Effect of elastomer on the properties of glue⁃free PP/EVA composite films

doi:10.19491/j.issn.1001-9278.2024.06.007

Abstract

Abstract:

Three⁃layer glue⁃free composite films based on a PP/EVA/elastomer blending system were prepared through melt blending and cast co⁃extrusion using EVA as an adhesive layer and different elastomers as a compatibilizer for the PP core layer and adhesive layer. The resultant blending system was analyzed by means of mechanical tests， DMA tests， rheological tests， and scanning electron microscopy， and the properties of the composite films were investigated. The results indicated that there was an optimal bonding effect on paper when using the EVA containing 18 wt% vinyl acetate. The PBE elastomer exhibited a more significant improvement in the mechanical properties than POE. The glass transition temperature of PP and EVA increased gradually with an increase in the PBE content， and meanwhile the curvature of Cole⁃Cole also increased gradually， indicating that the compatibility between PP and EVA became better and better. When the content of PBE in the EVA adhesive layer was 30 wt%， the tensile strength of the composite films reached a maximum value of 29 MPa. The adhesive strength of the composite films with paper reached at maximum value of 9 N/15 mm at a PBE content of 20 wt%. The core layer and adhesive layer cannot be peeled off for the composite films at a PBE content of 25 wt%. The composite films are robust without delamination in this case. The optimal loading of PBE in the adhesive layer was determined to be 25 wt%.

Key words: glue?free composite film, ethylene/vinyl acetate copolymer, elastomer, blending modification

CLC Number:

TQ317.2

SU Yuhang, ZHOU Yuhong, LIN Yuanzhi, MAO Jianquan, WANG Yongxiang, LIU Xiang, YU Li, KE Junmu. Effect of elastomer on the properties of glue⁃free PP/EVA composite films[J]. China Plastics, 2024, 38(6): 44-50.

Figures/Tables 19

Fig.1. Structure diagram of glue⁃free composite membrane

POE（PBE）/%	PP/%	EVA/%
0	50.0	50.0
5	47.5	47.5
10	45.0	45.0
15	42.5	42.5
20	40.0	40.0
25	37.5	37.5

Tab.1. Ratio of the PP/EVA/POE （PBE） blending systems

一区/℃

二区/℃

三区/℃

四区

/℃

Tab.2. Setting of the processing temperature

Fig.2. Schematic diagram of the three⁃layer co⁃extrusion casting machine

PBE/%	EVA/%
0	100
5	95
10	90
15	85
20	80
25	75
30	70
35	65

Tab.3. Adhesive layer（ EVA+PBE ） hybrid system ratio

项目

机筒

1区/℃

机筒

2区/℃

机筒

3区/℃

机筒

4区/℃

过渡区

1区/℃

过渡区

2区/℃

分配器上/

℃

分配器下/

℃

模头

1区/℃

模头

2区/℃

模头

3区/℃

左侧板/

℃

右侧板/

℃

模唇/

℃

Tab.4. Temperature setting for the casting film

Fig.3. Effect of different vinyl acetate EVA contents on the paper adhesion strength

Fig.4. Effect of elastomer contents on the impact strength of Charpy beams in PP/EVA mixed system

Fig.5. Effect of elastomer contents on the tensile strength of PP/EVA hybrid system

Fig.6. Effect of elastomer contents on the elongation at break of PP/EVA blends

Fig.7. Effect of PBE contents on the loss factor of PP/EVA blends

PP/EVA/PBE（质量分数）	T_g/℃
PP/EVA/PBE（质量分数）	EVA	PP
50/50/0	-16.34	15.21
47.5/47.5/5	-16.18	15.14
45/45/10	-15.16	15.00
42.5/42.5/15	-14.22	14.50
40/40/20	-14.15	14.28
37.5/37.5/25	-13.21	13.14

Tab.5. Effect of PBE contents on Tg of PP/EVA blends

Fig.8. Cole⁃Cole curves of different PBE contents of PP/EVA/PBE blends

Fig.9. SEM of PP/EVA/PBE blends

Fig.10. Effects of different contents of PBE on the longitudinal tensile strength and elongation at break of the films

Fig.11. Effect of different PBE contents on the paper adhesion strength

PBE含量/%	黏合层与芯层剥离强度/N·（15mm）^-1
0	1.1
5	1.3
10	2.6
15	2.7
20	4.1
25	无法剥离
30	无法剥离
35	无法剥离

