Monte Carlo simulation of styrene-acrylonitrile single chain

doi:10.16085/j.issn.1000-6613.2023-1889

Abstract

Abstract:

The composition and distribution of polymer chains are of paramount importance for the performance of polymers. To address this, this paper, based on a monomer formulation from a certain company, firstly established a binary copolymer chain growth model. Employing the Monte Carlo method, we simulated the chain growth process of styrene-acrylonitrile copolymer single chains and analyzed how the monomer ratio affected the conversion rate and acrylonitrile binding ratio. Additionally, we investigated the impact of staged feedstock addition on product structure uniformity. The results reveal that, when the conversion rate exceeded 91%, the variation in acrylonitrile binding rate exceeded 0.5%, leading to an uneven distribution of the copolymer. Within the simulately studied range, a lower acrylonitrile content in the feedstock (greater than 25%) results in a more uniform copolymer product, widening the adjustable conversion rate range. When the acrylonitrile content in the feedstock ranged from 27%—35% and the conversion rate exceeded 85.0%, the instantaneous binding rate of acrylonitrile fluctuated within a range of only ±0.5%, and the average binding rate of acrylonitrile exhibited variations of less than 1%. Furthermore, a staged feedstock approach proved effective in enhancing the sequence uniformity of the copolymer. When the monomer ratio shifted from 67/33 with a conversion rate of 91% to 98%, the instantaneous acrylonitrile binding rate fluctuated by less than ±0.5%, and the average binding rate of acrylonitrile exhibited variations of less than 1%. These findings provided a foundational dataset and theoretical guidance for similar system studies and the stable production of industrial products.

Key words: polymer polyether polyols, Monte Carlo method, monomer ratio, binary copolymerization, single-chain simulation

摘要：

聚合物链组成和分布对聚合物的性能具有十分重要的意义。基于此，本文参考某企业的单体配方，首先建立了二元共聚链增长模型，并采用Monte Carlo法对苯乙烯-丙烯腈共聚单链的链增长过程进行了模拟，分析对比了单体比对转化率及丙烯腈结合率的影响，考察了分批加料对链结构均匀性的影响。结果表明：当转化率高于91%时，丙烯腈结合率的变化率大于0.5%，造成共聚物分布不均；在考察的单体比范围内，原料中丙烯腈含量越低（大于25%），展现出来的共聚产物越均匀，可调节的转化率范围就越宽；当原料中丙烯腈为27%~35%，转化率在85.0%以上时，丙烯腈瞬时结合率的变化率仅在±0.5%的范围内波动，且丙烯腈平均结合率的变化小于1%；分批进料能有效提高共聚物的链结构均匀性，当单体比为67/33的转化率由91%提升至98%时，丙烯腈瞬时结合率的变化率小于±0.5%，且丙烯腈平均结合率的变化小于1%。上述研究结果为其他类似体系研究及工业生产稳定产品提供了一定的数据基础和理论指导。

关键词: 聚合物多元醇, Monte Carlo法, 单体比, 二元共聚, 单链模拟

CLC Number:

TQ316

XU Yanhong, CHEN Yu, YUAN Xiangqian, LIU Jichang, ZHAO Jigang. Monte Carlo simulation of styrene-acrylonitrile single chain[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6068-6076.

徐燕红, 陈钰, 袁向前, 刘纪昌, 赵基钢. 基于Monte Carlo法的苯乙烯-丙烯腈单链模拟[J]. 化工进展, 2024, 43(11): 6068-6076.

Figures/Tables 13

原料中丙烯腈质量分数/%	F₂/%			F₂的差值Δ/%
原料中丙烯腈质量分数/%	转化率 5% (C₅)	转化率 65% (C₆₅)	转化率 95% (C₉₅)	Δ₁(C₆₅-C₅)	Δ₂(C₉₅-C₆₅)
45	31.8	33.2	100.0	1.4	66.8
40	30.9	32.4	99.2	1.5	66.8
35	29.9	31.1	74.4	1.2	43.3
33	29.7	31.1	47.8	1.4	16.7
31	29.9	28.7	32.1	-0.4	3.4
30	29.6	29.1	31.4	-0.5	1.3
27	28.1	26.9	25.4	-1.2	-1.5
25	27.3	26.0	18.0	-1.3	-8.0

原料中丙烯腈质量分数/%	开始突变时的C/%	达到峰值时的C/%	达到峰值时的 $d F 2 d C$ /%
45	69	85	4.5
40	79	91	6.2
35	87	95	16.8
33	91	96	22.1
31	95	98	33.1
30	95.5	99	52.7
27	96.5	100	-29.9
25	91	98.5	-5.7

原料中丙烯腈质量分数/%	开始突变时的C/%	达到峰值时的C/%	达到峰值时的 $d F 2 d C$ /%
45	69	85	4.5
40	79	91	6.2
35	87	95	16.8
33	91	96	22.1
31	95	98	33.1
30	95.5	99	52.7
27	96.5	100	-29.9
25	91	98.5	-5.7

原料中丙烯腈质量分数/%	转化率为 3.5%时的f₂/%	f₂变化 1%后/%	f₂变化1%时的转化率/%	C差值Δ/%
45	31.2	32.2	69.4	65.9
40	30.5	31.5	77.0	73.5
35	29.6	30.6	87.7	84.2
33	29.2	30.2	94.0	90.5
31	28.6	29.6	97.4	93.9
30	28.3	29.3	98.9	95.4
27	27.5	26.5	100.0	96.5
25	26.9	25.9	93.8	90.3

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