双DOPO悬垂型阻燃剂化学修饰水性聚氨酯的性能

刘超; 陈雨鑫; 尹付琳; 梁旭阳; 肖寒; 宝冬梅; 龙丽娟; 周国永

doi:10.13801/j.cnki.fhclxb.20220913.001

双DOPO悬垂型阻燃剂化学修饰水性聚氨酯的性能

doi: 10.13801/j.cnki.fhclxb.20220913.001

1.
贵州民族大学　化学工程学院，贵阳 550025
2.
国家复合改性聚合物材料工程技术研究中心，贵阳 550014

基金项目: 国家自然科学基金(51863004)；贵州省省级科技计划项目(黔科合基础-ZK[2022]一般216)；贵州民族大学科研项目(GZMUZK[2021]YB09)；贵州民族大学引进人才项目(0703001001018020)

详细信息

通讯作者:
周国永，博士，教授，硕士生导师，研究方向为功能高分子化学合成技术　E-mail: gyzhou@gzmu.edu.cn

中图分类号: O633
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出版历程
- 收稿日期: 2022-07-25
- 修回日期: 2022-08-23
- 录用日期: 2022-09-02
- 网络出版日期: 2022-09-14
- 刊出日期: 2023-05-15

Chemical modification of waterborne polyurethane with double DOPO pendant flame retardant

1.
School of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China
2.
National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014, China

Funds: National Natural Science Foundation of China (51863004); Guizhou Provincial Science and Technology Projects (ZK[2022]216); Research Fund of Guizhou Minzu University (GZMUZK[2021]YB09); Scientific Research Fund for the Talents Introduction of Guizhou Minzu University (0703001001018020)

摘要

摘要: 为提高普通水性聚氨酯(WPU)耐热性、阻燃性和力学性能等，本文以9, 10-二氢-9-氧-10-磷菲-10氧化物(DOPO)和2, 2′-二烯丙基双酚A(DABA)为原料，通过“一步法”化学合成了双DOPO悬垂型阻燃剂DDBA，采用红外光谱(FTIR)和核磁共振(NMR)表征了其化学结构，并用其化学修饰WPU制备新型水性聚氨酯(DDBA/WPU)。研究了DDBA对DDBA/WPU胶膜材料耐水性、耐热性、阻燃性及力学性能的影响。通过水接触角、吸水率、热失重(TG)、锥形量热(CONE)、电镜扫描(SEM)、氧指数(LOI)、垂直燃烧(UL-94)、万能试验机等评价胶膜的相关性能。研究结果表明：随着DDBA添加量的增大，胶膜的耐水性、耐热性、阻燃性及力学性能不断提升，当DDBA的添加质量比为20%时，水接触角可达134.56°，提高了106.06%，吸水率降低了33.29%。耐受温度提高了60℃，LOI值为35.9%，烟气释放总量(TSP)和平均有效燃烧热(AEHC)分别减小了85.42%和55.76%，最大热释放速率(pHRR)、总释放热(THR)、CO₂的释放量分别下降了35.40%、51.20%、58.49%，点燃时间延长了15 s，CO释放量提高了163.46%，拉伸强度可达25.7 MPa，约为改性前WPU的9.51倍。
- DDBA /
- 水性聚氨酯 /
- 耐水性 /
- 耐热性 /
- 阻燃性 /
- 力学性能
Abstract: In order to improve the heat resistance, flame retardancy and mechanical properties of traditional water-based polyurethane (WPU), in this study 9,10-dihydro-9-oxo-10-phosphenanthrene-10 oxide (DOPO) and 2,2’-diallylbisphenol A (DABA) were used as starting materials, and the chemical synthesized double DOPO pendant flame retardant DDBA, the chemical structure was characterized by infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR), and a new waterborne polyurethane (DDBA/WPU) was prepared by chemically modifying waterborne polyurethane (WPU). The effects of DDBA on water resistance, heat resistance, flame retardancy and mechanical properties of DDBA/WPU film were studied. Evaluation of the films by water contact angle, water absorption, thermal weight loss (TG), cone calorimetry (CONE), scanning electron microscope (SEM), oxygen index (LOI), vertical combustion (UL-94), universal testing machine related performance. The research results show that with the increase of DDBA addition, the water resistance, heat resistance, flame retardancy and mechanical properties of the film continue to improve. When the addition mass ratio of DDBA is 20%, the water contact angle can reach 134.56°, an increase of 106.06%, and the water absorption rate is reduced by 33.29%, the temperature resistance is increased by 60°C. Its LOI value is 35.9%, the total flue gas release (TSP) and average effective heat of combustion (AEHC) decreased by 85.42% and 55.76%. The maximum heat release rate (pHRR), total heat release (THR) and CO₂ release decreased by 35.40%, 51.20%, 58.49%, ignition time is prolonged by 15 s, CO release increased by 163.46%. The tensile strength can reach 25.7 MPa, which is about 9.51 times than that of WPU before modification.
- DDBA /
- waterborne polyurethane /
- water resistance /
- heat resistance /
- flame retardancy /
- mechanical propert