Tab.6. Effect of PBE contents on the peel strength of film adhesive layer and core layer

Fig.12. Enlarged view of cross⁃section of the PP/PP/EVA film

Fig.13. Enlarged view of cross⁃section of the PP/PP/EVA/25%PBE film

References 15

1	王仁龙.一种复合纸塑包装材料及其制备方法［J］.塑料包装，2023，33（2）：42⁃47.
	WANG R L.Composite paper⁃plastic packaging material and preparation method thereof［J］.plastic packaging，2023，33（2）：42⁃47.
2	陈铸红，王红兵.免底涂剂双向拉伸聚丙烯预涂基膜制备及性能研究［J］.安徽化工，2020，46（6）：60⁃63.
	CHEN C H， WANG H B.Preparation and performance study of primer⁃free biaxially oriented polypropylene pre⁃coated base film［J］.Anhui Chemical Industry，2020，46（6）：60⁃63.
3	张伟，何新快，蔡佑星，等.水基乳液型纸塑复合黏合剂的制备［J］.湖南工业大学学报，2009，23（2）：20⁃23.
	ZHANG W， HE X K， CAI Y X，et al.Preparation of water⁃based emulsion paper⁃plastic composite adhesives［J］.Journal of Hunan University of Technology，2009，23（2）：20⁃23.
4	邹斌.无溶剂低摩擦纸塑复膜胶的研究［J］.塑料包装，2022，32（2）：5⁃10.
	ZOU B.Research on solvent⁃free low⁃friction paper⁃plastic laminating adhesives［J］.plastic packaging，2022，32（2）：5⁃10.
5	杨红艳，顾雪梅，周兰.聚丙烯/乙烯⁃丙烯酸共聚物共混物的相容性及性能［J］.合成橡胶工业，2016，39（ 3）： 220 -224.
	YANG H Y， GU X M， ZHOU L.Compatibility and properties of polypropylene/ethylene⁃ acrylic acid copolymer blends［J］.synthetic rubber industry，2016，39（ 3）： 220 -224.
6	王兵，赵家森.EVA/PP共混体系相容性相态及结晶形态的考察［J］.中国塑料， 1999，13（3）：23⁃26.
	WANG B， ZHAO J S.Investigation of compatibility， phase and crystal morphology of EVA/PP blending system［J］.China Plastics，1999，13（3）：23⁃26.
7	RAMIREZ⁃VARGAS E. Morphological and mechanical properties of polypropylene ［PP］/poly（ethylene vinyl ace⁃tate）［EVA］ blends ［J］.Poiymer Engineering and Science，2000，40（10）；32⁃38.
8	Xia Ying， Ren Qinglong， Zhang Fengfeng，et al.Study on the toughening mechanism of PP/EVA dynamically crosslinked blend ［J］.Journal of Macromolecular Science， Part A，2016，53，（8） 523⁃529.
9	殷锦捷，屈晓莉.EVA对PP/EVA 共混物力学性能的影响［J］.塑料科技，2007，35（1）：32 -34.
	YIN J J， QU X L.Effect of EVA on mechanical properties of PP/EVA blends［J］.Plastics Technology，2007，35（1）：32 -34.
10	Ferrofino Aníbal G， Failla Marcelo D， Quinzani Lidia M.Rheological and thermal properties of polypropylene blends based in a low molecular weight EVA ［J］.J Appl Polym Sci，2020，11（1），1⁃11.
11	Canto L B.On the coarsening of the phase morphology of PP/EVA blends during compounding in a twin screw extruder ［J］.Polymer Testing，2014，34（2），175⁃182.
12	白玉光，关颖，李树丰.新型弹性体 POE及其应用技术进展［J］.弹性体，2011，21（2）：85⁃90.
	BAI Y G， GUAN Y， LI S F.New elastomer POE and its application technology progress［J］.Elastomer，2011，21（2）：85⁃90.
13	王国栋，方园园，宋文波.丙烯基弹性体催化剂的研究进展［J］.石油化工，2021，50（9）：960⁃966.
	WANG G D， FAN Y Y， SONG W B.Research progress of propylene⁃based elastomer catalysts［J］.Petrochemical，2021，50（9）：960⁃966.
14	杨凯.茂金属催化的乙烯⁃辛烯共聚物及其共混物的流变学研究［D］.上海：上海交通大学，2007.
15	余学康，杨斌，夏茹，等.聚乙烯/EVA共混体系相分离行为的动态流变研究［J］.化工新型材料，2014，42（12）：101⁃103.
	YU X K， YANG B， XIA R，et al.Dynamic rheological study of phase separation behavior of polyethylene/EVA blends［J］.New chemical materials，2014，42（12）：101⁃103.

