耐紫外光老化CO2共聚物的合成与性能

doi:10.11944/j.issn.1000-0518.2019.11.190210

摘要/Abstract

摘要：

CO₂基塑料(PPC)是通过CO₂与环氧丙烷共聚所得的生物降解高分子,由于PPC的耐紫外老化性能较差,随紫外线的照射不仅PPC的相对分子质量快速下降,且其拉伸强度和断裂伸长率等力学性能也迅速降低,而农用地膜长期处于紫外线照射的环境中,因此亟待改善PPC的耐紫外老化性能。本文设计合成了含紫外吸收基团的单体2-羟基-4(2,3-环氧丙氧基)二苯甲酮(HEB),与CO₂和环氧丙烷进行三元共聚制备了耐紫外光老化的CO₂共聚物(PPCH)。在保证PPCH相对分子质量不低于5.0×10⁴的前提下,PPCH中HEB单元的摩尔分数最高可达0.32%,相应地其玻璃化转变温度(T_g)和起始热分解温度(T_d-5%)分别为26.7和216.9 ℃,拉伸强度达到30.97 MPa。普通PPC经过240 h的紫外辐照后,其数均相对分子质量下降了67.8%,相应地其拉伸强度和断裂伸长率分别下降了10.1%和40.1%。即使PPCH中的HEB摩尔分数仅为0.06%,经过240 h辐照后其数均相对分子质量仅下降了6.2%,相应地其拉伸强度和断裂伸长率也仅分别下降了1.7%和13.3%,证明PPCH具有较强的耐紫外老化性能,原因在于其主链含有HEB单元,对紫外光具有较好的吸收性能。 PPCH的紫外吸收性能随HEB单元在聚合物中含量的增加而增强,因此随着共聚物中引入的HEB单元含量增加,PPCH的相对分子质量和力学性能的保持率均得到了大幅度提高。另一方面,对PPCH共聚物与相同二羟基二苯甲酮(BP)含量的PPC/BP共混物进行120 h的50 ℃热水萃取实验,PPCH显示出稳定的紫外光吸收性能,而PPC/BP共混物的紫外吸收性能随热水萃取时间的增长而快速下降,表明三元共聚反应能够有效解决普通共混物面临的小分子紫外吸收剂的外迁移问题。

关键词: CO₂, CO₂共聚物, 三元共聚反应, 耐紫外光老化性能, 力学性能

Abstract:

CO₂ based plastics (PPC) is a high molecular mass copolymer of carbon dioxide and propylene oxide. PPC is quite sensitive to ultraviolet (UV) irradiation and its molecular mass decreases quickly with UV-irradiation accompanied by significant loss of mechanical strength. To improve the UV irradiation resistance of PPC is of key importance for its application as agricultural mulching film, which is always under UV irradiation during the whole coverage. In this work, an epoxide with UV absorber function, i.e., 2-hydroxy-4(2,3-epoxypropoxy)benzophenone (HEB), was designed and prepared. By means of terpolymerization of CO₂, propylene oxide and HEB, terpolymer PPCH with UV absorber side chain was successfully synthesized, where the chemical structure as well as the HEB content was determined by ¹H NMR spectroscopy. Under the premise of ensuring PPCH molecular mass not less than 5.0×10⁴, the maximum molar fraction of HEB incorporated into the PPCH terpolymer was 0.32%, and such PPCH showed a tensile strength of 30.97 MPa, a glass transition temperature (T_g) of 26.7 ℃, and the temperature at 5% mass loss of thermal decomposition (T_d-5%) of 216.9 ℃. When PPC was exposed under UV irradiation for 240 h, its number-average molecular mass decreased by 67.8%, accompanied by 10.1% loss of tensile strength and 40.1% loss of elongation at break. As a comparison, the number-average molecular mass of PPCH with 0.06% molar fraction HEB showed only 6.2% decrease correspondingly. It showed 1.7% loss of tensile strength and 13.3% decrease of elongation at break, indicating that PPCH had improved UV-irradiation resistance performance due to the existence of UV absorbable functional group like HEB. PPCH and PPC blended with similar 2,4-dihydroxyl benzophenone (BP) content were compared for hot water (50 ℃) extraction test. No BP was extracted in PPCH providing stable UV absorption performance, while the PPC/BP blend showed sharp drop in UV absorption upon hot water extraction. Therefore, terpolymerization of CO₂, propylene oxide with UV absorbable monomer is an effective way to improve the UV irradiation resistance performance of CO₂ copolymer.

