528
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1980, 79, 528-532
fom.
(10) Butler, G. B. J. folym. Sci. 1980, 48, 279. (11) Butler, 0. B.; Guilbault, L. J.; Turner, S. R. folym. Lett. 1971, 9 , 115. (12) Turner, S. R.; Guilbault, L. J.; Butler, G. B. J. Org. Chem. 1971, 36, 2838. (13) Miller, F. F.; Gilbert, H. Canadian Patent 569262, Jan 20, 1959. (14) Yang, N. C.; Gaonie, Y. J . Am. Chem. SOC.,1984, 86, 5023. (15) Wagener, K. B.; Turner, S. R.; Butler, G. B. folym. Lett. 1972, 70, 805. (16) Lai, Y. C. Ph.D. Dissertation, Unlversity of Florida, 1980. (17) Wagener, K. B.; Turner, S. R.; Butler, G. B. J . Org. Chem. 1972, 37, 1454. (18) Wagener, K. B.; Butler, G. B. J . Org. Chem. 1973, 38, 3070. (19) Matyjaszewski, K. A.; Wagener, K. B.; Butler, G. B. folym. Lett. 1979, 77. 129. (20) Huisgen, R. 2.Chem. 1988, 8 , 290. (21) Von Gustorf, E. K.; White, D. V.; Kim, 8.; Hess, K.; Leitlch, J. J . Org. Chem., 1970, 35, 1155. (22) Matyjaszewski, K. A.; Wagener, K. B.; Butler, G. B. fotym. Lett. 1979, 17. 65. (23) Ohashi, S.; Butler, G. B. J . Org. Chem. 1980, In press. (24) Hoffmann, H. M. R. Angew. Chem. Int. Ed. Engl. 1989, 8 , 556. (25) Ruch, W. E. M.S. Thesls, University of Florida, 1973. (26) Wamhoff, H.; Wald, K. Chem. Ber. 1977, 770, 1699. (27) Williams, A. G.; Butler, G. B. J . Org. Chem. 1980, 45, 1232.
(28) Williams, A. G.; Butler, G. 8. Lett. 1980, 76. 313. (29) Ohashi, S.; Ruch, W. E.; Butler, G. 8. J. Org. Chem. 1980, In press. (30) Fettes, E. “Chemical Reactions of Polymers”, Why-Interscience: New York, 1964. (31) Butler, G. B.; Wllliams, A. G. J. folym. Sci., folym. Chem. Ed. 1979, 77s 1117. (32) LeOng, K. W.; Butler, G. B. J . Maaomol. SCi.-chem. 1980, A74(3), 287. (33) Ohashi, S.; Leong, K. W.; Matyjaszewski, K.; Butler, G. 8. J . Org. chem. inso. .- - -, 45. . - , 3467. - .- . . (34) Chen, T. C. S.; Butler, G. 8. J. Macromol. Sci.-Chem. 1980. In press. (35) Rout, S. P.; Butler, G. B. folym. Bull. 1980, 2, 513. (36) Saville. B. J . Chem. Soc.. D 1971. 72. 635. i37j Flory, P. J.; Rehner, J. J . Chem. fhys. W43, 7 7 , 521. (38) Rutkowska, M.; Kwiatkowskl, A. J . folym. Sci. Symp. 1975, 53, 141. (39) Nlelsen, L. E. J. Macroml. Sc/.-Rev. Macromol. Chem. 1989. C3(1), 69. (40) Hergenrother, W. L. J . Appl. folym. Sci. 1972, 76, 2611. (41) Gancarz, I.; Kaskawskl, W. J . folym. Sci., folym. Chem. Ed. 1979, 77, 1523.
Received for review July 2, 1980 Accepted August 4, 1980
Cyclopolymerization of N,N-Dialkyldiallylammonium Halides. A Review and Use Analysis Raphael M. Ottenbrlte’ and Wllllam S. Ryan, Jr.’ Department of Chemistty, Virginia Commonwealth Un/vers&, Richmond, Virginia 23284
The formation of cyclic structures during the polymerization process has led to many interesting and useful potymers. The most extensively studied have been the diallyl systems which were initially reported to form six-membered rings. However, studies of monocyclic reactions and model compounds and polymers indicate that the reaction is kinetically controlled and preferentially produces five-membered rings.
