杜仲橡胶-丁苯橡胶复合体系的共硫化及其动静态力学性能

邓琳僡; 殷德贤; 向万坤; 孙泉; 丁晓冬; 赵秀英

doi:10.13801/j.cnki.fhclxb.20220105.001

杜仲橡胶-丁苯橡胶复合体系的共硫化及其动静态力学性能

doi: 10.13801/j.cnki.fhclxb.20220105.001

1.
北京化工大学　北京市新型高分子材料制备与加工重点实验室，北京 100029
2.
中国船舶工业系统工程研究院，北京 100094

基金项目: 国家重点研发计划项目(2017YFB0306904)

详细信息

通讯作者:
赵秀英，博士，教授，研究方向为弹性体材料科学与工程 E-mail: zhaoxy@mail.buct.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2021-11-02
- 修回日期: 2021-12-14
- 录用日期: 2021-12-19
- 网络出版日期: 2022-01-05
- 刊出日期: 2022-12-01

Co-vulcanization of eucommia ulmoides gum-styrene butadiene rubber composite system and its dynamic and static mechanical properties

1.
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China
2.
Systems Engineering Research Institute of China State Shipbuilding Cooperation, Beijing 100094, China

摘要

摘要: 将杜仲橡胶(EUG)与丁苯橡胶(SBR)共混，制备了EUG-SBR橡胶复合材料。通过剥离实验和拉伸实验表征其共硫化的情况；通过拉伸实验，SEM、DMA和XRD研究了EUG含量对复合材料动静态性能的影响。结果表明，硫化体系：促进剂N, N-二环己基-2-苯并噻唑磺酰胺(DZ)的质量比为1.0%(以EUG-SBR的质量为基准，下同)、促进剂二硫化四甲基秋兰姆(TMTD) 0.1%、硫磺1.5%可以使两种橡胶达到更好的共硫化，剥离强度达到4.2 kN/m，EUG-SBR(EUG∶SBR质量比为70∶30)复合材料的拉伸强度达到6.3 MPa。复合材料中的EUG晶区主要以β晶型存在，随着EUG含量增多，复合材料的结晶度和熔融温度明显提高。EUG相的引入会使复合材料的损耗因子峰值tanδ_max下降，同时大幅提高复合材料的储能模量，在10℃时EUG-SBR复合材料的储能模量会从质量比5%EUG时的3.0×10⁶ Pa提高到35%EUG时的1.7×10⁷ Pa。同时晶区的存在起到物理交联点的作用，提升复合材料的拉伸强度和定伸应力。
- 杜仲橡胶 /
- 丁苯橡胶 /
- 共硫化 /
- 阻尼 /
- 模量 /
- 晶体 /
- 渝渗
Abstract: Eucommia ulmoides gum (EUG) was blended with styrene butadiene rubber (SBR) to prepare EUG-SBR composites. The co-vulcanization was characterized by stripping experiments and tensile experiments, and the effect of EUG content on the dynamic properties of the composites was studied via tensile experiment, SEM, DMA and XRD. The results display that the prepared sulfide formula (mass ratio of accelerant N, N-dicyclohexyl-2-benzothiazole sulfonamide (DZ) 1.0% (based on the mass of EUG- SBR), accelerant tetramethylthiuram disulfide (TMTD) 0.1%, sulfur 1.5%) could achieve better co-vulcanization of the two rubbers. The stripping strength of the two rubbers reaches 4.2 kN/m and the tensile strength (mass ratio of SBR∶EUG=70∶30) could reach 6.3 MPa. The EUG phase in the composites mainly exists in β-crystalline form, and with the EUG content increasing, the crystallinity and melt temperature of the composites are significantly improved. The introduction of EUG decreases the peak loss factor tanδ_max value and increases the storage modulus of the composites. At temperatures of 10 ℃, the storage modulus of EUG-SBR composites increases from 3.0×10⁶ Pa (with 5% mass of EUG) to 1.7×10⁷ Pa (with EUG of 35%). At the same time, the presence of crystal zone plays a role of physical crosslinking points to improve the tensile strength and fixed elongation stress of composites.
- eucommia ulmoides gum /
- styrene butadiene rubber /
- co-vulcanization /
- damping /
- storage modulus /
- crystal /
- percolation

