Impact modification of lactic acid based poly(ester-urethanes) by blending

Branched biodegradable poly(ester-urethane)(PEU) was blended with two elastic biodegradable copolymers in proportions 5, 10, 15, and 20 wt % to investigate their effect on this hard and brittle polymer. Copolymer of L-lactide and ϵ-caprolactone, P(L-LA50/CL50), was synthesized by ring-opening polymerization and the other elastic poly(L-lactic acid-co-ϵ-caprolactone)urethane, P(LA50/CL50)U, was prepared by direct polycondensation of L-lactic acid and ϵ-caprolactone, followed with urethane bonding. In addition, four elastic biodegradable copolymers, three of them P(L-LA/CL) and one P(LA/CL)U, were blended with linear PEU to investigate their modifying effect on PEU. These compositions studied were 10, 15, and 20 wt % of P(L-LA40/CL60), P(L-LA60/CL40), P(L-LA80/CL20), and P(LA40/CL60)U in PEU. Blending was done in a batch mixer. PEU became more ductile when blended with P(L-LA/CL) and P(LA/CL)U, and its impact resistance improved markedly. In general, an addition of 15 wt % of copolymer appeared to give the most desirable mechanical properties. Moreover, the more L-lactide in the P(L-LA/CL) copolymer, the better was the miscibility of the blends, as shown by dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). One P(L-LA/CL) was also blended with poly(DL-lactide) (PDLLA) to see if the dispersion of rubbery copolymer particles was the same in PDLLA and PEU. A well-known commercial nonbiodegradable rubber [styrene/ethylene/butylene copolymer (SEBS)] was blended with linear PEU to compare its effect on impact strength. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1335–1343, 1997     

Ternary‐phase poly(ester‐urethane)/elastomer/filler composites

Impact‐modified and reinforced composites, consisting of biodegradable poly(ester‐urethane) (PEU), poly(L ‐lactic acid‐co‐ϵ‐caprolactone‐urethane) elastomer, and various organic and inorganic fillers, were prepared by melt blending, and their properties were investigated. The impact strength increased with elastomer addition, and the addition of particulate or fibrous fillers as a third component increased the stiffness. Therefore, the balance between the impact strength and stiffness of the amorphous PEU was significantly improved. Composites with elastomer and 15 wt % particulate fillers, that is, wollastonite, Aktisil, and talc, showed excellent impact strength. However, effective impact modification was lost in highly constrained systems. Dynamic mechanical thermal analysis confirmed the phase separation of elastomer and showed a marked increase in the glass‐transition temperature for the PEU matrix in binary blends with wollastonite, talc, and glass fiber. Scanning electron microscopy studies showed good adhesion of the components. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1531–1539, 2001     

Lactic acid based poly(ester-urethane)s: The effects of different polymerization conditions on the polymer structure and properties

A two-step process for lactic acid polymerization is studied: in the first step the lactic acid is condensation-polymerized to a low-molecular-weight hydroxyl-terminated prepolymer; and then the molecular weight is raised by joining prepolymer chains together using diisocyanate as the chain extender. The resulting polymer is a thermoplastic poly(ester-urethane). In this study, we synthesized three different prepolymers and used three different diisocyanates as chain extenders. All of the prepolymers were hydroxyl-terminated, and their weight average molecular weights were 5,500 g/mol, 11,900 g/mol, and 26,000 g/mol. One of the diisocyanates was aliphatic, and the other two were stiff cycloaliphatic diisocyanates. The results indicate that of the tested diisocyanates, high weight average molecular weight can be achieved only by using aliphatic 1,6-hexamethylene diisocyanate. The cycloaliphatic diisocyanates produced poly(ester-urethane)s with weight average molecular weights which were quite low, but due to the stiffness of the polymer chains the glass transition temperatures can be as high as 60°C. The 1,6-hexamethylene diisocyanate (HDI) results also indicate that the molecular weight and network formation can be controlled independently by the amount of diisocyanate used and the polymerization conditions. Only the poly(ester-urethane)s which were produced with HDI had good mechanical properties, while the stiff diisocyanates produced very brittle polymers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 865–873, 1997     

Lactic acid based poly(ester-urethanes): Use of hydroxyl terminated prepolymer in urethane synthesis

