CN102260489A - 一种树枝状梳形聚合物增稠剂及其制备和应用 - Google Patents
一种树枝状梳形聚合物增稠剂及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种树枝状梳形聚合物增稠剂及其制备和应用；它是单体(A)和单体(B)的共聚物，单体(A)为一种或多种水溶性不饱和带烯链的物质，单体(B)是至少一种通式结构如下的物质：通式结构中R1、R2选择H或C1～C12烷基；R3、R4、R5选择H或C1～C8烷基、C1～C8烷基芳基、C1～C8烷基醚或C1～C8烷基酯；A选择COO-或OH；单体(A)的含量占单体(A)和单体(B)总质量的70～99.99％，单体(B)的含量占单体(A)和单体(B)总质量的0.01～30％；粘度比相近分子量普通聚丙烯酰胺高30％，用做油田渗透率小于400mD油藏聚合物驱。
Description
技术领域
本发明涉及一种树枝状梳形聚合物增稠剂及其制备和应用。
背景技术
聚丙烯酰胺抗盐性能差，必须使用淡水配制，才能得到经济的粘度，聚合物溶液的粘度也较稳定。为此，解决聚丙烯酰胺的抗盐问题就成为世界油田化学领域的研究热点之一。
中国发明专利(CN 011367989)的一种梳形抗盐聚合物增稠剂(梳形聚合物)，已在油田一类油藏得到大量应用，用污水直接配制且在污水中的增粘性能比聚丙烯酰胺提高了50％以上，增油降水效果非常显著，成为油田一类油藏(渗透性较好)三次采油用新一代驱油剂，但这种梳形抗盐聚合物工业品的分子量比聚丙烯酰胺大，溶解速度比聚丙烯酰胺慢，在油田二类油藏(渗透性较一类油藏差)应用时，注入性能存在一些问题。油田二类油藏开展三次采油是油田下一步提高采收率的重点，由于油田二类油藏的渗透率比一类油藏低，需采用分子量较低、抗盐性能好、溶解速度与聚丙烯酰胺一致的新型抗盐聚合物。
针对油田二类油藏三次采油的需求，我们发展了梳形抗盐聚合物增稠剂，研制成功一种辫状梳形抗盐聚合物增稠剂，并分别申请了美国发明专利(US 7304116)和中国发明专利(CN 2005100752911)，该聚合物在分子量较低的情况下，抗盐性能好，但由于在中性水中溶解速度较慢，必须在一定碱性条件下的溶解速度才与聚丙烯酰胺一致，因此，辫状梳形抗盐聚合物增稠剂用于油田二类油藏复合驱的效果很好，而用于油田二类油藏聚合物驱的新型抗盐聚合物还需攻关研究。
发明内容
本发明的目的是解决较低分子量聚合物的抗盐问题，提供一种分子量比梳形抗盐聚合物低，具有良好水溶性、增稠水介质能力强，聚合物分子在水溶液中呈现树枝状梳形结构，且抗盐性能优良，适用于油田二类油藏聚合物驱的共聚物增稠剂，使油田可以采用产出水配制聚合物驱用聚合物，并且聚合物溶液的粘度比相近分子量普通聚丙烯酰胺高30％以上，从而提高二类油藏聚合物驱的经济效益和推广应用领域。
本发明的具体内容为：
一种树枝状梳形聚合物增稠剂，它是由单体(A)和单体(B)共聚而成的共聚物，单体(A)为一种或多种水溶性不饱和带烯链的单体，该单体可以是丙烯酰胺，乙烯基吡咯烷酮类，2-丙烯酰胺基-2-甲基丙磺酸类，丙烯酸类中的一种或多种；单体(B)是至少一种通式结构为：
的单体，通式中：R1、R2可以相同，也可以不相同，可选H或C1～C12烷基；R3、R4、R5可以相同，也可以不相同，可选H或C1～C8烷基、C1～C8烷基芳基、C1～C8烷基醚或C1～C8烷基酯；A可选COO-或OH。R1、R2的筛选主要影响共聚物溶液的弹性，随碳数的增加，共聚物溶液的弹性增大；R3、R4、R5的筛选主要影响共聚物溶液的抗盐性能，随碳数的增加，共聚物溶液的抗盐能力增强。
单体(B)的制备是将30～60％羟基酸或多元醇，溶于乙醇中再加入6～12％二卤代烯，加热回流并滴加40～50％苛性钠溶液至中性，蒸馏除去乙醇和水而得。羟基酸可选羟基戊二酸、二羟基马来酸、半乳糖二酸、苹果酸、柠檬酸、亚酒石酸等或上述化合物的混合物。多元醇可选甘油、丁三醇、戊三醇、己三醇、庚三醇、辛三醇、异戊四醇、丁四醇等或上述化合物的混合物。二卤代烯可选二氯乙烯、二氯丙烯、二氯丁烯、二溴乙烯、二溴丙烯、二溴丁烯等或上述化合物的混合物。
本发明的树枝状梳形聚合物增稠剂中的单体(A)含量占单体(A)和单体(B)总质量百分比的70～99.99％，优选方案为90～99.9％，单体(B)的含量占单体(A)和单体(B)总质量百分比的0.01～30％，优选方案为0.1～10％，聚合体系中单体与水的质量浓度为10～50％，优选方案为15～40％。
