Solution polymerization, polymer

The authors collected the test data shown in Table 9.10. From these data it can be noted that the number-average molecular weight, or Af , of a commercial emulsion SBR such as IISRP 1500 or 1712 is typically 90,000-175,000. The primary molecular weight of a solution-polymerized polymer produced with an anionic lithium catalyst can, in contrast, be increased toward 250,000 without gelation. In addition, emulsion-polymerized SBR contains only about 92% rubber hydrocarbon as a result of the presence of residues from the production process solution polymers tend to be near 100% hydrocarbon. As a consequence, the authors concluded that the number-average molecular weight... 

Brantley and Day then conducted a study to compare the tire performance of emulsion- and solution-polymerized SBR [12]. The authors noted that solution-polymerized polymers, which tend to have a narrower molecular weight distribution and lower Tg than equivalent emulsion-polymerized polymers, have lower hysteretic properties. Tliey then showed that a solution SBR with the same bound styrene as an emulsion SBR will give lower rolling resistance, improved dry traction, and better tread wear. Emulsion SBR, however, tends to show better wet skid, wet traction, and wet handling performance. Kern and Futamura later elaborated on this work by evaluating the impact of... 

W. Wang, Y. Guo, J.U. Otaigbe, Synthesis and characterization of novel biodegradable and biocompatible poly(ester-urethane) thin films prepared by homogeneous solution polymerization, Polymer 49 (2008) 4393-4398. 

In mass polymerization bulk monomer is converted to polymers. In solution polymerization the reaction is completed in the presence of a solvent. In suspension, dispersed mass, pearl or granular polymerization the monomer, containing dissolved initiator, is polymerized while dispersed in the form of fine droplets in a second non-reactive liquid (usually water). In emulsion polymerization an aqueous emulsion of the monomer in the presence of a water-soluble initiator Is converted to a polymer latex (colloidal dispersion of polymer in water). 

The type of initiator utilized for a solution polymerization depends on several factors, including the solubiUty of the initiator, the rate of decomposition of the initiator, and the intended use of the polymeric product. The amount of initiator used may vary from a few hundredths to several percent of the monomer weight. As the amount of initiator is decreased, the molecular weight of the polymer is increased as a result of initiating fewer polymer chains per unit weight of monomer, and thus the initiator concentration is often used to control molecular weight. Organic peroxides, hydroperoxides, and azo compounds are the initiators of choice for the preparations of most acryUc solution polymers and copolymers. 

Solution Polymerization. Solution polymerization is widely used ia the acryhc fiber iadustry. The reactioa is carried out ia a homogeaeous medium by usiag a solveat for the polymer. Suitable solveats can be highly polar organic compounds or inorganic aqueous salt solutions. 

Dimethylformamide [68-12-2] (DME) and dimethyl sulfoxide [67-68-5] (DMSO) are the most commonly used commercial organic solvents, although polymerizations ia y-butyrolactoae, ethyleae carboaate, and dimethyl acetamide [127-19-5] (DMAC) are reported ia the hterature. Examples of suitable inorganic salts are aqueous solutioas of ziac chloride and aqueous sodium thiocyanate solutions. The homogeneous solution polymerization of acrylonitrile foUows the conventional kinetic scheme developed for vinyl monomers (12) (see Polymers). 

Chain transfer is an important consideration in solution polymerizations. Chain transfer to solvent may reduce the rate of polymerization as well as the molecular weight of the polymer. Other chain-transfer reactions may iatroduce dye sites, branching, chromophoric groups, and stmctural defects which reduce thermal stabiUty. Many of the solvents used for acrylonitrile polymerization are very active in chain transfer. DMAC and DME have chain-transfer constants of 4.95-5.1 x lO " and 2.7-2.8 x lO " respectively, very high when compared to a value of only 0.05 x lO " for acrylonitrile itself DMSO (0.1-0.8 X lO " ) and aqueous zinc chloride (0.006 x lO " ), in contrast, have relatively low transfer constants hence, the relative desirabiUty of these two solvents over the former. DME, however, is used by several acryhc fiber producers as a solvent for solution polymerization. 

Pseudoplastic fluids are the most commonly encountered non-Newtonian fluids. Examples are polymeric solutions, some polymer melts, and suspensions of paper pulps. In simple shear flow, the constitutive relation for such fluids is... 