The formation of cyclic structures in the polymer chain from acryclic monomers and comonomers during the polymerization process was first discovered in the early 1950’s. During the next 20 years several interesting cyclopolymerizationsystems have been developed and their mechanism of cyclization investigated as reported by Cotter and Matzner (I). However, the one system that has the greatest industrial potential and utilization is that of diallylammoniumhalide. This polymer alone accounts for over 200 patents and publications. Because of ita general importance and uniqueness, a survey of its discovery, characterization, and utilization is presented here.
Initial Discovery of Cyclopolymerization For a number of years polymer chemists have been interested in developing ion-exchangeresins for purification and isolation of materials. In 1949,Butler and Bunch (2) prepared tri- and tetraallyl quaternary ammonium salts which were polymerized to form highly cross-linked, water-insoluble polymers. These materials proved to be very brittle as well as having low tensil and mechanical strengths. In an attempt to improve the properties of this polymer system, Butler and Ingley (3) reacted diallyl quaternary ammonium bromide salts (1) to produce a polymer that was water-soluble and non-gel forming. Later, Butler and Goette ( 4 ) observed that diallyl-Pvinyloxyethyl quaternary ammonium bromides (2) also produced a water-soluble polymer and that the P-vinylDepartment of Applied Research, Philip Morris Research Center, Richmond, Va. 0198-4321/80/1219-0528$01.00/0
\ \
I
CH-CH,
3
2
oxyethyl group was unreacted. Additionally, Butler and Johnson (5)found that diallylammonium bromides containing propargyl groups (3) produced water-soluble polymers with the propargyl groups remaining unreacted. Thus, it was found that (a) allylammonium bromide itself does not polymerize (3),(b) bis (N,N-disubstituted)-1,4diamino-2-butene dibromide does not polymerize (6),(c) those monomers containing NJV-diallyl groups produced water-soluble polymers (3),and (d) water-insoluble polymers were obtained from monomers that had three or more allyl groups attached to a quaternary ammonium site (4). To explain the formation of water-soluble, noncrosslinked polymers when diallyl quaternary ammonium salts were polymerized, Butler and Angelo (7) proposed a chain growth mechanism which produced cyclic structures. The mechanism involved an attack by the radical initiator on the y-carbon of one of the allyl double bonds, followed by intramolecular cyclization at the y-position of the second allylic double bond (Figure 1). The resultant cyclic radical then attacks a second monomer molecule, and the chain grows by an alternating repetition of the process. This type of polymerization has become known as cyclo0 1980 American Chemlcal Society
Ind. Eng. Chem. Prod. Res. Dev., Vol. 19, No. 4, 1980 529
Table I. Change in Ring Size with Substituents R
-1
-9 (4)
A l t e r n a t e Repetition of ( 2 ) and ( 3 )
/ \ d K
R
R
A i
10 -
Figure 1. Proposed pathway for the formation of six-membered cyclopolymers.
