防污剂在溶胀聚合物中扩散的模拟研究

doi:10.6040/j.issn.1671-9352.0.2018.031

《山东大学学报(理学版)》 ›› 2018, Vol. 53 ›› Issue (11): 18-25, 34.doi: 10.6040/j.issn.1671-9352.0.2018.031

防污剂在溶胀聚合物中扩散的模拟研究

程栋材^1,²(),黄志雄^1,*(),任润桃²,王晶晶²,叶章基²,张亮³,王跃平²

1. 武汉理工大学特种功能材料技术教育部重点实验室, 湖北武汉 430070
2. 海洋腐蚀与防护重点实验室, 福建厦门 361101
3. 创腾科技有限公司, 上海 200237

收稿日期:2018-01-23 出版日期:2018-11-01 发布日期:2018-11-14
通讯作者: 黄志雄 E-mail:cdch102504@vip.163.com;Zhixiongh@whut.edu.cn
作者简介:程栋材(1977—)，男，博士研究生，研究方向为海洋防污研究. E-mail：cdch102504@vip.163.com
基金资助:
国家自然科学基金资助项目(51173141);工信部高技术船舶项目

Release of the antifoulant in equilibrium swollen polymer: molecular dynamics simulation

Dong-cai CHENG^1,²(),Zhi-xiong HUNAG^1,*(),Run-tao REN²,Jing-jing WANG²,Zhang-ji YE²,Liang ZHANG³,Yue-ping WANG²

1. Technology & Key Laboratory of Special Functional Materials of the Ministry of Education, Wuhan University of Technology, Wuhan 430070, Hubei, China
2. Science and Technology on Marine Corrosion and Protection Laboratory, Xiamen 361101, Fujian, China
3. NeoTrident Company, Shanghai 200237, China

Received:2018-01-23 Online:2018-11-01 Published:2018-11-14
Contact: Zhi-xiong HUNAG E-mail:cdch102504@vip.163.com;Zhixiongh@whut.edu.cn
Supported by:
国家自然科学基金资助项目(51173141);工信部高技术船舶项目

摘要/Abstract

摘要：

利用Materials Studio软件进行分子动力学模拟研究平衡溶胀结构聚合物。调查溶胀前后聚合物玻璃化温度,水与链段在平衡溶胀态下的动力学、不同含水量下水分子的局部动力学和防污剂分子扩散行为,从分子角度解释包覆防污剂的受控释放机制。模拟发现处于平衡溶胀态下, 3种P(MMA-co-n-BMA)玻璃化温度分别降低21.72、17.27、14.40 K,水的动力学性质接近本体水,并且高于聚合物链段2个指数;溶胀聚合物处于橡胶态时,防污剂的有效扩散明显增加。结果表明，聚合物的含水量与玻璃化温度是控制防污剂分子扩散的关键因素。

关键词: 防污剂, 分子动力学, 平衡溶胀, 玻璃化温度, 均方位移

Abstract:

To investigate the release of the antifouling molecules in equilibrium swelling (ES) states, molecular dynamics (MD) simulation was performed to analyze the diffusion of 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT) molecule in P(MMA-co-n-BMA) immersed in water. The glass transition temperature (T_g) was simulated in the dry and equilibrium swelling states, and the dynamics of water and the pendant groups in the ES state were investigated, as well as the influence of water content on the local dynamics of water. The diffusion mechanisms of DCOIT were also analyzed. T_g values of three P(MMA-co-n-BMA)s in the ES state are from 14.84, 17.27 K to 21.73 K lower than in the dry state. Water has the higher mobility than the pendant groups by approx. 2 orders of magnitude in ES systems and has dynamic properties on the same level as those of bulk water. The diffusion of a large-mass penetrant can be controlled effectively with water and T_g as the crucial factors, and the diffusion ability of DCOIT is significantly enhanced when the swollen matrix is in the rubbery state.

Key words: antifoulant, molecular dynamics, equilibrium swelling, glass transition temperature, mean-square displacement

中图分类号:

TQ630.1

程栋材,黄志雄,任润桃,王晶晶,叶章基,张亮,王跃平. 防污剂在溶胀聚合物中扩散的模拟研究[J]. 《山东大学学报(理学版)》, 2018, 53(11): 18-25, 34.

