磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能

doi:10.16085/j.issn.1000-6613.2021-2515

化工进展 ›› 2022, Vol. 41 ›› Issue (10): 5549-5557.DOI: 10.16085/j.issn.1000-6613.2021-2515

磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能

李婷¹(), 杜少辉²^,³(), 崔锦峰¹^,³(), 王仰辉²^,³, 李虎林²^,³, 郭润兰¹, 王蓬²^,³, 王振军²^,³, 郭军红¹, 杨保平¹

^1.兰州理工大学石油化工学院，甘肃兰州 730050
^2.甘肃恒达环保集团有限公司，甘肃静宁 743400
^3.甘肃省纸制品包装工程技术研究中心，甘肃静宁 743400

收稿日期:2021-12-09 修回日期:2022-04-03 出版日期:2022-10-20 发布日期:2022-10-21
通讯作者: 崔锦峰
作者简介:李婷（1996—），女，硕士研究生，研究方向为本征阻燃聚合物纸张施胶剂。E-mail：2524284872@qq.com。
杜少辉（1990—），男，学士，研究方向为造纸及纸制品包装。E-mail：393083830@qq.com。

Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks

LI Ting¹(), DU Shaohui²^,³(), CUI Jinfeng¹^,³(), WANG Yanghui²^,³, LI Hulin²^,³, GUO Runlan¹, WANG Peng²^,³, WANG Zhenjun²^,³, GUO Junhong¹, YANG Baoping¹

^1.College of Petrochemical Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.Gansu Hengda Environmental Protection Group Limited Company, Jingning 743400, Gansu, China
^3.Gansu Paper Products Packaging Engineering Technology Research Center, Jingning 743400, Gansu, China

Received:2021-12-09 Revised:2022-04-03 Online:2022-10-20 Published:2022-10-21
Contact: CUI Jinfeng

摘要/Abstract

摘要：

以甲苯二异氰酸酯（TDI）、聚乙二醇（PEG）为单体，二羟甲基丙酸（DMPA）和磷-硼杂化预聚物PBHP为扩链剂，通过逐步加聚制备不同组分的含磷、硼元素的阻燃水性聚氨酯（FRWPU）。FRWPU与聚磷酸铵（APP）、季戊四醇（PER）、三聚氰胺（MEL）膨胀阻燃体系复配制备阻燃纸张施胶剂。采用红外光谱（FTIR）、核磁共振波谱（NMR）、热重分析（TGA）、扫描电镜（SEM）、接触角测定、X射线光电子能谱（XPS）和垂直燃烧测试对FRWPU分散体、FRWPU薄膜、未施胶纸样和施胶纸样进行了表征。研究表明，随着PBHP加入量的提高，薄膜的疏水性增强，FRWPU40的接触角为85.4°，较FRWPU0提高了35.3%；同时，薄膜的最大热分解速率下降，800℃的残留质量从0上升到7.80%；施胶纸样的最大热分解速率下降，残留质量提高，平均炭化长度减小。当PBHP含量为50%时，残炭量为27.84%，较FPU0/IFR提高了30.6%；平均炭化长度为5.9cm，较FPU0/IFR降低了30%。SEM结果表明，施胶纸样燃烧后表面生成更加致密的炭层，阻燃性能提高。

关键词: 磷硼预聚物, 嵌段共聚, 水性聚氨酯, 阻燃, 纸张施胶剂

Abstract:

