丁二酰亚胺无灰分散剂的绿色合成工艺研究
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摘要
无灰分散剂是润滑油的主要添加剂之一。它的作用是将油泥、漆膜和积炭的前体分散在油中，阻止其形成油泥、漆膜和积炭，延长换油期和内燃机的使用寿命。本文采用绿色工艺合成聚异丁烯丁二酰亚胺无灰分散剂，根除液氯污染源，真正做到了绿色环保。
本合成实验包括烃化过程和胺化过程两部分。(1)烃化过程：将聚异丁烯(PIB)与马来酸酐(MA)均匀混合，在氮气保护和一定温度(80～180℃)下，以过氧化苯甲酰(BPO)为引发剂，引发烃化反应3～15h，得到产物聚异丁烯丁二酸酐(PIBSA，简称烯酐)产品。实验中考察反应气氛、反应温度、反应时间、搅拌速率、引发剂用量及其加入方式、马来酸酐用量及其加入方式对烃化反应的影响，以确定反应的优化条件。结果发现，实验在N_2保护下进行，BPO／PIB质量比为0.035，MA／PIB摩尔比为1.3，反应温度为150℃，反应时间为12h，搅拌速率为250rpm，引发剂过氧化苯甲酰以丁酮为溶剂分六次，时间间隔为30分钟，均量地加入反应器时，烃化反应物聚异丁烯的转化率最高。(2)胺化过程：在40～80℃下将烃化产物烯酐PIBSA和一定量的二乙烯三胺(DETA)混合均匀，在一定温度(90～150℃)下，反应2～10h；抽真空，减压蒸馏脱水、过滤，得到聚异丁烯丁二酰亚胺无灰分散剂(TEPA)产品。实验中考察反应温度、反应时间、搅拌速率和二乙烯三胺用量及其加入方式对胺化反应的影响。当反应温度为140℃，反应时间为6h，搅拌速率为200rpm，PIBSA／DETA摩尔比为1.1，二乙烯三胺在低温50℃下，缓慢连续滴加到反应器中时，胺化产物聚异丁烯丁二酰亚胺无灰分散剂的产率最高。
通过烃化产物和胺化产物的红外光谱分析，并分别与其标准谱图对照比较，看出产物红外谱图与标准谱图相符，可以确认烃化产物和胺化产物即为聚异丁烯丁二酸酐和聚异丁烯丁二酰亚胺无灰分散剂。以油泥斑点分散试验法对合成产物聚异丁烯丁二酰亚胺无灰分散剂进行低温分散性能测试。结果表明，本实验合成获得的聚异丁烯丁二酰亚胺无灰分散剂产品具有低温分散性能。TEPA的油泥斑点分散值SDT随着反应温度的升高先有所增加，尔后开始下降，适宜的胺化反应温度为140℃；SDT基本不随二乙烯三胺用量的增加而变化，但当DETA／PIBSA
摩尔比大于1.3时，SDT开始下降，适宜的DETA／PIBSA摩尔比为1.1。
Ashless dispersant is one of the important additives of lubricating oil, and is to disperse the precursors of oil sludge, paint film and carboning in oil, which can prevent their formations and prolong the operating life of engine and the oil change period. In this paper a green process was applied to synthesize ashless dispersant of polyisobutylene succinimide (TEPA) without pollution source of liquid chlorine.
