The first example of the copolymerization of cyclic acid anhydrides with oxetane by bulky titanium bisphenolates

The copolymerization of oxetane with glutaric anhydride was found to proceed with bulky titanium bisphenolate ( 1 ) as the initiator. The ¹H NMR spectrum of the produced copolymer shows that the copolymer contains both alternating units and oxytrimethylene units in the polymer main chain. 1 was also effective for the copolymerization of oxetane with other cyclic acid anhydrides, affording the corresponding copolymers. With the titanium bisalkolate complex ( 4 ), a copolymer rich in alternating sequences was obtained.     

Poly(1,3-cyclohexadiene-alt-α-fluoroacrylonitrile): Synthesis and structural analysis of a new alternating copolymer

Poly(1,3-cyclohexadiene-alt-α-fluoroacrylonitrile) [poly(1,3-CHD/α-FAN)], an alternating copolymer of α-fluoroacrylonitrile and 1,3-cyclohexadiene has been prepared in bulk using varied monomer feed ratios and AIBN as initiator at 65°C. Elemental and ¹H-NMR analyses indicate that the copolymer contains an equimolar composition of α-FAN and 1,3-CHD as observed for alternating copolymers with donor-acceptor polymerizations. A 2-D ¹H-COSY NMR experiment indicates that the copolymer contains 1,4-linkages across the cyclohexene unit while more reliable ¹³C-NMR spectra suggests the copolymer to contain both 1,2- and 1,4-linkages. Poly(1,3-CHD/α-FAN) exhibits improved thermal stability relative to the alternating copolymer of 1,3-CHD and α-chloroacrylonitrile due to a higher resistance to HF elimination relative to HCl elimination.     

二烷基锡聚合物的研究——Ⅲ.顺丁烯二酸二丁基锡酯与丙烯酸甲酯、丙烯酸丁酯的共聚合

Benzoyl peroxide (BPO) was used for initiator in copolymerization of dibutyltin maleate (DBTM, M₂) with methyl acrylate (MA, M₁) in benzene and the reactivity ratios of copolymerization r1 and r2 were found to be 12.67 and 0.03, respectively. But in copolymerization of DBTM (M₂) with butyl acrylate (BA, M₁) r1 and r2 were 11.1 and 0> respectively. The cc-polymerization conditions, such as amount of initiator, ratios of monomers and addition method of initiator were examined. Copolymers were characterized by ¹H-NMR,IR,elemental and TG analyses. MA-DBTM copolymer is a white and brittle solid, while BA-DBTM copolymer is a transparent elastomer at room temperature.     

Polymerization of ε-Caprolactone and its Copolymerization with γ-Butyrolactone using Metal Complexes

Solution polymerization of ε-caprolactone (ε-CL) was performed using four different initiators namely: tin(II) octanoate (Sn(Oct)₂)/ethanolamine, aluminium Schiff's base complex-HAPENAlOⁱPr, lithium diisopropyl amide (LDA) and aluminium isopropoxide. The reaction conditions varied with the initiator used. LDA gave rise to the most rapid polymerization with the highest amount of cyclic species as detected by ¹³C NMR. However, no cyclic species were detected when HAPENAlOⁱPr was used as initiator. The tin(II) octanoate/ethanolamine system lead to an α,ω-dihydroxy-polycaprolactone (PCL). The copolymerization of ε-CL was then performed with the hard to oligomerize γ-butyrolactone using the four initiators. GPC (Gel Permeation Chromatography) analyses showed the formation of copolymers. The highest incorporation of polybutyrolactone (PBL) in the copolymer was obtained using HAPENAlOⁱPr as evidenced by ¹H NMR. ¹³C NMR indicated the presence of pseudoperiodic random copolymers with short blocks of PCL whose block length varied with initiator used. The longest and shortest block length were obtained using Sn(Oct)₂ and HAPENAlOⁱPr respectively as calculated from ¹³C NMR. The reactivity ratios were determined using the Finemann-Ross method at low conversion with HAPENAlOⁱPr as initiator. The values obtained, r_CL = 19.4 and r_BL = 0.11, confirmed the presence of long blocks of CL units in the copolymer.     

