Influence of DMF on the polymerization of tert‐butyl acrylate initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator

BACKGROUND: In a number of studies it has been shown that 2,2,6,6‐tetramethylpiperidinooxy (TEMPO)‐mediated polymerization of acrylates is not facile. Therefore, the object of the study reported here was to prepare poly[styrene‐block‐(tert‐butyl acrylate)] (PS‐b‐PtBA) block copolymers using 4‐oxo‐TEMPO‐capped polystyrene macroinitiator as an initiator, in the presence of small amounts of N,N‐dimethylformamide (DMF). The kinetic analysis and the effect of DMF on the reaction mechanism are also discussed. RESULTS: PS‐b‐PtBA block copolymer was prepared through polymerization of tert‐butyl acrylate (tBA) initiated by 4‐oxo‐TEMPO‐capped polystyrene macroinitiator at 135 °C. The polymerization rate of tBA could be increased by adding a small amount of DMF, and the number average molecular weight of the PtBA block in PS‐b‐PtBA reached 10 000 g mol^?1 with narrow polydispersity. The activation rate constant k_act?tBA of alkoxyamine increased and the recombination rate constant k_rec?tBA decreased with increasing DMF concentration. CONCLUSION: DMF was shown to be a rate‐enhancing additive for the polymerization of tBA using a 4‐oxo‐TEMPO‐capped polystyrene macroinitiator. From the kinetic analysis, it was concluded that the improvement of polymerization with the addition of DMF was due to an increase in k_act?tBA and a decrease in k_rec?tBA. Copyright © 2008 Society of Chemical Industry     

Nitroxide‐mediated ‘living’ free radical synthesis of novel rod–coil diblock copolymers with polystyrene and mesogen‐jacketed liquid‐crystal polymer segments

The synthesis of rod–coil diblock copolymers with narrow polydispersity was achieved for the first time by TEMPO‐mediated ‘living’ free radical polymerization of styrene and 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene. The block architecture of the two diblock copolymers thus prepared, MPCS‐block‐St (5400/2400) and MPCS‐block‐St (10 800/8700), was confirmed by GPC, ¹H and ¹³C NMR and DSC studies. The liquid‐crystalline behaviour of the copolymers was studied by DSC and polarized optical microscope. It was observed that both copolymers showed two distinct glass transitions, corresponding to polystyrene and poly(‐2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene). Above the glass transition temperature of rigid block, liquid‐crystalline phase was formed. The clearing point of the phase is higher than the polymer decomposition temperature. © 2000 Society of Chemical Industry     

Preparation and kinetic analysis of PS‐b‐PBA block copolymer by 4‐oxo‐TEMPO capped polystyrene macroinitiators

Polystyrene‐block‐poly(n‐butyl acrylate) block copolymers were prepared from 4‐oxo‐2,2,6,6‐tetramethylpiperidinooxy (4‐oxo‐TEMPO) capped polystyrene macroinitiators at a high temperature, 165°C. It was found that the number‐average molecular weight of PBA chains in block copolymers could reach above 10,000 rapidly at early stage of polymerization with a narrow polydispersity index of 1.2–1.4, but after that, the polymerization seemed to be retarded. Furthermore, according to the kinetic analysis, the concentration of 4‐oxo‐TEMPO was increased mainly by the hydrogen transfer reaction of hydroxylamine (4‐oxo‐TEMPOH) to growing radicals during polymerization. This increase in 4‐oxo‐TEMPO concentration could retard the growth of polymer chains. The rate constant of the hydrogen transfer reaction of 4‐oxo‐TEMPOH to growing radicals, k_H, estimated by the kinetic model is about 9.33 × 10⁴M^‐1s^?1 at 165°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nitroxide‐terminated poly(styrene‐co‐diethyl fumarates) and derived block copolymers

