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CN1059844C - 取代聚乙炔气体分离膜的表面氯化－胺化改性方法 - Google Patents

取代聚乙炔气体分离膜的表面氯化－胺化改性方法 Download PDF

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CN1059844C
CN1059844C CN96101719A CN96101719A CN1059844C CN 1059844 C CN1059844 C CN 1059844C CN 96101719 A CN96101719 A CN 96101719A CN 96101719 A CN96101719 A CN 96101719A CN 1059844 C CN1059844 C CN 1059844C
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chlorination
amination
membrane
gas
substituted polyacetylene
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CN1154264A (zh
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郑国栋
许观藩
邱雪鹏
徐纪平
张金兰
邢晶
闻久绵
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Changchun Institute of Applied Chemistry of CAS
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Abstract

本发明属于取代聚乙炔气体分离膜的表面氯化-胺化改性方法。
本发明将膜材料的甲苯溶液在玻璃板上流延成膜，干燥后，在真空下干燥24h，膜的气相氯化-胺化用纯氯或它与N2的混合体在动态情况下，反应气体流速为1～200ml/min，反应时间为5s-24h，在氯化结束后，抽真空，通入二元胺蒸汽，胺化时间为5s～2h。
本发明所用原料气体和蒸汽价格较低，对设备及安全方面无特殊要求，很容易制取αo2/N2为3～4，Po2≥1×102Barrer的富氧膜材料。

Description

取代聚乙炔气体分离膜的表面氯化－胺化改性方法
本发明属于取代聚乙炔气体分离膜的表面氯化一胺化改性方法。
本发明涉及具有下列链结构的取代聚乙炔类高分子膜材料的氯化一胺化改性：
Figure C9610171900031
其中R1为C1～C4烷基，R2为Si(CH2)2或(CH2)n，(n＝O～2)，R3和R4为C1～C6烷基，R5为C1～C12烷基，m≥1000。
这一类膜具有高的气体透过性，尤其是下列链结构的聚三甲硅基丙炔(PTMSP)：n=0，R1=R3＝R4=R5=CH3，是迄今所知气透性最高的高分子膜材料，氧气透过系数可达104Barrer，但这类材料透气稳定性差，分离系数低，如PTMSP膜的氧氮分离系数
Figure C9610171900032
为1.3～1.5，这限制了其作为分离膜的应用。
表面改性方法是克服这个缺点的一个有效手段。美国专利4,657,564提供了一种氟化改性方法，可使
Figure C9610171900033
至少提高50％，但该专利最大的缺点是使用非常活泼和毒性极大的氟，除了其价格高外，还对在反应设备和安全防护方面有较高要求。
本发明是采用气相氯化一胺化改性的方法，成本较低，反应易于控制，根据对比试验，PTMSP膜在氟化和氯化达到相同的
Figure C9610171900034
值时，氯化膜的 值较高。但是不论是氟化或是氯化，所得膜的气透性尚不够稳定，随着放置时间的延长，
Figure C9610171900036
及
Figure C9610171900037
发生变化。本发明采用氯化一胺化方法，即气相氯化后再用二元胺蒸汽进行气相交联，达到膜的气透性稳定化。
被改性膜按下法制备：将浓度为2～3％膜材料的甲苯溶液，在玻璃板上流涎成膜，经过约一周的缓慢干燥后，在真空下干燥24h。膜的气相氯化一胺化分两阶段进行。第一阶段为气相氯化，用纯氯或它与N2的混合气体，浓度为0.01～100％，可在静态或动态中进行。在动态情况下，反应气体流速为1～200ml/min，反应时间为5s～24h。第二阶段为胺化，在氯化结束后，抽真空，通入处于一定蒸气压的二元胺蒸汽(压力1×102～1×105Pa)，胺化时间为5s～2h。
本发明的改性方法，所用原料气体和蒸汽价格较低，对设备及安全方面无特殊要求，很容易制取
Figure C9610171900041
为3～4，气透性比较稳定，的富氧膜材料。
实施例1  静态氯化：将放有PTMSP膜的反应瓶与贮气瓶相连，经氮气置换空气后，注入纯氯或其与氮的混合气，经一定时间t后，用氮气置换30min。在表1中给出用10％和100％氯气反应后，表面Cl/C原子比(用XPS测定)与t的关系，表2给出了100％氯气氯化后PTMSP膜的气透性数据。
实施例2  动态氯化：在管式反应器中放有PTMSP膜，用流动氮气冲洗后，再通入氯与氮气的混合物，经一定时间后，用氮气置换30min。表3列出氯化PTMSP膜表面组成和气透性数据。
实施例3用流动氯化方法将PTMSP膜经流速为1mL/min的10％氯气处理15min后，用氮气置换30min，抽空，通入蒸汽压为4×103Pa的乙二胺蒸汽10min后取出，膜的气透稳定性如表4所示。
                     表1氯化PTMSP膜表面的Cl/C原子比(静态)
氯气浓度，％  氯化时间    Cl/C 氯气浓度，％  氯化时间    Cl/C
    10        7s          O.05315s         0.1001min        0.1815min        0.23315min       0.26560min       0.316     100       5s          0.09450s         O.2902min        0.35115min       0.44160min       0.499
         表2 100％氯气改性后PTMSP膜的气透性(静态)氯化时间，min    1/12    1       5       30
Figure C9610171900051
Barrer      7250    3300    1100    500
Figure C9610171900052
           1.80    2.75    3.75    3.90
          表3氯化PTMSP膜表面组成和气透性
氯气浓度  流速  氯化时间                               
Figure C9610171900053
试样号                       Cl/C    C/Si   O/C             ％     mL/min    min                           Barrer1    -       -         -     -       6.13   O.026   8610   1.392    1       40        5     0.138   6.44   O.059   7710   1.823    1       40        15    0.221   6.07   0.115   3760   2.234    1       40        30    O.357   5.87   0.200   2000   3.215    10      40        1/12  0.039   6.43   0.072   9830   1.456    10      40        1     O.173   6.63   0.158   4930   1.977    10      40        5     O.298   6.54   0.136   2250   2.258    10      40        15    O.432   6.20   0.226   570    4.579    10      40        30    0.540   6.57   0.210   460    4.3210   10      200       5     O.441   6.32   0.233   540    4.52
                表4改性PTMSP膜的气透稳定性改性后放置时间，天                0       7    91    170
                  
