• Title/Summary/Keyword: 에스테르화 반응

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(Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers ((感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構)

  • Kim, Kwang-Sup;Shim, Jyong-Sup
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.166-174
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    • 1966
  • The multistep mechanism of photosensitized curing reaction cinnamoylated photosensitive polymer is proposed from the energy level diagram of cinnamic acid and sensitizer, and from the fact that excess of sensitizer brings the sensitivity to a limiting value etc. Various factors which have effects on the ability of sensitizer are also discussed. The mechanism involves following steps: activation to the first excited singlet states of cinnamoyl group(C) and sensitizer(S) by their absorption of photon, their intersystem crossing to the lowest triplet state, bimolecular internal quenching by formation of excimer of sensitizer, triplet excitation energy transfer and intermolecular addition between cinnamoyl group in ground state and that in triplet state. The rate equation derived from this mechanism is $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ where $I^c_{abs}\;and\;I^s_{abs}$: the rates of absorption of photon by cinnamoyl group and sensitizer $K_n$: Constants. It is proved with the cinnamate of poly(glyceryl phthalate)(PGC) in the absence of sensitizer using the infrared analytical method and successfully applied for the experimental data reported on the effects of the degree of cinnamoyl esterification and the concentration of sensitizer upon the sensitivity.

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Synthesis and characterization of hydrophobic and hydrophilic cellulose derivative by esterification (친수성과 소수성을 동시에 가지는 아세틸화 셀룰로스 에테르의 합성 및 특성 평가)

  • Kim, Taehong;Lee, Sangku;Son, Byunghee;Paik, Hyun-Jjong;Yoon, Sanghyeon;Lee, Heesoo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.23 no.1
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    • pp.31-36
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    • 2013
  • Acetylated Cellulose Ether (ACE), cellulose-based amphiphilic polymer with hydrophilic and hydrophobic, was synthesized and investigated in terms of its solubility and wettability for organic solvents and water. Acetyl group was substituted to the cellulose ether in a hydrophilic polymer by esterification. As a result of FT-IR, the peak corresponding to the hydroxyl group decreased and carboxyl acid peak increased with increasing reaction time and temperature, which signified the increase in the degree of acetylation of the ACE. There were similar thermal decomposition behaviors before and after esterification reaction until $800^{\circ}C$ so that the reaction occurred without significant structural changes of cellulose backbones. The solubility parameter of the ACE had a range of 18.5~26.4, and its viscosity and turbidity were controlled according to the solubility parameter of organic solvents. The ACE showed the hydrophilicity because the contact angle of the ACE was higher than the cellulose ether. These results confirmed that the ACE had the hydrophobicity and hydrophilicity due to the ether which was glucosidic bonding between the glucose units and un-reacted hydroxyl functional groups in the ACE.

Polyvinylchloride Plasticized with Acetylated Monoglycerides Derived from Plant Oil (아세틸화 모노글리세라이드계 가소제 합성 및 PVC 가소성능에 관한 연구)

  • Lee, Sangjun;Yuk, Jeong-Suk;Kim, A-Ryeon;Choung, Ji Sun;Shin, Jihoon;Kim, Young-Wun
    • Applied Chemistry for Engineering
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    • v.28 no.1
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    • pp.42-49
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    • 2017
  • To replace phthalate plasticizer for PVC, acetylated monoglyceride (AMG) plasticizers were prepared from plant oil and their plasticization effects were also investigated. Transesterification of coconut oil by glycerol followed by acetylation with acetic anhydride gave AMG-CoCo (Coco : Coconut Oil). In addition, AMG-GMO (GMO : Glycerol monooleate) and AMG-GMO-Epoxy were synthesized by acetylation and epoxidation with glycerol monooleate. It was found that the thermal stability of AMG plasticizers increased in the following order: AMG-GMO-Epoxy > AMG-GMO > AMG-CoCo and all three plasticizers were thermally more stable than those of common petroleum-based plasticizer DOP (Dioctyl phthalate). The tensile strain values of the PVC containing AMG compounds were ca. 770~810%, while tensile strength values were ca. 19~22 MPa, which were higher than those of PVC containing DOP. DMA (Dynamic Mechanical Analysis) results showed that the miscibility of AMG-GMO-Epoxy in PVC was excellent and the $T_g$ of PVC containing AMG-GMO-Epoxy at 50 phr decreased down to $24^{\circ}C$. Finally, the leaching experiment result showed that the weight loss values of PVC containing AMG-GMO and AMG-GMO-Epoxy at 50 phr were as low as 2 and 1%, respectively, indicating that they have high water migration resistance. The above findings suggested that AMG-GMO-Epoxy could be one of plant oil-based PVC plasticizers to replace DOP.

