Gelation adversely affects the aqueous adiabatic terpolymerization of acrylamide (AM), sodium acrylate (NaAA),and 2-methacryloyloxyethyl trimethylammonium chloride (DMC). Here, the mixed dispersants sorbitan monooleat...Gelation adversely affects the aqueous adiabatic terpolymerization of acrylamide (AM), sodium acrylate (NaAA),and 2-methacryloyloxyethyl trimethylammonium chloride (DMC). Here, the mixed dispersants sorbitan monooleate (Span80) and polyoxyethylene sorbitan monooleate (Tween 80) were introduced to the terpolymerization system in an attemptto mitigate the gel effect. This enabled the preparation of high-performance amphoteric polyacrylamides, which werecharacterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. The influences of the dispersanttype and content as well as the hydrophilic-lipophilic balance (HLB) on the gel effect were examined, and the mechanismunderlying the suppression of the gel effect was considered. The obtained results indicated that the gel effect can beeffectively mitigated using an aqueous adiabatic terpolymerization system containing mixed Span 80/Tween 80 dispersantsat various contents. In particular, mixed dispersant contents of 0.6%–0.8% with HLB values of 5.0–6.0 afforded the optimalperformance (e.g., high viscosity, fast aqueous dissolution time, and the like).展开更多
Teroolymerization of enichlorohydrin（ECH）-maleic anhydride（MAn）-carbon dioxide（CO;） was carried out by using Y(P;);-Al（i-Bu）;as catalyst for the first time.The terpolymersobtained were characterized by IR and;...Teroolymerization of enichlorohydrin（ECH）-maleic anhydride（MAn）-carbon dioxide（CO;） was carried out by using Y(P;);-Al（i-Bu）;as catalyst for the first time.The terpolymersobtained were characterized by IR and;H-NMR.It was foundthat the composition of the teroolymer was influenced by theaddition mode,initial monomer charge ratio,etc.展开更多
Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical struct...Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.展开更多
Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one electron-accepting monomer, i.e. acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in d...Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one electron-accepting monomer, i.e. acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in dioxane as diluent at 65°C for 150 min has been studied. The kinetic expression is Rpα[I]0.8[Sty] 1.2[VA] 1.4 [AN]1.2. The terpolymer composition was determined by the Kelen-Tüdos method. The values of reactivity ratios using r1 (Sty + VA) = 0.1 and r2 (AN) = 0.005. The overall activation energy is 46 kJ●mol●L–1. The formation of terpolymer is confirmed by the FTIR spectra showing bands at 3030 cm–1, 1598 cm–1, and 2362 cm–1, confirming the presence of phenyl, acetoxy and nitrile group respectively. The terpolymer has been characterized by 1H-Nuclear Magnetic Resonance, 13C-Nuclear Magnetic Resonance. The Differential Scanning Calorimetric curve shows the Tg of the polymer as 149.5°C. A scanning electron microscope confirms the polymer to be phosphorus free. Electron.Spin.Resonance spectra confirms phenyl radical responsible for initiation.展开更多
A convenient one-pot terpolymerization of CO2, propylene oxide （PO）, and L-lactide （L-LA） in short polymerization time （10 h or shorter） to afford poly（propylene carbonate-lactide） with excellent mechanical pr...A convenient one-pot terpolymerization of CO2, propylene oxide （PO）, and L-lactide （L-LA） in short polymerization time （10 h or shorter） to afford poly（propylene carbonate-lactide） with excellent mechanical property and thermal stability using Y（CCl3COO）3-ZnEtz-glycerin rare-earth ternary catalyst is reported. The yield of the co- polymerization was between 69.7 and 111.7 g/（g Zn）, corresponding to L-LA/PO molar feed ratio varying from 0 to 0.1, and the number average molecular weight was between 5.5×10^4 and 11.9 × 10^4. The L-LA content in the ter- polymer increased from 1.1% to 34.7% when L-LA/PO molar feed ratio changed from 0.01 to 0.1. Introducing L-LA as the third comonomer could significantly improve the mechanical strength and thermal stability of PPC. For the terpolymer obtained from L-LA/PO molar feed ratio of 1：50, the elongation at break reached 40.5%, which is 3 times of that of pure PPC, and the thermal decomposition temperature increased by 32℃ compared with pure PPC.展开更多
