环氧大豆油⁃癸二酸低分子量聚酯对PVC增塑性能的研究

doi:10.19491/j.issn.1001-9278.2023.11.010

中国塑料 ›› 2023, Vol. 37 ›› Issue (11): 87-94.DOI: 10.19491/j.issn.1001-9278.2023.11.010

环氧大豆油⁃癸二酸低分子量聚酯对PVC增塑性能的研究

杨洋, 韩宇, 翁云宣, 宋鑫宇, 黄志刚, 张彩丽()

北京工商大学化学与材料工程学院，塑料卫生与安全质量评价技术北京市重点实验室，北京 100048

收稿日期:2023-03-17 出版日期:2023-11-26 发布日期:2023-11-22
通讯作者: 张彩丽（1989—），女，副教授，从事生物降解高分子研究，zhangcaili@btbu.edu.cn
E-mail:zhangcaili@btbu.edu.cn
基金资助:
国家重点研发计划(2019YFD1101201);北京市属高校教师队伍建设支持计划优秀青年人才项目(BPHR202203050);北京市科协2023-2025年青年人才托举工程(BYESS2023052);国家自然科学基金项目(52073004)

Plasticizing effect of low molecular weight polyesters synthesized from epoxidized soybean oil for poly（vinyl chloride）

YANG Yang, HAN Yu, WENG Yunxuan, SONG Xinyu, HUANG Zhigang, ZHANG Caili()

Beijing Key Laboratory of Quality Evaluation Technology for Hygiene and Safety of Plastics，College of Chemistry and Materials Engineering，Beijing Technology and Business University，Beijing 100048，China

Received:2023-03-17 Online:2023-11-26 Published:2023-11-22
Contact: ZHANG Caili E-mail:zhangcaili@btbu.edu.cn

摘要/Abstract

摘要：

将环氧大豆油（ESO）与癸二酸（SA）进行开环固化反应，通过控制反应时间得到3种不同分子量的环氧大豆油⁃癸二酸低分子聚酯（ESO⁃SA₅、ESO⁃SA₉和ESO⁃SA₁₃），并对其化学结构进行了表征；再以ESO⁃SA _n 为增塑剂，研究其分子量和添加量对聚氯乙烯（PVC）增塑效果、热性能及力学性能的影响；此外，对比了不同成型方式（溶剂流延膜和熔融压制膜）对PVC增塑膜性能的影响；最后，分析了热稳定剂的加入对熔融压制膜性能的影响。研究表明，不同成型方式制备的PVC增塑膜中，均为添加30份ES0⁃SA₉的增塑膜具有最好的性能，包括增塑效果、力学性能（断裂伸长率269.6 %，拉伸强度28.7 MPa）及热性能（初始热分解温度284.3 ℃）等；熔融压制使PVC与增塑剂分子之间能到达更好的混合效果，可实现分子水平的混合；由于钙锌稳定剂与基体的相容性较差且同时破坏了ESO⁃SA _n 在PVC中形成的增塑网络结构，热稳定剂的加入反而导致增塑膜的力学性能及热性能等出现一定程度的降低。

关键词: 聚氯乙烯, 环氧大豆油, 生物基增塑剂, 低分子量聚酯

Abstract:

The epoxide functional groups of epoxidized soybean oil （ESO） were cross⁃linked with succinic acid （SA） through a ring opening reaction， and three types of epoxidized soybean oil⁃succinic acid copolymers （ESO⁃SA₅， ESO⁃SA₉ and ESO⁃SA₁₃） with different molecular weights were obtained through regulating the reaction time， and their chemical structures were characterized. The thermal and mechanical properties of poly（vinyl chloride）（PVC） modified by using ESO⁃SA _n as a plasticizer were studied， and the effects of the molecular weight and addition amount of ESO⁃SA _n on the plasticizing effect were investigated. In addition， the effect of molding method （solvent casting film and melt pressing film） on the properties of plasticized PVC film was compared. Finally， the effect of thermal stabilizer on the properties of melt⁃pressing film was investigated. The results indicated that among the plasticized films prepared by different molding methods， the plasticized film containing 30 phr ESO⁃SA₉ exhibited the best performance， including plasticizing effect， mechanical properties （elongation at break of 269.6 % and tensile strength of 28.7 MPa）， and thermal properties （initial thermal degradation temperature of 284.3 °C）. A better mixing effect between the PVC and plasticizer at a molecular level could be achieved. Owing to the poor compatibility between calcium⁃zinc stabilizer and matrix as well as the destruction of the plasticizing network structure formed by ESO⁃SA_n in PVC， the addition of thermal stabilizer resulted in a decrease to some extent in the mechanical and thermal properties of the plasticized films.

