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Haloacetaldehyde Polymers and Macromolecular Asymmetry

OTTO VOGL Department of Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01002-4350. e-mail: vogl@polysci.umass.edu
Received 5 April 2000; accepted 13 April 2000

ABSTRACT: Polyhaloaldehydes play a special role in aldehyde polymerization. The most prominent trihaloacetaldehyde polymer, polytrichloroacetaldehyde, opened the door to new concepts in polymer chemistry: rst, cryotachensic polymerization, the separation of the initiation step from the propagation steps with the ceiling temperature principle for the fabrication of insoluble and infusible polymers, and second, the concept of macromolecular asymmetry and

stereospecic and conformationally specic polymerization. Trichloroacetaldhyde could be readily polymerized with a wide range of anionic (and also some cationic) initiators. When the anionic polymerization was initiated with chiral anions, it gave polychloral of one helix sense. To understand the genesis of the polymerization, the oligomerization was investigated to learn how the stereochemistry of the polymerization was established, also in chiral form. All

10 uoro-, chloro-, and bromosubstituted trihaloacetaldehydes were synthesized as necessary and polymerized, and the polymers were investigated. 2000 John Wiley
& Sons, Inc. J Polym Sci A: Polym Chem 38: 26232634, 2000

Keywords: haloaldehyde polymers; polychloral; macromolecular asymmetry; polybromal; bulk size; side groups; oligomers; optical activity

O. VOGL

Otto Vogl was born in Austria on November 6, 1927. He was educated in Austria, obtaining his Ph.D. in chemistry from the University of Vienna in 1950 when he was 22 years old. In 1948, he was appointed as an instructor at his university and served until 1953, when he went to the United States of America. After postdoctoral work at the University of Michigan and Princeton University, he joined the DuPont Co. and worked for 14 years in research at the Polychemicals and Central Research Department. In 1970, he was offered a professorship at the University of Massachusetts, which he accepted, and in 1983, he was appointed Herman F. Mark Professor, an endowed chair, at Polytechnic University in Brooklyn, NY. He retired in 1995 to his present position as Professor Emeritus at the University of Massachusetts. Otto Vogl is still very active as the editor of Progress in Polymer Science and is writing scientic and semiscientic articles of general interest. Most of Otto Vogls accomplishments in science, teaching, and profes-

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sional societies have been recorded in a recent article (J Polym Sci A: Polym Chem 2000, 38, 2293). Two aspects of his activities have made him unique in the scientic polymer community: his international activity and his interaction with the polymer industry. After his tenure as the chairman of the ACS Division of Polymer Chemistry, he created the international committee of the polymer division to provide a mechanism for the division to interact internationally in polymer chemistry. He became the chairman of the international committee and served for 14 years. During this time, he made agreements with the Society of Polymer Science, Japan, the French polymer group, the Italian polymer group, and the polymer division of the German Chemical Society. Not all these initiatives ourished, but the Japanese interaction, started in 1974, became a successful cooperation that lasted for many years and resulted in two joint meetings, in Palm Springs and Kyoto. This bilateral interaction was the seed for the creation of the Pacic Polymer Federation (PPF), which is now an organization of 17 member organizations with an estimated membership of 60,000 scientists. Otto Vogl was the rst industrial professor at Kyoto University in 1968 under the sponsorship of the head of the Department of Synthetic Chemistry, Professor Furukawa. Otto Vogl continued his interactions in Japan. He maintained his close cooperation with the Kyoto and Osaka polymer schools and was a frequent visitor to Japan. In 1980, he was a visiting professor, supported by the Society of the Promotion of Science, for one semester. Recently, in 1996, he received the unique and prestigious Monbushu professorship, an appointment by the Ministry of Science, Research, and Sports, and he was located at the Kyoto Institute of Technology. Otto Vogls interaction and commitment to Osaka University has lasted since his rst appointment as an adjunct professor in 1968. His visits, teaching at the university, and cooperation in scientic research were recognized with an honorary doctoral degree, the second such degree to be granted in the history of Osaka University. In his interaction with Japanese universities, Vogl was responsible for agreements of cooperation between the following institutions: Kyoto Institute of Technology and Polytechnic University of New York, Osaka University and the University of Massachusetts, and now Osaka University and the Royal Institute of Technology of Stockholm, Sweden. He was and is also committed to polymer science and teaching in Sweden. Since 1971 he has been a frequent visitor to Sweden and has taught 20-h short courses about every 5 years at the Royal Institute of Technology. He was a member of the oversight committee of the Swedish National Science Foundation on Organic and Biochemical Synthesis and the chairman of a similar committee on Polymer Science in 1988. Numerous were his visits to places that were not always easily accessible but where attention was desirable. Most prominently were his visits to the eastern countries of Europe: Poland, Czechoslovakia, and Romania. He also paid visits to China, where he spent 1 month almost 20 years ago, invited by the Ministry of Education, setting up a polymer program at the University of Wuhan and giving a 20-h short course at Wuhan University and also at East China Normal University, now the Textile University of China, in Shanghai. Otto Vogl is well-known for his scientic achievements and for his activities in professional societies. He was a member and acted as the chairman of national committees on polymer science, was active in