polymerization although the terms intra-intermolecular polymerizationand transannular polymerization have been used in the literature. This proposed mechanism was supported by Simpson et al. (8),who reported that the free-radical polymerization of diallyl phthalates produced a polymer in which 40% of the monomer units were in a cyclic-type structure along the polymer chain. Additional support for the mechanism was provided by Marvel and West (9),who reported the cyclopolymerization of monomers having a seven-membered chain containing a 1,6-diene system. Butler et al. (10) experimentally confirmed the cyclic structures proposed for the soluble polymers by degrading the cyclic poly(dially1ammonium)bromide. The degradation products obtained were similar to those expected by the cleavage of the postulated piperidium bromide rings from the polymer chain. Investigation of Monomolecular Cyclization In the early 1960's, most workers in the field of cyclopolymerization of 1,6-dienes generally accepted the fact that six-membered rings are formed exclusively during polymerization. However, a second cyclic structure involving a five-memberedrings is also possible. In this case, the initial radical attack on the terminal carbon of one allyl group would give rise to a secondary radical (7)which could either intramolecularly attack the terminal y-carbon of the other allyl group giving the six-membered ring or it could attack the @-carbonof that group to produce a five-membered ring. The formation of a six-membered ring would
\Nd
/ R
1
\
R
7
11
X
Y
R
H H H H H CN CN CN
H CN CN COOEt COOEt COOEt COOEt CN
H H CH, CH, H
H
CH3 CH3
I
I1 0 0 0 0
44 84 100
100
100 100 100 100 56
16 0 0
involve a 2 O radical intermediate (8) in the propagation step whereas formation of the five-membered ring would involve a less stable loradical (11). Based on this rationale, it was assumed that the six-membered ring would be the prevalent structure (11). Further, the six-membered ring was considered to be the thermodynamic product since a six-membered structure is of lower energy than a five-membered ring. In fact, Berlin and Butler (12) stated that "A five-membered ring has never been reported in cyclic polymerization involving symmetrical 1,6-diene system with terminal methylene groups". Due to the complexity of studying the mechanism of the cyclization process in the actual polymerization process, several studies were initiated to determine the mode of intramolecular cyclization of monomer units. Brace (13,14) investigated the free-radical addition of perfluoroalkyl iodides to N-substituted diallylamines and found, contrary to previous reports on intramolecular cyclization, that five-memberedrings (14) were obtained in 95% yield with no observable six-membered product. Following this
Ch
CN
12
13
C'N
14
observation, Brace found five-membered ring formation to occur with several systems; 1,gheptadiene (15), diallyl ether (16),diethyl diallyl malonate, and ethyl diallyl acetate (17). It was evident from these studies that a fivemembered ring was formed in preference to a six-membered ring in the monomeric intramolecular additions of a radical to a C5-C6 double bond. In the cyclization of unsaturated radicals, the direction of ring closure varied strikingly with changes in radical structure. Walling and Pearson (18) attributed the formation of methylcyclopentane from 5-hexenyl mercaptan to attack of the radical at the least hindered carbon of the double bond. Julia (19, 20) reviewed several effects of substitution on ring formation and has shown that as the number of stabilizing substituents, such as ester and cyano, increased from 1 to 2 on the radical carbon of 4-hexene that the products changed from ~ 1 0 0 %cyclopentyl to ~100% cyclohexyl (Table I). He has further shown that the cyclization reaction was reversible when the 1-position was disubstituted while it was irreversible when monosubstituted. He also reported that increased temperatures favored the formation of six-membered thermodynamic products. Additional studies by Hawthorne and Solomon (21) showed that increasing the bulk of the 0-alkyl substituents favored formation of the six-memberedradical because the
Ind. Eng. Chem. Prod. Res. Dev., Vol. 19, No. 4, 1980
530
H
bulky alkyl groups hindered formation of the five-membered ring whereas cyclization to the six-membered ring involved attack on an unsubstituted terminal methylene and would be less hindered by the P-substitutents, It was concluded that although the transition state altered the relative rates for the formation of five-membered and six-membered rings, the reactions were kinetically and not thermodynamically controlled. Similar work by Hawalkylallyl) thorne et al. (22)with poly(N-methyl-N,N-bis-(2 amines) (18) indicated that both piperidine (19) and pyrrolidine (20) rings were present in the polymer chains,
1 cn,
CHI
20
18
R =H
-
R = CH, R = Et
R = iPr
> 90%
40
60
60
40 acyclic acyclic
R = t-Bu
with the proportionality depending upon the bulk of the 2-alkyl substituent. Spectroscopic Studies of Ring Size Direct studies of the interaction of a number of radicals generated in aqueous solution from diallylamine and related compounds were carried out by Beckwith et al. (23,241. Their ESR spectra studies indicated that the radicals rapidly added to the y position of one of the double bonds (22) and the slower cyclization step occurred by attack at the P-carbon of the second allyl group to produce a five-membered ring (20).
2)
tort R.