Key words: poly（vinyl chloride）, epoxidized soybean oil, bio?based plasticizer, low molecular weight polyester

中图分类号:

TQ314.24

杨洋, 韩宇, 翁云宣, 宋鑫宇, 黄志刚, 张彩丽. 环氧大豆油⁃癸二酸低分子量聚酯对PVC增塑性能的研究[J]. 中国塑料, 2023, 37(11): 87-94.

YANG Yang, HAN Yu, WENG Yunxuan, SONG Xinyu, HUANG Zhigang, ZHANG Caili. Plasticizing effect of low molecular weight polyesters synthesized from epoxidized soybean oil for poly（vinyl chloride）[J]. China Plastics, 2023, 37(11): 87-94.

图/表 13

参考文献 31

1	Bueno⁃Ferrer C， Garrigós M C， Jiménez A. Characterization and thermal stability of poly（vinyl chloride） plasticized with epoxidized soybean oil for food packaging［J］. Polymer Degradation and Stability， 2010，95（11）： 2 207⁃2 212.
2	Choi M S， Rehman S U， Kim H， et al. Migration of epoxidized soybean oil from polyvinyl chloride/polyvinylidene chloride food packaging wraps into food simulants［J］. Environmental Science and Pollution Research， 2018， 25： 5 033⁃5 039.
3	Ali M， Lu Y， Ahmed S， et al. Effect of modified cardanol as secondary plasticizer on thermal and mechanical properties of soft polyvinyl chloride［J］.ACS Omega， 2020，（5）：17 111⁃17 117.
4	Li M， Xia J， Ding H， et al. Optimal design， characterization， and thermal stability of bio⁃based Ca/Na/Zn composite stabilizer derived from myrcene for poly（vinyl chloride）［J］. Polymer Degradation and Stability， 2017，139： 117⁃129.
5	Yao L， Chen Q， Xu W，et al. Preparation of cardanol based epoxy plasticizer by click chemistry and its action on poly（vinyl chloride）［J］. Journal of Applied Polymer Science， 2017，134：44890.
6	Chen J， Liu Z， Li X，et al.Thermal behavior of epoxidized cardanol diethyl phosphate as novel renewable plasticizer for poly（vinyl chloride）［J］. Polymer Degradation and Stability， 2016，126：58⁃64.
7	Kumar S. Recent developments of biobased plasticizers and their effect on mechanical and thermal properties of poly（vinyl chloride）： a review［J］.Industrial & Engineering Chemistry Research， 2019，58：11 659⁃11 672.
8	Thirupathiah G， Satapathy S， Palanisamy Aruna. Studies on epoxidised castor oil as co⁃plasticizer with epoxidised soyabean oil for PVC processing［J］. Journal of Renewable Materials， 2019，7：775⁃785.
9	Chen J， Liu Z， Nie X， et al. Murray， plasticizers derived from cardanol： synthesis and plasticization properties for polyvinyl chloride（PVC）［J］. Journal of Polymer Research， 2018，25：1⁃14.
10	Greco A， Ferrari F， Maffezzoli A. Effect of the epoxidation yield of a cardanol derivative on the plasticization and durability of soft PVC［J］.Polymer Degradation and Stability， 2016，134：220⁃226.
11	Jia P， Zhang M， Hu L， et al. Cardanol groups grafted on poly（vinyl chloride）⁃synthesis， performance and plasticization mechanism［J］.Polymers （Basel）， 2017，9：1⁃12.
12	Wang M， Li S， Ding H， et al. Construction of efficient tung⁃oil⁃based thermal stabilizers bearing imide and epoxy groups for PVC［J］.New Journal of Chemistry， 2020，44：4 538⁃4 546.
13	Chen J， Nie X， Jiang J.Synthesis of a novel bio⁃oil⁃based hyperbranched ester plasticizer and its effects on poly（vinyl chloride） soft films［J］.ACS Omega，2020，5：5 480⁃5 486.
14	Luo X， Chu H， Liu M.Synthesis of bio⁃plasticizer from soybean oil and its application in poly（vinyl chloride） films［J］.Journal of Renewable Materials，2020，8：1 295⁃1 304.
15	Karmalm P， Hjertberg T， Jansson A.Thermal stability of poly（vinyl chloride） with epoxidised soybean oil as primary plasticizer［J］.Polymer Degradation and Stability， 2009，94：2 275⁃2 281.