We studied a two step process for lactic acid polymerization: in the first step, the lactic acid is condensation polymerized to a low molecular weight hydroxyl terminated prepolymer and then the molecular weight is raised by joining prepolymer chains together using diisocyanate as the chain extender. The resulting polymer is a thermoplastic poly(ester-urethane). The polymer samples were carefully characterized with ¹³C-NMR, GPC, DSC, and IR. The results indicate that high conversions of lactic acid can be achieved, as well as independent control of the stereostructure, long chain branches, molecular weight average, and molecular weight distribution. Lactic acid is converted into a poly(ester-urethane) with a weight average molecular weight as high as 390,000 g/mol and a glass transition temperature of 53.7°C. The analyzed content of the monomer in the prepolymer is less than 1 mol % and the lactide content 2.4 mol %, while the final poly(ester-urethane) is essentially monomer and lactide free. The mechanical properties of the poly(ester-urethane) are comparable to those of polylactides. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1091–1100, 1997     

Crystallization and melting behavior of biodegradable poly(ethylene succinate‐co‐6 mol % butylene succinate)

The crystallization, melting behavior, and spherulitic growth kinetics of biodegradable poly(ethylene succinate‐co‐6 mol % butylene succinate) [P(ES‐co‐6 mol % BS)] were investigated and compared with those of the homopolymer poly(ethylene succinate) (PES) in this work. The crystal structure of P(ES‐co‐6 mol % BS) was the same as that of neat PES, but the crystallinity decreased slightly because of the incorporation of the butylene succinate content. The glass‐transition temperature decreased slightly for P(ES‐co‐6 mol % BS) compared to that for neat PES. The melting point of P(ES‐co‐6 mol % BS) decreased apparently; moreover, the equilibrium melting point was also reduced. Two melting endotherms were found for P(ES‐co‐6 mol % BS) after isothermal crystallization; this was ascribed to the melting, recrystallization, and remelting mechanism. The spherulitic growth rate of P(ES‐co‐6 mol % BS) was slower than that of neat PES at a given crystallization temperature. Both neat PES and P(ES‐co‐6 mol % BS) exhibited a crystallization regime II to III transition; moreover, the crystallization regime transition temperature of P(ES‐co‐6 mol % BS) shifted to a low temperature compared with that of neat PES. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blends of poly(2,6-dimethyl-1,4-phenylene oxide)/ poly(styrene-co-methacrylic acid)/ poly(ethyl methacrylate-co-4-vinylpyridine)

Summary The miscibility of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with poly(styrene-co-acrylic acid) (SAA) or poly(styrene-co-methacrylic acid) (SMA) containing respectively up to 22 mol % of acrylic or methacrylic acid was studied by Differential Scanning Calorimetry and viscosimetry. All PPO/SAA or PPO/SMA blends containing 60% or less by weight of PPO were miscible and showed only one glass transition temperature (Tg). Above 60% of PPO, two Tg's were however observed for the blends in which the acid content in the SAA or SMA reaches 20% or 12% by mole respectively; the higher Tg is slightly lower than the one of pure PPO, while the lower one corresponds to a miscible blend of lower content of PPO.A DSC study showed that depending on the blend ratio, two or three glass transition temperatures were observed when a copolymer of ethyl methacrylate containing 8 mol % of 4-vinylpyridine (EM4VP-8) was added to miscible PPO/SMA-12 blends. The PPO dissolution in the SMA-12 copolymer was affected by the specific interactions that occurred between this latter copolymer and the EM4VP-8.     

Inexpensive Fabrication and Characterization of Crystalline Poly(o-Anthranilic Acid-co-o-Phenylenediamine) Emeraldine Base/Bentonite Nanocomposites

Copolymers of o-anthranilic acid and o-phenylenediamine/hydrophilic bentonite nanocomposites were synthesized by 1:1 molar ratios of the respective monomers with different percentages of nanoclay through modified in situ chemical copolymerization. The results obtained were justified by measuring the Fourier transform infrared of poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites. Ultraviolet–visible spectra of poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were investigated. The thermal stability was studied, and it was found that poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were thermally more stable than pure copolymer. X-ray diffraction patterns of copolymer poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base and poly(o-anthranilic acid-co-o-phenylenediamine) emeraldine base/bentonite nanocomposites were studied.     

