• 제목/요약/키워드: copolymerization kinetics

검색결과 17건 처리시간 0.02초

폴리부틸렌테레프탈레이트와 파라아세톡시벤조산의 용융공중합 속도론에 대한 고찰 (Kinetic Consideration of Melt-copolymerization of Poly(butylene terephthalate) (PBT) and p-Acetoxybenzoic Acid (ABA))

  • 김도경;박수영;박종래
    • 폴리머
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    • 제24권1호
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    • pp.16-22
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    • 2000
  • 폴리부틸렌테레프탈레이트 (poly(butylene terephthalate), PBT)와 파라아세톡시벤조산 (p-acetoxybenzoic acid, ABA)을 용융 에스테르 교환반응시킴으로써 주쇄 고분자에 강직한 벤젠고리가 도입된 poly(butylene terephthalate-co-oxybenzoate) (PBOT)를 합성하였다. PBT와 ABA를 다양한 조성비에서 중합하는 과정의 속도론적 고찰을 통해 ABA의 단독중합 속도상수와 PBT에의 공중합 속도상수 및 그 비를 구하였으며 각각의 활성화에너지를 구하였다. PBT와 ABA의 조성비를 4/6, 5/5, 6/4로 하고 온도를 각각 250, 260, 27$0^{\circ}C$로 하여 실험한 결과 공중합반응은 ABA함량이 낮고 또 그 전환율이 크지 않을 경우 의사 2차반응으로 볼 수 있었다. 이때의 공중합 속도에 대한 단독중합 속도의 비는 1.08에서 3.17사이의 값을 가졌으며, ABA함량과 온도가 높을수록 큰 값을 가졌다. 이로써 PBT/ABA계의 공중합은 반응온도가 높고 ABA의 조성비가 클수록 ABA의 블록성이 강해지는 경향을 나타내었다.

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연속반응기에서 ${\alpha}$-Methylstyrene과 Acrylonitrile 라디칼 공중합 속도론 (The Kinetics of Radical Copolyerization of ${\alpha}$-Methylstyrene with Acrylonitrile in a CSTR)

  • 김남석;박근호
    • 한국응용과학기술학회지
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    • 제19권1호
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    • pp.33-42
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    • 2002
  • Copolymerization of ${\alpha}$-Methylstyrene(AMS) with Acrylonitrile(AN) was carried out with benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a continuous stirred tank reactor. Reaction volume and residence time were 0.6 liters and 3 hours, respectively. The monomer reactivity ratios, $r_{AMS}$ and $r_{AN}$ determined by both the Kele$T{\"{u}}d\"{o}s$ method and the Fineman-Ross method were $r_{AMS}$=0.16(0.14), $r_{AN}$=0.04(0.06). The cross-termination factor ${\Phi}$ of the copolymer over the entire AMS composition ranged from 0.75 to 0.92. The ${\Phi}$ factors of poly(AMS-co-AN) were increased with increasing AMS content. The simulated conversions and copolymerization rates were compared with the experimental results. It was observed that the average time to reach dynamic steady-state was three times the residence time.

Poly(Styrene-co-2-Hydroxypropylacrylate)의 라디칼 공중합 및 열분해 속도론 (The Kinetics of Radical Copolymerization and Thremal Decoposition of Poly(Styrene-co-2- Hydroxypropylacrylate))

  • 김남석
    • 한국응용과학기술학회지
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    • 제26권2호
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    • pp.205-212
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    • 2009
  • Solution copolymerization of Styrene(St.) with 2-Hydroxypropylacrylate(2-HPA) was carried out with Benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a batch reactor. Reaction volume and reaction time were 0.3 liters, 8 hours respectively. The time to reach steady state was about the six time. The monomer reactivity ratios, $r_1$(St.) and $r_2$(2-HPA) were determined by both the Kelen-Tudos method and the Fineman-Ross method ; $r_1$(St.)=0.376(0.330), $r_2$(2-HPA)=0.408(0.778). The activation energy of thermal decomposition was in the range of $33{\sim}55kcal/mol$.

