J Inorg Organomet Polym (2016) 26:921–931 DOI 10.1007/s10904-016-0413-8
REVIEW PAPER
Arenetricarbonylchromium Complexes in Polymerization Transformations by Radical Initiation of Vinyl Polymerization Lyudmila Semenycheva1 • Alexander Artemov1 • Natalia Valetova1 Julia Matkivskaja1 • Alexei Moykin1
•
Received: 21 April 2016 / Accepted: 5 July 2016 / Published online: 30 July 2016 Springer Science+Business Media New York 2016
Abstract The article is devoted to the systematization of investigations of arenetricarbonylchromium complexes in radical polymerization transformation at the initiation of vinyl polymerization. The presented data are shown that these compounds are promising and interesting model systems for the study of the phenomenon of the metal atom action on the reactivity of the monomer p-bond. The correlation between the structure of metal-containing monomers and polymerization parameters, as well as the molecular mass properties of the resulting polymers, are discussed. Keywords Arenetricarbonylchromium complexes (Co)polymerization Radical initiation Stable radical A weak inhibition Reversible inhibition
1 Introduction Arenetricarbonylchromium complexes (ACC) attracts the attention of researchers, primarily as substrates for subtle organic synthesis Tricarbonylchromium fragment can significantly changes the reactivity of the organic ligand owing to its electronic and steric properties, leading to the shielding of the one side of the molecule. This effect allows to conduct selective and original syntheses. The influence of tricarbonylchromium fragment on the organic ligand interaction with electrophilic or nucleophilic species, as
& Lyudmila Semenycheva
[email protected] 1
N.I. Lobachevsky State University of Nizhni Novgorod – National Research University, 603950, Gagarin Avenue, 23, Nizhny Novgorod, Russia
well as on the ligand cycloaddition, was considered in quoted literature [1–18]. This fragment is able, depending on the situation, either compensate deficiency of the electron density as donor, or accept the excess of this one as acceptor. These features of organometallics provide the stabilization of the intermediate and as a result reduce the activation energy of the processes with their participation. Therefore the reactions of organic ligand, in presence of arenetricarbonylchromium complexes, are going on considerable easier than in the case of uncoordinated ligands. The data of experiments and theoretical calculations are summarized in the quoted literature, which are published since the 60 s of the last century [1–18]. The radical polymerization involving ACC, having double bond in the organic ligand, attracted the attention of scientists later. The information about the reactivity of ACC in radical vinyl polymerization, obtained for a number of similar compounds, is shown in Fig. 1. Reactivity in radical polymerization of ACC with a double bond in organic ligand determinates by the electronic and steric properties of its molecular structure. It is known [19] that the upper limit temperature of the polymerization of the vinyl monomers, such as styrene, alkyl (meth) acrylates, etc. is a more significant for the mechanism of reaction as a temperature of polymer synthesis. It was found that the thermodynamic parameters, namely, heat capacity in the 5–450 K temperature interval, enthalpy of phase transitions, etc. for ACC with the double bond in the organic ligand differ from the properties of their uncoordinated analogues, in general [20]. In this order the main aim of this review is to analyze experimental data for radical polymerization of vinyl monomers occurs in presence of ACC with the double bond in the organic ligand, which are going on at the different condition of the (co) polymerization.