The random ring-opening terpolymerization of CO_(2),epoxides,and lactones remains challenging,mainly because CO_(2)/epoxide copolymerization and lactone ring-opening polymerization typically proceed at very different ...The random ring-opening terpolymerization of CO_(2),epoxides,and lactones remains challenging,mainly because CO_(2)/epoxide copolymerization and lactone ring-opening polymerization typically proceed at very different rates.Herein,we report the preparation of novel statistical terpolymers with random distributions of carbonate and ester units(up to 40%junction units)via the one-pot reaction ofβ-propiolactone(BPL),epoxides,and CO_(2) under mild conditions using a binary catalyst system consisting of SalcyCo(III)OTs(Salcy=N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane;OTs=p-toluenesulfonate)and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.Since this catalytic system could yield similar reaction rates for alternating epoxide/CO_(2) copolymerization and BPL polymerization,terpolymers with nearly identical compositions were produced at various time points.CO_(2) played an important role in preventing intra-and/or intermolecular transesterification side reactions.Thereby,the terpolymerization proceeded in a controlled manner,allowing for the fine-tuning of molecular weight and composition.Two-dimensional nuclear magnetic resonance(NMR)analysis and density functional theory(DFT)calculations suggested that the nucleophilic attack of the coordinated BPL by carbonate ions cleaved the alkyl C–O bond predominantly rather than the acyl C(=O)–O bond,typically observable during the nucleophilic ring-opening polymerization of BPL.These findings have opened up a new avenue for preparing a broad family of biodegradable polymers with adjustable properties.展开更多
For the production of reactive polyurethane cross-linkinger and curing agents, 2, 4-diisocyanate toluene （TDI） terpolymer, which possesses the rigid structures of hexatomic ring and three reactive functional groups,...For the production of reactive polyurethane cross-linkinger and curing agents, 2, 4-diisocyanate toluene （TDI） terpolymer, which possesses the rigid structures of hexatomic ring and three reactive functional groups, was synthesized and characterized by the Fourier transform infrared （FFIR）, the gel permeation chromatography （GPC） and the chemical analysis methods. The reaction conditions were studied and optimized. A tracking research on the polymerization process of TDI was taken by using the GPC. The formation processes of the terpolymer, oligomers and higher-polymers were also dealt with. Results show that the TDI terpolymer can be prepared in the presence of Cat-3 catalyst and at the reaction temperature of （60 ±2）℃. The reaction time is short, its outcomes have narrow molecular weights distribution, namely molecular weights from 530 to 550, Mw/Mn =1.10, and the mass fraction of NCO is （25. 0 ± 0. 5）%. With the reaction time prolonging, however, TDI can be further higher-polymedzed to form higher-polymers. Benzoyl chloride （0. 4%, mass fraction）, as the stabilizing agent, can effectively inhibit the occurrence of higher-polymerization. The obtained TDI terpolymer can be stable for more than half a year.展开更多
Using supported multi-componem zinc dicarboxylate catalyst, poly（1,2-propylene carbonate-co-1,2-cyclohexylene carbonate） （PPCHC） was successfully synthesized from carbon dioxide （CO2） with propylene oxide （PO）...Using supported multi-componem zinc dicarboxylate catalyst, poly（1,2-propylene carbonate-co-1,2-cyclohexylene carbonate） （PPCHC） was successfully synthesized from carbon dioxide （CO2） with propylene oxide （PO） and cyclohexene oxide （CHO）. The conversion of epoxides dramatically increased up to 89.7% （yield： 384.2 g of polymer per g of Zn） with increasing reaction temperature from 60℃ to 80℃. The optimized reaction temperature is 80℃. The chemical structure, the molecular weight, as well as thermal and mechanical properties of the resulting terpolymers were investigated extensively. When CHO feed content （mol%） is lower than 10%, the PPCHC terpolymers have number average molecular weight （Ma） ranging from 102 × 10^3 to 202 × 10^3 and molecular weight distribution （MWD） values ranging from 2.8 to 3.5. In contrast to poly（propylene carbonate） （PPC）, the introduction of small amount of CHO leads to increase in the glass transition temperature from 38.0℃ to 42.6℃. Similarly, the mechanical strength of the synthesized terpolymer is greatly enhanced due to the incorporation of CHO. These improvements in mechanical and thermal properties are of importance for the practical application of PPC.展开更多
A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimeta...A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR,1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.展开更多
This contribution reports an efficient approach for preparing polycarbonate block terpolymers by immortal stepwise copolymerization of CO2 with different epoxides in the presence of enol chain transfer,mediated by rob...This contribution reports an efficient approach for preparing polycarbonate block terpolymers by immortal stepwise copolymerization of CO2 with different epoxides in the presence of enol chain transfer,mediated by robust cobalt catalyst systems consisting of the fluorine substituted salen Co(Ⅲ)NO3 or biphenol-linker bimetallic Co(Ⅲ)complex in conjunction with an ionic cocatalyst,PPNX(PPN=bis(triphenylphosphine)iminium,X=NO3–or 2,4-dinitrophenoxide).Various polycarbonate block terpolymers were obtained in perfectly unimodal distribution of their molecular weights with narrow polydispersity.They all possessed only one broad glass transition temperature,which could be adjusted by altering the length of different polycarbonate segments.展开更多
