Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer

ZHANG Chao; YU Erlei; WANG Heyun; WANG Ziqing; XIONG Xinyang; HUANG Dong; SONG Xiaoling; WEI Zhong

doi:10.12434/j.issn.2097-2547.20240114

您当前的位置：

首页 >

文章列表页 >

Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer

- Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer
- Vol. 49, Issue 12, Pages: 60-67(2024)
- 作者机构：
  
  1.石河子大学化学化工学院化工绿色过程国家重点实验室孵化基地，新疆石河子 832003
  2.新疆天业（集团）有限公司，新疆石河子 832000
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240114
  CLC： TQ414.6
- Published：25 December 2024，
  
  Received：22 March 2024，
  
  Revised：28 April 2024，
- 稿件说明：
移动端阅览
张超,于二雷,王贺云等.环保型增塑剂油酸基聚酯的合成及增塑性能研究[J].低碳化学与化工,2024,49(12):60-67.

ZHANG Chao,YU Erlei,WANG Heyun,et al.Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):60-67.
张超,于二雷,王贺云等.环保型增塑剂油酸基聚酯的合成及增塑性能研究[J].低碳化学与化工,2024,49(12):60-67. DOI： 10.12434/j.issn.2097-2547.20240114.

ZHANG Chao,YU Erlei,WANG Heyun,et al.Synthesis and plasticizing performance study of environmentally friendly oleic acid-based polyester plasticizer[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):60-67. DOI： 10.12434/j.issn.2097-2547.20240114.

摘要

增塑剂邻苯二甲酸二辛酯（DOP）存在生殖毒性和耐迁移性差的问题。选用油酸甲酯作为主要原料，通过双键环氧化、环氧基水解和本体酯交换反应合成了超支化聚酯（HBPE），随后通过丁酰化合成了IA-HBPE聚酯，可作为绿色低毒的生物基增塑剂。采用FTIR和

H-NMR对不同增塑剂样品化学结构进行了表征。随后通过溶液铸膜法制备了聚氯乙烯（PVC）复合材料，测试了不同PVC复合材料的玻璃化转变温度、力学性能、热稳定性和耐迁移性等。结果表明，IA-HBPE聚酯与PVC有良好的相容性，IA-HBPE聚酯增塑的PVC材料玻璃化转变温度从75.0 ℃下降到-5.0 ℃。IA-HBPE聚酯增塑的PVC材料断裂伸长率高达402.0%，而DOP增塑的PVC材料断裂伸长率仅为289.5%。相较于DOP，IA-HBPE聚酯在PVC材料中的抽出率和挥发率分别降低了22.99%和7.08%，IA-HBPE聚酯的耐迁移性更加优良。IA-HBPE增塑的PVC材料在220 ℃以下可以保持良好的热稳定性，满足实际热加工的要求。基于油酸的超支化聚酯是一种高效、环保的新型增塑剂，有望成为DOP的替代品。

Abstract

The plasticizer dioctyl phthalate (DOP) has issues of reproductive toxicity and poor migration resistance. Methyl oleate was selected as the primary raw material to synthesize hyperbranched polyethylene (HBPE) through processes including double bond epoxidation

epoxy group hydrolysis and bulk transesterification. This was followed by butyrylation to synthesize IA-HBPE polyester

which can serve as a green

low-toxicity bio-based plasticizer. The chemical structures of different plasticizer samples were characterized using FTIR and

H-NMR. Subsequently

polyvinyl chloride (PVC) composites were prepared using the solution casting method

and the glass transition temperature

mechanical properties

thermal stability and migration resistance of different PVC composites were tested. The results show that IA-HBPE polyester has good compatibility with PVC

and the glass transition temperature of PVC material plasticized with IA-HBPE polyester decreases from 75.0

℃ to -5.0 ℃. The elongation at break of PVC material plasticized with IA-HBPE polyester reach 402.0%

compared to 289.5% for PVC material plasticized with DOP. Compared to DOP

the extraction rate and volatilization rate of IA-HBPE polyester in PVC materials are reduced by 22.99% and 7.08%

respectively

indicating superior migration resistance of IA-HBPE polyester. PVC materials plasticized with IA-HBPE can maintain good thermal stability below 220 ℃

meeting the requirements for practical thermal processing. The hyperbranched polyester based on oleic acid is an efficient

environmentally friendly new plasticizer

showing promise as a replacement for DOP.

