Catalytic synthesis and characterization of an alternating copolymer from carbon dioxide and propylene oxide using zinc pimelate

New zinc pimelate catalysts used for copolymerization of carbon dioxide and propylene oxide have been synthesized in high yield by a magnetic stirring method. The regular molecular structure of the zinc pimelate was confirmed by Fourier‐transform infrared spectroscopy and wide‐angle X‐ray diffraction techniques. Accordingly, poly(propylene carbonate) (PPC) can be synthesized from carbon dioxide and propylene oxide using these zinc pimelate catalysts. High catalytic efficiency (95.2 gram polymer per gram catalyst or 21 300 g of polymer per mole of zinc) was achieved by optimizing the PO/catalyst ratio. NMR measurement revealed that the PPC synthesized had an alternating copolymer structure. The thermal properties of PPC were determined by modulated differential scanning calorimetry and thermogravimetric analysis. The results demonstrated that the PPC copolymer exhibited an extremely high glass transition temperature of 44.27 °C and decomposition temperature of 257 °C, comparable with values reported in literature. Copyright © 2003 Society of Chemical Industry     

Synthesis and characteristics of a novel aliphatic polycarbonate,poly[(propylene oxide)‐co‐(carbon dioxide)‐co‐(γ‐butyrolactone)]

A novel aliphatic polycarbonate, poly[(propylene oxide)‐co‐(carbon dioxide)‐co‐(γ‐butyrolactone)] [P(PO? CO₂? GBL)], was synthesized by the copolymerization of carbon dioxide, propylene oxide (PO) and γ‐butyrolactone (GBL). The resulting copolymers were determined by FTIR and NMR spectral analysis with viscosity‐average molecular weights (M_v) from 50 000 to 120 000 g mol^?1. According to elemental analysis, the calculated data of elemental contents in P(PO? CO₂? GBL)44 were close to the found data. The result showed that GBL was inserted into the backbone of poly[(propylene oxide)‐co‐(carbon dioxide)] successfully. GBL offered an ester structural unit that gave the copolymer better degradability. The correlations between reaction conditions and properties were studied. When GBL content increased, the M_v and the glass transition temperature (T_g) of the copolymers improved relative to an identical copolymer without GBL. Prolonging the reaction time of the copolymerization resulted in increases in M_v and T_g. P(PO? CO₂? GBL) exhibited a high T_g above 40 °C. The rate of backbone degradation increased with increasing GBL content. Copyright © 2005 Society of Chemical Industry     

Selective copolymerization of carbon dioxide with propylene oxide catalyzed by a nanolamellar double metal cyanide complex catalyst at low polymerization temperatures

Traditional cobalt-zinc double metal cyanide complex [Zn-Co(III)DMCC] catalysts could catalyze the copolymerization of carbon dioxide (CO₂) with propylene oxide (PO) to afford poly (propylene carbonate) (PPC) with high productivity. But the molecular weight (MW) of PPC and the polycarbonate selectivity were not satisfied. In this work, by using a nanolamellar Zn-Co(III) DMCC catalyst, the CO₂-PO copolymerization was successfully performed to yield PPC with high molecular weight (M_n: 36.5 kg/mol) and high molar fraction of CO₂ in the copolymer (FCO₂: 74.2%) at low polymerization temperatures (40∼80 °C). Improved selectivity (FCO₂: 72.6%) and productivity of the catalyst (6050 g polymer/g Zn) could be achieved at 60 °C within 10 h. The influences of water content on CO₂-PO copolymerization were quantitatively investigated for the first time. It was proposed that trace water in the reaction system not only acted as an efficient chain transfer agent, which decreased MW of the resultant copolymer, but also strongly interacted with zinc site of the catalyst, which led to low productivity of PPC and more amounts of cyclic propylene carbonate (cPC). These conclusions were also supported by the apparent kinetics of CO₂-PO copolymerization. ESI-MS results showed that all polymers have two end alkylhydroxyl groups. It was thus proposed that the alkylhydroxyl groups came from the initiation reaction of Zn-OH in the catalyst and the chain transfer reaction by H₂O. The proposed mechanism of chain initiation, propagation and chain transfer reaction were proved by the experimental results.     

