酚醛树脂/聚氨酯复合体系的研究
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摘要
本文将端羟基封端和端羧基封端的聚氨酯（PU）预聚物分别与酚醛树脂（PF）固化，制备了两种体系的增韧复合物。文中利用红外光谱对PF/PU共混物的分子结构进行了定性分析，利用扫描电镜对共混物冲击断面形貌进行了表征、用简支梁冲击试验机按国标测试PF/PU共混物的冲击强度，并按国标测试共混物体积收缩率，最后利用热重分析对PF/PU共混物的热稳定性进行测试。同时将两种PF/PU体系的共混物增韧各项性能进行对比，并对两种不同体系的增韧机理进行了讨论。研究结果表明：（1）增加促进剂用量，提高固化温度对共混物的凝胶速度有明显的促进作用，但凝胶速度过快会导致低分子物挥发不完全，影响固化效果，通过对比我们选择的固化条件为：促进剂用量3.5%，固化温度为80℃。（2）冲击实验结果表明二种PU预聚物均能提高PF的冲击强度，增韧效果与PU质量分数WPU有关；而端羧基PU能使复合物冲击强度达到的最大值比端羟基PU稍大。（3）随着聚氨酯预聚物加入量的增加，PF/PU共混物的体积收缩率明显变小，并能达到负值，但共混物仍具有良好的热稳定性。（4）通过红外光谱对PF/PU共混物分子结构进行的定性分析、以及扫描电镜对冲击断面形貌进行的分析，可证明聚氨酯预聚物增韧酚醛树脂的机理是：两个体系都是由于高分子量的线形氨基甲酸酯结构而增韧；端羟基PU与PF在共固化中产生化学键效应，参与PF的固化；而端羧基PU则与PF形成半互穿网络而增韧。
The hydroxyl-terminated and carboxyl-terminated PU-prepolymer were prepared and cured respectively with PF. The molecule structures of two composite systems were characterized by means of FT-IR, and cured-sample morphologies were analyzed by SEM. By means of the measurement of properties of PF, impact strength, volume shrinkage and thermal stability of PF/PU composite, effect of PU on PF has been investigated and the toughening differentials have been compared , then two kinds of toughening mechanisms have been discussed. The results show that :(1) The cure is accelerated by increasing the usage of cure catalyst and cure temperature, but cure effect is bad with too fast speed, so 3.5% cure catalyst and 80℃ cure temperature were cheese. (2) The results of impact experiments show that impact strength of PF is improved and improvement lever is related to WPU; but effect of carboxyl-terminated PU-prepolymer is better, that is to say the interpenetrating networks have priority at toughening of thermosetting resin. (3) volume shrinkage of composite decreases greatly with WPU increasing, even can arrive a negative number, but thermal stability is still good.(4)toughening mechanism is that :the formation of high molecular linear amino formate construct is the toughening reason; hydroxyl-terminated PU-prepolymer and PF react to produce chemical bond effect which participate cure; carboxyl-terminated PU-prepolymer and PF form semi-IPN which make toughened PF occur maximum.
The hydroxyl-terminated and carboxyl-terminated PU-prepolymer were prepared and cured respectively with PF. The molecule structures of two composite systems were characterized by means of FT-IR, and cured-sample morphologies were analyzed by SEM. By means of the measurement of properties of PF, impact strength, volume shrinkage and thermal stability of PF/PU composite, effect of PU on PF has been investigated and the toughening differentials have been compared , then two kinds of toughening mechanisms have been discussed. The results show that :(1) The cure is accelerated by increasing the usage of cure catalyst and cure temperature, but cure effect is bad with too fast speed, so 3.5% cure catalyst and 80℃ cure temperature were cheese. (2) The results of impact experiments show that impact strength of PF is improved and improvement lever is related to WPU; but effect of carboxyl-terminated PU-prepolymer is better, that is to say the interpenetrating networks have priority at toughening of thermosetting resin. (3) volume shrinkage of composite decreases greatly with WPU increasing, even can arrive a negative number, but thermal stability is still good.(4)toughening mechanism is that :the formation of high molecular linear amino formate construct is the toughening reason; hydroxyl-terminated PU-prepolymer and PF react to produce chemical bond effect which participate cure; carboxyl-terminated PU-prepolymer and PF form semi-IPN which make toughened PF occur maximum.