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Fig. 1 Arenetricarbonylchromium complexes: a styrenetricarbonylchromium (SCC), where R1 = R2 = R3 = H, p-metylstyrenetricarbonylchromium (PCC), where R1 = Me, R2 = R3 = H, a-methylstyrenetricarbonylchromium (MCC), where R1 = R3 = H,R2 = Me, stilbenetricarbonylchromium (STC), whereR1 = R2 = H, R3 = Ph, ethylcinnamaterticarbonylchromium (ECC), where R1 = R2 = H, R3 = C (O) OEt. b allylbenzenetricarbonylchromium biphenylbutadienetricar(ACC), where R = CH2–CH=CH2, bonylchromium (BCC), where R = CH=CH–CH=CH-Ph
2 Features of Radical (co) Polymerization of Vinyl Monomers in the Presence of ACC at a Radical Initiation It is well known [19], that styrene is an active monomer. Radical, formed by reacting of styrene with an initiating radical stabled due to conjugation of phenyl group and the unpaired electron and has a low reactivity. A simple comparison of the structure of molecules of styrene and metal-containing monomers, (MCM) considered (see. Fig. 1) indicates that the attack of the double bond of ligands of ACC by initiating radical formed will still considerably better stability than in the case of styrene. This is due to steric constraints posed by the volume of tricarbonylchromium group, as well as electronic effects of delocalization of the electron density of ACC benzene ring, coordinated with tricarbonylchromium fragment. In addition, as shown by the results of, the upper limit value of the polymerization temperature for styreneticarbonylchromium (SCC), as a representative of metal-containings monomer (MCM) of this class, is in the area of 360 K (*90 C) [21]. We can assume that for its structural analogues (Fig. 1) this temperature will be close to the same value. It means that necessary temperature for gomopolimerization should be below than mentioned temperature. The absence of polymer formation in the case of SCC at about 100 C, revealed in [22–24], is caused, most likely, by the low ceiling temperature of SCC polymerization. Polystyrenetricarbonylchromium, Poly-p-metylstyrenetricarbonylchromium [25, 26], were synthesized at 50 C in following solvents: ethyl acetate, benzene, toluene, dibutyl ether, which are capable to form the complexes with ACC (apparently choice of solvent is also one of the factors ensuring homopolymer formation). The characteristics of these polymers are given in Table 1.
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The data listed in the Table 1 indicate that the ability of solvent to form complexes with a radical plays a significant role for the yield of the polymer. The homopolymer was not observed at the initiation of polymerization in hexane, because it does not form complexes (Table 1, line 5). Polystyrenetricarbonylchromium and poly-p-metylstyreneticarbonylchromium are amorphous powders. The structure of polystyrenetricarbonylchromium was confirmed by physical and chemical methods. The stretching vibration of the CH bond, assigns to the sp3-hybrid carbon atom, locates in the IR spectra of polymer at 3026 cm-1, the stretching vibrations of the C = C bond of aromatic ring at 1452 cm-1 and the non-planar bending vibration of the CH bond in the aromatic ring at 700 cm-1 was observed. Two very strong bands at 1961 and 1877 cm-1 belong to the CO bond stretching mode in tricarbonylchromium group. In the 1H NMR spectrum (solvent—acetone-d6) the polymer SCC singlets assigned to methylene protons and methine groups, respectively, at 2.04 and 2.97 ppm and multiplet of the benzene protons at 5.60 ppm were observed. The protons signals of the vinyl group, which for the monomer SCC as a multiplet at 6.30 ppm are found to be, was not detected in the spectrum of the synthesized polymer SCC. It should also be noted that gomopolymerization in cases of MCC, 1,4-bis (1-methylvinyl) benzolticarbonylchromium [27, 28], STC [29, 30], ECC [31], MCC [26, 30], ACC [32], BCC [33] at 500C, it does not take place, which is obviously due to the low limited polymerization temperature for them in comparison to SCC. According to modern concepts, the injection in situ of stable radicals effects noticeable on the kinetic parameters of the processes, on the molecular-mass characteristics of polymers, and even on the reaction mechanism. The character of action depends on a number of reasons: nature of the organic monomer, MCM nature, temperature and other. Experimental data obtained by polymerization of alkyl(meth)acrylates and styrene have shown that ACC change the course of radical polymerization of indicated vinyl monomer, which is determined by the nature of MCM. We have described three mechanisms of polymerization differ on the kinetic characteristics, composition and properties of the polymers: • Copolymerization with considerably lower speed in comparison with the homopolymerization of vinyl monomers. The features of such reaction determinate by the properties of the initiating radical and the secondary radical, generated from MCM, while their stability is provided by the steric effect of voluminous tricarbonylchromium group, as well as by the conjugation of the electron with the electron density of benzene ring.