Key words: carbon dioxide, carbon dioxide copolymer, terpolymerization, ultraviolet irradiation resistance, mechanical performance

蔡毅,郭洪辰,曹瀚,高凤翔,周庆海,王献红. 耐紫外光老化CO₂共聚物的合成与性能[J]. 应用化学, 2019, 36(11): 1248-1256.

CAI Yi,GUO Hongchen,CAO Han,GAO Fengxiang,ZHOU Qinghai,WANG Xianhong. Synthesis and Properties of Ultraviolet-Irradiation Resistant Carbon Dioxide Copolymer[J]. Chinese Journal of Applied Chemistry, 2019, 36(11): 1248-1256.

参考文献

[1]	Inoue S,Koinuma H,Tsuruta T.Copolymerization of Carbon Dioxide and Epoxide[J]. J Polym Sci,Part B:Polym Lett,1969,7:287-292.
[2]	Coates G W,Moore D R.Discrete Metal-Based Catalysts for the Copolymerization of CO2 and Epoxides:Discovery, Reactivity, Optimization, and Mechanism[J]. Angew Chem Int Ed,2004,43:6618-6639.
[3]	Klaus S,Lehenmeier M W,Anderson C E,et al. Recent Advances in CO2/Epoxide Copolymerization-New Strategies and Cooperative Mechanisms[J]. Coord Chem Rev,2011,255:1460-1479.
[4]	Qin Y S,Sheng X F,Liu S J,et al. Recent Advances in Carbon Dioxide Based Copolymers[J]. J CO2 Util,2015,11:3-9.
[5]	Grignard B,Gennen S,Jerome C,et al. Advances in the Use of CO2 as a Renewable Feedstock for the Synthesis of Polymers[J]. Chem Soc Rev, 2019,48:4466-4514.
[6]	Kamphuis A J,Picchioni F,Pescarmona P P.CO2-Fixation into Cyclic and Polymeric Carbonates:Principles and Applications[J]. Green Chem,2019,21:406-448.
[7]	Nakano K,Kamada T,Nozaki K.Selective Formation of Polycarbonate over Cyclic Carbonate:Copolymerization of Epoxides with Carbon Dioxide Catalyzed by a Cobalt(Ⅲ) Complex with a Piperidinium End-Capping Arm[J]. Angew Chem Int Ed,2006,45:7274-7277.
[8]	Sujith S,Min J K,Seong J E,et al. Highly Active and Recyclable Catalytic System for CO2/Propylene Oxide Copolymerization[J]. Angew Chem Int Ed,2008,47:7306-7309.
[9]	Wang Y, Qin Y S,Wang X H,et al. Trivalent Titanium Salen Complex:Thermally Robust and Highly Active Catalyst for Copolymerization of CO2 and Cyclohexene Oxide[J]. ACS Catal,2014,5:393-396.
[10]	Zhuo C W,Qin Y S,Wang X H,et al. Steric Hindrance Ligand Strategy to Aluminum Porphyrin Catalyst for Completely Alternative Copolymerization of CO2 and Propylene Oxide[J]. Chinese J Polym Sci,2017,36:252-260.
[11]	Zhuo C W,Qin Y S,Wang X H,et al. Temperature-Responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide[J]. Chinese J Chem,2018,36:299-305.
[12]	Liu S J,Miao Y Y,Qiao L J,et al. Controllable Synthesis of a Narrow Polydispersity CO2-Based Oligo(Carbonate-Ether) Tetraol[J]. Polym Chem,2015,6:7580-7585.
[13]	Liu S J,Qin Y S,Qiao L J,et al. Cheap and Fast: Oxalic Acid Initiated CO2-Based Polyols Synthesized by a Novel Preactivation Approach[J]. Polym Chem,2016,7:146-152.
[14]	Huang Z,Wang Y,Zhang N,et al. One-Pot Synthesis of Ion-Containing CO2-Based Polycarbonates Using Protic Ionic Liquids as Chain Transfer Agents[J]. Macromolecules,2018,51:9122-9130.
[15]	Yang G W,Zhang Y Y,Wang Y Y,et al. Construction of Autonomic Self-healing CO2-Based Polycarbonates via One-Pot Tandem Synthetic Strategy[J]. Macromolecules,2018,51:1308-1313.
[16]	Ren G J,Miao Y Y,Qiao L J,et al. Toughening of Amorphous Poly(Propylene Carbonate) by Rubbery CO2-Based Polyurethane:Transition from Brittle to Ductile[J]. RSC Adv,2015,5:49979-49986.
[17]	Qin Y S,Wang X H.Carbon Dioxide-Based Copolymers:Environmental Benefits of PPC, an Industrially Viable Catalyst[J]. Biotechnol J,2010,5:1164-1180.
