新型磷氮系阻燃剂的合成及其阻燃性能研究
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摘要
近年来，火灾日益频繁，造成的损失日益严重。据报道，仅1997年，我国发生火灾14万起，死2722人，直接经济损失15.4亿元。火灾每年给世界各国都造成大量的人员伤亡和财产损失。现在，人们日益认识到，合理地对材料阻燃是减少火灾的战略措施之一。阻燃材料(特别是阻燃高分子材料)和阻燃技术正成为全球研究的热点。
由于含磷氮化合物作为阻燃剂显示出了良好的阻燃性能，其发烟量少，基本上不产生有毒气体，前景看好。因此，我们合成了三个系列共计26个含磷氮化合物，以期找到具有开发前景的新型膨胀型阻燃剂。
1．以1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]-4-氯甲酰基辛烷和一系列胺反应，合成了8个双环笼状磷酸酯酰胺类化合物Ⅰa-h。
2．首次采用5,5-二甲基-2-氯-2-氧-1,3,2-二氧杂己内磷酸酯和50％的水合肼反应合成了化合物5,5-二甲基-2-肼基-2-氧-1,3,2-二氧磷杂己内酰磷酸酯，产率58.9％；再以此化合物与取代苯甲醛反应，合成了8个未见文献报导的化合物Ⅱa-h。
3．采用5,5-二甲基-2-氯-2-氧-1,3,2-二氧杂己内磷酸酯和胺反应，合成了10个未见文献报导的目标化合物Ⅲa-j。
4．对以上所合成的化合物用元素分析、IR、~1H NMR、和MS对其结构进行了表征。
5．对以上所合成的化合物进行了醇酸清漆的阻燃测试。三个系列的化合物在醇酸清漆中的添加量为1％时均能达到自熄的效果。
／迄巴八 硕士学位论文
w MASTER’S THESIS
6．对以上所合成的化合物进行了在环氧树脂（EAI）的阻燃测试，mi和四
其阻燃效果明显优于其它的化合物，可能的原因是其磷含量较大（分为
16二3％和15刀2．％＼残炭率和炭层结构与磷的含量有关：磷的含量增大，
残炭率也相应增大。添加了阻燃剂的样条有发泡膨胀现象，样条迅速炭化，
且无熔融、滴落和弯卷等现象。
7．对部分具有代表性化合物进行了热重（TG）和差热（DTA）分析表明：这
些化合物最高失重速率的温区均在 220～400 ’C，这与大部分高分子材料的
热氧降解温区重叠，具有较好的阻燃配伍性能。
In recent years, fire disasers were on the increase and made great property losses. In our country, in 1997, there were 140 thousand fire and 2722 fire deaths. Direct losses caused by fire added up to 1.54 billions. Fire disasers make great number of deaths and heavy property losses every year all over the world. Now people increasely realize that, treating inflammable materials with fire retardant is one of the strategic measures to prevent and decrease fire. Flame retardant material, especially flame retardant polymeric material, and flame retardant technology became research hotspot all over the world.
Nitrogen-phosphorus compounds are a family of promising flame retardants, which have many advantages: they themselves and their gases or vapors evolved during combustion have low toxicity. Nitrogen-phosphorus compounds as flame retaedant has a positive prospect.
1. Eight amide derivatives I a-h were synthesized by the substitute reaction of 1-oxo-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane-4-acyl chloride with
various amines.
2. Compound 5,5-dimethyl-2-hydrazino-2-oxo-l,3,2-dioxaphosphorinane was synthesized by 5,5-dimethyl-2-chloro-2-oxo-1,3,2-dioxaphosphorinane and hydrazine hydrate for the first time. Then 8 novel title compounds,
II a-h,were synthesized by 5,5-dimethyl-2-hydrazino-2-oxo-1,3,2-dioxaphos phorinane and substituted benzaldehydes.
3. Ten novel title compounds, III-j, were synthesized by 5.5-dimethyl-2-chloro -2-oxo-1,3,2-dioxaphosphorinane and various amines.
