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高分子化学 - 第六章 配位聚合

高分子化学 - 第六章 配位聚合

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Published by Shawn Zheng

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Published by: Shawn Zheng on Apr 06, 2009
Copyright:Attribution Non-commercial

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04/29/2012

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\u7b2c\u516d\u7ae0 \u914d\u4f4d\u805a\u5408
6.1\u914d\u4f4d\u805a\u5408\uff08coordination polymerization\uff09\u7684\u57fa\u672c\u6982\u5ff5
1953 \u5e74\u5fb7\u56fd\u5316\u5b66\u5bb6Ziegler\u7528Al(C2H5)3-TiCl4\u4f7f\u4e59\u70ef\u5728\u5e38\u538b\u4e0b\u805a\u5408\u83b7\u5f97\u4e86\u65e0\u652f\u94fe\u7684\u9ad8\u7ed3\u6676\u5ea6PE
\uff08\u9ad8\u5bc6\u5ea6PE\uff0cHDPE\uff09\u3002
1954 \u5e74\u610f\u5927\u5229\u5316\u5b66\u5bb6Natta\u7528Al(C2H5)3-TiCl3\u5f15\u53d1\u5242\u6210\u529f\u5730\u5c06\u96be\u4ee5\u805a\u5408\u7684\u7684\u4e19\u70ef\u5408\u6210\u89c4\u6574\u5ea6\u5f88\u9ad8

\u7684\u805a\u5408\u7269\u3002
Goodrich-Gulf \u516c\u53f8\u91c7\u7528 (C2H5)3-TiCl4\u4f7f\u5f02\u620a\u4e8c\u70ef\u805a\u5408\uff0c\u5236\u5f97\u987a\u5f0f 1,4 \u542b\u91cf\u5f88\u9ad8\uff0895-97%\uff09\u7684
\u805a\u5f02\u620a\u4e8c\u70ef\uff0c\u5ba3\u5e03\u4e86\u5408\u6210\u5929\u7136\u6a61\u80f6\u7684\u6210\u529f\u3002

1. \u914d\u4f4d\u805a\u5408\uff08coordination polymerization\uff09\u5b9a\u4e49
\u914d\u4f4d\u805a\u5408\u6700\u65e9\u662f Natta \u7528 Ziegler-Natta \u5f15\u53d1\u5242\u5f15\u53d1 \u03b1 \u70ef\u5f84\u805a\u5408\u89e3\u91ca\u673a\u7406\u65f6\u63d0\u51fa\u7684\u65b0\u6982\u5ff5\u3002

\u4e00\u79cd\u65b0\u578b\u7684\u52a0\u805a\u53cd\u5e94\uff0c\u4ece\u8bcd\u4e49\u4e0a\u6765\u8bf4\u662f\u5355\u4f53\u4e0e\u5f15\u53d1\u5242\u7ecf\u8fc7\u914d\u4f4d\u65b9\u5f0f\u8fdb\u884c\u7684\u805a\u5408\u53cd\u5e94\u3002
\u662f\u6307\u70ef\u7c7b\u5355\u4f53\u7684\u78b3\uff0d\u78b3\u53cc\u952e\u9996\u5148\u5728\u8fc7\u6e21\u91d1\u5c5e\u5f15\u53d1\u5242\u6d3b\u6027\u4e2d\u5fc3\u4e0a\u8fdb\u884c\u914d\u4f4d\u3001\u6d3b\u5316\uff0c\u968f\u540e\u5355\u4f53\u5206\u5b50\u76f8
\u7ee7\u63d2\u5165\u8fc7\u6e21\u91d1\u5c5e\uff0d\u78b3\u952e\u4e2d\u8fdb\u884c\u94fe\u589e\u957f\u7684\u8fc7\u7a0b\u3002
\u94fe\u589e\u957f\u53cd\u5e94\u53ef\u8868\u793a\u5982\u4e0b\uff1a