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several professional societies, and inuenced the publication of a number of scientic journals and books. He also was a deciding factor in the development of polymer science by taking initiatives in organizing meetings. In Japan with Junji Furukawa, Vogl created the U.S.Japan Seminars on Polymer Chemistry and organized the rst in Hakone. These meetings started in 1972 and have been held on a regular basis for almost 30 years. With Cristofer I. Simionescu, he organized the rst U.S.Romanian Symposium on Polymer Science in Iasi. With Bengt Ranby, he organized the second U.S.Sweden Seminar on Polymer Photochemistry in Pasadena, CA, and with Roger Epton he organized the rst Euro-American Symposium at St. Johns College in Oxford, England. He was the vice chairman of the 34th IUPAC Conference on Macromolecules in Amherst, MS in 1982 and was the chairman of the symposium Polymers for the Next Decade honoring Herman F. Mark on his 90th birthday at the Plaza Hotel in New York in 1985. As the president of the PPF, he organized the rst Pacic Polymer Conference in Maui, Hawaii in 1989. Vogls contributions to technical and economic development in the polymer eld, however, are not well-known. His background at DuPont gave him a substantial advantage in recognizing problems of industrial importance. He was rst called to an important industrial position in 1976, when he was asked to reorganize the research activities of the Division of Plastic Materials of Montedison in Italy (a $1.5 billion enterprise at that time). In his new position (as a director of the company), he successfully reorganized the research organization, and within 6 months, the supercatalysts to produce polypropylene highly efciently were discovered, which made Montedison and its successor companies in the polypropylene business the dominant force in polypropylene production and business worldwide. Some years later, Otto Vogl was asked as chairman of a scientic committee to advise the Vice President for Enichemica Research in Milan, Italy, Italo Trapasso, in streamlining the poly(vinyl chloride) business. For several years, Otto Vogl was also a member of a three-man academic group that advised the Vice President of Research of Westinghouse Corporation on the electric and mechanical properties of materials. Otto Vogl was also, for 5 years, a member of the Supervisory Board of Chemie Linz GmbH. He was also a major scientic advisor to PCD, the Polyolen Company of OeMV. He has also been, for the last 10 years, a member of the International Supervisory Committee of the Doppler Foundation in Austria. Vogls interactions with U.S. industry were also demonstrated when he was the prime mover to establish CUMIRP, the Center of University of Massachusetts Industrial Research on Polymers. Over the years, Otto Vogl had an extensive consulting schedule that included Tennessee Eastman, Eastman Kodak, Dow Chemicals, Alcon, Shell, and Merck, but ultimately and for the last 2 decades he consulted for DuPont. He was also a regular visitor and lecturer worldwide to academia and industry in Japan. His extensive industrial contacts allowed him, with U.S. industrial support, to create and establish the Pacic Polymer Federation. On his 70th birthday, his city of birth, Traiskirchen, Austria, honored him by establishing a permanent exhibition room in his name in its city museum and dedicating it to his accomplishments.

