高分子复配改性高等级公路沥青研究
摘要
公路交通是促进国民经济发展的重要力量，现代化的高等级公路对沥青路面材料提出了更高的要求，因此，改性沥青的研究是当前国内外普遍关注的重大研究课题。
针对我国国产沥青绝大多数含蜡量高、温度感应性强、路用性能差的特点，本文采用特制的粉末丁苯橡胶(SBR)，并复配以有机金属皂(自制)、增强剂、增塑剂、天然沥青矿、废橡胶粉等不同改性剂对我国国产沥青进行改性，现已研制成功XW型系列改性沥青。试验结果表明，XW型改性沥青的各项指标达到或超过了中华人民共和国行业标准《公路改性沥青路面施工技术规范》的技术要求，能够用于高等级公路的建设。
本文的研究工作包括以下内容：
第一部分：选题的意义及国内外研究进展。
通过对国内外沥青产品的比较，阐明了对国产沥青改性的必要性。并从沥青和改性沥青两大方面，综述了国内外在这一领域的研究进展，对改性沥青的发展历史、体系标准、分类、制备、应用等做了详细地论述。
第二部分：实验部分。
除列出本文实验所需的原料、设备以及实验方法和测试方法外，还列出了对XW型改性沥青进行测试的交通部甲级资质单位的测试设备。
第三部分：沥青改性效果及改性机理探讨。
首先对沥青中共混SBS、SBR、APP、有机金属皂、纤维等改性剂的改性效果进行了比较，在此基础上，采用在沥青中分散性好并对沥青改性效果较好的粉末SBR，复配多种改性剂对国产沥青进行综合改性，测定了软化点、针入度、延度、蜡含量、四组分、旋转薄膜烘箱老化的延度及针入度比等指标，并经交通部(北京)公路科学研究所和山东省交通科学研究所交通建设工程检测中心检验。结论：该改性沥青质量符合规范规定的技术要求。实验结果显示，软化点提高，针入度减小，沥青高温稳定性提高：低温(5℃)延度有显著改善，其低温抗裂性能尤其突出；薄膜加热试验的残留物针入度损失极小，而且残留物仍有很大的5℃延度，表明此改性沥青有良好的抗老化性能；蜡含量明显减少，对沥青性能有明显改善。同时又结合美国战略公路研究计划(SHRP)进行了测试，根据SHRP沥青规范，对沥青进行性能分级。结果表明改性沥青等级为PG64—34，较基质沥青性能提高了一个等级，应用范围明显加宽。
另外，还采用了元素分析、显微照相、扫描电镜(SEM)、热分析(TG，DTG，DSC)、红外光谱分析等分析方法对沥青进行表征，探讨了可能的改性机理。
本研究课题是甘肃省科委定向攻关项目，也是西北师范大学科技创新工程重大项目。经2002年5月查新检索，采用粉末SBR和天然沥青矿改性沥青在国内尚属首创，有机金属皂和废橡胶粉改性沥青虽有研究，但如本文之复配改性尚未见相同报道。
Asphalt is an important low-cost thermo-plastic material which is widely used for construction, in particular as road-paving. Therefore it is exposed to a wide range of load and weather conditions. Increasing traffic factors, such as heavier loads, higher traffic volume and higher tire pressure demand higher performance pavements. However, this kind of materials does not have good mechanical properties because it is hard and brittle in cold weather, and soft and fluid in a hot environment.
In order to solve these problems, We modified asphalt in this paper by powdered Styrene Butadiene Rubber(SBR) blend with organic acids soaps, asphltite, reinfocer, plasticizer and waste automobile tyres powder. The best ratio was obtained through orthogonal design. Softening point, ductility, penetration degree and these properties after Rotary Thin Film Oven Test(RTFOT) aging of modified asphalt have been determined. The qualification test also did by Transportation Department of China and Institute of Highway of Shandong Province. The results show that the polymer blends less susceptible to temperature and increasing substantially its all-round performance. The properties of modified asphalt are higher than original asphalt and meet the Specification for Construction of Highway Modified Asphalt Pavement(JTJ 036-98) of China, so that it can be used as highway pavements.
The sample also measured according to Strategic Highway Research Program (SHRP) of USA such as PAY, DSR and BBR. The performance grade of modified asphalt was increased.
The microstrcture of the modified asphalt was characterized by SEM, FT-IR, TG-DTG, DSC and microscopy, and then, we discussed the possible mechanism of the modification.
Three parts are included in this paper:
Part one: The review of asphalt and modified asphalt of highway asphalt binders.
Part two: The material and instrument employed in this paper.
Part three: The results of our research and the mechanism discussion.
In this paper, powdered SBR and asphltite were firstly used to modify asphalt for highway pavements in China. We got satisfied results.
This work was supported by the Science and Technology Commission of Gansu Province and the NWNU-KJCXGC-03 of Northwest Normal University.