Synthesis and Reaction of 1,5,3,7-Diazadiphosphocine-1,5-Dicarboxylic Acids (1,5,3,7-Diazadiphosphocine-1,5-Dicarboxylic Acids의 합성과 반응)

  • Cho, Seung-Hwan;Song, Ju-Hyun;Lee, Do-Hun;Lee, Yong-Gyun;Park, Yu-Mi;Choi, Soon-Kyu;Hahn, Jung-Tai;Jung, Dai-Il
    • Journal of Life Science
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    • v.17 no.7 s.87
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    • pp.910-914
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    • 2007
  • In order to synthesize new bioactive compounds and contrasting agents, reactions of glycine and glutamic acid as an animo acid with paraformaldehyde and hypophosphorous acid were executed. Products are 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid 1 and 3,7-dihydroxy-3,7- dioxoperhydre-1,5,3,7-diazadiphosphocine-1,5-di-(2-glu taric acid) 3. 2-[5-(1,2-Dicarboxyethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7] diazadiphosphocan-1-yl]-succinic acid 2 by using aspartic acid was not obtained. Esterification of 3,7- dihydroxy-3,7-dioxoperkydro-1,5,3,7-diaza-diphosphocine-1,5-diacetic acid 1 by treatment of methanol, ethanol, and propanol were executed. 3,7-Dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3.7-dihydroxy-3,7-dioxoperhydro-1,5,3,f-diazadiphosphocine-1.5-diacetic acid ethyl ester 5, and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6 were respectively synthesized in good yields. Continuously, we will try synthesis of novel compounds and evaluation of biological activity.

Synthesis and Properties of Poly(ester-imide) Resin for High Temperature Resistant Electrical Insulation (고내열성 전기 절연용 Poly(ester-imide) 수지의 합성 및 물성)

  • Huh, Wansoo;Lee, SangWon;Kim, Jeongyeol;Park, Leesoon;Kim, Soonhak;Haw, JungRim
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.767-771
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    • 1999
  • Poly(ester-imide)(PEI) for the electrical insulation coating was synthesized and evaluated with one-step method as well as two-step method. For the synthesis of poly(ester-imide), imide repeat unit of N,N'-(4,4'-diphenylmethane) bistrimellitimide(DID) was initially made from trimellitic anhydride(TMA) and methylene dianiline(MDA), followed by the second stage reaction of esterification. One-step reaction was performed by reaction of TMA, MDA, dimethyl terephthalate(DMT), ethylene glycol(EG), and 1,3,5-tris-(2-hydroxy ethyl) isocyanurate(THEIC) in m-cresol solvent at a time. The synthesized poly(ester-imide) was cured with xylene, P-5030K(phenol-formaldehyde resin), TK-8(TDI type blocked polyisocyanate) and tetrapropyltitanate(TPT). It was found that the content of hydroxyl group, amount of DMT, and imide repeat unit played important role for the properties of electrical insulation coating film.

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Synthesis of Functional Copolyester, its Blend with PET, and Properties of Carbon Black Dry Color (기능성 폴리에스테르 공중합체의 합성, PET와의 블렌드 및 카본 블랙 Dry Color의 물성)

  • Park, Lee Soon;Lee, Dong Chan;Kim, Jin Kon;Huh, Wan Soo
    • Applied Chemistry for Engineering
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    • v.7 no.3
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    • pp.496-503
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    • 1996
  • Aromatic and aliphatic copolyesters for the dispersing agent were synthesized by two stage reaction, esterification and polycondensation. Copolyesters were blended with PET in the melt state and their thermal and rheological properties were investigated. From GPC analysis Mn's and Mw's of copolyesters were about 30000 and 65000g/mol, respectively. From DSC experiment copolyesters had melting range of $90{\sim}150^{\circ}C$. Copolymer composition was in good agreement with comonomer feed ratio from $^1H$-NMR analysis. Copolyesters and SPA (standard sample) were blended with PET in the melt state. From DSC experiment, copolyesters and SPA were miscible with PET. From the dynamic melt viscosity experiment, melt viscosity of blended sample was increased as the content of aromatic copolyester was increased, while it was decreased as the content of aliphatic and SPA were increased. As for volume resistivity of dry color containing carbon black and copolyesters with dispersing time, aromatic copolyester showed highest value. It was conferred from this result that aromatic copolyester was the best dispersing agent for carbon black in PET resin.

