Support Effect of Nanosized Hierarchical Silicalite-1 Zeolite on the Properties of Ziegler-Natta Catalyzed Polypropylene

doi:10.7503/cjcu20200331

Abstract

Abstract:

Due to the characteristics of special pore structure, large specific surface area, excellent stability and unique shape selectivity, zeolites inorganic porous material has become excellent green inorganic supports. Herein, nanosized hierarchical silicalite-1(S-1) zeolite with MFI topology was used as the inorganic support for Ziegler-Natta catalyst. The physicochemical properties of nanosized S-1 support were characterized in detail by X-ray diffraction(XRD), scanning electron microscopy, nitrogen adsorption-desorption, and other characterization methods. The effects of S-1 support on properties of polypropylene were also studied. In propy- lene polymerization, the larger specific surface area and hierarchical characteristics of the nanozied inorganic support S-1 are beneficial to increase the loading of Ziegler-Natta and improve the diffusion of reactants and products. Besides, the S-1 support can serve as a morphology-directed template, thus exhibiting a replica effect on the polypropylene product. Likewise, the crystallinity and isotactic index of the polymer products are improved in the propylene polymerization reaction at the same pressure and reaction temperature, due to the shape-selective effect and the replica effect of the hierarchical S-1 inorganic support. Consequentially, the S-1 support is conducive to improving the melting point of polypropylene products.

Key words: Inorganic hierarchical porous support, Ziegler-Natta catalyst, Confined space, Propylene poly- merization

CLC Number:

O643.3

TrendMD:

HUANG Pai, ZHOU Guangyuan, LIU Bo, WANG Lei, ZHANG Jiaqi. Support Effect of Nanosized Hierarchical Silicalite-1 Zeolite on the Properties of Ziegler-Natta Catalyzed Polypropylene[J]. Chem. J. Chinese Universities, 2020, 41(9): 2025.

Figures/Tables 6

Product	Catalyst			DSC		χ_c^b(%)	GPC		T_ca^c(%)
Product	n(Ti)/μmol	n(Al)/n(Ti)	10^-3Activity/ (kg·mol $T i - 1$ ·h^-1·MPa^-1)	T_c/℃	T_m/℃	χ_c^b(%)	10^-4M_w	PDI	T_ca^c(%)
PP?TMS?1	51.4	612	1.28	156.3	158.2	33.1	25.3	3.33	83.2
PP?TMS?2	42.8	553	1.56	152.8	156.5	31.4	27.3	3.78	85.9
PP?TMS?3	38.1	427	1.94	158.4	157.1	29.5	25.8	3.86	89.1
PP?TMS?4	47.4	568	1.85	154.4	157.3	32.3	29.4	4.21	86.6
PP?TMS?5	51.8	627	2.05	158.5	157.3	29.3	32.4	3.52	88.8
PP?TMS?6	65.9	691	2.53	159.5	158.3	35.1	40.2	2.89	86.9
PP?TMS?7	81.4	755	2.67	158.3	156.2	31.9	38.3	2.99	91.1
PP?TMS?8	56.1	816	2.41	158.7	158.4	33.5	35.1	3.21	85.9

Product	Catalyst			DSC		χ_c^b(%)	GPC		T_ca^c(%)
Product	n(Ti)/μmol	n(Al)/n(Ti)	10^-3Activity/ (kg·mol $T i - 1$ ·h^-1·MPa^-1)	T_c/℃	T_m/℃	χ_c^b(%)	10^-4M_w	PDI	T_ca^c(%)
PP?TMS?1	51.4	612	1.28	156.3	158.2	33.1	25.3	3.33	83.2
PP?TMS?2	42.8	553	1.56	152.8	156.5	31.4	27.3	3.78	85.9
PP?TMS?3	38.1	427	1.94	158.4	157.1	29.5	25.8	3.86	89.1
PP?TMS?4	47.4	568	1.85	154.4	157.3	32.3	29.4	4.21	86.6
PP?TMS?5	51.8	627	2.05	158.5	157.3	29.3	32.4	3.52	88.8
PP?TMS?6	65.9	691	2.53	159.5	158.3	35.1	40.2	2.89	86.9
PP?TMS?7	81.4	755	2.67	158.3	156.2	31.9	38.3	2.99	91.1
PP?TMS?8	56.1	816	2.41	158.7	158.4	33.5	35.1	3.21	85.9