4. All the title compounds were confirmed by DR., 'H NMRx MS and elementary analysis.
5. Applied the compounds to alkyd resin varnish to test their Flame
resistance.All of the compounds give effect of self-extinguish in 1s with 1% addition in alkyd resin varnish.
6. Applied the compounds to expoxy resin (E-44) to test their Flame resistance. Compounds IIIi and IIIj have better flame resistance than others in epoxy resin (E-44). Because they are more phosphorus-containing than that of the others. The amount of charred residue increases with increasing phosphorus content in a material. The formation of more compact charred crust surface with increasing phosphorus content in material.The samples foamed and expanded during combustion process. They carbonize and extinguish after deviate from fire, without melting and dropping and with low smoking.
7. TG and DTA analysis of some of the compounds were discussed. Most of the compounds begin to decompose at 220 C and have certain thermal stability. They decompose rapidly during 220-400 C and overlapping many polymeric material' decomposition temperature ranger and show good fireproofing compatibility with materials.
由于含磷氮化合物作为阻燃剂显示出了良好的阻燃性能，其发烟量少，基本上不产生有毒气体，前景看好。因此，我们合成了三个系列共计26个含磷氮化合物，以期找到具有开发前景的新型膨胀型阻燃剂。
1．以1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]-4-氯甲酰基辛烷和一系列胺反应，合成了8个双环笼状磷酸酯酰胺类化合物Ⅰa-h。
2．首次采用5,5-二甲基-2-氯-2-氧-1,3,2-二氧杂己内磷酸酯和50％的水合肼反应合成了化合物5,5-二甲基-2-肼基-2-氧-1,3,2-二氧磷杂己内酰磷酸酯，产率58.9％；再以此化合物与取代苯甲醛反应，合成了8个未见文献报导的化合物Ⅱa-h。
3．采用5,5-二甲基-2-氯-2-氧-1,3,2-二氧杂己内磷酸酯和胺反应，合成了10个未见文献报导的目标化合物Ⅲa-j。
4．对以上所合成的化合物用元素分析、IR、~1H NMR、和MS对其结构进行了表征。
5．对以上所合成的化合物进行了醇酸清漆的阻燃测试。三个系列的化合物在醇酸清漆中的添加量为1％时均能达到自熄的效果。
／迄巴八 硕士学位论文
w MASTER’S THESIS
6．对以上所合成的化合物进行了在环氧树脂（EAI）的阻燃测试，mi和四
其阻燃效果明显优于其它的化合物，可能的原因是其磷含量较大（分为
16二3％和15刀2．％＼残炭率和炭层结构与磷的含量有关：磷的含量增大，
残炭率也相应增大。添加了阻燃剂的样条有发泡膨胀现象，样条迅速炭化，
且无熔融、滴落和弯卷等现象。
7．对部分具有代表性化合物进行了热重（TG）和差热（DTA）分析表明：这
些化合物最高失重速率的温区均在 220～400 ’C，这与大部分高分子材料的
热氧降解温区重叠，具有较好的阻燃配伍性能。
In recent years, fire disasers were on the increase and made great property losses. In our country, in 1997, there were 140 thousand fire and 2722 fire deaths. Direct losses caused by fire added up to 1.54 billions. Fire disasers make great number of deaths and heavy property losses every year all over the world. Now people increasely realize that, treating inflammable materials with fire retardant is one of the strategic measures to prevent and decrease fire. Flame retardant material, especially flame retardant polymeric material, and flame retardant technology became research hotspot all over the world.
Nitrogen-phosphorus compounds are a family of promising flame retardants, which have many advantages: they themselves and their gases or vapors evolved during combustion have low toxicity. Nitrogen-phosphorus compounds as flame retaedant has a positive prospect.
1. Eight amide derivatives I a-h were synthesized by the substitute reaction of 1-oxo-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane-4-acyl chloride with
various amines.
