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Synthesis of Allyl Dimethyl Dehydroabietyl Ammonium Chloride and its Surface Activities.

Byline: Da-Xiong Xu, Zhao-Sheng Cai, Xue-Mei Zhu, Li-Jun Pei and Zhan-Qian Song

Summary: Allyl dimethyl dehydroabietyl ammonium chloride (ADMDHAC) was synthesized from dehydroabietylamine (DHA) and allyl chloride. The synthesis was carried out in two steps. First, DHA was transformed into N,N-dimethyl dehydroabietyl amine (DMDHA) through Eschweiler-Clarke Reaction. Second, the ADMDHAC was obtained after the DMDHA had reacted with allyl chloride and recrystallized using a solvent composed of diethyl ether and ethanol. Critical micelle concentrations (cmc) of ADMDHAC at 25 C was found to be 2.851A-10-4 mol.L-1, and its surface tension value at cmc (cmc) was determined to be 30.6 mN.m-1, these data suggested that ADMDHAC could be used as a good alternative of benzalkonium chloride (BC).

Keywords: Critical micelle concentrations (cmc); Surface activities; Eschweiler-Clarke Reaction; Allyl dimethyl dehydroabietyl ammonium chloride (ADMDHAC)

Introduction

Rosin is one of natural chemicals obtained from pine trees, and its total output is about multimillion tons annually [1-6]. The main component of rosin is the mixture of C20 monocarboxylic diterpenic resin acids including the abietic-type acids and pymaric-type acid, and percentage of these resin acids in the rosin is ca. 90% [1-3]. The rosin could be transformed into disproportionated rosin through disproportionation at 200 to 240 C, and the major component of disproportionated rosin is dehydroabietic acid [2,5-8].

Dehydroabietylamine (DHA) is a chemicals derived from dehydroabietic acid [9]. As a friendly material to environment, DHA had obtained many applications in different fields, such as the synthesis of pesticides and pharmaceuticals, the preparation of surfactants and corrosion inhibitors, the manufacture of epoxy resins, etc [9-16]. Among all of these applications, the preparation of surfactants using DHA as starting materials may be the most important one.

DHA could be utilized for preparing anionic, cationic, nonionic and amphoteric surfactants, but the synthesis of cationic surfactant using DHA as one of basic materials is studied more extensively [6, 15, 17, 18]. The preparation of cationic surfactant based on DHA could be actualized through following methods [17-19]: (1) the DHA is reacted with halohydrocarbon directly, (2) the DHA is modified with the quaternary salt containing reactive group, (3) the DHA is transformed into N,N-dimethyl dehydroabietylamine (DMDHA) through Eschweiler-Clarke Reaction and then reacted with halohydrocarbon. We herein reported the preparation of allyl dimethyl dehydroabietyl ammonium chloride (ADMDHAC) using method (3). Meanwhile, the surface activities including critical micelle concentration (cmc) and surface tension at cmc (cmc) for ADMDHAC in aqueous solution were also investigated. The preparation of ADMDHAC was presented as Scheme-1.

Experimental

Materials and Apparatus

Dehydroabietylamine (DHA) was purchased from Wanjing New-material Co., Ltd of Hangzhou (Hangzhou, People's Republic of China), and purified according to literature [25, 26]. Allyl chloride, 2,2,6,6-tetramethyl- 1-piperidinyloxy (TEMPO), formic acid and formaldehyde were purchased from Sinopharm Chemical Reagent Co., Ltd (Shanghai, People's Republic of China). All other chemicals were of reagent grade and used without purification as received.

Fourier transform infrared (FT-IR) spectra were recorded with KBr pellets on a Nicolet Nexux FT-IR 670 spectrometer. Sixteen scans at a resolution of 4 cm-1 were averaged and referenced against air.

1H-NMR spectrum was obtained with Bruker AV-300 spectrometer at 300.13 MHz and measured in DMSO-d6 solution at 30 0.5C, and the sample was dissolved in a 5 mm diameter tube at a concentration of ca 20 mg/mL.

Measurements of cmc and cmc

After dissolving a certain amount quaternary salts in double distilled water, some of solution was taken out from volumetric flask and diluted with double distilled water by duplicate diluting method or decuple diluting method, and a series of solutions containing different concentration of quaternary salt were obtained. The surface tension () of aqueous solution with different concentration for ADMDHAC was measured with JYM-200D automatic tensiometer (Shipeng Testing Equipmen Co., Ltd of Chengde, People's Republic of China) connected to a thermostatted water bath maintained at 25 C, and three replicas were performed in each case. The curves reflected the relationship between and concentration (c) of quaternary salt was plotted, and the cmc and cmc of quaternary salt in aqueous solution were obtained from the experimental curve.

