CN101580584B - Efficient preparation method of block sulfonated aromatic poly (thio) ether - Google Patents
Efficient preparation method of block sulfonated aromatic poly (thio) ether Download PDFInfo
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- CN101580584B CN101580584B CN2009100693818A CN200910069381A CN101580584B CN 101580584 B CN101580584 B CN 101580584B CN 2009100693818 A CN2009100693818 A CN 2009100693818A CN 200910069381 A CN200910069381 A CN 200910069381A CN 101580584 B CN101580584 B CN 101580584B
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- thiophenol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 poly (thio) Polymers 0.000 title claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 43
- 125000003118 aryl group Chemical group 0.000 title abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 42
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000012634 fragment Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000009736 wetting Methods 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 150000008378 aryl ethers Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 11
- 230000035484 reaction time Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 28
- FNBBNRGOHBQXCM-UHFFFAOYSA-N [S].OC1=CC=CC=C1 Chemical compound [S].OC1=CC=CC=C1 FNBBNRGOHBQXCM-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 239000005864 Sulphur Substances 0.000 description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RKHQZMOCQHXUBC-UHFFFAOYSA-N phenol;potassium Chemical compound [K].OC1=CC=CC=C1 RKHQZMOCQHXUBC-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 0 *1c(cccc2)c2-c2ccccc12 Chemical compound *1c(cccc2)c2-c2ccccc12 0.000 description 3
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001473 noxious effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- MILSYCKGLDDVLM-UHFFFAOYSA-N CC(C)(c1ccccc1)c1ccccc1 Chemical compound CC(C)(c1ccccc1)c1ccccc1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 1
- QEGNUYASOUJEHD-UHFFFAOYSA-N CC1(C)CCCCC1 Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N CCc1ccccc1 Chemical compound CCc1ccccc1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a high efficiency preparation method of block sulfonated aromatic poly (thio) ether. In the invention, a sulfonated monomer, a non-sulfonated monomer and a bis (thio) phenol monomer are adopted as starting raw materials and react for 10 to 24 hours under the carbonate alkaline condition of an aprotic solvent with high boiling point with the temperature being controlled between 150 DEG C and 200 DEG C so as to effectively prepare a block sulfonated aromatic poly (thio) ether macromolecular compound. In the preparation method, a toluene organic solvent is omitted, the step of azeotropic water division is omitted, the technology is simplified, the use of a large number of organic, flammable, volatile and toxic solvents and subsequent complicated waste liquid recycling processes are avoided, the volume of reaction liquid is reduced, the reaction time is shortened, energy consumption is reduced, the cost of the production technology is reduced, and the work efficiency is increased.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to the preparation method of sulfonated poly aromatic (sulphur) ethers high molecular polymer, block sulfonated poly aromatic (sulphur) the ether high efficiency preparation method of a kind of novelty of saying so more specifically.
Background technology
Sulfonated poly aromatic (sulphur) ether can be made film, sheet, plate, pipe, fiber, coating and other structured materials, be used for aerospace, aviation, nuclear industry, electronic industry, shipbuilding industry, automotive industry and mechanotronics etc., the desirable selection that also can be used as separation membrane is handled at film waters such as reverse osmosis, nanofiltration, ultrafiltration, micro-filtration, osmotic distillation, ion-exchange, electrodialysis, and the Proton Exchange Membrane Fuel Cells field has a wide range of applications.Contain wetting ability and lipotropy part simultaneously in sulfonated poly aromatic (sulphur) the ethers macromolecular material, the passage that the former provides water molecules to see through, the latter then provides material required mechanical property.In random sulfonated poly aromatic (sulphur) the ether macromolecular chain, wetting ability, lipophilic group distribute with very short fragment, and in block sulfonated poly aromatic (sulphur) the ether macromolecular chain, wetting ability, lipotropy part are alternately distributed with long fragment.This orderly relatively arrangement in block sulfonated poly aromatic (sulphur) the ether macromolecular structure helps promoting being separated of hydrophilic, lipophilic portion, thereby may form ionic channel, to improve the selectivity of mould material.The sulfonated monomers polymerization of adopting at present extensively, the sulfonated poly aromatic ether macromolecular material that adopts the back sulfonation method to make than before has lot of advantages, for example chemical stability height, ionic group position and ratio control accurately, avoid side reaction generation such as chain rupture etc.But adopt at present in the sulfonated monomers polymerization technology, adopt toluene dehydrating step usually, afterwards toluene is steamed, improve temperature of reaction again to finish polymerization.This not only can cause a large amount of organic inflammable, volatile, uses of noxious solvent and follow-up complicated waste liquid recycling process, also can cause long reaction times, bigger reaction solution volume and higher energy consumption, cause finally that synthesis technique efficient based on this method is low, cost is high.