针对我国国产沥青绝大多数含蜡量高、温度感应性强、路用性能差的特点，本文采用特制的粉末丁苯橡胶(SBR)，并复配以有机金属皂(自制)、增强剂、增塑剂、天然沥青矿、废橡胶粉等不同改性剂对我国国产沥青进行改性，现已研制成功XW型系列改性沥青。试验结果表明，XW型改性沥青的各项指标达到或超过了中华人民共和国行业标准《公路改性沥青路面施工技术规范》的技术要求，能够用于高等级公路的建设。
本文的研究工作包括以下内容：
第一部分：选题的意义及国内外研究进展。
通过对国内外沥青产品的比较，阐明了对国产沥青改性的必要性。并从沥青和改性沥青两大方面，综述了国内外在这一领域的研究进展，对改性沥青的发展历史、体系标准、分类、制备、应用等做了详细地论述。
第二部分：实验部分。
除列出本文实验所需的原料、设备以及实验方法和测试方法外，还列出了对XW型改性沥青进行测试的交通部甲级资质单位的测试设备。
第三部分：沥青改性效果及改性机理探讨。
首先对沥青中共混SBS、SBR、APP、有机金属皂、纤维等改性剂的改性效果进行了比较，在此基础上，采用在沥青中分散性好并对沥青改性效果较好的粉末SBR，复配多种改性剂对国产沥青进行综合改性，测定了软化点、针入度、延度、蜡含量、四组分、旋转薄膜烘箱老化的延度及针入度比等指标，并经交通部(北京)公路科学研究所和山东省交通科学研究所交通建设工程检测中心检验。结论：该改性沥青质量符合规范规定的技术要求。实验结果显示，软化点提高，针入度减小，沥青高温稳定性提高：低温(5℃)延度有显著改善，其低温抗裂性能尤其突出；薄膜加热试验的残留物针入度损失极小，而且残留物仍有很大的5℃延度，表明此改性沥青有良好的抗老化性能；蜡含量明显减少，对沥青性能有明显改善。同时又结合美国战略公路研究计划(SHRP)进行了测试，根据SHRP沥青规范，对沥青进行性能分级。结果表明改性沥青等级为PG64—34，较基质沥青性能提高了一个等级，应用范围明显加宽。
另外，还采用了元素分析、显微照相、扫描电镜(SEM)、热分析(TG，DTG，DSC)、红外光谱分析等分析方法对沥青进行表征，探讨了可能的改性机理。
本研究课题是甘肃省科委定向攻关项目，也是西北师范大学科技创新工程重大项目。经2002年5月查新检索，采用粉末SBR和天然沥青矿改性沥青在国内尚属首创，有机金属皂和废橡胶粉改性沥青虽有研究，但如本文之复配改性尚未见相同报道。
Asphalt is an important low-cost thermo-plastic material which is widely used for construction, in particular as road-paving. Therefore it is exposed to a wide range of load and weather conditions. Increasing traffic factors, such as heavier loads, higher traffic volume and higher tire pressure demand higher performance pavements. However, this kind of materials does not have good mechanical properties because it is hard and brittle in cold weather, and soft and fluid in a hot environment.
In order to solve these problems, We modified asphalt in this paper by powdered Styrene Butadiene Rubber(SBR) blend with organic acids soaps, asphltite, reinfocer, plasticizer and waste automobile tyres powder. The best ratio was obtained through orthogonal design. Softening point, ductility, penetration degree and these properties after Rotary Thin Film Oven Test(RTFOT) aging of modified asphalt have been determined. The qualification test also did by Transportation Department of China and Institute of Highway of Shandong Province. The results show that the polymer blends less susceptible to temperature and increasing substantially its all-round performance. The properties of modified asphalt are higher than original asphalt and meet the Specification for Construction of Highway Modified Asphalt Pavement(JTJ 036-98) of China, so that it can be used as highway pavements.
The sample also measured according to Strategic Highway Research Program (SHRP) of USA such as PAY, DSR and BBR. The performance grade of modified asphalt was increased.
The microstrcture of the modified asphalt was characterized by SEM, FT-IR, TG-DTG, DSC and microscopy, and then, we discussed the possible mechanism of the modification.
Three parts are included in this paper:
Part one: The review of asphalt and modified asphalt of highway asphalt binders.
Part two: The material and instrument employed in this paper.
Part three: The results of our research and the mechanism discussion.
In this paper, powdered SBR and asphltite were firstly used to modify asphalt for highway pavements in China. We got satisfied results.
This work was supported by the Science and Technology Commission of Gansu Province and the NWNU-KJCXGC-03 of Northwest Normal University.
引文
1．沈金安，沥青及沥青混合料路用性能，人民交通出版社，2001
2．张德义，石油化工动态，1999，7(1)：11-14
3．江茂修，卢人严，石化技术，1999，6(2)：117-123
4．关玲，石油沥青，2001，15(3)：1—4
5．李正西，现代化工，1999，19(1)：34
6．陈仕周，石油沥青，1997，11(1)：46-48
7．黄伟祈，石油沥青，1996，10(4)：38-45
8．戈彩虹，王志荣，赵黎清，内蒙古石油化工，24：113—116
9．何粤虹，石油沥青，1999，13(1)：28-31
10．戈彩虹，赵黎清，郭克雄，王志荣，石油沥青，11(4)：24-27
11．郭燕生，张玉贞，程健，石油沥青，1997，11(3)：1-7
12．刘柏泉，何玉兰，石油沥青，1999，13(2)：24-29
13．韩刚，尹亚雄，石油沥青，1999，13(2)：42-45
14．李健，张琛，石油沥青，1999，13(2)：30-33
15．宁爱民，冯敏奇，石油沥青，1997，11(2)：6-11
16．李首先，黄伟祈，龙军，石油沥青，1997，11(4)：9-12
17．陈惠敏，石油沥青，1992，4：59-64
18. United States Patent:
1. 5,973,037 Styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture
2. 5,938,832 Crumb rubber modified asphalt with enhanced settling characteristics
3. 5,936,015 Rubber-modified asphalt paving binder
4. 5,929,144 Plasticized styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture
5. 5,902,852 Asphalt cement modification
6. 5,891,224 Rubber modified asphalt type of water-proofing compositions
7. 5,866,211 Rubber modified asphalt type of water-proofing compositions
8. 5,851,276 Crumb rubber modified asphalt with improved settling properties
9. 5,837,756 Polymer for asphalt cement modification
10. 5,744,524 Polymer modified asphaltic compositions with improved dispersion and products therefrom
11. 5,733,955 Asphalt cement modification
12. 5,704,971 Homogeneous crumb rubber modified asphalt
13. 5,683,498 Process for preparing rubber-modified asphalt compositions
14. 5,674,313 Rubber modified asphalt type of water-proofing composition
15. 5,637,640 Asphalt cement modification
16. 5,583,168 One-stage abrasive absorption process for producing tire.rubber modified asphalt cement systems and products thereof
17. 5,534,568 Asphalt cement modification
18. 5,516,817 Flame retardant modified asphalt-based material and products therefrom
19. 5,460,852 Method for applying polymer modified asphalt coating to corrugated pipes
20. 5,451,621 SBS-modified, asphalt-based material with resistance to crosslinking