2. Compound 5,5-dimethyl-2-hydrazino-2-oxo-l,3,2-dioxaphosphorinane was synthesized by 5,5-dimethyl-2-chloro-2-oxo-1,3,2-dioxaphosphorinane and hydrazine hydrate for the first time. Then 8 novel title compounds,
II a-h,were synthesized by 5,5-dimethyl-2-hydrazino-2-oxo-1,3,2-dioxaphos phorinane and substituted benzaldehydes.
3. Ten novel title compounds, III-j, were synthesized by 5.5-dimethyl-2-chloro -2-oxo-1,3,2-dioxaphosphorinane and various amines.
4. All the title compounds were confirmed by DR., 'H NMRx MS and elementary analysis.
5. Applied the compounds to alkyd resin varnish to test their Flame
resistance.All of the compounds give effect of self-extinguish in 1s with 1% addition in alkyd resin varnish.
6. Applied the compounds to expoxy resin (E-44) to test their Flame resistance. Compounds IIIi and IIIj have better flame resistance than others in epoxy resin (E-44). Because they are more phosphorus-containing than that of the others. The amount of charred residue increases with increasing phosphorus content in a material. The formation of more compact charred crust surface with increasing phosphorus content in material.The samples foamed and expanded during combustion process. They carbonize and extinguish after deviate from fire, without melting and dropping and with low smoking.
7. TG and DTA analysis of some of the compounds were discussed. Most of the compounds begin to decompose at 220 C and have certain thermal stability. They decompose rapidly during 220-400 C and overlapping many polymeric material' decomposition temperature ranger and show good fireproofing compatibility with materials.