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Even now when he has reached emeritus status, Otto Vogl is still very active, presenting lectures and writing scientic and more general articles. He enjoys writing the life stories of his older friends, called Personalities in Polymer Science. He has written over 60 articles on this subject in Polymer News. He continues as Editor-in-Chief of Progress in Polymer Science, an Elsevier publication, and is American Editor of Monatshefte, where he published his rst article in 1948. In the earlier Highlight article in Journal of Polymer Science Part A: Polymer Chemistry, his contribution to several aspects of aldehyde polymerization is pointed out. Initially, he discovered the polymerization of higher aliphatic aldehydes and their isotactic polymers, the parallel of polymers of higher olens. Otto Vogl later turned to the study of haloaldehydes. They are not affected by the a priori oxidative instability that could not be handled for higher aldehyde polymers. Polychloral was the polymer of choice for another attempt to develop a commercial product based on a polyaldehyde. It almost succeeded. As for his contributions to the polymerization of haloaldehyde monomers, he 1. Selected polychloral for the investigations (72% chlorine). 2. Conrmed that polychloral is isotactic, the only polymer that exists only in a stereoregular, isotactic form. 3. Discovered cryotachensic polymerization (the separation of the initiation from the propagation step based on the ceiling temperature concept). 4. Uncovered the concept of optical activity based on macromolecular asymmetry. 5. Prepared the rst samples of optically active polychloral (based on macromolecular asymmetry) by cryotachensic polymerization initiated with a chiral initiator. With his research group, he 1. Determined the bulk size requirement of the side group for exclusive isotactic polymerization (with Yamada, Lipp, and Campbell). 2. Made the rst reliable measurements of the optical activity of polychloral lms (with Corley). 3. Established the stereochemistry of the initiation and rst polymerization steps and the development of stereo- and conformational specicity [genesis of p[olymerization]; (with Zhang, Jaycox, and Hatada)]. 4. Developed reliable methods to measure the optical activity of solids in the powder form (with Bartus). 5. Calculated the helical structures of a number of isotactic polyhaloaldehydes (with Atkins).

INTRODUCTION
After the conclusion of the initial work on the polymerization of higher aliphatic aldehydes1,2 we realized that they could not be efciently end-capped and further stabilized against thermal and oxidative degradation.3 Polychloral was a priori more stable, so we decided to concentrate on the polymerization of perhaloaldehydes and to develop polychloral as the most interesting and desirable aldehyde polymer.

POLYMERS OF HALOGENATED DERIVATIVES OF ACETALDEHYDE

The polymerization behavior of monochloroacetaldehyde (MCA)4 and dichloroacetaldehyde (DCA)5 is intermediate between the behaviors of acetaldehyde and chloral. Replacing chlorine atoms of the trichloromethyl group with hydrogen results in an increased reactivity of the monomers toward cationic polymerization. Effective initiators for the polymerization of DCA include a num-

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ber of well-known Lewis acids. Some bases, namely, tert-phosphines, tert-amines, and quaternary ammonium salts, which are excellent initiators of chloral polymerization, do not initiate the polymerization of MCA or DCA.6

Table I. Physical Properties and Polymerization Ceiling Temperatures ( T c s) of Haloacetaldehydes Haloaldehyde CH2FCHO CHF2CHO CH2ClCHO CHCl2CHO CF3CHO CF2ClCHO CF2BrCHO CFCl2CHO CFClBrCHO CCl3CHO CFBr2CHO CCl2BrCHO CClBr2CHO CBr3CHO bp (C) 64 27 85 89 19 18 43 56 80 98 116 127 148 174 T c (C)

PERHALOACETALDEHYDES
Perhaloacetaldehydes with chlorine, bromine, and uorine atoms in the trihalomethyl group are possible (we did not consider iodine as a possible substituent), allowing 10 combinations of trihaloacetaldehydes.2 We synthesized and characterized those that were not previously known, and we investigated the polymerization of all 10 perhaloacetaldehydes. They polymerize under conditions similar to those for chloral but with some subtle differences. The polymerizations were readily carried out with anionic initiators but less efciently with cationic initiators.716

85 63 48 41 33 11 7 15 40 75

CEILING TEMPERATURES OF ALDEHYDE POLYMERIZATION

The ceiling temperature (Tc) of polymerization is dened as the temperature at which the rate of polymerization of a 1 M monomer solution is equal to the rate of the depolymerization of the polymer, which is in equilibrium with the monomer. In a simpler way, it is the temperature of a 1 M monomer/polymer equilibrium, above which the monomer is the stable species and below which the polymer is the more stable species.17 For vinyl polymerizations, Tc considerations are not very important because the Tcs are very high (perhaps 300 C higher than the corresponding aldehyde polymers). The Tc of polyethylene has never been determined. One reason is that the equilibrium cannot be readily established because depolymerization is accompanied by thermal degradation to side products other than the monomer. Estimates can be made that are based on the thermal degradation and heat of polymerization (22 kcal/mol). It should be well above 400 C, perhaps even 500 C. Higher substitution on the vinyl double bond of ethylene, especially of bulky groups, reduced the Tc drastically. Methyl methacrylate (12 kcal/mole) has a Tc of 165 C, and the Tc of methyl ethacrylate is even lower. Aldehyde polymers are much less stable, and formaldehyde polymerization has a Tc of about 125 C (the most reliable value is 119 C) at a heat of polymerization of 12.5 kcal/mol. Various methods have been used to determine the Tc of the polymerization of various monomers. The Tc determinations assume that both monomer