16	Aydın R S T， Akyol E， Hazer B. Influence of soybean oil blending with polylactic acid （PLA） films： in vitro and in vivo evaluation［J］.Journal of the American Oil Chemists' Society， 2017，94：413⁃424.
17	Liu W， Qiu J， Fei M E，et al. Manufacturing of thermally remoldable blends from epoxidized soybean oil and poly（lactic acid） via dynamic cross⁃linking in a twin⁃screw extruder［J］.Industrial & Engineering Chemistry Research， 2018，57：7 516⁃7 524.
18	Han Y， Shi J， Mao L，et al.Improvement of compatibility and mechanical performances of PLA/PBAT composites with epoxidized soybean oil as compatibilizer［J］.Industrial & Engineering Chemistry Research，2020，59：21 779⁃21 790.
19	Chen J， Li X， Wang Y， et al.Synthesis and application of environmental soybean oil‐based epoxidized glycidyl ester plasticizer for poly（vinyl chloride）［J］.European Journal of Lipid Science and Technology， 2016，119： 1600216.
20	Olivieri G V， De Quadros J V， Giudici R.Epoxidation reaction of soybean oil： experimental study and comprehensive kinetic modeling［J］.Industrial & Engineering Chemistry Research， 2020，59：18 808⁃18 823.
21	Kim S W， Kim J G， Choi J I， et al.Synthesis of glycidylethylhexylphthalate and its effects on poly（vinyl chloride） films as a novel plasticizer［J］.Journal of Applied Polymer Science， 2005，96：1 347⁃1 356.
22	Chen J， Liu Z， Jiang J， et al.A novel biobased plasticizer of epoxidized cardanol glycidyl ether： synthesis and application in soft poly（vinyl chloride） films［J］.RSC Advances， 2015，5：56 171⁃56 180.
23	Sun B， Chaudhary B I， Shen C Y， et al.Thermal stability of epoxidized soybean oil and its absorption and migration in poly（vinylchloride）［J］.Polymer Engineering & Science， 2013，53：1 645⁃1 656.
24	Hammarling L， Gustavsson H， Svensson K， et al.Migration of epoxidized soya bean oil from plasticized PVC gaskets into baby food［J］.Food Additives and Contaminants， 1998，15：203⁃208.
25	Ray D， Roy P， Sengupta S，et al.A study of dynamic mechanical and thermal behavior of starch/poly（vinylalcohol） based films［J］.Journal of Polymers and the Environment， 2009，17：49⁃55.
26	Bocqué M， Voirin C， Lapinte V， et al.Petro⁃based and bio⁃based plasticizers： chemical structures to plasticizing properties［J］.Journal of Polymer Science Part A： Polymer Chemistry， 2016，54：11⁃33.
27	Feng Y， Chu Z， Man L， et al.Fishbone⁃like polymer from green cationic polymerization of methyl eleostearate as biobased nontoxic PVC plasticizer［J］.ACS Sustainable Chemistry & Engineering， 2019，7：18 976⁃18 984.
28	Satapathy S， Palanisamy A.Mechanical and barrier properties of polyvinyl chloride plasticized with dioctyl phthalate， epoxidized soybean oil， and epoxidized cardanol［J］.Journal of Vinyl and Additive Technology， 2021，27：599⁃611.
29	Feng G， Ma Y， Zhang M， et al.Synthesis of bio⁃base plasticizer using waste cooking oil and its performance testing in soft poly（vinyl chloride） films［J］.Journal of Bioresources and Bioproducts， 2019，4：99⁃110.
30	Tan J， Liu B， Fu Q， et al.Role of the oxethyl unit in the structure of vegetable oil⁃based plasticizer for PVC： an efficient strategy to enhance compatibility and plasticization［J］. Polymers （Basel）， 2019，11：779.
31	Lim K， Ching Y， Gan S.Effect of palm oil bio⁃based plasticizer on the morphological， thermal and mechanical properties of poly（vinyl chloride）［J］.Polymers，2015，7：2 031⁃2 043.

