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¡ª¡ªGowariker VR, Viswanathan N V, Sreedhar J. Polymer Science. New York:

John Wiley & Sons, 1986.6

UNIT 2 Chain Polymerization

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Many olefinic and vinyl unsaturated compounds are able to form chain-0like macromolecules through elimination of the double bond, a phenomenon first recognized by Staudinger. Diolefins

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polymerize in the same manner, however, only one of the two double bonds is eliminated. Such reactions occur through the initial addition of a monomer molecule to an initiator radical or an initiator ion, by which the active state is transferred from the initiator to the added monomer. In the same way by means of a chain reaction, one monomer molecule after the other is added (2000~20000 monomers per second) until the active state is terminated through a different type of reaction. The polymerization is a chain reaction in two ways: because of the reaction kinetic and because as a reaction product one obtains a chain molecule. The length of the chain molecule is proportional to the kinetic chain length.

StaudingerµÚÒ»¸ö·¢ÏÖÒ»ÀýÏÖÏó£¬Ðí¶àÏ©ÌþºÍ²»±¥ºÍÏ©Ìþͨ¹ý´ò¿ªË«¼ü¿ÉÒÔÐγÉÁ´Ê½´ó·Ö×Ó¡£¶þ

Ï©ÌþÒÔͬÑùµÄ·½Ê½¾ÛºÏ£¬È»¶ø£¬½öÏÞÓÚÁ½¸öË«¼üÖеÄÒ»¸ö¡£ÕâÀà·´Ó¦ÊÇͨ¹ýµ¥Ìå·Ö×ÓÊ×Ïȼӳɵ½Òý·¢¼Á×ÔÓÉ»ù»òÒý·¢¼ÁÀë×ÓÉ϶ø½øÐеģ¬¿¿ÕâЩ·´Ó¦»îÐÔÖÐÐÄÓÉÒý·¢¼ÁתÒƵ½±»¼Ó³ÉµÄµ¥ÌåÉÏ¡£ÒÔͬÑùµÄ·½Ê½£¬½èÖúÓÚÁ´Ê½·´Ó¦£¬µ¥Ìå·Ö×ÓÒ»¸ö½ÓÒ»¸öµØ±»¼Ó³É£¨Ã¿Ãë2000¡«20000¸öµ¥Ì壩ֱµ½»îÐÔÖÐÐÄͨ¹ý²»Í¬µÄ·´Ó¦ÀàÐͶøÖÕÖ¹¡£¾ÛºÏ·´Ó¦ÊÇÁ´Ê½·´Ó¦µÄÔ­ÒòÓÐÁ½ÖÖ£ºÒòΪ·´Ó¦¶¯Á¦Ñ§ºÍÒòΪ×÷Ϊ·´Ó¦²úÎïËüÊÇÒ»ÖÖÁ´Ê½·Ö×Ó¡£Á´·Ö×ӵij¤¶ÈÓ붯Á¦Ñ§Á´³¤³ÉÕý±È¡£

One can summarize the process as follow (R. is equal to the initiator radical): Á´Ê½·´Ó¦¿ÉÒÔ¸ÅÀ¨ÎªÒÔϹý³Ì£¨R¡¤Ï൱ÓëÒý·¢¼Á×ÔÓÉ»ù£©£ºÂÔ

One thus obtains polyvinylchloride from vinylchloride, or polystyrene from styrene, or polyethylene from ethylene, etc.

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The length of the chain molecules, measured by means of the degree of polymerization, can be varied over a large range through selection of suitable reaction conditions. Usually, with commercially prepared and utilized polymers, the degree of polymerization lies in the range of 1000 to 5000, but in many cases it can be below 500 and over 10000. This should not be interpreted to mean that all molecules of a certain polymeric material consist of 500, or 1000, or 5000 monomer units. In almost all cases, the polymeric material consists of a mixture of polymer molecules of different degrees of polymerization.

½èÖúÓھۺ϶ȹÀËãµÄ·Ö×ÓÁ´³¤£¬ÔÚÒ»¸ö´ó·¶Î§ÄÚ¿ÉÒÔͨ¹ýÑ¡ÔñÊÊÒ˵ķ´Ó¦Ìõ¼þ±»¸Ä±ä¡£Í¨³££¬Í¨¹ý´óÁ¿µØÖƱ¸ºÍÀûÓþۺÏÎ¾ÛºÏ¶ÈÔÚ1000¡«5000·¶Î§ÄÚ£¬µ«ÔÚÐí¶àÇé¿öÏ¿ɵÍÓÚ500¡¢¸ßÓÚ10000¡£Õâ²»Ó¦¸Ã°ÑËùÓоۺÏÎï²ÄÁϵķÖ×ÓÁ¿Àí½âΪÓÉ500£¬»ò1000£¬»ò5000¸öµ¥Ìåµ¥Ôª×é³É¡£ÔÚ¼¸ºõËùÓеÄÊÂÀýÖУ¬¾ÛºÏÎï²ÄÁÏÓɲ»Í¬¾ÛºÏ¶ÈµÄ¾ÛºÏÎï·Ö×ӵĻìºÏÎï×é³É¡£

Polymerization, a chain reaction, occurs according to the same mechanism as the well-known chlorine-hydrogen reaction and the decomposition of phosegene.

¾ÛºÏ·´Ó¦£¬Á´Ê½·´Ó¦£¬ÒÀÕÕÓëÖÚËùÖÜÖªµÄÂÈ£¨Æø£©-Ç⣨Æø£©·´Ó¦ºÍ¹âÆøµÄ·Ö½â»úÀí½øÐС£ The initiation reaction, which is the activation process of the double bond, can be brought about by heating, irradiation, ultrasonics, or initiators. The initiation of the chain reaction can be observed most clearly with radical or ionic initiators. These are energy-rich compounds which can add suitable unsaturated compounds (monomers) and maintain the activated radical, or ionic, state so that further monomer molecules can be added in the same manner. For the individual steps of the growth reaction one needs only a relatively small activation energy and therefore through a single activation step (the

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actual initiation reaction) a large number of olefin molecules are converted, as is implied by the term ¡°chain reaction¡±. Because very small amounts of the initiator bring about the formation of a large amount of polymeric material (1:1000 to 1:1000), it is possible to regard polymerization from a superficial point of view as a catalytic reaction. For this reason, the initiators used in polymerization reactions are often designated as polymerization catalysts, even though, in the strictest sense, they are not true catalysts because the polymerization initiator enters into the reaction as a real partner and can be found chemically bound in the reaction product ,i.e. ,the polymer, In addition to the ionic and radical initiators there are now metal complex initiators (which can be obtained, for example, by the reaction of titanium tetrachloride or titanium trichloride with aluminum alkyls), which play an important role in polymerization reactions (Ziegler catalysts) ,The mechanism of their catalytic action is not yet completely clear.

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