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应用化学
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应用化学  2020, Vol. 37 Issue (1): 32-39    DOI: 10.11944/j.issn.1000-0518.2020.01.190152
  研究论文 本期目录 | 过刊浏览 | 高级检索 |
聚氯乙烯表皮成分对加成型硅橡胶固化的影响
王晓伟a,付志磊a,刘芳a,潘鸽a,许东华a*(),管东波b,窦艳丽b,石彤非a,姚卫国b*()
a中国科学院长春应用化学研究所,高分子物理与化学国家重点实验室 长春 130022
b吉林大学材料科学与工程学院,教育部汽车材料重点实验室 长春 130025
Effect of Polyvinyl Chloride Skin Composition on Vulcanization of Additive Silicone Rubber
WANG Xiaoweia,FU Zhileia,LIU Fanga,PAN Gea,XU Donghhuaa*(),GUAN Dongbob,DOU Yanlib,SHI Tongfeia,YAO Weiguob*()
aState Key Laboratory of Polymer Physics and Chemistry,Changchun Institute ofApplied Chemistry, Chinese Academy of Sciences,Changchun 130022,China
b Key Laboratory of Automobile Materials,Ministry of Education,College ofMaterials Science and Engineering,Jilin University,Changchun 130025,China
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摘要 

采用流变学方法研究了双组分加成型硅橡胶在不同聚氯乙烯(PVC)表皮上的固化动力学,并利用红外光谱、核磁共振波谱、电感耦合等离子体质谱仪等手段分析了PVC表皮成分,以确定导致双组分加成型硅橡胶不固化的具体原因。 结果表明,PVC表皮中导致硅橡胶不固化的主要元素为P元素。 在固定硅橡胶厚度为1 mm的情况下,当PVC表皮中的P元素质量分数低于3×10-3%时,浇注在其上的双组分加成型硅橡胶依然能固化;而当PVC表皮中的P元素质量分数超过约2.4×10-2%时,虽然浇注在其上的双组分加成型硅橡胶的中间层依然能固化,但与PVC表皮接触部分的硅橡胶不固化,且不固化层厚度随P元素质量分数增加而增加。 本文还研究了在P元素质量分数低于3×10-3%的PVC表皮上,降低硅橡胶厚度至微米级时的固化行为,在P元素质量分数低于3×10-3%的PVC表皮上,当硅橡胶厚度低于2 μm时,硅橡胶出现不完全固化现象。 双组分加成型硅橡胶在含有P元素的PVC表皮表面的固化行为主要是由硅橡胶样品中铂催化剂总含量及PVC表皮中的P元素含量确定的,同时也会受到双组分加成型硅橡胶反应速率以及铂催化剂、P元素在硅橡胶中的扩散速率的影响。

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王晓伟
付志磊
刘芳
潘鸽
许东华
管东波
窦艳丽
石彤非
姚卫国
关键词 聚氯乙烯硅橡胶模具流变    
Abstract

In this paper, the curing kinetics of two-component addition silicone rubber on different polyvinyl chloride (PVC) skins was studied with rheological method. The components of PVC skins were analyzed to determine the mechanism of uncuring of two-component addition silicone rubber by using Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance (NMR), and inductively coupled plasma mass spectrometer (ICP-MS). The results show that phosphorus (P) is the main element in the PVC skin that causes the difficulty in curing of silicone rubber. At the fixed silicone rubber thickness of 1 mm, when the content(mass fraction) of P element in the PVC is below 3×10-3%, the two-component addition silicone rubber casted on the PVC skin can still be solidified completely; when the content of P in the PVC skin exceeds about 2.4×10-2%, although the intermediate layer of two-component addition silicone rubber can be cured, the layer contacting PVC skins fails to cure, and the thickness of the uncured layer increases with the content of P. Besides, reducing the thickness of silicone rubber to micron on the skin of PVC with P element content less than 3×10-3%, especially less than 2 μm, the silicone rubber can not cure completely. The consequences mentioned above indicate that the curing behavior of two-component addition silicone rubber on the surface of PVC skin containing P element is mainly influenced by the total content of platinum catalyst in silicone rubber and the content of P element in PVC skin, while the reaction rate of two-component addition silicone rubber and diffusion rates of platinum catalyst and P element in the silicone rubber have ffects as well.

