Study on modification and foaming behavior of PHBV through chain extension

doi:10.19491/j.issn.1001-9278.2022.08.012

Abstract

Abstract:

The chain⁃extended poly（3?hydroxybutyrate?co?3?hydroxyvalerate）（PHBV） compound were prepared through melt blending using ethylene?glycidyl methacrylate copolymer （CE） as chain extender. Then， a series of PHBV foams were prepared using a super critical CO₂ foaming method at 160 oC and 20 MPa. The results indicated that the PHBV compounds exhibited a lower crystallization temperature and a lower melting temperature measured at high pressure using differential scanning calorimetry compared to that measured at normal pressure. The introduction of CE enhanced the complex viscosity and storage modulus of PHBV compounds. The PHBV foams showed a gradual increase in cell density and volume expansion ratio but a decrease in cell size with an increase in the CE content.

Key words: poly（3?hydroxybutyrate?co?3?hydroxyvalentate）, chain expansion, foam, rheological property, super critical carbon dioxide

CLC Number:

TQ328

GUO Xiaolei, LUO Jingyun, DING Xin, WANG Yuchen, NIE Minghan, SONG Jiajie, ZHANG Yan’e, HU Jing. Study on modification and foaming behavior of PHBV through chain extension[J]. China Plastics, 2022, 36(8): 73-79.

Figures/Tables 9

References 15

1	LIN H R， KUO C J， LIN Y J. Synthesis and characterization of biodegradable polyhydroxy butyrate⁃based polyurethane foams［J］. Journal of Cellular Plastics， 2003， 39（2）： 101⁃116.
2	ALIREZA J， YOTTHA S， CREIG C， et al. Processing of poly（hydroxybutyrate⁃co⁃hydroxyvalerate）⁃based bionanocomposite foams using supercritical fluids［J］. Chinese Journal of Materials Research， 2012， 27（11）： 1 506⁃1 517.
3	Li G， Qi R， Lu J， et al. Rheological properties and foam preparation of biodegradable poly （butylene succinate）［J］. Journal of Applied Polymer Science， 2013， 127（5）： 3 586⁃3 594.
4	XU J K， ZHANG L， LI D L， et al. Foaming of poly（3⁃hydroxybutyrate⁃co⁃3 hydroxyvalerate） with supercritical carbon dioxide： foaming performance and crystallization beha⁃vior［J］. ACS Omega， 2020， 5： 9 839⁃9 845.
5	白忠爱，陈彦模，和晶. 羟基丁酸戊酸共聚酯（PHBV）的反应性挤出［J］. 高分子材料科学与工程，2009，25（12）：119⁃121，125.
	BAI Z A， CHEN Y M， HE J. The reactive extrusion of poly（3⁃hydroxybutyrate⁃co⁃3⁃hydroxyvalerate）（PHBV）［J］. Polymer Materials Science and Engineering， 2020， 5： 9 839⁃9 845.
6	王艳宁，金江彬. 扩链剂TMP⁃6000对聚乳酸/聚（3⁃羟基丁酸⁃co⁃3⁃羟基戊酸酯）共混物性能的影响［J］. 中国塑料，2019，33（11）：71⁃77.
	WANG Y N， JIN Y B. Effect of chain extender TMP⁃6000 on properties of poly（lactic acid）/ poly（3⁃hydroxybutyrate ⁃co⁃3⁃hydroxyvalerate） blends［J］. China Plastics， 2019， 33（11）：71⁃77.
7	DASDEMIR M， MAZE B， ANANTHARAMAIAH N， et al. Reactive compatibilization of polyamide 6/polyethy⁃lene nonwoven based thermoplastic composites［J］. Euro⁃pean Polymer Journal， 2015， 63： 194⁃206.
8	CUI C N， HUANG J T. Synthesis and characterization of poly（butylenes succinate） with control different end group［J］. Advanced Materials & Processes， 2012， 430/432： 497‐500.
9	TARIK S， VALERIE M， FREDERIC B， et al. Polyolefins/poly（3⁃hydroxybutyrate⁃co⁃hydroxyvalerate） blends compatibilization： morphology， rheological， and mechanical properties［J］. Journal of Applied Polymer Science， 2013， 127： 1 148⁃1 156.
10	LUO J Y， SUN W， ZGOU H F， et al. Bioderived and biodegradable poly（3⁃hydroxybutyrate⁃co⁃3⁃hydroxyvalera⁃te） nanocomposites based on carbon nanotubes： microstructure observation and EMI shielding property improvement［J］. ACS Sustainable Chemistry & Engineering， 2021， 9： 10 785⁃10 798.
11	HAN S， JIANG C， YU K S， et al. Influence of crystallization on microcellular foaming behavior of polyamide 6 in a supercritical CO₂⁃assisted［J］. Journal of Applied Polymer Science， 2020， 137： 49183.
12	Li Y， Mi J G， Fu H， et al. Nanocellular foaming beha⁃viors of chain⁃extended poly（lactic acid） induced by isothermal crystallization［J］. ACS Omega， 2019， 4： 12 512⁃12 523.
13	OLUWABUNMI K E， ZHAO W H， DSOUZA N A. Carbon capture utilization for biopolymer foam manufacture： thermal， mechanical and acoustic performance of PCL/PHBV CO₂ foams ［J］. Polymer Chemistry， 2021， 13： 2559.
14	TIWARY P， PARK C B， KONTOPOULOU M. Transition from microcellular to nanocellular PLA foams by controlling viscosity， branching and crystallization［J］. European Polymer Journal， 2017， 91： 283‐296.
15	NAJAFL N， HEUZEY M C， CARREAU P J， et al. Rheological and foaming behavior of linear and branched polylactides［J］. Rheologica Acta， 2014， 53： 10‐11.

