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The Reactivity of Hydroxyl Groups at Different Tactic Sequences on Poly( Vinyl Alcohol) in the Addition Reaction with Vinyl Sulfoxides and Vinyl Sulfones

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The Reactivity of Hydroxyl Groups at Different Tactic Sequences on Poly( Vinyl Alcohol) in the Addition Reaction with Vinyl Sulfoxides and Vinyl Sulfones Polymer Journal, Vol. 23, No.9, pp 1105-1109 (1991) The Reactivity of Hydroxyl Groups at Different Tactic Sequences on Poly( vinyl alcohol) in the Addition Reaction with Vinyl Sulfoxides and Vinyl Sulfones Kiyokazu IMAI, Tomoo SHIOMI, Yasuyuki TEZUKA, and Takashi TSUKAHARA Department of Material Science and Technology, Nagaoka University of Technology, Kamitomioka, Nagaoka, Niigata 940-21, Japan (Received March 7, 1991) ABSTRACT: The reactivity of hydroxyl groups in different tactic sequences on poly(vinyl alcohol) was studied in the Michael type addition reaction with vinyl sulfoxides and vinyl sulfones. By the 13C NMR anaysis on the methine carbon signal in unreacted vinyl alcohol units for the obtained sulfinylethyl and sulfonylethyl poly(vinyl alcohol)s, it was concluded that the reactivity order of hydroxyl groups in different tractic sequences was isotactic > heterotactic > syndiotactic. KEY WORDS Reactivity I Tacticity I Poly( vinyl alcohol) I Vinyl Sulfoxide I Vinyl Sulfone I Michael Addition Reaction I We have recently described new membrane different tactic sequences has been so far materials for the selective accumulation and examined for poly(vinyl chloride) in the sub­ the separation of pollutant sulfur dioxide based stitution 7 - 9 or the abstraction 10 reactions, and on sulfoxide- and sulfone-modified polymers also for poly( vinyl chloroformate), 11 where the produced through a Michael-type addition substituent at the isotactic sequence exhibited reaction of hydroxyl groups in poly(vinyl al­ higher reactivity than those at the syndiotactic cohol), 1 - 3 cellulose4 and ethylene/vinyl alco­ counterpart. It was also shown in the hol copolymer5•6 with a variety of vinyl sulf­ modification reaction of poly(vinyl alcohol) oxides and vinyl sulfones. that the acetalization 12 - 15 and the ketaliza­ The control on not only the total content of tion 16 took place preferentially at the isotactic sulfoxide or sulfone groups but also the sequence in which the energitically favorable distribution of functional groups along the equatorial-equatorial conformation can be polymer chains is considered to be of a maintained at the produced six-membered significant importance to optimize the permse­ 1,3-dioxane ring skeleton. lective property which retaining the sufficient mechanical strength of the product. Since the EXPERIMENTAL reactivity of substituent groups along the polymer chain can be influenced by the tactic Reagents sequence, we have examined in the present A series of vinyl sulfoxides and sulfones was study on the reactivity of hydroxyl groups at synthesized by the method described in the the different tactic sequences on poly(vinyl preceding papers. 1 •2 Poly( vinyl alcohol) was alcohol) in the addition reaction with vinyl obtained from Kuraray Co. (PVA 117H, sulfoxides and vinyl sulfones. DP = 1700, the degree of saponification: The reactivity of substituent groups m > 99.8%) and used after the Soxhlet extraction 1105 K. IMAI et a/. CHz=CHSOzR + HzO RSOzCHzCHzOH NaOH CHz=CHS0 R --(CH2-yH7j" + CH2=CHS02R -fCH2-yHt,nfCH2 -yHl;; 2 (RS0 CH CHz) 0 OH or DMSO OH OCH2CH2S02R 2 2 2 R=CH 3 ,c2H5 Scheme 2. Scheme 1. with methanol. Dimethylsulfoxide (DMSO) for 13C) as internal standards. was dried over molecular sieves 4A. Other reagents were used after conventional purifica­ RESULTS AND DISCUSSION tion procedures. The addition reaction of vinyl sulfoxides and Reaction of Poly( vinyl alcohol) with Vinyl of vinyl sulfones with poly(vinyl alcohol) was Suifoxides and with Vinyl Suifones found to proceed both in aqueous and in The addition reaction of vinyl sulfoxides and DMSO solution by adding sodium hydroxide of vinyl sulfones with poly( vinyl alcohol) was as a catalyst. Nevertheless, the concurrent side performed either in aqueous solution or in reaction was observed between vinyl sulfoxides DMSO with the addition of sodium hydroxide or sulfones and water present in the reaction as a catalyst. 1 •2 The reaction products with mixture either as a solvent or as a medium to vinyl sulfoxides were isolated by the precipita­ solubilize the catalyst in DMSO. Thus the tion into either directly acetone-methanol products of high degrees of sulfinylation or (8 : 2) mixture (for the samples ofless than 50% sulfonylation were obtained when the reaction substitution) or acetone after the dialysis (for was carried out in DMSO solution in the the samples of more than 50% substitution). presence of minimal amount of water (ca. The reaction products with vinyl sulfones were 2 wt%) to dissolve a catalyst, sodium hydrox­ isolated by the precipitation into methanol. The ide, in the medium, and with the addition of products were then subjected to the repeated an excess amount of vinyl sulfoxides or vinyl precipitation and finally vacuum-dried at 45°C sulfones compared to the hydroxyl group for 2 days. The degree of substitution in the concentration of poly(vinyl alcohol). The products was determined by comparing the 1 H almost complete substitution of hydroxyl NMR signal intensity of substituent groups groups on poly( vinyl alcohol) was thus attained with main chain groups. 