Photoinitiated crosslinking of ethylene-propylene-diene terpolymer （EPDM） blends filled with calcium carbonate, talc and calcined kaolin （CK） in the presence of benzil dimethyl ketal as photoinitiator and trimethy...Photoinitiated crosslinking of ethylene-propylene-diene terpolymer （EPDM） blends filled with calcium carbonate, talc and calcined kaolin （CK） in the presence of benzil dimethyl ketal as photoinitiator and trimethylolpropane triacrylate as crosslinker and their related properties have been studied by different analytical methods, The results from gel content and heat extension determination show that the efficiency ofphotocrosslinking of EPDM increases with increasing the content of diene and its molecular weight. The EPDM blends with 100 phr different inorganic fillers can be photocrosslinked to gel content of above 60% by 5 s UV-irradiation under optimum conditions. Under the same conditions of irradiation, the orders of photocrosslinking rate and final gel content are EPDM/CaCO3 〉 EPDM/talc 〉 EPDM/CK. The data from thermogravimetric analysis, dynamic mechanical thermal analysis, electrical properties, mechanical tests and scanning electron microscopy show that UV irradiation crosslinking apparently enhances the thermal stability, mechanical properties and electrical properties of the photocrosslinked EPDM/inorganic filler samples. Although the attenuated total-reflection FTIR data show that inorganic fillers can promote the surface photo-oxidation of EPDM/inorganic filler samples with increasing the irradiation time, the above related properties of the photocrosslinked EPDM blends irradiated within 5 s are enough to satisfy many applications in the cable industry.展开更多
4-tert-butylstyrene-EPDM-divinylbenzene graft terpolymer (PBED) was prepared by graft cross-polymerization in toluene using BPO as an initiator. The gel-PBED and solPBED were isolated from extraction of tetrahydrofura...4-tert-butylstyrene-EPDM-divinylbenzene graft terpolymer (PBED) was prepared by graft cross-polymerization in toluene using BPO as an initiator. The gel-PBED and solPBED were isolated from extraction of tetrahydrofuran (THF), and then they were identified by IR spectroscopy. The maximum oil-absorptivity of gel-PBED produced from the optinum reaction conditions was 8 420% but its swelling rate was very low. The highest oil-absorptivity of photocrosslinked sol-PBED film was 5 800%. Although its oil absorbency was not as high as gel-PBED' s, swelling rate was higher than that of gelPBED and was suitable for commercial purpose. After swelling in oil, neither gel PBED nor photocrosslinked sol-PBED film having high oil-absorptivity had sufficient mechanical strength to be taken out of oil wholly. As is known, composite technique is one of the useful methods for reinforcing them. Fibers, sponges and non-woven cloths were used as reinforcers or supporters in this work. Oil-absorptivities and swelling kinetics were evaluated by method ASTM (F726 - 81 ) and an experimental equation. The mechanical properties and the morphologies of some composites were measured by tensile tester and SEM , respectively.展开更多
Amphiphilic terpolymer（TPR） exhibits good film-forming behavior on pure water observed by means ofπ-A isotherms.To gain insight into physical properties of TPR,the films have been deposited on silicon substrates at...Amphiphilic terpolymer（TPR） exhibits good film-forming behavior on pure water observed by means ofπ-A isotherms.To gain insight into physical properties of TPR,the films have been deposited on silicon substrates at different surface pressure by Langmuir-Blodgett（LB） technique.It was found that the increase in peak intensities of stretching mode was due to orderly packing of the films.The contact angles increased with increasing surface pressure,indicating an increase in hydrophobicity due to dense packing of chains of TPR.The cyclic voltammetric measurements indicated that TPR showed good current shielding effect for electron-transfer.In a word,LB films of TPR can produce a variety of structures with varied topography,enabling us to control not only the functionality of the surface,but also the interfacial transport characteristics.展开更多