Summary of the invention
The objective of the invention is to overcome in the prior art use a large amount of organic inflammable, volatile, noxious solvents and follow-up waste liquid recycling process is complicated, the reaction times is long, the reaction solution volume is big and energy consumption than problems such as height, provide a kind of block sulfonated poly aromatic (sulphur) ether novel preparation method.Mainly be to utilize the poly aromatic that the sulfonated monomers polymerization obtains repeatably, sulfonation degree is controlled, chemical stability is high (sulphur) ether material.For achieving the above object, the invention provides following technical scheme:
The preparation method of a kind of block sulfonated poly aromatic (sulphur) ether is characterized in that comprising following step:
(1) be starting raw material with sulfonated monomers, two (sulphur) phenol monomer, add two (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent, temperature is controlled at 150-200 ℃, makes with (sulphur) phenol to be end group or to be the wetting ability fragment of end group with the halogen.
(2) be starting raw material with non-sulfonated monomers, two (sulphur) phenol monomer, add two (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent, temperature is controlled at 150-200 ℃, makes with (sulphur) phenol to be end group or to be the lipotropy fragment of end group with the halogen.
What (3) with (sulphur) phenol of step (1) preparation be that wetting ability fragment and the step (2) of end group prepare is the lipotropy fragment of end group with the halogen, press 1: 1 mixed of end group mole number, make mixed solution, add carbonate as alkali, reaction is 10-24 hour in high boiling non-protonic solvent, temperature of reaction is controlled at 150-200 ℃, wherein mixed solution: the mole number 1 of alkali: 2-2.25;
(4) with step (1) preparation what with the halogen be that wetting ability fragment and the step (2) of end group prepare is the lipotropy fragment of end group with (sulphur) phenol, press 1: 1 mixed of end group mole number, make mixed solution, add carbonate as alkali, reaction is 10-24 hour in high boiling non-protonic solvent, temperature of reaction is controlled at 150-200 ℃, wherein mixed solution: the mole number 1 of alkali: 2-2.25;
(5) with in the slow impouring deionized water of the reaction solution that obtains in (3) and (4), obtain the white fiber shaped polymer, under 60-80 ℃ of condition, soaked 5-10 hour then, repeat 3-5 time, filter, oven dry, vacuum-drying obtains block sulfonated poly aromatic (sulphur) ether.
Preparation method of the present invention, wherein the mol ratio of (sulphur) phenol and sulfonated monomers or non-sulfonated monomers can guarantee that greater than 1 prepared fragment end is phenol or thiophenol; The mol ratio of two (sulphur) phenol and sulfonated monomers or non-sulfonated monomers can guarantee that less than 1 prepared fragment end is halogen.
Preparation method of the present invention, wherein wetting ability, the segmental length of lipotropy from 2000 to 20000.Described high boiling non-protonic solvent is N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or N-Methyl pyrrolidone.Described carbonate is Na
2CO
3, K
2CO
3Or Cs
2CO
3
Block of the present invention is meant in the macromolecular chain that wetting ability, lipotropy part are alternately distributed with long fragment, and the wetting ability fragment is made with two (sulphur) phenol monomers are synthetic by sulfonated monomers; The lipotropy fragment is made with two (sulphur) phenol monomers are synthetic by non-sulfonated monomers.
The more detailed preparation method of the present invention is as follows:
(1) be starting raw material with sulfonated monomers, two (sulphur) phenol monomer, add two (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent; The preferred reaction time is 10-18 hour.Whole temperature of reaction is 150-200 ℃.Make the wetting ability fragment.
(2) reaction solution that obtains in cools off, leaves standstill, filters, and in the filtrate impouring Virahol, white precipitate is separated out, filter, and excessive washed with isopropyl alcohol, vacuum-drying obtains the wetting ability fragment.
(3) be starting raw material with non-sulfonated monomers, two (sulphur) phenol monomer, add two (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent; The preferred reaction time is 10-18 hour.Whole temperature of reaction is 150-200 ℃.Make the lipotropy fragment.
(4) reaction solution that obtains in (3) is cooled off, leaves standstill, filters, in the filtrate impouring methyl alcohol, white precipitate is separated out, filter, and the excessive methanol washing, vacuum-drying obtains the lipotropy fragment.
(5) mol ratio of two (sulphur) phenol and sulfonated monomers or non-sulfonated monomers is phenol or thiophenol greater than 1 to guarantee prepared fragment end in (1) and (3).
(6) mol ratio of two (sulphur) phenol and sulfonated monomers or non-sulfonated monomers is halogen less than 1 to guarantee prepared fragment end in (1) and (3).