21. 5,436,285 Recycled rubber in a polymer modified asphalt and a method of making same
22. 5,397,818 Process for producing tire rubber modified asphalt cement systems and products thereof
23. 5,393,819 Asphalt modifier
24. 5,393,811 Composition and method for improving the storage stability, of polymer modified asphalts
25. 5,364,894 Emulsification of asphalt and modified asphalt with primary emulsifier polymers comprised of acrylic acid type monomers
26. 5,348,994 Polymer-modified functionalized asphalt compositions and methods of preparation (C-2747)
27. 5,340,391 Performance-modified cold-applied asphalt compositions
28. 5,336,705 Polymer-modified, oxidized asphalt compositions and methods of preparation
29. 5,331,028 Polymer-modified asphalt composition and process for the preparation thereof
30. 5,302,638 Asphalt/O-modified polyethylene
31. H1,250 Modification of asphalt
32. 5,256,710 Method of producing, using and composition of phenolic-type POlymer modified asphalts or bitumens
33. 5,248,407 Storage stable polymer modified asphalt paving binder
34. 5,221,703 Engineered modified asphalt cement
35. 5,217,530 Performance-modifled asphalt pavements using recycled roofing waste
36. 5,095,055 Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577)
37. 5,085,896 Latex-modified asphalt emulsion tiecoat mastic coating system
38. 5,070,123 Method for improving the storage stability of polymer modified asphalt
39. 5,059,300 Asphalts modified by solvent deasphalted bottoms and phosphoric acid
40. 5,047,457 Acrylate polymer modified asphalt compositions
41. 5,039,342 Modified asphalt cement compositions and methods of producing the same
42. 5,019,610 Process for the production of polymer-modified asphalts and asphalts emulsions
43. 5,002,987 Modified asphalt cement
44. 4,889,880 Modified asphalt compositions
45. 4,868,233 Polyethylene modified asphalts,'～
46. 4,833,184 Acrylate polymer modified asphalt compositions
47. 4,780,146 Modified asphalt
48. 4,731,399 Latex modified asphalt foams
49. 4,677,146 Modified asphalt compositions comprising a nitrogen derivative of an esterified copolymer
50. 4,560,414 Modifier for paving asphalt
51. 4,554,023 Modified asphalt
52. 4,548,650 Diatomite-modified asphalt membranes and slurry seals
53. 4,528,241 Chemically modified asphalts and glass fibers treated therewith
54. 4,518,741 Chemically modified asphalts and glass fibers treated therewith
55. 4,508,770 Road repair material of knitted unidirectional glass roving mat coated with elastomeric modified asphalt
56. 4,507,365 Chemically modified asphalt protective coating solution and. concrete coated with same
57. 4,499,215 Modified asphalt-epoxy resin composition
58. 4,485,145 Chemically modified high oil asphalt
59. 4,485,144 Chemically modified asphalts and glass fibers treated therewith
60. 4,485,142 Chemically modified high oil asphalt
61. 4,444,947 Chemically modified high oil asphalt
62. 440,816 Rubber-modified asphalt composition
63. 436,864 Aqueous emulsions of acrylamide and rubber modified asphalts
64. 4,436,767 Slurry seal method using acrylamide and rubber modified asphaltic emulsion
65. 4,419,489 Easily emulsifiable acrylamide and rubber modified asphalts
66. 404,316 Chemically modified asphalt compositions
67. 4,403,067 Chemically modified asphalt joint sealing compositions
68. 4,394,482 Modified asphalt composition
69. 4,394,481 Cationic arcylamide and rubber modified asphalts
70. 4,384,099 Cationic amine modified asphalt compositions
71. 4,384,075 Cationic alkenyl azabenzene and rubber modified asphalts
72. 4,384,074 Cationic chemically modified asphalts
73. 4,384,073 Cationic alkenyl azabenzene chemically modified asphalts
74. 4,383,081 Cationic acrylamide chemically modified asphalts
75. 4,378,447 Cationic amine modified asphalt compositions
76. 4,360,473 Boron-modified asphalts
77. 4,349,388 Asphalt compositions modified with organo silane compounds
78. 4,347,171 Chemically modified asphalt joint sealing compositions
79. 4,338,231 Modified asphalt compositions
80. 4,335,186 Chemically modified asphalt compositions
81. 4,332,707 Synergistic solvent solution ofxylene and stoddard solvent for chemically modified asphalt
82. 4,332,705 Asphalt composition modified with a rubbery polymer
83. 4,332,704 Modified asphalt compositions
84. 4,325,854 Solvent solutions of chemically modified asphalts
85. 4,316,829 Modified asphalt compositions
86. 4,301,051 Chemically modified asphalt compositions
87. 4,292,371 Asphalt compositions modified with organo silane compounds
88. 4,282,038 Coil impregnant with modified asphaltite base
89. 4,273,685 Rubber modified asphalt compositions
90. 4,273,588 Asphalt compositions modified with organo silane compounds
91. 4,244,747 Modified asphalt paving compositions
92. 4,243,426 Asphalt compositions modified with organo-silane compounds
93. 4,234,346 High strength modified asphalt paving composition
94. 4,166,752 Chemically modified asphalt compositions
95. 4,022,635 Modified asphaltite potting composition
96. 3,931,439 Modified asphalt hydraulic sealer
19. SU Patent:
1. 2169161 Method of preparing bituminous material composition.