The mechanical properties and the crystal morphological structures of the dynamically photocrosslinked polypropylene(PP)/ethylene-propylene-diene terpolymer(EPDM) blends have been studied by means of mechanical tests,...The mechanical properties and the crystal morphological structures of the dynamically photocrosslinked polypropylene(PP)/ethylene-propylene-diene terpolymer(EPDM) blends have been studied by means of mechanical tests, wide-angle X-ray diffraction(WAXD), and differential scanning calorimetry(DSC). The dynamically photocrosslinking of the PP/EPDM blends can improve the mechanical properties considerably, especially the notched Izod impact strength at low temperatures. The data obtained from the mechanical tests show that the notched Izod impact strength of the dynamically photocrosslinked sample with 30% EPDM at -20 ℃ is about six times that of the uncrosslinked sample with the same EPDM component. The results from the gel content, the results of WAXD, and the DSC measurements reveal the enhanced mechanism of the impact strength for the dynamically photocrosslinked PP/EPDM blends as follows: (1) There exists the crosslinking of the EPDM phase in the photocrosslinked PP/EPDM blends; (2) The β-type crystal structure of PP is formed and the content of α-type crystal decreases with increasing the EPDM component; (3) The graft copolymer of PP-g-EPDM is formed at the interface between the PP and EPDM components. All the above changes of the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of the PP/EPDM blends at low temperatures.展开更多
The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence...The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.展开更多
A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)(PEO_(113)-b-PVBC_(130)-b-Pt BS_(x)or E_(113)V_(130)T_(x))triblock terpolymers with various lengths x(=20,33,66,104,215...A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)(PEO_(113)-b-PVBC_(130)-b-Pt BS_(x)or E_(113)V_(130)T_(x))triblock terpolymers with various lengths x(=20,33,66,104,215)of Pt BS block were synthesized via a two-step reversible addition-fragmentation chain transfer(RAFT)polymerization.The E_(113)V_(130)T_(x)triblock terpolymers were non-crystalline because the PVBC and Pt BS blocks strongly hindered the crystallization of PEO block.The effects of Pt BS block length x on the phase structures of E_(113)V_(130)T_(x)triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering(SAXS)and transmission electron microscopy(TEM).It was found that with increasing x from20 to 215,the phase structure of E_(113)V_(130)T_(x)triblock terpolymers became more ordered and changed from disordered structure,hexagonally-packed cylinder(HEX),hexagonally perforated layer(HPL),to lamellar(LAM)phase structures.Temperature-variable SAXS measurements showed that the HEX,HPL and LAM phase structures obtained for E_(113)V_(130)T_(66),E_(113)V_(130)T_(104)and E_(113)V_(130)T_(215)by thermal annealing,respectively,were thermodynamically stable in the temperature range of 30-170℃.展开更多
The transition behaviour of the blends of isotactic polypropylene (i-PP) with ethylene-propylene terpolymer (EPDM) containing 42 wt% propylene was investigated by dynamic mechanical analysis technique (DMA). Owing to ...The transition behaviour of the blends of isotactic polypropylene (i-PP) with ethylene-propylene terpolymer (EPDM) containing 42 wt% propylene was investigated by dynamic mechanical analysis technique (DMA). Owing to its high propylene content, EPDM is compatible with i-PP to some degree. The interaction between the two components was strengthened. As expected, for partially compatible system the glass transition temperature of i-PP in the blends shifted to lower temperature. It was found that there existed two transitions, αEPDM and βEPDM, for the EPDM used in this work. The former was considered to be the glass transition of the random chain segments of EPDM, while the latter the local motion of the long ethylene sequences in EPDM. The unusual transition behaviour of αEPDM in the blends was explained in terms of the greater thermal expansion of EPDM and the compatibility of the two components. On the other hand, the βEPDM changed with the composition of the blends in a regular manner.展开更多
Copolycondensation mechanisms for the terpolyester system from m-methoxy-p-acetoxybenzoic acid,p-acetoxybenzoic acid and poly(ethylene terephthalate)are first investigatedby high resolution proton NMR spectroscopy at ...Copolycondensation mechanisms for the terpolyester system from m-methoxy-p-acetoxybenzoic acid,p-acetoxybenzoic acid and poly(ethylene terephthalate)are first investigatedby high resolution proton NMR spectroscopy at 400 MHz.A series of reactivity ratios of thecopolycondensation reactions are given.The results shown that the m-methoxy-p-acetoxybenzoicacid tends to homopolymerize,while the p-acetoxybenzoic acid,and the ethylene terephthalate unitespecially,tend to copolymerize with the m-methoxy-p-acetoxybenzoic acid.展开更多
The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above a...The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.展开更多
基金the Project of Science and Technology Program of Guangzhou City of China(Project Nol.201604020004)for the financial support to this research.
