CN1648647A - 聚异丁烯分子量的测定方法 - Google Patents
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Abstract
一种聚异丁烯分子量的测定方法,包括(1)将聚异丁烯样品溶于含有内标物的氘代试剂中制成聚异丁烯溶液,再加入驰豫试剂制得待测样品,(2)用13C-核磁共振波谱法对待测样品进行测定,得到碳谱谱图,(3)通过碳谱图中烷碳区的峰面积与烯碳区峰面积比值或亚甲基区的峰面积与α亚甲基的峰面积比值求得聚异丁烯的聚合度,再由聚合度计算得到分子量。该法测试时不用配制标样即可准确测定聚异丁烯的数均分子量。
Description
技术领域
本发明为一种聚异丁烯分子量的测定方法,具体地说,是一种用核磁共振法测定聚异丁烯分子量的方法。
背景技术
在润滑油或润滑脂中,通常需要加入抗氧剂以防止油品在使用过程中发生氧化变质。一种常用的性能良好的抗氧剂是聚异丁烯丁二酰亚胺类化合物,它是由聚异丁烯、丁二酰和多烯多胺反应生成的缩聚物,其中聚异丁烯基来自活性或非活性的低聚异丁烯产物。
聚异丁烯分子量是研制聚异丁烯产品的重要测定参数,其测定方法有多种。目前,用于测定聚异丁烯各种平均分子量及分子量分布的方法为凝胶渗透色谱法(GPC)。另外,蒸气压渗透法(VPO)也可有效测定聚异丁烯的数均分子量。VPO和GPC法都需要已知分子量的标准样品,并绘制相应的标准曲线。在测试时需将样品溶于毒性较大的苯溶剂中,且用样量较大,一般需要 克的样品。上述方法由于需要建立标准曲线,样品的测试值会受到建立标准曲线时所取样品数值的限制,对于超出标样分子量范围的样品测定不准。
发明内容
本发明的目的是提供一种采用核磁共振法测定聚异丁烯分子量的方法,该法不需标样即可有效测定聚异丁烯的分子量。
本发明提供的聚异丁烯分子量的测定方法,包括如下步骤:
(1)将聚异丁烯样品溶于含有内标物的氘代试剂中制成聚异丁烯溶液,再加入驰豫试剂制得待测样品,
(2)用13C-核磁共振波谱法对待测样品进行测定,得到碳谱谱图,
(3)通过碳谱图中烷碳区的峰面积与烯碳区峰面积比值或亚甲基区的峰面积与α亚甲基的峰面积比值求得聚异丁烯的聚合度,再由聚合度计算得到分子量。
本发明采用13C-核磁共振波谱法测定聚异丁烯的数均分子量,通过比较谱图中烷基碳原子数与具有“端基碳”特性的碳原子数的比值确定出聚异丁烯样品的平均分子量,因此,不需配制标准样品即可直接测定聚异丁烯的数均分子量。
附图说明
图1为聚异丁烯的13C-核磁共振谱图。
图2为聚异丁烯的13C-核磁共振谱图中烷碳区谱图。
具体实施方式
本发明采用13C-核磁共振法测定聚异丁烯的数均分子量,测定时需将聚异丁烯样品溶于氘代试剂配制成溶液,所述氘代试剂中含有内标物,以便确定谱图中各基团的化学位移(δ)。另外,在配制的聚异丁烯溶液中还需加入驰豫试剂,以便提高信噪比,进行定量测定。
本发明方法中所述的氘代试剂选自氘代氯仿或氘代苯,优选氘代氯仿。配制的聚异丁烯溶液的浓度为1~40质量%,加入的驰豫试剂在聚异丁烯溶液中的浓度为1~100毫摩尔/升。所述的内标物为四甲基硅烷,驰豫试剂为乙酰丙酮铬或乙酰丙酮铁,优选乙酰丙酮铬。
本发明方法应用13C-核磁共振波谱法使用的核磁共振波谱仪中磁场可由电磁铁或超导磁体产生,即核磁共振波谱仪可选用电磁铁型或超导磁体型。
根据定义,聚异丁烯的数均分子量由下式求得,
Mn=56×n
式中,Mn为聚异丁烯的数均分子量,n为聚合度,56为异丁烯分子量。