2. 857182 Road surfacing binder compsn.—contg. Butadiene-styrene elastomer petroleum asphaltite, cationic surfacant and petroleum distn, residue 范耀华，沥青，10:351-365
20．张登良，沥青路面，人民交通出版社，1998
21．张登良，沥青与沥青混合料，人民交通出版社
23．谭忆秋，赵晶，张肖宁，石油沥青，1998，12(4)：16-20
24．黄卫东，吕伟民，石油沥青，1997，11(2)：1-5
25. J. Shim-ton, K.A. Kennedy, M.R. Piggott, Rubber Chemistry and Technology, 1979,53:88-105
26. Jim H. Collins, Mark G. Bouldin, Rubber World, 1992, 8:32-69
27. L. H. Lewandowski, Rubber Chemistry and Technology, 1994, 67:447-480
28. T. F. Yen, J. G. Erjman, AnaL Chem, 1961, 33:1587
29．王志延，靳长征，韩宪琐，娄小珍，沥青加热技术，人民交通出版社，1998
30．原健安，石油沥青，1999，13(1)：16-21
31．韦松龄，冯敏奇，于世海，宁爱民等，石油沥青，1996，10(4)：23-31
32．张争奇，张登良，国外公路，1997，17(1)：38-42
33．凌语珍，吕伟民，石油沥青，1998，12(1)：47-49
34．于世海，郭长新，宁爱民，石油沥青，1997，11(1)：28—36
35．于世海，李健，董兆德，邢风钦等，石油炼制与化工，1998，29(10)：34-39
36. Austin H., British 9793(May 25, 1843)
37. Hancock G.L., British 9952(Nov. 21, 1843)
38. D.C.Thompsom, Bituminous Material: Asphalt Tars and Pitches, 1979, 1
39. S. Shuler, G.A.Epps, Paper No.41 Presented at a Meeting of the Rubber Division,American Chemical Society, Philadelphis, May 4-7, 1982
40. Blanco R., Rodriguez R., J. Polym, Sci., 1995, 56(1): 57-64
41．余叔藩译 性能分级沥青结合规范和试验(Superpave 丛书，第1册，美国沥青协会，1994,7)，交通部重庆公路科学研究所，1997．12
42．王仕峰，王迪珍，橡胶工业，2000，47(8)：503—506
43. TEH Fu Yen, J. Gordon Erdman, Sidney S. Poilack, Anal. Chem., 33(11): 1587-94
44. James R. Couper, Anal. Chem., 55(5): 257-302
45. Macak, J.V.M. Nabivach, P. Buryan, J. Chromat. Ogr., 209(3): 472-475
46. Bockrotch. B.C., R.B. Lacount, R.P. Noceti, Fuel 59(9): 621.626
47. Grelnke. R.A, L.H.O. Connor, Anal. Chem., 52(12): 1877-81
48. Fischer. P, J.W. Stadelhofer, M.Zander, Fuel, 57(6): 345-52
49. Rouxhet. P.R, P.L. Robin, Fuel 57(9): 533-40
50. Rulz. J.M, B.M. Carden, AnaL Chem., 54(4): 688-91
51. J.R. Benson, Roads Bridges, 1955, 98(4)
52. James R. Couper, Analytical Chemistry, 1983, 55(5): 257-309
53. B.R. Currell, B. Robinson, Talanta, 1967, 14:421-424
54. Hendrik Reerink, Jan Lijzenga, Analytical Chemistry, 1975, 47(13): 2160-2167
55. J.C. Petersen, Analytical Chemistry, 1975, 47(1): 112-117
56. Jacqueline de Merlier, J. Leveque, J. Curchod, Rubber Chemistry and Technology,1963, 40:457-476
57．范恩荣，玻璃钢/复合材料，1997，4：42-43
58. M.G. Bouldin, J.H. Collins, A. Berker, Rubber Chemistry and Technology,1990, 64:577-600
59．袁睛棠，石油沥青，1996，10(4)：5—8
60．交通部公路科学研究所等，首都机场高速公路沥青面层改性沥青混合料路用性能的试验研究，1995.9
61．原健安，石油沥青，1997，11(4)：13—18
62．刘楠，中国化工报，1999年9月7日
63．沈金安，石油沥青，1996，10(4)：14—22
64．中华人民共和国行业标准，公路改性沥青路面施工技术规范(JTJ036-98)，中华人民共和国交通部，1999
65．殷岳川，公路沥青路面施工，人民交通出版社，2000
66. S. Piazza, A. Arcozzi, Rubber Chem. Technol, 1980, 53:994
67. K.W. Mckay, W.A. Gros., J. of Appl. Polym. Sci., 1995, 56:947
68. R. Blanco, R.Rodriguez, M. Garcia-Garduno, V.M. Castano, J. of Appl. Polym. Sci.,1995, 56:57-64
69．杨京伟，徐瑞清，鲍浪，北京化工大学学报，1997，24(4)：38-44
70．孙玉琴，石化技术，1996，3(1)：62-66
71．赵晶，谭忆秋，张肖宁，石油沥青，1999，13(1)：12—15
72．彭永恒，邰连河，季辉，赵晶等，石油沥青，1997，11(4)：28—33
73. A. Adedeji, T. Jrunfelder, Polym. Eng. Sci. 36(12): 1707-1723
74. A. ADEDEJI, T. GRUNFE LDER, F.S. BATES, C.W. MACOSKO et al., Polymer Engineering and Sicence, 1996, 36(12): 1707-1723
75. A.Adedeji, A.M. Jamieson, Macromoleculs, 1995, 28:5255
76．景彦平，周凯，原健安，郝培文，华东公路，1998，4：64-67
77．H. Esser,Rubber Chem. and Technol, 1962, 10:1049-1063
78．United States Patent: 5, 925, 695 Curable composition, A cured article therefrom, An asphalt emulsion, An asphalt mixture for paving, and a cured article therefrom
79．沈化荣，吕伟民，石油沥青，1999，13(2)：19—23
80．李立寒，张南鹭，石油沥青，1997，11(3)：22—29
81．沈金安，改性沥青与SMA路面，人民交通出版社，1999
82．中国石油化工集团公司沥青情报站，国内改性沥青新产品的开发及市场形式与对策，2000.1.5
83．贾永明，筑路机械与施工机械化，1997，3：20-22
84．何玉兰，广石化科技，1998，3：56-62
85．史为宇，李文奇，王政恩，史金生，第七次全国石油沥青技术交流会论文集，中国石油化工集团公司沥青情报站，2000.5
86．中石化总公司沥青情报站，美国战略公路研究计划(SHRP)沥青结合料规范及试验方法介绍，1994.3
87．程源，合成橡胶工业，2001，24(2)：65—66
88．韩秀山，从慰然，张卫华，化工新型材料，2001，29(10)：17—19
89．朱三棣，粉煤灰，2000，3：31-33
90．陶国良，杨基和，王占华，龚方红等，江苏石油化工学院学报，2000，12(3)：16—19
91．薛风清，糜月琴，钟秦，陶国良，中国建筑防水，2000，6：18—21
92．孔宪明，王陆，废胶粉改性沥青的应用实践
93．J02251571 Material for improving asphalt for pavement-comprises asphaltite,aq.soln. contg.surface active agent and mineral oil or vegetable oil
94．沈金安，国外公路，2000，2
95．柳浩，王建国，石效民，石油沥青，2001，2
96．吴义祥，毕娟，天津市政工程，2001，13(3)：42—43
97．杨雄麟，杨倩燕，现代化工，1992，5：20-23
98．罗荫培，专利公开号：1287133，专利申请号：00119617.0 用于道路的改性沥青材料
99．GB2350366 FR2792943 BR200001644 CA2301928 New styrene-butadiene rubber latex, especially for coating aggregate for bituminous concrete, comprises a sulfonate-type and a high molecular weight ethylene oxide-propylene oxide-ethylene oxide polymer