Copolymerization of styrene (S) and diethyl fumarate (DEF) at 125°C in the presence of 2,2,6,6‐ tetramethylpiperidin‐1‐yloxyl radical (TEMPO) and initiated with a thermal initiator, 2,2′‐azobisisobutyronitrile (AIBN), was studied. The molar fraction of DEF in the feed, F_DEF, varied within 0.1–0.9. An azeotropic composition, (F_DEF)_A = 0.38, was found for the copolymerization under study. At F_DEF = 0.1–0.4, a quasi‐living process was observed, transforming to a retarded conventional radical copolymerization at a higher content of DEF in the initial mixtures. The obtained TEMPO‐terminated S‐DEF copolymers were used to initiate polymerization of styrene. Poly(styrene‐ co‐diethyl fumarate)‐block‐polystyrene copolymers were prepared with molecular weight distributions depending on the amount of inactive polymer chains in macroinitiators, as indicated by size‐exclusion chromatography. A limited miscibility of the blocks in the synthesized block copolymers was revealed by using differential scanning calorimetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2432–2439, 2002     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Copolymerization and addition of styrene and N‐phenylmaleimide in the presence of nitroxide

The copolymerization and addition reaction of styrene (S) with N‐phenylmaleimide (PMI), either neat or in xylene, have been found to proceed at 125°C in the presence of 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO) radicals. TEMPO‐terminated alternating S‐PMI copolymers and comonomer adducts were obtained. The amounts of the low molecular weight compounds increased with the increasing content of PMI in the initial mixture. The reaction suggests formation of monofunctional unimolecular initiators. In the autopolymerization of neat comonomers, a mediating role of TEMPO was observed. The synthesized copolymers containing TEMPO end groups were used as macroinitiators to initiate polymerization of styrene. The molecular weight distributions of resulting poly(styrene‐alt‐N‐phenylmaleimide)‐block‐polystyrene copolymers indicated the presence of both low molecular weight termination products and some copolymer precursor. The copolymers and comonomer adducts were characterized using the nitrogen analysis, size‐exclusion chromatography (SEC), and NMR spectroscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1093–1099, 2000     

Synthesis and characterization of novel rod–coil diblock copolymers of poly(methyl methacrylate) and liquid crystalline segments of poly(2,5‐bis[(4‐methoxyphenyl)oxycarbonyl] styrene)

Liquid crystalline diblock copolymers with different molecular weights and low polydispersities were synthesized by atom transfer radical polymerization of methyl methacrylate (MMA) and 2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene (MPCS) monomers. The block architecture (coil‐conformation of MMA segment and rigid‐rod of MPCS segment) of the copolymer was experimentally confirmed by a combination of ¹H nuclear magnetic resonance and gel permeation chromatograph techniques. The liquid crystalline behaviour of the copolymer was studied using differential scanning calorimetry and polarized optical microscope. It was found that the liquid crystalline behaviour was dependent on the number average molecular weight of the rigid segment. Only those copolymers with M_n(GPC) of the rigid block above 9200 g mol^?1 could form liquid crystalline phases higher than the glass transition temperature of the rigid block. The random copolymers MPCS‐co‐MMA were also synthesized by conventional free radical polymerization. The molar content of MPCS in MPCS‐co‐MMA had to be higher than 71% to maintain liquid crystalline behaviour. © 2003 Society of Chemical Industry     

Preparation of well‐defined block copolymer having one polystyrene segment and another poly(styrene‐alt‐maleic anhydride) segment with RAFT polymerization

Block copolymers, polystyrene‐b‐poly(styrene‐co‐maleic anhydride), have been prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization technique using three different approaches: 1‐phenylethyl phenyldithioacetate (PEPDTA) directly as RAFT agent, mediated polystyrene (PS) block as the macromolecular PS‐RAFT agent and mediated poly(styrene‐maleic anhydride) (SMA) block with alternating sequence as the macromolecular SMA‐RAFT agent. Copolymers synthesized in the one‐step method using PEPDTA as RAFT agent possess one PS block and one SMA block with gradient structure. When the macromolecular RAFT agents are employed, copolymers with one PS block and one alternating SMA block can be produced. However, block copolymers with narrow molecular weight distribution (MWD) can only be obtained using the PS‐RAFT agent. The MWD deviates considerably from the typical RAFT polymerization system when the SMA is used as the RAFT agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Synthetic Approach to Star‐Like Polymers of Styrene and Butyl Acrylate by Linking Reactions using Functionalized Methacrylates