- R-y) *low
21
22
*
Figure 2. Model structure of intramolecular cyclization.
dered in the formation of the five-membered ring. The six-membered ring formation is hindered by a terminal hydrogen which lies in the nodal plane directly between the radical carbon and the terminal carbon of the double bond. Using an open shell Unrestricted Hartree-Fock (UHF) CND0/2 survey, we (29) simulated the unique system reported by Julia (19) in which he was able to establish an equilibrium between the isomeric five-membered and the six-membered rings in refluxing hexane. We studied the rotation of the 6-carbon for two different conformations, one favoring a six-membered chain form (Figure 2) and the other with a distorted chain which was skewed toward a “pentane-Pucker’’ five-membered ring. The angle B was varied and substituents (X= -H, -CN, -CH3) were chosen to study the effect of radical stabilization on C1. Calculations for all B values showed that energies were lower for the “pentane-pucker” conformation than the chain form. This is in agreement with Julia’s (19) observation that lower temperatures favored the formation of cyclopentane type products. Further, the lowest energy was observed a t the same angle (SO0) for all substituents studied, which implied that these substituents in this situation have little effect in determining ring size preference. More significant effects were observed in the calculations when substitutents were placed on c6 (Y = -H, -F, -CH3); the methyl group makes c6 more positive (+0.4033) compared to the (26 unsubstituted situation (+0.1836) while C5 was (-0.1032) and (-0.2369), respectively. Since C1 is negative, the interaction between C, and c6 is favored by ion-pair attraction in the transition intermediate, thus favoring six-membered ring formation. These data are in agreement with Julia’s (19)experimental observation of 100% six-membered ring for terminal methyl substitution. A similar change was observed for fluoride at C6. Since coulombic effects can occur through space and are not limited to orbital distances, they are a longer range effect and appear to be a contributing factor in determining ring size preferences.
RTrtH’ 23
Studies of the 13C NMR spectra of the polymers obtained by the radical-induced cyclopolymerization of Nsubstituted diallyl amines by Jones et al. (25) indicated that the polymers contained cis- and trans-substituted pyrrolidine rings in a 5:l ratio. Lancaster et al. (26)compared the 13C NMR spectrum of poly(dimethyldially1ammonium) chloride with the spectra of the model compounds 1,1,3,4-tetramethylpyrroliniumiodide and l71,3,5-tetramethylpiperidinium iodide and concluded that the polymer consisted entirely, if not exclusively, of fivemembered rings linked mainly in a 3,4-cis configuraion. We compared the 13C spectra of partially reduced fivemembered ring model polymer, poly(171,3,4-tetramethylpyrrolidinium) bromide, to that of poly(diallyldimethy1ammonium) bromide and confirmed these findings (27). Molecular Orbital Evaluation of Ring Size Preference It is evident from the literature cited above that 1,6diene systems undergo cyclization reactions relatively easily and are under kinetic control forming five-membered rings. There are several factors that influenced this cyclization process: (a) relative conformational stability of six-membered over five-membered cyclic products, (b) radical stabilization of the initial site. (c) Electronic “push-pull” effects of substituents a t the 5- and 6-positions, and (d) possible steric effects. Butler and Raymond (28) observed that for an intramolecular approach of the radical to the double bond that the common plane of the p-orbitals is less sterically hin-
Preparation of Diallylammonium Polymers Extensive industrial research on the homopolymerization and copolymerization of dialkyl-diallyl ammonium salts with potential commercial utilization has been carried out during this time. In 1960, Butler et al. (30) patented the cyclopolymerization of symmetrical diallylammonium chloride and bromide salts. Originally,the polymerization reaction was initiated by tert-butylhydroperoxide, azobisisobutyronitrile, or peracetic acid and carried out at