One‐pot regioselective and stereoselective terpolymerization of rac‐lactide,CO2 and rac‐propylene oxide with TPPMCl (M = Cr,Co, Al)/PPNCl binary catalyst

Tetraphenyl porphyrin metal compound (TPPMCl) (where the TPPMCl was TPPCrCl, TPPCoCl, TPPAlCl), in combination with cocatalyst PPNCl (bis(triphenylphosphine)iminium chloride, the molar ratio of TPPMCl to PPNCl was 1:0.5), was used to catalyze the polymerization of racemic lactide (rac‐LA) in racemic propylene oxide (rac‐PO) medium and the terpolymerization of rac‐LA, CO₂ and rac‐PO. It was found that these TPPMCl/PPNCl binary catalysts could initiate the stereoselective polymerization of rac‐LA in rac‐PO medium to form enriched isotactic polylactide (PLA) (P_i ≥ 68.0%) and terpolymerization of CO₂, rac‐LA, rac‐PO to form PPC‐PLA‐PPO (PPC, poly(propylene carbonate); PPO, poly(propylene oxide)) multiblock copolymer. In particular the PPC‐PLA‐PPO multiblock copolymer thus formed displayed high regioregularity and stereoregularity, and has high head‐to‐tail structure content in the PPC block (H‐T% ≥ 63.6%) and high isotacticity in the PLA block (P_i ≥ 64.0%). The influence of catalyst formula, the monomer feeding ratio, reaction temperature, carbon dioxide pressure and reaction time on the terpolymerization was investigated by ¹H NMR, ¹³C NMR, gel permeation chromatography, DSC and TGA. © 2018 Society of Chemical Industry     

Synthesis and characterization of alternating copolymer from carbon dioxide and propylene oxide

High yield and pure zinc glutarate catalysts used for copolymerization of carbon dioxide and propylene oxide have been synthesized in different solvents by ultrasonic methodology. For the purposes of comparison, low‐yield zinc glutarates were also synthesized via mechanical stirring method with other synthetic conditions remaining unchanged. Fourier Transform Infrared Spectroscopy and wide‐angle X‐ray diffraction techniques confirmed the presence of high‐quality zinc glutarate catalysts. Accordingly, poly(propylene carbonate) (PPC) can be synthesized from carbon dioxide and propylene oxide using the zinc glutarate catalysts. It was confirmed that the as‐prepared PPC had an alternating copolymer structure together with high molecular weight. The thermal and mechanical properties of the obtained PPC copolymer were determined by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile test. DSC and TGA results showed that the PPC copolymer exhibited high glass transition temperature (39.39°C) and decomposition temperature (278°C) when compared to their corresponding values reported in the literature. Tensile test showed that the PPC film exhibited superior mechanical strength. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2327–2334, 2002     

Copolymerization of carbon dioxide and propylene oxide with zinc glutarate as catalyst in the presence of compounds containing active hydrogen

To enhance the catalytic copolymerization of CO₂ and propylene oxide catalyzed by zinc glutarate, the influence of trace of water, ethanol, and propanal on the catalytic activity, the resulted copolymer structure, and the molecular weight and molecular weight distribution of the copolymer were investigated extensively. The experimental results showed that the catalytic activity decreased remarkably in the presence of either trace of ethanol or water, but increased in the presence of trace of propanal. Both ¹H‐NMR and ¹³C‐NMR spectra suggested that the content of carbonate linkages of resulted copolymer was not effected obviously in the presence of above‐mentioned impurities, giving completely alternating poly(propylene carbonate) (PPC). GPC results indicated that these impurities reduced the molecular weights but broadened the molecular weight distributions of resulted copolymers. Finally, the byproduct contents including both propylene carbonate determined by GC and polyether increased with the increase of three impurity concentrations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Double metal cyanide complexes synthesized by solvent‐free grinding method for copolymerization of CO2 and propylene oxide