文摘Gelation adversely affects the aqueous adiabatic terpolymerization of acrylamide (AM), sodium acrylate (NaAA),and 2-methacryloyloxyethyl trimethylammonium chloride (DMC). Here, the mixed dispersants sorbitan monooleate (Span80) and polyoxyethylene sorbitan monooleate (Tween 80) were introduced to the terpolymerization system in an attemptto mitigate the gel effect. This enabled the preparation of high-performance amphoteric polyacrylamides, which werecharacterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. The influences of the dispersanttype and content as well as the hydrophilic-lipophilic balance (HLB) on the gel effect were examined, and the mechanismunderlying the suppression of the gel effect was considered. The obtained results indicated that the gel effect can beeffectively mitigated using an aqueous adiabatic terpolymerization system containing mixed Span 80/Tween 80 dispersantsat various contents. In particular, mixed dispersant contents of 0.6%–0.8% with HLB values of 5.0–6.0 afforded the optimalperformance (e.g., high viscosity, fast aqueous dissolution time, and the like).
文摘Teroolymerization of enichlorohydrin（ECH）-maleic anhydride（MAn）-carbon dioxide（CO;） was carried out by using Y(P;);-Al（i-Bu）;as catalyst for the first time.The terpolymersobtained were characterized by IR and;H-NMR.It was foundthat the composition of the teroolymer was influenced by theaddition mode,initial monomer charge ratio,etc.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.51703228,51673201,21835006)Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-201903)。
文摘Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.
文摘Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one electron-accepting monomer, i.e. acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in dioxane as diluent at 65°C for 150 min has been studied. The kinetic expression is Rpα[I]0.8[Sty] 1.2[VA] 1.4 [AN]1.2. The terpolymer composition was determined by the Kelen-Tüdos method. The values of reactivity ratios using r1 (Sty + VA) = 0.1 and r2 (AN) = 0.005. The overall activation energy is 46 kJ●mol●L–1. The formation of terpolymer is confirmed by the FTIR spectra showing bands at 3030 cm–1, 1598 cm–1, and 2362 cm–1, confirming the presence of phenyl, acetoxy and nitrile group respectively. The terpolymer has been characterized by 1H-Nuclear Magnetic Resonance, 13C-Nuclear Magnetic Resonance. The Differential Scanning Calorimetric curve shows the Tg of the polymer as 149.5°C. A scanning electron microscope confirms the polymer to be phosphorus free. Electron.Spin.Resonance spectra confirms phenyl radical responsible for initiation.
文摘A convenient one-pot terpolymerization of CO2, propylene oxide （PO）, and L-lactide （L-LA） in short polymerization time （10 h or shorter） to afford poly（propylene carbonate-lactide） with excellent mechanical property and thermal stability using Y（CCl3COO）3-ZnEtz-glycerin rare-earth ternary catalyst is reported. The yield of the co- polymerization was between 69.7 and 111.7 g/（g Zn）, corresponding to L-LA/PO molar feed ratio varying from 0 to 0.1, and the number average molecular weight was between 5.5×10^4 and 11.9 × 10^4. The L-LA content in the ter- polymer increased from 1.1% to 34.7% when L-LA/PO molar feed ratio changed from 0.01 to 0.1. Introducing L-LA as the third comonomer could significantly improve the mechanical strength and thermal stability of PPC. For the terpolymer obtained from L-LA/PO molar feed ratio of 1：50, the elongation at break reached 40.5%, which is 3 times of that of pure PPC, and the thermal decomposition temperature increased by 32℃ compared with pure PPC.