J Inorg Organomet Polym (2016) 26:921–931 Table 1 Information about the conditions of preparation and properties of polymers
No
Solvent
923
Polymer (yield after 6 h) (%)
Colour
Chromium content (wt%) in sample
in theory
21.3
21.7
Polystyrenetricarbonylchromium 1
Ethylacetate
32
2
Benzene
55
Light yellow
21.4
3
Toluenea
60
21.3
4
Dibutyl ether
8
21.4
5
Hexane
Trace
21.3
Poly-p-metilstyreneticarbonylchromium
a
6
Ethylacetate
18
7
Benzene
21
Light yellow
20.5
20.5
Polymerization in the presence of boron triisobutyl (BTI), as a complexing agent [25], [BTI] = 0.1 mol/l
• The weak inhibition of polymerisation of vinyl monomers is observed when injected into the polymer STC and ECC. Secondary radical formed in this case in comparison with those of SCC is more complicated steric due to organic radical connected with a double bond. • Pseudo-living -polymerization of vinyl monomers by the mechanism of reversible inhibition occurs in the case of MCC, whose interaction with the initiating or increasing radical leads to a tertiary radical, as well as ACC and BCC are the sources of allyl metal-containing radicals. 2.1 Copolymerization Vinyl Monomers with Tricarbonylchromium Complexes of Arenes with Double Bond in the Organic Ligand First of all we would like to attract attention to the fact that when choosing a radical initiator for MCM was preferred AIBN, although other initiators have been used in several studies. Kinetic studies [34–36] of polymerization process indicate that the speed of polymerization of the monomers in the presence of tricarbonylchromium complexes, usually significantly less than individual organic monomers. This consistent pattern was found in the copolymers of styrene with SCC [34], methyl methacrylate, butyl acrylate, and butyl acrylate with PCC [35, 36]. MCM incorporated into the polymer chain (the chromium content in the polymer was found by the spectrophotometric methods [37]). The study of copolymers films with the different chromium content, has shown that their spectra have the SCC characteristic bands (similar to these ones in the homopolymer, discussed earlier [36, 38]). Observed effect is found to be at polymerization by a certain speed reduction in the copolymerization of two monomers and forming of the radicals with very different activity [19]. The values of relative activity, calculated depending on the copolymer
composition at 5.7 % conversion of the monomer mixture, shown in Table 2. The step of macromolecules formation was examined in detail by UV spectroscopy for the SCC and methyl methacrylate (MMA) [26, 38, 42]. It was found that the electronic spectrum of the SCC in hexane and MMA (Fig. 1, the range of 1 to MMA) has an absorption band at 365 nm, corresponding to a transition ligand–metal (interpretation of the spectrum bands was carried out in accordance with the data [43]). The intensity of this band increases significantly with the decrease of temperature to -45 C. At the heating of the solution up to room temperature the spectrum of the MMA, presented above, is reproduced. Addition of MMA to hexane solution of SCC reduces the intensity of the band at 365 nm. Moreover, its intensity decreases symbatically with increasing of MMA concentrations (Fig. 2a). Calculated complexation constant by the method [43] for the interaction between SCC and MMA is 0.060 [26, 38, 42]. The effect of reducing of the band intensity similar to process with MMA occurs as well, if instead of MMA the other solvents, such as ethyl acetate i.e. acrylate hydrogenated analogue (Fig. 2b), is used. However, in this case the decrease of the intensity of the absorption band at 365 nm is smaller than in the presence of MMA. Constant of formed complex between SCC and ethyl acetate is equal 0.033. The EPR method in variant of spin trapping techniques allowed to reveal the interaction between SCC and radical initiator, accompanied with the growth of the corresponding radicals. At the addition of MMA at of copolymerization of SCC with acrylic monomers in the EPR spectrum the triplet having splitting constant (aN = 1.53 mT), assigns to the spin-adduct of metylmethacrylate radical, the triplet of triplets (aN = 1.51 mT; aN = 1.01 mT) of adduct, formed as a result of hydrogen atom transfer from the growing macroradical of MMA, or from a radical initiator were observed. Therefore we can conclude that thereby realized