[18]	GAO Fengxiang,ZHOU Qinghai,QIN Yusheng,et al. Preparation of Carbon Dioxide-Propylene Oxide Copolymer Foam:CN. Preparation of Carbon Dioxide-Propylene Oxide Copolymer Foam:CN,103304977.A[P].2013 -09-18(in Chinese). 高凤翔,周庆海,秦玉升,等. 一种二氧化碳-环氧丙烷共聚物泡沫塑料及其制备方法:中国,103304977.A[P].2013-09-18.
[19]	Liu Z R,Hu J J,Gao F X,et al. Biodegradable and Resilient Poly(propylene carbonate) Based Foam from High Pressure CO2 Foaming[J]. Polym Degrad Stabil,2019,165:12-19.
[20]	ZHOU Qinghai,WANG Xianhong,GAO Fengxiang,et al. Fabrication of Full Biodegradable Films Based on Polypropylene Carbonate:CN. Fabrication of Full Biodegradable Films Based on Polypropylene Carbonate:CN,101402789.2009-04-08(in Chinese). 周庆海,王献红,高凤翔,等. 以聚碳酸1,2-丙二酯为基体的全生物降解薄膜及制法:中国, 101402789.2009-04-08.
[21]	Muthuraj R,Mekonnen T.Recent Progress in Carbon Dioxide (CO2) as Feedstock for Sustainable Materials Development:Co-polymers and Polymer Blends[J]. Polymer,2018,145:348-373.
[22]	Liu S J,Wang X H.Polymers from Carbon Dioxide:Polycarbonates, Polyurethanes[J]. Curr Opin Green Sustainable Chem,2017,3:61-66.
[23]	Jackson R A,Oldland S R,Pajaczkowski A.Diffusion of Additives in Polyolefins[J]. J Appl Polym Sci,1968,12:1297-1309.
[24]	Uhde W J,Woggon H.New Results on Migration Behavior of Benzophenone-Based UV Absorbents from Polyolefins in Foods[J]. Die Nahrung,1976,20(2):185-194.
[25]	Li C F,Li Y,Chen Z L,et al. Simultaneous Determination of Migration Amounts of Antioxidants and Ultraviolet Absorbents Byhighperformance Liquid Chromatographyin Food Contact Materials[J]. Chinese J Chromatogr,2014,6:616-622.
[26]	Lin Q B,Liang X Z,Su Q Z,et al. Effect of Graphene on the Migration of Two Ultraviolet Absorbents from Graphene-LDPE Composite Films into a Fatty Food Simulant[J]. Food Packaging Shelf,2017,12:9-15.
[27]	Bailey D,Tirrell D,Pinazzi C,et al. Polymers of 2,4-Dihydroxy-4'-vinylbenzophenone, New Polymeric Ultraviolet Absorbers[J]. Macromolecules,1978,11(2):312-320.
[28]	Parmar R J,Saxena S,Parmar J S.Copolymerization of UV-Absorbers, II[J]. Angew Makromol Chem,1998,259:1-5.
[29]	LI Hua,ZHEN Yubin,WANG Lin.Study on Synthesis of Polymeric Ultraviolet Absorber I. Emulsion Polymerization of Acrylate Containing 2-Hydroxy-4-Acryloyloxbenzonphenone[J]. China Synth Resin Plast,2004,2:56-58,70(in Chinese). 李华,郑玉斌,王林. 聚合型紫外线吸收剂的合成研究I.含2-羟基-4-丙烯酸酯基二苯甲酮的丙烯酸酯类乳液聚合[J]. 合成树脂及塑料,2004,2:56-58,70.
[30]	Liu N,Pan J Q,Lau W W Y. Preparations and Properties of New Monomeric Light Stabilizers[J]. Polym Degrad Stabil,1999,63(1):71-77.
[31]	ZHANG Yaming,CAI Yi,ZHOU Qinghai,,et al. Preparation of a Zinc-Dicarboxylate Catalyst, Modified Zinc-Dicarboxylate Catalyst and Carbon Dioxide-Epoxy Copolymer:CN,105418907A[P].2016-03-23(in Chinese). 张亚明,蔡毅,周庆海,等. 一种二元羧酸锌催化剂、改性二元羧酸锌催化剂和二氧化碳-环氧化合物共聚物的制备方法:中国,105418907 A[P].2016-03-23.
[32]	ZHANG Mingzheng,LI Ran,HUANG Dan.Microwave Syntheses and Characterization of 1,2-Epoxy Propyl Ether Aromatic Ketone UV Absorbents[J]. Chemistry,2014,77(12):1201(in Chinese). 张明政,李然,黄丹. 1,2-环氧丙醚基芳香酮紫外线吸收剂的微波合成和表征[J]. 化学通报,2014,77(12):1201.
[33]	ZHAO Yi,DAN Yi.Synthesis of a Reactive UV-Stabilizer and Its Application in Styrenic Polymers[J]. Polym Mater Sci Eng,2006,5:74-77(in Chinese). 赵义,淡宜. 应型紫外线吸收剂的制备及高分子化[J]. 高分子材料科学与工程,2006,5:74-77.

