纤维素苯甲酸酯接枝二乙二醇十六烷基醚的制备及性能

doi:10.7503/cjcu20160816

摘要/Abstract

摘要：

分别以1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)和1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)/N,N-二甲基乙酰胺(DMAc)为溶剂体系, 以微晶纤维素(聚合度为220)和苯甲酰氯(BC)为原料制备纤维素苯甲酸酯(CB). 探索了溶剂体系、反应温度和投料比对产物取代度、溶解性和熔融性能的影响. 结果表明, 以[Amim]Cl为溶剂时, 随着反应温度的升高(60~80 ℃)或体系中苯甲酰氯与葡萄糖单元环(AGU)投料量的增加(3∶1~9∶1), 产物的溶解性和熔融性能均提高, 取代度也随之升高(0.13~2.98); 以[Emim]Ac/DMAc为溶剂时, 产物中苯甲酰基的接枝度较低, 且共聚物中引入乙酰基不适合制备纤维素-g-苯甲酰氯. 初步探讨了在[Amim]Cl中合成纤维素苯甲酸酯接枝二乙二醇十六烷基醚(CB-g-E₂C₁₆)固-固相变材料的性能, 研究结果表明, CB-g-E₂C₁₆相变材料的相变温度为12.7~29.1 ℃, 相变焓为12~24 J/g, 在294 ℃仍能保持热稳定性, 为该类纤维素基固-固相变材料的可熔融加工奠定了理论基础.

关键词: 微晶纤维素, 接枝反应, 离子液体, 固-固相变材料

Abstract:

Cellulose benzoate(CB) was prepared with microcrystalline cellulose(degree polymerization, DP=220) and benzoyl chloride(BC) as the raw materials. The ionic liquid 1-allyl-3-methyl imidazole chloride([Amim] Cl) and 1-ethyl-3-methyl imidazole acetate([Emim]Ac)/N,N-dimethyl acetamide were used as the solvent respectively. The effects on the degrees of substitution and solubility as well as melting property have been explored in different solvents, different reaction temperatures and different molar ratios. The results showed that the solubility and melting performance as well as the degrees of substitution(0.13—2.98) of the products were improved, with the increases of reaction temperatures(60—80 ℃) and the molar ratios of benzoyl chloride(3∶1—9∶1) in [Amim]Cl, by ¹H NMR, FTIR, DSC, TG and thermal stage microscope. The grafting degrees of substitution of benzoyl were low, and the acetyl was introduced in copolymer when [Emim]Ac/DMAc was used as the solvent. It was demonstrated the dissolution system is not suitable for the reaction of cellulose grafting benzoyl chloride. Preliminary exploration has been carried out to synthesize BC-g-polyoxyethylene(2) hexadecyl ether solid-solid phase change material(CB-g-E₂C₁₆) in the [Amim]Cl. The results showed that the phase transition temperatures and enthalpy of phase change of CB-g-E₂C₁₆were 12.7—29.1 ℃and 12—24 J/g, respectively. The thermostability was 294 ℃. It laid a certain foundation for subsequent detailed exploration about the performances of the cellulose based phase change materials.

Key words: Microcrystalline cellulose, Grafting reaction, Ionic liquid, Solid-solid phase change material

中图分类号:

O631

TrendMD:

韩娜, 王秀芳, 璩庭司, 钱勇强, 吕亚红. 纤维素苯甲酸酯接枝二乙二醇十六烷基醚的制备及性能. 高等学校化学学报, 2017, 38(6): 1099.

HAN Na, WANG Xiufang, QU Tingsi, QIAN Yongqiang, LU Yahong. Preparation and Properties of Cellulose Benzoate and Preliminary Exploration About Cellulose Benzoate-g-polyoxyethylene(2) Hexadecyl Ether^†. Chem. J. Chinese Universities, 2017, 38(6): 1099.

图/表 16

Table 1 Degrees of substitution and reaction conditions of cellulose and acyl chloride

Sample	Molar ratio of acyl chloride to AGU	Temperature/℃	Time/h	DS^a	Sample	Molar ratio of acyl chloride to AGU	Temperature/℃	Time/h	DS^a
S-1	6∶1^b	50	2	0.81	S-9	5∶1^b	70	2	0.76
S-2	3∶1^b	60	2	0.13	S-10	6∶1^b	70	2	1.05
S-3	4∶1^b	60	2	0.56	S-11	9∶1^b	70	2	2.98
S-4	5∶1^b	60	2	0.63	S-12	4∶1^b	80	2	0.69
S-5	6∶1^b	60	2	0.97	S-13	5∶1^b	80	2	0.80
S-6	9∶1^b	60	2	2.80	S-14	6∶1^b	80	2	1.82
S-7	3∶1^b	70	2	0.18	S-15	12∶1^c	50	2	2.05
S-8	4∶1^b	70	2	0.62