\u94fe\u589e\u957f\u8fc7\u7a0b\u7684\u672c\u8d28\u662f\u5355\u4f53\u5bf9\u589e\u957f\u94fe\u7aef\u7edc\u5408\u7269\u7684\u63d2\u5165\u53cd\u5e94
2.\u914d\u4f4d \u805a\u5408\u7684 \u7279\u70b9
\u5355\u4f53\u9996\u5148\u5728\u8fc7\u6e21\u91d1\u5c5e\u4e0a\u914d\u4f4d\u5f62\u6210
-\u7edc\u5408\u7269
\u8bc1\u636e\uff1a\u4e59\u70ef\u548cPt\u3001Pd \u751f\u6210\u7edc\u5408\u7269\u540e\u4ecd\u53ef\u5206\u79bb \u5236\u5f97\u4e864-\u7532\u57fa-1-\u620a\u70ef\uff0dVCl3 \u7684\u7edc\u5408\u7269
\u53cd\u5e94\u662f\u9634\u79bb\u5b50\u6027\u8d28: \u589e\u957f\u7684\u6d3b\u6027\u7aef\u6240\u5e26\u7684\u53cd\u79bb\u5b50\u7ecf\u5e38\u662f\u91d1\u5c5e\uff08\u5982Li\uff09\u6216\u8fc7\u6e21\u91d1\u5c5e\uff08\u5982Ti\uff09
\u95f4\u63a5\u8bc1\u636e\uff1a
-\u70ef\u70c3\u7684\u805a\u5408\u901f\u7387\u968f\u53cc\u952e\u4e0a\u70f7\u57fa\u7684\u589e\u5927\u800c\u964d\u4f4e
\u76f4\u63a5\u8bc1\u636e\uff1a
\u7528\u6807\u8bb0\u5143\u7d20\u7684\u7ec8\u6b62\u5242\u7ec8\u6b62\u589e\u957f\u94fe
\u5f97\u5230\u7684\u805a\u5408\u7269\u65e014C\u653e\u5c04\u6027\uff0c\u8868\u660e\u52a0\u4e0a\u7684\u662fH\uff0b\uff0c\u800c\u94fe\u7aef\u662f\u9634\u79bb\u5b50\uff0c\u56e0\u6b64\uff0c\u914d\u4f4d\u805a\u5408\u5c5e\u4e8e\u914d\u4f4d\u9634\u79bb
\u5b50\u805a\u5408
\u589e\u957f\u53cd\u5e94\u662f\u7ecf\u8fc7\u56db\u5143\u73af\u7684\u63d2\u5165\u8fc7\u7a0b
\u63d2\u5165\u53cd\u5e94\u5305\u62ec\u4e24\u4e2a\u540c\u65f6\u8fdb\u884c\u7684\u5316\u5b66\u8fc7\u7a0b\uff1a
\u5355\u4f53\u7684\u63d2\u5165\u53cd\u5e94\u6709\u4e24\u79cd\u53ef\u80fd\u7684\u9014\u5f84
> \u4e00 \u7ea7\u63d2 \u5165
\u4e0d\u5e26\u53d6\u4ee3\u57fa\u7684\u4e00\u7aef\uff08\u03b1 \u78b3\uff09\u5e26\u8d1f\u7535\u8377\uff0c\u4e0e\u8fc7\u6e21\u91d1\u5c5e\u76f8\u8fde\u63a5\uff0c\u79f0\u4e3a\u4e00\u7ea7\u63d2\u5165\uff0c\u4e19\u70ef\u7684\u5168\u540c\u805a\u5408\u4e3a\u4e00
\u7ea7\u63d2\u5165
> \u4e8c \u7ea7\u63d2 \u5165