Solution polymerization of VDE in fluorinated and fluorochlorinated hydrocarbons such as CEC-113 and initiated with organic peroxides (99), especially bis(perfluoropropionyl) peroxide (100), has been claimed. Radiation-induced polymerization of VDE has also been investigated (101,102). Alkylboron compounds activated by oxygen initiate VDE polymerization in water or organic solvents (103,104). Microwave-stimulated, low pressure plasma polymerization of VDE gives polymer film that is <10 pm thick (105). Highly regular PVDE polymer with minimized defect stmcture was synthesized and claimed (106). Perdeuterated PVDE has also been prepared and described (107). 

The wide variety of ketomethylene and amino ketone monomers that could be synthesized, and the abiUty of the quinoline-forming reaction to generate high molar mass polymers under relatively mild conditions, allow the synthesis of a series of polyquinolines with a wide stmctural variety. Thus polyquinolines with a range of chain stiffness from a semirigid chain to rod-like macromolecules have been synthesized. Polyquinolines are most often prepared by solution polymerization of bis(i9-amino aryl ketone) and bis (ketomethylene) monomers, where R = H or C H, in y -cresol with di-y -cresyl phosphate at 135—140°C for a period of 24—48 h (92). 

Other than fuel, the largest volume appHcation for hexane is in extraction of oil from seeds, eg, soybeans, cottonseed, safflower seed, peanuts, rapeseed, etc. Hexane has been found ideal for these appHcations because of its high solvency for oil, low boiling point, and low cost. Its narrow boiling range minimises losses, and its low benzene content minimises toxicity. These same properties also make hexane a desirable solvent and reaction medium in the manufacture of polyolefins, synthetic mbbers, and some pharmaceuticals. The solvent serves as catalyst carrier and, in some systems, assists in molecular weight regulation by precipitation of the polymer as it reaches a certain molecular size. However, most solution polymerization processes are fairly old it is likely that those processes will be replaced by more efficient nonsolvent processes in time. 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

Solution Polymerization. In this process an inert solvent is added to the reaction mass. The solvent adds its heat capacity and reduces the viscosity, faciUtating convective heat transfer. The solvent can also be refluxed to remove heat. On the other hand, the solvent wastes reactor space and reduces both rate and molecular weight as compared to bulk polymerisation. Additional technology is needed to separate the polymer product and to recover and store the solvent. Both batch and continuous processes are used. 

Solution polymerization can use various solvents, primarily aUphatic and aromatic hydrocarbons. The choice of solvent is usually dictated by cost, avaHabihty, solvency, toxicity, flammabiUty, and polymer stmcture. SSBR polymerization depends on recovery and reuse of the solvent for economical operation as well as operation under the air-quaUty perrnitting of the local, state, and federal mandates involved. 

Anionic polymerization offers fast polymerization rates on account of the long life-time of polystyryl carbanions. Early studies have focused on this attribute, most of which were conducted at short reactor residence times (< 1 h), at relatively low temperatures (10—50°C), and in low chain-transfer solvents (typically benzene) to ensure that premature termination did not take place. Also, relatively low degrees of polymerization (DP) were typically studied. Continuous commercial free-radical solution polymerization processes to make PS, on the other hand, operate at relatively high temperatures (>100° C), at long residence times (>1.5 h), utilize a chain-transfer solvent (ethylbenzene), and produce polymer in the range of 1000—1500 DP. 

Solution Polymerization. Solution polymerization of vinyl acetate is carried out mainly as an intermediate step to the manufacture of poly(vinyl alcohol). A small amount of solution-polymerized vinyl acetate is prepared for the merchant market. When solution polymerization is carried out, the solvent acts as a chain-transfer agent, and depending on its transfer constant, has an effect on the molecular weight of the product. The rate of polymerization is also affected by the solvent but not in the same way as the degree of polymerization. The reactivity of the solvent-derived radical plays an important part. Chain-transfer constants for solvents in vinyl acetate polymerizations have been tabulated (13). Continuous solution polymers of poly(vinyl acetate) in tubular reactors have been prepared at high yield and throughput (73,74). 

Solution Polymerization. In solution polymerization, a solvent for the monomer is often used to obtain very uniform copolymers. Polymerization rates ate normally slower than those for suspension or emulsion PVC. Eor example, vinyl chloride, vinyl acetate, and sometimes maleic acid are polymerized in a solvent where the resulting polymer is insoluble in the solvent. This makes a uniform copolymer, free of suspending agents, that is used in solution coatings (99). 

Glass-Transition Temperature. The T of PVP is sensitive to residual moisture (75) and unreacted monomer. It is even sensitive to how the polymer was prepared, suggesting that MWD, branching, and cross-linking may play a part (76). Polymers presumably with the same molecular weight prepared by bulk polymerization exhibit lower T s compared to samples prepared by aqueous solution polymerization, lending credence to an example, in this case, of branching caused by chain-transfer to monomer. 

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