연속반응기에서 Styrene과 n-Butylmethacrylate의 용액 공중합의 속도론 (The Kinetics of Solution Copolymerization of styrene and n-Butylmethacrylate in a Continuous Stirred Tank Reactor(CSTR))

  • 김남석;설수덕
    • 공업화학
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    • 제8권3호
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    • pp.347-356
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    • 1997
  • 스티렌(St)과 n-부틸메타크릴레이트(n-BMA)를 용매인 톨루엔에서 과산화벤조일(BPO)를 개시제로 사용하여 $80^{\circ}C$에서 연속반응기를 사용하여 용액공중합을 행하였다. 반응물 부피, 체류시간은 각각 0.6L, 3시간으로 하였다. 단량체 반응성비 $r_1$(St)과 $r_2$(BMA)는 Kelen-Tudos방법 (또는 Fineman-Ross방법)으로 결정하였다. : $r_1$=0.75(0.67), $r_2$=0.61(0.56). 공중합체의 가교정지인자, $\phi$값은 스티렌의 전체 조송에 대해 0.44~0.78값을 가지고 공중합체내 스티렌 조송이 증가할수록 $\phi$값도 증가하고 있다. 스티렌과 부틸메타크릴레이트의 공중합반응은 2차 반응속도식에 따랐으며 시뮬레이션한 전환율과 공중합 속도를 실험결과와 비교하였다. 동족인 정상상태에 도달하는 평균시간은 체류시간의 3.5배였다.

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Poly(sodium acrylate-co-acrylamide-co-2-hydroxyethyl acrylate)의 제조와 고흡수 특성 (Preparation and Super-Water-Absorbency of Poly(sodium acrylate-co-acrylamide-co-2-hydroxyethyl acrylate))

  • Zhang Yuhong;Deng Min;He Peixin
    • 폴리머
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    • 제30권4호
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    • pp.286-292
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    • 2006
  • Super water-absorbent resins were prepared by inverse suspension copolymerization of sodium acrylate, acrylamide and 2-hydroxyethyl acrylate using N, N'-methylene-bis-acrylamide as cross-linker. For the suspension copolymerization, monohexadecyl phosphate was employed as the dispersing agent, cyclohexane as the dispersing medium and potassium persulfate as the initiator. The dependence of water-absorption capacity on the amount of crosslinking agent, oil/water ratio, degree of neutralization and the composition of the copolymer were systematically investigated. Furthermore, the swelling kinetics of the super water-absorbent copolymer was carried out. The absorption of the resins is more than 1800 g/g for deionized water and 100 g/g for 0.9% NaCl solution, respectively. The copolymers showed an increased salt resistance and enhanced water retention of soil.

Interchange Reaction Kinetics and Sequence Distribution of Liquid Crystalline Poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)

  • Rhee, Do-Mook;Ha, Wan-Shik;Youk, Ji-Ho;Yoo, Dong-Il
    • Fibers and Polymers
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    • 제2권2호
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    • pp.86-91
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    • 2001
  • Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) [copoly(ET/CPT)] was prepared using poly(ethylene terephthalate) (PET) as a flexible spacer, terephthalic acid (TPA), and chlorohydroquinone diacetate (CHQDA). All reactions involved in the copolymerization were investigated using some model compounds: TAP was used for acidolysis, diphenylethyl terephthalate (DPET) for interchange reaction between PET chains, and 야-o-chlorophenyl terephthalate (DOCT) and di-m-chlorophenyl terephthalate (DMCT) for interchange reaction between PET and rigid rodlike segments. Activation energies obtained for the acidolysis of PET with TPA and for interchange reaction of PET with DPET, DOCT, and DMCT were 19.8 kcal/mol, 26.5 kcal/mole, and 45.9 kcal/mole, respectively. This result supports that the copolymerization proceeds through the acidolysis of PET with TPA first and subsequent polycondensation between carboxyl end group and CHQDA or acetyl end group, which is formed from the reaction of CHQDA and TPA. Also, it was found that ester-interchange reaction can be influenced by the steric hindrance. Copoly(ET/CPT)s obtained has ethylene acetate end groups formed from acetic acid hydroxy ethylene end groups and showed almost the random sequence distribution for all compositions.

