聚乳酸基聚磷酸酯改性复合材料的制备及其阻燃抑烟性能

杨华维; 杨兴才; 闵样; 班大明

doi:10.13801/j.cnki.fhclxb.20220917.001

聚乳酸基聚磷酸酯改性复合材料的制备及其阻燃抑烟性能

doi: 10.13801/j.cnki.fhclxb.20220917.001

贵州师范大学　化学与材料科学学院，贵阳 550001

基金项目: 国家自然科学基金(51763005)；贵阳市科技计划项目(筑科合同 [2021]1001号)

详细信息

通讯作者:
班大明，博士，教授，硕士生导师，研究方向为功能高分子材料　E-mail: bdaming@gznu.edu.cn

中图分类号: O634.5；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2022-08-03
- 修回日期: 2022-09-07
- 录用日期: 2022-09-10
- 网络出版日期: 2022-09-19
- 刊出日期: 2023-07-15

Flame retardancy and smoke suppression of poly(lactic acid) composites modified by polyphosphate

School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China

Funds: National Natural Science Foundation of China (51763005); Guiyang Science and Technology Planning Project ([2021]1001)

摘要

摘要: 由于聚乳酸(PLA)极易燃烧，并伴有严重的熔滴现象，严重阻碍了在包装、汽车、电气和电子工业等诸多领域的应用，为解决此问题，以PLA为基体，聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯(POPP)为阻燃剂，采用熔融共混热压法制备了不同含量的阻燃PLA复合材料。通过极限氧指数(LOI)、垂直燃烧(UL-94)测试、热重分析(TG)和锥形量热等方法研究了PLA复合材料的阻燃性和抑烟性能。结果表明：当POPP的添加量为4wt%时，PLA复合材料的垂直燃烧可达到V-0级，极限氧指数为34.8%。与纯PLA相比，POPP/PLA-4的烟雾释放速率和总烟释放量分别下降了85.83%和77.65%，极大地改善了PLA材料的抑烟性能。此外，对锥形量热测试后的残炭微观结构和热降解行为分析表明，POPP在PLA燃烧过程中的阻燃机制以气相为主、凝聚相为辅。POPP热降解释放出•PO和•PO₂自由基，与•H和•OH结合终止气相燃烧循环；在凝聚相中，POPP促进PLA分子间交联成炭，表面形成连续且致密的炭层，提高基材的阻燃性能。
- 聚乳酸 /
- 聚磷酸酯 /
- 改性 /
- 热降解 /
- 抑烟性能
Abstract: Due to poly(lactic acid) (PLA) was easy to burn and accompanied by serious droplet phenomenon, its application in many fields such as packaging, automotive, electrical and electronic industries were seriously limited. And in order to solve this problem, PLA was used as matrix and poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate) (POPP) was used as flame retardant. PLA composites with different contents were prepared via melting blending and hot-compression method. The flame retardant properties and smoke suppression of PLA composites were investigated by means of limited oxygen index (LOI), vertical burning test (UL-94), thermogravimetric analysis (TG) and cone calorimetric test etc. The results show that the LOI of PLA composite with 4wt% POPP is 34.8%, and it reaches a UL-94 V-0 rating. Comparing with pure PLA, the smoke production rate and total smoke production of POPP/PLA-4 are respectively reduced by 85.83% and 77.65%, which dramatically improve the smoke suppression performance of PLA materials. Moreover, the results of microstructure of char residues after cone calorimeter and thermal degradation behavior analysis reveal that the excellent flame-retardant performance of PLA composites are followed a flame-retardant mechanism of gaseous phase at superiority. This is attributed to •PO and •PO₂ decomposed by POPP quenching •H and •OH. Otherwise, by promoting the intermolecular crosslinking of PLA, a continuous and dense carbon layer on the surface is formed, which improve flame retardancy of PLA composites.
- poly(lactic acid) /
- polyphosphate /
- modification /
- thermal degradation /
- smoke suppression

HTML全文

图 2 PLA复合材料在50 kW/m²下的锥形量热测试结果：(a) 热释放速率(HRR)；(b) 总释放热(THR)；(c) 烟雾释放速率(SPR)；(d) 总烟释放量(TSP)

Figure 2. Cone calorimetric results of PLA composites at an external heat flux of 50 kW/m² as a function of burning duration: (a) Heat release rate (HRR); (b) Total heat release (THR); (c) Smoke production rate (SPR); (d) Total smoke production (TSP)

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图 1 聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯 (POPP) 的合成

Figure 1. Synthesis route of poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate) (POPP)

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图 3 PLA复合材料的TG (a)和DTG (b)曲线

Figure 3. TG (a) and DTG (b) curves of PLA composites

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图 4 PLA复合材料锥形量热测试后残炭的照片：(a) PLA-0；(b) POPP/PLA-4

Figure 4. Digital photographs of residual char after cone calorimetric test of PLA composites: (a) PLA-0; (b) POPP/PLA-4

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图 5 POPP/PLA-4复合材料锥形量热测试后残炭的SEM图像

Figure 5. SEM images of residual char after cone calorimetric test of POPP/PLA-4 composite