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图 1 不同配方EUG-SBR复合材料的硫化曲线

Figure 1. Vulcanization curves of different formula EUG-SBR composites

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图 2 不同配方EUG-SBR复合材料的剥离力-位移曲线

Figure 2. Peeling force-displacement curves of different formula EUG-SBR composites

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图 3 不同配方EUG-SBR复合材料的应力-应变曲线

Figure 3. Stress-strain curves of different formula EUG-SBR composites

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图 4 EUG-SBR复合材料的AFM对数模量

((a)-(d)) EUG-SBR mass ratios of 5∶95, 15∶85, 25∶75 and 35∶65

Figure 4. AFM logarithmic modulus of EUG-SBR composites

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图 5 EUG-SBR复合材料的DSC曲线

Figure 5. DSC curves of EUG-SBR composites

T_g—Glass transition temperature; T_p—Crystallization melting peak temperature

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图 6 EUG-SBR复合材料的XRD图谱

Figure 6. XRD patterns of EUG-SBR composites

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图 7 EUG-SBR复合材料的动态热机械分析(DMA)图谱：(a) 储能模量-温度曲线；(b) 损耗因子-温度曲线

Figure 7. Dynamic thermal mechanical analysis (DMA) spectra of EUG-SBR composites: (a) Storage modulus-temperature curves; (b) Loss factor-temperature curves

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图 8 EUG-SBR复合材料应力-应变曲线

Figure 8. Stress-strain curves of EUG-SBR composites

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表 1 杜仲橡胶-丁苯橡胶(EUG-SBR)共硫化研究用配方

Table 1. Formulations for eucommia ulmoides gum-styrene butadiene rubber (EUG-SBR) co-vulcanization research %

Formulation	Raw rubber	ZnO	Stearic acid (SA)	Accelerator CZ	Accelerator DZ	Accelerator NS	Accelerator TMTD	Insoluble sulfur (S)
Formulation 1	100	4	1	0.8	–	–	–	1.8
Formulation 2	100	4	1	–	1	–	0.1	1.5
Formulation 3	100	4	1	–	–	1	–	1.5
Notes: CZ—N-cyclohexyl-2-benzothiazole sulfonamide; DZ—N, N-dicyclohexyl-2-benzothiazole sulfonamide; NS—N-tert-butyl-2-benzothiazole sulfonamide; TMTD—Tetramethylthiuram disulfide.

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表 2 不同配方EUG-SBR复合材料的剥离强度

Table 2. Peel strength of different formula EUG-SBR composites

Formulation	Average peel force/N	Peel strength/(kN·m⁻¹)
Formulation 1	41	1.6
Formulation 2	104	4.2
Formulation 3	57	2.3

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表 3 不同配方EUG-SBR复合材料的力学性能

Table 3. Mechanical properties of different formula EUG-SBR composites

Formulation	Tensile strength/MPa	Elongation at break/%	Stress at 100%/MPa	Stress at 300%/MPa	Hardness (Shore A)
Formulation 1	2.9	383	1.3	2.0	51
Formulation 2	6.2	416	1.7	3.2	60
Formulation 3	5.1	429	1.6	2.8	58

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表 4 EUG-SBR复合材料的结晶度X_c

Table 4. Crystallinity X_c of EUG-SBR composites

EUG/SBR mass ratio	X_c/%
0∶100	0.00
5∶95	0.00
15∶85	1.43
25∶75	5.33
35∶65	7.49
100∶0	31.12

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表 5 不同EUG含量 EUG-SBR复合材料力学性能

Table 5. Mechanical properties of EUG-SBR composites with different EUG contents

EUG/SBR mass ratio	Tensile strength/MPa	Elongation at break/%	Stress at 100%/MPa	Stress at 300%/MPa	Hardness (Shore A)
0∶100	2.2	413	0.9	1.5	41
5∶95	2.2	389	0.9	1.5	42
15∶85	2.6	408	1.0	1.6	44
25∶75	5.2	464	1.4	2.3	54
35∶65	9.1	480	1.8	3.3	61

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