and polymer are in solution. If the polymer precipitates as polymerization proceeds, the equilibrium is disturbed, the heat of crystallization or solidication is added, and the Tc now consists of the heat of polymerization and the heat of crystallization. To cause depolymerization now requires a higher temperature.18 All aldehyde polymers precipitate during the polymerization, which allowed us to accurately determinate the Tc of the individual aldehyde polymerization by opacity measurement. Aldehyde polymerizations were initiated above the ceiling Tc and cooled at a constant rate, and the point of the rst cloud formation was determined.1214 This could be done with a light sensor to improve the accuracy of the visual measurement. The polymerization temperatures were now measured at several concentrations and then extrapolated to a 1 M concentration. Tc determinations of chloral were carried out by turbidimetry at the University of Massachusetts as laboratory experiments for 1st-year polymer science graduate students for many years, and the Tc of chloral polymerization is probably the best known and most reliable Tc in the literature.19 The values of the Tcs of haloacetaldehye polymerizations are shown in Table I. For reasons explained later, the boiling points of the monomers are also recorded. The Tcs of the polymerization for the trihaloacetaldehydes ranged from a high of 85 C for uoral to 75 C for bromal.8 16 This was to be expected, with the larger bulk of the tribromomethyl group as the substituent causing the most steric crowding as the polymer was being formed.20,21 However, larger sizes of the trihalomethyl group guaranteed an increased stereospecicity of the polymerization. In light of the van der Waals radii, it was not surprising that the increased size of the triha-

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lomethyl group almost guaranteed complete stereospecicity in the polymer. Hence, only isotactic helical polymers were formed in the polymerization of the last seven aldehydes in Table I.22 It also demonstrated for the rst time that stereospecic polymers can be formed without stereospecic catalysts. Any initiator can give stereospecic polymers if the monomer structure and the resulting polymer have the proper spatial relationship. Trying to understand the formation of stereospecicity inspired us to study the embryonic state of the polymerization as described in the section on oligomerization. The last trihaloacetaldehyde that we studied was uorochlorobromoacetaldehyde and its polymers.2326 Fluorochlorobromoacetaldehyde is the only trihaloacetaldehyde that has a chiral center in the trihalo side group. The aldehyde could be prepared in its racemic form or in a highly enriched enantiomeric form from racemic or chiral uorochlorobromoacetate and then polymerized. For the chiral aldehyde, we were trying to synthesize an isotactic polymer that had not only optical activity based on the contribution of the monomer unit but also optical activity based on macromolecular asymmetry (helicity) in the main polymer chain. However, the optical purity (95%) of the monomer was not high enough to test this hypothesis. The polymers only showed the optical rotation of the monomer. The polymerization of bromal with anionic initiators gave a semicrystalline, insoluble, and infusible polymer.12 The large size of the tribromomethyl group causes considerable steric crowding in the polymer; consequently, the Tc was found to be 75 C.

A new thrust developed when Nowak and Whalley,31,32 with samples of polychloral (metachloral) that were still ill-characterized, started to carry out IR investigations. They concluded, surprisingly and correctly, that polychloral was an isotactic linear polymer. As we know today, chloral can only polymerize to an isotactic structure. Despite studies over a period of 50 years, the polymerization of chloral was still poorly understood. We became involved with this exciting polymer that seemed to be as intractable as a problem as it was as a polymer because the polymer was insoluble in any solvent and in the monomer.33,34 The way the monomer and initiator were added led to solid-state structures of polychloral samples that had no relationship to the initiator/monomer ratio. The immediate coating of the incoming initiator (solution) with polychloral prevented further polymerization. In this way, the following question became essential: How do you mix monomer and initiator and prevent immediate polymerization? Our earlier knowledge of the Tc of the polymerization became important.