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Effects of NaCl/H3PO4 Flame Retardant Treatment on Lyocell Fiber for Thermal Stability and Anti-oxidation Properties (NaCl/H3PO4 내염화 처리가 라이오셀 섬유의 열 안정 및 내산화 특성에 미치는 영향)

  • Kim, Eun Ae;Bai, Byong Chol;Jeon, Young-Pyo;Lee, Chul Wee;Lee, Young-Seak;In, Se Jin;Im, Ji Sun
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.418-424
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    • 2014
  • The improved thermal stability and anti-oxidation properties of Lyocell fiber were studied based on flame retardant treatment by using NaCl/$H_3PO_4$ solution. The optimized conditions of flame retardant treatment were studied on various maxing ratio of NaCl and $H_3PO_4$ and the mechanism was proposed through experimental results of thermal stability anti-oxidation. The IPDT (integral procedural decomposition temperature), LOI (limited oxygen index) and $E_a$ (activation energy) increased 23, 30 and 24% respectively via flame retardant treatment. It is noted that thermal stability and anti-oxidation improved based on char and carbon layer formation by dehydrogenation and dissociation of C-C bond resulting the hindrance of oxygen and heat energy into polymer resin. The optimized conditions for efficient flame retardant property of Lyocell fiber were provided using NaCl/$H_3PO_4$ solution and the mechanism was also studied based on experimental results such as IDT (initial decomposition temperature), IPDT, LOI and $E_a$.

Na3PO4 Flame Retardant Treatment on Lyocell Fiber for Thermal Stability and Anti-oxidation Properties (라이오셀의 열 안정 및 내산화 특성 향상을 위한 Na3PO4 내염화 처리)

  • Kim, Hyeong Gi;Kim, Eun Ae;Lee, Young-Seak;In, Se Jin
    • Fire Science and Engineering
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    • v.29 no.2
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    • pp.25-32
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    • 2015
  • The improved thermal stability and anti-oxidation properties of lyocell fiber were studied based on flame retardant treatment by using $Na_3PO_4$ solution. The optimized conditions of flame retardant treatment were studied on various concentrations of $Na_3PO_4$ and the mechanism was proposed through experimental results of thermal stability and anti-oxidation. The integral procedural decomposition temperature (IPDT), limiting oxygen index (LOI) and activation energy ($E_a$) increased 30, 160% respectively via flame retardant treatment. It is noted that thermal stability and anti-oxidation improved based on char and carbon layer formation by dehydrogenation and dissociation of C-C bond resulting the hindrance of oxygen and heat energy into polymer resin. The optimized conditions for efficient flame retardant property of lyocell fiber were provided using $Na_3PO_4$ solution and the mechanism was also studied based on experimental results such as initial decomposition temperature (IDT), IPDT, LOI and $E_a$.

Scouring Effect of PAPE(Polyoxyethylene Alkyl Phosphoric Ester) on Cotton Fibres (면섬유에 대한 폴리옥시에틸렌 알킬 인산에스테르의 정련효과)

  • Ha, Youn-Shick;Kwak, Gyeong-Do;Chang, Yoon-Ho
    • Applied Chemistry for Engineering
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    • v.10 no.7
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    • pp.974-978
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    • 1999
  • This study was concerned with the scouring effect of anionic surfactants, PAPE(sodium polyoxyethylene alkyl phosphoric ester) for cotton fibres. Sodium polyoxyethylene(7) nonylphenyl phosphoric ester(CPB-1) and the sodium polyoxyethylene(7) tridecyl phosphoric ester(CPB-2) were synthesized by the phosphoric esterification reaction from NP-7(polyoxyethylene(7) nonylphenyl ether) and TDA-7(polyoxyethylene(7) tridecyl ether) as scouring agents. Defoaming ability, fibre wetting time and absorbency rate of scouring agents were investigated. Being compared with the conventional scouring agent(Ultravon GP; Ciba-guyge Co.), CPB-1 and CPB-2 showed a higher defoaming ability in the cotton scouring process at room temperature. And CPB-1 has a higher wetting effect than the agents, CPB-2 or GP in distilled water bath but CPB-2 showed more scouring effect in 1.2 wt % NaOH solution bath.

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The Variation of Surface Area in Porous Poly(Styrene-co-Divinylbenzene) Resin Beads (다공성 스티렌-디비닐벤젠 공중합 수지입자의 표면적 변화)

  • Kim, Yong-Man;Ihm, Son-Ki;Kim, Jong-Chan;Lee, Dong-Keun;Ahn, Jou-Hyeon
    • Applied Chemistry for Engineering
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    • v.7 no.5
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    • pp.843-848
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    • 1996
  • Porous resin beads of Poly(styrene-co-divinylbenzene) have been prepared by suspension polymerization. The bead could be made porous in the region above 30wt% of the crosslinking agent(divinylbenzene ) and the porogenic agent(toluene), respectively. The specific surface area of porous beads increased with increasing the concentrations of divinylbenzene and toluene. The specific surface area of the porous resin bead decreased, when sulfonated with concentrated sulfuric acid. The catalytic activity of sulfonated resin catalyses increased with increasing the degree of crosslinking in the liquid-phase reesterification of ethyl acetate with 1-propanol. The adsorbed quantity of sodium dodecylbenzene sulfonate in an aqueous solution also increased with increasing surface area of porous resins.

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