马来海松基环氧纳米复合材料的制备及性能研究

doi:10.3969/j.issn.0253-2417.2021.01.002

摘要/Abstract

摘要：

以松香为原料，通过Diels-Alder加成制备了马来海松酸酐（MPA），再经过酯化、闭环反应得到了马来海松基环氧树脂（MPA-ER），并用FT-IR和¹H NMR对MPA和MPA-ER的结构进行了表征。进一步将多壁碳纳米管（MWCNTs）与MPA-ER共混制备了一系列的MPA-ER/MWCNTs复合材料，对其力学性能和热性能进行了表征，并探究了不同MWCNTs添加量对马来海松基环氧纳米复合材料力学性能和热性能的影响。研究结果表明：FT-IR和¹H NMR证实成功制备了MPA和MPA-ER。MWCNTs在MPA-ER中分散均匀，断面具有河流状纹路，MWCNTs的添加使得MPA-ER/MWCNTs的力学性能显著提高，当MWCNTs的添加量为1.2%（以MPA-ER质量计，下同）时，复合材料MPA-ER/MWCNTs（1.2）的力学性能达到最优，冲击韧性、拉伸强度、弯曲强度和断裂伸长率分别为15.11 kJ/m²、40.42 MPa、105.45 MPa和14.80%，与MPA-ER相比分别增加了159%、160%、102%和135%。同时，锥形量热测试中MPA-ER/MWCNTs（1.2）复合材料的峰值热释放速率和残炭率分别为324 kW/m²和9.18%，与MPA-ER相比，峰值热释放速率下降了14%，残炭率增加了68%，表明MWCNTs的添加使得MPA-ER/MWCNTs的热稳定性和阻燃性有所提高，MPA-ER/MWCNTs（1.2）复合材料阻燃性能的提高主要归因于添加MWCNTs有效地增加了环氧树脂的交联密度，使其在内部形成比较致密的炭层，进而通过部分隔绝外部热量和空气来达到阻燃的效果。

关键词: 松香, 环氧树脂, 碳纳米管, 复合材料, 阻燃性能

Abstract:

Maleopimaric anhydride(MPA) was prepared from rosin by Diels-Alder addition, and then maleopimaric epoxy resin(MPA-ER) was prepared by esterification and closed-loop reaction. The structures of MPA and MPA-ER were characterized by FT-IR and ¹H NMR.A series of MPA-ER/MWCNTs composites were prepared by blending multi-wall carbon nanotubes(MWCNTs) with MPA-ER, the mechanical and thermal properties of the composites were characterized, and the effects of MWCNTs addition on the mechanical and thermal properties of maleopimaric epoxy nanocomposites were investigated. The results of FT-IR and ¹H NMR showed that MPA and MPA-ER were successfully prepared. MWCNTs were well dispersed in MPA-ER, and the cross-section had river-shaped texture features. The mechanical properties of MPA-ER/MWCNTs were significantly improved by adding MWCNTs. When the addition of MWCNTs was 1.2%(calculated by the mass of MPA-ER, similarly hereinafter), the mechanical properties of the composite MPA-ER/MWCNTs(1.2) were optimized. Its impact toughness, tensile strength, bending strength and elongation at break were 15.11 kJ/m², 40.42 MPa, 105.45 MPa and 14.80%, which increased by 159%, 160%, 102% and 135% compared with those of MPA-ER, respectively.At the same time, in cone calorimeter test, the peak heat release rate and carbon residue rate of MPA-ER/MWCNTs(1.2) composite were 324 kW/m² and 9.18%, respectively.Compared with MPA-ER, the peak heat release rate decreased by 14%, and the carbon residue rate increased by 68%, which indicated that the addition of MWCNTs also improved the thermal stability and flame retardancy of MPA-ER/MWCNTs.The improvement of flame retardancy of MPA-ER/MWCNTs(1.2) composites was mainly attributed to the effective increase of crosslinking density of epoxy resin by adding MWCNTs, and forming a relatively dense carbon layer in the interior of epoxy resin, and then the flame retardant effect was achieved by partially isolating the external heat and air.

Key words: rosin, epoxy resin, carbon nanotube, composites, flame retardance

中图分类号:

TQ35
S785

陶潘, 吴程宇, 毛世英, 王美鑫, 李健. 马来海松基环氧纳米复合材料的制备及性能研究[J]. 林产化学与工业, 2021, 41(1): 7-14.

Pan TAO, Chengyu WU, Shiying MAO, Meixin WANG, Jian LI. Preparation and Properties of Maleopimaric-based Epoxy Nanocomposite[J]. Chemistry and Industry of Forest Products, 2021, 41(1): 7-14.