CRYOTACHENSIC POLYMERIZATION
Polymerizations of chloral in the past had been erratic, and the polymerizations were irreproducible and erroneous. The polymers were powdery, insoluble, and infusible and could not be puried or properly characterized. With the full understanding of the Tc phenomena16 (not known before 1956), it became clear that the Tc could be manipulated to produce haloaldehyde polymers in the highest yield possible and to fabricate solid pieces of the polymer:

POLYCHLORAL
Polychloral is an exceptional haloaldehyde polymer. The rst description of polychloral is based on a report of the chlorination of ethyl alcohol in 1832.27 Liebig described one of the reaction products as a horn-like mass that was left after the chlorination; it was described as insoluble. Investigations of this peculiar form of chloral were followed by a few patents in the beginning of the century, most prominently by Erdmann.28 Beginning in 1913, a number of investigations by Boeseken continued in the ensuing years and led to the description of a so-called metachloral.29,30 We know today that this metaldehyde of chloral was not a cyclic tetramer of an aldehyde, as known from acetaldehyde, but in fact was a linear polymer. Polymerizations carried out under various conditions with different initiators gave powdery polymer samples in greatly differing yields. The polymers were investigated well with the means of characterization available at that time.

It became clear that it was essential to separate the initiating step of the polymerization from the polymerization steps. Chloral was a very convenient monomer to investigate cryotachensic polymerization because there

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is a liquid range of 40 C between the boiling point of 98 C and the polymerization temperature of neat chloral, 59 C.19 Fluoral cannot be subjected to the same conditions of polymerization because the boiling point of uoral is 104 C lower than the Tc. (see also Table I). When highly puried chloral (preferably with less than 100 ppm of undesirable impurities to obtain optimal mechanical properties for the polymer) was initiated above the polymerization temperature (59 C for neat chloral), the initiated monomer could be handled (again, at all times above the Tc). For example, it could be inserted into an assembly to fabricate lms or sheets or solid pieces (for subsequent machining) of polychloral. The assembly would then be immersed into a cooling bath (ice bath), and the polymerization was performed to produce the nal object. Much of the cryotachensic chloral polymerization occurs in the gel state.35,36 Fabrication by this technique faces a problem. This technique of monomer casting is associated with a volume shrinkage of about 20 25% from the monomer to the polymer. This problem can be handled with exible spacers between the plates for lm or sheet casting or with a stovepipe technique for larger pieces. This technique allows the initiated monomer to seep into the cavities as the polymerization progresses. When lms are made, the polymerization proceeds from the cold surface of the glass plates that are used for lm casting and separated by an elastomeric Lycra lament as spacers. The polymerization of neat chloral leads to conversions of 88 90% to polychloral. The remaining monomer is tightly associated in a molecular complex with the polymer (as established by broadline NMR spectroscopy)37 and cannot be removed completely by evaporation or by heat treatment. Solvent extraction will remove the entire monomer, and when the monomer is removed by extraction, it does not reassociate when the polymer is exposed again to fresh monomer. When the polymerization is carried out in an inert solvent, conversions up to 98% can be achieved, but the mechanical structure of the polychloral is foamlike.

isocyanate block. When a hindered aliphatic isocyanate such as isopropylisocyanate was used as the comonomer, the isocyanato growing end cannot propagate.41 As a consequence, a stable chloral homopolymer was obtained with a urethane end group. Another class of comonomers for chloral polymerizations are ketenes; aromatic ketenes such as diphenylketene are the most effective comonomers. They gave random copolymers with polyester groups in the polymer chain. Copolymers were also prepared between pairs of the 10 perhaloacetaldehydes and between pairs of one of the aldehydes and aromatic isocyanates. These polymers were only briey characterized and not further studied.

BLENDS
Because polychloral is insoluble and intractable, blends of polychloral must be made by a two-step polymerization technique. Blends of polychloral with polystyrene, poly(methyl methacrylate), and poly(methyl acrylate) as addition polymers were successfully prepared.42,43 In the rst technique, the addition polymers were dissolved in chloral monomer, and the cryotachensic chloral polymerization was carried out. In the second case, porous polychloral samples were prepared and imbibed with addition monomers containing radical initiators, and the radical polymerization was carried out for interpenetrating networks (IPNs) with a crosslinking agent. The structures of these blends and IPNs were investigated, and their mechanical properties were measured.44