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924 Table 2 Constants copolymerization of styrene, SCC and PCC with vinyl monomers (M2)
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No
M2
Styrenea
SCC
PCC
AIBN
1
Styrene
2
MMA
DPA
r1
r2
r1
r2
1
1
*0
1.39b
–
*0
0.71
d
–
*0
c
–
–
0.52
0.46
r1
3
Methylacrylate
0.75
0.18
*0
0.75
4
Butylacrylate
0.76
0.19
*0
0.75d
*0
d
5 a
Vinylchloride
AIBN
d
35
d
0.08
1.00
*0 –
r2
r1
DPA r2
r1
r2
–
–
d
1.44
*0
1.10d
–
–
–
–
–
[19]
b
[39, 40]
c
[39, 41]
d
[36, 42]
Fig. 2 UV-spectrum SCC (a) in the MMA-hexane, (b) in ethyl acetate-hexane
chain transfer to monomer. In the EPR spectrum of polystyrenetricarbonylchromium spin-adduct radical, which was observed in the absence of the MMA, at addition of MMA was not detected. These data together with the ones about the formation of donor–acceptor complexes confirm the radical mechanism of processes along with complex formation in quite real copolymerization for reaction of SCC with methyl methacrylate. It is well known [44–46] that in this case the complex of copolymerizable monomers is bunded to the growing radical, having a small complexation constant (K = 0.01–1), whereas SCC complexation constant with MMA is about 0.06. Chain growth should going on in this case as a result of binding of growing radical to the monomer complex, like in Scheme 1. The end of the polymer chain in this case is always the polymethylmethacrylate radical (see [38] as well): Methods of synthesis of a monomer mixture and a compensation method—dosing of butylacrylate (BA) to a solution of SCC were used to obtain a metal-containing
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copolymer at the base of SCC and BA [47]. The results showed that BA polymerization with SCC lead to yield of copolymers *30–50 % in both cases. Infrared spectroscopy method is used for the qualitative study of the structure and identification of the obtained metal-containing copolymers. The data show that BA polymerization with SCC leads to the yield of copolymers about 30–50 % in both cases. Infrared spectroscopy was used for the study of the structure and identification of the formed metalcontaining copolymers. The characteristic IR bands, corresponding to stretching of SCC fragment, was described above, and the bands located at 1724, 1163 cm-1 indicate on the presence of C=O and C–O groups of polybutylacrylate. The amount of ACC in copolymer samples was calculated according to the spectrophotometry method. It was found that in the copolymer comprises SCC about 20 % and a monomer mixture about 50 %. The results were confirmed by atomic emission spectrometry as well. The data for molecular mass distribution (MMD) of copolymers using GPC with dual detection by
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925
Scheme 1 Chain growth for monomer complex of SCC and MMA
Fig. 3 GPC curves SCC-BA copolymer, registered on refractometric (1) and ultraviolet (2) detectors
refractometric and UV detector were obtained. Curve lines for compensation and the polymerization of a monomer mixture are identical. The values of polidispersity coefficient (Mw/Mn) are low 2.1–2.2. In the Fig. 3a chromatogram of copolymer synthesized by compensation method is shown. Clearly that SCC links in copolymer, caught by a UV detector (Fig. 3, curve 2), are evenly generated in the copolymer BA-SCC (curve line 1) during the polymerization time. This result can be interpreted by the peculiarities of the polymer chain in the copolymerization of the SCC with alkyl (meth) acrylates, and with their complex formation, detected for example in the MMA-SCC mixture. Molecular mass characteristics of the polymers with vinyl monomers ACC [28, 30, 34–36, 40] was studied by GPC method. As in the case studied of copolymerization of two organic monomers, one of which has a specific activity close to zero (for example, vinyl esters—alkyl(meth)acrylates [48, 49]) to copolymers. Their molecular masses are less than in the case of organic homopolymers formed under the same conditions. The difference between molecular masses of copolymers and organic homopolymer increases with concentrations increasing of MCM. This fact is in full agreement with the theory of radical copolymerization [19, 50]. If for initiation of the polymerization of styrene with SCC AIBN or peroxide initiator (benzoyl peroxide) is used
