인과 할로겐 성분을 함유하는 난연 고분자 재료: 1. 제조

설차동; 이희연; 박인환

Polymer(Korea), Vol.15, No.2, 191-200, April, 1991

Export Citation

인과 할로겐 성분을 함유하는 난연 고분자 재료: 1. 제조

Polymeric Flame Retardants Containing Phosphorus and Halogen Components : 1. Preparation

설차동, 이희연, 박인환

초록

할로페놀과 포스포러스 옥시클로라이드를 반응시켜 할로페닐디클로로 포스페이트를 얻고 이들을 가수분해시켜 인과 할로겐 성분을 함유하고 있는 난연 단량체들을 합성하였다. 아울러 이들 난연 단량체와 톨루엔-2,4-디아소시아네이트를 우레탄 반응시켜 난연 고분자 재료를 제조하였다. 그리고 제조된 난연 재료들이 구조들은 IR과 ¹H-NMR 분석에 의해 각각 확인 되었다. 한편 난연제 모두에 대해서는 용해성, 열안정성, 흡습성 등의 물성 평가가 이루어졌는데 그 결과는 다음과 같다. 1. DMF와 DMSO에만 용해하는 난연 고분자 재료는 내용제성이 좋을 것으로 사료되었고, 반면 난연 단량체는 대부분의 유기용매에 용해되어 내용제성이 좋지 않을 것으로 사료되었다. 2. 제조된 모든 난연 재료들은 TGA상의 초기 분해되는 온도가 165℃ 이상이었으며, 초기 분해온도 범위에서는 난연 단량체가 난연 고분자 재료보다 좋은 열안정성을 나타냈으나, 난연 원소들의 열분해가 주로 이루어진다고 사료되는 180∼540℃ 범위에서는 오히려 난연 고분자 재료가 난연 단량체에 비하여 양호한 내열성을 보였다. 또한 700℃ 이상에서의 Char의 양도 난연 고분자 재료가 상대적으로 많이 형성되었다. 3. 난연 재료의 내흡습성은 난연 고분자 재료들이 난연 단량체보다 양호하였는데, 동일류에서는 할로겐이 보다 많이 치환된 페놀 유도체 구조를 가진 것들이 더욱 좋지 않은 것으로 나타났다.

Halophenyldichloro phosphates were obtained from the 1:1 mol reaction of halophenols with phosphorus oxychloride. Hydrolysis of the halophenyldichloro phosphates resulted in flame retardant monomers containing phosphorus and halogen components. Polymeric flame retardants were also prepared by the urethane reaction of the monomers with toluene-2,4-diisocyanate. The structures of the monomers and polymers were characterized by IR and ¹H-NMR spectroscopy. All the prepared flame retardants were evaluated by the physical properties such as solubility, thermal stability, and moisture absorbability, etc. The results were as follows. 1. The polymers which were soluble only in DMF and DMSO were extremely solvent-resistant, whereas the monomers showed good solubilities in most of organic solvents. 2. In TGA, all the prepared flame retardants began its weight loss from decomposition above 165℃. The thermal stabilities of the monomers compared to the polymers in the initial decomposition temperature were relatively good, but those of the monomers compared to the polymers in the critical area of 180∼540℃ were bad. And the combustion of the polymers brought about great increases in char content. 3. The moisture-resistant properties of the polymers were better than those of the monomers. Also, the moisture absorptions in all of them increased with increasing halogen contents.

[References]

Testing for Public Safety, Underwriters' Laboratories Inc. (1978)
UL 94, 2, Sept. 1973 Edition with Supplements of May 1975, July 1976 and May 1978 : Tests for Flammability of Plastic Materials for Parts in Devices and Appliances (1978)
DIN 40802, Part 1, Feb. 1976: Merallkaschierte Basismaterialien fur Gedruckte Schaltungen, Prufung (1976)
VDE 0318, Part la/.... 75, Draft 1, and DIN 7735, Part la, Draft Dec. 1975 : VDE-Bestimmung fur die Schichtpre β stoff-Erzeuhgnisse Hartpapier Hartgewebe und Hartmatte, Prufverfahren (1975)
DIN 53459, May 1975 : Prufung mit Kunstoffen. Beurteilung des Verhaltens Wahrend und nach Beruhrung mit einem Gluhstab (1975)
Sanders HJ, Chem. Eng. News, plain (1978)
Arend G, Pascik I, Ger. Offen., 2,653,768
Masai T, Kate Y, Fukui N, Japan 73-43, 373
Dow Chemical Co., Neth. Appl. 78-68, 614
Kobayashi E, Kamagami S, Japan Kokai 75-92, 995
Cerny J, Vivant F, Fr. Demance 2,314,221
Humbrecht R, Swiss, 598,316
Nametz RC, U.S. Patent, 3,268,619
Taniyama S, Taniguchi M, Japan Kokai 77-16, 551
Matsuyama K, Watanabe H, Japan Tokyo Koho 78-41, 175
Honig ML, Weil ED, U.S. Patent, 4,152,373
Kruth V, Rev. Mod. Plast., 34, 854 (1977)
Fos DW, Ger. Offen, 2,757,557
Dow Chemical Co., Fr. 2,094,398
Izutu H, Ishikawa H, Ger. Offen, 2,712,319
Johnson BH, Johnson EF, U.S. Patent, 3,901,847
Basle RK, Kunststoffe, 66, 10 (1976)
Pitts JJ, J. Fire Flammability, 3, 51 (1972)
Stackman RW, Ind. Eng. Chem. Prod. Res. Dev., 21, 332 (1982)
Natansohn A, J. Appl. Polym. Sci., 32, 2961 (1986)
Annakutty KS, Klahore K, Polymer, 29, 756 (1988)
Maguire MM, Shaw G, J. Chem. Soc., 1479 (1953)
Conant JB, Macdonald AD, J. Am. Chem. Soc., 42, 2337 (1920)
Conant JB, Macdonald AD, McBKinney A, J. Am. Chem. Soc., 43 (1928)
Wiley RH, Trinler WA, J. Polym. Sci., 42, 113 (1960)
Analytical Methods and Equipments, 404 (1970)
Kolthoff IM, Sandell EB, Meehan EJ, Bruckenstein, Quantitive Chemical Analysis, 4th the Macmillan Co., London, 1126 (1971)
Gainsly M, Dow J, Fundamentals and Practice in Adhesion and Adhesives, p. 127 (1954)
Hock CW, J. Polym. Sci. C: Polym. Lett., 139 (1963)
Hock CW, Adhes. Age, 7, 21 (1964)