HTML全文

图 1 新型水性聚氨酯(DDBA/WPU)乳液合成路线

Figure 1. New waterborne polyurethane (DDBA/WPU) emulsion synthesis route

IPDI—Isophorone diisocyanate; PPG1000—Polypropylene glycol 1000; DBTDL—Dibutyltin dilaurate; BDO—1, 4-butanediol; DMPA—Dimethylolpropionic acid; DOPO—9, 10-dihydro-9-oxygen-10-phosphophene-10 oxide; DABA—2, 2'-diallyl bisphenol A

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图 2 ((a1), (a2), (a3)) DOPO的¹³C-NMR、 ¹H-NMR、³¹P-NMR；((b1), (b2)) DABA的¹³C-NMR、¹H-NMR；(b3)主要原料的FTIR；((c1), (c2), (c3)) DDBA的¹³C-NMR、¹H-NMR、³¹P-NMR

Figure 2. ((a1), (a2), (a3)) ¹³C-NMR, ¹H-NMR, ³¹P-NMR of DOPO; ((b1), (b2)) ¹³C-NMR, ¹H-NMR of DABA; (b3) FTIR of main raw material; ((c1), (c2), (c3)) ¹³C-NMR, ¹H-NMR, ³¹P-NMR of DDBA

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图 3 DDBA/WPU的红外图谱

Figure 3. FTIR spectra of DDBA/WPU

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图 4 (a) DDBA/WPU胶膜的水接触角和表面能；(b) DDBA/WPU胶膜的吸水率

Figure 4. (a) Water contact angle and surface energy of DDBA/WPU films; (b) Water absorption of DDBA/WPU films

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图 5 (a) DDBA/WPU胶膜的TG曲线；(b) DDBA/WPU胶膜的DTG曲线；(c) 不同温度下DDBA/WPU胶膜的变化

Figure 5. (a) TG curves of DDBA/WPU film; (b) DTG curves of DDBA/WPU film; (c) Changes of DDBA/WPU adhesive films at different temperatures

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图 6 DDBA/WPU胶膜的DSC曲线

T_g—Glass transition temperature

Figure 6. DSC curves of DDBA/WPU films

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图 7 DDBA/WPU胶膜的热释放速率(HRR) (a)、总释放热(THR) (b)和有效燃烧热(EHC) (c)

Figure 7. Heat release rate (HRR) (a), total heat release (THR) (b) and effective heat of combustion (EHC) (c) of the DDBA/WPU film

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图 8 DDBA/WPU胶膜的烟气释放总量(TSP) (a)、烟气释放速率(SPR) (b)和 CO (c)、CO₂ (d)生成速率

Figure 8. Total amount of flue gas released (TSP) (a) and flue gas release rate (SPR) (b) of the DDBA/WPU film and CO (c), CO₂ (d) generation rate

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图 9 DDBA/WPU锥形量热残留物的表面形貌和元素分布图

Figure 9. Surface morphologies and element distribution of DDBA/WPU conical calorimetric residues

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图 10 (a) DDBA/WPU锥形量热残留物的表面微观形貌；((b), (c)) DDBA/WPU锥形量热计残留物的正面和侧面宏观照片

Figure 10. (a) Surface micromorphologies of the residue from DDBA/WPU cone calorimetry; ((b), (c)) Macrophotographs of the residue from the DDBA/WPU cone calorimeter front and side

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图 11 DDBA/WPU LOI测试后图片

Figure 11. Picture after DDBA/WPU LOI test

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图 12 DDBA及DDBA/WPU燃烧过程的阻燃机制图

Figure 12. Diagram of the flame retardant mechanism of DDBA and DDBA/WPU combustion process