Studies on inherently radiopaque acrylate copolymers for biomedical applications

Poly(glycidyl methacrylate-co-ethyl methacrylate) and poly(glycidyl methacrylate-co-butyl methacrylate) random copolymers (with 50–50 mol % of monomers) were made radiopaque by grafting iodine moieties through the ring opening reaction of the epoxy groups. The percentage weight of grafted iodine in the copolymers was found to be as high as 19%. The iodinated copolymers showed higher glass transition temperature and thermal stability in comparison with the parent copolymers. Iodinated copolymer of poly(glycidyl methacrylate-co-ethyl methacrylate) has improved glass transistion temperature than iodinated poly(glycidyl methacrylate-co-butyl methacrylate). Radiographic analysis of these iodinated copolymers showed excellent radiopacity. The in vitro cytotoxicity tests revealed cytocompatibility with cells. These radiopaque copolymers are expected to find application as dental and orthopedic cements. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel blends of alternating propene-carbon monoxide copolymers and styrenic copolymers

Summary Alternating propene-carbon monoxide copolymers (P-CO) were melt-blended with polystyrene, poly(styrene-co-acrylonitrile) (SAN), and with poly(styrene-co-maleic anhydride) (SMA). P-CO forms homogeneously miscible blends with SAN containing 25 wt% AN at the investigated blend compositions. The transparent blends have single, intermediate glass transition temperatures that fit the Fox equation. The elastic properties of P-CO at room temperature disappear upon blending with SAN because the T _g is driven above RT. Polystyrene and SMA are not miscible with P-CO and form heterogeneous blends with two glass transitions. This demonstrates that both the polarity of the styrenic copolymer and the nature of the comonomer govern its phase behavior. Received: 14 January 1999/Revised version: 19 April 1999/Accepted: 19 April 1999     

Metal ion sorption properties of water-insoluble resins based on sodium styrene sulfonate and different comonomers

A set of water-insoluble resins based on sodium styrene sulfonate and different comonomers were synthesized. The resins poly(mono-2-(methacryloyloxy)ethyl succinate-co-sodium 4-styrene sulfonate) P(MOES-co-SSNa), poly(2-acrylamido glycolic acid-co-sodium 4-styrene sulfonate) P(AGA-co-SSNa), poly(acrylamide-co-sodium 4-styrene sulfonate) P(AAm-co-SSNa), and poly(2-(dimethylamine)ethyl acrylate-co-sodium 4-styrene sulfonate) P(DMAEA-co-SSNa) were synthesized by solution radical polymerization. The metal ion retention properties were studied by batch procedure for Cd(II), Zn(II), Pb(II), and Hg(II). Resins performance was compared with a poly(sodium 4-styrene sulfonate) (PSSNa) resin in order to evaluate the effect of comonomer on sorption properties. The effect of pH, time, temperature, and maximum retention capacity were studied. In addition, sorption experiments were carried out under competitive ion conditions to study the selectivity of resins. The resins P(AAm-co-SSNa) and P(AGA-co-SSNa), showed the most important differences compared with PSSNa resin, the former present higher sorption and the latter presented selectivity for Hg(II) at pH 2.     

Polychelates of poly(acrylic acid-co-acrylamide)with Cu(II), Co(II), and Ni(II) Synthesis and properties

SUMMARY Polychelates were obtained by addition of an aqueous solution of the poly(acrylic acid-co-acrylamide) to an aqueous solution of Cu(II), Co(II), and Ni(II). All the polychelates were insoluble in water and in common organic solvents. The polychelates were characterized by elemental analysis, FT-IR spectroscopy thermogravimetry, and showed tetrahedral arrangement for Co(II) and Ni(II). Magnetic and conductivity studies for all the polychelates were also carried out. The poly(acrylic acid-co-acrylamide) behaved as semiconductor. Received: 25 July 1997/Revised version: 1 December 1997/Accepted: 5 December 1997     

生物可降解聚乳酸的制备及其性能研究

以L-乳酸(LLA)为原料合成L-丙交酯,通过L丙交酯开环聚合制备高分子量的聚乳酸(PLA)。考察反应温度、反应时间以及催化剂用量对PLA的影响,获得优化的聚合工艺条件。GPC测得PLA的重均分子量可达21.9×104g/mol。FTIR和旋光度测试表明产物为聚L-乳酸(PLLA)。DSC和XRD测试证明:PLLA为结晶性材料,熔点为170℃,属于α'-和α-相共存的混合晶型。拉伸测试表明:高分子量的PLLA具有良好的力学性能。     

Synthesis and characterization of poly(urethane‐co‐imidine)s having pendent phenyl and benzylidene groups using bisphthalides,bislactones and blocked polyurethane prepolymers