[Referenced By]

[1] Testing for Public Safety, Underwriters' Laboratories Inc. (1978)

[2] UL 94, 2, Sept. 1973 Edition with Supplements of May 1975, July 1976 and May 1978 : Tests for Flammability of Plastic Materials for Parts in Devices and Appliances (1978)

[3] DIN 40802, Part 1, Feb. 1976: Merallkaschierte Basismaterialien fur Gedruckte Schaltungen, Prufung (1976)

[4] VDE 0318, Part la/.... 75, Draft 1, and DIN 7735, Part la, Draft Dec. 1975 : VDE-Bestimmung fur die Schichtpre β stoff-Erzeuhgnisse Hartpapier Hartgewebe und Hartmatte, Prufverfahren (1975)

[5] DIN 53459, May 1975 : Prufung mit Kunstoffen. Beurteilung des Verhaltens Wahrend und nach Beruhrung mit einem Gluhstab (1975)

[6] Sanders HJ, Chem. Eng. News, plain (1978)

[7] Arend G, Pascik I, Ger. Offen., 2,653,768

[8] Masai T, Kate Y, Fukui N, Japan 73-43, 373

[9] Dow Chemical Co., Neth. Appl. 78-68, 614

[10] Kobayashi E, Kamagami S, Japan Kokai 75-92, 995

[11] Cerny J, Vivant F, Fr. Demance 2,314,221

[12] Humbrecht R, Swiss, 598,316

[13] Nametz RC, U.S. Patent, 3,268,619

[14] Taniyama S, Taniguchi M, Japan Kokai 77-16, 551

[15] Matsuyama K, Watanabe H, Japan Tokyo Koho 78-41, 175

[16] Honig ML, Weil ED, U.S. Patent, 4,152,373

[17] Kruth V, Rev. Mod. Plast., 34, 854 (1977)

[18] Fos DW, Ger. Offen, 2,757,557

[19] Dow Chemical Co., Fr. 2,094,398

[20] Izutu H, Ishikawa H, Ger. Offen, 2,712,319

[21] Johnson BH, Johnson EF, U.S. Patent, 3,901,847

[22] Basle RK, Kunststoffe, 66, 10 (1976)

[23] Pitts JJ, J. Fire Flammability, 3, 51 (1972)

[24] Stackman RW, Ind. Eng. Chem. Prod. Res. Dev., 21, 332 (1982)

[25] Natansohn A, J. Appl. Polym. Sci., 32, 2961 (1986)

[26] Annakutty KS, Klahore K, Polymer, 29, 756 (1988)

[27] Maguire MM, Shaw G, J. Chem. Soc., 1479 (1953)

[28] Conant JB, Macdonald AD, J. Am. Chem. Soc., 42, 2337 (1920)

[29] Conant JB, Macdonald AD, McBKinney A, J. Am. Chem. Soc., 43 (1928)

[30] Wiley RH, Trinler WA, J. Polym. Sci., 42, 113 (1960)

[31] Analytical Methods and Equipments, 404 (1970)

[32] Kolthoff IM, Sandell EB, Meehan EJ, Bruckenstein, Quantitive Chemical Analysis, 4th the Macmillan Co., London, 1126 (1971)

[33] Gainsly M, Dow J, Fundamentals and Practice in Adhesion and Adhesives, p. 127 (1954)

[34] Hock CW, J. Polym. Sci. C: Polym. Lett., 139 (1963)

[35] Hock CW, Adhes. Age, 7, 21 (1964)