MECHANISM AND STEREOCHEMISTRY OF CHLORAL POLYMERIZATION

As the side-group bulkiness of the haloaldehydes increases, the isotacticity of the polymer becomes prevalent, leading to stereospecic and conformationally specic polymers, with polychloral the most prominent example. Chloral polymerization with anionic initiators proceeds by propagation of the alkoxide,45 and the rate of polymerization has been studied.46 Cationic polymerization has also been investigated with selected Lewis acid catalysts.47 It became clear that cryotachensic polymerization could also be carried out with a chiral anionic initiator. If the initiation was stereospecic (meso or racemo), it was expected to prepare helical polychloral of only onehanded helices, which would give a polymer chain with macromolecular asymmetry based on helicity. The rst chiral initiating anions that we studied were steroid alcohols, primarily cholesteroxide.33 These chiral alkox-

COPOLYMERS
Cryotachensic polymerization can also be carried out as copolymerization. With isocyanates, the best comonomers,38,39 various paths can take place. With aromatic isocyanates, preferably p-chlorophenylisocyanate, random copolymers of chloral were obtained. Aliphatic isocyanates, that is, n-butylisocyanates, were also investigated as comonomers. A block copolymer was produced.40 It consisted of the initial chloral homopolymer block followed by a short intermediate composition but ultimately followed by a terminal alternating chloral/

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ides could be obtained by the reaction of butyl lithium with chiral n-octanol,48 cholesterol, or other 3-hydroxysteroid derivatives.49 51 Polychloral obtained with these chiral initiators was optically active, and the chiral initiating fragment remained at the beginning of the polymer chain. Through the study of the polymerization of several of the perhaloacetaldehydes, it became clear that the sidegroup size and bulk played an essential role in the stereospecicity of the polymerization. If the side group was greater than 4 , stereospecic and conformationally specic polymerization prevailed, leading to rigid helical polyhalocetaldehyde structures. Below this bulk size, atactic polymer structures were also observed.

HALOACETALDEHYDE POLYMERS AND MACROMOLECULAR ASYMMETRY

The polychloral structure has been established by solidstate NMR55,56 and nuclear quadrupole resonance (NQR)57 to be a tactic polymer. The X-ray diffraction determination of an oriented piece proved it to have an isotactic helical structure with an approximately 4/1 helix with a repeat distance of about 5.2 58 (unlike the former claim, a repeat of 6.6 , which was an obvious error). Chloral polymer, like other helical polymers, consists of a 50/50 mixture of left-handed and right-handed helices. Films of optically active polychloral were prepared with chiral initiators, and their optical activity was measured.59 They often had very high optical rotations. The degree of the rotation of the polychloral samples depended on the effectiveness of the initiation and the geometry of the alignments of the chiral macromolecules growing from the cooled glass surfaces during the polymerization.49 51 The values of the optical rotation may be different when the measurements are done in the solid state as compared to solution measurements.60 It could also be that the optical rotation could have been done down the c axis of the helical macromolecular bundles. Powdered chiral polychloral was used successfully to separate polymer racemates of polymers.61

STABILITY AND STABILIZATION OF HALOALDEHYDE POLYMERS

It was recognized early on that polychoral would need little or no stabilization against autoxidation and photooxidation. The polymer obtained by both anionic and cationic polymerization has end groups that are so sterically hindered that few reactions can take place. In fact, the polymer end groups cannot even been ingrown or occluded. Polymerization can continue by the addition of more chloral monomer (or comonomer).52 No bimolecular reaction to terminate the polymerization is possible at the end of the polymerization. The polymerization can only be terminated by the addition of a proton to the growing alkoxide, which results in a hydroxy-terminated polymer. Stabilization can also be achieved with cations capable of decomposition53 and with other post-treatments.54 Unlike polyformaldehyde, polychloral has a rigid helical structure, whose acetalic hydrogen cannot be abstracted by radicals because they are positioned inside a tight polymer helix that also has the trichloromethyl group attached to each acetalic carbon atom, which provides tight chlorine surfaces for the polychloral surface. Polychlorals with the best stabilizing end groups have thermal stabilities in excess of 250 C. Different end groups provide various degrees of stability in the polychloral samples. It is important to remember that each polymer chain has two end groups and that the end group of the lower thermal stability determines the stability of the polymer. This is why cationic polychloral samples obtained with aluminum trichloride as the initiator have the best thermal stability. It is believed that they have two chlorine end groups. Acetate-terminated polymers are less stable. Hydroxyl-terminated samples have hemiacetal end groups and are somewhat more stable than the alkoxide-terminated polymers.