样品	数均分子量/g·mol^-1	重均分子量/g·mol^-1
SA	202	—
ESO	951	—
ESO⁃SA₅	1 492	1 853
ESO⁃SA₉	1 693	2 009
ESO⁃SA₁₃	1 923	2 162

样品	数均分子量/g·mol^-1	重均分子量/g·mol^-1
SA	202	—
ESO	951	—
ESO⁃SA₅	1 492	1 853
ESO⁃SA₉	1 693	2 009
ESO⁃SA₁₃	1 923	2 162

成型方式	样品	断裂伸长率/%			拉伸强度/MPa
成型方式	样品	10份增塑剂	20份增塑剂	30份增塑剂	10份增塑剂	20份增塑剂	30份增塑剂
溶剂流延膜	PVC/DOP	123.4±27.7	144.0±12.4	195.6±27.5	16.9±0.8	13.8±1.3	16.2±2.4
	PVC/ESO⁃SA₅	0.3±0.1	41. 6±16.1	33.3±2.7	21.9±2.4	24.3±0.7	9.4±0.6
	PVC/ESO⁃SA₉	109.7±17.5	189.0±10.0	255.1±10.7	18.8±1.1	16.5±2.8	16.7±4.3
	PVC/ESO⁃SA₁₃	2.6±0.3	232.2±3.1	220.9±4.1	19.7±0.1	18.9±3.0	7.5±0.3
熔融压制膜	PVC/ESO⁃SA₉	—	162.9±16.2	269.6±25.7	—	34.1±2.6	28.7±3.5
	PVC/ESO⁃SA₁₃	—	140.8±21.9	202.9±20.0	—	33.4±4.8	24.4±1.6
	PVC/ESO⁃SA₉⁃s	—	12.3±3.0	197.4±32.5	—	31.2±2.1	21.9±2.2
	PVC/ESO⁃SA₁₃⁃s	—	66.3±8.4	207.9±26.5	—	36.0±1.4	23.9±0.6
	PVC/ESO	—	199.2±47.0	203.2±13.9	—	36.8±2.1	23.4±3.0

成型方式	样品	断裂伸长率/%			拉伸强度/MPa
成型方式	样品	10份增塑剂	20份增塑剂	30份增塑剂	10份增塑剂	20份增塑剂	30份增塑剂
溶剂流延膜	PVC/DOP	123.4±27.7	144.0±12.4	195.6±27.5	16.9±0.8	13.8±1.3	16.2±2.4
	PVC/ESO⁃SA₅	0.3±0.1	41. 6±16.1	33.3±2.7	21.9±2.4	24.3±0.7	9.4±0.6
	PVC/ESO⁃SA₉	109.7±17.5	189.0±10.0	255.1±10.7	18.8±1.1	16.5±2.8	16.7±4.3
	PVC/ESO⁃SA₁₃	2.6±0.3	232.2±3.1	220.9±4.1	19.7±0.1	18.9±3.0	7.5±0.3
熔融压制膜	PVC/ESO⁃SA₉	—	162.9±16.2	269.6±25.7	—	34.1±2.6	28.7±3.5
	PVC/ESO⁃SA₁₃	—	140.8±21.9	202.9±20.0	—	33.4±4.8	24.4±1.6
	PVC/ESO⁃SA₉⁃s	—	12.3±3.0	197.4±32.5	—	31.2±2.1	21.9±2.2
	PVC/ESO⁃SA₁₃⁃s	—	66.3±8.4	207.9±26.5	—	36.0±1.4	23.9±0.6
	PVC/ESO	—	199.2±47.0	203.2±13.9	—	36.8±2.1	23.4±3.0

