Modeling of butadiene emulsion polymerization process for stereoisomerization

doi:10.11949/0438-1157.20241253

Abstract

Abstract:

The stereoisomer ratios affect the product properties of emulsion polymerized butadiene. The emulsion polymerization process of butadiene was studied in a reaction calorimeter with potassium persulfate as initiator and sodium abietic acid/potassium laurate/sodium alkyl naphthalene sulfonate as emulsifier at reaction temperature of 65—75℃ and initiator feeding ratio (the mass of initiator added to every 100 units of mass of monomer) of 0.35%—1.38%. The rigorous process mechanism model for emulsion polymerization by free radicals is established, and the parameters were adjusted using the conversion data. The chain growth activation energies of 1,4-cis, 1,4-trans and 1,2-vinyl were 39.10, 38.50 and 13.20 kJ/mol, respectively. The pre-exponential factors were 28.37, 23.90 and 11.70 L/(mol·s), respectively, and the model could predict the stereoisomer ratios within the error range. The simulation results show that the stereoisome changes with the reaction time, and the significant change of the stereoisomer ratio occurs at the beginning of the reaction. After the conversion rate reaches 20%, the three stereoisomer ratios tend to be stable. The proportion of 1,4-cis and 1,4-trans increased, and the proportion of 1,2-vinyl decreased with increasing temperature. The stereoisomer ratios are insensitive to initiator feeding ratio.

Key words: stereoisomerization, polybutadiene, emulsions, radical, kinetic modeling

摘要：

立体异构比例影响乳聚丁二烯（polybutadiene latex，PBL）的产品性能。在反应量热装置中以过硫酸钾作为引发剂，以松香酸钠/月桂酸钾/烷基萘磺酸钠作为乳化剂，研究了在反应温度为65~75℃、引发剂投料比（对每100单位质量单体添加引发剂的质量）为0.35%~1.38%下的丁二烯乳液聚合过程；建立了乳液法自由基聚合的严格过程机理模型，运用转化率数据进行参数整定，1, 4-顺式（1, 4-cis）、1, 4-反式（1, 4-trans）和1, 2-乙烯基（1, 2-vinyl）三种立构的链增长活化能分别为39.10、38.50、13.20 kJ/mol，指前因子分别为28.37、23.90、11.70 L/(mol·s)，模型可以在误差范围内预测立体异构比例。模拟结果表明：立构比例随反应时间变化，立构比例的大幅变化发生在反应初期，在转化率达到20%后，三种立构比例均趋于稳定；温度升高，1, 4-cis和1, 4-trans比例增大，1, 2-vinyl比例减小；立构比例对引发剂投料比不敏感。

关键词: 立体异构, 聚丁二烯, 乳液, 自由基, 动力学模型

CLC Number:

Yuxuan WU, Cheng CHANG, Xueping GU, Lianfang FENG, Cailiang ZHANG. Modeling of butadiene emulsion polymerization process for stereoisomerization[J]. CIESC Journal, 2025, 76(2): 879-887.

吴雨轩, 常诚, 顾雪萍, 冯连芳, 张才亮. 面向立体异构的丁二烯乳液聚合过程模型化[J]. 化工学报, 2025, 76(2): 879-887.

Figures/Tables 16

Fig.1 Three stereoisomers of polybutadiene

Fig.2 Reaction calorimetric apparatus1,2—liquid metering pump; 3—316Ti jacketed reactor; 4—electric heating rod and its power sensor

Table 1 Design of experimental conditions

Alias	Reaction temperature/℃	Feeding ratio/%
temp-65	65	0.69
temp-70	70
temp-75	75
init-0.35	70	0.35
init-0.69		0.69
init-1.38		1.38

Fig.3 1H NMR spectrum of temp-70

Fig.4 Chain growth reaction of three stereoisomers of polybutadiene

Table 2 The stereoisomeric framework for emulsion polymerization is considered

Item		Reaction	Reaction rate
init-dec		I $\overset{k_{i}}{\to}$ nM·	$r_{i} = 2 f k_{i} [I]$
1,4-cis	propagation	P _m_,_n_,_l·+ M_c $\overset{k_{p, c}}{\to}$ P _m_+1,_n_,_l·	$r_{p, c} = k_{p, c} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_c $\overset{k_{t r M, c}}{\to}$ D _m_,_n_,_l + M_c·	$r_{t r M, c} = k_{t r M, c} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, c}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, c} = k_{t r C T A, c} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, c}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, c} = 2 k_{t d, c} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, c}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, c} = 2 k_{t c, c} {[M \cdot]}_{p}^{2}$
1,4-trans	propagation	P _m_,_n_,_l·+ M_t $\overset{k_{p, t}}{\to}$ P _m_,_n_+1,_l·	$r_{p, t} = k_{p, t} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_t $\overset{k_{t r M, t}}{\to}$ D _m_,_n_,_l + M_t·	$r_{t r M, t} = k_{t r M, t} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, t}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, t} = k_{t r C T A, t} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, t}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, t} = 2 k_{t d, t} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, t}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, t} = 2 k_{t c, t} {[M \cdot]}_{p}^{2}$
1,2-vinyl	propagation	P _m_,_n_,_l·+ M_v $\overset{k_{p, v}}{\to}$ P _m_,_n_,_l₊₁·	$r_{p, v} = k_{p, v} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_v $\overset{k_{t r M, v}}{\to}$ D _m_,_n_,_l + M_v·	$r_{t r M, v} = k_{t r M, v} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, v}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, v} = k_{t r C T A, v} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, v}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, v} = 2 k_{t d, v} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, v}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, v} = 2 k_{t c, v} {[M \cdot]}_{p}^{2}$