Dong-cai CHENG,Zhi-xiong HUNAG,Run-tao REN,Jing-jing WANG,Zhang-ji YE,Liang ZHANG,Yue-ping WANG. Release of the antifoulant in equilibrium swollen polymer: molecular dynamics simulation[J]. JOURNAL OF SHANDONG UNIVERSITY(NATURAL SCIENCE), 2018, 53(11): 18-25, 34.

图/表 9

表1

图1

图2

表2

图3

表3

表4

图4

表5

参考文献 35

1	DIEGO M Y , SØREN K , KIM D J . Antifouling technology: past, present and future steps towards efficient and environmentally friendly antifouling coatings[J]. Progress in Organic Coatings, 2004, 5 (2): 75- 104.
2	叶章基, 陈珊珊, 马春风, 等. 新型环保海洋防污材料研究进展[J]. 表面技术, 2017, 46 (12): 62- 70.
	YE Zhangji , CHEN Shanshan , MA Chunfeng , et al. Development of novel environment-friendly antifouling materials[J]. Surface Technology, 2017, 46 (12): 62- 70.
3	LARS N , ATTA A A , MARIAM M , et al. Molecular release from painted surfaces: free and encapsulated biocides[J]. Progress in Organic Coatings, 2010, 69 (1): 45- 48. doi: 10.1016/j.porgcoat.2010.05.002
4	赵相宽, 白秀琴, 袁成清. 绿色生物防污剂及控制释放技术研究进展[J]. 舰船科学技术, 2017, 39 (1): 6- 11. doi: 10.3404/j.issn.1672-7619.2017.01.002
	ZHAO Xiangkuan , BAI Xiuqin , YUAN Chengqing . Progress in green biological antifoulant and controlled release technologies[J]. Ship Science and Technology, 2017, 39 (1): 6- 11. doi: 10.3404/j.issn.1672-7619.2017.01.002
5	ANYAOGU K C , FEDOROV A V , NECKERS D C . Synthesis, characterization, and antifouling potential of functionalized copper nanoparticles[J]. Langmuir, 2008, 24 (8): 4340- 4346. doi: 10.1021/la800102f
6	NORDSTIERNA L , ABDALLA A A , NORDIN M , et al. Comparison of release behaviour from microcapsules and microspheres[J]. Progress in Organic Coatings, 2010, 69 (1): 49- 51. doi: 10.1016/j.porgcoat.2010.05.003
7	汪小伟, 尹卫平, 付玉彬, 等. 镀铜微管对防污剂的控制释放性能[J]. 材料开发与应用, 2005, 20 (1): 19- 22. doi: 10.3969/j.issn.1003-1545.2005.01.006
	WANG Xiaowei , YIN Weiping , FU Yubin , et al. Controlled release of antifouling agent in copper metalized tubules[J]. Development and Application of Materials, 2005, 20 (1): 19- 22. doi: 10.3969/j.issn.1003-1545.2005.01.006
8	汪小伟, 时清亮, 付玉彬. 铜微球对防污剂异噻唑酮的控释作用[J]. 精细化工, 2007, 24 (10): 944- 947. doi: 10.3321/j.issn:1003-5214.2007.10.003
	WANG Xiaowei , SHI Qingliang , FU Yubin . Performance of controlledrelease of isothiazoline antifouling agent in coppermicrospheres[J]. Fine Chemicals, 2007, 24 (10): 944- 947. doi: 10.3321/j.issn:1003-5214.2007.10.003
9	汪小伟, 付玉彬, 张经纬, 等. 纳米钛酸管对防污剂异噻唑酮的控释作用[J]. 精细化工, 2007, 24 (3): 213- 216. doi: 10.3321/j.issn:1003-5214.2007.03.002
	WANG Xiaowei , FU Yubin , ZHANG Jingwei , et al. Performance of controlled release of antifouling agent in nanotubes of titanic acid[J]. Fine Chemicals, 2007, 24 (3): 213- 216. doi: 10.3321/j.issn:1003-5214.2007.03.002
10	史航, 石建高, 陈晓蕾, 等. 包埋苯甲酸钠微球的制备及在海洋防污涂料中的抑菌研究[J]. 高分子通报, 2011, 1 (1): 9- 12.
	SHI Hang , SHI Jiangao , CHEN Xiaolei , et al. Preparation of encapsulated sodium benzoate and antibacterial application in marine antifouling coating[J]. Polymer Bulletin, 2011, 1 (1): 9- 12.
11	VRENTAS J S , DUDA J L . Diffusion in polymer-solvent systems Ⅰ. Reexamination of the free-volume theory[J]. J Polym Sci Part B Poly Phys, 1977, 15 (3): 403- 416. doi: 10.1002/pol.1977.180150302
12	VRENTAS J S , DUDA J L . .Diffusion in polymer—solvent systems Ⅱ. A predictive theory for the dependence of diffusioncoefficients on temperature, concentration, and molecular weight[J]. J Polym Sci Part B Poly Phys, 1977, 15 (3): 417- 439. doi: 10.1002/pol.1977.180150303
13	ARUZZI S. Diffusion of small molecules in polymeric glasses: a modelling approach[D]. Boston: Massachusetts Institute of Technology, 1990.
14	GUSEV A A , ARIZZI S , SUTER U W . Dynamics of light gases in rigid matrices of dense polymers[J]. J Chem Phys, 1993, 99 (3): 2221- 2227. doi: 10.1063/1.465283
15	HWANG S T . Fundamentals of membrane transport[J]. Korean J Chem Eng, 2011, 28 (1): 1- 15. doi: 10.1007/s11814-010-0493-z