由阳离子聚合得到的聚异丁烯包括由纯异丁烯聚合得到的活性聚异丁烯,由混合碳四烯烃聚合得到的非活性聚异丁烯,以及其他聚合方法得到的残余一个双键的低聚烯烃。一般聚异丁烯分子结构有三种类型。第一种为α型聚异丁烯,具有CH2=CCH3R型结构,如式(I)所示,特点是聚合后双键位于链的末端。第二种为β型聚异丁烯,具有(CH3)2C=CHR型结构,如式(II)所示,特点是双键向链中移动了一个碳原子,即双键位于β位。第三种为T型聚异丁烯,特点是双键位于链中,与双键碳即烯碳连接的四个氢原子均被烷基取代,如式(III)所示。不同类型的聚异丁烯中双键碳原子在碳谱中的出峰位置介于δ100~160ppm之间,如图1所示;而其烷基碳原子出峰位置介于δ0~70ppm之间,如图2所示。
本发明(3)步中聚异丁烯的聚合度可根据核磁共振谱图用双键法或亚甲基法求得。
用双键法计算聚合度的方法是:准确测定图1所示的烷碳区中由烷基碳产生峰的总面积和双键区烯碳产生峰的总面积,峰面积由积分法求得,再由式(1)计算聚异丁烯的聚合度,
n=1/2(I饱和/I双键+1) (1)
式(1)中,I饱和为烷碳区峰面积总和,I双键为烯碳区峰面积总和。
用亚甲基法计算聚合度的方法是:准确测定碳谱中亚甲基区各峰的总面积和α亚甲基峰的面积,由式(2)计算聚异丁烯的聚合度,
n=ICH2/Iα型CH2×α+1 (2)
式(2)中,ICH2为亚甲基区(δ50~62ppm)各峰的总面积,Iα型CH2为α型亚甲基(δ53.7ppm)峰的面积,α为聚异丁烯中α型聚异丁烯的摩尔百分含量。ICH2、Iα型CH2由图2所示的亚甲基区的峰面积求出。图2所示的聚异丁烯碳谱的烷碳区可以细分成三个次区域:亚甲基区、季碳区和甲基区。图2中小图为亚甲基区放大图,其中箭头所指的参考峰为α亚甲基峰,即与α型聚异丁烯链端双键相邻的亚甲基产生的峰,其它峰为其它亚甲基产生的峰。式(2)中,α值由图1双键区峰求得,在图1小图中,两高峰为α型双键,即位于链端部的双键产生的峰,此α型双键峰面积和与双键区各峰总面积的百分比即为α值。
下面通过实例进一步说明本发明,但本发明并不限于此。
实例1
取0.20克聚异丁烯样品,装入1.5毫升可封口的样品瓶中,快速加入0.5毫升氘代氯仿(CDCl3),封口后摇匀;将该溶液移入已经装有10毫克驰豫试剂乙酰丙酮铬的Φ5mm核磁样品管中;加帽并用封口胶带密封。在室温下,用Varian INOVA500型核磁共振仪(Varian公司生产)在125.64MHz的共振频率下测得聚异丁烯的13C-核磁共振谱图。用双键法测定样品的数均分子量,与蒸气压渗透法(VGO)测定结果的对比数据见表1。
实例2
按实例1的方法测定聚异丁烯样品的13C-核磁共振谱图,由亚甲基法测定样品的数均分子量,与蒸气压渗透法(VGO)测定结果的对比数据见表2。
表1
样品序号 | 扫描次数 | I饱和 | I双键 | Mn | Mn(VPO法) |
1 | 3100 | 71.0 | 2.0 | 1022 | 999 |
2 | 12100 | 164.0 | 2.0 | 2324 | 2306 |
表2
样品序号 | α,% | ICH2 | Iα型CH2 | Mn | Mn(VPO法) |
1 | 63.3 | 100.00 | 3.96 | 951 | 999 |
2 | 83.8 | 100.00 | 1.89 | 2539 | 2306 |
Claims (8)
1、一种聚异丁烯分子量的测定方法,包括如下步骤:
(1)将聚异丁烯样品溶于含有内标物的氘代试剂中制成聚异丁烯溶液,再加入驰豫试剂制得待测样品,
(2)用13C-核磁共振波谱法对待测样品进行测定,得到碳谱谱图,
(3)通过碳谱图中烷碳区的峰面积与烯碳区峰面积比值或亚甲基区的峰面积与α亚甲基的峰面积比值求得聚异丁烯的聚合度,再由聚合度计算得到分子量。
2、按照权利要求1所述的方法,其特征在于所述的氘代试剂选自氘代氯仿或氘代苯。