引文
1 李淑燕等.有关酚醛树脂的最新研究进展.高分子材料,1991,4(1):
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2 高月静等.玻璃纤维增强线性高分子复合增韧剂改性酚醛塑料的研究.塑料,1996,25(6): 30～32
3 张明善等.酚醛树脂与CPE弹性体共混增韧的研究.中国塑料,1991,5(3):44～50
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5 梁亚东.电工用热固性模塑料的应用和发展.绝缘材料通讯,2000,4:25～29
6 潘建光等.注射型酚醛树脂模塑料发展概况.绝缘材料通讯,2000,6:19～22
7 陈祥宝.高性能树脂基体.化学工业出版社,1998:24～25
8 闫联生.高性能酚醛树脂研究进展.玻璃钢/复合材料,2000,11:47～50
9 齐暑华等.混杂纤维增强酚醛热固性注塑料.工程塑料应用，1999,27(6):15～17
10 刘震云等.改性酚醛树脂复合材料.纤维复合材料,1999,16(1):32～35
11 Y.Daspet.Phenolic SMC and light weight laminates are result of recent resin developments.Reinforced Plastics , 1992,6:182～184
12 l.R.Samuel, W.V.Lewisburg. Phenolic foam composition and use thereof for "in place" foaming. U.S.Patent 328,694,Oct,25,1994
13 刘浩.酚醛泡沫塑料的研究.绝缘材料通讯,2000,2:14～16
14 王鹏飞等.刚性球粒在PEK-C/PF共混树脂复合材料中的增韧增强.玻璃钢/复合材料,2000,1:19～21
15 张垣等.磨擦材料基体－酚醛树脂改性研究.玻璃钢/复合材料,1999,5:24～26
16 范儆等.酚醛树脂的共聚改性.材料导报,1998,5:57～60
17 王文广.塑料改性实用技术.中国轻工业出版社,1990:212～233
18 夏天祥等.低温固化PVAc/UP体系低收缩控制研究进展.玻璃钢/复合材料,1999,6:49～51
19 冯青平等.低收缩相态结构的研究综述.玻璃钢/复合材料,2000,7:
43～45
20 张少国.低收缩剂.玻璃钢复合材料,2000,3:54～55
21 G.霍尔登等.热塑性弹性体.傅志峰译.化学工业出版社,2000:23～24
22 万勇军等.聚氨酯/乙烯基酯树脂互穿聚合物网络结构与性能的研究.塑料工业,1998,26(6):19～21
23 C.F.Blaich.Polyurethane Technology. John wiley and Sons,1969:
224～226
25 许美萱等.不饱和聚酯/聚氨酯互穿网络聚合物的合成.应用化学,
1995,12(2):72～75
26 H.D.Wu et al.Pultruded Fiber-Reinforced Polyurethane-Toughened Phenolic ResiⅠ.Reactivity and Morphology. Dic.Angew.Makromol.Chem, 1996,35:235～245
27 沈家瑞等.聚合物共混物与合金.华南理工大学出版社，1999:74～89
28 吴培熙等.聚合物共混改性.中国轻工业出版社，1996:86～91
29 王文广.塑料改性实用技术.中国轻工业出版社，2000:34～76
30 赵孝彬,杜磊.聚合物共混的相容性及相分离.高分子通报,2001,4:
75～80
31 范连华,胡春圃.反应注射成型聚氨酯互穿聚合物网络的进展.高分子通报,1997,3:129～134
32 范儆等.酚醛树脂的共聚改性,材料导报,1998,5:57～60
33 陈平.热固性树脂的增韧方法和增韧机理.热固性树脂,1996,2:42～46
34 朱立新.BMC用不饱和聚酯树脂的聚氨酯增韧改性.绝缘材料通讯,
2000:17～21
35 傅源明等.聚氨酯弹性体及其应用.化学工业出版社，1999:6～10
36 钱瑞莉.聚氨酯改性酚醛泡沫塑料.辽宁化工,1994，6：18～20.