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图 13 DDBA/WPU拉伸性能曲线图

Figure 13. DDBA/WPU tensile properties curve

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图 14 (a) DDBA/WPU胶膜脆断SEM图像；(b) DDBA/WPU胶膜正常拉断SEM图像

Figure 14. (a) SEM images of DDBA/WPU films brittle fracture; (b) SEM images of normal DDBA/WPU films fracture

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表 1 DDBA含量对WPU乳液性能的影响

Table 1. Effect of DDBA content on the properties of WPU emulsion

n(DDBA)/%	Performance
n(DDBA)/%	Exterior	Particle size/nm	PDI	Viscosity/(MPa·s)	Stability
WPU	Pan blue light	57.62	0.119	22.7	*
2.5	Pan blue light	63.84	0.057	25.5	*
5	Yellowish	74.00	0.097	26.8	*
7.5	Yellowish	78.02	0.108	28.7	*
10	Pale yellow	87.74	0.046	31.3	*
12.5	Pale yellow	99.09	0.025	32.8	*
15	Pale yellow	110.60	0.019	33.2	*
17.5	Milky white	128.20	0.035	34.9	*
20	Milky white	147.50	0.139	36.3	*
Notes: * indicates stable (>6 months); n(DDBA)—Mass fraction based on the total mass of IPDI and PPG1000; PDI—Polymer dispersibility index.

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表 2 WPU和DDBA/WPU热分解数据

Table 2. Thermal decomposition data of WPU and DDBA/WPU

n(DDBA)/%	T_10%/℃	T_maxI/℃	T_maxII/℃	T_maxIII/℃	T_maxIV/℃	Char yield/%
WPU	118.4	110.0	272.8	317.3	357.4	0.9
5	120.1	115.7	275.3	343.6	389.5	1.1
10	123.5	113.5	282.5	345.7	382.8	1.2
15	284.8	168.4	293.4	342.5	378.2	1.9
20	291.7	196.2	298.9	350.0	390.3	2.3
Note: T_10%(℃), T_maxI(℃), T_maxII(℃), T_maxIII(℃), T_maxIV(℃)—Temperature of 10% weight loss, the maximum weight loss temperature of the first, second, third and fourth stages.

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表 3 DDBA/WPU胶膜的锥形量热数据

Table 3. Cone calorimetry data of the DDBA/WPU films

n(DDBA)/%	TTI/s	pHRR/(kW·m²)	THR/(MJ·m²)	ACOY/(kg·kg⁻¹)	ACO₂Y/(kg·kg⁻¹)	CO/CO₂	AEHC/(MJ·kg⁻¹)	TSP/(m²·m⁻²)
WPU	9	1214.93	134.41	0.052	4.65	0.011	35.53	1235.02
5	17	1190.58	104.82	0.054	3.13	0.017	23.04	1204.53
10	20	1017.85	104.53	0.063	3.05	0.021	20.36	518.29
15	22	792.08	97.64	0.087	2.70	0.032	18.08	425.63
20	24	784.87	65.06	0.137	1.93	0.071	15.72	180.80
Note: TTI, pHRR, THR, ACOY, ACO₂Y, CO/CO₂, AEHC, TSP—Ignition time, maximum heat release rate, total heat release, average CO generation, average CO₂ generation, and ratio of CO to CO₂ generation, the average effective heat of combustion, the total amount of flue gas released.

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表 4 DDBA/WPU的氧指数(LOI)和垂直燃烧 (UL-94)等级

Table 4. Oxygen index (LOI) value and vertical combustion (UL-94) rating of DDBA/WPU

n(DDBA)/%	Vertical burning test
	After-flame time
	LOI/%	${\bar {t_1}}/{\rm{s}} $	${\bar {t_2}}/{\rm{s}} $	UL-94 rating	Dripping
WPU	21.9	76.0	78.2	Unrated	Yes
5	26.8	11.3	10.7	V-1	No
10	29.3	8.7	7.5	V-1	No
15	32.4	4.9	5.4	V-1	No
20	35.9	2.9	1.6	V-0	No
Notes: The after-flame of specimen burned to the clamp in the first flame application; ${\bar {t_1}} $, ${\bar {t_2}} $—Reignition time; V-0 for each individual sample combustion duration ${\bar {t_1}} $ or ${\bar {t_2}} $≤10 s, burning particles or drips does not ignite skim cotton; V-1 for each individual sample combustion duration ${\bar {t_1}} $ or ${\bar {t_2}} $≤30 s, burning particles or drips does not ignite skim cotton.

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