亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

doi:10.19491/j.issn.1001-9278.2020.06.002

中国塑料 ›› 2020, Vol. 34 ›› Issue (6): 7-13.DOI: 10.19491/j.issn.1001-9278.2020.06.002

亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

梁娟¹^,², 蒋泽文¹^,², 公维光¹^,², 孟鑫¹^,²()

^1.华东理工大学化工学院产品工程系，上海市多相结构材料化学工程重点实验室，上海 200237
^2.华东理工大学体育学院，上海 200237

收稿日期:2019-12-02 出版日期:2020-06-26 发布日期:2020-06-26
基金资助:
国家自然科学基金项目(21576086)

Effect of Phosphite⁃Functionalized Polysilsesquioxane on Flame Retardancy of Polylactic Acid

Juan LIANG¹^,², Zewen JIANG¹^,², Weiguang GONG¹^,², Xin MENG¹^,²()

^1.Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237，China
^2.Research & Development Center for Sports Materials, East China University of Science and Technology, Shanghai 200237, China

Received:2019-12-02 Online:2020-06-26 Published:2020-06-26
Contact: Xin MENG E-mail:mengxin@ecust.edu.cn

摘要/Abstract

摘要：

将聚氨基环氧基硅氧烷（PSQ）以及亚磷酸酯功能化的聚氨基环氧基硅氧烷（PPSQ）与聚乳酸（PLA）通过熔融共混制备了扩链PLA。研究了亚磷酸酯基团的引入对PSQ在PLA中的扩链和阻燃性能的影响，探究PPSQ在PLA中的阻燃机理。结果表明，相比于PSQ，PPSQ可以明显提高PLA的分子量和复合黏度，具有更好的扩链作用；PPSQ的引入可以明显改善PLA的阻燃性能，使得PLA?PPSQ的极限氧指数提高至25.4 %，比纯PLA提升了31.6 %，且使得PLA的热释放速率峰值和总热释放量分别下降了18.1 %和16.6 %。分析可知，由于亚磷酸酯基团的引入，促使PLA?PPSQ中的硅元素在燃烧过程中向炭层表面迁移形成更多富含碳化硅和氧化硅的致密炭层，起到隔热隔氧的作用，进而发挥优异的阻燃性能。

关键词: 聚乳酸, 亚磷酸酯, 聚硅氧烷, 扩链, 阻燃, 机理

Abstract:

The chain?extended PLA was prepared by blending PLA with poly(amino?epoxy) silsesquioxane (PSQ), and phosphate?functionalized poly(amino?epoxy) silsesquioxane (PPSQ). The effect of phosphite ester groups on the chain extension and flame retardancy of PSQ in PLA matrix was investigated, and the flame retardant mechanism of PPSQ was further studied in detail. The results showed that the PPSQ significantly improved the molecular weight and complex viscosity of PLA in comparison of PSQ, indicating that the PLA?PPSQ compound achieved a better chain?extension effect. The incorporation of PPSQ also enhanced the flame retardancy of PLA and led to a limiting oxygen index of 25.4 vol% for the chain?extended PLA, which increased by 31.6 % compared to pure PLA. Furthermore, the heat release rate and total heat release of PLA?PPSQ compound also decrease by 18.1 % and 16.6 %, respectively. On the basis of the flame retardant mechanism, the introduction of phosphite ester groups into PSQ can promote the migration of silicon to the surface during the combustion of PLA?PPSQ compound and forms a dense carbon layer rich in silicon carbide and silicon oxide. Such a carbon layer can effectively inhibit the transfer of heat and oxygen and endows PLA with excellent flame retardancy accordingly.

Key words: polylactic acid, phosphite, polysilsesquioxane, chain extension, flame retardancy, mechanism

中图分类号:

TQ323.6

梁娟, 蒋泽文, 公维光, 孟鑫. 亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究[J]. 中国塑料, 2020, 34(6): 7-13.

Juan LIANG, Zewen JIANG, Weiguang GONG, Xin MENG. Effect of Phosphite⁃Functionalized Polysilsesquioxane on Flame Retardancy of Polylactic Acid[J]. China Plastics, 2020, 34(6): 7-13.

图/表 10

图1 PPSQ化学结构

Fig. 1 Chemical structure of PPSQ

图2 PPSQ扩链改性PLA的机理示意图

Fig. 2 Chain?extending mechanism of PPSQ on PLA

样品	分子量/kg·mol^-1
PLA	141.4±3.1
PLA?PSQ	152.5±2.6
PLA?PPSQ	170.1±3.5

表1 PLA、PLA?PSQ和PLA?PPSQ的分子量

Tab. 1 Molecular weight of PLA, PLA?PSQ and PLA?PPSQ

图3 PLA、PLA?PSQ和PLA?PPSQ的复数黏度随时间变化的曲线

Fig. 3 Complex viscosity of PLA, PLA?PSQ and PLA?PPSQ versus time

样品

极限氧指数/%

PLA

PLA?PSQ

PLA?PPSQ

19.3

23.6

25.4

表2 PLA、PLA?PSQ和PLA?PPSQ的极限氧指数

Tab. 2 Limiting oxygen index of PLA, PLA?PSQ and PLA?PPSQ

图4 PLA、PLA?PSQ和PLA?PPSQ的锥形量热曲线

Fig. 4 Cone calorimetry curves of PLA, PLA?PSQ and PLA?PPSQ

样品	PHRR/kW·m^-2	THR/MJ·m^-2	残炭量/%
PLA	461.1	78.5	3.3
PLA?PSQ	422.3	69.5	11.3
PLA?PPSQ	377.5	65.5	24.3