[33, 40] the kinetic parameters and the relative activity of components in this reaction are comparable. In [42, 51] the radicals were initiated using organoelement peroxide (di-tret-butylperoksitrifenilantimony (DPA), which interaction with SCC leads to formation of butoxy radical [52]. In the EPR spectrum (Fig. 4) DPA-SCC system (spin-trap—2-methyl-2-nitrozopropan) observed spinadducts tret.butoxy radicals [t-BuO-N (O)-Bu-t] triplet with constant aN = 2.73 mT—homolytic decay products of organoelement peroxide by reacting the latter with SCC and triplet of doublets (aN = 1.50 mT and aN = 0.16 mT), belonging to the spin-adduct, product of fixation trap terminal radical SCC growth, were observed. It is interesting, that constant of splitting at hydrogen atom is in this spin adduct less than in the spin-adduct radical of polystyrene (aN = 1.50 mTlaN = 0.22 mTl). This fact is probably connected with the conjugation of spin density with the vacant d-orbitals of the metal atom of ACC fragment. Formation of adduct at-BuON (O) Bu-t indicates on the generation of butoxylene radicals by the interaction of organoelement peroxide with ACC. Similar spin-adducts—alkoxyradicals appear in the case of coparticipation with DPA and toluenetricarbonylchromium. Radical copolymerization of SCC with vinyl monomers in the presence of DPS in mild temperature interval (25–35 C) and at a sufficiently low concentration of initiator (0.1 mol%) was observed. The values of relative activities of vinyl monomers in this case are similar to those in the presence of AIBN. This was shown by the study of monomer pairs SCC –BA and PCC- MMA (Table 1). In Table 3 are listed the values of the initial rate of polymerization of styrene and MMA together with SCC– DPA added in catalytic amounts. These data indicate that the polymerization rates of the monomers are comparable with those at initiating of AIBN. At the same time, the values of molecular mass (MM) of polymers are significantly less in the case of element-containing initiator. It is demonstrated for chain transfer reactions at participation of SCC and DPA as well (Table 1) [19]. The copolymer of styrene and SCC also obtained on the catalyst system NiBr2 (PPh3) 2/Zn/PhBr [53, 54]. It was
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Fig. 4 EPR spectra (the spin-trap—2-methyl-2-nitropropane) [SCC] = [peroxide] = 0.08 mol/l): a SCC -DPA (solvent—hexane, benzene). b The system SCC-DPA in the presence of MMA (solvent—benzene) Table 3 The data about the rate of polymerization of vinyl monomers on various initiators and molecular mass of the polymers [42]
Monomer
Initiatora (mol %)
T (C)
Starting speed [V 9 105 (mol/l s)]
Methyl methacrylate
AIBN, 0.10
40
5.0
MWb – 1 100 000
SCC-DPA, 0.10c
30
9.1
163 000 105 000
Styrene
AIBN, 0.10
40
1.5
493 000
SCC-DPA, 0.05c 0.10
30 30
– 0.9
87 000 56 000 –
a
The ratio of TCC (SCC): DPA = 1: 1
b
Values of molecular mass are given to 15–20 % conversion of the polymer
c
Conversion of the polymer is 32 %
established that the overall yield in the presence of investigated copolymers does not depend on the ratio of monomers in the reaction mixture. If the concentration of organochromium compounds in the initial monomer mixture changes from 0.05 up to 50 mol %, of the copolymer yield remained *40 %. The values of number average molecular mass of chromium oligomers constitute 3600–5500. Thus, the chromium-containing polymers can be prepared with uniform metal distribution in the polymer matrix when introduced into a monomer mixture of vinyl monomers and SCC or PCC. Slowing the process compared with the process of the homopolymerization of vinyl monomers, the suppression of gel formation and the effect of the copolymer with low values of MM are character features in this case.