37 王贵友.含有双酚A链段的聚氨酯网络研究.功能高分子学报,2001,2:138～142
38 刘棋.影响预聚体质量因素的探讨. 第六次聚氨酯泡沫塑料生产、科研技术交流会论文集.1999:162～165
39 吴存雷.聚氨酯预聚体技术及其应用.聚氨酯工业,2000,15(3):1～4
H.Y.Jyi et al.Effects of Chemical Structureof Polyurethane-Based low-prolileAdditives on the Miscibility,Curing Behavior,Volume Shrindage,Glass TransitionTemperatures,and Mechanical properties for Ststems.Ⅰ:Miscibility,curing Behavior,and Volume.Journal of Applied
40 Polymer Science, 2000,78:543～557
41 殷荣忠，山永年. 酚醛树脂及其应用.化学工业出版社,1990:87～101
42 C.H.Chun.Preparation of Polurethane-Phenolic resin foam plastic.CN 1,085,576
43 曹莲亿.红外光谱研究酚醛树脂.合成树脂及塑料,1990,1:48～51
44 G.C.Pimental, A.L.McClellan. The Hydrogen Bond, Freeman and Company. San Francisco and London, 1960:425～431
45 H.Ishida et al.Mechanical Characterization of Near-Zero Shrindage Polybenzoxazines, J.Polym.Sci.Part B:Polym.Physica,1996,34:1019～
1200
46 R.Saito et al.Thickening behaviour and shrinkage control of low profile unsaturated polyester resins.Polymer, 1996,37:12～34
47 王荣秋.固化树脂收缩率测定的几种方式.纤维复合材料,1994,2:
40～45
48 H.D. WU et al. Pultruded Fiber-Reinforced Polyurethane-Toughened Phenolic Resin.Ⅱ.Mechanical Properties,Thermal Properties,and Flame Resistance. Dic.Angew.Makromol.Chem, 1996，35：227～235.
49 D.J.Hourston. Toughening of Epoxy Resins with Thermoplastical Trifuctional epoxy resin-polyethenrimide blends.Polymer,1992,33(7):
1379～1383
50 Y.Daspet.Phenolic SMC and light weight laminates are result of recent resin developments.Reinforced Plastics ,1992,6:182～184
29～32
2 高月静等.玻璃纤维增强线性高分子复合增韧剂改性酚醛塑料的研究.塑料,1996,25(6): 30～32
3 张明善等.酚醛树脂与CPE弹性体共混增韧的研究.中国塑料,1991,5(3):44～50
4 朱永茂等.注塑型抗冲击酚醛树脂模塑料的研制.绝缘材料讯,2000,2:5～7
5 梁亚东.电工用热固性模塑料的应用和发展.绝缘材料通讯,2000,4:25～29
6 潘建光等.注射型酚醛树脂模塑料发展概况.绝缘材料通讯,2000,6:19～22
7 陈祥宝.高性能树脂基体.化学工业出版社,1998:24～25
8 闫联生.高性能酚醛树脂研究进展.玻璃钢/复合材料,2000,11:47～50
9 齐暑华等.混杂纤维增强酚醛热固性注塑料.工程塑料应用，1999,27(6):15～17
10 刘震云等.改性酚醛树脂复合材料.纤维复合材料,1999,16(1):32～35
11 Y.Daspet.Phenolic SMC and light weight laminates are result of recent resin developments.Reinforced Plastics , 1992,6:182～184
12 l.R.Samuel, W.V.Lewisburg. Phenolic foam composition and use thereof for "in place" foaming. U.S.Patent 328,694,Oct,25,1994
13 刘浩.酚醛泡沫塑料的研究.绝缘材料通讯,2000,2:14～16
14 王鹏飞等.刚性球粒在PEK-C/PF共混树脂复合材料中的增韧增强.玻璃钢/复合材料,2000,1:19～21
15 张垣等.磨擦材料基体－酚醛树脂改性研究.玻璃钢/复合材料,1999,5:24～26
16 范儆等.酚醛树脂的共聚改性.材料导报,1998,5:57～60
17 王文广.塑料改性实用技术.中国轻工业出版社,1990:212～233