表3 PLA、PLA?PSQ和PLA?PPSQ的锥形量热测试结果

Tab. 3 Cone calorimetry results of PLA, PLA?PSQ and PLA?PPSQ

图5 PLA、PLA?PSQ和PLA?PPSQ燃烧后炭层表面SEM照片

Fig. 5 SEM micrographs of surfaces residues of PLA, PLA?PSQ and PLA?PPSQ after cone calorimetry test

图 6 PLA、PLA?PSQ和PLA?PPSQ燃烧后残炭的FTIR图谱

Fig. 6 FTIR spectra of PLA, PLA?PSQ and PLA?PPSQ after cone calorimetry test

32.7

42.4

PLA?PPSQ

1.70

1.40

表4 ICP和EDS测试扩链PLA燃烧产物硅、磷含量

Tab. 4 EDS and ICP results of chain?extended PLA after cone calorimetry test

参考文献 33

1	CASTRO A E, INIGUEZ F F, SAMSUDIN H, et al. Poly (lactic acid)—Mass Production, Processing, Industrial Applications, and End of Life[J]. Advanced Drug Delivery Reviews, 2016, 107: 333⁃366.
2	FARAH S, ANDERSON D G, LANGER R. Physical and Mechanical Properties of PLA, and Their Functions in Widespread Applications—A Comprehensive Review[J]. Advanced Drug Delivery Reviews, 2016, 107: 367⁃392.
3	CARRASCO F, PAGES P, GAMEZ P J, et al. Proces⁃sing of poly(lactic acid): Characterization of Chemical Structure, Thermal Stability and Mechanical Properties[J]. Polymer Degradation & Stability, 2010, 95(2): 116⁃125.
4	HOSSEIN P F, PEIGHAMBARDOUST S J, DAVARAN S, et al. Development and Characterization of PLA⁃MPEG Copolymer Containing Ion Nanoparticle⁃Coated Carbon Nanotubes for Controlled Delivery of Docetaxel[J]. Polymer, 2017, 117: 117⁃131.
5	CAIRNS M L, DICKSON G R, ORR J F, et al. Electron⁃Beam Treatment of Poly(lactic acid) to Control Degradation Profiles[J]. Polymer Degradation & Stability, 2011, 96(1): 76⁃83.
6	HASAN H K, FUGANG X, MAJHER S, et al. Antibacterial Poly(lactic acid) (PLA) Films Grafted with Electrospun PLA/Allyl Isothiocyanate Fibers Food Packaging[J]. Journal of Applied Polymer Science, 2016, 133(2):726⁃736.
7	RHIMA, JONGWHAN, PARK, et al. Bio⁃Nanocompo⁃sites for Food Packaging Applications[J]. Progress in Polymer Science, 2013, 38(10⁃11): 1 629⁃1 652.
8	BADIA J D, GIL C O, RIBES G A. Long⁃Term Properties and End of Life of Polymers from Renewable Resources[J]. Polymer Degradation & Stability, 2017, 137: 35⁃57.
9	BOETKER J, WATER J J, AHO J, et al. Modifying Release Characteristics from 3D Printed Drug⁃Eluting Products[J]. European Journal of Pharmaceutical Sciences, 2016, 90: 47⁃52.
10	XIN W, MAN J, ZHOU Z, et al. 3D Printing of Polymer Matrix Composites: A Review and Prospective[J]. Composites Part B Engineering, 2017, 110: 442⁃458.
11	SHAFFER S, YANG K, VARGAS J, et al. On Redu⁃cing Anisotropy in 3D Printed Polymers via Ionizing Radiation[J]. Polymer, 2014, 55(23): 5 969⁃5 979.
12	GUO Y, SHAN H, ZUO X, et al. Incorporation of Cellulose with Adsorbed Phosphates into Poly (lactic acid) for Enhanced Mechanical and Flame Retardant Properties[J]. Polymer Degradation & Stability, 2017, 144: 24⁃32.
13	NAMPOOTHIRI K M, NAIR N R, JOHN R P. An Overview of the Recent Developments in Polylactide (PLA) Research[J]. Bioresource Technology, 2010, 101(22): 8 493⁃8 501.
14	TAWIAH B, YU B, FEI B. Advances in Flame Retardant Poly(lactic acid)[J]. Polymers, 2018, 10(8): 22.
15	MAULDIN T C, ZAMMARANO M, GILMAN J W, et al. Synthesis and Characterization of Isosorbide⁃Based Polyphosphonates as Biobased Fame⁃Retardants[J]. Polymer Chemistry, 2014, 5(17): 5 139⁃5 146.
16	KIUCHI Y, IJI M, YANAGISAWA T, et al. Flame⁃Retarding Polylactic⁃Acid Composite Formed by Dual Use of Aluminum Hydroxide and Phenol Resin[J]. Polymer Degradation & Stability, 2014, 109: 336⁃342.