Two active double metal cyanide (DMC) complexes were successfully synthesized by solvent‐free grinding method. Their structures were characterized by FTIR spectrometer and X‐ray diffractometer. The results showed that Complex 1 (double metal cyanide complex with K₃Fe(CN)₆ and ZnCl₂) and Complex 2 (double metal cyanide complex with K₃Fe(CN)₆ and Zn(CH₃COO)₂) had the same structures, crystal forms, and lower crystallinity as both of them synthesized by conventional solvent‐based methods, respectively. Investigations on grinding conditions indicated that Complex 1 ground 14 min at a high grinding strength could achieve low crystallinity and showed substantially amorphous structures. Two speculated structures of DMC were given. The alternating copolymerization of CO₂ and propylene oxide with Complex 1 as catalyst obtained anticipated poly(propylene carbonate) (PPC) with very high catalytic activity. The PPC produced by optimized Complex 1 has molecular weight (M_n) up to 98,000 and narrow polydispersity of 1.93 with more than 90% carbonate linkages. Compared with Complex 1 , Complex 2 displayed low catalytic activity but high selectivity mainly due to the electron atmosphere and strong steric hindrance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Copolymerization of carbon dioxide and epoxides with a novel effective Zn–Ni double‐metal cyanide complex

A novel double‐metal cyanide complex based on Zn[Ni(CN)₄] was prepared and used as a catalyst for the copolymerizations of carbon dioxide and propylene oxide (PO) and carbon dioxide and cyclohexene oxide (CHO). The copolymers were characterized by IR and ¹H‐NMR, and the effects of temperature, pressure, solvent, and preparative methods for the catalysts on catalytic activity and composition of the copolymer were investigated. The results show that this novel catalyst exhibited its highest catalytic efficiency at about 500 g/g of Zn[Ni(CN)₄] for PO and CO₂, whereas the catalytic efficiency for CHO and CO₂ was merely between 5.6 and 22.5 g/g of Zn[Ni(CN)₄]. The molar fraction of carbonate linkages for PO–CO₂ and CHO–CO₂ copolymers reached about 0.6 and 0.3, respectively. The results show that a lower temperature and a higher CO₂ pressure were favorable for the incorporation of CO₂ into the copolymer, and the nonpolar solvents were better media for copolymerization. As a complexing agent, glycol ether exhibited better promoting effects on catalytic efficiency among those investigated, but the catalysts prepared by different complexing agents showed no significant differences in the compositions of the copolymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enzymatic degradation of poly(propylene carbonate) and poly(propylene carbonate-co--caprolactone) synthesized via CO2 fixation

Poly(propylene carbonate) (PPC) and poly(propylene carbonate-co--caprolactone) (PPCCL) were synthesized via the zinc glutarate catalyzed copolymerization of carbon dioxide (CO₂) and propylene oxide (PO) without and with -caprolactone (CL), respectively. In addition, poly(-caprolactone) (PCL) was prepared via the homopolymerization of CL with the aid of methyl triflate catalyst. The polymer products were characterized in terms of their chemical compositions, molecular weights, and thermal properties. Films of these polymers were tested with a series of enzymes (four different families and a total of 18 enzymes) in a phosphate buffer in order to characterize their enzymatic degradabilities. This is the first report demonstrating that PPC films exhibit positive enzymatic degradability with Rhizopus arrhizus lipase, esterase/lipase ColoneZyme A, and Proteinase K. Moreover, PPCCL films exhibited positive enzymatic degradability with most of the enzymes utilized in our study, and thus PPCCL has an enzymatic degradability comparable to that of PCL. In particular, the PPCCL films exhibit excellent enzymatic degradability with Pseudomonas lipase, Rhizopus arrhizus lipase, and esterase/lipase ColoneZyme A. Considering its excellent enzymatic degradability, the PPCCL terpolymer has potential biomedical applications. In conclusion, ZnGA-catalyzed copolymerizations of CO₂ and PO with or without CL are chemical fixation processes of CO₂ that can be used to produce enzyme-degradable aliphatic polymers.     