\u5e26\u6709\u53d6\u4ee3\u57fa\u4e00\u7aef\u5e26\u8d1f\u7535\u8377\u5e76\u4e0e\u53cd\u79bb\u5b50\u76f8\u8fde\uff0c\u79f0\u4e3a\u4e8c\u7ea7\u63d2\u5165\uff0c\u4e19\u70ef\u7684\u95f4\u540c\u805a\u5408\u4e3a\u4e8c\u7ea7\u63d2\u5165
\u4e24\u79cd\u63d2\u5165\u6240\u5f62\u6210\u7684\u805a\u5408\u7269\u7684\u7ed3\u6784\u5b8c\u5168\u76f8\u540c\uff0c\u4f46\u7814\u7a76\u53d1\u73b0\uff1a\u4e19\u70ef\u7684\u5168\u540c\u805a\u5408\u662f\u4e00\u7ea7\u63d2\u5165\uff0c\u4e19\u70ef\u7684\u95f4
\u540c\u805a\u5408\u5374\u4e3a\u4e8c\u7ea7\u63d2\u5165\u3002

\u51e0\u79cd\u805a\u5408\u540d\u79f0\u542b\u4e49\u7684\u533a\u522b
>\u914d\u4f4d\u805a\u5408\uff08coordination polymerization\uff09\u3001\u7edc\u5408\u805a\u5408\uff08insertion polymerization\uff09
\u5728\u542b\u610f\u4e0a\u662f\u4e00\u6837\u7684\uff0c\u53ef\u4e92\u7528\u3002\u4e00\u822c\u8ba4\u4e3a\uff0c\u914d\u4f4d\u6bd4\u7edc\u5408\u8868\u8fbe\u7684\u610f\u4e49\u66f4\u660e\u786e\uff0c\u914d\u4f4d\u805a\u5408\u7684\u7ed3\u679c\uff1a\u53ef\u4ee5
\u5f62\u6210\u6709\u89c4\u7acb\u6784\u805a\u5408\u7269\uff1b\u4e5f\u53ef\u4ee5\u662f\u65e0\u89c4\u805a\u5408\u7269\u3002
>\u5b9a\u5411\u805a\u5408\uff08stereoregular polymerization\uff09\u3001\u6709\u89c4\u7acb\u6784\u805a\u5408\uff08stereospecific polymerization)

\u8fd9\u4e24\u8005\u662f\u540c\u610f\u8bed\uff0c\u662f\u4ee5\u4ea7\u7269\u7684\u7ed3\u6784\u5b9a\u4e49\u7684\uff0c\u90fd\u662f\u6307\u4ee5\u5f62\u6210\u6709\u89c4\u7acb\u6784\u805a\u5408\u7269\u4e3a\u4e3b\u7684\u805a\u5408\u8fc7\u7a0b\u3002
\u4efb\u4f55\u805a\u5408\u8fc7\u7a0b\uff08\u5305\u62ec\u81ea\u7531\u57fa\u3001\u9633\u79bb\u5b50\u3001\u9634\u79bb\u5b50\u3001\u914d\u4f4d\u805a\u5408\uff09\u6216\u4efb\u4f55\u805a\u5408\u65b9\u6cd5\uff08\u5982\u672c\u4f53\u3001\u60ac\u6d6e\u3001\u4e73
\u6db2\u548c\u6eb6\u6db2\u7b49\uff09\uff0c\u53ea\u8981\u80fd\u5f62\u6210\u6709\u89c4\u7acb\u6784\u805a\u5408\u7269\uff0c\u90fd\u53ef\u79f0\u505a\u5b9a\u5411\u805a\u5408\u6216\u6709\u89c4\u7acb\u6784\u805a\u5408\u3002