Figure C9610171900061
Barrer 8800              1050未改性
                         1.40              1.5510％Cl2             
Figure C9610171900063
Barrer 3580              4020氯化15min            
Figure C9610171900064
       3.09              1.60
Figure C9610171900065
             Barrer       710    790  800   810氯化一胺化
                         3.56   3.66 3.57  3.58

Claims (1)

1.一种取代聚乙炔气体分离膜的表面氯化-胺化改性方法，是涉及具有下列链结构的取代聚乙炔类高分子膜材料：
Figure C9610171900021
其中R1为C1～C4烷基；R2为Si(CH2)2或(CH2)n，这里n＝0～2；R3和R4为C1～C6烷基；R5为C1～C12烷基；m≥1000，其特征在于将浓度为2-3％膜材料的甲苯溶液在玻璃板上流延成膜，经过约一周的缓慢干燥后，在真空下干燥24h，膜的气相氯化-胺化分两阶段进行，第一阶段为气相氯化，用纯氯或它与N2的混合体浓度为0.01～100％可在静态或动态中进行，在动态情况下，反应气体流速为1～200ml/min，反应时间为5s-24h，第二阶段为胺化，在氯化结束后，抽真空，通入蒸气压为1×102～1×105Pa的二元胺蒸汽，胺化时间为5s～2h。
CN96101719A 1996-01-10 1996-01-10 取代聚乙炔气体分离膜的表面氯化－胺化改性方法 Expired - Fee Related CN1059844C (zh)

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Publication number Priority date Publication date Assignee Title
US4657564A (en) * 1985-12-13 1987-04-14 Air Products And Chemicals, Inc. Fluorinated polymeric membranes for gas separation processes
US4859215A (en) * 1988-05-02 1989-08-22 Air Products And Chemicals, Inc. Polymeric membrane for gas separation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657564A (en) * 1985-12-13 1987-04-14 Air Products And Chemicals, Inc. Fluorinated polymeric membranes for gas separation processes
US4859215A (en) * 1988-05-02 1989-08-22 Air Products And Chemicals, Inc. Polymeric membrane for gas separation

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