Thermally stable aliphatic polycarbonate containing bulky carbazole pendants

To improve the thermal and mechanical properties of poly(propylene carbonate) (PPC), the terpolymers were synthesized by the terpolymerization of CO₂ with PO and a third monomer, N-(2,3-epoxylpropyl)carbazole (NEC) using supported zinc glutarate as catalyst. The catalytic activity, molecular weight, carbonate unit content, as well as the thermal and mechanical properties were investigated extensively. The experimental results showed that the catalytic activity, molecular weight, and carbonate unit content decreased with the incorporation of NEC. The introduction of NEC increased the glass transition temperature from 38.0 to 44.1°C. Moreover, the thermal decomposition temperature (T_g-5%) of the terpolymer (278°C) was much higher than that of pure PPC (238°C). Accordingly, the mechanical properties proved to be enhanced greatly as evidenced by tensile tests due to the incorporation of bulky carbazole moieties. These improvements in thermal and mechanical properties are of very importance for the process of PPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Block copolymerization of carbon dioxide with cyclohexene oxide and 4-vinyl-1-cyclohexene-1,2-epoxide in based poly(propylene carbonate) by yttrium-metal coordination catalyst

The coordination system, Y(CF₃CO₂)₃ (I)-Zn(Et)₂ (II)-m-hydroxybenzoic acid (III), was found to be the most active catalyst to generate poly(propylene carbonate) (PPC) from carbon dioxide and propylene oxide (PO) in 1,3-dioxolane. A high yield and a high molecular weight could be obtained at the conditions of a II/I molar ratio of 20, a III/II molar ratio of 1.0, a temperature of 60 °C, and a pressure of 2.76 MPa. The carbonate content in the resultant PPC was found to be nearly 100%.The block copolymerization in the based PPC was carried out by in situ introducing an epoxide other than PO right after the copolymerization of carbon dioxide with PO using the same catalyst system. The IR and ¹H NMR spectra as well as the measured molecular weights verified the resulting copolymers were block copolymers. For the block copolymerization of CO₂ with cyclohexene oxide and CO₂ with 4-vinyl-1-cyclohexene-1,2-epoxide in the based PPC, the yield as well as the cyclohexene carbonate and the 4-vinyl-1-cyclohexene carbonate contents were found to increase with increasing temperature. The most appropriate temperature was around at 80 °C. The weight-average molecular weights of the block copolymers lay in a range from 2.44×10⁵ to 3.16×10⁵, the polydispersity in a range from 5.0 to 6.3, and the 10% weight loss temperature in a range from 226 to 253 °C. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC, poly(cyclohexene carbonate), and poly(4-vinyl-1-cyclohexene carbonate), indicating the desired properties of a polymer can be achieved via block copolymerization.     

Inhibitory effect of hydrogen bonding on thermal decomposition of the nanocrystalline cellulose/poly(propylene carbonate) nanocomposite

Biodegradable poly(propylene carbonate, PPC) is a typical noncrystalline polymer from the copolymerization of carbon dioxide (CO₂) with propylene oxide (PO). But it is easy to be degraded to propylene carbonate (PC) via backbiting route during heat process (above 170°C), which limits its application. This work reports the introduction of biodegradable nanocrystalline cellulose (NCC) which was exfoliated from microcrystalline cellulose (MCC) by acid hydrolysis into PPC, affording a biodegradable PPC/NCC nanocomposite with improved thermal decomposition temperatures (the initial decomposition temperature, T_5wt% was up to 265°C). Impressively, the thermal decomposition of PPC to PC at 200°C within 4.0 h was dramatically inhibited by introducing NCC, which was evident by ¹H NMR spectra. This could be attributed to the hydrogen bonding interaction between NCC and PPC. Moreover, the film of PPC/NCC nanocomposite had not deformed when it was heated at 110°C for 4 h. In application, such biodegradable nanocomposite is a promising disposable package material. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39847.     

Thermally stable poly(propylene carbonate) synthesized by copolymerizing with bulky naphthalene containing monomer

To enhance the thermal and mechanical properties of poly(propylene carbonate) (PPC), the terpolymers were synthesized from carbon dioxide, propylene oxide, and a third monomer, [(2‐naphthyloxy)methyl]oxirane (NMO) using supported zinc glutarate as catalyst. The structure of these terpolymers was confirmed by ¹H NMR spectroscopy. The catalytic activity, molecular weight, carbonate unit content, as well as thermal and mechanical properties were investigated extensively. The experimental results showed that the catalytic activity, molecular weight, and carbonate unit content decreased with the incorporation of NMO. DSC measurements indicated that the introduction of NMO increased the glass transition temperature from 38 to 42°C. TGA tests revealed that the thermal decomposition temperature (T_g?5%) of the synthesized terpolymer increased significantly, being 34°C higher than that of pure PPC. Accordingly, the mechanical properties proved also to be enhanced greatly as evidenced by tensile tests. These thermal and mechanical improvements are of importance for the practical process and application of PPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Copolymerization of propylene oxide and carbon dioxide in the presence of diphenylmethane diisoyanate

