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improvement is continuous processing illustrated in Fig. 14.1; computer modeling has also been described.
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In the continuous process, styrene, butadiene, soap, initiator, and activator (an auxiliary initiating agent) are pumped continuously form storage tanks through a series of agitated reactors at such a rate that the desired degree of conversion is reached at the last reactor. Shortstop is added, the latex warmed with steam, and the unreacted butadiene flashed off. Excess styrene is steam-stripped, and the latex finished as shown in Fig. 14.1.
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SBR prepared from the original GR-S recipe is often called hot rubber; cold rubber is made at 5¡æ by using a more active initiator system. Typical recipes are given in Table 14.1 At 5¡æ ,60% conversion to polymer occurs in 12~15h.
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Cold SBR tire treads are superior to those of hot SBR. Polymers with abnormally high molecular weight (and consequently too tough to process by ordinary factory equipment) can be processed after the addition of up to 50 parts of petroleum-base oils per hundred parts of rubber (phr). These oil extenders make the rubbers more processible at lower cost and with little sacrifice in properties; they are usually emulsified and blended with the latex before coagulation.
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Recent trends have been toward products designed for specific uses. The color of SBR, which is important in many nontire uses, has been improved by the use of lighter-colored soaps, shortstops, antioxidants, and extending oils. For example, dithiocarbamates are substituted for hydroquinone as shortstop; the latter is used on hot SBR where dark color is not objectionable. A shortstop such as sodium dimethyldithiocarbamate is more effective in terminating radicals and destroying peroxides at the lower temperatures employed for the cold rubbers.
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Free-radical dissociative initiators that function by dissociation of a molecule or ion into two radical species are normally limited to inorganic persulfates in the case of butadiene polymerization.
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The other important class of free-radical initiators, redox systems, contain two or more components that react to produce free radicals. Dodecyl mercaptan added to control molecular weight also appears to aid free-radical formation by reaction with persulfate. The commercial importance of such chain-transfer agents or
16
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modifiers cannot be overemphasized. Without molecular weight control the rubbers would be too tough to process.
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--------Tate D p , Bechea T W. Encyclopedia of Polymer Science and Engineering, 2nd ed.
Vol. 2. Editor-in-chilf Kroschwitz JI. New York: John wiley & Sons, 1985. 553~555
C ¾ÛºÏÎï²ÄÁϵļӹ¤¡¢ÐÔÄܺÍÓ¦Óà UNIT 21 Polymer Processing µÚ¶þʮһµ¥Ôª ¾ÛºÏÎï¼Ó¹¤
Polymer processing , in its most general context , involves the transformation of a solid ( sometimes liquid ) polymeric resin , which is in a random form (e. g. powder, pellets , beads ), to a solid plastics product of specified shape , dimensions , and properties. This is achieved by means of a transformation process: extrusion, molding, calendering , coating , thermoforming , etc. The process, in order to achieve the above objective, usually involves the following operations: solid transport , compression, heating, melting, mixing, shaping, cooling, solidification, and finishing . Obviously, these operations do not necessarily occur in sequence, and many of them take place simultaneously.
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Shaping is required in order to impart to the material the desired geometry and dimensions. It involves combinations of viscoelastic deformations and heat transfer, which are generally associated with solidification of the product from the melt. ³ÉÐÍÊÇΪÁ˸øÓè²ÄÁÏËùÐèÒªµÄ¼¸ºÎÐÎ×´ºÍ³ß´ç¡£ËüÉæ¼°Õ³µ¯ÐαäºÍÈÈ´«µÝ£¬ÕâÖÖÕ³µ¯ÐαäºÍÈÈ´«µÝÊǺͲúÆ·´ÓÈÛÌåµÄ¹Ì»¯£¨»òÀäÈ´£©ÏàÁªÏµµÄ¡£
Shaping includes : (1) two-dimensional operations , e.g. dieforming, calendering and coating , and (2) three-dimensional molding and forming operations. Two-dimensional processes are either of the continuous , steady state type )e.g. film and sheet extrusion , wire coating , paper and sheet coating ,calendering ,fiber spinning , pipe and profile extrusion , etc. ) or intermittent as in the case of extrusions associated with intermittent extrusion
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blow moulding. Generally, moulding operations are intermittent, and, thus, they tend to involve unsteady state conditions. Thermoforming, vacuum forming, and similar processes may be considered as secondary shaping operations, since they usually involve the reshaping of an already shaped form. In some cases, like blow molding, the process involve primary shaping (parison formation) and secondary shaping (parison inflation ). ³ÉÐͰüÀ¨£º£¨1£©¶þÔª²Ù×÷£¬ÀýÈ磬¿ÚÄ£³ÉÐÍ¡¢Ñ¹ÑÓºÍÍ¿·ó£¬£¨2£©ÈýÔªµÄÄ£ÐͺͳÉÐͲÙ×÷¡£¶þÔªµÄ²Ù×÷ҪôÊÇÁ¬ÐøµÄ£¬¹Ì¶¨ÐÎ×´£¨ÀýÈ籡ĤºÍ°å²Ä£¬µçÏßÍ¿²¼£¬Ö½ºÍÆ½ÃæÍ¿²¼£¬Ñ¹ÑÓ£¬ÏËάÀÉ죬¹Ü²ÄºÍÐͲļ·³öµÈµÈ¡££© ҪôÊǼäЪʽµÄ£¬ÔÚ¼·³öµÄÇé¿öϰéÓмäЪ¼·³ö´µÄ¤¡£Í¨³££¬Ä£ËܲÙ×÷ÊǼäЪµÄ£¬È»¶øÍ¬Ê±ÇãÏòÓڷǹ̶¨Ìõ¼þ¡£ÈȳÉÐÍ£¬Õæ¿Õ³ÉÐÍ£¬ºÍÏàËÆµÄ¼Ó¹¤¿ÉÒÔÈÏΪÊǶþ´Î³ÉÐͲÙ×÷£¬ÒòΪËüÃÇͨ³£°üÀ¨ÒѳÉÐÍÐÎ×´µÄÔٴγÉÐÍ¡£ÔÚijЩÇé¿öÏÂÏñ´µÄ££¬¼Ó¹¤°üÀ¨Ê״γÉÐÍ£¨ÐÍÅß³ÉÐÍ£©ºÍ¶þ´Î³ÉÐÍ£¨ÐÍÅßÅòÕÍ£©¡£
Shaping operations involve simultaneous or staggered fluid flow and heat transfer. In two-dimensional processes, solidification usually follows the shaping process, whereas solidification and shaping tend to take place simultaneously inside the mold in three dimensional processes. Flow regimes, depending on the nature of the material, the equipment, and the processing conditions, usually involve combinations of shear, extensional, and squeezing flows in conjunction with enclosed (contained) or free surface flows.