100. SU1726427 Asphalt-concrete mixt.-contains bitumen, butadiene-styrene rubber prodn. Waste crushed limestone and sand
101．虞勋忠，王永森，谢旭峰，任志博，公路，1996，1
102．罗炳章，虞勋忠，李云华，道路工程学术会议论文集(沥青路面专辑)，1991
103．李云华，CT型金属皂沥青的研究及路用效果，(鉴定日期：19901119)
104．李稳宏，王维周，贺建勋，西北大学学报，1991，21(3)：73-78
105．周鸿顺，汤发有，石油化工，1994，23(10)：693-697
106．李梅，刘小权，张河军，陆景富，郑州轻工业学院学报，1997，12(2)：67-70
107．刘祖愉，现代化工，1998，9：23-25
108．刘祖愉，新型碳材料，1998，13(1)：43-48
109. United States Patent: 4, 234, 346 High strength modified asphalt paving composition
110．交通部阳离子乳化沥青课题协作组，阳离子乳化沥青路面，人民交通出版社，1998
111．黄彭，石油沥青，1998，12(4)：9-15
112. Amir F. Bissada, Ali A. Anani, Rubber Chemistry and Technology, 1983, 57:1-18
113．张凤毛，山东建材学院学报，1998，12(1)：74-76
114. Yvonne Becker, Maryro P. Mendez, Yajaira Rodriguez, VISION TECNOLOGICA,2001, 9(1): 39
115．沈金安，公路交通科技，1998，15(1)：2-9
116．原健安，石油沥青，1997，11(4)：13-18
117．申爱琴，付菁，李明国，李芳霞，石油沥青，2000，14(3)：23—28
118．吕伟民，李立寒，石油沥青，1998，12(3)：7-11
119. S. Piazza, A. Arcozzi, C. Verga, Rubber Chemistry and Technology, 1981, 53,994-1005
120. ABDELLATIF AIT-KADI, BRAHIM BRAHIMI, MOSTO BOUSMINA,POLYMER ENGINEERING AND SCIENCE, 1996, 36(12):1724-1733
121. J60141740 High mechanical strength powdered rubber compsn-including inorganic base and alcohol soln.
122. J56036548 J83054106 Rubber-asphalt paving compsn-prepd, by blending vulcanised rubber particles mineral aggregate, asphalt and polyurethane particles
123. SU-857182 Road surfacing binder compsn.-contg, butadienel-styrene elastomer petroleum asphaltite, cationic surfactant and petroleum distn. Residue
124. Huang Shin-Che, Huh Jung-Do, Robertson Raymond E., Tia Mang, Materials for the New Millennium Proceedings of the Materials Engineering Conference, 1996.2 p1367-1378
125. J57087461 Asphaltic waterproofing compsn.-consisting of straight and blown asphalt, vulcanised rubber and olefin copolymer
126．郝培文，王强，牛长友，石油沥青，1999，13(2)：46-48
127．原健安，石油沥青，1998，12(1)：14-18
128．樊统江，石油沥青，1993，1：32-35
129．陈信忠，温贵安，张隐西，石油沥青，2001，15(1)：28-32
2．张德义，石油化工动态，1999，7(1)：11-14
3．江茂修，卢人严，石化技术，1999，6(2)：117-123
4．关玲，石油沥青，2001，15(3)：1—4
5．李正西，现代化工，1999，19(1)：34
6．陈仕周，石油沥青，1997，11(1)：46-48
7．黄伟祈，石油沥青，1996，10(4)：38-45
8．戈彩虹，王志荣，赵黎清，内蒙古石油化工，24：113—116
9．何粤虹，石油沥青，1999，13(1)：28-31
10．戈彩虹，赵黎清，郭克雄，王志荣，石油沥青，11(4)：24-27
11．郭燕生，张玉贞，程健，石油沥青，1997，11(3)：1-7
12．刘柏泉，何玉兰，石油沥青，1999，13(2)：24-29
13．韩刚，尹亚雄，石油沥青，1999，13(2)：42-45
14．李健，张琛，石油沥青，1999，13(2)：30-33
15．宁爱民，冯敏奇，石油沥青，1997，11(2)：6-11
16．李首先，黄伟祈，龙军，石油沥青，1997，11(4)：9-12
17．陈惠敏，石油沥青，1992，4：59-64
18. United States Patent:
1. 5,973,037 Styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture
2. 5,938,832 Crumb rubber modified asphalt with enhanced settling characteristics
3. 5,936,015 Rubber-modified asphalt paving binder
4. 5,929,144 Plasticized styrene ethylene butylene styrene (SEBS) copolymer rubber modified asphalt mixture
5. 5,902,852 Asphalt cement modification
6. 5,891,224 Rubber modified asphalt type of water-proofing compositions
7. 5,866,211 Rubber modified asphalt type of water-proofing compositions
8. 5,851,276 Crumb rubber modified asphalt with improved settling properties
9. 5,837,756 Polymer for asphalt cement modification
10. 5,744,524 Polymer modified asphaltic compositions with improved dispersion and products therefrom
11. 5,733,955 Asphalt cement modification
12. 5,704,971 Homogeneous crumb rubber modified asphalt
13. 5,683,498 Process for preparing rubber-modified asphalt compositions
14. 5,674,313 Rubber modified asphalt type of water-proofing composition
15. 5,637,640 Asphalt cement modification
16. 5,583,168 One-stage abrasive absorption process for producing tire.rubber modified asphalt cement systems and products thereof
17. 5,534,568 Asphalt cement modification
18. 5,516,817 Flame retardant modified asphalt-based material and products therefrom
19. 5,460,852 Method for applying polymer modified asphalt coating to corrugated pipes
20. 5,451,621 SBS-modified, asphalt-based material with resistance to crosslinking
21. 5,436,285 Recycled rubber in a polymer modified asphalt and a method of making same
22. 5,397,818 Process for producing tire rubber modified asphalt cement systems and products thereof
23. 5,393,819 Asphalt modifier
24. 5,393,811 Composition and method for improving the storage stability, of polymer modified asphalts
25. 5,364,894 Emulsification of asphalt and modified asphalt with primary emulsifier polymers comprised of acrylic acid type monomers
26. 5,348,994 Polymer-modified functionalized asphalt compositions and methods of preparation (C-2747)
27. 5,340,391 Performance-modified cold-applied asphalt compositions