> Zigler-Natta\u805a\u5408\uff1a
\u91c7\u7528Zigler-Natta\u5f15\u53d1\u5242\u7684\u4efb\u4f55\u5355\u4f53\u7684\u805a\u5408\u6216\u5171\u805a\u5408\u3002\u6240\u5f97\u7684\u53ef\u4ee5\u662f\u7acb\u6784\u89c4\u6574\u7684\uff0c\u4e5f\u53ef\u4ee5\u662f\u65e0\u89c4\u7684\u3002
\u4e59\u4e19\u6a61\u80f6\u7684\u5236\u5907\u91c7\u7528Zigler-Natta\u50ac\u5316\u5242\uff0c\u5c5e\u914d\u4f4d\u805a\u5408\uff0cZigler-Natta\u805a\u5408\uff0c\u4f46\u7ed3\u6784\u662f\u65e0\u89c4\u7684\uff0c\u4e0d\u662f
\u5b9a\u5411\u805a\u5408\u3002
3.\u914d\u4f4d \u805a\u5408\u5f15 \u53d1\u5242\u4e0e \u5355\u4f53
\u5f15\u53d1\u5242\u548c\u5355\u4f53\u7c7b\u578b
-\u70ef\u70c3
\u6709\u89c4\u7acb\u6784\u805a\u5408
Ziegler-Natta \u5f15\u53d1\u5242
\u4e8c\u70ef\u70c3
\u73af\u70ef\u70c3
\u6709\u89c4\u7acb\u6784\u805a\u5408
-\u70ef\u4e19\u57fa\u954d\u578b\u5f15\u53d1\u5242\uff1a\u4e13\u4f9b\u4e01\u4e8c\u70ef\u7684\u987a\u3001\u53cd 1,4 \u805a\u5408
\u70f7\u57fa\u9502\u5f15\u53d1\u5242\uff08\u5747\u76f8\uff09
\u6781\u6027\u5355\u4f53
\u4e8c\u70ef\u70c3
\u6709\u89c4\u7acb\u6784\u805a\u5408
\u5f15\u53d1\u5242\u7684\u76f8\u6001\u548c\u5355\u4f53\u7684\u6781\u6027
\u975e\u5747\u76f8\u5f15\u53d1\u5242\uff0c\u7acb\u6784\u89c4\u6574\u5316\u80fd\u529b\u5f3a
\u6781\u6027\u5355\u4f53: \u5931\u6d3b
-\u70ef\u70c3\uff1a\u5168\u540c
\u5747\u76f8\u5f15\u53d1\u5242\uff0c\u7acb\u6784\u89c4\u6574\u5316\u80fd\u529b\u5f31
\u6781\u6027\u5355\u4f53: \u5168\u540c
-\u70ef\u70c3\uff1a\u65e0\u89c4
\u914d\u4f4d\u5f15\u53d1\u5242\u7684\u4f5c\u7528
>\u63d0\u4f9b\u5f15\u53d1\u805a\u5408\u7684\u6d3b\u6027\u79cd\uff1b
>\u63d0\u4f9b\u72ec\u7279\u7684\u914d\u4f4d\u80fd\u529b

\u4e3b\u8981\u662f\u5f15\u53d1\u5242\u4e2d\u8fc7\u6e21\u91d1\u5c5e\u53cd\u79bb\u5b50\uff0c\u4e0e\u5355\u4f53\u548c\u589e\u957f\u94fe\u914d\u4f4d\uff0c\u4fc3\u4f7f\u5355\u4f53\u5206\u5b50\u6309\u7167\u4e00\u5b9a\u7684\u6784\u578b\u8fdb\u5165\u589e\u957f
\u94fe\u3002\u5373\u5355\u4f53\u901a\u8fc7\u914d\u4f4d\u800c\u201c\u5b9a\u4f4d\u201d\uff0c\u5f15\u53d1\u5242\u8d77\u7740\u8fde\u7eed\u5b9a\u5411\u7684\u6a21\u578b\u4f5c\u7528\u3002
\u4e00\u822c\u8bf4\u6765\uff0c\u914d\u4f4d\u9634\u79bb\u5b50\u805a\u5408\u7684\u7acb\u6784\u89c4\u6574\u5316\u80fd\u529b\u53d6\u51b3\u4e8e\uff1a

> \u5f15 \u53d1\u5242 \u7684 \u7c7b\u578b
> \u7279 \u5b9a\u7684 \u7ec4 \u5408\u4e0e \u914d \u6bd4
> \u5355 \u4f53\u79cd \u7c7b
> \u805a \u5408\u6761 \u4ef6

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