卡拉胶包覆APP微球阻燃水性环氧树脂

doi:10.7503/cjcu20180416

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (2): 385.doi: 10.7503/cjcu20180416

卡拉胶包覆APP微球阻燃水性环氧树脂

王娜^1,²(), 杨菲¹, 张静¹, 方庆红^1,²

1. 沈阳化工大学中西高等材料研究院, 沈阳 110142
2. 辽宁省橡胶弹性体重点实验室, 沈阳 110142

收稿日期:2018-06-06 出版日期:2019-02-10 发布日期:2018-11-15
作者简介:
联系人简介: 王娜, 女, 博士, 教授, 博士生导师, 主要从事阻燃高分子材料方面的研究. E-mail: iamwangna@syuct.edu.cn
基金资助:
辽宁省高端人才计划(批准号: [2016]864)、辽宁省高校创新人才计划(批准号: [2017]053)、沈阳市国际合作项目(批准号: 17-51-6-00)、沈阳市中青年科技创新人才计划(批准号: RC170118)和沈阳市科技局中西高等材料研究院项目(批准号: 18-005-6-04)资助

Inflame-retardant Water-borne Epoxy Resin of APP Microsphere with Carrageenan Cladding^†

WANG Na^1,^2,^*(), YANG Fei¹, ZHANG Jing¹, FANG Qinghong^1,²

1. Sino-Spanish Advanced Materials Institute, Shenyang 110142, China
2. Liaoning Provincial Key Laboratory of Rubber & Elastomer, Shenyang University of Chemical Technology, Shenyang 110142, China;

Received:2018-06-06 Online:2019-02-10 Published:2018-11-15
Contact: WANG Na E-mail:iamwangna@syuct.edu.cn
Supported by:
† Supported by the Top Talents Program of Liaoning Province, China(No. [2016]864), the Innovative Talents Program of Universities in Liaoning Province, China(No. [2017]053), the International Cooperation Project, Shenyang Municipal Science and Technology Bureau, China(No. 17-51-6-00), the Technological Innovation Talents Program for Youngs and Middles of Shenyang, Shenyang Municipal Science and Technology Bureau, China(No. RC170118) and the Sino-Spanish Advanced Materials Institute, Shenyang Municipal Science and Technology Bureau, China(No. 18-005-6-04)

摘要/Abstract

摘要：

以氯化钡提纯k-卡拉胶, 经过氧化氢降解, 通过反相乳液聚合的方式制备了一系列卡拉胶包覆聚磷酸铵(APP)阻燃微球(k-CM/APP); 将其加入到水性环氧树脂(EP)中, 制备了3种钢结构防火涂层EP2, EP3和EP4. 利用红外光谱(IR)、扫描电子显微镜(SEM)及元素分析(EDS)对k-CM/APP的结构及形貌进行了表征. 利用极限氧指数(LOI)、垂直燃烧(UL-94)、背温测试法、热重分析(TG)、锥形量热(CONE)、附着力测试、 IR和SEM等方法分析了涂层的阻燃、隔热及力学性能. 结果表明, k-CM/APP(3/1)球形结构完整, 800 ℃时的残炭量高达59.5%. 与其它阻燃涂层体系相比, 添加了k-CM/APP(3/1)的EP3防火涂层的极限氧指数达到28.5%, UL-94达到了V-0级, 60 min防火涂层耐火温度为253 ℃. 相比于纯EP涂层, EP3涂层的热释放速率峰值降低了58.26%, 总热释放量降低了20.84%, 附着力达到8.74 MPa.

关键词: 卡拉胶微球, 聚磷酸铵, 水性环氧树脂, 阻燃性

Abstract:

After k-carrageenan was purified by barium chloride and degraded by hydrogen oxidation, a series of k-carrageenan/ammonium polyphosphate(k-CM/APP) inflame-retardant microsphere was prepared using inverse emulsion polymerization method. Then k-CM/APP was added to water-borne epoxy resin to prepare EP2, EP3, EP4 steel structure fire retardant coating. The structure and morphology of k-CM/APP were represented by using infrared spectrograph(IR), scanning electron microscope(SEM), energy dispersive spectrometry(EDS). The limit oxygen index(LOI), vertical combustion(UL-94), back temperature test method, thermogravimetry(TG), cone calorimeter, adhesion tester, IR and SEM were used for analyzing the flame retardant property, heat-insulating property, thermal property and mechanical property. Research results showed that k-CM/APP spherical structure was complete, and the carbon residue at 800 ℃ reached 59.5%. Compared with other fire retardant coatings, the LOI of the EP3 fire retardant coating with added k-CM/APP(3/1) reached 28.5%, UL-94 reached the class V-0, and the fire-resistant temperature of 60 min fire retardant coating was 253 ℃. Compared with pure EP coating, the heat release rate peak of EP2 coating was decreased by 58.26% and the total heat release quantity was decreased by 20.84%, adhesion reached 8.74 MPa.

