Synthesis of N⁃phenylmaleimide copolymer and its heat⁃resistant modification effect on PVC resin

doi:10.19491/j.issn.1001-9278.2024.07.009

Abstract

Abstract:

A poly（N⁃phenylmaleimide⁃styrene⁃acrylonitrile） copolymer （PNSA） latex with a uniform molecular structure and good compatibility with PVC was successfully prepared through seed emulsion polymerization combined with a semi⁃continuous feeding method. PNSA/PVC blends were prepared through directly compounding PNSA with PVC resin， and its heat⁃resistant modification effect was evaluated. The results indicated that the PNSA latex exhibited a random structure and a uniform particle⁃size distribution ranging from 155.6 to 249.3 nm. The molecular structure of PNSA is uniform. The differential scanning calorimetry curve shows a single glass transition temperature （T_g） for PNSA， suggesting its excellent compatibility with PVC resin. When the addition amount of PNSA was increased from 0 to 50 wt%， the blends presented an increase in T_g from 84.8 to 107.2 ℃， and their Vicat softening temperature increased from 71.2 to 91.9 ℃. In addition to heat⁃resistant modification， the mechanical properties of the blends were also improved to a certain extent. This study is conducive to further expanding the application field of PVC.

Key words: poly（vinyl chloride）, N?phenylmaleimide, free radical copolymerization, seed emulsion polymerization, heat?resistant modification

CLC Number:

TQ325.3

SUN Fangfang, SONG Yunyun. Synthesis of N⁃phenylmaleimide copolymer and its heat⁃resistant modification effect on PVC resin[J]. China Plastics, 2024, 38(7): 49-54.

Figures/Tables 9

Fig.1. Molecular structure of PNSA copolymer

Fig.2. FTIR of PNSA copolymer with different NMPI contents

Fig.3. Particle size and distribution of PNAS latexes with different emulsifier contents

Fig.4. SEM of and PNSA latex particles with different emulsifier contents and PNAS seed

Fig.5. TEM of PNSA latex particles with different emulsifier contents and PNSA seed

Fig.6. DSC curves of PNSA copolymer with different amounts of NMPI monomers

Fig.7. DSC curves of PNSA/PVC composites with different amounts of PNAS copolymer

PNSA含量/%	维卡软化温度/℃
0	71.2
10	75.5
20	80.4
30	84.3
40	88.6
50	91.9

Tab.1. Vicat softening temperature of PNAS/PVC composites with different PNSA contents

Fig.8. Mechanical properties of PVC/PNAS composite with different PNSA compositions

