三维网笼状聚N-羟甲基丙烯酰胺/聚乙二醇半互穿网络复合相变微球的制备及热性能

刘玲伟; 邹新全; 张鸿; 叶泳铭; 赵云鹤; 石军峰; 闫铭; 朱浩彤; 周炜东; 于跃

doi:10.13801/j.cnki.fhclxb.20200831.004

三维网笼状聚N-羟甲基丙烯酰胺/聚乙二醇半互穿网络复合相变微球的制备及热性能

doi: 10.13801/j.cnki.fhclxb.20200831.004

大连工业大学　纺织与材料工程学院，大连 116034

基金项目: 辽宁省教育厅基础研究项目(J2019018)；大连市科技创新基金(2019J12GX047)

详细信息

通讯作者:
张鸿，博士，教授，硕士生导师，研究方向为高分子材料加工改性　 E-mail：zhang_hong1234@sina.com

中图分类号: TB324
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出版历程
- 收稿日期: 2020-06-08
- 录用日期: 2020-08-11
- 网络出版日期: 2020-09-01
- 刊出日期: 2021-04-08

Preparation and thermal properties of three-dimensional cage-like PolyN-methylethylamine/Polyethylene glycol semi-interpenetrating network composite phase change microspheres

School of Textile and Engineering, Dalian Polytechnic University, Dalian 116034, China

摘要

摘要: 以N-羟甲基丙烯酰胺(N-MA)和聚乙二醇(PEG)共晶为原料，通过乳液聚合制得聚N-羟甲基丙烯酰胺(PN-MA)/PEG半互穿网络(SIPN)复合相变材料(CPCM)。利用FTIR、XRD、差示扫描量热仪(DSC)、SEM、EDS等方法对PN-MA/PEG SIPN型CPCM的结构与性能进行了研究。结果表明：所得PN-MA/PEG SIPN型CPCM结晶焓和熔融焓达到78.38 J/g和82.31 J/g，结晶温度和熔融温度分别为36.88℃和32.05℃；CPCM中PN-MA和PEG之间是物理作用，并未发生其它的化学反应；得到的CPCM呈球形，尺寸比较均匀，由粒径200 nm左右的小球聚集形成10~15 μm左右的大球，球内呈现细密的三维网笼状结构；PEG在交联PN-MA网络的限制下被很好地固载，且仍有良好的结晶性能。
- 聚乙二醇 /
- N-羟甲基丙烯酰胺 /
- 复合相变材料 /
- 半互穿网络 /
- 乳液聚合
Abstract: Using N-methylol acrylamide (N-MA) and polyethylene glycol (PEG) eutectic as raw materials, poly-N-methylol acrylamide (PN-MA)/PEG semi-interpenetrating network was prepared by emulsion polymerization (SIPN) composite phase change material (CPCM). The structure and performance of (PN-MA)/PEG CPCM were characterized using FTIR, XRD, differential scanning calorimeter (DSC), SEM, EDS and other methods. The results show that the crystallization enthalpy and melting enthalpy of the obtained CPCM reach 78.38 J/g and 82.31 J/g, and the crystallization temperature and melting temperature are 36.88°C and 32.05°C respectively; the interaction between PN-MA and PEG in CPCM is physical link, no other chemical reaction occurs; the obtained CPCM is spherical and the size is relatively uniform. The small spheres with a diameter of about 200 nm are aggregated to form large spheres with a diameter of 10 μm to 15 μm. The sphere presents a dense three-dimensional net cage structure; PEG is well supported under the constraints of the cross-linked PN-MA network, and still has good crystallization performance.
- polyethylene glycol /
- N-hydroxymethyl acrylamide /
- composite phase change materials /
- semi-interpenetrating network /
- emulsion polymerization

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图 1 半互穿网络(SIPN)型聚N-羟甲基丙烯酰胺(PN-MA)/聚乙二醇(PEG)共晶复合相变材料(CPCM)反应流程

Figure 1. Semi-interpenetrating network (SIPN) type poly N-methylol acrylamide (PN-MA)/polyethylene glycol (PEG) eutectic composite phase change material (CPCM) reaction process

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图 2 不同N-MA含量的(PN-MA)/ PEG CPCM的DSC曲线(反应温度为75℃、反应时间为6 h、油水质量比为2∶1)

Figure 2. DSC curve of (PN-MA)/ PEG CPCM with different N-MA contents (Reaction temperature is 75℃, reaction time is 6 h, oil to water mass ratio is 2∶1)

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图 3 不同反应时间的(PN-MA)/ PEG CPCM的DSC曲线(N-MA质量分数为18wt%、反应温度为75℃、油水质量比为2∶1)

Figure 3. DSC curves of (PN-MA)/ PEG CPCM at different reaction time (N-MA mass fraction is 18wt%, reaction temperature is 75℃, oil to water mass ratio is 2∶1)

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图 4 不同反应温度的(PN-MA)/ PEG CPCM的DSC曲线(N-MA质量分数为18wt%、反应时间为6.5 h、油水质量比为2∶1)

Figure 4. DSC curves of (PN-MA)/ PEG CPCM at different reaction temperatures (N-MA mass fraction is 18wt%, reaction time is 6.5 h, oil to water mass ratio is 2:1)

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图 5 不同的油水比的CPCM的DSC曲线(N-MA质量分数18wt%、反应时间为6.5 h、反应温度为75℃)

Figure 5. DSC curves of CPCM with different oil-water ratios (N-MA mass fraction is 18wt%, reaction time is 6.5 h, reaction temperature is 75℃)

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图 6 PEG共晶 (a)，反应6 h (b)、反应6.5 h(c)、反应7 h (d)、反应7.5 h (e)、反应8 h (f) 的CPCM的FTIR图谱 (N-MA质量分数为18wt%、反应温度为75℃、油水质量比为2:1)