1·2 with 8 times excess of methyl or ethyl vinyl sulfoxides, which 3 times excess was sufficient N M R Measurements with methyl and ethyl vinyl sulfones. 1H and 13C NMR measurements were A series of sulfoxide- and sulfone-modified carried out at 270 MHz and at 67.8 MHz, poly(vinyl alcohol) derivatives with various respectively, with a JEOL JNM GX 270 degrees of substitution was then subjected to apparatus by using a 5 mm¢ C-H dual probe 13C NMR measurements. The methine region in D 20 at 40oC and the dimethyl sulfoxide-d6 spectra of vinyl alcohol units in the reaction (DMSO-d6 ) at 60oC. Chemical shift values were products between either methyl vinyl sulfoxide calibrated either from 3-(trimethylsilyl)propi­ or methyl vinyl sulfone and poly( vinyl alcohol) onic acid sodium salt-d4 (0 ppm in D 2 0) or were shown in Figure 1. The methine carbon DMSO signal (2.50 ppm for 1 H and 43.5 ppm signals in vinyl alcohol units were observed to 1106 Polym. J., Vol. 23, No.9, 1991 Reactivity and Tacticity on PV A a b tion from the analysis of the methine carbon signals on vinyl alcohol units. The results for the reaction products of poly(vinyl alsohol) with two different types of vinyl sulfoxides and vinyl sulfones having methyl and ethyl substituents were summarized in Figure 2. It is clearly seen that hydroxyl groups located at the isotactic sequence were preferentially consumed at the early stage of the reaction in all examples, while those at the heterotactic sequence and in particular those at the syndiotactic sequence were apparently less reactive. In Figure 3, the relative content of hydroxyl groups in each tactic sequence at various degrees of substitution was listed for a series of sulfoxide-modified poly(vinyl alcohol)s obtained by the reaction with methyl, ethyl, t-butyl and phenyl vinyl sulfoxides, respec­ tively. This indicates that the reactivity of hydroxyl groups at the sequential unsub­ 72 70 68 PPM 72 70 68 PPM stituted vinyl alcohol units is not appreciably Figure l. 13C NMR methine region spectra of vinyl influenced by the bulkiness of the substituent alcohol units in the reaction products of poly( vinyl alcohol) in vinyl sulfoxides. Thus the kinetic retardation with (a) methyl vinyl sulfoxide and with (b) methyl vinyl observed particularly in the reaction with sulfone at various degrees of substitution. (The degree of t-butyl vinyl sulfoxide is thought to be caused substitution for (a): 83, 55, 32, and 0%, and for (b): 81, 46, 26, and 0% from the top to the bottom, respectively.) by the steric hinderance of the introduced t-butyl groups on polymer chain to suppress the further access of the vinyl sulfoxide toward resolve into three major peaks for the whole the neighboring hydroxyl groups. Besides, the examined range of the degree of substitution introduction of alkylsulfinyl ethyl groups on and were scarcely affected by the introduction poly(vinyl alcohol) causes the polymer coil of sulfinyl- or sulfonylethyl substituted mono­ shrinkage 1 and this may reduce the reactivity mer units. Thus the methine carbon signals on of hydroxyl groups at the late stage of the vinyl alcohol units were remained to be reaction. indicative to their tactic environment, i.e., at The observed higher reactivity of hydroxyl 71.8 (isotactic ), 70.2 (heterotactic ), and 68.4 groups at the isotactic sequence on poly(vinyl (syndiotactic) ppm, respectively. 17 On the alcohol) may be accounted by the conforma­ other hand, the methine carbon signals on tional consideration ofisotactic and syndiotac­ sulfinyl- and sulfonylethyl derivative units tic sequences in poly( vinyl alcohol), 18 where appeared as complicated multiplets at around the isotactic (mm) sequence prefers the 78 ppm, presumably due to the influence of the TG + GT conformation, while the TTTT comonomer distribution pattern and the tactic conformation prevails in the syndiotactic (rr) arrangements. One could therefore estimate the sequence in polar solvents like DMSO and relative content of hydroxyl groups in each H 2 0. Consequently, hydroxyl groups at the tactic sequence at various degrees of substitu- isotactic sequence are considered to be less Polym. J., Vol. 23, No.9, 1991 l\07 K. IMAI et a/. a c 1.0 r-------------1:::1-1 l.Or---------I[]:,{:::I 0.8 0.8 0 "0 "' 0"' : 0.6 0 c ..g 0.4 u u. 0.2 0 20 40 100 0 20 40 60 60 100 Degree of substitution (mol'/,) Degree of substitution (mol'/,) b d 1.0 1.0 0.8 0.8 "0"' "' ] 0.6 0 0.6 0 0 c c .2 .2 u u u. u. 0. 40 60 60 100 100 Degree of substitution (mol'/,) Degree of substitution (mol'/,) Figure 2.
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