Preparation and Characterization of Cellulose Propionate-g-diethylene Glycol Hexadecyl Ether Solid-solid Phase Change Material†

doi:10.7503/cjcu20141027

Abstract

Abstract:

A series of cellulose propionate-g-diethylene glycol hexadecyl ether(CP-g-E₂C₁₆) solid-solid phase change materials was prepared by chemical grafting method with dibutyl tin dilaurate(DBTDL) as the catalyst, cellulose as the matrix material, diethylene glycol hexadecyl ether as the functional substance. The structure, phase change properties and thermal stability were characterized using Fourier transform infrared spectroscopy(FTIR), hydrogen nuclear magnetic resonance spectrum(¹H NMR), differential scanning calorimetry(DSC), thermogravimetric analysis(TG) and wide-angle X-ray diffraction(XRD). The results showed that CP-g-E₂C₁₆ solid-solid phase change materials were prepared. CP-g-E₂C₁₆ copolymers with different feeding ratios, substitute degree and grating percents of E₂C₁₆ are in the range of 0.12—0.37 and 17.1%―33.4%, respectively. The onset melting temperatures of CP-g-E₂C₁₆ are in the range of 25—34 ℃, the melting enthalpy increases from 40 to 62 J/g. The thermal resistant temperatures of CP-g-E₂C₁₆ are all higher than 237 ℃, which are 21—40 ℃ higher than E₂C₁₆. All the products show good temperature-adjusting performance for solid-solid phase transition, which is expected to be used in cellulose-based thermo-regulating fiber field.

Key words: Cellulose, Diethylene glycol hexadecyl ether, Solid-solid phase change material, Thermal denaturation

CLC Number:

O631

TrendMD:

WANG Dong, HAN Na, ZHANG Xingxiang, WANG Lejun, WANG Ning, LI Wei, YU Wanyong, LI Zhinan. Preparation and Characterization of Cellulose Propionate-g-diethylene Glycol Hexadecyl Ether Solid-solid Phase Change Material^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1221.

Figures/Tables 11

Table 1 Feeding ratio and composition of raw materials

Sample	n(Prepolymer)∶n(CP)	n(CP₂O)∶n(CELL)	m(CELL)/g	m(AmimCl)/g	V(CP₂O)/mL
a	4∶1	2∶1	1.0	19.2	1.6
b	4∶1	4∶1	1.0	19.2	3.2
c	4∶1	6∶1	1.0	19.2	4.8
d	4∶1	8∶1	1.0	19.2	6.4
e	6∶1	2∶1	0.7	12.8	1.1
f	6∶1	4∶1	0.7	12.8	2.2
g	6∶1	6∶1	0.7	12.8	3.2
h	6∶1	8∶1	0.7	12.8	4.3
i	8∶1	2∶1	0.5	9.6	0.8
j	8∶1	4∶1	0.5	9.6	1.6
k	8∶1	6∶1	0.5	9.6	2.4
l	8∶1	8∶1	0.5	9.6	3.2

Fig.1 FTIR spectra of E2C16(a), cellulose(b), prepolymer(c) and CP-g-E2C16 copolymers(d, sample g)

Scheme 1 Synthesis of cellulose propionate-g-diethylene glycol hexadecyl ether

Fig.2 1H NMR spectrum of CP-g-E2C16 copolymers(sample g) DSP=0.14, DSE2C16=0.22.

Table 2 1H NMR analysis of CP-g-E2C16 samples

Sample	b	c	d	f	g	h	j	k	l
$w E 2 C 16$ (%)	19.4	17.1	25.9	32.2	25.9	33.4	31.3	24.8	32.2
$D S P$	0.10	0.16	0.41	0.09	0.14	0.31	0.15	0.21	0.18
$D S E 2 C 16$	0.14	0.12	0.24	0.32	0.22	0.37	0.31	0.21	0.33

Table 2 1H NMR analysis of CP-g-E2C16 samples

Sample	b	c	d	f	g	h	j	k	l
$w E 2 C 16$ (%)	19.4	17.1	25.9	32.2	25.9	33.4	31.3	24.8	32.2
$D S P$	0.10	0.16	0.41	0.09	0.14	0.31	0.15	0.21	0.18
$D S E 2 C 16$	0.14	0.12	0.24	0.32	0.22	0.37	0.31	0.21	0.33

Fig.3 DSC curves of E2C16, CP and CP-g-E2C16 copolymers

Table 3 DSC data of CP-g-E2C16 copolymers and native materials

Sample	n(Prepolymer)∶n(CP)	n(CP₂O)∶n(CELL)	Heating			Cooling
Sample	n(Prepolymer)∶n(CP)	n(CP₂O)∶n(CELL)	T_onset/℃	T_p/℃	ΔH_m/(J·g^-1)	T_onset/℃	T_p/℃	ΔH_c/(J·g^-1)
E₂C₁₆			28	35	94	19	25	93
CP		6∶1			0			0
c	4∶1	6∶1	28	35	45	13	23	45
g	6∶1	6∶1	27	35	48	11	22	48
k	8∶1	6∶1	25	36	52	11	23	52

Fig.4 TG(A) and DTG(B) curves of CP(a), E2C16(b),CEll(c) and CP-g-E2C16 copolymersPpartly enlarge TG curve of (A). d. sample c; e. sample g; f. sample k.

Table 4 Thermogravimetic analysis of CP-g-E2C16 copolymers

Sample	T_5%/℃	T_onset/℃	T_p/℃	Mass fraction(%)
CELL	321	317	335	75.6
E₂C₁₆	256	246	295	98.0
CP	171	138	285	82.8
c	298	289	332	92.1
g	296	285	329	93.0
k	287	276	319	94.2

Fig.5 XRD patterns of CELL, E2C16 and CP-g-E2C16 copolymers at 0 ℃

Fig.6 Typical GPC molecular weight distribution data for CP-g-E2C16 copolymers(sample d) in DMF at 40 ℃

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