(7) wetting ability, the segmental length of lipotropy can be controlled by the mol ratio of two (sulphur) phenol and sulfonated monomers or non-sulfonated monomers.
(8) wetting ability, the segmental length of lipotropy from 2000 to 20000.
(9) be that the wetting ability fragment of end group is with middle what prepare is the lipotropy fragment of end group with the halogen by (3) and (4) by preparation in (1) and (2) with (sulphur) phenol, press 1: 1 mixed of end group mole number, to add (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent; The preferred reaction time is 10-18 hour.Whole temperature of reaction is 150-200 ℃.
(10) be that the wetting ability fragment of end group is with middle what prepare is the lipotropy fragment of end group with (sulphur) phenol by (3) and (4) with the halogen by preparation in (1) and (2), press 1: 1 mixed of end group mole number, to add (sulphur) phenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in high boiling non-protonic solvent; The preferred reaction time is 10-18 hour.Whole temperature of reaction is 150-200 ℃.
(11) with in the slow impouring deionized water of the reaction solution that obtains in (9) and (10), obtain the white fiber shaped polymer, under 60-80 ℃ of condition, soaked 5-10 hour then, repeat 3-5 time, filter, oven dry, vacuum-drying obtains block sulfonated poly aromatic (sulphur) ether.
What be illustrated especially is: step (9) is to be the wetting ability fragment of end group and be the segmental further polymerisate of lipotropy of end group with the halogen with (sulphur) phenol; (10) referring to the halogen is the wetting ability fragment of end group and be the segmental further polymerisate of lipotropy of end group with (sulphur) phenol.This is two kinds of preparation methods with block polymer of same composition.
The sulfonated poly aromatic of indication (sulphur) ether comprises among the preparation method of the present invention: sulfonated poly aromatic (sulphur) ether sulfone, sulfonated poly aromatic (sulphur) ether ketone, sulfonated poly aromatic (sulphur) ether nitrile or sulfonated poly aromatic (sulphur) ether phosphine oxide.Typical polymkeric substance comprises:
x＝0，S
Ar
1: the monocycle, dicyclo, condensed ring, volution or the heterocyclic aromatic ring that contain 1-2 sulfonic acid or its salt group;
Ar
2: the monocycle, dicyclo, condensed ring, volution or the heterocyclic aromatic ring that do not contain sulfonic acid or its salt group;
Ar
3: two (sulphur) phenol systems of monocycle, dicyclo, condensed ring, volution or heterocyclic that contain a contraposition or a position;
M=H, first family basic metal, amine NR
1R
2R
3(R
1, R
2, R
3=H, the C1-C6 alkyl or aryl)
Single or the disubstituted aromatic substituent of R=.
Has general formula C
nH
2nThe linear or chain substituting group of non-annularity fat;
Has general formula C
nH
2n-2The ring-shaped fat substituting group,
The integer of n:1-12.
R
4=fat or aromatic substituent.
The experimental installation that the present invention adopts is connected and composed by bubbler 1, straight type Glass tubing 2, mechanical stirring 3, oil bath device 4 as shown in Figure 2.The experimental installation of existing preparation sulfonated poly aromatic ether as shown in Figure 3, by reflux condensing tube 1, bubbler 2, water trap 3, mechanical stirring 4, water trap piston 5, oil bath device 6 grades connect and compose.
The viscosity test condition that the present invention adopts: the intrinsic viscosity of block sulfonated poly aromatic (sulphur) ether macromolecular compound adopts the Ubbelohde viscosimetry to measure, and probe temperature is 25 ℃, and solvent is the nmp solution that contains the 0.05M lithiumbromide.
The positively effect that experimental installation preparation method of the present invention is compared with prior art had is:
(1) inventor studies through repetition test, it is starting raw material that a kind of employing sulfonated monomers, non-sulfonated monomers and two (sulphur) phenol monomer are provided, carbonate is as alkali, the method of the block sulfonated poly aromatic of efficient production (sulphur) ether macromolecular compound in high boiling non-protonic solvent, involved monomer and high molecular structure are as shown in Figure 1.Listed polymkeric substance adopts this method all can prepare among Fig. 1.
(2) cut off toluene organic solvent among the preparation method of the present invention, saved the step that azeotropic divides water, simplified technology, the use of a large amount of organic inflammable, volatile, noxious solvents and follow-up complicated waste liquid recycling process have been avoided, reduce the reaction solution volume, shortened the reaction times, reduced energy consumption, make the cost of production technique reduce, improved working efficiency.
(3) experimental installation of the present invention has replaced division box by straight type Glass tubing, has simplified synthetic equipment and has formed.
(4) block sulfonated poly aromatic (sulphur) ether that adopts the inventive method to obtain is compared with the disclosed preparation method of prior art, has higher intrinsic viscosity, and promptly higher molecular weight has been guaranteed the physical strength of the film forming properties and the practical application film of material.