图/表 8

图1

图2

图3

表1

图4

图5

图6

表2

参考文献 28

1	MANTZARIDIS C , BROCAS A L , LLEVOT A , et al. Rosin acid oligomers as precursors of DGEBA-free epoxy resins[J]. Green Chemistry, 2013, 15 (11): 3091- 3098. doi: 10.1039/c3gc41004h
2	丘雨玲, 郭晓亮, 卢传巍, 等. 功能性乙基纤维素-松香复合膜的合成与性能表征[J]. 林产化学与工业, 2020, 40 (2): 42- 48.
	QIU Y L , GUO X L , LU C W , et al. Synthesis and characterization of functional ethyl cellulose-rosin hybrid membrane[J]. Chemistry and Industry of Forest Products, 2020, 40 (2): 42- 48.
3	ROSU L , MUSTATA F , VARGANICI C D , et al. Thermal behaviour and fungi resistance of composites based on wood and natural and synthetic epoxy resins cured with maleopimaric acid[J]. Polymer-Plastics Technology and Materials, 2019, 160, 148- 161.
4	ZHANG Y , DONG Y , LI X , et al. Proanthocyanidin encapsulated in ferritin enhances its cellular absorption and antioxidant activity[J]. Journal of Agricultural and Food Chemistry, 2019, 67 (41): 11498- 11507. doi: 10.1021/acs.jafc.9b03903
5	李侨光, 刘鹤, 商士斌, 等. 松香及其衍生物改性高分子材料的研究进展[J]. 林产化学与工业, 2017, 37 (4): 23- 29.
	LI Q G , LIU H , SHANG S B , et al. Research progress of rosin and its derivatives in polymer synthesis[J]. Chemistry and Industry of Forest Products, 2017, 37 (4): 23- 29.
6	ZHANG Y, DONG Y X, ZHOU J H, et al. Peptide-mediated immobilization on magnetoferritin for enzyme recycling[J/OL]. Nanomaterials, 2019, 9(11): 1-12[2020-01-30].https://doi.org/10.3390/nano9111558.
7	CHEN C H , TUNG S H , JENG R J , et al. A facile strategy to achieve fully bio-based epoxy thermosets from eugenol[J]. Green Chemistry, 2019, 21 (16): 4475- 4488. doi: 10.1039/C9GC01184F
8	HUANG X J, YANG X X, LIU H, et al. Bio-based thermosetting epoxy foams from epoxidized soybean oil and rosin with enhanced properties[J/OL]. Industrial Crops and Products, 2019, 139: 1-9[2020-02-20].https://doi.org/10.1016/j.indcrop.2019.111540.
9	HUANG K , ZHANG J W , LI M , et al. Exploration of the complementary properties of biobased epoxies derived from rosin diacid and dimer fatty acid for balanced performance[J]. Industrial Crops and Products, 2013, 49, 497- 506. doi: 10.1016/j.indcrop.2013.05.024
10	GUO L Z, YANG X X, DONG F H, et al. A pinene-based silane crosslinker for improved mechanical strength/transparency of room-temperature vulcanizing silicone rubber[J/OL]. Materials Chemistry and Physics, 2020, 247: 1-26[2020-02-20].https://doi.org/10.1016/j.matchemphys.2020.122868.
11	NAGATANI M , TSURUMAKI A , TAKAMATSU K , et al. Preparation of epoxy resins derived from lignin solubilized in tetrabutylphosphonium hydroxide aqueous solutions[J]. International Journal of Biological Macromolecules, 2019, 132, 585- 591. doi: 10.1016/j.ijbiomac.2019.03.152
12	MORA A S , TAYOUO R , BOUTEVIN B , et al. Synthesis of biobased reactive hydroxyl amines by amination reaction of cardanol-based epoxy monomers[J]. European Polymer Journal, 2019, 118, 429- 436. doi: 10.1016/j.eurpolymj.2019.06.020
13	PARK S , PARK S , JANG D H , et al. Anti-fogging behavior of water-absorbing polymer films derived from isosorbide-based epoxy resin[J]. Materials Letters, 2016, 180, 81- 84. doi: 10.1016/j.matlet.2016.05.114
14	李健, 饶小平, 宋湛谦, 等. 丙烯海松酸及其噻二唑衍生物的制备及抑菌活性[J]. 林产化学与工业, 2014, 34 (3): 55- 59.