28. 5,336,705 Polymer-modified, oxidized asphalt compositions and methods of preparation
29. 5,331,028 Polymer-modified asphalt composition and process for the preparation thereof
30. 5,302,638 Asphalt/O-modified polyethylene
31. H1,250 Modification of asphalt
32. 5,256,710 Method of producing, using and composition of phenolic-type POlymer modified asphalts or bitumens
33. 5,248,407 Storage stable polymer modified asphalt paving binder
34. 5,221,703 Engineered modified asphalt cement
35. 5,217,530 Performance-modifled asphalt pavements using recycled roofing waste
36. 5,095,055 Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577)
37. 5,085,896 Latex-modified asphalt emulsion tiecoat mastic coating system
38. 5,070,123 Method for improving the storage stability of polymer modified asphalt
39. 5,059,300 Asphalts modified by solvent deasphalted bottoms and phosphoric acid
40. 5,047,457 Acrylate polymer modified asphalt compositions
41. 5,039,342 Modified asphalt cement compositions and methods of producing the same
42. 5,019,610 Process for the production of polymer-modified asphalts and asphalts emulsions
43. 5,002,987 Modified asphalt cement
44. 4,889,880 Modified asphalt compositions
45. 4,868,233 Polyethylene modified asphalts,'～
46. 4,833,184 Acrylate polymer modified asphalt compositions
47. 4,780,146 Modified asphalt
48. 4,731,399 Latex modified asphalt foams
49. 4,677,146 Modified asphalt compositions comprising a nitrogen derivative of an esterified copolymer
50. 4,560,414 Modifier for paving asphalt
51. 4,554,023 Modified asphalt
52. 4,548,650 Diatomite-modified asphalt membranes and slurry seals
53. 4,528,241 Chemically modified asphalts and glass fibers treated therewith
54. 4,518,741 Chemically modified asphalts and glass fibers treated therewith
55. 4,508,770 Road repair material of knitted unidirectional glass roving mat coated with elastomeric modified asphalt
56. 4,507,365 Chemically modified asphalt protective coating solution and. concrete coated with same
57. 4,499,215 Modified asphalt-epoxy resin composition
58. 4,485,145 Chemically modified high oil asphalt
59. 4,485,144 Chemically modified asphalts and glass fibers treated therewith
60. 4,485,142 Chemically modified high oil asphalt
61. 4,444,947 Chemically modified high oil asphalt
62. 440,816 Rubber-modified asphalt composition
63. 436,864 Aqueous emulsions of acrylamide and rubber modified asphalts
64. 4,436,767 Slurry seal method using acrylamide and rubber modified asphaltic emulsion
65. 4,419,489 Easily emulsifiable acrylamide and rubber modified asphalts
66. 404,316 Chemically modified asphalt compositions
67. 4,403,067 Chemically modified asphalt joint sealing compositions
68. 4,394,482 Modified asphalt composition
69. 4,394,481 Cationic arcylamide and rubber modified asphalts
70. 4,384,099 Cationic amine modified asphalt compositions
71. 4,384,075 Cationic alkenyl azabenzene and rubber modified asphalts
72. 4,384,074 Cationic chemically modified asphalts
73. 4,384,073 Cationic alkenyl azabenzene chemically modified asphalts
74. 4,383,081 Cationic acrylamide chemically modified asphalts
75. 4,378,447 Cationic amine modified asphalt compositions
76. 4,360,473 Boron-modified asphalts
77. 4,349,388 Asphalt compositions modified with organo silane compounds
78. 4,347,171 Chemically modified asphalt joint sealing compositions
79. 4,338,231 Modified asphalt compositions
80. 4,335,186 Chemically modified asphalt compositions
81. 4,332,707 Synergistic solvent solution ofxylene and stoddard solvent for chemically modified asphalt
82. 4,332,705 Asphalt composition modified with a rubbery polymer
83. 4,332,704 Modified asphalt compositions
84. 4,325,854 Solvent solutions of chemically modified asphalts
85. 4,316,829 Modified asphalt compositions
86. 4,301,051 Chemically modified asphalt compositions
87. 4,292,371 Asphalt compositions modified with organo silane compounds
88. 4,282,038 Coil impregnant with modified asphaltite base
89. 4,273,685 Rubber modified asphalt compositions
90. 4,273,588 Asphalt compositions modified with organo silane compounds
91. 4,244,747 Modified asphalt paving compositions
92. 4,243,426 Asphalt compositions modified with organo-silane compounds
93. 4,234,346 High strength modified asphalt paving composition
94. 4,166,752 Chemically modified asphalt compositions
95. 4,022,635 Modified asphaltite potting composition
96. 3,931,439 Modified asphalt hydraulic sealer
19. SU Patent:
1. 2169161 Method of preparing bituminous material composition.