关键词

PVC增塑剂油酸超支化聚酯

Keywords

PVCplasticizeroleic acidhyperbranched polyester

references

钱俊峰, 吴中, 孙中华, 等. 低分子量聚四氢呋喃二苯甲酸酯的增塑性能分析[J]. 化工进展, 2021, 40(12): 6839-6845.

QIAN J F, WU Z, SUN Z H, et al. Analysis of plasticizing properties of low molecular weight polytetrahydrofuran dibenzoate [J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6839-6845.

李文博, 任亮, 陶子俊, 等. 异山梨醇基增塑剂的制备及其增塑PVC的性能[J]. 工程塑料应用, 2021, 49(4): 123-126.

LI W B, REN L, TAO Z J, et al. The design and preparation of isosorbide-based plasticizer and its application in poly(vinyl chloride) [J]. Engineering Plastics Application, 2021, 49(4): 123-126.

MA Y F, LIAO S L, LI Q G, et al. Physical and chemical modifications of poly(vinyl chloride) materials to prevent plasticizer migration—Still on the run [J]. Reactive and Functional Polymers, 2020, 147: 104458.

DHIFALLAH I, CLAVES D, BATISSE N, et al. Fluorination of PVC medical devices to prevent plasticizers migration [J]. International Journal of Pharmaceutics, 2023, 643: 123254.

FENOLLAR O, GARCIA-SANOGUERA D, SANCHEZ-NACHER L, et al. Mechanical and thermal properties of polyvinyl chloride plasticized with natural fatty acid esters [J]. Journal of Macromolecular Science: Part D—Reviews in Polymer Processing, 2013, 52(8): 761-767.

HABRI H H, AZMI I S, MUBARAK N M, et al. Auto-catalytic epoxidation of oleic acid derived from palm oil via in situ performed acid mechanism [J]. Catalysis Surveys from Asia, 2023, 27(3): 270-277.

OMRANI I, AHMADI A, FARHADIAN A, et al. Synthesis of a bio-based plasticizer from oleic acid and its evaluation in PVC formulations [J]. Polymer Testing, 2016, 56: 237-244.

LEDNIOWSKA K, NOSAL-KOVALENKO H, JANIK W, et al. Effective, environmentally friendly PVC plasticizers based on succinic acid [J]. Polymers, 2022, 14(7): 1295.

FENG S, JIANG P P, ZHANG P B, et al. Synthesis and evaluation of epoxidized vegetable oleic acid as a novel environmental benign plasticizer for polyvinyl chloride [J]. Journal of Applied Polymer Science, 2023, 140(3): e53331.

HUANG Y Z, YU E L, LI Y K, et al. Novel branched poly(ɛ-caprolactone) as a nonmigrating plasticizer in flexible PVC: Synthesis and characterization [J]. Journal of Applied Polymer Science, 2018, 135(32): 46542.

LI Y K, YU E L, YANG X M, et al. Multiarm hyperbranched polyester-b-poly(ε-caprolactone): Plasticization effect and migration resistance for PVC [J]. Journal of Vinyl and Additive Technology, 2019, 26(1): 35-42.

于二雷. 超支化聚合物增塑聚氯乙烯研究进展 [J]. 聚氯乙烯, 2020, 48(11): 1-3+6.

YU E L. Advance in plasticization of PVC by hyperbranched polymers [J]. Polyvinyl Chloride, 2020, 48(11): 1-3+6.

LEE K W, CHUNG J W, KWAK S Y. Synthesis and characterization of bio-based alkyl terminal hyperbranched polyglycerols: A detailed study of their plasticization effect and migration resistance [J]. Green Chemistry, 2016, 18(4): 999-1009.

