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Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites to Form Acrylate Graft Copolymers

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Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites to Form Acrylate Graft Copolymers SYNLETT0936-52141437-2096 Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart 2021, 32, 497–501 cluster 497 The Power of Transition Metals: An Unen- Synlett L. Li et al. Cluster Advances in Internal Plasticization of PVC: Copper-Mediated Atom-Transfer Radical Polymerization from PVC Defect Sites To Form Acrylate Graft Copolymers Longbo Lia O O wt% Plasticizer: 24% to 75% Yanika Schneiderb O Adrienne B. Hoeglundc O a Defect Sites Rebecca Braslau* O Allylic 2 Internal Chloride a Department of Chemistry and Biochemistry, University of California, BA 2EEA Plasticizer Santa Cruz, 1156 High Street, Santa Cruz, CA 95064, USA Tertiary [email protected] Chloride 3 mol% CuBr, 3 mol% PMDETA b EAG Laboratories, 810 Kifer Rd, Sunnyvale, CA 94086, USA DMF c 100 °C EAG Laboratories, 2672 Metro Blvd, Maryland Heights, MS 63043, 2 h USA PVC PVC-g-(PBA-co-P2EEA) Dedicated to Barry Trost: celebrating a lifetime of exploring the beauty Tg: 54 °C to –54 °C of transition-metal catalysis in organic synthesis. Published as part of the Cluster The Power of Transition Metals: An Unending Well-Spring of New Reactivity Corresponding Author Received: 07.12.2020 Previous work in this laboratory highlighted the use of Accepted: 15.01.2021 thermal azide/alkyne Huisgen cycloadditions to attach Published online: 12.02.2021 6,12,14,15 DOI: 10.1055/s-0037-1610764; Art ID: st-2020-v0624-c plasticizers to PVC. However, the nucleophilic-sub- stitution approach to attaching plasticizers requires at least Abstract Internally plasticized PVC copolymers were prepared by three synthetic steps from PVC, which is impractical on an grafting PVC with butyl acrylate and 2-(2-ethoxyethoxy)ethyl acrylate industrial scale. by atom-transfer radical polymerization, resulting in well-behaved poly- mers with a wide range of glass transition temperatures (–54 °C to 54 Polymerization offers alternative approaches to cova- °C). When the grafted side chains made up more than 50% of the poly- lent attachment of plasticizers to PVC. Copolymerization of mer by weight, the glass transition temperatures were below 0 °C. The vinyl chloride (VC) with monomers bearing plasticizers has covalent attachment of the plasticizing grafts requires one simple pro- been accomplished to give either block or random copoly- cedure starting from commercial PVC, making this strategy an industri- ally relevant and environmentally friendly alternative to the use of con- mers. Examples include block copolymers of PVC with po- 17,18 19 ventional small-molecule plasticizers. ly(butyl acrylate) (PBA) or poly(-caprolactone). In collaboration with Coelho,20 we have used random copoly- Key words polyvinyl chloride, copper catalysis, atom-transfer radical merization of VC with an acrylate bearing a mimic of di-2- Downloaded by: Thieme Chemistry Journals. Copyrighted material. polymerization, graft copolymerization, butyl acrylate, ethoxye- ethylhexyl phthalate (DEHP), the most common PVC plasti- thoxyethyl acrylate cizer. Alternatively, an attractive strategy involves the use of atom-transfer radical polymerization (ATRP)21 to grow graft Poly(vinyl chloride) (PVC) is one of the most widely copolymers from PVC chains.22–33 Commercial PVC contains used thermoplastics. Because pure PVC is rigid and brittle, allylic and tertiary chloride defect moieties in the back- plasticizers are used to increase the flexibility of PVC mate- bone.34 Percec and Asgarzadeh23 demonstrated the first ap- rials for a variety of applications, such as toys, medical de- plication of copper-mediated ATRP initiated from these ac- 1 vices, sports equipment, or building materials. Commonly tive sites, resulting in glass-transition temperature (Tg) val- used small-molecule plasticizers such as phthalates can mi- ues as low as –4 °C. We recently demonstrated the use of grate out of the PVC matrix;2 resulting not only in degrada- acrylates in ATRP from PVC to prepare PVC graft copoly- tion of mechanical properties, but also in health issues aris- mers by employing PBA and poly[2-(2-ethoxyethoxy)ethyl ing from exposure to these molecules. The covalent attach- acrylate] (P2EEA) to form flexible homogeneous PVC graft ment of plasticizers to PVC prevents plasticizer migration. copolymers.35 Our initial ATRP reactions were carried out Strategies to attach plasticizing moieties include nucleo- for over 24 hours, affording graft copolymers that were only philic substitution of the secondary chlorides on the PVC partially soluble in THF, DMF, or NMP, probably due to chains, as well as various polymerizations. Studies using the cross-linking. Here