耐紫外光老化CO₂共聚物的合成与性能

Synthesis and Properties of Ultraviolet-Irradiation Resistant Carbon Dioxide Copolymer

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	元宁, 马洁, 张晋玲, 张建胜. 蒸气辅助合成PCN-6（M）双金属有机框架材料及其CH₄和CO₂吸附性能[J]. 应用化学, 2023, 40(6): 896-903.
[2]	唐连波, 付大友, 陈琦, 奉阳润, 熊桠林, 王竹青. 碳量子点增强气液相化学发光检测二氧化碳[J]. 应用化学, 2022, 39(8): 1294-1302.
[3]	张超. 单原子催化剂电催化还原二氧化碳研究进展[J]. 应用化学, 2022, 39(6): 871-887.
[4]	吴雪婷, 于洋, 宋术岩, 张洪杰. 人工固碳技术—热催化还原CO₂催化剂的研究进展[J]. 应用化学, 2022, 39(4): 599-615.
[5]	唐永鑫, 聂立武. 环氧树脂掺量对发光树脂透水混凝土性能的影响[J]. 应用化学, 2022, 39(11): 1665-1671.
[6]	洪卫, 王立权, 林嘉平. 高分子多级微相结构与性能的研究进展[J]. 应用化学, 2021, 38(10): 1310-1325.
[7]	高丽敏, 李璐, 周光远, 王红华, 朱忠丽. 硅土/酚酞聚芳醚砜复合材料的制备及性能[J]. 应用化学, 2020, 37(5): 524-530.
[8]	郭红霞, 崔继方, 刘利. 氧空位增强光催化还原CO₂性能方面的研究进展[J]. 应用化学, 2020, 37(3): 256-263.
[9]	高佳, 宋夫交, 程文强, 葛艳, 许琦. Pd-Cu/ZrO₂催化CO₂加氢制甲醇的性能[J]. 应用化学, 2020, 37(2): 160-167.
[10]	范天博,陈思,姜宇,蔡勋,亢萍,李莉,张利,刘云义. 包覆重钙粉为填充剂的橡胶加工及性能[J]. 应用化学, 2019, 36(7): 790-797.
[11]	钟振兴, 刘桂兰, 李永海, 李连国, 黄燕, 张光宇, 苏朝晖. 1,2-丁二醇共聚对聚对苯二甲酸乙二醇酯结晶行为及力学性能的影响[J]. 应用化学, 2019, 36(2): 170-175.
[12]	李沛,张嘉琪,刘巍,陈全,唐毓婧,姬相玲,薛彦虎,孙广平. 4种低密度聚乙烯树脂的链结构及其性能[J]. 应用化学, 2019, 36(11): 1237-1247.
[13]	陈明锋, 刘玉惠, 范先谋, 杨松伟, 林金火, 刘灿培, 黄海滨. 不饱和聚酯片状模塑料的模压成型与性能[J]. 应用化学, 2018, 35(10): 1222-1226.
[14]	李陈浩洋, 崔西华, 姜伟, 陈斌. 氯化聚丙撑碳酸酯增容聚丙撑碳酸酯/秸秆粉复合材料的制备及性能[J]. 应用化学, 2017, 34(7): 744-748.
[15]	张伟钢, 徐国跃, 薛连海, 陈亚西. 3-氨丙基三乙氧基硅烷对聚氨酯/Al-Sm₂O₃复合涂层自然老化性能的影响[J]. 应用化学, 2017, 34(4): 430-435.