[1]	ZHANG Zhiqi, WANG Xiangdong, LIU Haiming, CHEN Shihong. Study on toughening modification and foaming behavior of biobased polyamide 56/polyamide 66 blends by polyamide elastomer [J]. China Plastics, 2024, 38(5): 55-60.
[2]	LIU Xue. New thesis and research on The First Forum on Technology Innovation and Application of Polymer Materials of the Journal of China Plastics [J]. China Plastics, 2024, 38(4): 124-128.
[3]	REN Guozhen, WANG Mengmeng, HUANG Jianjian, JIN Gang. Study on preparation and properties of PEEK/TLCP blends under volume elongation flow field [J]. China Plastics, 2023, 37(8): 1-7.
[4]	PAN Hongyang, CHEN Zongyong, LIAO Tingmao, YUAN Hong. Mechanical properties of polyolefin elastomer and its effect on pressure distribution of mattress body [J]. China Plastics, 2023, 37(11): 24-34.
[5]	YU Hongli, LIU Qian. Research progress in dielectric elastomer actuators for soft robots [J]. China Plastics, 2023, 37(10): 144-152.
[6]	MA Zhirui, YIN Tian, JIANG Zhikui, YANG Fan, ZHU Mengke, YANG Yang, HAN Yu, WENG Yunxuan, ZHANG Caili. Research progress in preparation and applications of PBS and its blends [J]. China Plastics, 2023, 37(10): 24-33.
[7]	HUANG Jiawei, HAN Xiaolong, WU You, JIN Yujuan, WANG Zhao. Toughening modification of poly （3⁃hydroxybutyrate⁃co⁃3⁃hydroxyvalerate） by bio⁃based engineering polyester elastomer [J]. China Plastics, 2022, 36(9): 24-31.
[8]	LEI Jingfa, SHEN Qiang, LIU Tao, SUN Hong, YIN Zhiqiang. Influence of fused deposition process parameters on static and dynamic mechanical properties of thermoplastic polyurethane elastomer [J]. China Plastics, 2022, 36(5): 29-35.
[9]	LI Suyuan, LIU Huipeng, GONG Shun, HUANG Guotao, LI Yucai, WU Xin, DENG Jianping, PAN Kai. Preparation and characterization of EVA foaming materials modified with thermoplastic polyamide elastomer [J]. China Plastics, 2022, 36(4): 6-14.
[10]	HU Huanbo, WU Wei, LI Ning, ZHAO Tianyu, ZOU Zhiqiang. Preparation and properties of TPEE/P（AA⁃co⁃AM） water absorbent elastomer [J]. China Plastics, 2022, 36(3): 9-14.
[11]	HUANG Jiawei, HAN Xiaolong, WU You, JIN Yujuan, GUO Maolin. Toughening modification of PHBV with EVA elastomer [J]. China Plastics, 2022, 36(12): 16-23.
[12]	LI Juan, WANG Yaqiao. Effect of polytetrafluoroethylene fibrillation on the foaming behavior of TPEE/PTFE composites [J]. China Plastics, 2022, 36(12): 38-43.
[13]	XU Bin, CHEN Zhiqiang, CHEN Yanfei, MA Ning. Application of twin⁃screw extruder for high⁃proportion solvent POE devolatilization and granulation [J]. China Plastics, 2022, 36(11): 108-111.
[14]	HUANG Guotao, GUI Yuan, LI Yucai, WU Xin, FENG Xinxing, DENG Jianping, WANG Cao, PAN Kai. Preparation and Characterization of EVA/Nylon Elastomer Microcellular Foaming Materials [J]. China Plastics, 2021, 35(9): 1-7.
[15]	ZHANG Ting, ZHANG Caili, SONG Xinyu, WENG Yunxuan. Research Progress in Preparation and Applications of PBAT Films [J]. China Plastics, 2021, 35(7): 115-125.