we report the preparation of soluble in- nucleophilic-substitution approach have focused on sul- ternally plasticized PVC graft copolymers under improved fides,3,4 amines,5 and azides (to form triazole linkages).6–16 conditions (Scheme 1). A variety of graft lengths were ex- © 2021. Thieme. All rights reserved. Synlett 2021, 32, 497–501 Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany 498 Synlett L. Li et al. Cluster O (PBA/PVC = 1.4:1.0). The other graft copolymers all showed O similar polyacrylate lengths of approximately graft/PVC = O O 1:1. This is consistent with the percentage conversions as Allylic 1 Chloride O determined by H NMR (Table 1) and from the gravimetric BA 2 Tertiary 2EEA yields (SI; Table S1). Not surprisingly, the percentage con- Chloride versions by 1H NMR before workup were higher than the 3 mol% CuBr, 3 mol% PMDETA DMF PVC gravimetric yields after workup due to loss of nongrafted 100 °C 2 h polymer and general material loss. The workup entailed PVC PVC-g-(PBA-co-P2EEA) precipitation of the crude polymer in MeOH; MeOH-soluble fractions were therefore lost. PVC-g-PBA shows pre-workup Scheme 1 Formation of internally plasticized graft copolymers by values that were closer to the to post-workup yields, as ATRP from defect sites on PVC nongrafted PBA is only partially soluble in MeOH, whereas the more polyether rich homopolymers and graft copoly- plored to generate graft copolymers with tunable flexibili- mers were more likely to be washed away during precipita- ties for a variety of applications. tion from MeOH. In our previous study,35 a control experiment was per- formed in the absence of PVC, indicating that up to 23% ho- Table 2 Composition of Graft Copolymers Based on 1H NMR Integration mopolymerization occurred. To minimize both this com- peting nongraft polymerization as well as undesired cross- Entry Initial molar ratio Polymer molar ratio Polymer molar ratio linking, the reaction duration was decreased from 24 hours [BA]/[2EEA] PBA/P2EEA (PBA + P2EEA)/PVC to 2 hours. Control reactions were conducted without PVC 1 BA only PBA only 1.4:1.0 for each monomer (BA and 2EEA) using 3 mol% of CuBr, and 2 3:1 3.0:1.0 1.0:1.0 3 mol% of N,N,N′,N′′,N′′-pentamethyldiethylenetriamine 3 1:1 1.0:1.0 0.9:1.0 (PMDETA) in DMF at 100 °C. Nongrafted homopolymer was formed in only 10% yield for BA and 6% for 2EEA (Table 1, 4 1:3 1.0:2.8 0.9:1.0 entries 1 and 2), significantly less than the 23% obtained af- 5 2EEA only P2EEA only 0.9:1.0 ter 24 hours. A series of graft copolymers were then pre- pared by using a polymerization time of two hours (entries The Tg values of these internally plasticized PVC graft 3–7).36 Five different monomer ratios (BA/2EEA) were in- copolymers were measured by differential scanning calo- vestigated, resulting in good conversions, ranging from 56 rimetry (DSC), using data from the second heating cycle. to 78%. More importantly, all these materials were soluble PVC graft copolymers made with molar ratios of 2.5:1.0 had in CDCl3, suggesting an absence of cross-linking. very low Tg values compared with PVC (Tg = 84 °C) (Figure 1). Only a single Tg was observed, indicating that there was a Table 1 Graft Polymerizations: Percentage Conversions no microphase separation. The least depressed Tg was seen for PVC-g-PBA (Tg = –25 °C), and the lowest Tg value was ob- b c Downloaded by: Thieme Chemistry Journals. Copyrighted material. Entry [PVC]/[BA]/[2EEA]/[CuBr]/[PMDETA] Conv. (%) served for PVC-g-25%PBA-co-75%P2EEA (Tg = –54 °C). This is consistent with our previous observation that 2EEA-rich 10:2.5:0:0.03:0.03 10 grafts are more efficient plasticizers compared with those 20:0:2.5:0.03:0.03 6 rich in BA. Some of the materials showed a melting tem- 31:2.5:0:0.03:0.03 78 perature (Tm) indicating these copolymers exhibit semi- 41:1.9:0.6:0.03:0.03 61 crystallinity, along with very low Tg values (SI; Table S4). 51:1.3:1.3:0.03:0.03 60 Thermogravimetric analysis (TGA) (Figure 2) and deriv- 61:0.6:1.9:0.03:0.03 56 ative thermogravimetry (DTG) (SI; Figure S4 and Table S2) of these internally plasticized PVC materials were used to 71:0:2.5:0.03:0.03 60 examine their thermal stabilities. PVC and PVC bearing a All polymerizations were conducted at 100 °C in DMF for 2 h. polyacrylate grafts exhibited two main stages of degrada- b Initial molar ratios. c Conversion of total monomers, as determined by 1H NMR. tion. The onset temperatures of the modified PVC samples were higher than those of unmodified PVC, because the un- stable allylic and tertiary chloride defect sites were re- 1H NMR was used to characterize the monomer ratios in placed by carbon grafts.37 The thermal stabilities of the PBA the PVC grafts (Table 2). The monomer-ratio calculation and P2EEA grafts were similar. method is shown in the Supporting Information (SI).
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