Radical copolymerization of cyclic diarsine with vinyl monomers

1,2,4,5‐Tetramethyltetrahydrodiarsenine ( 1 ), a cyclic diarsine compound, was stirred with styrene and a catalytic amount of 2,2′‐azobisisobutyronitrile (AIBN) as a radical initiator at 80 °C for 8 h in toluene to give a copolymer containing arsenic atoms in the backbone. The gel permeation chromatography (GPC) chromatogram of the copolymer showed a single peak. The number‐average molecular weight of the copolymer was estimated to be more than 10,000 by GPC analysis (CHCl₃, polystyrene standards). The structure of the copolymer was confirmed by the ¹H NMR and ¹³C NMR spectra. According to the integral ratio of peaks in the ¹H‐NMR spectrum, the content of 1 in the copolymer was smaller compared to the monomer feed ratio of 1 . Radical copolymerization of 1 with methyl methacrylate also provided the corresponding copolymer in the presence of AIBN, whereas copolymerization with vinyl acetate yielded no polymeric material. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3023–3028, 2004     

Study on biodegradable polymers: synthesis and characterization of poly(DL-lactic acid-co-l-lysine) random copolymer

Poly(DL-lactic acid-co-l-lysine) (PLAL) random copolymer was obtained by copolymerization of amino acid-N-carboxy anhydride with lactic acid anhydrosulphite in the presence of an initiator. The structures of the poly(DL-lactic acid-co-ε-cbz-l-lysine) and PLAL were characterized by IR, ¹H-NMR, ¹³C-NMR and elemental analysis. Different initiators were used to initiate the ring-opening copolymerization. Good agreement between calculated and actual compositions was observed in most cases when using dibutylzinc as initiator. The solubility of PLAL was discussed.     

The preparation,characterization, and application of cellulose–MMA graft copolymers. I. The aqueous-based preparation of cellulose–MMA graft copolymers

Cellulose-MMA graft copolymers have been produced using aqueous-based, Ce(IV)-initiated and periodate-initiated systems and also photochemical initiation. The reaction variables studied include the effect on grafting of varying the MMA monomer concentration, the initiator type and concentration, and also the reaction time. Of the three initiator types examined, the Ce (IV)-initiated and the photochemically-initiated systems are comparable in their effects on graft copolymer formation. Concurrent homopolymer formation was in the region of 50% by weight. Periodate-initiation leads to less efficient grafting of MMA onto cellulose, although homopolymer formation is also lower (typically <20% by weight). The characterization of the copolymeric products through their properties as solids and, as their carbanilated derivatives, through their solution properties has been undertaken. Values of the activation onergy of decomposition (E_A) of the cellulose-MMA graft copolymers decrease with increasing MMA content, ranging between 227 and 155kJ mol^?1. There is also a dependence on initiator type and grafting reaction conditions used (E_A (cellulose wood pulp) = 239 kJ mol^?1; E_A (PMMA) = 115 kJ mol^?1). Quantitative zeta-potential (ζ) determinations for cellulose-MMA graft copolymer samples produce negative surface charge density (σ) values. At a comparable MMA grafting level of 70–80%, values are of the order: photochemical (?730 esu/cm²) > periodate (?470 esu/cm²) > Ce (IV)-initiation (?351 esu/cm²). Characterization of carbanilate solutions (by rheological examination) and of dry, carbanilate films (by study of surface wetting behavior) highlighted differences in the physical conformation of copolymers prepared by the different initiation routes. The highly degradative effect on cellulose of a periodate initiator, in comparison with the Ce (IV)-initiation system, is reflected in significantly reduced molar mass values (typically, M_n 65,000 as opposed to 130,000 for Ce (IV)-initiated graft copolymer carbanilates).     