References 52

1	Mason M. R., Smith J. M., Bott S. G., Barron A. R., J. Am. Chem. Soc., 1993, 115, 4971―4983
2	Vriezema D. M., Aragones M. C., Elemans J., Cornelissen J., Rowan A. E., Nolte R. J. M., Chem. Rev., 2005, 105, 1445―1489
3	Vriezema D. M., Garcia P. M. L., Oltra N. S., Hatzakis N. S., Kuiper S. M., Nolte R. J. M., Angew. Chem., Int. Ed., 2007, 46, 7378―7382
4	Han J. J., Yoon W. J., Lee H. W., Choi K. Y., Polymer, 2008, 49, 4141―4149
5	Soga K., Shiono T., Takemura S., Kaminsky W., Makromol. Chem., Rapid Commun., 1987, 8, 305―311
6	Bertrand H., Cecile B., Eric C., Progress in Polymer Science, 2011, 36, 89―126
7	Wang X., Xu R. W., Zhu B. C., New J. Chem., 2016, 40, 8324―8333
8	Chen Z. K., Mao Y. H., Cao Y. C., Chin. J. Org. Chem., 2018, 38, 2937―2992
9	Xiao X., Fu Z., Fan Z., China Synthetic Resin and Plastics, 2015, 32(1), 76―79
10	Comotti A., Bracco S., Beretta M., Chem. Eur. J., 2015, 21(50), 18209―18217
11	An L. C., Han J. F., Zhang Y. H., Chinese J. Appl. Chem., 2018, 35(9), 1019―1025
12	Sun Q., Dai Z., Meng X., Chem. Soc. Rev., 2015, 44(17), 6018―6034
13	Kageyama K., Tamazawa J., Aida T., Science, 1999, 285, 2113―2115
14	Dong X. C., Wang L., Wang W. Q., Wang J. F., Chen T., Zhao Z. R., European Polymer Journal, 2005, 41, 797―803
15	Naga N., Mizunuma K., Macromol. Chem. Phys., 1998, 199, 113―121
16	Frauenrath H., Keul H., Hocker H., Macromol. Rapid Commun., 1998, 19, 391―402
17	Li Y., Yu J., Chem. Rev., 2014, 114(14) , 7268―7316
18	Morales P. P., Dominguez J. M., Bucio L., Alvarez F., Sedran U., Falco M., Catal. Today, 2011, 166, 25―38
19	Yeung K. L., Han W., Catal. Today, 2014, 236, 182―205
20	Corma A., Chem. Rev., 1997, 97, 2373―2420
21	Wang Z., Yu J., Xu R., Chem. Soc. Rev., 2012, 41, 1729―1741
22	Li J., Corma A., Yu J., Chem. Soc. Rev., 2015, 44, 7112―7127
23	Zhou M., Korelskiy D., Ye P., Grahn M., Hedlund J., Angew. Chem., Int. Ed., 2014, 53(13), 3492―3495
24	Li Y., Li L., Yu J., Chem., 2017, 3(6), 928―949
25	Yang G., Akhade S. A., Chen X., Liu Y., Lee M. S., Glezakou V. A., Rousseau R., Lercher J. A., Angew. Chem., Int. Ed., 2019, 58(11), 3527―3532
26	Peng B., Yao Y., Zhao C., Lercher J. A., Angew. Chem., Int. Ed., 2012, 51(9), 2072―2075
27	Zhang J., Wang L., Shao Y., Wang Y. Q., Gates B. C., Xiao F. S., Angew. Chem., Int. Ed., 2017, 56(33), 9747―9751
28	Liu L., Corma A., Chem. Rev., 2018, 118(10), 4981―5079
29	Zhang Y., Zhou G., Sun B., Zhao M., Zhang J., Chen F., Chem. Commun., 2014, 50(22), 2907―2909
30	Na K., Somorjai G. A., Catal. Lett., 2015, 145(1), 193―213
31	Mckeen J. C., Yan Y. S., Davis M. E., Chen. Mater., 2008, 20, 5122―5124
32	Turunen J. P., Haukka M., Pakkanen T. T., Appl J., Progress in Polymer Science, 2004, 93, 1812―1817
33	Van Looveren L. K., Geysen D. F., Vercruysse K. A., Wouters B. H., Grobet P. J., Lacobs P. A., Angew. Chem., Int. Ed., 1998, 37, 517―521
34	Lin S., Li J., Sharma R., Topics in Catalysis, 2010, 53(19), 1304―1310
35	Yang G., Wei Y., Xu S., J. Phy. Chem. C., 2013, 117(16), 8214―8222
36	Chen X., Vicente A., Qin Z., Ruaux V., Gilson J. P., Valtchev V., Chem. Commun., 2016, 52(17), 3512―3515
37	Pan Y., Chen G., Yang G., Chen X., Yu J., Inorg. Chem. Front., 2019, 6(5), 1299―1303
38	Yang G., Han J., Qiu Z., Chen X., Feng Z., Yu J., Inorg. Chem. Front., 2020, 7(10), 1975―1980
39	Zhang X., Liu D., Xu D., Asahina S., Cychosz K. A., Agrawal K. V., Wahedi Y. A., Bhan A., Hashimi S. A., Terasaki O., Thommes M., Tsapatsis M., Science, 2012, 336(6089), 1684―1687
40	Galli P., Haylock J. C., Macromol Symp., 1992, 63, 19―54
41	Galli P., Vecellio G., Progress in Polymer Science, 2001, 26, 1287―1336
42	Mori H., Ohnishi K., Terano M., MacromolRapid Commun., 1996, 17, 25―34
43	Mteza S. B., Hsu C. C., Bacon D. J., J.Polym. Sci. Pol. Chem., 1996, 34, 1693―1702
44	Bochkin A. M., Pomogailo A. D., Dyachkovskii F. S., React. Funct. Polym., 1988, 9, 99―107
45	Huang R., Malizia F., Pennini G., Koning C. E., Chadwick J. C., Macromol Rapid Commun., 2008, 29, 1732―1740
46	Baerlocher C., McCusker L. B., http://www.iza⁃online.org/
47	Lei J. H., Li D. L., Wang H. H., Zhou G. Y., Polymer., 2011, 52, 602―605
48	Lee S. Y., Kim S. K., Nguyen T. M., Chung J. S., Lee S. B., Choi K. Y., Macromolecules, 2011, 44, 1385―1392
49	Sano T. J., Hagimoto H., Jin J. Z. H., Oumi Y., Uozumi T., Soga K., Macromol. Rapid Commun., 2000, 21, 1191―1195
50	Soga K., Uozumi T., Arai T., Nakamura S., Macromol. Rapid Commun., 1995, 16, 379―382
51	Soga K., Ohnishi R., Doi Y., Polym. Bull., 1983, 9, 299―304
52	Silva A. A., Alves M. D., Dos S. J. Z. H., J. Appl. Polym. Sci., 2008, 109, 1675―1683