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2.2 Polymerization of Vinyl Monomers in the Presence of Tricarbonylchromium Complexes of Stilbene and Ethylcinnamate Chromium containing MCM organometallics, such as STC and ECC, generate in the presence of AIBN steric more complicated secondary radical than SCC and PCC (Schemes 2, 3). This mechanism can realize due to the presence, along with a second arenetricarbonylchromium fragment, second bulky substituent at the double bond: in the case of STC the phenyl and in the case of ECC the ester. Inhibition of polymerization was not observed, however, similar radical coordination to the double bond leads to the breakage chain owing the recombination reactions,
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Scheme 2 Chain growth for STC
Scheme 3 Chain growth for ECC
Fig. 5 a Differential kinetic curves of polymerization of MMA to a deep conversion at 70 C in the presence of 0.1 mol. % AIBN and STC. STC (mol. %): 1 0; 2 1; 3 4; 4 5. b, c MWD curves of PMMA
samples obtained in the presence of AIBN (0.1 mol. %) and STC (b) or ECC (c). Concentration of MCM (mol. %): b 1 0; 2 5; 3 15; 4 25; c 1 0; 2 10; 3 30; 4 50
Table 4 Molecular mass characteristics of the PMMA samples obtained in the presence of STC supplements No
The content of STC in the monomer mixture (mol %)
Conversion (%)
Mn 9 10-3
Mw 9 10-3
Mw/Mn
1
0
8.9
206
384
1.9
2
5
8.6
133
232
1.7
3
15
7.8
104
195
1.9
4
20
7.9
75
150
2.0
Initiator—AIBN (0.1 mol%). T = 55 C
disproportionation or transfer of hydrogen atom. There are fragments in the polymer, which do not contain SCC PCC, which are typical for the polymerization processes involving weak inhibitors [19] and for suppression gel effect, reducing polymer MW in comparison to these ones, forming in reaction without the addition of organometallics [29–31]. For example, a much smaller effect was revealed in gel polymerization of MMA with additives STC (5 mol%) than without of this one (Fig. 5a). STC does not
construct into the polymer chain in cases, if it is injected into the polymer in an concentration from 5 to 40 mol%. Traces of chromium in the polymer were detected regardless of the amount of added STC. Molecular mass characteristics of the polymer, calculated according to GPC analysis (Table 4; Fig. 5b), confirm the weak inhibition mechanism: MW of polymethylmethacrylate (PMMA), synthesized in the presence of different concentration of STC, decreases uniformly with increasing of STC amount.
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Fig. 6 a, b. Differential kinetic curves of polymerization of MMA to a deep conversion at 70 C (a), BA at 50 C (b) in the presence of 0.1 mol. % AIBN and MCC. MCC (mol %): a 1. 0; 2. 0.1; 3. 03; 4. 0.5; 5. 0.7; b 1. 0; 2. 0.1 3. 0.2;4. 0.3; 5. 0.4
Fig. 7 Curves of MWD samples of poly PMMA (a) and the polystyrene obtained at 70 C in the presence of the AIBN and MCC (a) and ACC (b) for different stages of the conversion Table 5 Molecular mass characteristics of PMMA and polystyrene synthesized in the presence of ACC and BCC at 70 C (AIBN initiator 0.1 and 0.8 mol%, respectively, in the case of MMA and styrene) No
Polymer
Additive (mol%)
1
PMMA
ACC, 1.0
Conversion of the polymer (mass%)
Mn 9 10-3
Mw 9 10-3
Mw/Mn
10
123
227
1.8
2
22
199
417
2.1
3
42
319
715
2.2
4
85
360
856
2.4
5
6
26
39
1.5
6
Polystyrene
ACC, 5.0
31
35
51
1.5
7
39
37
54
1.5
9
80
44
86
1.9
10
81
47
95
2.0
85
58
128
2.2
23
80
141
1.8
13
28
92
164
1.8
14
69
173
357
2.1
15
84
184
480
2.6
42 48
20 21
36 39
1.9 1.9
62
23
45
2.0
11 12
16 17
PMMA
Polystyrene
18
123
BCC, 1.5
BCC, 0.3
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Fig. 8 The dependence of the average/a,b (2, c (3)/, and middleviscosity/b (1), c (1, 2) MM PMMA (a, b) and polystyrene (b) in the presence of BCC (a, b), ACC (c) conversion at 70 C. the Initiator—
929
AIBN. Curve 3 is for polymetylmethacrylate in the presence of the AIBN without additives
•
• Scheme 4 Chain growth for MCC
• MWD curves for these polymers show (Fig. 5b) that the growth of the fashion content of STC is uniformly shifted to lower molecular mass, as is observed usually in the case of a weak inhibition [19]. 2.3 Polymerization of Vinyl Monomers in the Presence Tricarbonylchromium Complexes A-Methylstyrene, Allylbenzene, Diphenylbutadiene •
Polymerization of organic vinyl monomers are in the presence of MCC, BCC and ACC in the monomer mixture is going on with formation of polymers containing chromium tracks [30, 32, 33, 55]. It indicates on the absence of the copolymerization between mentioned metal-containing monomers and vinyl monomers. The rate of polymerization of MMA, BA, styrene in the presence of mentioned metal-containing
monomers and molecular mass characteristics of the polymer chain correlate with the state control mechanism for reversible inhibition, namely: There is a gel-suppression effect in cases of all examined monomers. (Fig. 6, for example, MMA and BA). MMD curves of samples of the polymers (Fig. 7, for example, MMA and styrene.) shifts in high molecular mass region with increasing monomer conversion. MW polymers have high values linearly increase (Table 5) analogically to conversion (Fig. 8).
