可再生阻燃疏水复合纸板的制备及其力学性能

万成婕; 陈景华; 杨小贤; 符学栋; 马兰; 许楚悦; 陈烨

doi:10.13801/j.cnki.fhclxb.20210702.003

可再生阻燃疏水复合纸板的制备及其力学性能

doi: 10.13801/j.cnki.fhclxb.20210702.003

上海理工大学　出版印刷与艺术设计学院，上海 200093

基金项目: 大学生创新创业项目(XJ2021450)

详细信息

通讯作者:
陈景华，博士，副教授，硕士生导师，研究方向为复合包装材料、阻燃材料　E-mail：cjhshl@163.com

中图分类号: TB34
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出版历程
- 收稿日期: 2021-04-20
- 修回日期: 2021-06-11
- 录用日期: 2021-06-27
- 网络出版日期: 2021-07-02
- 刊出日期: 2022-03-23

Preparation of flame retardant hydrophobic renewable composite paperboard and its mechanical properties

College of Communication and Art Design, University of Shanghai for Science and Technology, Shanghai 200093, China

摘要

摘要: 为了研制一种兼具阻燃性及疏水性并有优良力学性能的可再生复合纸板，本研究以聚磷酸铵(APP)-卡拉胶(KC)构建了膨胀型阻燃体系(IFR)，以正硅酸乙酯(TEOS)-甲基三甲氧基硅烷 (MTMS)@氢氧化镁铝(MAH)作为协同阻燃剂、以硅烷偶联剂KH550(AEMO)@SiO₂作为疏水性填料、以可再生纸浆为基材，制备了APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂)复合纸板，并测得其力学性能；采用垂直燃烧实验和极限氧指数(LOI)表征纸板的阻燃效果；采用FE-SEM表征微观形貌；通过FTIR分析燃烧前后功能团变化；利用TG分析其热稳定性；采用接触角(CA)测试、滚动角(SA)测试等来测定其疏水性能。测试结果发现，复合纸板吸水率为1.78 g·m⁻²、戳穿强度为6.4 J；边压强度为8.3 kN·m⁻¹、平压强度为360 kPa。采用优选配方(APP、KC、MTH、ATH的质量比为3∶2∶1∶1)时LOI达到32%；燃烧实验后得炭化长度为19 mm，续焰时间为0.5 s，灼焰时间为3 s。TG结果表明其残炭量为37.5%。SEM结果表明燃烧后的复合纸板表面具有发泡炭层且纤维完整。CA达110.2°，SA为12°，含水率较原纸版降低232%。APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂)复合纸板具有良好阻燃性、疏水性及力学性能。
- 阻燃性 /
- 膨胀型阻燃体系 /
- 疏水性 /
- 卡拉胶 /
- 复合纸板 /
- 力学性能
Abstract: The purpose of this paper is to study and prepare a kind of renewable composite paperboard with both flame retardancy and hydrophobicity, and to explore its flame retardancy, hydrophobicity and mechanical properties. The intumescent flame retardant system (IFR) was constructed with ammonium polyphosphate (APP)-carrageenan (KC), tetraethylorthosilicate(TEOS)-methyltrimethoxysilane (MTMS)@magnesium aluminum hydro-xide(MAH) as synergistic flame retardant, silane coupling agent KH550 (AEMO)@SiO₂ as hydrophobic filler. The flame retardant, hydrophobic and mechanical properties of APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard were tested. According to the national standard, the main physical properties of corrugated board were measured. The flame retardant effect of corrugated board was tested by vertical combustion test and limiting oxygen index (LOI). The microstructure was characterized by FE-SEM. FTIR was used to study the changes of functional groups before and after combustion. Its thermal stability was analyzed by thermogravimetry (TG). Contact angle (CA) test, rolling angle (SA) test and water absorption test were used to determine its hydrophobicity. The water absorption of composite paperboard is 1.78 g·m⁻², the puncture strength is 6.4 J, the edge pressure strength is 8.3 kN·m⁻¹, and the compressive strength is 360 kPa. The optimal formula is adopted (the mass ratio of APP, KC, MTH and ATH was 3∶2∶1∶1). The limiting oxygen index (LOI) reaches 32% at the same time. After the combustion experiment, the carbonization length is 19 mm, the flame duration is 0.5 s, and the ignition time is 3 s. TG results show that the carbon residue of APP-KC-[(TEOS-MTMS)@MAH]-[AEMO@SiO₂] composite paperboard is 37.5%. SEM results show that there is a foamed carbon layer on the surface of the composite board after combustion, and the fiber is still intact. The contact angle is 110.2°. The moisture content is 232% lower than that of base paper. APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard has good flame retardancy, hydrophobicity and mechanical properties.
- flame retardant /
- intumescent flame retardant /
- hydrophobicity /
- carrageenan /
- composite paperboard /
- mechanical property

HTML全文

图 1 聚磷酸铵(APP)-卡拉胶(KC)-[(正硅酸乙酯(TEOS)-甲基三甲氧基硅烷(MTMS))@氢氧化镁铝(MAH)]-(硅烷偶联剂KH550(AEMO)@SiO₂)纸板制备工艺流程图