引文
1 Gilman J W. Applied Clay Sci., 15(1999):31～49.
2 Gibert J P, Cuesta J M L, Bergeret A and Crespy A. Polym Degra and Stab., 67(2000):437～447
3 Price D, Milnes G J, Gao F. Polym Degra and Stab, 54 (1996):235～240.
4 Costes B, Henny Y. Polym Degra and Stab,54 (1996):329～332.
5 Kantrowitz F T, Foreman D U, Gutman W M, and Winkel R J. Atmospheric Environmant, 1995,22(29):3303～3307.
6 Yeh J T, Yang H M, Huang S S. Polym Degra and Stab, 50 (1995):229～234.
7 Wiseman D K. Plastics Compounding. 3 (1994):51～54
8 Green J. J. of Fire Sci, 15 (1997):52～67.
9 Green J. J. of Fire Sci, 12(1994):257～268.
10 Green J. J. of Fire Sci, 10 (1992):470～487.
11 Horacek H,Grabner R. Polym Degra and Stab,54(1996):205～215.
12 Redfern J P. Polym Degra and Stab,64(1999):561～572.
13 贡长生。现代化工，2(1996)：14～17
14 Buser H R.Environment Science Technology,20(1986):404.
15 Thoma H, Hauschulz G., Knorr E. and Hutzinger O.Chemosphere, 16(1987):277.
16 Atkinson P A, Haines P J, Skinner G A. Thermochimica Acta, 360 (2000):29～40.
17 Balabanovich A L, Engelmann J. Polym Degra and Stab,79 (2003):85～92.
18 Pielichowski K, Hamerton I. Polymer, 20 (1998):271.
19 Carrol W G, Grook J W, Haggio G A.(1971) British Pat 1,226,757.
20 Grook J W, Haggio G A.(1969)British Pat 1,158,544.
21 Buttgens W. Kerscher V, Neukircha E.(1987) European Pat EP-240806.
22 Boutevin B, Hervaud Y, Mouledous G. Polymer Bulletin, 41(1998):145～151
23 Chiu S H., Wang W K. Polym,39(1998): 1951～1955.
24 Zhu S, Shi W. Polym Degra and Stab, 80(2003):217～222.
25 汪志勇，胡源等。精细化工。1996，13(2)：31～34
26 Ibritght J A, Wilkison T C. US 4 696 964,1987
27 Hilhorst R,et al. Pur & Appl Chem., 1992, 64(11):1765.
28Leser M E, et al.Biotech Bioeng, 1993, 41 (4):489
29罗锐斌，殴育湘。精细化工。1993，10(4)：35～37
30张培成，郎斌，何颖。精细石油化工。1997(1)：9～11
31彭治汉，欧育湘。化学通报。1998(8)：39～42
32陈宇，高副业，欧育湘。精细化工。1998，15(3)：32～34
33张秀成，李斌，韩永臻。化学与粘合。2000(1)：22～24
34欧育湘。现代化工。1997(4)：9～11
35Kinugasa T. J Chem Eng Japan, 1994, 27(5):557
36徐旭荣，陈关喜等。精细化工。1997,14(5)：35～38
37吕彤，吴赞敏等。塑料化工。2001，29(1)：1～3
38宦双燕，扬兴钰，徐平勇。湖北化工。2001(2)：20～21
39宦双燕。华中师范大学硕士学位论文。2001
40Dekker M, et al. Chem EngSci, 1990.45(9):2949.
41Dungan S R,et al. J Colloid Interface Sci, 1991,145 (1):489.
42高副业，欧育湘。精细化工。1998，15(2)：35～37
43徐平勇。华中师范大学硕士学位论文。2000
44唐旭东，陈晓婷，王玉忠等。高等学校化学学报。1998，19(1)：1869～1871
45马志领，赵文革，徐立峰等。精细化工。1996，13(2)：26～28
46彭治汉，欧育湘。精细化工。1999，16(1)：20～23
47欧育湘，陈宇，王筱梅。阻燃高分子材料。北京：国防工业出版社，2001
48Halpem Y Niswander R. H. US 4454064. 1984
49Verkade J G, Reynolds L. J. Org Chem, 1960, 25,633.
50韩广甸。有机制备化学手册。中卷。北京：石油化学工业出版社，1977年。182
51李玉桂，王建基，韩淘等。化学学报，1988，46，679～685．
52李玉桂，朱雪峰，黄芹等。高等学校化学学报，1996，17(9)：1394～1398．
53李玉桂，李建敏，任海。高等学校化学学报，1992，13(2)：204～208．
54王筱梅，杨平。高分子材料科学与工程，1999，15(4)：81～83．
55Wang T S, Shau M D. J Appl Sci, 1998, Vol 70:1877～85.