2. 857182 Road surfacing binder compsn.—contg. Butadiene-styrene elastomer petroleum asphaltite, cationic surfacant and petroleum distn, residue 范耀华，沥青，10:351-365
20．张登良，沥青路面，人民交通出版社，1998
21．张登良，沥青与沥青混合料，人民交通出版社
23．谭忆秋，赵晶，张肖宁，石油沥青，1998，12(4)：16-20
24．黄卫东，吕伟民，石油沥青，1997，11(2)：1-5
25. J. Shim-ton, K.A. Kennedy, M.R. Piggott, Rubber Chemistry and Technology, 1979,53:88-105
26. Jim H. Collins, Mark G. Bouldin, Rubber World, 1992, 8:32-69
27. L. H. Lewandowski, Rubber Chemistry and Technology, 1994, 67:447-480
28. T. F. Yen, J. G. Erjman, AnaL Chem, 1961, 33:1587
29．王志延，靳长征，韩宪琐，娄小珍，沥青加热技术，人民交通出版社，1998
30．原健安，石油沥青，1999，13(1)：16-21
31．韦松龄，冯敏奇，于世海，宁爱民等，石油沥青，1996，10(4)：23-31
32．张争奇，张登良，国外公路，1997，17(1)：38-42
33．凌语珍，吕伟民，石油沥青，1998，12(1)：47-49
34．于世海，郭长新，宁爱民，石油沥青，1997，11(1)：28—36
35．于世海，李健，董兆德，邢风钦等，石油炼制与化工，1998，29(10)：34-39
36. Austin H., British 9793(May 25, 1843)
37. Hancock G.L., British 9952(Nov. 21, 1843)
38. D.C.Thompsom, Bituminous Material: Asphalt Tars and Pitches, 1979, 1
39. S. Shuler, G.A.Epps, Paper No.41 Presented at a Meeting of the Rubber Division,American Chemical Society, Philadelphis, May 4-7, 1982
40. Blanco R., Rodriguez R., J. Polym, Sci., 1995, 56(1): 57-64
41．余叔藩译 性能分级沥青结合规范和试验(Superpave 丛书，第1册，美国沥青协会，1994,7)，交通部重庆公路科学研究所，1997．12
42．王仕峰，王迪珍，橡胶工业，2000，47(8)：503—506
43. TEH Fu Yen, J. Gordon Erdman, Sidney S. Poilack, Anal. Chem., 33(11): 1587-94
44. James R. Couper, Anal. Chem., 55(5): 257-302
45. Macak, J.V.M. Nabivach, P. Buryan, J. Chromat. Ogr., 209(3): 472-475
46. Bockrotch. B.C., R.B. Lacount, R.P. Noceti, Fuel 59(9): 621.626
47. Grelnke. R.A, L.H.O. Connor, Anal. Chem., 52(12): 1877-81
48. Fischer. P, J.W. Stadelhofer, M.Zander, Fuel, 57(6): 345-52
49. Rouxhet. P.R, P.L. Robin, Fuel 57(9): 533-40
50. Rulz. J.M, B.M. Carden, AnaL Chem., 54(4): 688-91
51. J.R. Benson, Roads Bridges, 1955, 98(4)
52. James R. Couper, Analytical Chemistry, 1983, 55(5): 257-309
53. B.R. Currell, B. Robinson, Talanta, 1967, 14:421-424
54. Hendrik Reerink, Jan Lijzenga, Analytical Chemistry, 1975, 47(13): 2160-2167
55. J.C. Petersen, Analytical Chemistry, 1975, 47(1): 112-117
56. Jacqueline de Merlier, J. Leveque, J. Curchod, Rubber Chemistry and Technology,1963, 40:457-476
57．范恩荣，玻璃钢/复合材料，1997，4：42-43
58. M.G. Bouldin, J.H. Collins, A. Berker, Rubber Chemistry and Technology,1990, 64:577-600
59．袁睛棠，石油沥青，1996，10(4)：5—8
60．交通部公路科学研究所等，首都机场高速公路沥青面层改性沥青混合料路用性能的试验研究，1995.9
61．原健安，石油沥青，1997，11(4)：13—18
62．刘楠，中国化工报，1999年9月7日
63．沈金安，石油沥青，1996，10(4)：14—22
64．中华人民共和国行业标准，公路改性沥青路面施工技术规范(JTJ036-98)，中华人民共和国交通部，1999
65．殷岳川，公路沥青路面施工，人民交通出版社，2000
66. S. Piazza, A. Arcozzi, Rubber Chem. Technol, 1980, 53:994
67. K.W. Mckay, W.A. Gros., J. of Appl. Polym. Sci., 1995, 56:947
68. R. Blanco, R.Rodriguez, M. Garcia-Garduno, V.M. Castano, J. of Appl. Polym. Sci.,1995, 56:57-64
69．杨京伟，徐瑞清，鲍浪，北京化工大学学报，1997，24(4)：38-44
70．孙玉琴，石化技术，1996，3(1)：62-66
71．赵晶，谭忆秋，张肖宁，石油沥青，1999，13(1)：12—15
72．彭永恒，邰连河，季辉，赵晶等，石油沥青，1997，11(4)：28—33
73. A. Adedeji, T. Jrunfelder, Polym. Eng. Sci. 36(12): 1707-1723
74. A. ADEDEJI, T. GRUNFE LDER, F.S. BATES, C.W. MACOSKO et al., Polymer Engineering and Sicence, 1996, 36(12): 1707-1723
75. A.Adedeji, A.M. Jamieson, Macromoleculs, 1995, 28:5255
76．景彦平，周凯，原健安，郝培文，华东公路，1998，4：64-67