Using toluene diisocyanate (TDI) and polyethylene glycol (PEG) as monomers, dimethylpropionic acid (DMPA) and phosphorus-boron hybrid prepolymer PBHP as chain extender, FRWPU containing different phosphorus and boron elements was prepared by step polymerization. The paper sizing agent was prepared with ammonium polyphosphate (APP), pentaerythritol (PER) and melamine (MEL) expansion flame retardant system. FRWPU dispersion, FRWPU films, uncoated and coated paper samples were characterized by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), contact angle determination, X-ray photoelectron spectroscopy (XPS) and vertical combustion test. The results showed that with the increase of PBHP content, the hydrophobicity of the films increased, and the contact angle of FRWPU40 was 85.4°, which was 35.3% higher than that of FRWPU0. At the same time, the maximum thermal decomposition rate of the films decreased, and the residual mass at 800℃ increased from 0 to 7.80%. The maximum thermal decomposition rate of the coated paper samples decreased, the residual quality increased and the average carbonization length decreased. When the PBHP content was 50%, the carbon residue was 27.84%, which was 30.6% higher than FPU0/IFR. The average carbonization length was 5.9cm, 30% lower than that of FPU0/IFR. SEM results indicated that more dense carbon layer was formed on the surface of the coated paper after combustion, and the flame retardant performance was improved.

Key words: phosphorus and boron prepolymer, block copolymerization, waterborne polyurethane, flame retardant, paper sizing agent

中图分类号:

TQ072

李婷, 杜少辉, 崔锦峰, 王仰辉, 李虎林, 郭润兰, 王蓬, 王振军, 郭军红, 杨保平. 磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能[J]. 化工进展, 2022, 41(10): 5549-5557.

LI Ting, DU Shaohui, CUI Jinfeng, WANG Yanghui, LI Hulin, GUO Runlan, WANG Peng, WANG Zhenjun, GUO Junhong, YANG Baoping. Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5549-5557.

图/表 14

参考文献 21

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原料名称	质量分数/%
水性聚氨酯分散体	20~40
膨胀阻燃体系	30~40
水溶性淀粉	0~10
助剂	2~5
自来水	适量

原料名称	质量分数/%
水性聚氨酯分散体	20~40
膨胀阻燃体系	30~40
水溶性淀粉	0~10
助剂	2~5
自来水	适量

试样	T_5%/℃	T_maxⅠ/℃	T_maxⅠ/℃	800℃时残炭量/%
FRWPU0	223.5	287.9	419.9	0
FRWPU10	164.6	285.8	415.8	0.79
FRWPU20	167	277.8	426	1.77
FRWPU30	146.1	241.2	413.7	4.02
FRWPU40	164.6	242.2	404.7	5.9
FRWPU50	144.7	238.1	411.7	7.8

试样	T_5%/℃	T_maxⅠ/℃	T_maxⅠ/℃	800℃时残炭量/%
FRWPU0	223.5	287.9	419.9	0
FRWPU10	164.6	285.8	415.8	0.79
FRWPU20	167	277.8	426	1.77
FRWPU30	146.1	241.2	413.7	4.02
FRWPU40	164.6	242.2	404.7	5.9
FRWPU50	144.7	238.1	411.7	7.8

阶段	项目	未施胶	FPU0/IFR	FPU10/IFR	FPU20/IFR	FPU30/IFR	FPU40/IFR	FPU50/IFR
Ⅰ	T_Ⅰ/℃	约260	约230	约244	约242	约236	约244	约241
	M_Ⅰ/%	7.56	7.96	8.20	8.19	8.58	8.34	8.11
Ⅱ	T_Ⅱ/℃	260~370	230~320	244~322	242~330	236~319	244~324	241~327
	T_max/℃	348.8	311.1	309.7	308.9	308.7	308.7	308.5
	M_Ⅱ/%	52.62	37.2	32.85	36.67	31.79	31.58	35.17
Ⅲ	T_Ⅲ/℃	370以上	320以上	322以上	330以上	319以上	324以上	327以上
	M_Ⅲ/%	32.46	33.53	35.71	29.96	33.08	33.15	28.88
	800℃时的残炭量/%	7.36	21.31	23.24	25.18	26.55	26.93	27.84

磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能

Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks

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图/表 14

参考文献 21

相关文章 15

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试样	平均炭化长度/cm	平均续燃时间/s	平均灼燃时间/s
空白样	—	13	8
FPU0/IFR	8.4	0	0
FPU10/IFR	7.4	0	0
FPU20/IFR	7.5	0	0
FPU30/IFR	7.3	0	0
FPU40/IFR	6.9	0	0
FPU50/IFR	5.9	0	0

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