Synthesis process of ashless dispersant TEPA including alkylation and animation were studied in this paper. (1)Alkylation: Reactants of polyisobutylene (PIB) and maleic anhydride (MA) were firstly mixed uniformly and then were initiated to form polyisobutylene succinic anhydride (PIBSA) by dropping into benzoyl peroxide (BPO) in batches as initiator under the protection of N_2 and a reaction temperature (100 to 180℃). The effects of reaction atmosphere, reaction temperature and time, stirred speed, the contents and its adding ways of initiator and maleic anhydride were studied. Optimum reaction conditions were obtained as follows: under the protection of N_2, temperature of 150℃, reaction time of 12h, BPO/PIB mass ratio of 0.035, MA/PIB mole ratio of 1.3, stirred rate of 250rpm and dropping addition of BPO solution in butanone at 30min interval. Under these conditions, the highest conversion of PIB could be achieved. (2)Amination: Diethylenetriamine(DETA) was dropped into the the alkylation product (PIBSA) in batches under the protection of N_2 and temperature of 40℃ to 80℃. Amination reaction was carried out at temperature of 90℃ to 150℃ for 2h to 10h and then ashless dispersant of polyisobutylene succinimide (TEPA) would be obtained after dehydration with the operations of vacuum distillation and filtration. The effects of reaction temperature and time, stirred speed, the contents and its adding ways of diethylenetriamine were studied. Optimum amination conditions were determined as follows: PIBSA/DETA mole ratio of 1.1, reaction temperature of 140℃, amination time of 6h, amination stirred rate of 200rpm, and dropping addition of DETA at 50℃. Under these conditions, the highest yield of TEPA could be achieved.
Infra-red (IR) spectrometry was used to analyze the products of alkylation and
animation. IR analysis indicated that both of the results were accorded with their standards IR spectrum and that the products of alkylation and animation were polyisobutylene succinic anhydride and ashless dispersant TEPA. Low temperature dispersivity of ashless dispersant TEPA was analyzed by the sludge spot distribution test (SDT). The results showed that the ashless dispersant prepared had low temperature dispersivity. The SDT value of TEPA increased first and then declined with the rising of animation temperature, and the optimum reaction temperature was 140℃. SDT was constant and then decreased when DETA/PIBSA mole ratio was more than 1.3, and the optimum mole ratio of DETA/PIBSA was 1.1.
本合成实验包括烃化过程和胺化过程两部分。(1)烃化过程：将聚异丁烯(PIB)与马来酸酐(MA)均匀混合，在氮气保护和一定温度(80～180℃)下，以过氧化苯甲酰(BPO)为引发剂，引发烃化反应3～15h，得到产物聚异丁烯丁二酸酐(PIBSA，简称烯酐)产品。实验中考察反应气氛、反应温度、反应时间、搅拌速率、引发剂用量及其加入方式、马来酸酐用量及其加入方式对烃化反应的影响，以确定反应的优化条件。结果发现，实验在N_2保护下进行，BPO／PIB质量比为0.035，MA／PIB摩尔比为1.3，反应温度为150℃，反应时间为12h，搅拌速率为250rpm，引发剂过氧化苯甲酰以丁酮为溶剂分六次，时间间隔为30分钟，均量地加入反应器时，烃化反应物聚异丁烯的转化率最高。(2)胺化过程：在40～80℃下将烃化产物烯酐PIBSA和一定量的二乙烯三胺(DETA)混合均匀，在一定温度(90～150℃)下，反应2～10h；抽真空，减压蒸馏脱水、过滤，得到聚异丁烯丁二酰亚胺无灰分散剂(TEPA)产品。实验中考察反应温度、反应时间、搅拌速率和二乙烯三胺用量及其加入方式对胺化反应的影响。当反应温度为140℃，反应时间为6h，搅拌速率为200rpm，PIBSA／DETA摩尔比为1.1，二乙烯三胺在低温50℃下，缓慢连续滴加到反应器中时，胺化产物聚异丁烯丁二酰亚胺无灰分散剂的产率最高。
通过烃化产物和胺化产物的红外光谱分析，并分别与其标准谱图对照比较，看出产物红外谱图与标准谱图相符，可以确认烃化产物和胺化产物即为聚异丁烯丁二酸酐和聚异丁烯丁二酰亚胺无灰分散剂。以油泥斑点分散试验法对合成产物聚异丁烯丁二酰亚胺无灰分散剂进行低温分散性能测试。结果表明，本实验合成获得的聚异丁烯丁二酰亚胺无灰分散剂产品具有低温分散性能。TEPA的油泥斑点分散值SDT随着反应温度的升高先有所增加，尔后开始下降，适宜的胺化反应温度为140℃；SDT基本不随二乙烯三胺用量的增加而变化，但当DETA／PIBSA
摩尔比大于1.3时，SDT开始下降，适宜的DETA／PIBSA摩尔比为1.1。
Ashless dispersant is one of the important additives of lubricating oil, and is to disperse the precursors of oil sludge, paint film and carboning in oil, which can prevent their formations and prolong the operating life of engine and the oil change period. In this paper a green process was applied to synthesize ashless dispersant of polyisobutylene succinimide (TEPA) without pollution source of liquid chlorine.