Figure 1. Process flow chart of preparing ammonium polyphosphate (APP)-carrageenan (KC)-[(tetraethylorthosilicate(TEOS)-methyltrimethoxysilane (MTMS)@magnesium aluminum hydroxide(MAH)]-(silane coupling agent KH550 (AEMO)@SiO₂) flame retardant hydrophobic paper

Hac—Acetic acid; MTH—Magnesium hydroxide; ATH—Aluminium hydroxide; CMC—Carboxymethyl cellulose sodium

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图 2 APP-KC-MTH-ATH复合纸板燃烧实验法的部分结果图示

Figure 2. Results of combustion test results of APP-KC-MTH-ATH composite board

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图 3 APP-KC-MTH-ATH体系的反应原理

Figure 3. Reaction principle of APP-KC-MTH-ATH

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图 4 APP-KC-MTH-ATH复合纸板氧指数值实际值和预测值对比

Figure 4. Comparison of actual and predicted oxygen index values of APP-KC-MTH-ATH composite paperboard

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图 5 (TEOS-MTMS)@MAH与MAH的SEM图像

Figure 5. SEM images of (TEOS-MTMS)@MAH and MAH

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图 6 APP-KC-[(TEOS-MTMS)@MAH]复合纸板的FTIR图谱

Figure 6. FTIR spectra of APP-KC-[(TEOS-MTMS)@MAH] composite paperboard

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图 7 APP-KC-[(TEOS-MTMS)@MAH]复合纸板及对照样的TG曲线

Figure 7. TG curves of APP-KC-[(TEOS-MTMS)@MAH] composite paperboard and control sample

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图 8 原纸及APP-KC-[(TEOS-MTMS)@MAH]复合纸板未燃烧时的SEM图像

Figure 8. SEM images of unburned base paper and unburned APP-KC-[(TEOS-MTMS)@MAH] composite paperboard

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图 9 原纸纸板及APP-KC-[(TEOS-MTMS)@MAH]复合纸板燃烧后的SEM图像

Figure 9. SEM images of the paperboard and APP-KC-[(TEOS-MTMS)@MAH] composite board after combustion

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图 10 AEMO@SiO₂与纸板基材连接形式

Figure 10. Connection form of AEMO@SiO₂ and paperboard

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图 11 APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂)复合纸板与对照样的接触角实验结果

Figure 11. Experiment of contact angle between APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard and control sample

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图 12 APP-KC-[(TEOS-MTMS)@MAH]-AEMO@SiO₂复合纸板及对照样的相对含水率图

Figure 12. Relative moisture content of modified flame retardant andmodified and added hydrophobic filler

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表 1 APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@ SiO₂)复合纸板配方

Table 1. Formula of APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard

No	Components	Mass ratio
1	TEOS∶MTMS∶Hac∶D H₂O	34∶66∶5∶45
2	AEMO∶SiO₂∶Ethanol	2∶0.8∶97.2
3	Dry fiber quantity in paper pulp∶Total amount of flame retardant	4.5∶1

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表 2 SPSS设计APP、氢氧化镁(MTH)、氢氧化铝(ATH)和KC配比表

Table 2. SPSS design of APP, magnesium hydroxide (MTH), aluminium hydroxide (ATH) and KC ratio table

Order	Composition/g
Order	APP/g	MTH/g	ATH/g	KC/g
SPL1	0	0	0	0
SPL2	10	10	0	10
SPL 3	15	15	0	15
SPL 4	5	5	0	5
SPL 5	5	15	10	0
SPL 6	15	10	5	0
SPL 7	10	5	15	0
SPL 8	0	15	15	10
SPL 9	15	0	15	5
SPL10	0	10	10	5
SPL11	5	10	15	15
SPL12	5	0	5	10
SPL13	10	0	10	15
SPL14	10	15	5	5
SPL15	15	5	10	10
SPL16	0	5	5	15

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表 3 阻燃配方的燃烧实验及氧指数结果

Table 3. Combustion experiment and oxygen index results of flame retardant formulation

Order	Total amount of flame retardant/g	Damaged length/ mm	After flame time/s	Ignition time/s	Limiting oxygen index (LOI)/%
SPL1	0	200	10	35	17.2
SPL2	30	67	5	24	25.2
SPL3	45	22	5	16	29.5
SPL4	15	135	10	20	23.6
SPL5	30	72	5	9	28.8
SPL6	30	80	2	13	27.6
SPL7	30	62	1	6	26.4
SPL8	40	54	2	12	29.3
SPL9	35	68	4	8	28.5
SPL10	25	159	7	14	23.5
SPL11	45	19	0.5	3	33.4
SPL12	20	105	8	25	24.6
SPL13	35	32	2	15	30.6
SPL14	35	20	0.8	5	32.8
SPL15	40	18	0.7	3	33.2
SPL16	25	120	5	18	25

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表 4 APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂)复合纸板与对照样力学性能对比

Table 4. Comparison of mechanical properties between APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard and control sample

Sample	Puncture strength/J	Edge pressure strength/(kN·m⁻¹)	Flat compression strength /kPa	Water absorption/(g·m⁻²)
Base paperboard	5.7	5.2	323.20	2.56
APP-KC-[(TEOS-MTMS)@MAH] composite paperboard	6.1	6.2	355.25	2.32
APP-KC-[(TEOS-MTMS)@MAH]-(AEMO@SiO₂) composite paperboard	6.4	8.3	360	1.78

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