	LI J , RAO X P , SONG Z Q , et al. Synthesis and antibacterial activity of acrylpimaric acid and its thiadiazole derivatives[J]. Chemistry and Industry of Forest Products, 2014, 34 (3): 55- 59.
15	陶潘, 李健. 松香基环氧树脂的研究进展[J]. 广州化工, 2019, 47 (12): 17- 22, 26.
	TAO P , LI J . Research progress on rosin-based epoxy resin[J]. Guangzhou Chemical Industry, 2019, 47 (12): 17- 22, 26.
16	BOBADE S K , PALUVAI N R , MOHANTY S , et al. Bio-based thermosetting resins for future generation: A review[J]. Polymer-Plastics Technology and Engineering, 2016, 55 (17): 1863- 1896. doi: 10.1080/03602559.2016.1185624
17	黄活阳, 哈成勇, 李因文, 等. 溴化马来松香的合成、表征及其阻燃性的研究[J]. 天然产物研究与开发, 2009, 21 (6): 926- 929.
	HUANG H Y , HA C Y , LI Y W , et al. Study on synthesis, characterization and fire-retardant property of brominating maleic rosin[J]. Natural Product Research and Development, 2009, 21 (6): 926- 929.
18	黄活阳, 哈成勇, 李因文, 等. 溴化丙烯酸松香环氧树脂的合成及固化物的阻燃性[J]. 高分子材料科学与工程, 2009, 25 (6): 28- 31.
	HUANG H Y , HA C Y , LI Y W , et al. Synthesis of brominating acrylic rosin epoxy resin and flame retardation of the curing product[J]. Polymer Materials Science and Engineering, 2009, 25 (6): 28- 31.
19	DENG L L , HA C Y , SUN C N , et al. Properties of bio-based epoxy resins from rosin with different flexible chains[J]. Industrial & Engineering Chemistry Research, 2013, 52 (37): 13233- 13240.
20	DENG L L , SHEN M M , YU J , et al. Preparation, characterization, and flame retardancy of novel rosin-based siloxane epoxy resins[J]. Industrial & Engineering Chemistry Research, 2012, 51 (24): 8178- 8184.
21	王丹. 松香环氧树脂/聚氨酯生物基纳米复合材料的合成、固化及性能研究[D]. 保定: 河北大学, 2016.
	WANG D. Synthesis, curing and peoperties of rosin-epoxy resin/polyurethane bio-nanocomposites[D]. Baoding: Hebei University, 2016.
22	KINLOCH I A , SUHR J , LOU J , et al. Composites with carbon nanotubes and graphene: An outlook[J]. Science, 2018, 362 (6414): 547- 553. doi: 10.1126/science.aat7439
23	QIAN Y, DONG F, GUO L, et al.Preparation and properties of room temperature vulcanized silicone rubber using triethoxy(2-(4-methylcyclohex-3-en-1-yl)propyl)silane as a novel cross-linking agent[J/OL]. Polymer Degradation and Stability, 2020, 173: 1-27[2020-03-10].https://doi.org/10.1016/j.polymdegradstab.2019.109068.
24	LI R , MA Y , DONG Y , et al. Novel paclitaxel-loaded nanoparticles based on human H chain ferritin for tumor-targeted delivery[J]. ACS Biomaterials Science & Engineering, 2019, 5 (12): 6645- 6654.
25	KASHIWAGI T , DU F , DOUGLAS J F , et al. Nanoparticle networks reduce the flammability of polymer nanocomposites[J]. Nature Materials, 2005, 4 (12): 928- 933. doi: 10.1038/nmat1502
26	AMARO A M , BERNARDO L , PINTO D G , et al. The influence of curing agents in the impact properties of epoxy resin nanocomposites[J]. Composite Structures, 2017, 174, 26- 32. doi: 10.1016/j.compstruct.2017.04.050
27	FU J F , SHI L Y , ZHANG D S , et al. Effect of nanoparticles on the performance of thermally conductive epoxy adhesives[J]. Polymer Engineering & Science, 2010, 50 (9): 1809- 1819.
28	WANG F Z , DRZAL L T , QIN Y , et al. Enhancement of fracture toughness, mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets[J]. Composites Part A: Applied Science and Manufacturing, 2016, 87, 10- 22. doi: 10.1016/j.compositesa.2016.04.009