77．H. Esser,Rubber Chem. and Technol, 1962, 10:1049-1063
78．United States Patent: 5, 925, 695 Curable composition, A cured article therefrom, An asphalt emulsion, An asphalt mixture for paving, and a cured article therefrom
79．沈化荣，吕伟民，石油沥青，1999，13(2)：19—23
80．李立寒，张南鹭，石油沥青，1997，11(3)：22—29
81．沈金安，改性沥青与SMA路面，人民交通出版社，1999
82．中国石油化工集团公司沥青情报站，国内改性沥青新产品的开发及市场形式与对策，2000.1.5
83．贾永明，筑路机械与施工机械化，1997，3：20-22
84．何玉兰，广石化科技，1998，3：56-62
85．史为宇，李文奇，王政恩，史金生，第七次全国石油沥青技术交流会论文集，中国石油化工集团公司沥青情报站，2000.5
86．中石化总公司沥青情报站，美国战略公路研究计划(SHRP)沥青结合料规范及试验方法介绍，1994.3
87．程源，合成橡胶工业，2001，24(2)：65—66
88．韩秀山，从慰然，张卫华，化工新型材料，2001，29(10)：17—19
89．朱三棣，粉煤灰，2000，3：31-33
90．陶国良，杨基和，王占华，龚方红等，江苏石油化工学院学报，2000，12(3)：16—19
91．薛风清，糜月琴，钟秦，陶国良，中国建筑防水，2000，6：18—21
92．孔宪明，王陆，废胶粉改性沥青的应用实践
93．J02251571 Material for improving asphalt for pavement-comprises asphaltite,aq.soln. contg.surface active agent and mineral oil or vegetable oil
94．沈金安，国外公路，2000，2
95．柳浩，王建国，石效民，石油沥青，2001，2
96．吴义祥，毕娟，天津市政工程，2001，13(3)：42—43
97．杨雄麟，杨倩燕，现代化工，1992，5：20-23
98．罗荫培，专利公开号：1287133，专利申请号：00119617.0 用于道路的改性沥青材料
99．GB2350366 FR2792943 BR200001644 CA2301928 New styrene-butadiene rubber latex, especially for coating aggregate for bituminous concrete, comprises a sulfonate-type and a high molecular weight ethylene oxide-propylene oxide-ethylene oxide polymer
100. SU1726427 Asphalt-concrete mixt.-contains bitumen, butadiene-styrene rubber prodn. Waste crushed limestone and sand
101．虞勋忠，王永森，谢旭峰，任志博，公路，1996，1
102．罗炳章，虞勋忠，李云华，道路工程学术会议论文集(沥青路面专辑)，1991
103．李云华，CT型金属皂沥青的研究及路用效果，(鉴定日期：19901119)
104．李稳宏，王维周，贺建勋，西北大学学报，1991，21(3)：73-78
105．周鸿顺，汤发有，石油化工，1994，23(10)：693-697
106．李梅，刘小权，张河军，陆景富，郑州轻工业学院学报，1997，12(2)：67-70
107．刘祖愉，现代化工，1998，9：23-25
108．刘祖愉，新型碳材料，1998，13(1)：43-48
109. United States Patent: 4, 234, 346 High strength modified asphalt paving composition
110．交通部阳离子乳化沥青课题协作组，阳离子乳化沥青路面，人民交通出版社，1998
111．黄彭，石油沥青，1998，12(4)：9-15
112. Amir F. Bissada, Ali A. Anani, Rubber Chemistry and Technology, 1983, 57:1-18
113．张凤毛，山东建材学院学报，1998，12(1)：74-76
114. Yvonne Becker, Maryro P. Mendez, Yajaira Rodriguez, VISION TECNOLOGICA,2001, 9(1): 39
115．沈金安，公路交通科技，1998，15(1)：2-9
116．原健安，石油沥青，1997，11(4)：13-18
117．申爱琴，付菁，李明国，李芳霞，石油沥青，2000，14(3)：23—28
118．吕伟民，李立寒，石油沥青，1998，12(3)：7-11
119. S. Piazza, A. Arcozzi, C. Verga, Rubber Chemistry and Technology, 1981, 53,994-1005
120. ABDELLATIF AIT-KADI, BRAHIM BRAHIMI, MOSTO BOUSMINA,POLYMER ENGINEERING AND SCIENCE, 1996, 36(12):1724-1733
121. J60141740 High mechanical strength powdered rubber compsn-including inorganic base and alcohol soln.
122. J56036548 J83054106 Rubber-asphalt paving compsn-prepd, by blending vulcanised rubber particles mineral aggregate, asphalt and polyurethane particles
123. SU-857182 Road surfacing binder compsn.-contg, butadienel-styrene elastomer petroleum asphaltite, cationic surfactant and petroleum distn. Residue
124. Huang Shin-Che, Huh Jung-Do, Robertson Raymond E., Tia Mang, Materials for the New Millennium Proceedings of the Materials Engineering Conference, 1996.2 p1367-1378
125. J57087461 Asphaltic waterproofing compsn.-consisting of straight and blown asphalt, vulcanised rubber and olefin copolymer
126．郝培文，王强，牛长友，石油沥青，1999，13(2)：46-48
127．原健安，石油沥青，1998，12(1)：14-18
128．樊统江，石油沥青，1993，1：32-35
129．陈信忠，温贵安，张隐西，石油沥青，2001，15(1)：28-32