Key words: Carrageenan microsphere, Ammonium polyphosphate, Waterborne epoxy resin, Flame retardancy

中图分类号:

O636

TrendMD:

王娜, 杨菲, 张静, 方庆红. 卡拉胶包覆APP微球阻燃水性环氧树脂. 高等学校化学学报, 2019, 40(2): 385.

WANG Na,YANG Fei,ZHANG Jing,FANG Qinghong. Inflame-retardant Water-borne Epoxy Resin of APP Microsphere with Carrageenan Cladding^†. Chem. J. Chinese Universities, 2019, 40(2): 385.

图/表 11

Scheme 1 Synthesis mechanism of k-CM/APP

Table 1 Formulation of steel fireproof coating*

Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

Fig.1 SEM images of k-CM(A), k-CM/APP(2/1)(B), k-CM/APP(3/1)(C) and k-CM/APP(4/1)(D)

Table 2 Elemental analysis data of k-CM, k-CM/APP(2/1), k-CM/APP(3/1) and k-CM/APP(4/1)

Sample	Mass fraction(%)
Sample	S	Ba	P
k-CM	3.94	13.98	0
k-CM/APP(2/1)	3.54	11.18	8.72
k-CM/APP(3/1)	3.48	12.79	7.33
k-CM/APP(4/1)	3.21	12.56	6.36

Table 3 TG data of APP, k-CM/APP(2/1), k-CM/APP(3/1) and k-CM/APP(4/1)*

Sample	Temperature(5%)/℃	Temperature(20%)/℃	w₈₀₀(%)
APP	152.3	282.1	33.5
k-CM/APP(2/1)	170.1	218.8	53.7
k-CM/APP(3/1)	183.9	232.6	59.5
k-CM/APP(4/1)	176.7	228.5	55.7

Table 4 LOI and UL-94 test results of different samples

Sample	LOI(%)	UL-94	Droplet	Sample	LOI(%)	UL-94	Droplet
EP0	19.7	No rating	Yes	EP3	28.5	V-0	No
EP1	30.1	V-0	No	EP4	27.2	V-0	No
EP2	25.9	V-0	No

Scheme 2 Flame retardancy mechanism

Fig.2 Back temperature test of steel(a), EP0(b), EP1(c), EP2(d), EP3(e) and EP4(f)

Fig.3 Cone calorimeter curves of EP0(a), EP1(b) and EP3(c)(A) HRR vs. time; (B) THR vs. time; (C) SPR vs. time; (D) TSR vs. time.

Fig.4 SEM images of surface(A—C) and inside(D—F) of EP0(A, D), EP1(B, E) and EP3(C, F)

Fig.5 SEM images of chars of EP0(A), EP1(B) and EP3(C)

参考文献 30

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卡拉胶包覆APP微球阻燃水性环氧树脂

Inflame-retardant Water-borne Epoxy Resin of APP Microsphere with Carrageenan Cladding^†

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参考文献 30

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Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

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Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

卡拉胶包覆APP微球阻燃水性环氧树脂

Inflame-retardant Water-borne Epoxy Resin of APP Microsphere with Carrageenan Cladding†

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图/表 11

参考文献 30

相关文章 15

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Inflame-retardant Water-borne Epoxy Resin of APP Microsphere with Carrageenan Cladding^†

Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20

Sample	m(EP)/g	m(Curing agent)/g	m(H₂O)/g	m(APP)/g	m[k-CM/ APP(2/1)]/g	m[k-CM/ APP(3/1)]/g	m[k-CM/ APP(4/1)]/g
EP0	60	20	20	-	-	-	-
EP1	45	15	20	20	-	-	-
EP2	45	15	20	-	20	-	-
EP3	45	15	20	-	-	20	-
EP4	45	15	20	-	-	-	20