Metal-Containing initiator Systems. XXXVI. Synthesis of Block Copolymer of Methyl Acrylate and α-Methylbenzyl Methacrylate with Binary Initiator System of Cobaltocene and Bis(ethyl acetoacetato)copper(II)

Polymerizations of methyl acrylate (MA) and (DL)-α-methyl-benzyl methacrylate (MBMA) with binary initiator system of cobaltocene [Co(C₅H₅)₂] and bis(ethyl acetoacetato)copper(II) [Cu(eacac)₂] were studied in acetonitrile at 25°C. The molecular weight of the polymers obtained by MA was found to increase with time in the early stage of polymerization. Although MBMA was also polymerized by this system, asymmetric selective polymerization was not induced in the presence of (-)-sparteine. The synthesis of the block copolymer of MA and MBMA was attempted by using this initiator system. The block copolymer was obtained in 90% yield in the polymerization of MBMA with a polymer radical which prepared from MA with this system for 1 day. The yield of the block copolymer depended on the prepolymeriza-tion time of MA by this system. The resulting block copolymer was characterized by IR, ¹H-NMR, and gel-permeation chromatography.     

Spectral and chemical determination of copolymer composition of poly (butyl acrylate-co-glycidyl methacrylate) from emulsion polymerization

Batch emulsion polymerization was used for preparing poly(butyl acrylate-co-glycidyl methacrylate) with different copolymer compositions at 75 °C with potassium persulfate as an initiator. Solubility and gel content of the prepared copolymers were studied. Four different spectral (¹H-NMR and FTIR) and chemical (elemental analysis and titration) methods were used to determine the copolymer composition. The epoxy was used as a key functional group, particularly in FTIR and titration methods of quantification. Results obtained from the chemical methods showed good agreement with those of the spectral methods. Effects of some probable phenomena occurring during copolymerization were investigated to account for differences of data obtained from the different analytical methods. Finally, the methods were compared and ¹H-NMR and elemental analysis were recognized as preferred approaches for the copolymer composition determination.     

Soluble hyperbranched polymer through initiator-fragment incorporation radical copolymerization of ethylene glycol dimethacrylate and α-ethyl β-N-(α-methylbenzyl) itaconamate in benzene

The copolymerizations of ethylene glycol dimethacrylate (EGDM) with α-ethyl β-N-(α^′-methylbenzyl) itaconamates (RS- and S-EMBIs) derived from (RS)- and (S)-α-methylbenzylamines were conducted at 70 and 80 °C in benzene using dimethyl 2,2^′-azobisisobutyrate (MAIB) of high concentration as initiator. The copolymerization of EGBM (0.20 mol/l) and RS-EMBI (0.50 mol/l) with MAIB (0.50 mol/l) proceeded homogeneously without any gelation in benzene to give benzene-soluble copolymer in a yield of 55% based on the total weight of EGDM, RS-EMBI and MAIB. The copolymer was soluble in acetone, ethyl acetate, chloroform, tetrahydrofuran (THF), toluene, N,N-dimethylformamide and insoluble in n-hexane, methanol, dimethyl sulfoxide, and water. The copolymerization system involved ESR-observable propagating radicals derived from EGDM and RS-EMBI, of which the total concentration increased with time in spite of the homogeneous system. The copolymer consisted of EGDM unit (25 mol%), RS-EMBI unit (45 mol%), and methoxycarbonylpropyl group as MAIB-fragment (30 mol%). Such a large number of initiator fragments were incorporated into the copolymer as terminal groups through initiation and primary radical termination, leading to a conclusion that the copolymer was of hyperbranched structure (initiator-fragment incorporation radical copolymerization). Radius of gyration (R_g) and M_w of the copolymer by light scattering measurements in THF were 17.8 nm and 7.7 × 10⁵, respectively. Comparison of these values with those (R_g=27.6 nm and M_w=2.9×10⁵) of linear polystyrene also supported the above conclusion. Reflecting the compact hyperbranched structure, the intrinsic viscosity ([η]) of the copolymer was very low, [η]=0.075 dl/g at 25 °C in THF. The individual copolymer molecules were observed as a nanoparticle by TEM. The copolymerization of EGDM and S-EMBI with MAIB in benzene also gave similar results.     

Reactivities of monomers toward the 2-cyano-2-propyl radical by NMR study of end groups in copolymers

Copolymerizations of styrene (S) with methyl methacrylate (MMA) and methacrylonitrile (MAN) at 60°C were performed with azoisobutyronitrile as initiator, enriched in its methyl groups with ¹³C. From the NMR spectrum of a copolymer it is possible to compare the numbers of initiator fragments attached to the two types of monomer unit; this information can be used to study the competition between the monomers for capture of the radicals formed from the initiator. The velocity constants for addition of the 2-cyano-2-propyl radical to S, MMA, and MAN are in the proportions 1:0.56:0.34; it is concluded that polar effects are of some importance in the reactions of the radical.     