样品	T_c，r/℃	T_c，h/℃	T_m，r/℃	T_m，h/℃	ΔH_m/J·g^-1	X_c，h/%
PHBV	122.2	115.3	171.0	166.3	97.7	59.1
PHBV/CE1	118.0	111.7	170.7	167.1	88.9	57.2
PHBV/CE2	117.2	111.7	170.5	167.1	85.6	55.8
PHBV/CE3	115.9	109.2	169.3	167.1	74.3	50.1
PHBV/CE4	112.5	108.3	166.6	165.6	71.1	48.8
PHBV/CE5	112.4	106.3	166.6	164.1	70.5	47.2

样品	T_c，r/℃	T_c，h/℃	T_m，r/℃	T_m，h/℃	ΔH_m/J·g^-1	X_c，h/%
PHBV	122.2	115.3	171.0	166.3	97.7	59.1
PHBV/CE1	118.0	111.7	170.7	167.1	88.9	57.2
PHBV/CE2	117.2	111.7	170.5	167.1	85.6	55.8
PHBV/CE3	115.9	109.2	169.3	167.1	74.3	50.1
PHBV/CE4	112.5	108.3	166.6	165.6	71.1	48.8
PHBV/CE5	112.4	106.3	166.6	164.1	70.5	47.2

样品	泡孔密度/×10⁷ 个·cm^-3	泡孔尺寸/μm	发泡倍率
PHBV	0.86	66.7	2.7
PHBV/CE1	1.35	65.2	3.2
PHBV/CE2	1.67	57.3	3.5
PHBV/CE3	2.75	46.7	3.8
PHBV/CE4	3.68	34.7	3.9
PHBV/CE5	5.06	32.1	4.0

样品	泡孔密度/×10⁷ 个·cm^-3	泡孔尺寸/μm	发泡倍率
PHBV	0.86	66.7	2.7
PHBV/CE1	1.35	65.2	3.2
PHBV/CE2	1.67	57.3	3.5
PHBV/CE3	2.75	46.7	3.8
PHBV/CE4	3.68	34.7	3.9
PHBV/CE5	5.06	32.1	4.0

