CN1059844C - Surface chlorination-amination modification method of substituted polyacetylene gas separation membrane - Google Patents
Surface chlorination-amination modification method of substituted polyacetylene gas separation membrane Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- chlorination
- amination
- membrane
- gas
- substituted polyacetylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005576 amination reaction Methods 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title claims abstract description 13
- 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
- 238000000926 separation method Methods 0.000 title claims abstract description 7
- 238000002715 modification method Methods 0.000 title abstract 2
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 24
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012495 reaction gas Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229920003242 poly[1-(trimethylsilyl)-1-propyne] Polymers 0.000 description 12
- 230000035699 permeability Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention belongs to a surface chlorination-amination modification method of substituted polyacetylene gas separation membrane.
The present invention casts toluene solution of membrane material on glass plate to form membrane, after drying, the membrane is dried for 24h under vacuum, and the gas phase chlorination-amination of the membrane uses pure chlorine or it and N2The reaction gas flow rate of the mixture is 1-200 ml/min under the dynamic condition, the reaction time is 5s-24h, after chlorination is finished, vacuumizing is carried out, diamine steam is introduced, and the amination time is 5s-2 h.
The raw material gas and steam used in the invention have low price, have no special requirements on equipment and safety, and can be used for easily preparing alpha-o2/N2Is 3 to 4, Po2≥1×102Barrer's oxygen-enriched membrane material.
Description
The invention belongs to the surface chlorination one amination modifying method of substituted polyacetylene gas separation membrane.
The present invention relates to have chlorination one amination modifying of the substituted polyacetylene family macromolecule membrane material of following chain structure:
R wherein
1Be C
1～C
4Alkyl, R
2Be Si (CH
2)
2Or (CH
2)
n, (n=O～2), R
3And R
4Be C
1～C
6Alkyl, R
5Be C
1～C
12Alkyl, m 〉=1000.
This class film has high gas-premeable, the silica-based propine of poly-front three (PTMSP) of especially following chain structure: n=0, R
1=R
3=R
4=R
5=CH
3, be so far known to the highest macromolecule member material of gas permeability, oxygen transmission coefficient can reach 10
4Barrer, but the ventilative poor stability of this class material, separation is low, as the oxygen nitrogen separation of PTMSP film
Be 1.3～1.5, this has limited its application as diffusion barrier.
Surface modifying method is an effective means that overcomes this shortcoming.United States Patent (USP) 4,657,564 provide a kind of fluorination and modification process, can make
At least improve 50%, but the shortcoming of this patent maximum is to use very active and great toxicity fluorine, except its price height, also to having higher requirements aspect consersion unit and the security protection.
The present invention is the method that adopts gas phase chlorination one amination modifying, and cost is lower, and reaction is easy to control, and according to contrast test, the PTMSP film reaches identical fluoridizing with chlorination
During value, the chlorination film
Be worth higher.No matter but be to fluoridize or chlorination, the gas permeability of gained film is still stable inadequately, along with the prolongation of standing time,
And
Change.The present invention adopts chlorination one amination method, and it is crosslinked promptly to carry out gas phase with diamine steam again after the gas phase chlorination, reaches the gas permeability stabilisation of film.
The film that is modified is pressed the method preparation: with concentration is the toluene solution of 2～3% membrane materials, hydrostomia film forming on glass plate, and through after the slow drying in an about week, dry 24h under vacuum.Gas phase chlorination one amination of film is carried out in two stages.Phase I is a gas phase chlorination, with pure chlorine or it and N
2Mist, concentration is 0.01～100%, can static or dynamically in carry out.Under current intelligence, the reacting gas flow velocity is 1～200ml/min, and the reaction time is 5s～24h.Second stage is amination, after chlorination finishes, vacuumizes, and feeds the diamine steam (pressure 1 * 10 that is in certain vapour pressure
2～1 * 10
5Pa), the amination time is 5s～2h.
Method of modifying of the present invention, raw materials used gas and steam price are lower, and equipment and secure context are not had specific (special) requirements, are easy to produce
Be 3～4, gas permeability is more stable,
The oxygen permeable membrane material.
