• International Journal of Advanced Culture Technology
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• v.3 no.2
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• pp.100-109
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• 2015

Environmental problems from petroleum-based plastic wastes have been rapidly increasing in recent years. The alternative solution is focus on the development of environmental friendly plastic derived from renewable resource. Poly(lactic acid) (PLA) is a biodegradable polymer synthesized from biomass having potential to replace the petroleum-based non-degradable polymers utilizations. PLA can be synthesized by two methods: (1) ring-opening of lactide intermediate and (2) direct polycondensation of lactic acid processes. The latter process has advantages on high yields and high purity of polymer products, materials handling and ease of process treatments. The polymerization process of PLA synthesis has been widely studied in a laboratory scale. However, the mass scale production using direct polycondensation of lactic acid has not been reported. We have investigated the kinetics and scale-up process of direct polycondensation method to produce PLA in a pilot scale. The order of reaction is 2 and activation energy of lactic acid to lactic acid oligomers is 61.58 kJ/mol. The pre-polymer was further polymerized in a solid state polymerization (SSP) process. The synthesized PLA from both the laboratory and pilot scales show the comparable properties such as melting temperature and molecular weight. The appearance of synthesized PLA is yellow-white solid powder.

• Polymer Science and Technology
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• v.8 no.4
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• pp.384-390
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• 1997

• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.1029-1031
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• 2003

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.331-331
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• 2006

Polylactic acid (PLA) is a promising polymer because it can be derived from renewable resources and provides a biodegradable alternative to petrochemical based polymers. This research aims to synthesize PLA, through direct polycondensation and also tries to avoid the occurrence of separation by-product and the use of catalysts in the process. The polymerization of lactic acid was done at three different temperatures $150^{\circ}C,\;180^{\circ}C\;and\;200^{\circ}C$ for 90 h without catalysts and organic solvent. The proposed process provides results that are comparable to those that incorporate catalysts; during polymerization temperature was $180^{\circ}C$ the molecular weight of PLA obtained reached 42448 Da. The thermal properties of PLA analysis by Differential Scanning Calorimetry (DSC).

• Elastomers and Composites
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• v.54 no.4
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• pp.321-329
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• 2019

A series of poly(hyroxyamide)s (PHAs) was prepared by direct polycondensation reaction of 4,4'-(2,3-pyridinedioxy)dibenzoic acid and/or isophthalic acid with 3,3'-dihydroxybenzidine. The yield percentages of the products were high, and the inherent viscosities of the polymer in DMAc solution at 35℃ were 0.31-0.59 dL/g. All PHA polymers were found to be soluble in polar aprotic solvents such as DMAc, DMSO, NMP, and DMF. On the other hand, LiCl was required to dissolve IPHA-1 in aprotic solvents. Poly(benzoxazole)s (PBOs) were partially soluble in conc-H₂SO₄; IPBO-4, -5, and -6 were partially soluble in NMP only when LiCl was added to the solution, and the solution was heated. The PBO polymers showed a maximum weight loss in the temperature range of 654-680℃, and the char yields at 900℃ under nitrogen atmosphere exceeded 63%.

• Macromolecular Research
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• v.17 no.11
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• pp.901-906
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• 2009

Several aromatic optically active polyamides (PA)s were synthesized from 5-(2-phthalimidiylpropanoylamino)isophthalic acid with various aromatic diamines via direct polycondensation with triphenyl phosphite and pyridine in the presence of calcium chloride and N-methyl-2-pyrrolidone under microwave irradiation and conventional heating conditions. Under the optimized conditions, the reaction mixture was irradiated for 2 min. with a 100% irradiation power (900 W). The resulting polymers were obtained in high yield and moderate inherent viscosity ranging from 0.35 to 0.60 dL/g. All synthesized polymers showed excellent solubility in amide-type solvents. Thermogravimetric analysis revealed a 10% weight loss temperature and char yield at $600^{\circ}C$ in a nitrogen atmosphere of > $350^{\circ}C$ and > 58%, respectively, which suggests that the resulting PAs have good thermal stability.