[1]	YANG Jin, CHEN Pengran, GAO Peixin. Preparation and flame-retardant mechanism of epoxy foams synergistically modified with DIDOPO and POSS/EG [J]. China Plastics, 2022, 36(9): 38-45.
[2]	MIAO Dan, SONG Yuping, WANG Wenqian. Situation of China’s blow molding industry and tendency of key products， process and equipment during the period of “14th Five⁃Year Plan” [J]. China Plastics, 2022, 36(9): 57-62.
[3]	LI Juan, LI Ying, GUO Xiaolin, ZHANG Chen. Guidelines for the safety use of CO₂ foaming technology in the production of XPS foam industry in China [J]. China Plastics, 2022, 36(9): 160-166.
[4]	YANG Zhi, XI Wang, QIAN Lijun, HU Lishuang. Progressive flame⁃retardant actions of quaternary composite system in rigid polyurethane foams [J]. China Plastics, 2022, 36(8): 28-35.
[5]	LEI Yujie, CHEN Minghuan, WANG Jieyao, CHEN Wangzhi, LI Lei. Cross⁃linked foaming process and performance of recycled polyethylene [J]. China Plastics, 2022, 36(6): 124-129.
[6]	WANG Shuai, ZHANG Yudi, YANG Fukai, XU Xinyu. Preparation and properties of polyimide/multi⁃walled carbon nanotubes composite foams [J]. China Plastics, 2022, 36(6): 39-45.
[7]	SUN Wenbo, XIN Chunling, HE Yadong, ZHAI Yujiao, YAN Baorui. Influence of micro⁃foaming injection molding process on cell structure of glass⁃fiber⁃reinforced PBT products [J]. China Plastics, 2022, 36(5): 1-7.
[8]	JI Feng, GONG Weihua, ZHANG Yan, LUO Shuiyuan, YU Qingyu, ZHU Junqiu, GUO Jiangbin. Preparation of biodegradable PBAT foaming particles by supercritical carbon dioxide autoclave foaming technology [J]. China Plastics, 2022, 36(5): 122-126.
[9]	ZHANG Shucheng, TANG Wenbin, YU Tianjiao, XU Zhenzhen, XING Jian. Preparation and properties of polyurethane foams with different contents of polyether polyol [J]. China Plastics, 2022, 36(3): 104-109.
[10]	SONG Renda, WU Gaojian, CHEN Junxiang, ZHANG Youchen, YANG Weimin, XIE Pengcheng. Preparation and its electromagnetic shielding performance of PP/PET/CNTs foaming composites [J]. China Plastics, 2022, 36(2): 1-7.
[11]	HENG Yue, XUE Nanxiang, CHEN Zhuangxin, LEI Caihong, XU Ruijie. Dynamic rheological behavior and compatibility of polyethylene/paraffin oil blends [J]. China Plastics, 2022, 36(2): 13-18.
[12]	LI Qiwei, WANG Cuicui, ZHENG Haijun, CHEN Jihe, WANG Ge, CHENG Haitao. Effects of multiple extrusions on mechanical and foaming properties of polypropylene/bamboo fiber composites [J]. China Plastics, 2022, 36(2): 56-60.
[13]	WANG Xiaodong, HUA Lei, DONG Aijuan, LUO Lihua. Study on measurement method of gas evolution of foaming agent ADC based on thermogravimetric analysis [J]. China Plastics, 2022, 36(1): 142-147.
[14]	ZHU Nenggui, SHEN Chao, LI Shengnan, ZENG Xiangbu, JIANG Tuanhui, ZHANG Xiang. Study on preparation and foaming properties of polypropylene/fly ash micro foaming composites [J]. China Plastics, 2022, 36(1): 78-83.
[15]	HUANG Guotao, GUI Yuan, LI Yucai, WU Xin, FENG Xinxing, DENG Jianping, WANG Cao, PAN Kai. Preparation and Characterization of EVA/Nylon Elastomer Microcellular Foaming Materials [J]. China Plastics, 2021, 35(9): 1-7.