Citation: 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. doi: 10.11944/j.issn.1000-0518.2019.11.190210 shu

Synthesis and Properties of Ultraviolet-Irradiation Resistant Carbon Dioxide Copolymer

CAI Yi ^a,b ,
GUO Hongchen ^a,b ,
CAO Han ^c ,
GAO Fengxiang ^a ,
ZHOU Qinghai ^a ,
WANG Xianhong ^a,b,,

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Acdemy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
University of Science and Technology of China, Hefei 230026, China

Corresponding author: WANG Xianhong, xhwang@ciac.ac.cn
Received Date: 15 July 2019
Revised Date: 20 August 2019
Accepted Date: 10 September 2019

Fund Project: the Science and Technology Service Network Initiative of Chinese Academy of Sciences(STS) KFJ-STS-QYZD-047Supported by the Science and Technology Service Network Initiative of Chinese Academy of Sciences(STS)(No.KFJ-STS-QYZD-047)

Figures(7)

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.
- carbon dioxide,
- carbon dioxide copolymer,
- terpolymerization,
- ultraviolet irradiation resistance,
- mechanical performance
1. [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. doi: 10.1002/pol.1969.110070408
2. [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. doi: 10.1002/anie.200460442
3. [3]
  Klaus S, Lehenmeier M W, Anderson C E. Recent Advances in CO₂/Epoxide Copolymerization-New Strategies and Cooperative Mechanisms[J]. Coord Chem Rev, 2011,255:1460-1479. doi: 10.1016/j.ccr.2010.12.002
4. [4]
  Qin Y S, Sheng X F, Liu S J. Recent Advances in Carbon Dioxide Based Copolymers[J]. J CO₂ Util, 2015,11:3-9. doi: 10.1016/j.jcou.2014.10.003
5. [5]
  Grignard B, Gennen S, Jerome C. Advances in the Use of CO₂ as a Renewable Feedstock for the Synthesis of Polymers[J]. Chem Soc Rev, 2019,48:4466-4514. doi: 10.1039/C9CS00047J
6. [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. doi: 10.1039/C8GC03086C
7. [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. doi: 10.1002/anie.200603132
8. [8]
  Sujith S, Min J K, Seong J E. Highly Active and Recyclable Catalytic System for CO₂/Propylene Oxide Copolymerization[J]. Angew Chem Int Ed, 2008,47:7306-7309. doi: 10.1002/anie.200801852
9. [9]
  Wang Y, Qin Y S, Wang X H. 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. [10]
  Zhuo C W, Qin Y S, Wang X H. 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. [11]
  Zhuo C W, Qin Y S, Wang X H. Temperature-Responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide[J]. Chinese J Chem, 2018,36:299-305. doi: 10.1002/cjoc.201800019
12. [12]
  Liu S J, Miao Y Y, Qiao L J. Controllable Synthesis of a Narrow Polydispersity CO₂-Based Oligo(Carbonate-Ether) Tetraol[J]. Polym Chem, 2015,6:7580-7585. doi: 10.1039/C5PY00556F
13. [13]
  Liu S J, Qin Y S, Qiao L J. Cheap and Fast:Oxalic Acid Initiated CO₂-Based Polyols Synthesized by a Novel Preactivation Approach[J]. Polym Chem, 2016,7:146-152. doi: 10.1039/C5PY01338K
14. [14]
  Huang Z, Wang Y, Zhang N. One-Pot Synthesis of Ion-Containing CO₂-Based Polycarbonates Using Protic Ionic Liquids as Chain Transfer Agents[J]. Macromolecules, 2018,51:9122-9130. doi: 10.1021/acs.macromol.8b01834
15. [15]
  Yang G W, Zhang Y Y, Wang Y Y. Construction of Autonomic Self-healing CO₂-Based Polycarbonates via One-Pot Tandem Synthetic Strategy[J]. Macromolecules, 2018,51:1308-1313. doi: 10.1021/acs.macromol.7b02715
16. [16]
  Ren G J, Miao Y Y, Qiao L J. Toughening of Amorphous Poly(Propylene Carbonate) by Rubbery CO₂-Based Polyurethane:Transition from Brittle to Ductile[J]. RSC Adv, 2015,5:49979-49986. doi: 10.1039/C5RA07142A
17. [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. doi: 10.1002/biot.201000134
18. [18]
  GAO Fengxiang, ZHOU Qinghai, QIN Yusheng, et al. Preparation of Carbon Dioxide-Propylene Oxide Copolymer Foam: CN, 103304977.A[P]. 2013-09-18(in Chinese).
19. [19]
  Liu Z R, Hu J J, Gao F X. Biodegradable and Resilient Poly(propylene carbonate) Based Foam from High Pressure CO₂ Foaming[J]. Polym Degrad Stabil, 2019,165:12-19. doi: 10.1016/j.polymdegradstab.2019.04.019
20. [20]
  ZHOU Qinghai, WANG Xianhong, GAO Fengxiang, et al. Fabrication of Full Biodegradable Films Based on Polypropylene Carbonate: CN, 101402789.2009-04-08(in Chinese).
21. [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. doi: 10.1016/j.polymer.2018.04.078
22. [22]
  Liu S J, Wang X H. Polymers from Carbon Dioxide:Polycarbonates, Polyurethanes[J]. Curr Opin Green Sustainable Chem, 2017,3:61-66. doi: 10.1016/j.cogsc.2016.08.003
23. [23]
  Jackson R A, Oldland S R, Pajaczkowski A. Diffusion of Additives in Polyolefins[J]. J Appl Polym Sci, 1968,12:1297-1309. doi: 10.1002/app.1968.070120603
24. [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. doi: 10.1002/food.19760200212
25. [25]
  Li C F, Li Y, Chen Z L. 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. [26]
  Lin Q B, Liang X Z, Su Q Z. 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. doi: 10.1016/j.fpsl.2017.01.008
27. [27]
  Bailey D, Tirrell D, Pinazzi C. Polymers of 2, 4-Dihydroxy-4'-vinylbenzophenone, New Polymeric Ultraviolet Absorbers[J]. Macromolecules, 1978,11(2):312-320. doi: 10.1021/ma60062a006
28. [28]
  Parmar R J, Saxena S, Parmar J S. Copolymerization of UV-Absorbers, II[J]. Angew Makromol Chem, 1998,259:1-5. doi: 10.1002/(SICI)1522-9505(19981001)259:1<1::AID-APMC1>3.0.CO;2-6
29. [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. doi: 10.3969/j.issn.1002-1396.2004.02.014
30. [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. [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).
32. [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.
33. [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. doi: 10.3321/j.issn:1000-7555.2006.05.018
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