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图 6 (a) PLA-0和POPP/PLA-4的XPS图谱；PLA-0 (b)和POPP/PLA-4 (c)的C1s XPS图谱；(d) POPP/PLA-4的P2p XPS图谱

Figure 6. (a) XPS spectra of PLA-0 and POPP/PLA-4; C1s XPS spectra of PLA-0 (b) and POPP/PLA-4 (c); (d) P2p XPS spectra of POPP/PLA-4

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图 7 PLA复合材料的拉曼光谱：(a) PLA-0；(b) POPP/PLA-4

Figure 7. Raman spectra of PLA composites: (a) PLA-0; (b) POPP/PLA-4

I_D/I_G—Intensity ratio between peak D and peak G

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图 8 PLA-0 (a)和POPP/PLA-4 (b)的3D TG-FTIR图

Figure 8. 3D TG-FTIR of PLA-0 (a) and POPP/PLA-4 (b)

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图 9 TG试验中纯PLA及其复合材料的FTIR图谱：(a) PLA-0；(b) POPP/PLA-4

Figure 9. FTIR spectra of volatile from pure PLA and its composites during TG test: (a) PLA-0; (b) POPP/PLA-4

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图 10 PLA复合材料的阻燃机制

Figure 10. Flame retardant mechanism for PLA composites

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表 1 聚乳酸(PLA)复合材料的配方及P含量

Table 1. Formulation and P contents of poly(lactic acid) (PLA) composites

Sample	PLA/wt%	POPP/wt%	P/wt%
PLA-0	100	0	0.00
POPP/PLA-1	99.5	0.5	0.07
POPP/PLA-2	99	1	0.13
POPP/PLA-3	98	2	0.27
POPP/PLA-4	97	3	0.40
POPP/PLA-5	96	4	0.54
Note: POPP—Poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate).

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表 2 PLA复合材料的阻燃测试结果

Table 2. Results of flame retardant performances for PLA composites

Sample	Limiting oxygen index/%	Dripping	Cotton ignited	UL-94 rating
PLA-0	16.3	Heavy dripping	Yes	No rating
POPP/PLA-1	24.0	Heavy dripping	Yes	V-2
POPP/PLA-2	25.2	Heavy dripping	Yes	V-2
POPP/PLA-3	26.2	Dripping	No	V-0
POPP/PLA-4	29.8	Dripping	No	V-0
POPP/PLA-5	34.8	Dripping	No	V-0

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表 3 纯PLA和PLA复合材料的锥形量热数据

Table 3. Cone calorimetry data for pure PLA and PLA composites

Sample	TTI/s	Pk-HRR/ (kW·m⁻²)	THR/ (MJ·m⁻²)	SPR/ (m²·s⁻¹)	TSP/ (m²·m⁻²)	Av-COY/ (kg·kg⁻¹)	Av-EHC/ (MJ·kg⁻¹)	FPI/ (s·m²·kW⁻¹)	Residue/%
PLA-0	43	580.7	115.3	0.120	51.0	0.023	14.1	0.074	0.7
POPP/PLA-3	35	571.9	109.9	0.079	26.5	0.032	14.3	0.061	0.4
POPP/PLA-4	31	518.3	89.0	0.017	11.4	0.046	12.0	0.060	15.5
Notes: TTI—Time to ignition; Pk-HRR—Peak of heat release rate; Av-COY—Average of CO yield; Av-EHC—Average of effective heat of combustion; FPI—Fire performance index; THR—Total heat release ; SPR—Smoke production rate; TSP—Total smoke production.

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表 4 氮气氛围下PLA复合材料的TG和DTG结果

Table 4. TG and DTG results under nitrogen atmosphere for PLA composites

Sample	T_5%/℃	T_10%/℃	T_50%/℃	T_max/℃	R₆₀₀/%
PLA-0	338	358	383	385	0.00
POPP	350	389	537	493, 551	32.90
POPP/PLA-1	339	360	385	387	0.75
POPP/PLA-2	334	358	384	386	0.66
POPP/PLA-3	321	353	381	384	0.51
POPP/PLA-4	322	352	383	386	0.71
POPP/PLA-5	319	347	382	387	0.56
Notes: T_x%—Temperature corresponding to mass loss xwt% of material; T_max—Temperature corresponding to maximum thermal degradation rate; R₆₀₀—Residue at 600℃.

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表 5 纯PLA及复合材料的力学性能结果

Table 5. Test results of mechanical properties of pure PLA and its composites

Sample	Impact strength/(kJ·m⁻²)	Elongation at break/%	Tensile strength/MPa
PLA-0	14.66$ \pm $0.50	7.22$ \pm $0.40	31.81$ \pm $0.50
POPP/PLA-1	11.10$ \pm $0.30	4.08$ \pm $0.30	14.49$ \pm $0.40
POPP/PLA-2	14.41$ \pm $0.20	5.31$ \pm $0.50	16.57$ \pm $0.30
POPP/PLA-3	12.56$ \pm $0.40	3.80$ \pm $0.30	16.16$ \pm $0.30
POPP/PLA-4	12.72$ \pm $0.30	5.13$ \pm $0.20	22.08$ \pm $0.20
POPP/PLA-5	8.41$ \pm $0.30	6.24$ \pm $0.50	23.53$ \pm $0.40

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