CHOI W, CHUNG J W, KWAK S Y. Unentangled star-shape poly(ε-caprolactone)s as phthalate-free PVC plasticizers designed for non-toxicity and Improved migration resistance [J]. ACS Applied Materials & Interfaces, 2014, 6(14): 11118-11128.

TESTUD B, PINTORI D, GRAU E, et al. Hyperbranched polyesters by polycondensation of fatty acid-based ABn-type monomers [J]. Green Chemistry, 2017, 19(1): 259-269.

SOKOŁOWSKA M, NOWAK-GRZEBYTA J, STACHOWSKA E, et al. Enzymatically catalyzed furan-based copolyesters containing dilinoleic diol as a building block [J]. RSC Advances, 2023, 13(32): 22234-22249.

HAWKER C J, LEE R, FRECHET J M J. One-step synthesis of hyperbranched dendritic polyesters [J]. Journal of the American Chemical Society, 2002, 113(12): 4583-4588.

MAOU S, MEFTAH Y, TAYEFI M, et al. Preparation and performance of an immiscible PVC-HDPE blend compatibilized with maleic anhydride (MAH) via in-situ reactive extrusion [J]. Journal of Polymer Research, 2022, 29(5): 161-171.

VIKHAREVA I N, AMINOVA G K, MAZITOVA A K. Development of a highly efficient environmentally friendly plasticizer [J]. Polymers, 2022, 14(9): 1888-1904.

LYU Y, PANG J G, GAO Z J, et al. Characterization of the compatibility of PVC/PLA blends by aid of rheological responses [J]. Polymer, 2019, 176: 20-29.

SHARSHIR A I, FAYEK S A, EL-GAWAD A F A, et al. Impact of γ-irradiation and SBR content in the compatibility of aminated (PVC/LLDPE)/ZnO for improving their AC conductivity and oil removal [J]. Scientific Reports, 2022, 12(1): 19616-19631.

LUO W, YANG Y, HAN Y, et al. Synergistic effect of thermal stabilization and plasticization of epoxidized cardanol esters on PVC [J]. Journal of Polymers and the Environment, 2023, 31(12): 5126-5136.

ZHANG H F, ZHU F F, FU Q H, et al. Mechanical properties of renewable plasticizer based on ricinoleic acid for PVC [J]. Polymer Testing, 2019, 76(7): 199-206.

TAN J H, LIU B W, FU Q H, 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, 2019, 11(5): 779-794.

CHEN J, WANG Y G, HUANG J R, et al. Synthesis of tung-oil-based triglycidyl ester plasticizer and its effects on poly(vinyl chloride) soft films [J]. ACS Sustainable Chemistry & Engineering, 2018, 6(1): 642-651.

JIA P Y, ZHANG M, HU L H, et al. Synthesis and application of phosphaphenanthrene groups-containing soybean-oil-based plasticizer [J]. Industrial Crops & Products, 2015, 76: 590-603.

JI S F, GAO C H, WANG H Z, et al. Application of a bio‐based polyester plasticizer modified by hydrosilicon-hydrogenation reaction in soft PVC films [J]. Polymers for Advanced Technologies, 2019, 30(4): 1126-1134.

PAN S Y, HOU D L, CHANG J M, et al. A potentially general approach to aliphatic ester-derived PVC plasticizers with suppressed migration as sustainable alternatives to DEHP [J]. Green Chemistry, 2019, 21(23): 6430-6440.

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Hidden dangers in fire protection of PVC projects and countermeasures to solve them

Related Author

WEI Zhong

SONG Xiaoling

HUANG Dong

XIONG Xinyang

ZHAO Yong-fu

Related Institution

Xinjiang Tianye (Group) Co., Ltd.

Fire Brigade of Wuhai Municipal Public Security Bureau

Postal code：610225
Tel：028-85964717 Email：dthxyhg@swchem.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：152541 Visits Today：298

⁰