基金supported by the National Natural Science Foundation of China(NSFCgrant nos.21690073 and 21920102006)the Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R14).
文摘The random ring-opening terpolymerization of CO_(2),epoxides,and lactones remains challenging,mainly because CO_(2)/epoxide copolymerization and lactone ring-opening polymerization typically proceed at very different rates.Herein,we report the preparation of novel statistical terpolymers with random distributions of carbonate and ester units(up to 40%junction units)via the one-pot reaction ofβ-propiolactone(BPL),epoxides,and CO_(2) under mild conditions using a binary catalyst system consisting of SalcyCo(III)OTs(Salcy=N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane;OTs=p-toluenesulfonate)and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.Since this catalytic system could yield similar reaction rates for alternating epoxide/CO_(2) copolymerization and BPL polymerization,terpolymers with nearly identical compositions were produced at various time points.CO_(2) played an important role in preventing intra-and/or intermolecular transesterification side reactions.Thereby,the terpolymerization proceeded in a controlled manner,allowing for the fine-tuning of molecular weight and composition.Two-dimensional nuclear magnetic resonance(NMR)analysis and density functional theory(DFT)calculations suggested that the nucleophilic attack of the coordinated BPL by carbonate ions cleaved the alkyl C–O bond predominantly rather than the acyl C(=O)–O bond,typically observable during the nucleophilic ring-opening polymerization of BPL.These findings have opened up a new avenue for preparing a broad family of biodegradable polymers with adjustable properties.
文摘For the production of reactive polyurethane cross-linkinger and curing agents, 2, 4-diisocyanate toluene （TDI） terpolymer, which possesses the rigid structures of hexatomic ring and three reactive functional groups, was synthesized and characterized by the Fourier transform infrared （FFIR）, the gel permeation chromatography （GPC） and the chemical analysis methods. The reaction conditions were studied and optimized. A tracking research on the polymerization process of TDI was taken by using the GPC. The formation processes of the terpolymer, oligomers and higher-polymers were also dealt with. Results show that the TDI terpolymer can be prepared in the presence of Cat-3 catalyst and at the reaction temperature of （60 ±2）℃. The reaction time is short, its outcomes have narrow molecular weights distribution, namely molecular weights from 530 to 550, Mw/Mn =1.10, and the mass fraction of NCO is （25. 0 ± 0. 5）%. With the reaction time prolonging, however, TDI can be further higher-polymedzed to form higher-polymers. Benzoyl chloride （0. 4%, mass fraction）, as the stabilizing agent, can effectively inhibit the occurrence of higher-polymerization. The obtained TDI terpolymer can be stable for more than half a year.
基金financially supported by the China High-Tech Development 863 Key Program(No.2010AA0349)Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme(2010)+1 种基金Guangdong Province Sci.&Tech.Bureau(Key Strategic Project Grant No.2008A080800024)Guangdong Education Bureau(Key Project) and Chinese Universities Basic Research Founding
文摘Using supported multi-componem zinc dicarboxylate catalyst, poly（1,2-propylene carbonate-co-1,2-cyclohexylene carbonate） （PPCHC） was successfully synthesized from carbon dioxide （CO2） with propylene oxide （PO） and cyclohexene oxide （CHO）. The conversion of epoxides dramatically increased up to 89.7% （yield： 384.2 g of polymer per g of Zn） with increasing reaction temperature from 60℃ to 80℃. The optimized reaction temperature is 80℃. The chemical structure, the molecular weight, as well as thermal and mechanical properties of the resulting terpolymers were investigated extensively. When CHO feed content （mol%） is lower than 10%, the PPCHC terpolymers have number average molecular weight （Ma） ranging from 102 × 10^3 to 202 × 10^3 and molecular weight distribution （MWD） values ranging from 2.8 to 3.5. In contrast to poly（propylene carbonate） （PPC）, the introduction of small amount of CHO leads to increase in the glass transition temperature from 38.0℃ to 42.6℃. Similarly, the mechanical strength of the synthesized terpolymer is greatly enhanced due to the incorporation of CHO. These improvements in mechanical and thermal properties are of importance for the practical application of PPC.