Embodiment 1 static chlorination: the reaction bulb that will be placed with the PTMSP film links to each other with gas cylinder, behind the nitrogen replacement air, injects the gaseous mixture of pure chlorine or itself and nitrogen, behind certain hour t, uses nitrogen replacement 30min.In table 1, provide with behind 10% and 100% chlorine reaction, the relation of surface C l/C atomic ratio (measuring) and t with XPS, table 2 has provided the gas permeability data of PTMSP film after 100% chlorinated with chlorine.
Embodiment 2 dynamic chlorinations: in tubular reactor, be placed with the PTMSP film, after the flowing nitrogen flushing, feed the mixture of chlorine and nitrogen again, behind certain hour, use nitrogen replacement 30min.Table 3 is listed chlorination PTMSP film surface composition and gas permeability data.
After the mobile chlorination of embodiment 3 usefulness is the 10% chlorine treatment 15min of 1mL/min with the PTMSP film through flow velocity, use nitrogen replacement 30min, find time, feeding vapour pressure is 4 * 10
3Take out behind the ethylenediamine steam 10min of Pa, the saturating stability of the gas of film is as shown in table 4.
The Cl/C atomic ratio (static state) on table 1 chlorination PTMSP film surface
| Chlorine gas concentration, % time of chlorinating Cl/C | Chlorine gas concentration, % time of chlorinating Cl/C |
| 10 7s O.053 15s 0.100 1min 0.181 5min 0.233 15min 0.265 60min 0.316 | 100 5s 0.094 50s O.290 2min 0.351 15min 0.441 60min 0.499 |
Gas permeability (static state) time of chlorinating of PTMSP film after the table 2 100% chlorine modification, min 1,/12 15 30
Barrer 7,250 3,300 1,100 500
1.80 2.75 3.75 3.90
Table 3 chlorination PTMSP film surface composition and gas permeability
Chlorine gas concentration flow velocity time of chlorinating
Test piece number (Test pc No.) 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
Standing time after the saturating stable modification of gas of table 4 modification PTMSP film, sky 07 91 170
1.40 1.5510%Cl
2 
Barrer 3,580 4020 chlorination 15min
3.09 1.60
3.56 3.66 3.57 3.58
Claims (1)
1. the surface chlorination of a substituted polyacetylene gas separation membrane-amination modifying method, the substituted polyacetylene family macromolecule membrane material that relates to have following chain structure:
R wherein
1Be C
1～C
4Alkyl; R
2Be Si (CH
2)
2Or (CH
2)
n, n=0～2 here; R
3And R
4Be C
1～C
6Alkyl; R
5Be C
1～C
12Alkyl; M 〉=1000 is characterized in that with concentration being toluene solution casting film-forming on glass plate of 2-3% membrane material, through after the slow drying in an about week, dry 24h under vacuum, gas phase chlorination-the amination of film is carried out in two stages, and the phase I is a gas phase chlorination, with pure chlorine or it and N
2Mixture concentration be 0.01～100% can static or dynamically in carry out, under current intelligence, the reacting gas flow velocity is 1～200ml/min, the reaction time is 5s-24h, second stage is amination, after chlorination finishes, vacuumizes, feeding vapour pressure is 1 * 10
2～1 * 10
5The diamine steam of Pa, the amination time is 5s～2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96101719A CN1059844C (en) | 1996-01-10 | 1996-01-10 | Surface chlorination-amination modification method of substituted polyacetylene gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96101719A CN1059844C (en) | 1996-01-10 | 1996-01-10 | Surface chlorination-amination modification method of substituted polyacetylene gas separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1154264A CN1154264A (en) | 1997-07-16 |
| CN1059844C true CN1059844C (en) | 2000-12-27 |
Family
ID=5117225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96101719A Expired - Fee Related CN1059844C (en) | 1996-01-10 | 1996-01-10 | Surface chlorination-amination modification method of substituted polyacetylene gas separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1059844C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8043418B2 (en) * | 2006-12-08 | 2011-10-25 | General Electric Company | Gas separator apparatus |
| CN115382408A (en) * | 2022-08-12 | 2022-11-25 | 暨南大学 | Chemical vapor amination modified porous polymer film and preparation method and application thereof |
Citations (2)
| 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 |
-
1996
- 1996-01-10 CN CN96101719A patent/CN1059844C/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1154264A (en) | 1997-07-16 |
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