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[3]	LI Xin, NI Xu-Feng, SHEN Zhi-Quan. Copolymerization of Norbornene with Isoprene Catalyzed by TiCl₄/Al(#em/em#-Bu)₃ System [J]. Chem. J. Chinese Universities, 2012, 33(05): 1095.
[4]	XU De-Min, MA Zhi, MI Xia, KE Yu-Cai, HU You-Liang, WU Chun-Hong. Studies on Catalyst Containing Novel Asymmetric Diether forPropene Polymerization [J]. Chem. J. Chinese Universities, 2002, 23(5): 982.
[5]	QIAN Ming-Xing, ZHOU Bin, HE Ren, WANG Mei, HUANG Yong, WANG Hui . Ethylene Oligomerization Catalyzed by Ind₂Zr(OC₆H₄-p-Me)₂/Et_nAlCl_3-n [J]. Chem. J. Chinese Universities, 2001, 22(10): 1771.
[6]	CHEN Tian-Hong, LIN Shang-An. Studies on Block Copolymers of Isotactic Polystyrene and Poly(ethene-co-propene)(Ⅰ)──Synthesis of iPS-b-Poly(E-co-P) Block Copolymer [J]. Chem. J. Chinese Universities, 1997, 18(11): 1875.
[7]	XU Jun-Ting, FENG Lin-Xian, YANG Shi-Lin. Tacticity Distributions of Polypropylene Prepared with Supported Ziegler-Natta Catalysts [J]. Chem. J. Chinese Universities, 1997, 18(10): 1734.
[8]	LI Yue, LIN Shang-An. Effect of Ethylene Prepolymerization in C₂H₄/H₂ Atmosphere with Ti-Mg Catalyst on Gas-phase Ethylene Polymerization [J]. Chem. J. Chinese Universities, 1996, 17(7): 1154.
[9]	CAO Zhan-Xian, ZHOU Ke-Yan . Oligomerization Reaction of 1-Butenes (Ⅸ) --The Discussion of Oligomerization Reaction Mechanism in System of the Nickel Carboxylate and Ethyl aluminum Chloride [J]. Chem. J. Chinese Universities, 1993, 14(11): 1600.
[10]	FAN Zhi-qiang, FENG Lin-xian, YANG Shi-lin . Plurality of Active Centers on Heterogeneous Ziegler-Natta Catalysts (Ⅱ)——Kinetic Parameters of Four Kinds of Active Centers [J]. Chem. J. Chinese Universities, 1992, 13(1): 137.
[11]	Chen Dian-bao, Kong Xian-si, Liu Li, Tang Xue-ming . UV-Vis Spectral Studies of 1,2-Polymerization System of Butadiene Catalized by Molybdenum Tetrachloride [J]. Chem. J. Chinese Universities, 1991, 12(2): 276.
[12]	Fan Zhi-qiang, Feng Lin-xian, Yang Shi-lin . Plurality of Active Centers on Heterogeneous Ziegler-Natta Catalysts(Ⅰ)--Studies on the Molecular-Weight Distribution of Polymer Synthesized by Titanium Catalysts [J]. Chem. J. Chinese Universities, 1991, 12(12): 1681.