Poly(urethane‐co‐imidine)s were prepared using amine blocked polyurethane (PU) prepolymer. The PU prepolymer was prepared by the reaction of poly(propylene glycol) (PPG₂₀₀₀) and 2,4‐tolylene diisocyanate (TDI) and end capped with N‐methyl aniline. The PU prepolymer was then reacted with bisphthalides and bislactones, until the evolution of carbon dioxide ceased. Polymerization reactions with bispthalides and bislactone took more time than with dianhydrides. Polymers were characterized by FTIR, GPC, TG and DSC analyses. Molecular weights of the poly(urethane‐co‐imidine)s were found to be lower than that of poly(urethane‐co‐imide)s. Compared to poly(urethane‐co‐imide)s all poly(urethane‐co‐imidine)s showed high glass transition temperature and crystallization peak in DSC. The thermal stability of the polyurethanes was found to increase with the introduction of imidine component. © 2001 Society of Chemical Industry     

Influence of Poly(L-lactic acid) Molecular Weight on the Encapsulation Efficiency of Urea in Microcapsule Using a Simple Solvent Evaporation Technique

Poly(L-lactic acid) microencapsulated urea was prepared in water-in-oil-in-water (W₁/O/W₂) system by the solvent evaporation technique. The influence of poly(L-lactic acid) molecular weight on the percent loading, encapsulation efficiency, and the microcapsule morphology was studied using poly(L-lactic acid) having different number average molecular weights (M_n). Using the higher M_n, the smoother shell with complete encapsulation microcapsules was formed. Moreover, the percent loading and encapsulation efficiency of urea also increased with the poly(L-lactic acid) molecular weight. At 80,000 g/mol of poly(L-lactic acid), the obtained microcapsule gave the highest both percent loading (32%) and encapsulation efficiency (56%). The urea control release study of the prepared microcapsules was implemented by in vitro testing. The encapsulated urea was gradually released from the microcapsules, approximately 53, 29, and 22% of poly(L-lactic acid) at 3,000, 30,000, and 80,000 g/mol, respectively, for a month. These results presented the possibility of the prepared poly(L-lactic acid) microcapsules-encapsulated urea for urea control release that could be utilized in agricultural applications.     

A new class of transparent polymeric materials. III. Miscible blends of poly(N-methylmaleimide-alt-isobutene) with poly(acrylonitrile-co-styrene) and the properties of the blends

The blend miscibility of poly(N-methylmaleimide-alt-isobutene) [poly-(MeMI-IB)] with poly(acrylonitrile-co-styrene) (SAN) was investigated by means of measurement of the glass transition temperature of the blends. Poly(MeMI-IB) was found to be miscible with SAN of a specific range of acrylonitrile (AN) contents in the copolymer to produce transparent moldings. The refractive index changed from 1.58 to 1.53 and the dispersion decreased with increasing the amount of poly(MeMI-IB) in the blends. The stress optical coefficient of poly(MeMI-IB) was found to be reduced by the blending of SAN. The glass transition temperature, flexural modulus, and surface hardness of the blends increased with an increase in the amount of poly(MeMI-IB) in the blend. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 925–929, 1997     

端羟基聚乳酸的扩链改性研究

乳酸与2,2-(1,3-亚苯基)-二恶唑啉(1,3-PBO)直接熔融缩聚成端羟基乳酸预聚物(PLBO),以聚乙二醇(PEG)和六亚甲基二异氰酸酯(HDI)聚合制得的端异氰酸酯基聚乙二醇(PEG-NCO)为扩链剂,以二月桂酸二丁基锡为催化剂,对PLBO进行扩链以制备可完全生物降解的聚酯氨酯(PEU)。采用乌氏黏度法、FTIR、DSC、XRD、TG、SEM等方法对各聚合物的结构和性能进行了表征。结果表明:以n(—OH)/n(—NCO)=1的比例投料、反应温度165℃、反应压力0.096 MPa、反应时间20 min为PLBO扩链反应的最佳条件;PEU的最大黏均分子量为44 700;PEG的引入使得PEU的玻璃化转变温度均小于PLA与PLBO,且柔韧性提高;PEU热稳定性提高,分解过程分为两步,第一步为PEU链段中的PLA失重,第二步为PEG-NCO链段的降解;PEU的结晶度降低,进一步说明扩链后聚合物的柔韧性增强。     

Synthesis and characterization of temperature‐responsive poly(vinyl alcohol)‐based copolymers