To improve the thermal and mechanical properties of poly(propylene carbonate) (PPC), the copolymerization of CO₂ with PO was successfully carried out in the presence of a third monomer, 4,4′-diphenylmethane diisocyanate (MDI) using supported multi-component zinc dicarboxylate as catalyst. Chemical structure, the molecular weight, as well as thermal and mechanical properties of the resulting new copolymers were fully investigated. The experimental results show that the yield increases with increasing MDI feed content from 0 to 2 wt.%. The introduction of MDI leads to an increase in the molecular weight of PPC with light crosslinking. When the MDI feed content is lower than 3 wt.%, the PPC copolymers have number average molecular weight (Mn) ranging from 153 K to 424 K g/mol and molecular weight distribution (MWD) values ranging from 1.71 to 2.79. The resulting PPC copolymers show higher glass transition temperature (Tg) and decomposition temperature compared with poly(propylene carbonate) (PPC) without MDI. Considering the gel content of the resulting copolymers, the optimized MDI feed content should be smaller than 1.5 wt.% based on PO content. The introduction of small amount of MDI provides a very effective way to improve the mechanical properties and thermal stabilities of PPC due to the increase in its molecular weight.     

Copolymerization of carbon dioxide and propylene oxide with neodymium trichloroacetate-based coordination catalyst

The copolymerizations of carbon dioxide (CO₂) and propylene oxide (PO) were performed using new ternary rare-earth catalyst. It was found that the rare-earth coordination catalyst consisting of Nd(CCl₃COO)₃, ZnEt₂ and glycerine was very effective for the copolymerization of PO with CO₂. The effects of the relative molar ratio and addition order of the catalyst components, copolymerization reaction time, and operating pressure as well as temperature on the copolymerization were systematically investigated. At an appropriate combination of all variables, the yield could be as high as 6875 g/mol Nd per hour at 90 °C in a 8 h reaction period.     

Kinetics of the copolymerization of alkylene oxides with glycidyl methacrylate

In the present study, the kinetics of copolymerization reaction of propylene oxide (PO) and butylene oxide (BO) with glycidyl methacrylate (GMA) in the presence of BF₃ · O(C₂H₅)₂ catalyst were investigated. The kinetic parameters and activation energy of the copolymerization reaction were calculated. The amounts of reacting PO, BO, and GMA during copolymerization were determined by chromatographic method, because the same copolymerization conditions were carried out for them. It was determined that the copolymerization rate of PO (r₀) and BO (r₀) was higher than that of GMA, but activation energy (E) of GMA was higher than that of PO and BO. The rate of reaction, the rate constant, and activation energy were calculated from the amount of copolymer obtained with respect to time. The structures of synthesized copolymers were determined by the spectral and chemical analysis methods. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Copolymerization of carbon dioxide and propylene oxide using various zinc glutarate derivatives as catalysts

Various zinc dicarboxylate catalysts were synthesized by the reaction of zinc oxide with eleven different glutaric acid derivatives, and their coordination characteristics were investigated by infrared spectroscopy. The electronic nature and steric hinderance of substituents influenced the coordination of the carboxylate and the zinc metal ion. The coordination characteristics were classified into three categories: (i) compounds exhibiting bridging bidentate coordinating bonding modes, such as syn‐anti and syn‐syn bridging; (ii) compounds with only unidentate coordination; and (iii) compounds with mixed coordinations of unidentate and bridging bidentate. All the zinc carboxylate catalysts produced poly(propylene carbonate)s (PPCs) by the copolymerization of carbon dioxide and propylene oxide. The first category of catalysts produced relatively higher yields than the other categories. Zinc glutarate without any substituent, which is a catalyst in the first category, produced PPC with the highest yield and the highest molecular weight. The catalytic activity of zinc glutarate was suppressed by incorporation of substituents. The suppression of the catalytic activity might be due to the variation in the Lewis acidity of the zinc site as well as changes in the morphological structure caused by the substituents. Methylaluminoxane was also evaluated as a catalyst for the copolymerization, but it produced copolymers containing a large amount of ether linkages.     