531
Ind. Eng. Chem. Prod. Res. Dev., Vol. 19, No. 4, 1980
50-80 “C in polar solvents such as water or dimethylformamide. Butler (31) reported that polymers obtained from the chloride salt of the monomer had significantly higher intrinsic viscosity than those from the bromide salt. Comparing the polymers obtained from dialkyldiallyl ammonium salts in dimethyl sulfoxide initiated by ammonium persulfate to those obtained from the tert-butylhydroperoxide-water system, Negi et al. (32)confirmed Butler’s findings that the quaternary ammonium chlorides polymerized more readily and produced higher molecular weight polymers than the bromide salts. This inhibition of polymerization was attributed to the ease of oxidation of the bromide ion by the persulfate which can result in both the consumption of the initiating species and the generation of bromine which can terminate the growing chain. Boothe et al. (33) in an investigation of factors affecting the homopolymerization of dimethyldiallylammonium chloride reported that polymers with the highest solution viscosity and lowest residual monomer content were obtained from a 65% monomer solution catalyzed by ammonium persulfate. They also found that the additiion of 200 ppm of sodium ethylenediaminetetraacetate (Na4EDTA) improved the rate as well as the degree of polymerization. However, it is not known whether the N+EDTA was participating in the initiation or functioning as a chelating agent for trace metals present in the reaction mixture. It was also found that extreme monomer purity was necessary to obtain a high molecular weight polymer. If the monomer was contaminated with even small amounts of allyl alcohol or dimethylamine, the polymer molecular weight was reduced. Consequently, preparation of a high-purity monomer by careful control of the synthesis reaction (34)and purification steps (35)is essential to remove these chain-transfer agents and other impurities. Copolymerization of Diallylammonium Halide The diallyl quaternary ammonium monomers have been copolymerized with a number of monomers to produce a variety of cationic copolymers; an example is the cyclocopolymerization of diallylammonium compounds with sulfur dioxide to produce water soluble cationic polysulfones. These polymerizations have been carried out in solvents such as dimethyl sulfoxide, methanol, and acetone with free-radical initiators ammonium persulfate, ammonium nitrate, azobisisobutyronitrile, tert-butylhydroperoxide, and dilauroyl peroxide (36-38). The 1:l copolymers were initially assigned a repeating six-membered ring structure. Subsequent work by Amemiya et al. (39) indicated that a more likely structure consists of a pyrrolidinium ring.
Table 11. Some Industrial Uses of Polv(diallv1ammonium) Halide use company I. Flocculants waste water
Calgon Corp. Sankyo Chemical Industries Ltd. Calgon Corp. Calgon Corp. Calgon Corp. Calgon Corp.
sewage sludge water purification coal floatation foam floatation metal sulfides Calgon Corp. crude potassium salts electroconductive fibers Calgon Corp. 11. Paper Additives antistatic agents fluorescent whiteners paperboard reinforcement retention agents electroconductive coatings
111. Electroplating zinc
ref 60,62 61 63 64 65 66 67,68 69
Nitto Bosaki Co., Ltd., 70 Calgon Corp. 71 Mobil Oil A-G in 72 Germany Mitsubishi Chemical In- 73 dustries Co., Ltd. Calgon Corp. 74 Mitsubishi Petrochemical 75 Co., Ltd. 76 Calgon Corp. 77 Nalco Chemical Corp. Japan Metal Finishing Co., Enthone Inc. Furukawa Electric Co., Ltd. Furukawa Electric Co., Ltd.
78 79 80
Toyobo Co., Ltd. Nippon Senka Kogyo Co., Ltd. Asahi Chemical Industry Co., Ltd.
82 83
V. Cosmetic Additives hair
Giliette Co.
85
VI. Biocide water bacteria and algae
Calgon Corp. Calgon Corp.
86 87
VII. Demulsifier dispersed oils
Nalco Chemical Corp.
44
Toshin Chemical Co., Ltd.
88
Tennant Co.