Summary: Coupling reactions between terminal functionalized polymer chains were chosen for the synthesis of star‐like polymers consisting of polystyrene and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] arms. For the preparation of terminal functionalized polymer chains a side reaction of the 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) mediated free radical polymerization of methacrylates could be used successfully to convert TEMPO terminated polymers into end functionalized polymers. The number of functionalized monomer units attached to the polymer chain is directly related to the TEMPO concentration during this reaction. Different polystyrenes and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] block copolymers were functionalized with a variable number of epoxide and alcohol groups at the chain end. For the determination of the optimal reaction parameters for the coupling reactions between these polymer chains, epoxy functionalized polystyrenes were converted with hydroxy functionalized polystyrenes under basic and acidic conditions. By activation with sodium hydride or boron trifluoride star‐like polymers were synthesized under mild conditions. The transfer of the reaction conditions to coupling reactions between end functionalized polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] copolymers showed that star‐like polymers with more than 12 arms were formed using boron trifluoride as activating agent.

     

Preparation and application of sulfonated poly(1‐octene‐co‐styrene)

In this article, 1‐octene and styrene was copolymerized by the supported catalyst (TiCl₄/ID/MgCl₂). Subsequently, by sulfonation reaction, sulfonated poly(1‐octene‐co‐styrene)s which were amphiphilic copolymers were prepared. The copolymerization behavior between 1‐octene and styrene is moderate ideal behavior. Copolymers prepared by this catalyst contain appreciable amounts of both 1‐octene and styrene. Increase in the feed ratio of styrene/1‐octene leads to increase in styrene content in copolymer and decrease in molecular weight. As the polymerization temperature increases, the styrene content in the copolymers increases, however, the molecular weight decreases. Hydrogen is an efficient regulator to lower the molecular weights of poly(1‐octene‐co‐styrene)s. The sulfonation degree of the sulfonated poly(1‐octene‐co‐styrene)s increased as the styrene content in copolymer increased or the molecular weight decreased. Thirty‐six hour is long enough for sulfonation reaction. The sulfonated poly(1‐octene‐co‐styrene)s can be used as effective and durable modifying agent to improve the wettability of polyethylene film and have potential application in emulsified fuels and for the stabilization of dispersions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Hydrogen bonding interactions of styrene‐maleimide copolymers with diaminotriazine derivatives

Poly(styrene‐co‐N‐maleimide) precursor and poly(styrene‐co‐N‐maleimide)‐block‐polystyrene have been synthesized by quasiliving radical polymerization. Low molecular weight compounds with the sites specific for the complementary binding to the maleimide moieties via triple hydrogen bonds, 2,4‐diamino‐6‐n‐alkoxy(C‐4, C‐8, and C‐12)‐s‐triazines, have been prepared. Hydrogen bonding between diaminotriazine and maleimide units in the copolymer–diaminotriazine mixtures has been investigated by FTIR. Microphase separated structure in the block copolymer‐diaminotriazine mixtures has been confirmed by DSC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2338–2346, 2006     

Synthesis of hydroxyl‐terminated copolymer of styrene and 4‐vinylpyridine via nitroxide‐mediated living radical polymerization