3、按照权利要求1所述的方法,其特征在于所述的内标物为四甲基硅烷。
4、按照权利要求1所述的方法,其特征在于所述的驰豫试剂为乙酰丙酮铬或乙酰丙酮铁。
5、按照权利要求1所述的方法,其特征在于所述的聚异丁烯溶液的浓度为1~40质量%,驰豫试剂在聚异丁烯溶液中的浓度为1~100毫摩尔/升。
6、按照权利要求1所述的方法,其特征在于13C-核磁共振波谱法采用的波谱仪为电磁铁型或超导磁体型。
7、按照权利要求1所述的方法,其特征在于(3)步中聚异丁烯的聚合度由式(1)求得,
1/2(I饱和/I双键+1) (1)
式(1)中,I饱和为烷碳区峰面积总和,I双键为烯碳区峰面积总和。
8、按照权利要求1所述的方法,其特征在于(3)步中聚异丁烯的聚合度由式(2)求得,
ICH2/Iα型CH2×α+1 (2)
式(2)中,ICH2为亚甲基区各峰的总面积,Iα型CH2为α亚甲基的峰面积,α为聚异丁烯中α型聚异丁烯的摩尔百分含量。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102539285A (zh) * | 2011-12-31 | 2012-07-04 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | 一种分析110甲基乙烯基硅橡胶分子量的重量挤压法 |
CN108152318A (zh) * | 2017-12-22 | 2018-06-12 | 黄河三角洲京博化工研究院有限公司 | 一种定量核磁共振氢谱测定合成对聚异丁烯苯酚过程中转化率的方法 |
CN108195869A (zh) * | 2018-02-07 | 2018-06-22 | 广州天赐高新材料股份有限公司 | 瓜尔胶羟丙基三甲基氯化铵取代度的检测方法 |
CN110389147A (zh) * | 2018-04-18 | 2019-10-29 | 中昊晨光化工研究院有限公司 | 一种基于核磁共振测定全氟聚醚的结构和分子量的方法 |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102539285A (zh) * | 2011-12-31 | 2012-07-04 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | 一种分析110甲基乙烯基硅橡胶分子量的重量挤压法 |
CN102539285B (zh) * | 2011-12-31 | 2014-08-27 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | 一种分析110甲基乙烯基硅橡胶分子量的重量挤压法 |
CN108152318A (zh) * | 2017-12-22 | 2018-06-12 | 黄河三角洲京博化工研究院有限公司 | 一种定量核磁共振氢谱测定合成对聚异丁烯苯酚过程中转化率的方法 |
CN108152318B (zh) * | 2017-12-22 | 2020-07-31 | 黄河三角洲京博化工研究院有限公司 | 一种定量核磁共振氢谱测定合成对聚异丁烯苯酚过程中转化率的方法 |
CN108195869A (zh) * | 2018-02-07 | 2018-06-22 | 广州天赐高新材料股份有限公司 | 瓜尔胶羟丙基三甲基氯化铵取代度的检测方法 |
CN110389147A (zh) * | 2018-04-18 | 2019-10-29 | 中昊晨光化工研究院有限公司 | 一种基于核磁共振测定全氟聚醚的结构和分子量的方法 |
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