Ziegler-Natta催化剂合成丙烯/1-丁烯共聚物
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摘要
分别采用2种工业用Ziegler-Natta催化剂进行丙烯/1-丁烯淤浆共聚合研究,结果发现内给电子体结构对共聚合活性、共聚物组成、序列分布和产物相对分子质量都具有一定影响。通过调节反应物中丙烯/1-丁烯比例,分别合成了相对分子质量较高(重均相对分子质量30万～50万)和相对分子质量较低(重均相对分子质量10万～15万)且组成递变的2组丙丁共聚物。2组共聚物的结晶性能、热性能、拉伸性能和光学性能都随共聚物组成和序列分布的变化有所差异。
In this paper, propylene/1-butene slurry copolymerization was carried out using two kinds of industrial Ziegler-Natta catalysts. The results show that the catalyst internal electron donor structure has influences on the copolymerization activity, copolymer composition, sequence distribution and molecular weight of the products. Two series of copolymers with controllable compositions were synthesized by adjusting the feeding ratio of propylene to 1-butene, and the weight average molecular weight is also designed as 3×10~5～5×10~5 and 1×10~5～1.5×10~5, respectively. The copolymer composition and sequence distribution have effects on the crystallization behavior, thermal properties, tensile performance and optical properties of the polymers.
In this paper, propylene/1-butene slurry copolymerization was carried out using two kinds of industrial Ziegler-Natta catalysts. The results show that the catalyst internal electron donor structure has influences on the copolymerization activity, copolymer composition, sequence distribution and molecular weight of the products. Two series of copolymers with controllable compositions were synthesized by adjusting the feeding ratio of propylene to 1-butene, and the weight average molecular weight is also designed as 3×10~5～5×10~5 and 1×10~5～1.5×10~5, respectively. The copolymer composition and sequence distribution have effects on the crystallization behavior, thermal properties, tensile performance and optical properties of the polymers.
引文
[1] Dong J Y, Hu Y. Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry [J]. Coord. Chem. Rev., 2006, 250: 47-65.
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[3] Mao Y, Li X, Burger C, et al. Structure development during stretching and heating of isotactic propylene-1-butylene random copolymer: from unit cells to lamellae [J]. Macromolecules, 2012, 45: 7061-7071.
[4] 张春雨, 董博, 张贺新, 等. 本体共聚合制备丙烯/1-丁烯合金及表征[J]. 高等学校化学学报, 2014, 35(9): 2014-2018. Zhang C Y, Dong B, Zhang H X, et al. Preparation and characterization of propylene/1-butene alloy with bulk copolymerization [J]. Chemical Journal of Chinese Universities, 2014, 35(9): 2014-2018.
[5] 张京春,郭梅芳,黄红红,等. 丙烯1-丁烯和丙烯/乙烯无规共聚无的表征及性能研究[J]. 中国科学:化学,2014,44(11):1771-1775. Zhang J C, Guo M F, Huang H H, et al. The characterization and performance study of propylene/1-butylene and propylene/ethylene random copolymers [J]. Scientia Sinica(Chimica), 2014, 44(11): 1771-1775.
[6] Silva F M, Lima E L, Pinto J C, et al. Synthesis of propylene/1-butene copolymers with Ziegler-Natta catalyst in gas-phase copolmerizations, 1 [J]. Macromol. Chem. Phys., 2005, 206: 2333-2341.
[7] Androsch R, Hohlfeld R, Frank W, et al. Transition from two-stage to direct melt-crystallization in isotactic random butane-1/propene copolymers [J]. Polymer, 2013, 54: 2528-2534.
[8] 王航. 丙烯/1-丁烯共聚物的制备及其结构与性能的研究[D].杭州:浙江大学, 2007. Wang H. Study on the preparation of poly(propylene-co-1-butene) and its relationship between structure and properties [D].Hangzhou: Zhejiang University, 2007.
[9] Shieh Y T, Lee M S, Chen S A. Crystallization behavior, crystal transformation, and morphology of polypropylene/polybutene-1 blends [J]. Polymer, 2001, 42: 4439-4448.
[10] Chien J, Nozaki T. Ethylene hexene copolymerization by heterogeneous and homogeneous Ziegler-Natta catalysts and the comonomer effect [J]. J. Polym. Sci. Part A: Polym. Chem., 1993, 31: 227-237.
[11] Randall J C. C-13 NMR determination of comonomer sequence distributions in propylene-butene-1 copolymers [J]. Macromolecules, 1978, 11: 592-597.
[12] Zhang Y. Monomer sequence distributions in propylene-1-butene random copolymers [J]. Macromolecules, 2004, 37: 2471-2477.
[13] Libster D, Aserin A, Garti N. Advanced nucleating agents for polypropylene [J]. Polym. Adv. Technol., 2007, 18: 685-695.
