of an axial water ligand of mesotetra(4-A/ -methylpyridyl)por-phinediaquocobalt(III) ions and that the stability constants of these products are comparable to those of NCS . 

There are two basic synthetic routes for star polymers (Scheme 12)-the core first method (polymerization from multifunctional initiators or microgels) and the arm first method (where growing polymer chain ends are reacted with a multifunctional terminating agent or a divinyl compound). Whereas the use of multifunctional initiators leads to stars with a well-known (but often low) number of arms, the use of microgels or divinyl compounds leads to a rather broad arm number distribution, where the average arm number can be quite high. 

Scheme 12 Synthesis of star-shaped polyelectrolytes by the a arm first and b core first methods...

The formation of PAA star polymers using the core first method has been demonstrated in the ATRP process by use of multifunctional initiators [111, 112]. In this method, the number of arms in the star polymer can be determined by the number of initiating sites on the initiator. Star-shaped PtBuA was prepared by the arm first method via ATRP, using divinylbenzene, 1,4-butanediol diacrylate, and EGDMA as coupling reagents [113]. 

Plants and plant products have long provided many modem drags and continue to provide the major source of medicines globally. The use of herbs has been long recognized as being the core first line treatment in the piimaiy health care of 70-80% of the worlds population (13-15) and while the total percentages... 

The fact that the correlation equation contains a constant can be explained by considering the action of the two testing machines. The constant strain machine records only the maximum force exerted on the specimen. For flexure tests, this is usually the point where the core first cracks. Additional resistance to breaking occurs as the paper tears and in the case of a board containing glass fiber, as the fibers pull out of the core. The force required for this second break may even exceed that for the initial core crack. 

Generally, there are two strategies to prepare star polymers the core-first strategy [37-44], and the arm-first strategy [45-52], The arm-first strategy starts with the linear arms first. Since the arms are prepared separately, many living/controlled polymerization techniques can be employed. Thus, the linear arms can be synthesized in a defined manner. Then one of the chain ends will be functionalized for further crosslinking reactions. Based on the functionalities of the chain ends, the arm-first methods can be divided into macroinitiator (MI) method and macromonomer (MM) method. 

Scheme 3 Core-first strategy for the synthesis of star polymers...

Based on the findings of the arm-first strategy, it is possible to obtain stars with well-defined arm length. The main problem of this strategy is the arm number distribution. Moreover, purification may cause many difficulties in the synthesis. In contrast, the core-first strategy requires multifunctional initiators and further polymerization initiated from the core. This is shown in Scheme 3. The maximum arm numbers of the stars are determined by the number of functionalities in the core. In the ideal case, the initiating efficiency of the core is close to unity, which will produce well-defined stars with precise numbers of arms. However, due to the steric hindrance and the limit of the polymerization techniques, it can be difficult to obtain full initiating efficiency. 

The first step for the core-first stars is the synthesis of multifunctional initiators. Since it is difficult to prepare initiators that tolerate the conditions of ionic polymerization, mostly the initiators are designed for controlled radical polymerization. Calixarenes [39, 58-61], sugars (glucose, saccharose, or cyclodextrins) [62-68], and silsesquioxane NPs [28, 69] have been employed as cores for various star polymers. For the growth of the arms, mostly controlled radical polymerizations were used. There are only very rare cases of stars made from nitroxide-mediated radical polymerization (NMRP) [70] or reversible addition-fragmentation chain transfer (RAFT) techniques [71,72], In the RAFT technique one has to differentiate between approaches where the chain transfer agent is attached by its R- or Z-function. ATRP is the most frequently used technique to build various star polymers [27, 28],... 

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