17	RONG Y, HU W, LIANG X, et al. Synthesis, Mecha⁃nical Properties and Fire Behaviors of Rigid Polyurethane Foam with A Reactive Flame Retardant Containing Phosphazene and Phosphate[J]. Polymer Degradation & Stability, 2015, 122: 102⁃109.
18	LI S, DENG L, XU C, et al. Making A Supertough Flame⁃Retardant Polylactide Composite through Reactive Blending with Ethylene⁃Acrylic Ester⁃Glycidyl Methacrylate Terpolymer and Addition of Aluminum Hypophosphite[J]. ACS Omega, 2017, 2(5): 1 886⁃1 895.
19	YUAN X Y, WANG D Y, CHEN L, et al. Inherent Flame Retardation of Bio⁃Based Poly (lactic acid) by Incorporating Phosphorus Linked Pendent Group into the Backbone[J]. Polymer Degradation & Stability, 2011, 96(9): 1 669⁃1 675.
20	CHEN L, CHAO R, YANG R, et al. Phosphorus⁃Containing Thermotropic Liquid Crystalline Polymers: A Class of Efficient Polymeric Flame Retardants[J]. Polymer Chemistry, 2014, 5(12): 3 737⁃3 749.
21	FINAA A, CAMINO G. Polypropylene⁃Polysilsesquioxane Blends[J]. European Polymer Journal, 2010, 46(1): 14⁃23.
22	HAN Z, FINA A, CAMINO G. Organosilicon Compounds as Polymer Fire Retardants [M]. Polymer Green Flame Retardants, 2014: 389⁃418.
23	JASH P, WILKIE C A. Effects of Surfactants on the Thermal and Fire Properties of Poly(methyl methacrylate)/Clay Nanocomposites[J]. Polymer Degradation & Stability, 2005, 88(3): 401⁃406.
24	HAN T, ZHONG X, SHI Y, et al. Control of Thermal Degradation of Poly(lactic acid) Using Functional Polysilsesquioxane Microspheres as Chain Extenders[J]. Journal of Applied Polymer Science, 2015, 132(20): 113⁃114.
25	LUO J, MENG X, GONG W, et al. Improving the Stability and Ductility of Polylactic Acid via Phosphite Functional Polysilsesquioxane[J]. RSC Advances, 2019, 9(43): 25 151⁃25 157.
26	HU Y D, XU P, GUI H G, et al Effect of Imidazolium Phosphate and Multiwalled Carbon Nanotubes on Thermal Stability and Flame Retardancy of Polylactide[J]. Composites Part A: Applied Science and Manufacturing, 2015, 77:147⁃153.
27	LIAO F, ZHOU L, JU Y, et al. Synthesis of A Novel Phosphorus⁃Nitrogen⁃Silicon Polymeric Flame Retardant and Its Application in Poly(lactic acid)[J]. Industrial & Engineering Chemistry Research, 2014, 53(24):10 015⁃10 023.
28	HUANG Y W, SONG M L, MA J J, et al. Synthesis of a Phosphorus/Silicon Hybrid and Its Synergistic Effect with Melamine Polyphosphates on Flame Retardant Polypropylene System[J]. Journal of Applied Polymer Science, 2013, 129(1):316⁃323.
29	WANG L, JIANG J, JIANG P, et al. Synthesis, Characteristic of A Novel Flame Retardant Containing Phosphorus, Silicon and Its Application in Ethylene Vinyl⁃Acetate Copolymer (EVM) Rubber[J]. Journal of polymer research, 2010, 17(6): 891⁃902.
30	LI Q, JIANG P, WEI P. Synthesis, Characteristic, and Application of New Flame Retardant Containing Phosphorus, Nitrogen, and Silicon[J]. Polymer Engineering & Science, 2010, 46(3): 344⁃350.
31	LAOUTID F, BONNAUD L, ALEXANDRE M, et al. New Prospects in Flame Retardant Polymer Materials: From Fundamentals to Nanocomposites[J]. Materials Science & Engineering R Reports, 2009, 63(3): 100⁃125.
32	MENG X, SHI G, CHEN W, et al. Structure Effect of Phosphite on the Chain Extension in PLA[J]. Polymer Degradation & Stability, 2015, 120: 283⁃289.
33	MENG X, SHI G, WU C, et al. Chain Extension and Oxidation Stabilization of Triphenyl phosphite (TPP) in PLA[J]. Polymer Degradation & Stability, 2016, 124:112⁃118.

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亚磷酸酯功能化聚硅氧烷扩链聚乳酸的阻燃性能研究

Effect of Phosphite⁃Functionalized Polysilsesquioxane on Flame Retardancy of Polylactic Acid

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