89,90
tin lead IV. Dye Fixing Agent cotton fabrics rayon fabrics
VIII. Coagulant ceramic industry
81
84
IX. Detergent Additives
questioned the authenticity of these copolymers and have suggested that they may in fact be complexes of “tenacious” mixtures of the homopolymers. 24
The copolymerization of diallyl quaternary ammonium monomers with vinylic or acrylic monomers have been extensively investigated (33,40-44). These polymers were prepared by processes similar to those used for the homopolymerization. The telomerization of dimethyldiallyl ammonium chloride with acrylamide and acrylic acid was disclosed by Schuller et al. ( 4 5 ) . The exact structure of any of these copolymers has not been completely elucidated; indeed, most workers have assumed a structure to conform to the stoichiometry of the reactants. However, some other workers (46,47) have
Industrial Uses of
N,N-DimethyldiallylammoniumPolymers The extensive industrial and commercial utilization of the home and copolymers of dialkyldiallylammonium salts have been developed based on the positive change along the polymer chain and the resultant water solubility. Presently, water treatment represents the major market area. the cationic polymer neutralizes the negatively charged colloidal or suspended particles and agglomerates them into larger masses which results in rapid solids-water separation by sedimentation or filtration. The utility of poly(dimethyldiallylammonium) chloride as a primary coagulant or coagulant aid in waste water clarification has
532
Ind. Eng. Chem. Prod. Res. Dev., Vol. 19, No. 4, 1980
been reported in numerous publications (Table IT) (43,48-52). Wang et al. (53) investigated magnetic sewage sludge dewatering technique in which poly(dimethyldially1ammonium) chloride was added as both flocculating agent and disinfectant. Hoover (51)and Schiller (54)found that copolymer of dimethyldiallylammonium chloride and acrylamide was an excellent flocculating agent for the suspended solid matter in sewage sludge (54). The copolymers of dimethyldiallylammonium chloride and SOz were reported to produce particularily good flocculants for kaolinite and bentonite clays (55,56). The paper industry represents another major use of quaternary cyclic ammonium polymers. These cationic polymers have been used to improve drainage, fines or filler retention, and paper strength through adsorption on the negatively charged pulp. With the homopolymer and the acrylamide copolymer, potential measurements were proportional to the amount of polymer adsorbed by the pulp fiber surface; further, poly(dimethyldially1ammonium) chloride was found to be useful as an electroconductive coating on paper in electrographic reproduction processes (57). Poly(acrylamide-co-dimethyIdiaIIyIammonium)chloride has also been used to aid the separation of aqueous ore, pulps, and mineral suspensions (42) and for flocculation of the oil-water emulsions in petroleum refinery wastewater (58,59). These and other claimed industrial uses are listed in Table 11.