Key wordspolyvinyl chloride    silicone rubber    mold    rheology
收稿日期: 2019-05-24           接受日期: 2019-08-28
基金资助:长春市科技计划科技创新“双十”工程重大科技攻关项目(17SS016)和吉林省科技厅科技发展计划项目(20190302092GX)资助
通讯作者: 许东华,姚卫国     E-mail: dhxu@ciac.ac.cn;wgyao@jlu.edu.cn
引用本文:   
王晓伟, 付志磊, 刘芳, 潘鸽, 许东华, 管东波, 窦艳丽, 石彤非, 姚卫国. 聚氯乙烯表皮成分对加成型硅橡胶固化的影响[J]. 应用化学, 2020, 37(1): 32-39.
WANG Xiaowei, FU Zhilei, LIU Fang, PAN Ge, XU Donghhua, GUAN Dongbo, DOU Yanli, SHI Tongfei, YAO Weiguo. Effect of Polyvinyl Chloride Skin Composition on Vulcanization of Additive Silicone Rubber. Chinese Journal of Applied Chemistry, 2020, 37(1): 32-39.
链接本文:  
http://yyhx.ciac.jl.cn/CN/10.11944/j.issn.1000-0518.2020.01.190152      或      http://yyhx.ciac.jl.cn/CN/Y2020/V37/I1/32
图1流变仪用铝夹具(A)和和环氧树脂表面粘有PVC表皮的自制夹具(B)的光学照片
Fig.1Picture of aluminum geometry of rheometer(A) and homemade geometry with PVC layer on epoxy resin(B)
图2在不同夹具上储能模量(G’)和损耗模量(G″)随反应时间的变化
Fig.2Storage modulus(G’) and loss modulus(G″) vs reaction time on different geometries
A.PVC Ⅰ; B.PVC Ⅱ; C.PVC Ⅲ; D.PVC Ⅳ; E.Control
图3硅橡胶在不同PVC表皮(Ⅰ/Ⅱ/Ⅲ/Ⅳ)上反应后的残留形貌
Fig.3Residual morphology of silicone rubber after vulcanization on different PVC skins(Ⅰ/Ⅱ/Ⅲ/Ⅳ)
图44种PVC表皮(Ⅰ/Ⅱ/Ⅲ/Ⅳ)的红外光谱图
Fig.4FTIR spectra of four types of PVC(Ⅰ/Ⅱ/Ⅲ/Ⅳ)
图54种PVC表皮(Ⅰ/Ⅱ/Ⅲ/Ⅳ)固体的核磁13C谱
Fig.513C NMR of four types of PVC(Ⅰ/Ⅱ/Ⅲ/Ⅳ)
104w(N)/% 104w(S)/% 104w(P)/% 104w(Pb)/% 104w(Cr)/% 104w(Hg)/% 104w(As)/% 104w(Bi)/% 104w(Sn)/% 104w(Sb)/%
0.00 22.47 243.60 9.40 7.44 0.21 0.18 0.00 0.00 0.00
0.00 29.98 260.90 5.78 9.48 0.50 0.30 0.00 0.00 0.00
0.00 97.20 18.54 6.31 12.41 2.87 0.15 0.00 0.00 0.00
0.00 29.93 28.19 3.66 21.68 0.32 0.13 0.00 0.00 0.00
表1PVC表皮中可能导致催化剂中毒元素的质量分数
Table 1The mass fraction of catalyst poisoning elements in the PVC skin
x(P)/% x(Pb)/% x(Cr)/% x(Hg)/% x(As)/% x(S)/%
89.80 0.51 1.63 0.01 0.02 8.02
87.95 0.29 1.90 0.02 0.04 9.79
15.25 0.77 6.10 0.36 0.05 77.48
39.82 0.79 18.27 0.09 0.09 40.96
表2自制PVC夹具中导致铂催化剂中毒的各元素占所有可能导致中毒元素的摩尔分数
Table 2The elements in self-made PVC geometries that cause poisoning of theplatinum catalyst account for the mole fraction of all possible poisoning elements
图6在未中毒表皮(PVC Ⅳ)上不同厚度硅橡胶反应后的残留形貌
Fig.6Residual morphology after reaction of silicone rubber on the skin of ⅣPVC with different thicknesses
A.1 μm; B.2 μm; C.3 μm; D.5 μm
图7硅橡胶在不同PVC表皮上的交联固化动态模型
Fig.7Cross-linking model of silicone rubber at different PVC skins
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