Synthesis of ADMDHAC

45.68 g purified DHA (ca. 160 mmol) was dissolved in 160 mL ethanol, then 55.2 g 80 % formic acid aqueous solution (ca. 960 mmol) and 66.68 g 36% formaldehyde aqueous solution (ca. 960 mmol) were added dropwise into the mixture with stirring in sequence, and allowed to react at room temperature for ca. 1.0 h. The temperature of mixture was elevated to 87 C and maintained at this temperature until the DHA had been exhausted according to the monitoring result of thin-layer chromatography (TLC) analysis (the duration for this process was ca. 12.0 h). The ethanol and water were removed from the reactant by distillation using rotary evaporator under vacuum, and the remainder was mixed with 200 mL saturated NaCl solution under continuous stirring. The mixture was treated with ca. 300 g 15% NaOH solution sufficiently before it was transferred into separatory funnel and extracted with 140 mL toluene for three times.

After the toluene layer was combined and washed with 50 mL distilled water for three times, the toluene was reclaimed by distillation using rotary evaporator under vacuum. The residual substance was distilled under high vacuum and distillation cut of 220 ~230 C/ 0.67 ~1.33 kPa, DMDHA, was obtained in the yield of 72.6 %. The mass content of DMDHA was 85.7% determined by HPLC.

13.10 g DMDHA (ca. 40 mmol) and 0.5 g TEMPO were dissolved in 100 mL ethanol. Then, 4.0 mL allyl chloride (ca. 48 mmol) was added into at room temperature. The temperature of reactant was elevated to 55 C and reacted at this temperature until the DMDHA had been exhausted according to the monitoring result of TLC analysis (the duration was ca. 72 h). After the reaction had been completed, the ethanol and remained allyl chloride were removed from the reactant by distillation using rotary evaporator under vacuum. The remainder was treated with 100 mL anhydrous diethyl ether under refluxing condition and refrigerate at -18 C in order to form the solid of quaternary salt. The mixture was separated by filtration and the solid was recrystallized using a solvent composed of anhydrous diethyl ether and ethanol (Vether:Vethanol =1.0:1.0).

The ADMDHAC was obtained with 86.1 % yield after the white crystal was separated from the solution and dried under vacuum at 50 C for ca. 12.0 h, and its melting point was 206 ~ 207 C determined by X4 Melting Point-Measuring Instrument.

Determination of Product Content

The mass content of ADMDHAC in product was determinated by IC. A standard curve reflected the relationship between Cl- mass concentration (mCl-) and absorbing peak area (A) was obtained through determinating the absorbing peak area of a series standard NaCl solutions which mass concentration had been ascertained previously. The product of quaternary salt (ca. 0.2 g) was dissolved in definite amount distilled water, then the solution was analyzed using IC and the absorbing peak area was obtained. Meanwhile, the distilled water was utilized as blank analysis.

The mCl- of sample solution was ascertained according to the standard curve. The content of ADMDHAC in product was calculated using Eq. 1.

Results and Discussions

Identification of Resonance in the Spectra

The FT-IR spectra of purified DHA, DMDHA and ADMDHAC were presented in Fig. 1, and the 1H-NMR spectrum of ADMDHAC was presented in Fig. 2.

In the FT-IR spectrum of purified DHA, the absorption bands at 3393 and 3328 cm-1 were assigned to N-H of primary amine, 2927 and 2865 cm-1 were ascribed to C-H of CH2 and CH3, 1613 cm-1 was assigned to dN-H of NH2, 1566 and 1498 cm-1 were assigned to C=C of aryl ring, 1460 and 1380 cm-1 were assigned to dC-H of CH3, 1064 cm-1 was assigned to C-N of amine, 883 and 822 cm-1 were ascribed to the dC-H of aryl, respectively [17, 18, 20].

Compared with DHA, the absorption bands reflected the N-H and dN-H of primary amine had disappeared in the FT-IR spectrum of DMDHA, and the intensity of absorption peaks reflected the C-H and dC-H of CH3 had increased. A peak at 3032 cm-1 in the FT-IR spectrum of ADMDHAC was ascribed to the C-H of =CH2, 1610 cm-1 was ascribed to das of quaternary group, 2952 and 2865 cm-1 were ascribed to the C-H of CH2 and CH3, 1461 and 1364 cm-1 were assigned to dC-H of CH3, 883 and 822 cm were ascribed to the dC-H of aryl, 958 and 627 cm-1 were respectively.

The presence of a wide peak at 3353 cm in the FT-IR spectrum of ADMDHAC was ascribed to the water in the sample [17, 18, 20].