Table 2 Reaction condition of cellulose and benzoyl chloride*

Sample	Mass fraction of cellulose(%)	Mass ratio of[Emim]Ac to DMAc	Added way	Mass ratio of BC to AGU	Temperature/℃	Time/h
SS-1	10	1∶0		6∶1	70	2
SS-2	10	1∶0		6∶1	80	2
SS-3	8	8∶2	Mix	6∶1	80	2
SS-4	8	7∶3	Mix	6∶1	80	2
SS-5	8	6∶4	Mix	6∶1	80	2
SS-6	8	5∶5	Mix	6∶1	80	2
SS-7	8	7∶3	Div	6∶1	80	2

Sheme 1 Mechanism of polymerization of cellulose, BC, CB and E2C16

Table 3 Fabrication conditions and yield of CB-g-E2C16 solid-solid phase change materials

Sample	Molar ratio of BC to AGU	T₁/℃	t₁/h	Molar ratio of E₂C₁₆ to AGU	T₂/℃	t₂/h	Yield(%)
D1^a	6∶1	70	2	4∶1	90	6	81.0
D2^b	6∶1	70	2	4∶1	90	6	32.2
D3^b	6∶1	70	2	4∶1	70	6	21.5

Fig.1 FTIR spectra of CB in [Amim]Cl at 60 ℃

Fig.2 FTIR spectra of CB or CA in different solutions

Fig.3 FTIR spectra of CB-g-E2C16

Fig.4 1H NMR spectra of CB(S-5, DS=0.97)

Fig.5 1H NMR spectra of CB, cellulose acetate CA and mixture esters

Table 4 Degrees of substitution of CB and CA mixed ester synthesized in [Emim]Ac*

Sample	Solvent	Molar ratio of benzoyl chloride to AGU	Temperature/℃	DS_B	DS_A	DS
SS-4	[Emim]Ac/DMAc/mix	6∶1	80	0.09	2.04	2.13
SS-7	[Emim]Ac/DMAc/div	6∶1	80	0.11	2.50	2.61
SS-2	[Emim]Ac	6∶1	80	0.15	2.71	2.86

Fig.6 Relation curves of substitution degreeand reaction temperature of CB in [Amim]ClMolar ratio of BC to AGu: a. 3∶1; b. 4∶1; c. 5∶1; d. 6∶1; e. 9∶1.

Fig.7 1H NMR spectra of CB-g-E2C16 (sample D2)

Table 5 Solubility of CB, CA and mixed esters in different solutions*

Sample	DS_A	DS_B	DMSO	DMF	Acetone
MCC			-	-	-
S-2		0.13	+	-	-
S-3		0.56	+	+	-
S-5		0.97	+	+	-
S-10		1.05	+	+	-
S-6		2.80	+	+	+
S-15	2.05		+	+	-
SS-2	2.71	0.15	+	+	-
SS-4	2.04	0.09	+	+	-
SS-7	2.50	0.11	+	+	-

Fig.8 POM images of sample S-10 at 50 ℃(A) and 270 ℃(B)

Table 6 DSC data of E2C16 and CB-g-E2C16

Sample	DS_B	DS_E	DS	$w E 2 C 16$ (%)	$T mp .$ /℃	ΔH_m/(J·g^-1)	Δ $H m *$ /(J·g^-1)	T_cp/℃	ΔH_c/(J·g^-1)	Δ $H c *$ /(J·g^-1)
E₂C₁₆				100	34.4	104	104	23.9	95	95
D1	1.05	1.24	2.29	0.52	23.9	23	54	15.0	24	49
D2	1.05	1.06	2.11	0.50	29.1	17	52	22.8	20	47
D3	1.05	1.01	2.06	0.50	12.7	12	52	18.7	15	47

Table 6 DSC data of E2C16 and CB-g-E2C16

Sample	DS_B	DS_E	DS	$w E 2 C 16$ (%)	$T mp .$ /℃	ΔH_m/(J·g^-1)	Δ $H m *$ /(J·g^-1)	T_cp/℃	ΔH_c/(J·g^-1)	Δ $H c *$ /(J·g^-1)
E₂C₁₆				100	34.4	104	104	23.9	95	95
D1	1.05	1.24	2.29	0.52	23.9	23	54	15.0	24	49
D2	1.05	1.06	2.11	0.50	29.1	17	52	22.8	20	47
D3	1.05	1.01	2.06	0.50	12.7	12	52	18.7	15	47

Table 7 TG analysis of CB-g-E2C16

Sample	T_do/℃	T_dp/℃	Mass loss(%)
Cellulose	319	335	85
E₂C₁₆	246	295	98
D1	281	320	89
D2	294	334	88
D3	282	325	87

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