本发明的树枝状梳形聚合物增稠剂中所用的引发剂为公开文献采用的引发剂。如过硫酸钾、过硫酸铵、过硫酸钠-亚硫酸钾、过硫酸铵-亚硫酸氢钠、过硫酸铵-雕白粉、过硫酸钾-雕白粉、偶氮二异丁腈、过硫酸铵-雕白粉-偶氮二异丁腈、过硫酸铵-亚硫酸氢钠-偶氮二异丁腈、过硫酸铵-雕白粉-偶氮二异丁腈。
本发明的树枝状梳形聚合物增稠剂中所用的聚合方法为公开文献采用的溶液聚合、乳液聚合和悬浮聚合方法，聚合条件为通氮气脱氧30分钟，加入0.15～0.2％引发剂，40～60℃下恒温6～14小时，得到粘弹性水凝胶产物。需要时可由普通技术如丙酮沉淀、捏合机、干燥机等干燥而得到固态产品。
本发明单体(B)的特点是与不饱和碳相连着二个含有两个离子基团或极性基团的侧链，且离子基团或极性基团位于侧链的尾部，因此本发明单体(B)是水溶性的，可与单体(A)溶液均相混合，易于共聚出高分子量聚合物，合成出的共聚物能完全溶于水介质。单体(B)的制备是容易，将30～60％羟基酸或多元醇，溶于乙醇中再加入6～12％二卤代烯，加热回流并滴加40～50％苛性钠溶液至中性，蒸馏除去乙醇和水而得本发明单体(B)。
本发明的树枝状梳形聚合物的无机盐含量最多占30％，Ca2 +、Mg2+多价阳离子最多占2％介质中，温度在室温至90℃范围内，水介质的粘度可得到增加，并在较长时间中具有良好的粘度保留率，增稠剂的用量注入水介质质量的0.05-1％。
由于采用了上述单体(A)和单体(B)共聚而得到的树枝状梳形聚合物增稠剂的技术方案，使得本发明聚合物具有极好的水溶性，得到抗盐性能优良的水溶性树枝状梳形聚合物增稠剂。
本发明的树枝状梳形聚合物分子量大大低于梳形抗盐聚合物，解决较低分子量聚合物的抗盐问题，可以采用产出水配制聚合物驱用聚合物，并且聚合物溶液的粘度比相近分子量普通聚丙烯酰胺高30％以上，可用于油田二类油藏(渗透率小于400mD)聚合物驱，提高二类油藏聚合物驱的经济效益和推广应用领域。本发明的树枝状梳形聚合物还可用于油田堵水调剖、深部调驱和深部液流转向。
附图说明
图1聚合物在二类油藏中的驱油效率对比
具体实施方式
实施例中，除另有说明外，各等份和百分比均以质量为单位。
单体(B)的制备：
实施例1
将30～60％羟基酸或多元醇，溶于乙醇中再加入6～12％二卤代烯，加热回流并滴加40～50％苛性钠溶液至中性，蒸馏除去乙醇和水即得本发明单体(B)。
树枝状梳形聚合物增稠剂的制备：
实施例2
在含15％的丙烯酰胺，5％单体(B)的水溶液中，单体(B)的结构式为：
通氮气脱氧30分钟，加入0.2％偶氮二异于腈引发剂，60℃下恒温14小时，得到粘弹性水凝胶产物。产物在捏合机中，90℃下干燥8小时，得到固态产品。
实施例3
在含12％丙烯酸胺，6％丙烯酸，2％单体(B)的水溶液中，单体(B)的结构式为：
加氢氧化钠调节溶液的pH＝8，通氮气脱氧30分钟，加入0.1％过硫酸铵和0.1％雕白粉，于40℃下恒温8小时，得到粘弹性水凝胶产物。产物经造粒机造粒，在回转干燥机中，90℃下干燥3小时，得到固态产品。
实施例4
在含7％丙烯酰胺，10％乙烯基吡咯烷酮，3％单体(B)的水溶液中，单体(B)的结构式为：
通氮气脱氧30分钟，加入0.15％偶氮二异丁腈引发剂，于60℃下恒温14小时，得到粘弹性水凝胶产物。
实施例5
在含15％丙烯酰胺，8％2-丙烯酰胺基-2-甲基丙磺酸，4％单体(B)的水溶液中，单体(B)的结构式为：
用碳酸钠调节溶液的pH至9，通氮气脱氧30分钟，0.1％过硫酸铵和0.1％亚硫酸氢钠，于60℃下恒温6小时，得到粘弹性水凝胶产物。
实施例6
将实施例3得到的固体产品与普通聚丙烯酰胺在相同条件下进行性能比较测试，从表1的测试结果可以看到，树枝状梳形聚合物的分子量与普通聚丙烯酰胺相近，但无论在大庆清水，还是在大庆污水中的粘度均比普通聚丙烯酰胺的高，特别是在大庆污水中的粘度比普通聚丙烯酰胺的提高了50％。从图1的岩心试验表明，在二类油藏进行聚合物驱，相同条件下，采用树枝状梳形聚合物可比普通聚丙烯酰胺提高采收率多0.91个百分点。说明树枝状梳形聚合物分子量较低、抗盐增稠性能较好，可以适应油田二类油藏聚合物驱的要求，也说明树枝状梳形聚合物的分子设计是成功的。
表1树枝状梳形聚合物的基本性能
注：大庆清水总矿化度1000mg/L，其中Ca2++Mg2+为15mg/L；大庆污水总矿化度4000mg/L，其中Ca2++Mg2+为60mg/L。
Claims (6)
1.一种树枝状梳形聚合物增稠剂，它是由单体(A)和单体(B)共聚而成的共聚物，其特征在于：单体(A)为一种或多种水溶性不饱和带烯链的单体，单体(B)是至少一种通式结构为：
