• 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.

• 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%.

• 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.

• 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.50 no.2
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• pp.138-145
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• 2015

A series of wholly aromatic poly(hydroxyamide)s(PHAs), containing varying amounts of 2,6-dimethylphenoxy group and quinoxaline ring in the main chain, were synthesized by a direct polycondensation method. The inherent viscosities of the PHAs in either DMAc or DMAc/LiCl solution at $35^{\circ}C$ were found to be in the range of 1.02~1.90 dL/g. In the solubility study, we observed that PHA 1, PHA 2, and PHA 3 were dissolved in aprotic solvents such as DMAc, NMP, DMF, and DMSO with LiCl on heating; however, PHA 4, PHA 5, and PHA 6 could be dissolved in aprotic solvents on heating without LiCl. For poly(benzoxazole)s(PBOs), the 10% and maximum weight loss temperatures were in the range of $582{\sim}622^{\circ}C$ and $630{\sim}659^{\circ}C$, respectively. Residues of PBOs at $900^{\circ}C$ were found to be relatively high, which were in the range of 65.3~70.8%.

• Elastomers and Composites
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• v.53 no.3
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• pp.141-149
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• 2018

A series of aromatic poly(o-hydroxyamide)s (PHAs) were synthesized by the direct polycondensation reaction of 4,4′-(2,3-quinoxalinedioxy) dibenzoic acid and/or 4,4′-(2,3-pyridinedioxy) dibenzoic acid with bis(o-aminophenol) including 2,2-bis-(amino-4-hydroxyphenyl)hexafluoropropane. The PHAs exhibited inherent viscosities in the range of 0.17-0.35 dL/g at $35^{\circ}C$ in a DMAc solution. These polymers showed low inherent viscosities and yielded brittle films. All the PHAs showed excellent solubility in aprotic solvents such as DMAc, DMSO, NMP, and DMF at room temperature and in less polar solvents such as pyridine and THF. However, all the PBOs were only partially soluble in $H_2SO_4$. The PBOs exhibited 10% weight loss at temperatures in the range of $537-551^{\circ}C$. The maximum weight loss temperature increased with an increase in the content of the quinoxaline-containing monomer. The residue of the PBOs showed a weight loss of 45.8-56.7% at $900^{\circ}C$ in a nitrogen atmosphere.

• Elastomers and Composites
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• v.51 no.3
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• pp.195-205
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• 2016

A series of aromatic poly(hydroxyamide)s (PHAs) containing varying oligo(oxyethylene) substituents and 1,3-phenylene imide ring unit in the main chain were synthesized by the direct polycondensation reaction. The inherent viscosities of the PHAs exhibited in the range of 0.89~1.12 dL/g in DMAc or DMAc/LiCl solution. The PH-2~5 copolymers were easily soluble in strong aprotic solvents: DMAc, NMP, DMSO etc. and the PH-5 copolymer was soluble in less polar solvents such as m-creasol and pyridine with LiCl salt on heating. However, all PBOs were quite insoluble in other solvents, but only partially soluble in sulfuric acid. All copolymers (PH-2~5) could afford the flexible and tough films by solution casting. We identified that the PHAs were converted to the PBOs by the thermal cyclization reaction in the range of $200{\sim}380^{\circ}C$. The 10% weight loss temperatures and char yields of the PBOs were recorded in the range of $382{\sim}647^{\circ}C$ and 38.7~73.1% values at $900^{\circ}C$. The tensile strength and initial modulus of the PH-5 in the copolmers showed the highest values of 2.46 GPa and 49.55 MPa, respectively. The LOI values of the PHAs were in the range 26.6~29.0%, and increased with increasing 1,3-phenylene imide ring unit.

• Elastomers and Composites
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• v.50 no.3
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• pp.175-183
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• 2015

A series of fluorinated aromatic poly(hydroxyamide)s (PHAs) were synthesized by direct polycondensation of diacides containing 2,6-dimethylphenoxy group and quinoxaline ring in the main chain with 2,2-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane. The PHAs had relatively low inherent viscosities in the range of 0.35~0.43 dL/g at $35^{\circ}C$ in DMAc solution. All PHAs exhibited excellent solubility in aprotic solvents such as NMP, DMAc, DMF and DMSO as well as in common organic solvents such as pyridine, THF, and m-cresol at room temperature. However, the poly(benzoxazole)s (PBOs) were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid. The PBOs showed glass transition temperatures between 233 and $284^{\circ}C$ by DSC and maximum weight loss temperatures in the range of $536-546^{\circ}C$ by TGA.

• Elastomers and Composites
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• v.55 no.3
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• pp.205-214
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• 2020

A series of wholly aromatic polyhyroxyamide (PHA) copolymers were prepared by direct polycondensation reaction of isophthalic acid and diacids containing bulky units with 3,3'-dihydroxybenzidine. The inherent viscosities of the PHAs measured at 35℃ in DMAc solution were in the range of 0.31-0.56 dL/g. The solubility study revealed that the PHAs were readily soluble in aprotic solvents such as, dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) at room temperature and in less polar solvent such as pyridine. However, the polybenzoxazole (PBO) copoymers were quite insoluble in all organic solvents except partially soluble in concentrated sulfuric acid and partially soluble in NMP containing LiCl. The PBO copolymers showed maximum weight loss temperature in the range of 593-632℃ and high char yields in the range of 65.0-71.2% at 900℃ in a nitrogen atmosphere.