The random copolymers of styrene (St) and 4‐vinylpyridine (4‐VP) with hydroxyl end group and low polydispersities were synthesized by nitroxide‐mediated living radical polymerization initiated by azobisisobutyronitrile (AIBN) and 4‐hydroxyl‐2,2,6,6–tetramethylpiperidine‐oxyl (TEMPO‐OH). The experimental results have shown that all synthesized copolymers have narrow molecular weight distribution. The conversion of monomers and the molecular weight of copolymer increased with polymerization time. The copolymerization rate is affected by molar ratios of HTEMPO to AIBN. ¹H‐Nuclear magnetic resonance spectra shows that one end of copolymers was capped by TEMPO‐OH moiety. The use of this method permits the copolymer with hydroxyl chain end and controllable molecular weight and molecular weight distribution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1842–1847, 2004     

Block copolymer synthesis and chain extension from TEMPO‐terminated chains formed by ultrasonic chain scission

Long poly(ethyl methacrylate) (M_n = 2,300,000) and polystyrene (M_n = 1,200,000) chains were subjected to ultrasonic scission in the presence of a radical scavenger, 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). This procedure yielded polymers with lower molecular weights and TEMPO terminal units. Application of these polymers in stable radical mediated polymerization of styrene resulted in chain extension and block copolymers, depending on the precursor polymer. Block copolymer formation was evidenced by NMR measurement, and chain extension was shown by GPC analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1950–1953, 2000     

A new synthetic approach to asymmetric amphiphilic ABA′ block copolymers by ATRP and click reactions

Well‐defined asymmetric amphiphilic ABA′ block copolymers composed of poly(ethylene oxide) monomethylene ether (MPEO) with different molecular weights as A or A′ block and poly(styrene) (PS) as B block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. First, bromine‐terminated diblock copolymer poly(ethylene oxide) monomethylene ether‐block‐poly(styrene) (MPEO‐PS‐Br) was prepared by ATRP of styrene initiated with macroinitiator MPEO‐Br, which was prepared from the esterification of MPEO and 2‐bromoisobutyryl bromide. Then, the azido‐terminated diblock copolymers MPEO‐PS‐N₃ were prepared through the bromine substitution reaction with sodium azide. Propargyl‐terminated MPEO with a different molecular weight was prepared under the basic condition from propargyl alcohol and p‐toluenesulfonyl‐terminated MPEO, which was prepared through the esterification of MPEO and p‐toluenesulfochloride using pyridine as solvent. Asymmetric amphiphilic ABA′ block copolymers, with a wide range of number–average molecular weights from 1.92 × 10⁴ to 2.47 × 10⁴ and a narrow polydispersity from 1.03 to 1.05, were synthesized via a click reaction of the azido‐terminated diblock copolymers and the propargyl‐terminated MPEO in the presence of CuBr and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABA′ block copolymers and corresponding precursors were characterized by NMR, IR, and GPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Exfoliated poly (styrene‐co‐methylstyrene) grafted‐polyaniline/layered double hydroxide nanocomposite synthesized by solvent blending method

Well defined poly (styrene‐co‐methylstyrene) grafted polyaniline/organo‐modified MgAl layered double hydroxide (LDH) was produced through solution intercalation method. After LDH nanoparticles were modified by the anion exchange reaction of MgAl (Cl) LDH with sodium dodecyl benzene sulfonate, Poly (styrene‐co‐methylstyrene) copolymers were synthesized by “living” free radical polymerization and then brominated with N‐bromosuccinimide. Afterwards, 1,4‐phenylenediamine was linked to brominated copolymers and prepared functionalized copolymer with amine. Poly (St‐co‐MSt)‐g‐PANI, has been synthesized by adding solution of ammonium persulfate and p‐toluenesufonic acid in DMSO solvent. Finally, Poly (styrene‐co‐methylstyrene) grafted‐Polyaniline/LDH nanocomposites were prepared by solution intercalation method. Characterization of these well‐defined nanocomposites included FT‐IR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimeter, transmission electron microscopy, and X‐ray diffraction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Specific interactions in poly(styrene‐co‐2‐hydroxyethyl acrylate)/poly(styrene‐co‐N,N‐dimethylacrylamide) systems