Acknowledgment The authors wish to thank Marian DeBardeleben of the Philip Morris, Inc., R and D Library for help in researching the literature. We also wish to thank Susan Howell for her many hours of work on the manuscript. Literature Cited (1) Cotter, R. J.; Matzner, M. "Ring Forming Polymerizations", Vol. 13a, p 32; Vol 138, p 291, Academic Press: New York, 1972. (2) Butler, G. B.; Bunch R . J. Am. Chem. Soc.1040, 71, 3120. (3) Butler, G. B.; Ingley, F. L. J. Am. Chem. Soc.1051, 73, 895. (4) Butler, G. B.; Goette, R. L. J. Am. Chem. SOC. 1052, 74, 1932. (5) Butler, G. B.; Johnson, R. A. J. Am. Chem. Soc. 1054, 76, 713. (6) Butler, G. 6.; Goette, R. L. J. Am. Chem. SOC.1054, 76, 2418. (7) Butler, G. B.; Angelo, R. J. J. Am. Chem. Soc.1057, 79, 3128. (8) Simpson, W.; Holt, T.; Zetie J. J. folym. Sci. 1053, 10, 489. (9) Marvel, C. S.; Vest, M. J. Am. Chem. Soc. 1057, 79, 5771. (10) Butler, G. B.; Crawshaw, A.; Miller, W. L. J. Am. Chem. SOC. 1058, 80, 3615. (11) Crawshaw, A.; Jones, A. G.J. Mecromol. Sci. Chem. 1072, A-6, 65. (12) Berlin, D.; Butler, G. B. J . Am. Chem. SOC. 1960 82, 2712. (13) Brace, N. 0. J. folym. Sci. Part A-1 1070, 8,2091. (14) Brace, N. 0. J. Org. Chem. 1071, 36, 3187. (15) Brace, N. 0. J. Am. Chem. SOC. 1084, 86, 523. (16) Brace, N. 0. J. Org. Chem. 1068, 3 1 , 2879. (17) Brace, N. 0. J. Org. Chem. 1060, 34, 2441. (18) Walling, C.; Pearson, M. S. J. Am. Chem. Soc. W64, 86, 2282. (19) Julla, M Acc. Chem. Res. 1071, 4, 386. (20) Julia, M. Bull. SOC. Chem. 1086 434. (21) Hawthorne, D. G.;Solomon, D. H. J. Macromol. Scl. Chem. 1076, A10, 923. (22) Hawthorne, D. G.;Johns. S.; Solomon, D.; Willings, R., J. Chem. Soc. Chem. Commun. 1075, 982. (23) Beckwith, A. J.; Ong, A. K.; Solomon, D. H. J. Mecromol. Sci. Chem. 1075, A - 9 , 115. (24) Beckwith. A. J.; Ong, A. K.; Solomon, D. H. J. Macromol. Scl. Chem. 1075, A-9, 125. (25) Johns, S. R.; Willing, R. I.; Middleton, S.; Ong, A. K. J. Macromol. Sci. Chem. 1076, A10, 875.
(26) Lancaster, J.; Baccel, L.; Panzer, H. J. Polym. Sci. folym., Lett. Ed. 1078. 14. 549. (27) Ottenbrlte; R. M.; Shlllady. D. D., IUPAC Symposia on Quaternary A m monium and Amine Polymers, Ghent, Belgium, 1979. (28) Butler, G. B.; Raymond, M. A. J. Org. Chem. 1085. 30, 2410. (29) Ottenbrite, R. M.;Shillady, D. D.; Ryan, W. S., Jr.; Abayasekara, D. R., Southeastern ACS Meeting, Roanoke, VA, 1979. (30) BGler. G.B.; Angel. R. J.; Crawshaw, A. US. Patent 2 926 181, 1980. (31) Butler, G. B. U.S. Patent 3 288 770. 1988. (32) Ne& Y.; Harada, S.; Ishizula, 0. J. W m . Scl., PettA- 11087, 5, 1951. (33) Boothe, J. E.; F W , Hoover, J. Macromol. Scl. chem.1070 A-4, 1419. (34) Boothe, J. E. U.S. Patent 3 481 163, 1989. (35) Boothe, J. E. U.S. Patent 3 472 740, 1969. (36) Harada, S.; Katayama, M. Macroml. Chem. 1088, 90, 177. (37) Harada, S.; Arai, K. Macromol. Chem. 1987, 107, 64. (38) Harada, S.; Aral. K. Macromol. Chem. 1067. 107, 78. (39) Amemlya. T.: Katayama, M.; Harada, S. Macromol. Chem. 1075, 178, 1289. (40) Nixon, A. C.; W i g a n , P. J.; William, P. H. U.S. Patent 3 278 474, 1968. (41) Schuller, W. H.; Thomas, W. M. U.S. Patent 2 923 701, 1960. (42) Boothe, J. E.. Llnke, W. F. US. Patent 3 147 218, 1984. (43) Suen, T. J., Schiller, A. M. US. Patent 3 471 805. 