OLIGOMERIZATION OF HALOACETALDEHYDES
The progress and success of the chloral polymerization were mastered through the efciency of the cryotachensic polymerization. The question of how the stereochemistry developed during the initial stage of polymerization was still an unanswered question. It became ultimately a question of understanding the development of the stereospecicity and conformational specicity. The monomer addition very soon provided an oligomer that was spatially highly restricted and developed a helical conformation early in the polymerization. To establish an understanding of this highly selective polymerization process, we studied the genesis of the chloral polymerization, the rst few steps of the oligomerization,62,63 and used the achiral and hydrocarbonsoluble initiator lithium tert-butoxide.64,65 When the initiating anion, tert-butoxide anion, is added to one molecule of chloral, the reaction product is a racemate of D- and L-chloral-terminated alkoxide. Meso addition to either enantiomer and further meso propagation gives right-handed or left-handed helical polymer molecules. Lithium tert-butoxide provides the relatively bulky tert-butoxide anion as the initiator for chloral

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polymerization. The effect of the initiator structure of the rst steps on the development of the stereochemistry of propagation were calculated,66 and the structure and absolute conguration of the initiation67 were determined by X-ray diffraction of the oligomers.68,69 On-line gel permeation chromatography/mass spectrometry, the mixture of chloral oligomers was analyzed, and the assignment of meso/racemo addition products of the dimers was established.70,71 At the temperature of initiation, above the Tc of polymerization, the solution consists essentially of chloral monomer and the lithium salt of the addition product of tert-butoxide to one molecule of chloral, a racemate of the chloral-terminated alkoxide. The addition of the tertbutoxide anion is essentially quantitative because the nucleophilicity of the tert-butoxide and the chloral-terminated alkoxide are orders of magnitude different. At the same time, the oligomeric chloral-terminated alkoxides are similar in nucleophilicity and are in equilibrium with the monomer choral. As the temperature is lowered, the equilibrium shifts toward higher oligomers. These oligomers, still in solution, also establish the most favored conguration and even conformation ultimately establishing an isotactic/helical structure. Much below T c , the higher oligomers precipitate, but the polymerization to high polymer continues in the gel state. By time the rst-turn pentamer is predominant (1.5 of the polychloral helix is formed), further monomer addition is not only stereospecic but also conformationally specic. Octamers of polychloral can easily be isolated, and decamers can be identied. The decamer structure amounts to three turns of the polychloral helix. At higher degrees of polymerization, the oligomers precipitate, and the polymerization continues in the gel state; the precipitation adds to the driving force of the polymerization as the equilibrium is shifted toward the higher molecular weight polymer. In practice, the oligomerization, caused by the controlled decrease of a temperature slightly below the polymerization (ceiling) temperature, was allowed to proceed until about 20 30% solid polymer had formed and the polymer had precipitated. The entire mixture was then quenched with acetic anhydride to freeze the equilibrium of oligomerization by acetylation of the growing alkoxide end groups. The individual acetate-capped chloral oligomers were isolated by crystallization (the unimer) or by high-pressure liquid chromatography (HPLC), and this was followed by crystal growth for the oligomers. The rigid helical pentamer (a racemate), which was nearly two turns of the helix, was isolated and chirally separated into helical macromolecular enantiomers.72 Each of the crystalline oligomers were subjected to X-ray analysis, and their absolute conguration was es-

tablished. Lithium tert-butoxide-initiated acetate-terminated chloral oligomers, starting from the unimer, have a rigid structure, as judged by NMR spectroscopy, because of the relatively bulky initiating tert-butoxide.65 Methyl-terminated oligomers (methyl-capped on both the initiating and terminal end) show exibility because of the small methyl end group. Lower oligomers were rotating, as demonstrated by their NMR spectrum, and the inversion temperature could be determined.73 The tetramer had an inversion temperature above room temperature, and for the pentamer, the inversion temperature was substantially higher. An interesting phenomena was noticed in the initiation of chloral polymerization. With ammonium chlorides and phosphines,2 the initiating end is a chlorine atom, and the alkoxide is the growing end. tert-Amines remain at the initiating end and labile ammonium end. We found that the polychloral initiated with tert-amines, especially pyridine, stuck ferociously to the glass plate. Pyridine-initiated chloral oligomers treated with carboxylic acid anhydrides gave diacylates. This means not only was the growing alkoxide end-capped but also that the labile ammonium group was removed by acylation.74 76 Ammonium-terminated high polymers were considered controlled-release agents for the drug chloral hydrate.