The signals at 7.15, 6.97 and 6.87 ppm in the 1H-NMR spectrum of ADMDHAC were assigned to the H of aryl ring. The signals at 6.11, 5.64 and 5.60 ppm were assigned to the H of ethylene, and that at 4.07 ppm and 3.34 ppm were ascribed to the H of CH2 of allyl and methyl connected with N of quaternary group respectively. The signals at 2.73~ 3.0, 3.17 and 3.43~3.51 ppm were assigned to the H of CH2 or CH that connected with aryl ring or the N of quaternary group.

The signals at 0.83~2.29 ppm were ascribed to the H of CH3 or CH2 that unconnected with aryl ring or the N of quaternary group [17, 18, 20].

All these data indicated the product from the reaction between DMDHA and allyl chloride in the existence of 2,2,6,6-tetramethyl- 1-piperidinyloxy (TEMPO) was allyl dimethyl dehydroabietyl ammonium chloride (ADMDHAC).

The Content of ADMDHAC in Product

The standard curve reflected the relation between mCl- and peak area based on NaCl was shown in Fig. 3, and the Ion Chromatography (IC) spectrum of ADMDHAC was shown in Fig. 4.

From Fig. 4, we could know the peak height was 28.94 s, the half peak width was 0.0873 min, and the peak area was 2.527 s.min. Furthermore, we could know the mCl- was 21.26 ppm according to the relation between peak area and mCl- displayed in Fig.3. Combined with the sample weight and the volume of solution, the content of ADMDHAC in the product could be calculated according to Eq. 1 and this value was 97.28 %.

The HLB, cmc and cmc of ADMDHAC

The value of hydrophilic/lipophilic balance

Table-1: Surface tensions of aqueous solution of ADMDHAC at different concentration.

###C, mol.L-1 A-106###1.585###2.512###3.981###6.457###10.47###16.22###25.12###40.74###64.57

###log C###-5.8###-5.6###-5.4###-5.19###-4.98###-4.79###-4.60###-4.39###-4.19

###, mN.m-1###67.1###53.4###46.6###43.6###41.8###39.8###38.2###37.3###36.1

###C, mol.L-1 A-104###1.047###1.622###1.995###2.512###3.236###4.074###4.786###6.457###7.943###10.47

###log C###-3.98###-3.79###-3.70###-3.60###-3.49###-3.39###-3.32###-3.19###-3.10###-2.98

###, mN.m-1###35.2###33.9###32.5###31.1###30.1###29.8###29.6###29.5###29.4###29.3

The critical micelle concentration (cmc) of ADMDHAC and its surface tension at cmc (cmc) in aqueous solution at 25 C were shown in Table-2. Compared with the cmc and cmc of benzalkonium chloride including dodecyldimethylbenzyl ammonium chlorides (BC12), tetradecyldimethylbenzyl ammonium chlorides (BC14) and hexadecyldimethylbenzyl ammonium chlorides (BC16) that reported by Farias and Gracia, et al [22-24], we could know the surface activity of ADMDHAC in aqueous solution was the best one among BC12, BC14, BC16 and ADMDHAC. The reasons may be concerned with the hydrophobic property of ADMDHAC was stronger than that of benzalkonium chloride.

Table-2: cmc, cmc and min of BC12, BC14, BC16 and ADMDHAC.

###BC12###BC14###BC16###ADMDHAC

###cmc / mol.L-1A-103###8.19###1.90###0.52###0.285

###cmc / mN.m-1###36.8###31.8###30.9###30.6

Meanwhile, the maximum surface excess (Gmax) of ADMDHAC in aqueous solution could be calculated as 2.59A-10-6 mol.m-2 using Gibbs equation, and the minimum surface area (Amin) of ADMDHAC on aqueous surface was 64.10 A 2. Combined the cmc and cmc of ADMDHAC in aqueous solution with the Gmax and Amin, we could know the efficiency of ADMDHAC, as a surfactant, was higher than that of common surfactants having carbon chain as hydrophobic moieties.

Conclusion

Allyl dimethyl dehydroabietyl ammonium chloride (ADMDHAC) was prepared by the reaction between DMDHA and allyl chloride in the existence of TEMPO. The analytical result of IC indicated that the content of ADMDHAC in product was more than 97 %. The critical micelle concentration (cmc) of ADMDHAC in aqueous solution was ca. 2.851A-10-4 mol.L-1 and the cmc was ca. 30.6 mN.m-1 at 25 C, these data were lower than that of BC12, BC14 or BC16, so the ADMDHAC, as a cationic surfactant, could be found much more application than that of benzalkonium chloride in some extent.

Acknowledgements

We gratefully acknowledged the support of National Natural Science Foundation of P.R. China (No. 31170543) and Research Fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (AE 201114). We also gratefully acknowledged the support of China Pharmaceutical University in analysis.

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