Figure 6. FTIR spectra of PEG eutectic (a), reaction 6 h of CPCM (b), reaction 6.5 h of CPCM (c), reaction 7 h of CPCM (d), reaction 7.5 h of CPCM (e), reaction 8 h of CPCM (f) (N-MA mass fraction is 18wt%, reaction temperature is 75℃, oil to water mass ratio is 2:1)

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图 7 最佳工艺下的(PN-MA)/PEG CPCM的SEM图像

Figure 7. SEM images of (PN-MA)/PEG CPCM under the best process

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图 8 最佳工艺下的(PN-MA)/PEG CPCM的EDS元素分析mapping图谱

Figure 8. EDS elemental analysis mapping spectra of (PN-MA)/PEG CPCM under the best process

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图 9 PEG共晶 (a)、反应6 h (b) 、6.5 h (c)、7 h (d)、7.5 h (e)、8 h (f) 的(PN-MA)/PEG CPCM的XRD图谱 (N-MA质量分数为18wt%、反应温度为75℃、油水质量比为2∶1)

Figure 9. XRD spectra of (PN-MA)/ PEG CPCM with PEG eutectic (a), reaction 6 h (b), 6.5 h (c), 7 h (d), 7.5 h (e), 8 h (f) (N-MA mass fraction is 18wt%, reaction temperature is 75℃, oil to water mass ratio is 2∶1)

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图 10 70℃下的PEG共晶和CPCM的形态

Figure 10. Comparison of PEG eutectic and CPCM at 70℃

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图 11 热循环100次前后的(PN-MA)/PEG CPCM的DSC曲线

Figure 11. DSC curves of (PN-MA)/PEG CPCM before and after 100 thermal cycles

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表 1 实验参数表

Table 1. Experimental parameter table

Parameter	a	b	c	d	e	f
Quality of N-MA/wt%	16	17	18	19	20	—
Temperature reflex/℃	60	65	70	75	—	—
Reaction time/h	6	6.5	7	7.5	8	—
Oil to water ratio	1.5∶1	2∶1	2.5∶1	3∶1	3.5∶1	4∶1
Note：a, b, c, d, e and f—Number of changes corresponding to the parameter.

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表 3 不同反应时间的(PN-MA)/PEG CPCM的DSC结果

Table 3. DSC results of (PN-MA)/PEG CPCM at different reaction time

Sample	Melting enthalpy/(J·g⁻¹)	Melting temperature/℃	Crystalline/(J·g⁻¹)	Crystallization temperature/℃
6 h	55.31	31.48	51.24	36.70
6.5 h	82.31	32.05	78.38	36.88
7 h	30.92	33.09	27.50	36.88
7.5 h	59.14	31.96	54.76	38.02
8 h	32.88	33.85	30.14	35.46

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表 2 不同N-MA含量的CPCM的DSC结果

Table 2. DSC results of CPCM with different N-MA contents

Content of N-MA	Melting enthalpy/(J·g⁻¹)	Melting temperature/℃	Crystalline/(J·g⁻¹)	Crystallization temperature/℃
16wt%	12.41	35.37	10.13	30.82
17wt%	27.06	31.58	25.20	35.37
18wt%	55.31	31.48	51.24	36.70
19wt%	49.56	32.81	45.67	36.81
20wt%	30.45	36.13	26.14	34.99

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表 4 不同油水比的(PN-MA)/ PEG CPCM的DSC结果

Table 4. DSC results of (PN-MA)/ PEG CPCM by different oil-water ratios

Oil to water ratio	Melting enthalpy/(J·g⁻¹)	Melting temperature/℃	Crystalline/(J·g⁻¹)	Crystallization temperature/℃
1.5∶1	49.46	31.58	46.32	37.55
2∶1	82.31	32.05	78.38	36.88
2.5∶1	41.42	31.67	37.81	37.83
3∶1	37.49	31.67	33.99	37.36
3.5∶1	43.55	31.48	40.30	37.88
4∶1	33.38	31.20	31.12	36.70

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表 5 文献中不同CPCM的热能存储特性

Table 5. Heat energy storage characteristics of different CPCM in the literature

PCM	Basis material	Phase-transition temperature/℃	Latent heat/ (J·g⁻¹)	Preparation process	Reference
Fatty acids	Melamine modified phenolic resin	32.93	87.67	Microcapsules	[23]
Orthoic acid-nutmeg acid	Expanded graphite	6.80	136.3	Porous material adsorption	[24]
PEG	Diatomite	27.70	87.09	Porous material adsorption	[25]
Paraffin wax	Diatomite	54.24	61.96	Porous material adsorption	[26]
Xylitol pentoconate	Plaster	52.58	43.89	Blend	[27]
Na₂SO₄	Porous ceramic	882.17	54.33	Vacuum impregnation	[28]
NaNO₃	Expanded perlite	307.35	178.4	Vacuum impregnation	[29]

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表 6 最佳工艺下的(PN-MA)/PEG CPCM的EDS能谱的元素分布数据

Table 6. EDS energy spectrum element distribution data for (PN-MA)/PEG CPCM under optimal process

Element	Line type	Apparent concentration	k ratio	Mass fraction/wt%	Mass fraction/ wt% Sigma	Atomic percentage	Standard sample label
C	K line	62.54	0.62541	60.97	0.24	68.74	C Vit
N	K line	19.06	0.03394	20.96	0.28	20.26	BN
O	K line	7.97	0.02682	12.51	0.13	10.59	SiO₂
S	K line	0.11	0.00094	0.08	0.01	0.03	FeS₂
Pt	M line	6.27	0.06275	5.49	0.08	0.38	Pt
Total	—	—	—	100.00	—	100.00	—

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