CHIRAL INITIATION OF CHLORAL OLIGOMERIZATION

Chloral oligomerization was also investigated with a chiral initiator, lithium borneoxide. The chiral initiation of chloral does not give racemates, as in achiral initiation, but instead diastereomers. This means that two sets of optically active helical oligomers and polymers could be expected.77 The oligomerization of chloral was investigated with borneoxide as the chiral initiator. It is not a good stereospecic initiator: the anion is not bulky enough, and the addition of chloral to borneoxide is only 60/40 stereospecic.78 81 From this initiation of the oligomerization, some of the individual compounds were isolated and characterized as they were at the beginning of the chiral growth of the chloral oligomerization. The oligomers up to a molecular weight of 1500 Da were of sufciently low molecular weight and could be handled by gas chromatography (GC) and HPLC as well as by potassium ionization of desorbed species (KIDS) mass spectrometric analysis. The oligomerization of bromal was also studied with achiral and chiral initiators,82 84 and even uoral oligomerization was studied.85 The low Tc of bromal poly-

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merization allowed only the unimer to be isolated and its X-ray crystal structure to be determined.

COOLIGOMERS
Chloral bromal cooligomerization was also investigated. Again, the low Tc of bromal polymerization caused great difculties.86,87 When successful, the oligomer structure was blocky. The oligomerization had apparently started with chloral polymerization and was then completed with the bromal addition, as expected from the substantial difference in the Tcs of the monomers.

STRUCTURE OF POLYALDEHYDES
As indicated earlier, polyaldehydes have a similarity to polyolens. They have a carbonyl oxygen atom instead of the methylene group. The COO length in the main chain of the acetal linkage is 1.41 instead of the 1.54 of the COC linkage in the main chain. The shorter distance of the COO linkage, together with the bulkiness of the methylene group, makes the basic structure of polyethylene and polyoxymethylene quite different. Polyethylene has a linear zigzag structure, whereas polyoxymethylene is helical; it is nearly a 2/1 helix with some slight distortions (29/16; 1.81 per monomer unit).88 It exists in the more stable monoclinic crystal structure and in an orthorhombic structure. All isotactic polymers (including polyolens) have helical conformations in the crystalline state. Polypropylene has a 3/1 helix with a 6.50 repeat. Polyacetaldehyde has a 4/1 helix with a 4.80 repeat, and poly(nheptaldhyde) is similar.89 The structures of the isotactic trihaloacetaldehydes have recently been calculated. Trihalogenated polyacetaldehydes have a helical structure with an approximate 11/3 repeat. Polyacetaldehyde is slightly distorted from a 4/1 helix90 (Fig. 1).

Figure 1. Helical structure of isotactic polyaldehydes.

isotactic, and conformationally specic helical polymers with calculated structures of 11/3 helices. When initiated with chiral initiators, chloral gave helical polymers of one screw sense whose optical activity was based on macromolecular asymmetry. The beginning or genesis of the polymerization was carefully studied through the isolation and characterization of the low oligomers and the observation of the development of the stereochemistry of the polymerization.9195
This work was carried out over a period of 40 years. I had the privilege of being associated with outstanding colleagues, coworkers, and students. I would like to recognize especially the late Henry C. Miller during the DuPont period; P. Kubisa, D. W. Lipp, B. Yamada, R. W. Campbell, L. S. Corley, G. D. Jaycox ,and W. J. Harris at the University of Massachusetts; J. Y. Zhang, F. Xi, T. R. Dole, and J. Bartus at Polytechnic University; Christoph Kratky of the University of Graz, Graz, Austria, for his cooperation in the determination of the absolute conguration of some of the oligomers; W. J. Simonsick, Jr. of DuPont Marshall Labs for the KIDS analyses; and our Japanese colleagues, K. Hatada, T. Kitayama, and K. Ute of Osaka University, for their long and dedicated cooperation and friendship. Without them, this work would not have been possible.

CONCLUSIONS
Over the last 40 years, the polymers of trihaloacetaldehydes have been extensively investigated. The result has been over 60 articles and patents and entirely new concepts in polymer chemistry. The concept of the Tc of polymerization was newly formulated because the relatively low Tc of these monomers allowed the exact determinations of the Tcs. The Tc was the key to the new fabrication concept for the polymerization of chloral: cryotachensic polymerization. Polychloral and other polytrihaloacetaldehydes are completely stereospecic,

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