1965. (44) Sackls, J. J. U.S. Patent 3 585 148, 1971. (45) Schuller, W. H.; RKxnas,W. M.; Moore, S. T.; House, W. R. U.S. Patent 2 684 058, 1959. (48) Jeffery, E. A.: Hodekln, J. H.; Solomon. D. H. J. Macromol. Scl. Chem. 1076;A- 10, 944(47) Jackson, M. B. J. Mecromol. Sci. Chem. 1077, A - 1 1 , 311. (48) Black, A. P.; Berkner, F. B.; Morgan, J. J. J. CdkM Interface Sci. 1068, 21. 628. (49) Possei:-H. S.; Reldies, A. H.; Weber, W. J., Jr. J. Am. Water Works Assoc. 1088. 60. 48. (50) Pressman, M.' J. Am. Water Woks Assoc. 1087, 59, 189. (51) Hoover, M. F.; Schapef, R. J.; Boothe, J. E. US. Patent 3 412 019, 1965. (52) Schaper, R. J. US. Patent 3 514 398, 1970. (53) Wang, L. K.; Wang, M. H.; Zieyler. R. C.; SWler, M. P. Ind. Eng. Chem. froduct Res. Dev. 1977, 16, 311. (54) Schiller, A. M. US. Patent 3 514 398, 1970; U.S. Patent 3 171 805, 1965. (55) Ueda, T.; Harada, S. J. Appl. folym. Sci. 1088, 12, 2383. (56) Ueda, T.; Harada, S. J. Appl. folym. Sci. 1068, 12, 2395. (57) Hoover, M. F.; Can, H. E. TappilO68, 51, 552. (58) Luthy, R. G.;selleck,R. E.; GaNoway, T . R. E n m . Scl. Technol. 1077, 11, 1211. (59) Sylvester, N. D.; Byeseda J. J.; Yadeta, 8. Ind. Eng. Chem. Product Res. Dev. 1070, 18, 57. (80) Sharper, A. J., Jr.; Sinkovib, G.;Noren, G. K. German Patent 2 544 840, 1976. (61) Nakayama, M. Japanese Patent 75 91148, 1975. (62) Lim, S. K.; Blwmquist, A. E.; Schape, R. J. German Patent 2 448 584, 1975. (83) Morgan, J. E.; Boothe, J. E. US. Patent 3 968 037, 1972. (64) Rausch, E. G.; Mu&, R. A. German Patent 2 311 222, 1973. (65) Antonetti, J. M. US. Patent 4 141 691, 1977. (66) Harte, W. L.; Antonetti, J. M.;Henricks, J. M. French Patent 2 175 174, 1973. (67) Kerwln, R. C.; Hart, W. L.; Antonetti, J. M. German Patent 2 259 009, 1973. (88) Zeh, H. J., Jr. German Patent 1 930 847, 1970. (69) Hoover, M. F.; Carothers, R. 0. U S . Patent 3 490 938, 1970. (70) Harada, S. T. Japanese Patent 72 17918, 1972. (71) Hoover, M. F. German Patent 1 814 597, 1987. (72) Mobil Oil, German Patent 2 628 571, 1977. (73) Nishi Kaji, T.; Kamata, 0.; Mori, K. Japanese Patent 77 14821 1, 1977. (74) Varveri, F. S.; Jula. R. J.; Hoover, F. French Patent 2 033 159, 1969. (75) Hayama, K.; Aoi, H.; Jto, I. Japanese Patent 79 85754, 1979. (76) Hwang, M. H. U.S. Patent 4 132 874, 1977. (77) Jansma, R. H.; Albrecht, W. E. US. Patent 4 084 034, 1976. (78) FuJlta,S.; Mwayama, K.; Kaneda, T. Japanese Patent 79 39328, 1979. (79) Zehnder, J. A.; Stevens, T. K. Belglan Patent 888 452, 1977. (80) Ohsawa, K. Japanese Patent 77 110230, 1977. (81) Ohsawa, K. Japanese Patent 77 110229, 1977. (82) Nose, K. Japanese Patent 78 134973, 1978. (83) Kishloka, H. Japanese Patent 78 70178, 1978. (84) Komoto. Y.; Isome, Y.; Kusunose, T. Japanese Patent 78 35018, 1978. (85) Sokoi, P. E. U.S. Patent 3 988 825, 1970. (86) Flock, H. G.,Jr.; Hoover, M. F. British Patent I 287 489, 1969. (87) Hoover, M. F. U S . Patent 3 539 884, 1968. (68) Tasaki, T.; Kawamata, N. Japanese Patent 78 93655, 1978. (89) Herpers, F. J., Jr.; Untied!, D. I. German Patent 2 717 849. 1978. (90) Herpers, F. J., Jr.; Untied!, D. I. U S . Patent 4 014 808, 1977.
Received
review May 27, 1980 Accepted July 16, 1980
for