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Synthesis and Properties of Partially Hydrolyzed Acrylonitrile-co-Acrylamide Superabsorbent Hydrogel

  • Pourjavadi, Ali;Hosseinzadeh, Hossein
    • Bulletin of the Korean Chemical Society
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    • 제31권11호
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    • pp.3163-3172
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    • 2010
  • In this work, a novel method to synthesis of an acrylic superabsorbent hydrogel was reported. In the two stage hydrogel synthesis, first copolymerization reaction of acrylonitrile (AN) and acrylamide (AM) monomers using ammonium persulfate (APS) as a free radical initiator was performed. In the second stage, the resulted copolymer was hydrolyzed to produce carboxamide and carboxylate groups followed by in situ crosslinking of the polyacrylonitrile chains. The results from FTIR spectroscopy and the dark red-yellow color change show that the copolymerization, alkaline hydrolysis and crosslinking reactions have been do take place. Scanning electron microscopy (SEM) verifies that the synthesized hydrogels have a porous structure. The results of Brunauer-Emmett-Teller (BET) analysis showed that the average pore diameter of the synthesized hydrogel was 13.9 nm. The synthetic parameters affecting on swelling capacity of the hydrogel, such as AM/AN weight ratio and hydrolysis time and temperature, were systematically optimized to achieve maximum swelling capacity (330 g/g). The swollen gel strength of the synthesized hydrogels was evaluated via viscoelastic measurements. The results indicated that superabsorbent polymers with high water absorbency were accompanied by low gel strength. The swelling of superabsorbent hydrogels was also measured in various solutions with pH values ranging from 1 to 13. Also, the pH reversibility and on-off switching behavior makes the hydrogel as a good candidate for controlled delivery of bioactive agents. Finally, the swelling of synthesized hydrogels with various particle sizes obey second order kinetics.

A Study on the Copolymerization Kinetics of Phenylethyl Acrylate and Phenylethyl Methacrylate

  • Lee, Han-Na;Tae, Gi-Yoong;Kim, Young-Ha
    • Macromolecular Research
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    • 제16권7호
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    • pp.614-619
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    • 2008
  • Copolymers of phenyl alkyl acrylates/methacrylates are used clinically as soft materials for the foldable intraocular lens (IOL) to treat cataracts. In this study, copolymers of 2-phenylethyl acrylate (PEA) and 2-phenylethyl methacrylate (PEMA) of various compositions were prepared using free radical polymerization in solution. The composition of the copolymers was determined by $^1H$-NMR analysis. The reactivity ratios of the monomers were calculated using the conventional Fineman-Ross or Kelen-Tudos method. The reactivity ratio of PEA ($r_1$) and PEMA ($r_2$) were estimated to be 0.280 and 2.085 using the Kelen-Tudos method, respectively. These values suggest that PEMA is more reactive in copolymerization than PEA, and the copolymers will have a higher content of PEMA units. The glass transition temperature ($T_g$) of the copolymers increased with increasing PEMA content. The molecular weight and polydispersity indices ($M_w/M_n$) of the polymers were determined by GPC. Overall, these results are expected to be quite useful in applications to foldable soft IOL materials.

Swelling Controlled Delivery of Antibiotic from a Hydrophilic Macromolecular Matrix with Hydrophobic Moieties

  • Shukla, Sandeep;Bajpai, Anil Kumar;Bajpai, Jaya
    • Macromolecular Research
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    • 제11권4호
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    • pp.273-282
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    • 2003
  • A hydrophilic macromolecular network containing hydrophobic moieties has been prepared by free radical copolymerization of acrylamide and styrene in the presence of poly(vinyl alcohol) (PVA) and its potential as controlled drug delivery carrier was evaluated with tetracycline as a model antibiotic drug. The amount of drug was assayed spectrophotometrically. The network was characterized by optical microscopy, infra-red spectroscopy and structural parameters such as average molecular weight between cross1inks ($M_c$), cross1ink density (q) and number of elastically effective chains ($V_e$) were evaluated. It was found that with increasing concentration of PVA, ST and MBA in the hydrogel, the release rate initially increases but after definite concentrations of the above components the release rate falls. In the case of AM, release rate constantly decreases with increasing AM concentration in the hydrogel.