Block and star block copolymers by mechanism transformation. II. Synthesis of poly(DOP‐b‐St) by combination of ATRP and CROP

Styrene underwent the ATRP process using an asymmetric difunctional initiator, 2‐hydroxylethyl 2′‐bromobutyrate in combination with CuBr and 2,2′‐bipyridine (bpy). Polystyrene with hydroxyl and bromine groups at each end of the polymer (HO‐PSt‐Br) was obtained, and used as a chain‐transfer agent in the cationic ring‐opening polymerization of 1,3‐dioxepane with triflic acid as initiator. The structures of the polymerization products were analyzed by ¹H NMR and GPC analyses, indicating the formation of block copolymer. The molecular weight distribution of the block copolymer was relatively narrow and the molecular weight of the polyDOP block was high. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 436–443, 2000     

Synthesis of polymeric hydrogels containing sulfonate group

The copolymerization of n‐dodecyl poly(oxyethylene)600 maleate (DPM‐13) with 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) has been studied in the range from 25 to 90 % DPM‐13 in the feed stock. The reactivity ratio has been determined for DPM‐13/AMPS copolymer. The copolymer compositions, utilized for determining the reactivity ratio, have been determined from nitrogen content and ¹H nuclear magnetic resonance (NMR) analysis. The copolymer was characterized by IR and ¹H‐NMR. Crosslinked poly(AMPS) and DPM‐13/AMPS copolymers were prepared in water in the presence of potassium persulfate as initiator, and 1,1‐trimethylolpropane trimethacrylate (TPT) as hexafunctional crosslinker. The percentage of TPT was varied from 0.4 to 2 wt% to study the effect of TPT content on the swelling properties of the prepared polymers. Copyright © 1999 John Wiley & Sons, Ltd.     

SYNTHESIS OF BLOCK COPOLYMER FROM 5,6 -BENZO-2-METHYLENE-1,3-DIOXEPANE AND METHYL ACRYLATE VIA ATOM TRANSFER RADICAL POLYMERIZATION

Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1, 3-dioxepane) (PMA-b-PBMDO) was synthesized by two-step atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl α-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) withterminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in theATRP of BMDO. The Structure of block copolymer was characterized by ~1H-NMR spectroscopy. Molecular weight andmolecular weight distribution were determined on a gel permeation chromatograph (GPC).     

POLYMERIZATION OF ETHYLENE METHYL PHOSPHATE IN THE PRESENCE OF SODIUM POLY(ETHYLENE GLYCOL)ATE*

Poly(ethylene methyl phosphate)-poly(ethylene glycol)-poly(ethylene methyl phosphate) triblockcopolymers carrying hydroxyl group at both chain ends were synthesized with sodium poly(ethyleneglycol)ate as initiator. The effects of the factors such as solvent, amount of the initiator and reaction timewere investigated. The copolymers were characterized by IR, ~1H-NMR, ~1H{~(31)P}-NMR, ~(13)C-NMR, ~(31)P{~1H}-NMR, and DSC. High molecular weight of the copolymer and high yield of the polymerization were achievedwithin 3 min at 25℃. The polymerization process was studied by ~(31)P{~1H}-NMR and transesterification wasfound during longer polymerization time.     

INTERPOLYMER ASSOCIATION OF ACRYLAMIDE COPOLYMERS WITH POLY(ETHYLENEIMINE): STABILITY,THERMODYNAMIC PARAMETERS,AND THEIR CORRELATION WITH THE COPOLYMER MICROSTRUCTURE

Acrylamide/vinyl acetate and acrylamide/vinyl propionate copolymers were prepared by solution polymerization using benzoyl peroxide as the initiator. The copolymer composition was determined from the percent nitrogen in the copolymers.