56徐应鳞等。高聚物材料的实用阻燃技术。化学工业出版社。1987。
57 LiX.,Ou Y X, Shi YS. Polym Degra and Stab, 2002,77(3):383～390.
58 Yang C P, Lee T W. J. Appl Polym Sci, 1986, 32, 3005
59 Green J, Chung J. J Fire Sci, 1990,8:254.
60 Hsiue G H, Shiao S J, Sha Y A. J Appl Polym Sci,2001 ;29:342～349.
61 Zhu S W, Shi W F. Polym Degre Stab,2002;75:543～547.
2 Gibert J P, Cuesta J M L, Bergeret A and Crespy A. Polym Degra and Stab., 67(2000):437～447
3 Price D, Milnes G J, Gao F. Polym Degra and Stab, 54 (1996):235～240.
4 Costes B, Henny Y. Polym Degra and Stab,54 (1996):329～332.
5 Kantrowitz F T, Foreman D U, Gutman W M, and Winkel R J. Atmospheric Environmant, 1995,22(29):3303～3307.
6 Yeh J T, Yang H M, Huang S S. Polym Degra and Stab, 50 (1995):229～234.
7 Wiseman D K. Plastics Compounding. 3 (1994):51～54
8 Green J. J. of Fire Sci, 15 (1997):52～67.
9 Green J. J. of Fire Sci, 12(1994):257～268.
10 Green J. J. of Fire Sci, 10 (1992):470～487.
11 Horacek H,Grabner R. Polym Degra and Stab,54(1996):205～215.
12 Redfern J P. Polym Degra and Stab,64(1999):561～572.
13 贡长生。现代化工，2(1996)：14～17
14 Buser H R.Environment Science Technology,20(1986):404.
15 Thoma H, Hauschulz G., Knorr E. and Hutzinger O.Chemosphere, 16(1987):277.
16 Atkinson P A, Haines P J, Skinner G A. Thermochimica Acta, 360 (2000):29～40.
17 Balabanovich A L, Engelmann J. Polym Degra and Stab,79 (2003):85～92.
18 Pielichowski K, Hamerton I. Polymer, 20 (1998):271.
19 Carrol W G, Grook J W, Haggio G A.(1971) British Pat 1,226,757.
20 Grook J W, Haggio G A.(1969)British Pat 1,158,544.
21 Buttgens W. Kerscher V, Neukircha E.(1987) European Pat EP-240806.
22 Boutevin B, Hervaud Y, Mouledous G. Polymer Bulletin, 41(1998):145～151
23 Chiu S H., Wang W K. Polym,39(1998): 1951～1955.
24 Zhu S, Shi W. Polym Degra and Stab, 80(2003):217～222.
25 汪志勇，胡源等。精细化工。1996，13(2)：31～34
26 Ibritght J A, Wilkison T C. US 4 696 964,1987
27 Hilhorst R,et al. Pur & Appl Chem., 1992, 64(11):1765.
28Leser M E, et al.Biotech Bioeng, 1993, 41 (4):489
29罗锐斌，殴育湘。精细化工。1993，10(4)：35～37
30张培成，郎斌，何颖。精细石油化工。1997(1)：9～11
31彭治汉，欧育湘。化学通报。1998(8)：39～42
32陈宇，高副业，欧育湘。精细化工。1998，15(3)：32～34
33张秀成，李斌，韩永臻。化学与粘合。2000(1)：22～24
34欧育湘。现代化工。1997(4)：9～11
35Kinugasa T. J Chem Eng Japan, 1994, 27(5):557
36徐旭荣，陈关喜等。精细化工。1997,14(5)：35～38
37吕彤，吴赞敏等。塑料化工。2001，29(1)：1～3
38宦双燕，扬兴钰，徐平勇。湖北化工。2001(2)：20～21
39宦双燕。华中师范大学硕士学位论文。2001
40Dekker M, et al. Chem EngSci, 1990.45(9):2949.
41Dungan S R,et al. J Colloid Interface Sci, 1991,145 (1):489.
42高副业，欧育湘。精细化工。1998，15(2)：35～37
43徐平勇。华中师范大学硕士学位论文。2000
44唐旭东，陈晓婷，王玉忠等。高等学校化学学报。1998，19(1)：1869～1871
45马志领，赵文革，徐立峰等。精细化工。1996，13(2)：26～28
46彭治汉，欧育湘。精细化工。1999，16(1)：20～23
47欧育湘，陈宇，王筱梅。阻燃高分子材料。北京：国防工业出版社，2001
48Halpem Y Niswander R. H. US 4454064. 1984
49Verkade J G, Reynolds L. J. Org Chem, 1960, 25,633.
50韩广甸。有机制备化学手册。中卷。北京：石油化学工业出版社，1977年。182
51李玉桂，王建基，韩淘等。化学学报，1988，46，679～685．
52李玉桂，朱雪峰，黄芹等。高等学校化学学报，1996，17(9)：1394～1398．
53李玉桂，李建敏，任海。高等学校化学学报，1992，13(2)：204～208．
54王筱梅，杨平。高分子材料科学与工程，1999，15(4)：81～83．
55Wang T S, Shau M D. J Appl Sci, 1998, Vol 70:1877～85.
56徐应鳞等。高聚物材料的实用阻燃技术。化学工业出版社。1987。
57 LiX.,Ou Y X, Shi YS. Polym Degra and Stab, 2002,77(3):383～390.
58 Yang C P, Lee T W. J. Appl Polym Sci, 1986, 32, 3005
59 Green J, Chung J. J Fire Sci, 1990,8:254.
60 Hsiue G H, Shiao S J, Sha Y A. J Appl Polym Sci,2001 ;29:342～349.
61 Zhu S W, Shi W F. Polym Degre Stab,2002;75:543～547.