• Macromolecular Research
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• v.17 no.10
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• pp.739-745
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• 2009

N,N'-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-L-amino acids 3a-g were synthesized by the condensation reaction of bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 1 with two equimolars of Lalanine 2a, L-valine 2b, L-leucine 2c, L-isoleucine 2d, L-phenyl alanine 2e, L-2-aminobutyric acid 2f and L-histidine 2g in an acetic acid solution. Seven new poly(amide-imide)s PAIs 5a-g were synthesized through the direct polycondensation reaction of seven chiral N,N'-(bicyclo[2,2,2]oct-7-ene-tetracarboxylic)-bis-L-amino acids 3a-g with bis(3-amino phenyl) phenyl phosphine oxide 4 by two different methods: direct polycondensation in a medium consisting of N-methyl-2-pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride ($CaCl_2$/pyridine (py), and direct polycondensation in a tosyl chloride (TsCl)/pyridine (py)/N,N-dimethylformamide (DMF) system. The polymerization reaction produced a series of flame-retardant and thermally stable poly(amide-imide)s 5a-g with high yield. The resulted polymers were fully characterized by FTIR, $^1H$ NMR spectroscopy, elemental analyses, inherent viscosity, specific rotation and solubility tests. Data obtained by thermal analysis (TGA and DTG) revealed that the good thermal stability of these polymers. These polymers can be potentially utilized in flame retardant thermoplastic materials.

• Elastomers and Composites
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• v.44 no.4
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• pp.436-441
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• 2009

Semi flexible polyesters containing aromatic rings and pentamethylene groups in the main chain were synthesized by direct polycondensation reaction. The structures of these polymers were investigated by $^1H$-NMR and FT-IR and the phase transition behavior was characterized with DSC, TGA and crossed polarizing microscope. Inherent viscosities ($\eta_{inh}$) of polymers measured in phenol/p-chlorophenol/1,1,2,2-tetrachloroethane were between 0.46 and 1.30 dL/g. As increasing the linearlity of rigid moieties in polyster, melting transition temperatures ($T_m$) increased and solubilities in organic solvents decreased. P-H, P-mH and P-4H of the polymers formed turbid melts that showed stir-opalescence and nematic phase at the broad anisotropic region, However, P-R, P-C and P-2B did not exhibit any textures related to the liquid crystallinity.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1028-1034
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• 1999

Poly(lactic acid) is expected to be one of the most promising biodegradable polymers. However, the high molecular weight polymer could be obtained by ring-opening polymerization process conventionally, which raises the production cost and decreases the final yield. In this study, linear and star-shaped poly(L-lactic acid)s were prepared by direct solution polycondensation method and their physical and thermal properties were examined. Tin compounds were found to be effective catalyst for the preparation of high molecular weight polymers. When 0.2g (0.5 wt % of monomer) of $SnCl_2$ and 100 mL of p-xylene were used, the polymer yield and molecular weight were relatively high. As a means to obtain higher molecular weight polymer easily in the direct polycondensation system, dipentaerythritol(dipet) or pentaerythritol(pet) was introduced as a multifunctional branching monomer to provide a star-shaped poly(lactic acid). Moderately high molecular weight polymers with the inherent viscosity values up to 1.14 dL/g(weight-average molecular weight of about 140000 by GPC) were obtained and could be cast strong and transparent films.

• Elastomers and Composites
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• v.52 no.2
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• pp.143-153
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• 2017

Herein we studied the characterization of the PBO films formed via solution casting and thermal cyclization of poly(o-hyroxyamide)s(PHAs) that were synthesized by direct polycondensation of 3,3'-dihydroxybenzidine with 4,4'-(2,3-quinoxalinedioxy) dibenzoic acid and/or 4,4'-(2,3-pyridinedioxy) dibenzoic acid. All the PHAs exhibited inherent viscosities in the range of 0.55~0.84 dL/g in DMAc solution. The copolymers, CPH-2-5, were partially soluble in less polar solvents like pyridine and THF. However, all the PBOs were not soluble in polar solvents, but only partially soluble in sulfuric acid. The temperatures corresponding to 10% weight loss of the PBOs with increasing content of quinoxalinedioxy unit were higher than those of the PHAs, and the char yields at $900^{\circ}C$ in $N_2$, tensile strength, and initial modulus of the PBOs were 1.1~1.3 times, 1.2~1.8, and 1.6~3.3 times higher, respectively, than those of the PHAs. The LOI value of CPB-2 was 38.5%, while that of CPB-1 was the highest at 40.0%. The LOI test confirmed that excellent flame retardants were synthesized.