单体(A)的含量占单体(A)和单体(B)总质量的70～99.99％，
单体(B)的含量占单体(A)和单体(B)总质量的0.01～30％。
2.根据权利要求1所述的树枝状梳形聚合物增稠剂，其特征在于：单体(A)是丙烯酰胺、乙烯基吡咯烷酮类、2-丙烯酰胺基-2-甲基丙磺酸类、丙烯酸类中的一种或多种。
3.一种权利要求1所述的树枝状梳形聚合物增稠剂的制备方法，其特征在于：(1)单体(B)的制备是将30～60％羟基酸或多元醇，溶于乙醇中再加入6～12％二卤代烯，加热回流并滴加40～50％苛性钠溶液至中性，蒸馏除去乙醇和水而得；
(2)单体(A)和单体(B)根据权利要求1质量比配制，聚合体系中单体(A)和单体(B)与水的质量浓度为10～50％；
(3)通氮气脱氧30分钟，加入0.15～0.2％引发剂，40～60℃下恒温6～14小时，得到粘弹性水凝胶产物。
4.根据权利要求3所述的树枝状梳形聚合物增稠剂的制备方法，其特征在于：羟基酸选自羟基戊二酸、二羟基马来酸、半乳糖二酸、苹果酸、柠檬酸、亚酒石酸等或上述化合物的混合物。多元醇可选甘油、丁三醇、戊三醇、己三醇、庚三醇、辛三醇、异戊四醇、丁四醇等或上述化合物的混合物。
5.根据权利要求3所述的树枝状梳形聚合物增稠剂的制备方法，其特征在于：二卤代烯选自二氯乙烯、二氯丙烯、二氯丁烯、二溴乙烯、二溴丙烯、二溴丁烯或上述化合物的混合物。
6.一种权利要求1所述的树枝状梳形聚合物增稠剂的应用，其特征在于：此增稠剂用做油田渗透率小于400mD油藏的聚合物驱，用量为注入水介质质量的0.05-1％。
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| CN102603966A (zh) * | 2012-03-12 | 2012-07-25 | 里群 | 用于油田调驱的交联聚合物微球及其制备方法 |
| CN104250380A (zh) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | 一种树枝状聚合物和树枝状聚合物单体及其制备方法和应用 |
| CN105154245A (zh) * | 2015-08-05 | 2015-12-16 | 张宏格 | 一种梳形聚醚组合物及其制造方法和应用该梳形聚醚组合物的液体洗涤剂 |
| CN104250358B (zh) * | 2013-06-25 | 2016-08-17 | 中国石油化工股份有限公司 | 一种超支化共聚物及其制备方法和应用 |
| US9475894B2 (en) | 2013-06-25 | 2016-10-25 | China Petroleum & Chemical Corporation | Dendritic polymer, dendritic polymer monomer, and hyperbranched copolymer |
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| CN1876751A (zh) * | 2005-06-10 | 2006-12-13 | 中国石油天然气股份有限公司 | 一种辫状梳形抗盐聚合物增稠剂 |
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| CN102603966A (zh) * | 2012-03-12 | 2012-07-25 | 里群 | 用于油田调驱的交联聚合物微球及其制备方法 |
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| CN104250380A (zh) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | 一种树枝状聚合物和树枝状聚合物单体及其制备方法和应用 |
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| CN105154245A (zh) * | 2015-08-05 | 2015-12-16 | 张宏格 | 一种梳形聚醚组合物及其制造方法和应用该梳形聚醚组合物的液体洗涤剂 |
| CN116655858A (zh) * | 2023-05-29 | 2023-08-29 | 大庆玮德化工有限公司 | 一种油田二元复合驱聚合物及其制备方法和应用 |
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