16	崔青, 张长桥, 修建新, 等. 稠油沥青质胶质降粘机理的分子动力学模拟[J]. 山东大学学报(工学版), 2017, 47 (2): 123- 129.
	CUI Qing , ZHANG Changqiao , XIU Jianxin . Molecular dynamic simulation on the mechanism of viscosity reduction to asphaltene and resin in heavy oil[J]. Journal of Shandong University(Engineering Science), 2017, 47 (2): 123- 129.
17	石静, 吕凯, 苑世领. 支链烷基苯磺酸盐在油水界面的分子动力学模拟[J]. 山东大学学报(工学版), 2012, 42 (2): 77- 82.
	SHI Jing , LYU Kai , YUAN Shiling . Molecular dynamics simulation of alkyl benzene sulfonate at the oil-water interface[J]. Journal of Shandong University(Engineering Science), 2012, 42 (2): 77- 82.
18	SUN H . Compass: an abinitioforce-field optimized for condensed-phase applications overview with details on alkane and benzene compounds[J]. J Phys Chem B, 1998, 102 (38): 7338- 7364. doi: 10.1021/jp980939v
19	CHENG Dongcai , HUANG Zhixiong , YE Zhangji , et al. Study of the equilibrium swelling of poly(methyl methacrylate-co-n-butyl methacrylate) immersed in water via MD simulation[J]. Chemical Engineering Science, 2017, 173: 483- 492. doi: 10.1016/j.ces.2017.08.007
20	BERENDSEN H J C , GRIGERA J R , STRAATSMA T P . The missing term in effective pair potentials[J]. J Phys Chem, 1987, 91 (24): 6269- 6271. doi: 10.1021/j100308a038
21	EWALD P P . Dieberechnungoptischer und elektrostatischergitterpotentiale[J]. Ann Phys, 1921, 369 (3): 253- 287.
22	SMITH W . A replicated data molecular dynamics strategy for the parallel Ewaldsum[J]. Comput Phys Commun, 1991, 67 (3): 392- 406.
23	VERLET L . Computer "experiments" on classical fluids i: thermodynamical properties of lennard-jones molecules[J]. Phys Rev, 1967, 159 (98): 98- 104.
24	O'SULLIVAN C , BRAYJD . Selecting a suitable time step for discrete element simulations that use the central difference time integration scheme[J]. Engineering Computations, 2004, 21 (2/4): 278- 303.
25	EHSAN G , MATTIAS H , KARL K , et al. Atomistic simulation of the shape-memory effect in dry and water swollen poly[(rac-ladtide)-co-glycolide] and copolymer urethanes thereof[J]. Macromol Chem Phy, 2014, 215 (1): 65- 75. doi: 10.1002/macp.201300507
26	TUNG K L , LU K T . Effect of tacticity of PMMA on gas transport through membranes: MD and MC simulation studies[J]. Journal of Membrane Science, 2006, 272 (1-2): 37- 49. doi: 10.1016/j.memsci.2005.07.028
27	ALLEN M P , TILDESLEY D J . Computer simulation of liquids[M]. Oxford: Oxford University Press, 1989: 78.
28	FOX T G . Influence of diluent and of copolymer composition on the glass temperature of a polymer system[J]. Bull Am Phys Soc, 1956, 1: 123- 132.
29	SMITH L S A , SCHMITZ V . The effect of water on the glass transitiontemperature of poly(methyl methacrylate)[J]. Polymer, 1988, 29 (10): 1871- 1878. doi: 10.1016/0032-3861(88)90405-3
30	LEE S H . Molecular dynamics simulation study of the ionic mobility of OH^-using the OSS2 model[J]. Bull Korean ChemSoc, 2006, 27 (8): 1154- 1158. doi: 10.5012/bkcs.2006.27.8.1154
31	WU C F , XU W J . Atomistic simulation study of absorbed water influence on structure and properties of crosslinked epoxy resin[J]. Polymer, 2007, 48 (18): 5440- 5448. doi: 10.1016/j.polymer.2007.06.038
32	JHON M S , ANDRADE J D . Water and hydrogels[J]. J Biomed Mater Res, 1973, 7 (6): 509- 522. doi: 10.1002/(ISSN)1097-4636
33	SHINGO U , JUN I , AKIRA T . Molecular dynamic simulation of swollen membrane of perfluorinated ionomer[J]. J Phys Chem B, 2005, 109 (9): 4269- 4278. doi: 10.1021/jp046434o
34	SUN Delin , ZHOU Jian . Effect of water content on microstructures and oxygen permeation in PSiMA-IPN-PMPC hydrogel: a molecular simulation study[J]. Chemical Engineering Science, 2012, 78: 236- 245. doi: 10.1016/j.ces.2011.11.020
35	SMIT E , MULDER M H V , SMOLDERS C A , et al. Modelling of the diffusion of carbon dioxide in polyimide matrices by computer simulation[J]. J Membrane Sci, 1992, 73 (2/3): 247- 257.