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The thermo-mechanical history experienced by the polymer during flow and solidification results in the development of microstructure (morphology, crystallinity, and orientation distributions) in the manufactured article. The ultimate properties of the article are closely related to the microstructure. Therefore, the control of the process and product quality must be based on an understanding of the interactions between resin properties, equipment design, operating conditions, thermo-mechanical history, microstructure, and ultimate product properties. Mathematical modeling and computer simulation have been employed to obtain an understanding of these interactions. Such an approach has gained more importance in view of the expanding utilization of computer aided design/computer assisted manufacturing/computer aided engineering (CAD/CAM/CAE) systems in conjunction with plastics processing.
¾ÀúÁËÁ÷¶¯ºÍ¹Ì»¯£¨»òÀäÈ´£©µÄ¾ÛºÏÎïÈÈ»úе¹ý³Ìµ¼ÖÂÁËÖÆÔìҵ΢½á¹¹µÄ±ä¸ï£¨ÐÎ̬ѧ¡¢½á¾§Ñ§ºÍÈ¡Ïò·Ö²¼£©¡£×îÖÕ²úÆ·µÄÐÔÄÜÓë΢½á¹¹½ôÃÜÏà¹Ø¡£Òò´Ë£¬¼Ó¹¤ºÍ²úÆ·ÖÊÁ¿µÄ¿ØÖƱØÐë»ùÓÚÊ÷Ö¬ÐÔÄÜ¡¢É豸Éè¼Æ¡¢²Ù×÷Ìõ¼þ¡¢ÈÈ»úе¹ý³Ì¡¢Î¢½á¹¹ºÍ×îÖÕ²úÆ·ÐÔÄÜÖ®¼äÏ໥×÷ÓõÄÀí½â¡£ÊýѧģÐͺͼÆËã»ú±»Í¬Ê±ÓÃÓÚ»ñµÃÕâЩÏ໥×÷ÓõÄÀí½â¡£¼øÓÚ½øÒ»²½ÀûÓüÆ
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The following discussion will highlight some of the basic concepts involved in plastics shaping operations. It will emphasize recent developments relating to the analysis and simulation of some important commercial processes, with due consideration to elucidation of both thermo-mechanical history and microstructure development. More extensive reviews of the subject can be found in standard references on the topic (1~6).
ÏÂÃæµÄÌÖÂÛ½«Öصã·ÅÔÚ°üÀ¨ËÜÁϳÉÐͲÙ×÷һЩ»ù±¾¸ÅÄîÉÏ¡£Êʵ±¿¼ÂÇ˵Ã÷ÈÈ»úе¹ý³ÌºÍ΢½á¹¹·¢Õ¹£¬½«Ç¿µ÷×î½ü¹ØÓÚ·ÖÎöºÍÒ»Ð©ÖØÒªÉÌÆ·¼Ó¹¤Ä£Ð͵ĽøÕ¹¡£ÔÚÉ϶ˣ¨1¡«6£©µÄ±ê×¼²Î¿¼ÖÐÄܹ»ÕÒµ½±¾Ö÷Ìâ¸ü¹ã·ºµÄ×ÛÊö¡£ As mentioned above, shaping operations involve combinations of fluid flow and heat transfer, with phase change, of a visco-elastic polymer melt. Both steady and unsteady state processes are encountered. A scientific analysis of operations of this type requires solving the relevant equations of continuity, motion, and energy (i.e. conservation equations).
ÈçÉÏÃæÌáµ½µÄ£¬³ÉÐͲÙ×÷°üÀ¨ÒºÌåÁ÷¶¯ºÍÈÈ´«µÝ£¬¶ÔÓÚÏà̬±ä»¯£¬»¹°üÀ¨Õ³µ¯ÐÔ¾ÛºÏÎïµÄÈÛÈÚ¡£Îȶ¨ºÍ·ÇÎȶ¨×´Ì¬¼Ó¹¤ÊÇÏà³åÍ»µÄ¡£ÕâÖÖµäÐͲÙ×÷µÄ¿ÆÑ§·ÖÎöÐèÒª½â¾öÏà¹ØÁ¬Ðø¡¢ÔËתºÍÄÜÁ¿Æ½ºâ£¨ÈçÊØºã·½³Ì£©¡£
¡ª¡ªAustarita G , Nicolas L. Polymer prscessing and properties
New York: Plenum press 1984, 1~3
UNIT 29 Synthetic Plastics UNIT 23 ¾ÛºÏÎï¼Ó¹¤
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