Amphiphilic copolymers of poly(styrene‐co‐2‐hydroxyethyl acrylate) (SHEA) and poly(styrene‐co‐N, N‐dimethylacrylamide) (SAD) of different compositions were prepared by free radical copolymerization and characterized by different techniques. Depending on the nature of the solvent and the densities of interacting species incorporated within the polystyrene matrices, novel materials as blends or interpolymer complexes with properties different from those of their constituents were elaborated when these copolymers are mixed together. The specific interpolymer interactions of hydrogen bonding type and the phase behavior of the elaborated materials were investigated by differential scanning calorimetry (DSC) and Fourier transform infra red spectroscopy (FTIR). The specific interactions of hydrogen bonding type that occurred within the SHEA and within their blends with the SAD were evidenced by FTIR qualitatively by the appearance of a new band at 1626 cm^?1 and quantitatively using appropriate spectral curve fitting in the carbonyl and amide regions. The variation of the glass transition temperature with the blend composition behaved differently with the densities of interacting species. The thermal degradation behavior of the materials was studied by thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate) triblock copolymer by atom transfer radical polymerization

The synthesis of triblock copolymer poly(octadecyl acrylate‐b‐styrene‐b‐octadecyl acrylate), using atom transfer radical polymerization (ATRP), is reported. The copolymers were prepared in two steps. First, polystyrene was synthesized by ATRP using α,α′‐dichloro‐p‐xylene/CuBr/bpy as the initiating system; Second, polystyrene was further used as macroinitiator for the ATRP of octadecyl acrylate to prepare ABA triblock copolymers in the presence of FeCl₂·4H₂O/PPh₃ in toluene. Polymers with controlled molecular weight (M_n = 17,000–23,400) and low polydispersity index value (1.33–1.44) were obtained. The relationship between molecular weight versus conversion showed a straight line. The effect of reaction temperature on polymerization was also investigated, showing a faster polymerization rate under higher temperature. The copolymers were characterized by FTIR, ¹H‐NMR, DSC, and GPC and the crystallization behavior of the copolymers was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1539–1545, 2004     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of PLLA‐PEOMA comb‐block‐comb type molecular brushes based on AGET ATRP and ring‐opening polymerization

BACKGROUND: Molecular brushes are types of macromolecules with densely grafted side chains on a linear backbone. The synthesis of macromolecular brushes has stimulated much interest due to their great potential in applications in various fields. Poly(L ‐lactide)–poly(ethylene glycol) methyl ether methacrylate (PLLA‐PEOMA) comb‐block‐comb molecular brushes with controlled molecular weights and narrow molecular weight distributions were successfully synthesized based on a combination of activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) and ring‐opening polymerization. The synthetic route is a combination of the ‘grafting through’ method for AGET ATRP of the PEOMA comb block and the ‘grafting from’ method for the synthesis of the PLLA comb block. Poly(2‐hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, and PLLA side chains and PEOMA side chains were grown from the backbones and the terminal sites of PHEMA, respectively. RESULTS: The number‐average degrees of polymerization of PLLA chains and poly[poly(ethylene glycol) methyl ether methacrylate] (PPEOMA) comb blocks were determined using ¹H NMR spectroscopy, and the apparent molecular weights and molecular weight distributions of the brush molecules were measured using gel permeation chromatography. The crystallization of the components in the comb‐block‐comb copolymers was also investigated. The crystallization of PLLA side chains is influenced by PLLA chain length and the content of PPEOMA in the molecular brushes. The comb‐block‐comb copolymer composed of hydrophobic PLLA and hydrophilic PEOMA can self‐assemble into a micellar structure in aqueous solution. CONCLUSION: A combination of AGET ATRP and ring‐opening polymerization is an efficient method to prepare well‐defined comb‐block‐comb molecular brushes. The physical properties of the molecular brushes are closely related to their structures. Copyright © 2009 Society of Chemical Industry