文摘A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR,1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.
基金financially supported by the National Natural Science Foundation of China (No. 21690073)the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT-17R14)
文摘This contribution reports an efficient approach for preparing polycarbonate block terpolymers by immortal stepwise copolymerization of CO2 with different epoxides in the presence of enol chain transfer,mediated by robust cobalt catalyst systems consisting of the fluorine substituted salen Co(Ⅲ)NO3 or biphenol-linker bimetallic Co(Ⅲ)complex in conjunction with an ionic cocatalyst,PPNX(PPN=bis(triphenylphosphine)iminium,X=NO3–or 2,4-dinitrophenoxide).Various polycarbonate block terpolymers were obtained in perfectly unimodal distribution of their molecular weights with narrow polydispersity.They all possessed only one broad glass transition temperature,which could be adjusted by altering the length of different polycarbonate segments.
基金supported by the National Natural Science Foundation of China(No.20704040)
文摘Photoinitiated crosslinking of ethylene-propylene-diene terpolymer （EPDM） blends filled with calcium carbonate, talc and calcined kaolin （CK） in the presence of benzil dimethyl ketal as photoinitiator and trimethylolpropane triacrylate as crosslinker and their related properties have been studied by different analytical methods, The results from gel content and heat extension determination show that the efficiency ofphotocrosslinking of EPDM increases with increasing the content of diene and its molecular weight. The EPDM blends with 100 phr different inorganic fillers can be photocrosslinked to gel content of above 60% by 5 s UV-irradiation under optimum conditions. Under the same conditions of irradiation, the orders of photocrosslinking rate and final gel content are EPDM/CaCO3 〉 EPDM/talc 〉 EPDM/CK. The data from thermogravimetric analysis, dynamic mechanical thermal analysis, electrical properties, mechanical tests and scanning electron microscopy show that UV irradiation crosslinking apparently enhances the thermal stability, mechanical properties and electrical properties of the photocrosslinked EPDM/inorganic filler samples. Although the attenuated total-reflection FTIR data show that inorganic fillers can promote the surface photo-oxidation of EPDM/inorganic filler samples with increasing the irradiation time, the above related properties of the photocrosslinked EPDM blends irradiated within 5 s are enough to satisfy many applications in the cable industry.
文摘4-tert-butylstyrene-EPDM-divinylbenzene graft terpolymer (PBED) was prepared by graft cross-polymerization in toluene using BPO as an initiator. The gel-PBED and solPBED were isolated from extraction of tetrahydrofuran (THF), and then they were identified by IR spectroscopy. The maximum oil-absorptivity of gel-PBED produced from the optinum reaction conditions was 8 420% but its swelling rate was very low. The highest oil-absorptivity of photocrosslinked sol-PBED film was 5 800%. Although its oil absorbency was not as high as gel-PBED' s, swelling rate was higher than that of gelPBED and was suitable for commercial purpose. After swelling in oil, neither gel PBED nor photocrosslinked sol-PBED film having high oil-absorptivity had sufficient mechanical strength to be taken out of oil wholly. As is known, composite technique is one of the useful methods for reinforcing them. Fibers, sponges and non-woven cloths were used as reinforcers or supporters in this work. Oil-absorptivities and swelling kinetics were evaluated by method ASTM (F726 - 81 ) and an experimental equation. The mechanical properties and the morphologies of some composites were measured by tensile tester and SEM , respectively.
基金financially supported by 863 project(No.2007AA03Z316)National Natural Science Foundation of China(Nos.20977021 and 30970829)+1 种基金National Natural Science Foundation of Heilongjiang Province (No.E-2007-12)State Key Lab of Urban Water Resource and Environment(No.2010TS07)
文摘Amphiphilic terpolymer（TPR） exhibits good film-forming behavior on pure water observed by means ofπ-A isotherms.To gain insight into physical properties of TPR,the films have been deposited on silicon substrates at different surface pressure by Langmuir-Blodgett（LB） technique.It was found that the increase in peak intensities of stretching mode was due to orderly packing of the films.The contact angles increased with increasing surface pressure,indicating an increase in hydrophobicity due to dense packing of chains of TPR.The cyclic voltammetric measurements indicated that TPR showed good current shielding effect for electron-transfer.In a word,LB films of TPR can produce a variety of structures with varied topography,enabling us to control not only the functionality of the surface,but also the interfacial transport characteristics.
