CN1056097C - 取代聚乙炔气体分离膜的紫外接枝的改性方法 - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 17
- 238000000926 separation method Methods 0.000 title claims abstract description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229920001197 polyacetylene Polymers 0.000 title claims abstract description 7
- 238000002715 modification method Methods 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000035699 permeability Effects 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 6
- 238000010559 graft polymerization reaction Methods 0.000 claims description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
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- 238000009738 saturating Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于取代聚乙炔气体分离膜的紫外接枝的改性方法。
本发明涉及具有下列链结构的取代聚乙炔高分子膜材料的紫外辐照接枝共聚改性：
其中R1为C1～C4烷基，R2为Si(CH3)2或(CH2)n(n＝0～2)，R3和R4为C1～C6烷基，R5为C1～C12烷基，m≥100。用这一方法可使这类膜的气体分离系数大为提高，如αO2/N2，可以从1.3～1.5增到＞4，同时气透稳定性明显改善。
用来接枝共聚的单体，包括气态或液态的烯烃类和含氧、氮和卤素的单体以及它们的混合物。膜周围的温度为-50℃～50℃，单体气(或汽)的分压为1×102～2×105Pa，反应时间为10min～36h。
Description
本发明属于取代聚乙炔气体分离膜的紫外接枝的改性方法。
具有下列链结构的聚三甲硅基丙炔(PTMSP)，
是迄今所知具有最高气透性的高分子膜材料，其氧透过系数PO2可达104×10-10ml(STP).cm.cm-2.s-1.1.3KPa-1(Barrer)，但这类膜作为气体分离膜时，其分离系数偏低，如膜的氧氮分离系数(αO2/N2)为1.3～1.5，这将大大限制其作为气体分离膜的应用。
进行膜的表面改性，是克服这个缺点的一个有效手段。美国专利4657567提供了气相氟化改性方法，可使膜的氧氮透过系数(αO2/N2)至少提高50％，Po2仍保留在有应用价值的范围内[～102×10-10ml(STP).cm.cm-2.s-1.1.3KPa-1(Barrer)〕，但这种方法使用非常活泼、毒性极大的氟气作为改性剂，除了价格昂贵外，还必须在反应设备和安全防护方面耗费大量资金，而且在操作上也有诸多不便。日本专利60 206403和60 257807提供紫外辐照改性方法，膜的氧氮透过系数(αO2/N2)可提高到2.7，对于其实际应用这是不够的。
本发明的目的是用紫外辐照，使膜在共聚单体存在下进行共辐照接枝聚合，从而达到表面改性的目的，改性膜的氧氮分离系数(αO2/N2)可达到＞4，PO2仍保留于＞102×10-10ml(STP).cm.cm-2.s-1.1.3KPa-1(Barrer)的水平，而且改性膜的气透稳定性得以改善。
本发明涉及具有下列链结构的取代聚乙炔高分子膜材料的紫外辐照接枝共聚改性：其中R1为C1～C4烷基，R2为Si(CH3)2或(CH2)n n＝(0～2)，R3和R4为C1～C6烷基，R5为C1～C12烷基，m≥1000，具体为聚三甲硅基丙炔(PTMSP)，用于改性的膜是以下列方法制得的：将浓度为2％～3％PTMSP的甲苯溶液在玻璃板上流延成膜，经过一周的缓慢干燥后，在真空下干燥24h，紫外辐照接枝聚合在石英管中进行，将装有上述膜的石英管抽真空，在惰性环境中与要接枝的单体一起，紫外辐照10min～36h，随辐照时间的增长，透氧系数(Po2)有所降低，膜的氧氮分离系数(αO2/N2)渐渐上升，膜周围的温度为-50～50℃，所用单体为烯烃及含氧、氮和卤素的单体以及它们的混合物，当所有的单体为液态时，膜周围单体的浓度受该温度下单体的饱和蒸汽压控制；在单体为气态时，直接控制气体的分压，单体气压范围为1×102～2×105Pa。
用紫外接枝共聚合方法进行改性，适用于各种不同类型的单体，包括其均聚物具有较低分离系数的单体，因为接枝率不大，而表面氧化对分离系数的提高起了大的作用。本方法的实验条件(如辐照时间等)幅度宽，易于操作。一个很大的优点是改性膜的气透稳定性好，克服了原始膜气透不稳定的缺点。