Table 2 The stereoisomeric framework for emulsion polymerization is considered

Item		Reaction	Reaction rate
init-dec		I $\overset{k_{i}}{\to}$ nM·	$r_{i} = 2 f k_{i} [I]$
1,4-cis	propagation	P _m_,_n_,_l·+ M_c $\overset{k_{p, c}}{\to}$ P _m_+1,_n_,_l·	$r_{p, c} = k_{p, c} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_c $\overset{k_{t r M, c}}{\to}$ D _m_,_n_,_l + M_c·	$r_{t r M, c} = k_{t r M, c} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, c}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, c} = k_{t r C T A, c} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, c}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, c} = 2 k_{t d, c} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, c}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, c} = 2 k_{t c, c} {[M \cdot]}_{p}^{2}$
1,4-trans	propagation	P _m_,_n_,_l·+ M_t $\overset{k_{p, t}}{\to}$ P _m_,_n_+1,_l·	$r_{p, t} = k_{p, t} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_t $\overset{k_{t r M, t}}{\to}$ D _m_,_n_,_l + M_t·	$r_{t r M, t} = k_{t r M, t} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, t}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, t} = k_{t r C T A, t} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, t}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, t} = 2 k_{t d, t} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, t}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, t} = 2 k_{t c, t} {[M \cdot]}_{p}^{2}$
1,2-vinyl	propagation	P _m_,_n_,_l·+ M_v $\overset{k_{p, v}}{\to}$ P _m_,_n_,_l₊₁·	$r_{p, v} = k_{p, v} {[M]}_{p} {[M \cdot]}_{p}$
	chat-mon	P _m_,_n_,_l· + M_v $\overset{k_{t r M, v}}{\to}$ D _m_,_n_,_l + M_v·	$r_{t r M, v} = k_{t r M, v} {[M]}_{p} {[M \cdot]}_{p}$
	chat-agent	P _m_,_n_,_l· + CTA $\overset{k_{t r C T A, v}}{\to}$ D _m_,_n_,_l + M·	$r_{t r C T A, v} = k_{t r C T A, v} {[C T A]}_{p} {[M \cdot]}_{p}$
	term-dis	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t d, v}}{\to}$ D _m_1,_n_1,_l₁ + D _m_2,_n_2,_l₂	$r_{t d, v} = 2 k_{t d, v} {[M \cdot]}_{p}^{2}$
	term-comb	P _m_1,_n_1,_l₁· + P _m_2,_n_2,_l₂· $\overset{k_{t c, v}}{\to}$ D _m₁₊_m_2,_n₁₊_n_2,_l₁₊_l₂	$r_{t c, v} = 2 k_{t c, v} {[M \cdot]}_{p}^{2}$

Table 3 Initial values of dynamic parameters

Item	Preexponential factor^①	Activation energy/(kJ/mol)
init-dec	2.54×10¹⁶	139.50
propagation	1.20×10⁸	38.93
chat-mon	8.80×10⁶	54.39
chat-agent	6.62×10⁶	52.20
term	2.47×10¹⁰	9.97

Table 4 Dynamic parameters of three stereoisomers

Item		Preexponential factor^①	Activation energy/(kJ/mol)	T_ref/K
init-dec		1.40×10^-5	139.50	343.15
1,4-cis	propagation	28.37	39.10	343.15
	chat-mon	4.07×10^-2	42.24	343.15
	chat-agent	25.80	41.31	343.15
	term-dis	2.02×10⁷	9.90	343.15
	term-comb	2.02×10⁷	9.90	343.15
1,4-trans	propagation	23.90	38.50	343.15
	chat-mon	4.07×10^-2	42.24	343.15
	chat-agent	25.80	41.31	343.15
	term-dis	2.02×10⁷	9.90	343.15
	term-comb	2.02×10⁷	9.90	343.15
1,2-vinyl	propagation	11.70	13.20	343.15
	chat-mon	4.07×10^-2	42.24	343.15
	chat-agent	25.80	41.31	343.15
	term-dis	2.02×10⁷	9.90	343.15
	term-comb	2.02×10⁷	9.90	343.15

Fig.5 Simulation and experimental results of conversion curves at different reaction temperatures

Fig.6 Simulation and experimental results of conversion curves at different initiator feeding ratios

Table 5 Simulation results and 1H NMR results of end-point stereoisomer ratios

Alias	Stereoisomer ratios/%	Simulation results/%	¹H NMR results/%	Relative error/%
temp-65	1,4-cis	42.9	42.8	0.23
	1,4-trans	36.9	35.0	5.43
	1,2-vinyl	20.3	22.2	8.56
temp-70	1,4-cis	44.3	44.7	0.89
	1,4-trans	37.4	38.4	2.60
	1,2-vinyl	18.3	16.9	8.28
temp-75	1,4-cis	45.5	44.0	3.41
	1,4-trans	38.2	39.5	3.29
	1,2-vinyl	16.3	16.5	1.21
init-0.35	1,4-cis	44.5	37.5	5.20
	1,4-trans	37.1	43.5	8.40
	1,2-vinyl	18.4	18.9	6.98
init-0.69	1,4-cis	44.3	44.7	0.89
	1,4-trans	37.4	38.4	2.60
	1,2-vinyl	18.3	16.9	8.28
init-1.38	1,4-cis	44.3	42.1	5.23
	1,4-trans	37.4	40.2	6.97
	1,2-vinyl	18.3	17.8	2.81

Fig.7 Simulation results of stereoisomer ratio curves at different reaction temperatures

Fig.8 Simulation results of stereoisomer ratio curves at different initiator feeding ratios

Fig.9 Effect of reaction temperature on stereoisomer ratios and monomer conversion

Fig.10 Effect of initiator feeding ratio on stereoisomer ratios and monomer conversion

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