• International Journal of Advanced Culture Technology
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• 제3권2호
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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.

• 한국고분자학회지:고분자과학과기술
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• 제8권4호
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• pp.384-390
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• 1997

• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.1029-1031
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• 2003

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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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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• 제54권4호
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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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• 제17권11호
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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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• 제17권10호
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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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• 제44권4호
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• pp.436-441
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• 2009

주사슬에 방향족 고리와 펜타메틸렌 그룹을 포함하고 있는 반유연성 폴리에스터가 direct polycondensation 에 의하여 합성되었다. 합성된 중합체의 구조는 $^1H$-NMR과 FT-IR에 의해, 상전이거동에 대해서는 DSC, TGA 및 직교된 편광현미경에 의하여 관찰되었다. 합성된 중합체의 고유점성도 ($\eta_{inh}$)는 0.46에서 1.30 dL/g 사이의 값으로 측정되었고, 분자사슬 중 강직사슬그룹의 선형성이 클수록 용융전이온도 ($T_m$)는 높았으며, 용해도 조사에 사용된 유기용매에 대한 용해도는 감소되었다. 그리고, 중합체들 중 P-H, P-mH, P-4H는 넓은 비등방성 영역에서 열방성 네마틱 액정상을 나타내었으나 P-R, P-C, P-2B는 액정상을 나타내지 않았다.

• 공업화학
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• 제10권7호
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• pp.1028-1034
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• 1999

p-Xylene을 용매로 사용하고, 몇 가지 다른 종류의 촉매를 사용하여 직접 축중합에 의해 직쇄형 폴리락트산 합성 실험을 하였다. 그 중 우수한 활성을 보인 촉매는 주석(Tin)계 촉매이었다. 촉매의 양과 용매의 양을 변화시켜 중합반응을 한 결과, 촉매 0.2g (0.5 wt % 모노머), 용매 100 mL 수준에서 보다 높은 분자량의 중합체를 얻을 수 있었으며, 이때 대수점성도 ${\eta}_{inh}$는 0.72 dL/g(중량평균분자량(GPC)=70500)이었다. 직접중합 반응 시스템에서 분자량을 더욱 향상시키기 위해 branching 모노머로서 다가알콜인 dipentaerythritol(dipet) 또는 pentaerythritol(pet)을 소량 도입하여 스타형 폴리락트산을 합성하였으며, 직쇄형에 비해 분자량 분포가 좁고, 향상된 분자량(최고 ${\eta}_{inh}$ = 1.14, ${\bar{Mw}}$ = 143,200)을 얻을 수 있었다. Dipet의 함량이 0.05~0.2 wt %일 때 보다 높은 분자량의 폴리락트산을 얻을 수 있었으며, 얻어진 중합체의 열적성질은 직쇄형에 비해 큰 차이가 없었다. 얻어진 고분자량의 중합체로부터 투명하고 강인한 필름을 성형할 수 있었다.

• Elastomers and Composites
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• 제52권2호
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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.