References 23

1	Czogała J， Pankalla E， Turczyn R. Recent attempts in the design of efficient PVC plasticizers with reduced migration ［J］. Materials， 2021， 14（4）： 844.
2	Liu Y， Zhou C， Li F， et al. Stocks and flows of polyvinyl chloride （PVC） in China： 1980⁃2050 ［J］. Resources， Conservation and Recycling， 2020， 154： 104584.
3	张东亮，倪鑫，胡杰.N⁃苯基马来酰亚胺改性酚醛/TiO₂纳米复合材料的制备及性能研究［J］.中国塑料，2014，28（7）：49⁃54.
	ZHANG D L， NI X， HU J. Preparation and properties of PPMF/TiO₂ nano⁃composites ［J］. China Plastics， 2014， 28（7）： 49⁃54.
4	Liu Y， He M， Yan W， et al. P （N⁃phenylmaleimide–alt–styrene） as a heat⁃resistant agent in the application of nylon 6 ［J］. Journal of Applied Polymer Science， 2019， 136（26）： 47689.
5	Wang J， Qiu H， Cheng B， et al. Preparation of a monodisperse poly （N⁃phenylmaleimide–acrylonitrile–styrene） structural nanolatex for heat⁃resistant modification of PVC［J］. Journal of Thermoplastic Composite Materials， 2019， 32（3）： 409⁃423.
6	Liu Y， He M， Zhang D， et al. P （N⁃Phenylmaleimide⁃Alt⁃Styrene） introduced with 4⁃carboxyl and its effect on the heat deflection temperature of nylon 6［J］. Materials， 2018， 11（11）： 2 330.
7	李远，李文振，钱正华，等. N⁃苯基马来酰亚胺/苯乙烯/α⁃甲基苯乙烯/马来酸酐四元共聚物的制备及对ABS的改性［J］. 高分子材料科学与工程， 2017， 33（6）：1⁃6.
	LI Y， LI W Z， QIAN Z H， et al. Synthesis of N⁃phenylmaleimide/ styrene/ Alpha⁃methyl styrene /maleic anhydride tetrapolymers and its modification to ABS resin ［J］. Polymers Materials Science and Engineering， 2017， 33（6）： 1⁃6.
8	Zhao C， Dong J， Li S， et al. Synthesis and characterization of heat⁃resistant N⁃phenylmaleimide⁃styrene⁃maleic anhydride copolymers and application in acrylonitrile⁃butadiene⁃styrene resin［J］.Journal of Applied Polymer Science， 2012， 126（1）：169⁃178.
9	Han S， Qixin Z， Anna Z， et al. Radical reaction extrusion copolymerization mechanism of MMA and N⁃phenylmaleimide and properties of products ［J］. RSC Advances， 2022， 12（40）： 26 251⁃26 263.
10	Long Y L， Jiang W， Wu X， et al. Grafted copolymerization of N⁃phenylmaleimide and styrene in porous polyvinyl chloride particles suspended in aqueous solution ［J］. Designed Monomers and Polymers， 2019， 22（1）： 66⁃78.
11	Howell B A， Zhang J. Thermal degradation of vinylidene chloride/ vinyl chloride copolymers in the presence of N⁃substituted maleimides［J］.Journal of Thermal Analysis and Calorimetry， 2006， 83（1）：83⁃86.
12	赵潜，刘玉飞，何敏，等.反应温度对N⁃苯基马来酰亚胺⁃马来酸酐二元共聚物结构及性能的影响［J］.高分子材料科学与工程，2018，34（11）：10⁃15.
	ZHAO Q， LIU Y F， HE M， et al. Effects of reaction temperature on structure and property of N⁃phenylmaleimide⁃maleic anhydride copolymer ［J］. Polymers Materials Science and Engineering， 2018， 34（11）： 10⁃15.
13	Liu J P， Song X， Yuan W， et al. Evaluation of the thermal stabilization effect of maleic anhydride derivatives on polyvinyl chloride ［J］. Advanced Materials Research， 2012， 535： 1 167⁃1 170.
14	Zhao X， Tian P， Deng J，et al. Synthesis and characterization of vinyl acetate/ N⁃phenylmaleimide copolymers and the corresponding polyvinyl alcohol/N⁃phenylmaleimide with color cycle change property［J］.Colloid and polymer science， 2022， 300： 11⁃20.
15	荔栓红. N⁃苯基马来酰亚胺型高分子耐热改性剂合成技术及流变学研究［D］.兰州：西北师范大学，2010.
16	Ma X， Ge H， Liu H. Enhanced interfacial adhesion in carbon fiber/poly （acrylonitrile⁃butadiene⁃styrene） composite through fiber surface treatment by an emulsion sizing ［J］. Polymer Composites， 37（10）： 2 940⁃2 949.
17	Matsumoto A， Yamamoto D. Radical copolymerization of N‐phenylmaleimide and diene monomers in competition with diels–alder reaction［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2016， 54（22）： 3 616⁃3 625.
18	Chaudhary V， Sharma S. Suspension polymerization technique： parameters affecting polymer properties and application in oxidation reactions［J］. Journal of Polymer Research， 2019， 26（5）： 102.
19	Babaei B， Najafi M， Ataeefard M. Production of electrophotographic toner using in stiu emulsion copolymerization of styrene⁃butyl acrylate［J］. Advanced Materials and New Coatings， 2021， 9（36）： 2 678⁃2 688.
20	Abdollahi A， Roghani⁃Mamaqani H， Salami⁃Kalajahi M. Morphology evolution of functionalized styrene and methyl methacrylate copolymer latex nanoparticles by one⁃step emulsifier⁃free emulsion polymerization［J］. European Polymer Journal， 2020， 133： 109790.
21	Tolue S， Moghbeli M R， Ghafelebashi S M. Preparation of ASA （acrylonitrile⁃styrene⁃acrylate） structural latexes via seeded emulsion polymerization［J］. European Polymer Journal， 2009， 45（3）：714⁃720.
22	胡雄杰，单国荣，翁志学.N⁃苯基马来酰亚胺/苯乙烯/丙烯腈/ɑ⁃甲基苯乙烯乳液共聚动力学［J］.化学反应工程与工艺，2006（1）：74⁃77.
	HU X J， SHAN G R， WENG Z X. Kinetics of N⁃Phenlymaleimide /styrene/ acrylonitrile/α⁃methylstyrene emulsion copolymerization ［J］. Chemical Reaction Engineering and Technology， 2006（1）： 74⁃77.
23	Zhao X H， Tian P， Deng J G， et al. Synthesis and characterization of vinyl acetate/N⁃phenylmaleimide copolymers and the corresponding polyvinyl alcohol/N⁃phenylmaleimide with color cycle change property［J］. Colloid and Polymer Science， 2021， 300：11⁃20.

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