18 夏天祥等.低温固化PVAc/UP体系低收缩控制研究进展.玻璃钢/复合材料,1999,6:49～51
19 冯青平等.低收缩相态结构的研究综述.玻璃钢/复合材料,2000,7:
43～45
20 张少国.低收缩剂.玻璃钢复合材料,2000,3:54～55
21 G.霍尔登等.热塑性弹性体.傅志峰译.化学工业出版社,2000:23～24
22 万勇军等.聚氨酯/乙烯基酯树脂互穿聚合物网络结构与性能的研究.塑料工业,1998,26(6):19～21
23 C.F.Blaich.Polyurethane Technology. John wiley and Sons,1969:
224～226
25 许美萱等.不饱和聚酯/聚氨酯互穿网络聚合物的合成.应用化学,
1995,12(2):72～75
26 H.D.Wu et al.Pultruded Fiber-Reinforced Polyurethane-Toughened Phenolic ResiⅠ.Reactivity and Morphology. Dic.Angew.Makromol.Chem, 1996,35:235～245
27 沈家瑞等.聚合物共混物与合金.华南理工大学出版社，1999:74～89
28 吴培熙等.聚合物共混改性.中国轻工业出版社，1996:86～91
29 王文广.塑料改性实用技术.中国轻工业出版社，2000:34～76
30 赵孝彬,杜磊.聚合物共混的相容性及相分离.高分子通报,2001,4:
75～80
31 范连华,胡春圃.反应注射成型聚氨酯互穿聚合物网络的进展.高分子通报,1997,3:129～134
32 范儆等.酚醛树脂的共聚改性,材料导报,1998,5:57～60
33 陈平.热固性树脂的增韧方法和增韧机理.热固性树脂,1996,2:42～46
34 朱立新.BMC用不饱和聚酯树脂的聚氨酯增韧改性.绝缘材料通讯,
2000:17～21
35 傅源明等.聚氨酯弹性体及其应用.化学工业出版社，1999:6～10
36 钱瑞莉.聚氨酯改性酚醛泡沫塑料.辽宁化工,1994，6：18～20.
37 王贵友.含有双酚A链段的聚氨酯网络研究.功能高分子学报,2001,2:138～142
38 刘棋.影响预聚体质量因素的探讨. 第六次聚氨酯泡沫塑料生产、科研技术交流会论文集.1999:162～165
39 吴存雷.聚氨酯预聚体技术及其应用.聚氨酯工业,2000,15(3):1～4
H.Y.Jyi et al.Effects of Chemical Structureof Polyurethane-Based low-prolileAdditives on the Miscibility,Curing Behavior,Volume Shrindage,Glass TransitionTemperatures,and Mechanical properties for Ststems.Ⅰ:Miscibility,curing Behavior,and Volume.Journal of Applied
40 Polymer Science, 2000,78:543～557
41 殷荣忠，山永年. 酚醛树脂及其应用.化学工业出版社,1990:87～101
42 C.H.Chun.Preparation of Polurethane-Phenolic resin foam plastic.CN 1,085,576
43 曹莲亿.红外光谱研究酚醛树脂.合成树脂及塑料,1990,1:48～51
44 G.C.Pimental, A.L.McClellan. The Hydrogen Bond, Freeman and Company. San Francisco and London, 1960:425～431
45 H.Ishida et al.Mechanical Characterization of Near-Zero Shrindage Polybenzoxazines, J.Polym.Sci.Part B:Polym.Physica,1996,34:1019～
1200
46 R.Saito et al.Thickening behaviour and shrinkage control of low profile unsaturated polyester resins.Polymer, 1996,37:12～34
47 王荣秋.固化树脂收缩率测定的几种方式.纤维复合材料,1994,2:
40～45
48 H.D. WU et al. Pultruded Fiber-Reinforced Polyurethane-Toughened Phenolic Resin.Ⅱ.Mechanical Properties,Thermal Properties,and Flame Resistance. Dic.Angew.Makromol.Chem, 1996，35：227～235.
49 D.J.Hourston. Toughening of Epoxy Resins with Thermoplastical Trifuctional epoxy resin-polyethenrimide blends.Polymer,1992,33(7):
1379～1383
50 Y.Daspet.Phenolic SMC and light weight laminates are result of recent resin developments.Reinforced Plastics ,1992,6:182～184