The stability constants and related thermodynamic parameters (e.g., ΔG°, ΔH°, and ΔS°,) of the interpolymer complexes with Poly(ethyleneimine) were determined by using Osada's method. These parameters have been correlated with the sequence distribution of monomer units in the copolymer chains which were obtained from ¹³C{¹H} NMR spectroscopy. The sequence distribution of the comonomer units in the copolymer chains influence the association between the copolymers and the polyelectrolyte which is reflected on the stability of the interpolymer complexes.     

Effect of grafted methyl methacrylate on the catalytic hydrogenation of natural rubber

The graft copolymerization of methyl methacrylate onto natural rubber was carried out by using a cumene hydroperoxide redox initiator. The graft copolymer was purified by extraction and then hydrogenated in the presence of OsHCl(CO)(O₂)(PCy₃)₂. The graft copolymer and hydrogenated product were characterized by proton nuclear magnetic resonance (¹H NMR). The rate of hydrogenation was investigated using a gas-uptake apparatus. The hydrogenation was observed to be inverse first-order with respect to rubber concentration. The addition of a small amount of poly(methyl methacrylate) demonstrated a beneficial effect on the hydrogenation of the grafted copolymer.     

四配位硅单体及其共聚物的制备和结构表征

研究了直接从无定形二氧化硅出发, 与乙二醇、氢氧化钾反应, 生成高反应活性的五配位硅钾化合物, 并以此为原料与含活泼氯的3-氯丙烯反应制备出含双键官能团的四配位硅单体. 讨论了合成单体的条件如温度、反应时间、反应物浓度、溶液pH值及溶剂等因素的影响. 然后以该四配位硅单体与甲基丙烯酸甲酯(MMA)在偶氮二异丁腈(AIBN)作引发剂下进行自由基聚合得到支链含硅共聚物. 并借助于红外光谱(IR)、核磁共振(¹³C和¹H, ²⁹Si)、能谱元素分析对合成的单体进行了结构表征; 用红外光谱(IR)、热失重谱(TG)、差示扫描量热谱(DSC)、凝胶渗透色谱法(GPC)等现代测试手段对支链含硅共聚物进行了结构表征及热性能分析. IR表明四配位硅单体在1646 cm^－1处是C＝C的伸缩振动吸收峰, 在共聚物中此峰消失; TG表明共聚物在249.6 ℃才开始失重, 552 ℃有机部分失重完毕; GPC分析表明共聚物的数均分子量为8.7万.     

Strontium‐based initiator system for ring‐opening polymerization of cyclic esters

An amino isopropoxyl strontium (Sr‐PO) initiator, which was prepared by the reaction of propylene oxide with liquid strontium ammoniate solution, was used to carry out the ring‐opening polymerization (ROP) of cyclic esters to obtain aliphatic polyesters, such as poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). The Sr‐PO initiator demonstrated an effective initiating activity for the ROP of ε‐caprolactone (ε‐CL) and L‐lactide (LLA) under mild conditions and adjusted the molecular weight by the ratio of monomer to Sr‐PO initiator. Block copolymer PCL‐b‐PLLA was prepared by sequential polymerization of ε‐CL and LLA, which was demonstrated by ¹H NMR, ¹³C NMR, and gel permeation chromatography. The chemical structure of Sr‐PO initiator was confirmed by elemental analysis of Sr and N, ¹H NMR analysis of the end groups in ε‐CL oligomer, and Fourier transform infrared (FTIR) spectroscopy. The end groups of PCL were hydroxyl and isopropoxycarbonyl, and FTIR spectroscopy showed the coordination between Sr‐PO initiator and model monomer γ‐butyrolactone. These experimental facts indicated that the ROP of cyclic esters followed a coordination‐insertion mechanism, and cyclic esters exclusively inserted into the Sr–O bond. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1934–1941, 2003     

Ring-opening copolymerization of α-chloromethyl-α-methyl-β-propionolactone with ε-caprolactone

α-Chloromethyl-α-methyl-β-propionolactone (CMMPL) has been copolymerized with ε-caprolactone (CL) using a wide range of feed compositions and aluminium triisopropoxide [Al(OⁱPr)₃] as an initiator. Random copolymers of CMMPL with CL were obtained. The pendant chloromethyl groups of the copolymer were converted to quaternary ammonium salts by reaction with pyridine, resulting in an increased hydrophilicity of the copolymers.