成型方式	样品	T_{d10 %}/℃	T_{d50 %}/℃
溶剂流延膜	PVC	258.2	305.6
	PVC/30DOP	268.9	305.8
	PVC/30ESO⁃SA₅	283.9	339.1
	PVC/30ESO⁃SA₉	282.2	339.0
	PVC/30ESO⁃SA₁₃	268.9	344.6
熔融压制膜	PVC/20ESO	296.5	339.5
	PVC/30ESO	303.1	347.7
	PVC/20ESO⁃SA₉	280.9	333.0
	PVC/30ESO⁃SA₉	284.3	337.1
	PVC/20ESO⁃SA₁₃	284.3	333.7
	PVC/30ESO⁃SA₁₃	286.4	339.2
	PVC/20ESO⁃SA₉⁃s	278.8	313.7
	PVC/30ESO⁃SA₉⁃s	281.4	310.7
	PVC/20ESO⁃SA₁₃⁃s	279.0	310.8
	PVC/30ESO⁃SA₁₃⁃s	281.4	310.7

环氧大豆油⁃癸二酸低分子量聚酯对PVC增塑性能的研究

Plasticizing effect of low molecular weight polyesters synthesized from epoxidized soybean oil for poly（vinyl chloride）

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

成型方式	样品	PVC	ESO⁃SA₅	ESO⁃SA₉	ESO⁃SA₁₃	ESO	DOP	Ca⁃Zn 稳定剂
溶剂流延膜	PVC	100	—	—	—	—	—	—
	PVC/10ESO⁃SA₅	100	10	—	—	—	—	—
	PVC/20ESO⁃SA₅	100	20	—	—	—	—	—
	PVC/30ESO⁃SA₅	100	30	—	—	—	—	—
	PVC/10ESO⁃SA₉	100	—	10	—	—	—	—
	PVC/20ESO⁃SA₉	100	—	20	—	—	—	—
	PVC/30ESO⁃SA₉	100	—	30	—	—	—	—
	PVC/10ESO⁃SA₁₃	100	—	—	10	—	—	—
	PVC/20ESO⁃SA₁₃	100	—	—	20	—	—	—
	PVC/30ESO⁃SA₁₃	100	—	—	30	—	—	—
熔融压制膜	PVC/10DOP	100	—	—	—	—	10	—
	PVC/20DOP	100	—	—	—	—	20	—
	PVC/30DOP	100	—	—	—	—	30	—
	PVC/20ESO⁃SA₉	100	—	20	—	—	—	—
	PVC/30ESO⁃SA₉	100	—	30	—	—	—	—
	PVC/20ESO⁃SA₁₃	100	—	—	20	—	—	—
	PVC/30ESO⁃SA₁₃	100	—	—	30	—	—	—
	PVC/20ESO	100	—	—	—	20	—	—
	PVC/30ESO	100	—	—	—	30	—	—
	PVC/20ESO⁃SA₉⁃s	100	—	20	—	—	—	4
	PVC/30ESO⁃SA₉⁃s	100	—	30	—	—	—	4
	PVC/20ESO⁃SA₁₃⁃s	100	—	—	20	—	—	4
	PVC/30ESO⁃SA₁₃⁃s	100	—	—	30	—	—	4