环氧复合材料 epoxy composites	MWCNTs添加量/% MWCNTs contents	冲击韧性/(kJ·m^-2) impact toughness	拉伸强度/MPa tensile strength	弯曲强度/MPa bending strength	断裂伸长率/% elongation at break
MPA-ER	—	5.84	15.53	52.33	6.31
MPA-ER/MWCNTS(0.3)	0.3	7.76	17.89	56.98	7.14
MPA-ER/MWCNTS(0.6)	0.6	9.52	21.25	65.34	7.57
MPA-ER/MWCNTS(0.9)	0.9	11.39	32.21	87.07	10.15
MPA-ER/MWCNTS(1.2)	1.2	15.11	40.42	105.45	14.80
MPA-ER/MWCNTS(1.5)	1.5	14.50	26.11	104.21	12.81
MPA-ER/MWCNTS(1.8)	1.8	10.87	23.01	89.73	10.50

环氧复合材料 epoxy composites	点燃时间/s time to ignition	峰值热释放速率/ (kW·m^-2) peak heat release rate	到达峰值时间/s time to peak	火灾燃烧指数/ (kW·m^-2·s^-1) fire growth rate index	残炭率/% char residue
MPA-ER	27	376	200	1.88	5.45
MPA-ER/MWCNTs(1.2)	37	324	280	1.16	9.18

[1]	于世涛, 邹昊学, 李娅娅, 张慧敏, 王宇婧. Fe₃O₄负载ZnO催化剂的制备及其催化合成松香甘油酯的研究[J]. 林产化学与工业, 2020, 40(6): 8-14.
[2]	张海波, 许嘉琍, 姚姝凤, 高宏, 商士斌. 马来松香季戊四醇酯对椪柑保鲜效果的研究[J]. 林产化学与工业, 2020, 40(6): 15-22.
[3]	陈健,吴国民,霍淑平,孔振武. 腰果酸环氧树脂的合成及其固化反应特性研究[J]. 林产化学与工业, 2020, 40(4): 41-46.
[4]	丘雨玲,郭晓亮,卢传巍,王春鹏,王基夫,储富祥. 基于乙基纤维素-马来海松酸酯的酸酐类环氧固化剂的固化及性能研究[J]. 林产化学与工业, 2020, 40(4): 57-62.
[5]	丘雨玲,郭晓亮,卢传巍,王春鹏,王基夫,储富祥. 功能性乙基纤维素-松香复合膜的合成与性能表征[J]. 林产化学与工业, 2020, 40(2): 42-48.
[6]	许吉,翟兆兰,闫鑫焱,宋湛谦,商士斌,饶小平. 改性松香对速生杨木性能提升的研究[J]. 林产化学与工业, 2020, 40(2): 55-62.
[7]	马红亮,陈健,焦健,邓拥军,孔振武,房桂干. 杨木纤维尺寸对环氧树脂复合材料力学性能的影响[J]. 林产化学与工业, 2020, 40(2): 104-108.
[8]	韩尊强,邢健雄,余晓娟,杨海艳,徐伟涛,王堃. 竹炭及其复合材料在超级电容器中的应用研究进展[J]. 林产化学与工业, 2020, 40(1): 8-16.
[9]	刘超,魏琳珊,尹小燕,卫民,蒋剑春,王奎. γ-戊内酯/水复合溶剂体系中金属硫酸盐催化半纤维素定向转化制备糠醛[J]. 林产化学与工业, 2020, 40(1): 17-24.
[10]	宋庭方,麦泳贤,田秀枝,邓海波,蒋学. 长链酰胺化纳米纤维素增强聚乳酸复合材料[J]. 林产化学与工业, 2020, 40(1): 31-36.
[11]	张玉杰,孔凡功,郭留柱,刘小克,赵鑫. 落叶松基复合材料SiO₂@C的制备及其对染料的吸附行为研究[J]. 林产化学与工业, 2020, 40(1): 120-128.
[12]	付飞,王丹,沈明贵,商士斌,宋湛谦,宋杰. 可自由基聚合的松香基苯并环丁烯单体的制备及其聚合性能研究[J]. 林产化学与工业, 2019, 39(6): 21-28.
[13]	韩春蕊, 周若男, 韩冰, 田超, 徐鹏飞, 宋先亮. 松香树脂酸及其衍生物的分子自组装研究进展[J]. 林产化学与工业, 2019, 39(5): 1-10.
[14]	李俊杰,董云,赵华平,马红霞. 膦腈环核腰果酚环氧树脂的制备及表征[J]. 林产化学与工业, 2019, 39(4): 100-104.
[15]	许嘉琍,张海波,姚姝凤,高宏,商士斌. 林业生物质基果蔬涂膜保鲜剂的研究进展[J]. 林产化学与工业, 2019, 39(3): 10-16.