文摘The mechanical properties and the crystal morphological structures of the dynamically photocrosslinked polypropylene(PP)/ethylene-propylene-diene terpolymer(EPDM) blends have been studied by means of mechanical tests, wide-angle X-ray diffraction(WAXD), and differential scanning calorimetry(DSC). The dynamically photocrosslinking of the PP/EPDM blends can improve the mechanical properties considerably, especially the notched Izod impact strength at low temperatures. The data obtained from the mechanical tests show that the notched Izod impact strength of the dynamically photocrosslinked sample with 30% EPDM at -20 ℃ is about six times that of the uncrosslinked sample with the same EPDM component. The results from the gel content, the results of WAXD, and the DSC measurements reveal the enhanced mechanism of the impact strength for the dynamically photocrosslinked PP/EPDM blends as follows: (1) There exists the crosslinking of the EPDM phase in the photocrosslinked PP/EPDM blends; (2) The β-type crystal structure of PP is formed and the content of α-type crystal decreases with increasing the EPDM component; (3) The graft copolymer of PP-g-EPDM is formed at the interface between the PP and EPDM components. All the above changes of the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of the PP/EPDM blends at low temperatures.
基金Projects supported by the Science Fund of the Chinese Academy of Sciences
文摘The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.
基金the National Natural Science Foundation of China(Nos.21875214,21674097 and 21774111)for financial support。
文摘A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)(PEO_(113)-b-PVBC_(130)-b-Pt BS_(x)or E_(113)V_(130)T_(x))triblock terpolymers with various lengths x(=20,33,66,104,215)of Pt BS block were synthesized via a two-step reversible addition-fragmentation chain transfer(RAFT)polymerization.The E_(113)V_(130)T_(x)triblock terpolymers were non-crystalline because the PVBC and Pt BS blocks strongly hindered the crystallization of PEO block.The effects of Pt BS block length x on the phase structures of E_(113)V_(130)T_(x)triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering(SAXS)and transmission electron microscopy(TEM).It was found that with increasing x from20 to 215,the phase structure of E_(113)V_(130)T_(x)triblock terpolymers became more ordered and changed from disordered structure,hexagonally-packed cylinder(HEX),hexagonally perforated layer(HPL),to lamellar(LAM)phase structures.Temperature-variable SAXS measurements showed that the HEX,HPL and LAM phase structures obtained for E_(113)V_(130)T_(66),E_(113)V_(130)T_(104)and E_(113)V_(130)T_(215)by thermal annealing,respectively,were thermodynamically stable in the temperature range of 30-170℃.
基金This Paper was presented before the Symposium on Polymers,Chengdu,P.R.China.Nov,14-18,1989
文摘The transition behaviour of the blends of isotactic polypropylene (i-PP) with ethylene-propylene terpolymer (EPDM) containing 42 wt% propylene was investigated by dynamic mechanical analysis technique (DMA). Owing to its high propylene content, EPDM is compatible with i-PP to some degree. The interaction between the two components was strengthened. As expected, for partially compatible system the glass transition temperature of i-PP in the blends shifted to lower temperature. It was found that there existed two transitions, αEPDM and βEPDM, for the EPDM used in this work. The former was considered to be the glass transition of the random chain segments of EPDM, while the latter the local motion of the long ethylene sequences in EPDM. The unusual transition behaviour of αEPDM in the blends was explained in terms of the greater thermal expansion of EPDM and the compatibility of the two components. On the other hand, the βEPDM changed with the composition of the blends in a regular manner.
文摘Copolycondensation mechanisms for the terpolyester system from m-methoxy-p-acetoxybenzoic acid,p-acetoxybenzoic acid and poly(ethylene terephthalate)are first investigatedby high resolution proton NMR spectroscopy at 400 MHz.A series of reactivity ratios of thecopolycondensation reactions are given.The results shown that the m-methoxy-p-acetoxybenzoicacid tends to homopolymerize,while the p-acetoxybenzoic acid,and the ethylene terephthalate unitespecially,tend to copolymerize with the m-methoxy-p-acetoxybenzoic acid.
基金Supported by the Foundation of Educational Ministry of China.
文摘The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.