多维度评价

Viewed

Full text

Abstract

Cited

Shared

Discussed

项目	30：70	40：60	50：50
相对分子质量	12 959.70	12 538.60	12 117.50
吸水率/%	26.31	27.12	27.37
水分子个数	257	260	253

MMA:n-BMA比率	T_g/K
	干态		溶胀态
	模拟计算	Fox方程计算	模拟计算
30：70	319.98	315.60	298.26
40：60	325.11	323.60	307.84
50：50	329.73	331.90	314.89

MMA:n-BMA比率	温度/K	自扩散系数/10^-5(cm²·s^-1)
MMA:n-BMA比率	温度/K	水	聚合物链段
	278	0.736	0.000 5
50：50	293	0.813	0.001 2
	308	1.226	0.002 8
	278	1.230	0.004 7
40：60	293	1.680	0.003 4
	308	2.447	0.008 9
	278	1.108	0.005 7
30：70	293	1.799	0.007 5
	308	2.574	0.012 5

含水量/%	水分子个数	比率/%			自扩散系数/10^-5(cm²·s^-1)
含水量/%	水分子个数	束缚水	弱束缚水	自由水	束缚水	弱束缚水	自由水
4.27	30	66.67	33.33	0.00	0.048	0.017	—
12.95	100	30.00	50.00	20.00	1.600	1.942	2.022
19.87	167	26.00	48.00	26.00	0.603	—	1.497
27.63	253	24.68	40.26	35.06	2.563	—	2.005
30.86	300	20.00	37.78	42.22	1.092	—	2.962

MMA:n-BMA比率	温度/K	自扩散系数/10^-6(cm²·s^-1)
	278	0.102
50：50	293	0.074
	308	0.190
	278	0.027
40：60	293	0.164
	308	0.196
	278	0.108
30：70	293	0.224
	308	0.313

防污剂在溶胀聚合物中扩散的模拟研究

Release of the antifoulant in equilibrium swollen polymer: molecular dynamics simulation

RichHTML

PDF (PC)

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 35

相关文章 3

多维度评价

本文评价

推荐阅读 10

[1]	马莹,张恒,苑世领. 分子模拟研究醇醚类表面活性剂耐盐机理[J]. 山东大学学报（理学版）, 2016, 51(7): 126-130.
[2]	潘龙强1,2,耿存亮1,慕宇光3,刘鑫4,胡毅5,潘景山4,周亚滨2,龚斌5,王禄山1*. 生物大分子的分子动力学模拟过程在百万亿次集群上的部署优化[J]. J4, 2012, 47(7): 14-19.
[3]	卢敏,罗飞,刘维清,魏望和 . ［111］晶向银纳米杆结构稳定性的分子动力学模拟[J]. J4, 2008, 43(1): 43-48 .