Ring‐opening copolymerization of maleic anhydride with propylene oxide by double‐metal cyanide

Ring‐opening copolymerization of maleic anhydride (MA) with propylene oxide (PO) was successfully carried out by using double‐metal cyanide (DMC) based on Zn₃[Co(CN)₆]₂. The characteristics of the copolymerization are presented and discussed in this article. The structure of the copolymer was characterized with IR and ¹H‐NMR. Number‐average molecular weight (M_n) and molecular weight distribution (MWD) of the copolymer were measured by GPC. The results showed that DMC was a highly active catalyst for copolymerization of MA and PO, giving high yield at a low catalyst level of 80 mg/kg. The catalytic efficiency reached 10 kg polymer/g catalyst. Almost alternating copolymer was obtained when monomer charge molar ratio reached MA/PO ≥ 1. The copolymerization can be also carried out in many organic solvents; it was more favorable to be carried in polar solvents such as THF and acetone than in low‐polarity solvents such as diethyl ether and cyclohexane. The proper reaction temperature carried in the solvents was between 90 and 100 °C. The M_n was in the range of 2000–3000, and it was linear with the molar ratio of conversion monomer and DMC catalyst. The reactivity ratio of MA and PO in this reaction system was given by the extended Kelen–Tudos equation: η=[r₁+(r₂/α)]ξ?(r₂/α) at some high monomer conversion. The value of reactivity ratio r₁(MA) = 0 for MA cannot be polymerized itself by DMC catalyst, and r₂(PO) = 0.286. The kinetics of the copolymerization was studied. The results indicated that the copolymerization rate is first order with respect to monomer concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1788–1792, 2004     

Alternating Copolymerization of Carbon Dioxide and Cyclohexene Oxide and Their Terpolymerization with Lactide Catalyzed by Zinc Complexes of N,N Ligands

For the alternating copolymerization of CO₂ and cyclohexene oxide, a variety of zinc acetate complexes with new aminoimidoacrylate ligands has been synthesized and tested as catalysts. All complexes catalyzed the reaction and structure‐activity investigations revealed that the highest activities and selectivities were reached when the ligand’s aromatic rings were 2,6‐substituted by alkyl groups of different size (isopropyl versus methyl) and when the ligand backbone embodied an electron‐withdrawing cyano group. Furthermore, these complexes catalyzed the terpolymerization of CO₂, cyclohexene oxide and lactide to give poly(cyclohexyl carbonate‐co‐lactide) and the composition of the polymer was adjustable by the monomer feed.     

Mechanical properties of block poly(propylene carbonate‐cyclohexyl carbonate) investigated by nanoindentation and DMA methodologies

To extend the practical application of poly(propylene carbonate) (PPC), the chemical methods were used to improve its mechanical properties. In this connection, random copolymer poly(propylene‐cyclohexyl carbonate) (PPCHC) and di‐block copolymers poly(propylene carbonate‐cyclohexyl carbonate) (PPC‐PCHC) were synthesized. Dynamic mechanical analysis (DMA), nanoindentation and nanoscratch test were applied to evaluate their mechanical properties. The storage's modulus, Young's modulus (E) and hardness (H) obtained from DMA and nanoindentation tests showed that the introduction of the third monomer cyclohexene oxide (CHO) can greatly improve the mechanical properties of PPC, and that the block copolymer PPC‐PCHC hand better mechanical properties than the random copolymer PPCHC. The annealing treated PPC‐PCHCs exhibited deteriorated mechanical properties as compared with untreated PPC‐PCHC. From the results of scratch tests, the plastic deformation of PPC‐PCHC was smaller than those of PPC and PPCHC. Meanwhile, the plastic deformations of the heat‐treated PPC‐PCHCs were smaller than the untreated PPC‐PCHC because of the possible rearrangement of the molecular chains of PPC‐PCHC. The scratch hardness (H_s) of the block copolymer PPC‐PCHC is larger than random polymer PPCHC and PPC, but lower than the values of heat‐treated samples indicating that the surfaces' hardness of block polymers increase after heat treatment. These different measurement methodologies provide a more precise assessment and understanding for the synthesized block polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013