A poly(vinyl alcohol) (PVA)/sodium acrylate (AANa) copolymer was synthesized to improve the water solubility of PVA at the ambient temperature. Furthermore, a series of temperature‐responsive acetalyzed poly(vinyl alcohol) (APVA)‐co‐AANa samples of various chain lengths, degrees of acetalysis (DAs), and comonomer contents were prepared via an acid‐catalysis process. Fourier transform infrared and ¹H‐NMR techniques were used to analyze the compositions of the copolymers. The measurement of the turbidity change for APVA‐co‐AANa aqueous solutions at different temperatures revealed that the lower critical solution temperature (LCST) of the copolymers could be tailored through the control of the molecular weight of the starting PVA‐co‐AANa, DA, and comonomer ratios. Lower LCSTs were observed for APVA‐co‐AANa with a longer chain length, a higher DA, and fewer acrylic acid segments. In addition, the LCSTs of the APVA‐co‐AANa aqueous solutions appeared to be salt‐sensitive. The LCSTs decreased as the concentration of NaCl increased. Moreover, atomic force microscopy images of APVA‐co‐AANa around the LCST also proved the temperature sensitivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of novel biodegradable polymeric prodrugs containing 5‐fluorouracil and 4‐amino‐N‐(2‐pyrimidinyl) benzene sulfonamide terminal groups

To develop novel biodegradable polymeric prodrugs with target‐directing and drug‐active functional groups, a series of polymeric antitumor prodrugs containing sulfadiazine and 5‐fluorouracil terminal groups were prepared via the two‐step reaction of chlorinated poly(lactic acid) or chlorinated poly(lactic acid‐co‐glycolic acid) with potassium sulfadiazine (SF‐K) and 1,3‐dihydroxymethyl‐5‐fluorouracil. The synthesized polymers were characterized by means of infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, gel permeation chromatography, viscosity measurements, differential scanning calorimetry, and ultraviolet (UV) spectroscopy. The GA/LA value was varied, so that the effects of the comonomer content on the solubility, thermal properties, and degradable behaviors were examined respectively. It was found that introducing the GA units could increase the melting temperature (T_m), the hydrolytic degradation, and the hydrophilicity, while it decreased the glass transition temperature (T_g). The drug content of 5‐FU measured by UV spectra is 56.3 in maximum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Studies on comonomer compositional distribution and its effect on some physical properties of bacterial poly(3‐hydroxybutyric acid‐co‐3‐hydroxypropionic acid)

Comonomer compositional distribution of bacterially synthesized poly(3‐hydroxybutyric acid‐co‐3‐hydroxypropionic acid) [P(3HB‐co‐3HP)] was investigated via solvent/non‐solvent fractionation techniques. The result indicates the presence of extremely broad comonomer compositional distribution in the original bacterial product. Furthermore, utilizing compositionally fractionated bacterial copolyesters with much narrower comonomer compositional distributions, the 3HP comonomer content‐dependence of their thermal and crystallization behavior was studied by means of differential scanning calorimeter (DSC) and polarized optical microscopy and the results compared with those of unfractionated copolyesters. It was revealed that the physical features of the fractionated copolyester P(3HB‐co‐3HP)s strongly depends on the 3HP comonomer content. In addition, to clarify the effect of the compositional distribution on the properties of the unfractionated copolyester, the miscibility between bacterial poly(3‐hydroxybutyric acid) [P(3HB)] and two fractionated P(3HB‐co‐3HP) samples with 11.3 and 14.9% 3HP was investigated for blends obtained by solvent casting techniques. The evidence of thermal analysis and spherulitic growth rates imply miscibility of the P(3HB)/3HB‐rich P(3HB‐co‐3HP) binary blends. © 1999 Society of Chemical Industry     

Molten ring-open copolymerization of L-lactide and cyclic trimethylene carbonate

The biodegradable poly(L -lactide-co-trimethylene carbonate) [poly(LLA-co-TMC)] was synthesized by molten ring-open copolymerization and the structure and properties of the copolymer were investigated by GPC, NMR, FTIR, DSC, and Instron testing. The copolymer with a higher LLA content had a higher initial molecular weight (M_n), but a lower final M_n. In contrast, the copolymer with a higher TMC content had a lower initial M_n, but its M_n increased with increasing reaction time and TMC content. The glass transition temperature (T_g), the melting temperature (T_m) and the crystallinity of the copolymer decreased with increasing TMC content. The elongation of the copolymer significantly increased with increasing TMC content while the toughness passed through a maximum. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1429–1434, 1998