[14] Hsu C C, Geil P H. Structure and properties of polybutlene crystallized from the glassy state. I. X-ray scattering, DSC, and torsion pendulum [J]. J. Macromol. Sci.: Phys., 1986, 25: 433-466.
[15] Nakamura K, Aoike T, Usaka K, et al. Phase transformation in poly(1-butene) upon drawing [J]. Macromolecules, 1999, 32: 4975-4982.
[16] Luo S, Yi P, Xiong Y, et al. Light-scattering capacity of ethylene-vinyl acetate copolymers in polypropylene: toward high haze and transmittance [J]. J. Appl. Polym. Sci., 2016, 133: DOI:10.1002/app.42844.
[17] Bernland K, Goossens J G P, Smith P, et al. On clarification of haze in polypropylene [J]. J. Polym. Sci. Part B: Polym. Phys., 2016, 54: 865-874.
[2] Corradini P. The discovery of isotactic polypropylene and its impact on pure and applied science [J]. J. Polym. Sci. Part A: Polym. Chem., 2004, 42: 391-395.
[3] Mao Y, Li X, Burger C, et al. Structure development during stretching and heating of isotactic propylene-1-butylene random copolymer: from unit cells to lamellae [J]. Macromolecules, 2012, 45: 7061-7071.
[4] 张春雨, 董博, 张贺新, 等. 本体共聚合制备丙烯/1-丁烯合金及表征[J]. 高等学校化学学报, 2014, 35(9): 2014-2018. Zhang C Y, Dong B, Zhang H X, et al. Preparation and characterization of propylene/1-butene alloy with bulk copolymerization [J]. Chemical Journal of Chinese Universities, 2014, 35(9): 2014-2018.
[5] 张京春,郭梅芳,黄红红,等. 丙烯1-丁烯和丙烯/乙烯无规共聚无的表征及性能研究[J]. 中国科学:化学,2014,44(11):1771-1775. Zhang J C, Guo M F, Huang H H, et al. The characterization and performance study of propylene/1-butylene and propylene/ethylene random copolymers [J]. Scientia Sinica(Chimica), 2014, 44(11): 1771-1775.
[6] Silva F M, Lima E L, Pinto J C, et al. Synthesis of propylene/1-butene copolymers with Ziegler-Natta catalyst in gas-phase copolmerizations, 1 [J]. Macromol. Chem. Phys., 2005, 206: 2333-2341.
[7] Androsch R, Hohlfeld R, Frank W, et al. Transition from two-stage to direct melt-crystallization in isotactic random butane-1/propene copolymers [J]. Polymer, 2013, 54: 2528-2534.
[8] 王航. 丙烯/1-丁烯共聚物的制备及其结构与性能的研究[D].杭州:浙江大学, 2007. Wang H. Study on the preparation of poly(propylene-co-1-butene) and its relationship between structure and properties [D].Hangzhou: Zhejiang University, 2007.
[9] Shieh Y T, Lee M S, Chen S A. Crystallization behavior, crystal transformation, and morphology of polypropylene/polybutene-1 blends [J]. Polymer, 2001, 42: 4439-4448.
[10] Chien J, Nozaki T. Ethylene hexene copolymerization by heterogeneous and homogeneous Ziegler-Natta catalysts and the comonomer effect [J]. J. Polym. Sci. Part A: Polym. Chem., 1993, 31: 227-237.
[11] Randall J C. C-13 NMR determination of comonomer sequence distributions in propylene-butene-1 copolymers [J]. Macromolecules, 1978, 11: 592-597.
[12] Zhang Y. Monomer sequence distributions in propylene-1-butene random copolymers [J]. Macromolecules, 2004, 37: 2471-2477.
[13] Libster D, Aserin A, Garti N. Advanced nucleating agents for polypropylene [J]. Polym. Adv. Technol., 2007, 18: 685-695.
[14] Hsu C C, Geil P H. Structure and properties of polybutlene crystallized from the glassy state. I. X-ray scattering, DSC, and torsion pendulum [J]. J. Macromol. Sci.: Phys., 1986, 25: 433-466.
[15] Nakamura K, Aoike T, Usaka K, et al. Phase transformation in poly(1-butene) upon drawing [J]. Macromolecules, 1999, 32: 4975-4982.
[16] Luo S, Yi P, Xiong Y, et al. Light-scattering capacity of ethylene-vinyl acetate copolymers in polypropylene: toward high haze and transmittance [J]. J. Appl. Polym. Sci., 2016, 133: DOI:10.1002/app.42844.
[17] Bernland K, Goossens J G P, Smith P, et al. On clarification of haze in polypropylene [J]. J. Polym. Sci. Part B: Polym. Phys., 2016, 54: 865-874.