PPG계 Polyurenthane Methacrylates의 합성과 경화특성

김주영; 서경도

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.4, 627-638, December, 1992

Export Citation

PPG계 Polyurenthane Methacrylates의 합성과 경화특성

A Study on the Synthesis and Curing Characteristics of PPG-type Polyurethane Methacrylates

김주영, 서경도

초록

분자량과 관능기수가 각각 다른 4가지의 polypropylene glycol(PPG)과 toluene-2, 4-diisocyanate(2, 4-TDI)를 이용하여 polyurethane prepolymer(NCO terminated)를 합성한 후 NCO기 말단에 2-hydroxyethyl methacrylate(2-HEMA)를 반응시켜 PPG계 polyurethane methacrylates 수지를, PPG대신에 bisphenol A(BPA)를 이용하여 BPA계 polyurethane dimethacrylate 수지를 합성하였다. 합성된 PPG계 polyurethane dimethacrylate 수지에 반응성희석제인 triethylene glycol dimethacrylate(TEGDMA), 중합개시제인 cumene hydroperoxide(CHP) 중합금지제인 hydroquinone(HQ)를 첨가하였을 때, 첨가량변화에 따른 토오크강도의 변화를 고찰하였고, BPA계 polyurethane dimethacrylate 수지와 블렌드하였을때의 조성비에 따른 토오크강도의 변화를 고찰하였다. 토오크 측정결과, TEGDMA 40wt%, cumene hydroperoxide 4wt%, hydroquinone 200 ppm이 첨가되었을 때, 가장 큰 토오크강도를 나타내었으며, PPG계와 BPA계를 블렌딩하였을 때는 PPG/BPA가 4/6일 때 가장 큰 토오크강도를 나타내었다. 반응성희석제인 triethylene glycol dimethacrylate(TEGDMA), 중합개시제인 cume hydroperoxide(CHP), 중합금지제인 hydroquinone(HQ)를 동일하게 첨가한 후, 분자량과 관능기수가 다른 PPG계 polyurethane dimethacrylate 수지들의 열경화시의 토오크강도를 측정한 결과, 관능기수가 같은 수지들(PD750, PD1000, PD2000)의 경우에는 분자량이 적은 수지(PD750)일수록 큰 토오크강도를 나타내었고, 관능기수가 많을수록(PT 700) 큰 토오크강도를 나타내었다. 개시제만을 첨가한 후, 열경화를 통해서 얻어진 PPG계 수지들의 겔들을 DSC분석을 통해서 Tg변화를 측정하여 본 결과, 경화시 분자량이 가장 적고, 관능기수가 가장 많은 PT700이 가장 큰 폭의 Tg증가를 나타내었으며, 분자량이 가장 큰 수지인 PD 2000이 가장 적은 폭의 Tg증가를 나타내었다. 그리고, Tg를 통해서 가교점간 분자량 Mc를 측정한 결과, 가장 큰 폭의 Tg를 보인 PT 700가 가장 적은 Mc를 가지고 있었다. 따라서, PT 700이 경화시 가장 조밀한 망목구조를 형성한다는 것을 확인할 수 있었다.

PPG and BPA-type polyurethane prepolymers(NCO terminated) were obtained from bisphenol A and four types of PPG, having different molecular weight and numbers of functional groups. PPG and BPA-type polyurethane dimethacrylates were synthesized by reacting PPG and BPA-type polurethane prepolymer with 2-HEMA respectively. PPG-type polyurethane dimethacrylates were formulated with initiator(CHP), inhibitor(hydroquinone) and reactive diluent(TEGDMA). The effect of formulation on the torque changes was studied. Four kinds of PPG-type polyurethane dimethacrylates, having different molecular weight and numbers of functional group, were formulated with the same amount of CHP, TEGDMA and hydroquinone. The effects of the molecular weight of PPG-type polyurethane dimethacrylate and functional group numbers of PPG-type polyurethane dimethacrylates on the torque were investigated. These results showed that the torque of PPG-type polyurethane dimethacrylates, having same numbers of functional group, increased with decreasing molecular weight of dimethacrylates and torque of PPG-type polyurethane dimethacrylate, having similar molecular weight, was increased with increasing the number of fuctional group. The glass-transition temperature(Tg) of gels obtained by thermosetting cure for the four kinds of PPG-type polyurethane dimethacrylates were measured by DSC and molecular weights between cross-links(Mc) were calculated from Tg changes.

[References]

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[1] Loctite Co., Japan Patent, 昭 45-12400 (1970)

[2] Loctite Co., Japan Patent, 昭 52-11443 (1976)

[3] Baccei LJ, U.S. Patent, 4,295,909 (1981)

[4] Baccei LJ, U.S. Patent, 4,309,526 (1982)

[5] Baccei LJ, Japan Patent, 昭 59-42685 (1984)

[6] Japan Patent, 昭 60-39711 (1985)

[7] Shepard TH, Gould FE, U.S. Patent, 3,595,969 (1971)

[8] Murray BD, Hauser M, Elliot JR, "Handbook of Adhesives," (I. Skeist, 3d)., 2nd, Ed. Reinhold, New York (1977)

[9] Emmors WD, U.S. Patent, 4,234,711 (1980)

[10] Brenner W, U.S. Patent, 4,216,134 (1886)

[11] Landrock AH, "Adhesives Technology Handbook," 137, Noyes, Publications (1985)

[12] Poyle E, "The Development and Use of Polyurethane Products," 16, McGraw-Hill, New York (1984)

[13] Bikales M, Menges O, "Encyclopedia of Polymer Science and Engineering," Wiley-Interscience, New York, Vol. 15 (1986)

[14] Odian G, "Principle of Polymerization," 2nd Ed., Wiley, New York (1986)

[15] Feti S, Maravigna P, Montaudo G, Polym. Degrad. Stabil., 4, 287 (1982)

[16] Nielson LE, J. Macromol. Sci.-Rev. Macromol. Chem. Phys., C3(1), 69 (1969)

[17] Fox TG, Loshrek S, J. Polym. Sci., 15, 371 (1965)

[18] Fox TG, Loshrek S, J. Polym. Sci., 15, 391 (1965)