The long-lived tertiary radical, which is formed by the interaction of initiating or growing radical with MCC, is able to bind reversibly with the double bond (Scheme 4): The formed radical is stable due to the conjugation between unpaired electron and the electron density of aromatic ring bounded with the tricarbonylchromium fragment as well as owing steric effects of metal-containing fragment. MCC reacts with growing macro radical of organic monomer at 70 C, forms with it a labile bond and may further decomposes the generation of the similar macro radical growth. As a result, there is an alternation of periods of ‘‘sleep’’ and ‘‘life’’ structures in the polymer chains, accompanied with growth of the polymer chain (Scheme 4). As was noted, in contrast to the SCC and PCC reaction, we could not obtain a homopolymer in the case of MCC [23], what can be considered as an additional proof of the stability of its radical.
Scheme 5 Chain growth for AHC
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Scheme 6 Chain growth for BHC
Discussed features of a controlled polymerization with the MCC were observed at the addition of BCC and ACC as well. Thus, the polymerization of styrene and MMA at 70 C passes without mentioned results in the presence of AHC and BHC at different concentration of components [32, 33]. The study of the initiation stage by the EPR method has shown that the interaction of AHC and BHC with radicals leads to formation of allyl radicals (Schemes 5, 6, respectively): Thus, the results of research arenetricarbonylchromium complexes as the additives in the radical polymerization of vinyl monomers allowed to establish a certain regularity in their effect on the parameters of polymerization and molecular mass properties of the resulting polymers. Secondary radicals of complexes SCC and PCC involved in the chain growth have a relative activity close to zero. Secondary radicals of ETS and ETSK control the kinetic of polymerization by weak inhibition mechanism. The formation of MCC tertiary radical and allyl radical of BHC and AHC, involved in the formation of macromolecules, has mechanism similar to reversible inhibition. Acknowledgments The work was supported by the Ministry of Education and Science of Russian Federation (task §2014/134, the agreement of 27 August 2013 year § 02.D.49.21.0003) using equipment of the center ‘‘New materials and resource-saving technologies’’ (project RFMEFI59414X0005).
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Lyudmila Semenycheva is a Doctorate in Chemical Sciences. Her research interests lay focus on radical reaction in the monomer medium, and metal-containing monomers (co)polymers with novel properties. Alexander Artemov is a Doctorate in Chemical Sciences. His research interests lay focus on the synthesis of arenetricarbonylchromium complexes, and study of their properties and applications. Natalia Valetova has done PhD in Chemistry. Her research interests lay focus on metal-containing monomers and synthesis of novel (co)polymers. Julia Matkivskaja is a postgraduate student. Her research interests lay focus on a radical (co)polymerization of vinyl monomers, polymeric viscosity modifiers, lubricants. Alexei Moykin has done PhD in Chemistry. His research interests lay focus on radical (co)polymerization of vinyl monomers, polymeric lubricating oil additives.
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