样品	增塑剂	断裂伸长率/%	拉伸强度/MPa	T_{d10 %}/^oC	玻璃化转变温度/℃	参考文献
PVC/ESOE	40份ESOE	1138.5	23.8	266.5	30.3	［19］
PVC/ESBO	40份ESBO	211.5	19.0	260.0	54.5	［28］
PVC/ECA/ESBO	50份ESOM	350.8	14.2	263.0	24.0	［29］
PVC/PME/DOP	15份PME	604.7	21.0	289.0	59.0	［27］
PVC/DA8	50份DA8	389.0	25.0	289.0	35.4	［30］
PVC⁃L/DOP/ALK	20份ALK	140.0	7.1	274.6	—	［31］
PVC⁃L/DiNP5/ALK	20份ALK	115.1	6.8	284.0	—	［31］
PVC/ESO⁃SA₉	30份ESO⁃SA₉	255.1	16.7	282.2	40.4	本研究
PVC/ESO⁃SA₉	30份ESO⁃SA₉	269.6	28.7	284.3	52.0	本研究

[1]	周迎鑫, 翁云宣, 吕怡晖. PVC保鲜膜中邻苯二甲酸酯的迁移行为研究[J]. 中国塑料, 2023, 37(8): 86-92.
[2]	韦代东, 李惠枝, 曾娟娟, 赵传国, 李士强. 生物基聚氨酯抗涂鸦自清洁涂料的制备及性能[J]. 中国塑料, 2023, 37(2): 15-21.
[3]	沈一蕊, 周文斌, 张菁菁, 赵承仲, 高华坤, 沈曙光, 刘德开, 蒋平平. 中长碳链氯化石蜡在聚氯乙烯制品中的应用及性能研究[J]. 中国塑料, 2023, 37(1): 31-37.
[4]	何安淇, 黄剑, 张莹, 孙华丽, 项爱民, 徐海云. 喷水灭火氯化聚氯乙烯管道的压力设计基础及国内外标准比较[J]. 中国塑料, 2022, 36(9): 131-139.
[5]	杨笑春, 于静, 张青. 壳聚糖对PVC热稳定性能影响研究[J]. 中国塑料, 2022, 36(7): 68-73.
[6]	邓天翔, 许利娜, 李守海, 张燕, 姚娜, 贾普友, 丁海阳, 李梅. PVC接枝改性及交联改性方法研究进展[J]. 中国塑料, 2022, 36(5): 140-148.
[7]	汤元君, 李璇, 董隽, 李国能, 罗冠群, 王卫民, 许友生. 废弃PVC塑料热解过程多尺度反应动力学特性研究[J]. 中国塑料, 2022, 36(5): 89-98.
[8]	贾垚, 张泽, 余正发, 崔永岩. 动态可逆交联聚氯乙烯的制备与二次加工测试[J]. 中国塑料, 2022, 36(3): 82-88.
[9]	杨羽轩, 柳召刚, 赵金钢, 黄旭博, 陈明光, 胡艳宏, 吴锦绣, 冯福山. 吡嗪⁃2，3⁃二羧酸镧的合成及其对聚氯乙烯稳定性的作用[J]. 中国塑料, 2022, 36(2): 103-110.
[10]	杨笑春, 于静, 张青. N⁃乙基哌嗪基邻苯二甲单酰胺酸锌对PVC热稳定性能的影响[J]. 中国塑料, 2022, 36(2): 125-130.
[11]	顾建国, 孙建凯, 侯培培, 何浩. 双轴取向聚氯乙烯管材最佳拉伸温度和径向拉伸比的研究[J]. 中国塑料, 2022, 36(11): 30-34.
[12]	高鸽, 李阳, 许洁, 王伟峰, 李哲. 过负荷故障聚氯乙烯铜导线绝缘材料热解行为变化研究[J]. 中国塑料, 2022, 36(11): 94-100.
[13]	冯珊, 蒋平平, 张萍波, 张哲铭, 张凯, 顾倩. 低挥发环保增塑剂对苯二甲酸二（2⁃丙基庚）酯的应用研究[J]. 中国塑料, 2022, 36(1): 135-141.
[14]	张耀成, 吴勇振, 李阳, 赵竹, 王国胜, 丁雪佳. 双季铵盐改性医用PVC抗菌材料[J]. 中国塑料, 2021, 35(7): 53-57.
[15]	刘祥贵, 方伟, 舒洪斌, 郑根稳, 刘海. 水滑石填充PVC复合材料的制备及性能研究[J]. 中国塑料, 2021, 35(7): 63-68.