Synthesis process of ashless dispersant TEPA including alkylation and animation were studied in this paper. (1)Alkylation: Reactants of polyisobutylene (PIB) and maleic anhydride (MA) were firstly mixed uniformly and then were initiated to form polyisobutylene succinic anhydride (PIBSA) by dropping into benzoyl peroxide (BPO) in batches as initiator under the protection of N_2 and a reaction temperature (100 to 180℃). The effects of reaction atmosphere, reaction temperature and time, stirred speed, the contents and its adding ways of initiator and maleic anhydride were studied. Optimum reaction conditions were obtained as follows: under the protection of N_2, temperature of 150℃, reaction time of 12h, BPO/PIB mass ratio of 0.035, MA/PIB mole ratio of 1.3, stirred rate of 250rpm and dropping addition of BPO solution in butanone at 30min interval. Under these conditions, the highest conversion of PIB could be achieved. (2)Amination: Diethylenetriamine(DETA) was dropped into the the alkylation product (PIBSA) in batches under the protection of N_2 and temperature of 40℃ to 80℃. Amination reaction was carried out at temperature of 90℃ to 150℃ for 2h to 10h and then ashless dispersant of polyisobutylene succinimide (TEPA) would be obtained after dehydration with the operations of vacuum distillation and filtration. The effects of reaction temperature and time, stirred speed, the contents and its adding ways of diethylenetriamine were studied. Optimum amination conditions were determined as follows: PIBSA/DETA mole ratio of 1.1, reaction temperature of 140℃, amination time of 6h, amination stirred rate of 200rpm, and dropping addition of DETA at 50℃. Under these conditions, the highest yield of TEPA could be achieved.
Infra-red (IR) spectrometry was used to analyze the products of alkylation and
animation. IR analysis indicated that both of the results were accorded with their standards IR spectrum and that the products of alkylation and animation were polyisobutylene succinic anhydride and ashless dispersant TEPA. Low temperature dispersivity of ashless dispersant TEPA was analyzed by the sludge spot distribution test (SDT). The results showed that the ashless dispersant prepared had low temperature dispersivity. The SDT value of TEPA increased first and then declined with the rising of animation temperature, and the optimum reaction temperature was 140℃. SDT was constant and then decreased when DETA/PIBSA mole ratio was more than 1.3, and the optimum mole ratio of DETA/PIBSA was 1.1.
引文
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[2] 黄文轩．润滑剂添加剂应用指南[M]．北京：中国石化出版社，2003年2月
[3] 梁治奇．润滑油生产及应用[M]．北京：化学工业出版社，2001年5月
[4] 张景河．现代润滑油与燃料添加剂[M]．北京：中国石化出版社，1991年12月
[5] Tim Cornitius. Ashless Additive Trend[J]. Lubricant World, 1998(9):30～33
[6] 颜志光．润滑材料与润滑技术[M]．北京：中国石化出版社，2001年6月
[7] 曼格，德雷泽尔．润滑剂与润滑[M]．北京：化学工业出版社，2003年2月
[8] 克拉曼．润滑剂及其有关产品[M]．北京：烃加工出版社，1990年7月
[9] 熊崇翔．单丁二酰亚胺无灰分散剂的制备方法[P]．CN：1157754A．1997
[10] 陈勇．聚异丁烯丁二酰亚胺无灰分散剂的生产、性能与应用[J]．化工科技市场，2000，23(11)：5～7
[11] Wisotsky, et al. Process for producing oil-soluble derivatives of unsaturated C_4～C_(10)[P]. US:4235786.1980
[12] 董浚修．润滑原理及润滑油[M]．北京：中国石化出版社，1998年9月
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