实例1：在17℃，以PTMSP膜与蒸汽压为2×104Pa烯丙胺进行共辐照，改性膜的有关数据见表1。g为接枝率：g＝(Wg-Wo)/Wo×100％(Wo，Wg分别为接枝前后的膜重)，表面组成用XPS测量得到的C/Si，N/C和O/C原子比表示，WCA为水接触角。表1用烯丙胺改性的PTMSP膜的有关数据改性时间，h 0 0.5 1 3 5 9 13 18 24
g，％ 0 -0.68 -0.20 0.29 1.29 3.84 5.36 13.28 23.85
C/Si 6.12 4.97 4.94 5.48 5.58 6.70 6.25 6.07 6.41
N/C - 0.004 0.006 0.027 0.032 0.070 0.065 0.066 0.069
O/C 0.026 0.099 0.108 0.130 0.163 0.176 0.170 0.161 0.183WCA，deg 102 102 96 97 93 61 32 25 16Po2，10-10ml(STP).cm.cm-2 8335 - 2790 772 660 308 - - -.s-1.1.3KPa-1(Barrer)￡αO2/N2 1.47 - 2.98 4.55 4.67 4.28 - - -
实例2：在48℃，PTMSP膜与气压为1×104Pa的氯乙烯共辐照，改性膜的表面组成和气透性如表2所示。
改性时间，h 0 1 3 10 24 36
C/Si 6.12 12.11 18.67 16.68 12.21 5.35
Cl/C - 0.013 0.017 0.064 0.072 0.031
O/C 0.026 0.419 0.437 0.490 0.478 0.485
Po2，10-10ml(STP).cm.cm-2.s-1. 8335 3004 922 - - -1.3KPa-1(Barrer)￡
αO2/N2 1.47 3.06 4.92 - - -
实例3：在0℃，PTMSP膜与蒸汽压4×103Pa丙烯腈共辐照接枝30min，改性膜的气透性数据为：Po2 2010×10-10ml(STP).cm.cm-2.s-1.1.3KPa-1(Barrer)￡，αO2/N2 3.89，放置15天和60天后，Po2，αO2/N2分别为2100，3.82和1922，4.00。
实例4：在不同的气压和温度下，PTMSP与不同单体共辐照接枝膜的气透稳定性如表3所示。改性 改 单体 改 初始 透性 60天后 气透性
气单体 性 气压 性 Po2，10-10ml αO2/N2 Po2，10-10ml αO2/N2
温 Pa 时 (STP).cm. (STP).cm
度 间 cm-2.s-1. cm-2.s-1.
℃ h 1.3KPa-1 1.3KPa-1
(Barrer)￡ (Barrer)￡烯丙胺 17 2×104 9 308 4.28 313 4.28醋酸乙烯 20 1.2×104 3 199 4.89 236 4.48酯苯乙烯 20 1×103 9 561 3.61 738 3.84乙烯 - 1×104 3 522 3.43 492 3.33
30丙烯 - 2×104 3 487 3.77 501 3.52
50四氟乙烯 0 2×104 3 575 4.40 566 4.51
Claims (1)
1.一种取代聚乙炔气体分离膜的紫外接枝的改性方法，其特征在于使用聚三甲硅基丙炔(PTMSP)，用于改性的膜是以下列方法制得的：将浓度为2％～3％PTMSP的甲苯溶液在玻璃板上流延成膜，经过一周的缓慢干燥后，在真空下干燥24h，紫外辐照接枝聚合在石英管中进行，将装有上述膜的石英管抽真空，在惰性环境中与要接枝的单体一起，紫外辐照10min～36h，随辐照时间的增长，透氧系数(Po2)有所降低，膜的氧氮分离系数(αO2/N2)渐渐上升，膜周围的温度为-50～50℃，所用单体为烯烃及含氧、氮和卤素的单体以及它们的混合物，当所有的单体为液态时，膜周围单体的浓度受该温度下单体的饱和蒸汽压控制；在单体为气态时，直接控制气体的分压，单体气压范围为1×102～2×105帕。
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| CN1133851A CN1133851A (zh) | 1996-10-23 |
| CN1056097C true CN1056097C (zh) | 2000-09-06 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60257807A (ja) * | 1984-06-06 | 1985-12-19 | Shin Etsu Chem Co Ltd | 気体分離用成形体 |
| CN1054016A (zh) * | 1990-02-13 | 1991-08-28 | 中国科学院长春应用化学研究所 | 选择性气体透过膜及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60257807A (ja) * | 1984-06-06 | 1985-12-19 | Shin Etsu Chem Co Ltd | 気体分離用成形体 |
| CN1054016A (zh) * | 1990-02-13 | 1991-08-28 | 中国科学院长春应用化学研究所 | 选择性气体透过膜及其制备方法 |
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