Description of drawings:
Fig. 1 is the structural formula of block sulfonated poly aromatic (sulphur) ether polymer;
The preparation facilities sketch of Fig. 2 block sulfonated poly aromatic ether for the present invention adopts, 1 bubbler wherein, 2 straight type Glass tubings, 3 mechanical stirring, 4 oil bath devices, 5 nitrogen;
The existing method of Fig. 3 adopts the preparation facilities sketch of block sulfonated poly aromatic ether, 1 reflux condensing tube wherein, 2 bubblers, 3 water traps, 4 mechanical stirring, 5 water trap pistons, 6 oil bath devices, 7 nitrogen.
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.The present invention is described further below in conjunction with comparative example.
Comparative example 1:
The lipotropy of phenol potassium ending segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 3, with 4,4 '-dichloro diphenyl sulfone (DCDPS, 14.3580g, 50mmol), 4,4 '-'-biphenyl diphenol (BP, 10.0838g, 54.2mmol), Anhydrous potassium carbonate (K
2CO
3, 8.6146g, 62.3mmol), 122mL N,N-dimethylacetamide (DMAc), 61mL toluene mix, and was heated to 140 ℃ of reflux water-dividings 4 hours.Boil off toluene, temperature of reaction is risen to 180 ℃, reacted 48 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 800mL methyl alcohol, is separated out white powder, filters, and methanol wash, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the lipotropy fragment of phenol potassium ending, 20.0g, yield: 96%, intrinsic viscosity: 0.23dL/g.
Comparative example 2:
The wetting ability of chlorine ending segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 3, with 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone (SDCDPS, 29.4750g, 60.0mmol), 4,4 '-'-biphenyl diphenol (BP, 9.3105g, 50mmol), Anhydrous potassium carbonate (K
2CO
3, 7.9471g, 57.5mmol), 194mL N-Methyl pyrrolidone (NMP), 97mL toluene mix, and was heated to 140 ℃ of reflux water-dividings 4 hours.Boil off toluene, temperature of reaction is risen to 180 ℃, reacted 96 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white powder, filters, and washed with isopropyl alcohol, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the wetting ability fragment of chlorine ending, 32.7g, yield: 93%, intrinsic viscosity: 0.17dL/g.
Comparative example 3:
Synthesizing of block polymer
By reaction unit shown in Figure 3, (10.0g is 2mmol) with comparative example 2 (10.0g, 2mmol) synthetic fragment polymkeric substance, Anhydrous potassium carbonate (0.6358g with comparative example 1,4.6mmol), NMP (100mL), toluene (50mL) mix, and was heated to 140 ℃ of reflux water-dividings 4 hours.Boil off toluene, temperature of reaction is risen to 180 ℃, reacted 96 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white fiber shape solid, filters, and washed with isopropyl alcohol, oven dry 100 ℃ of following vacuum-dryings 24 hours, obtains block polymer again, 18.0g, yield: 90%, intrinsic viscosity: 0.63dL/g.
Embodiment 1:
Phenol potassium ending lipotropy segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 2, with 4,4 '-dichloro diphenyl sulfone (DCDPS, 14.3580g, 50mmol), 4,4 '-'-biphenyl diphenol (BP, 10.0838g, 54.2mmol), Anhydrous potassium carbonate (K
2CO
3, 14.9820g 108.4mmol), 122mL N,N-dimethylacetamide (DMAc) mixes, and is heated to 180 ℃, reacted 24 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 800mL methyl alcohol, is separated out white powder, filters, and methanol wash, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the lipotropy fragment of phenol potassium ending, 20.4g, yield: 98%, intrinsic viscosity: 0.22dL/g.
Embodiment 2:
Chlorine ending lipotropy segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 2, with 4,4 '-dichloro diphenyl sulfone (DCDPS, 15.5641g, 54.2mmol), 4,4 '-'-biphenyl diphenol (BP, 9.3105g, 50mmol), Anhydrous potassium carbonate (K
2CO
3, 13.8210g 100mmol), 124mL N,N-dimethylacetamide (DMAc) mixes, and is heated to 180 ℃, reacted 24 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 800mL methyl alcohol, is separated out white powder, filters, and methanol wash, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the lipotropy fragment of phenol potassium ending, 20.6g, yield: 97%, intrinsic viscosity: 0.24dL/g.
Embodiment 3:
Phenol potassium ending wetting ability segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 2, with 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone (SDCDPS, 24.5625g, 50mmol), 4,4 '-'-biphenyl diphenol (BP, 11.0662g, 56.4mmol), Anhydrous potassium carbonate (K
2CO
3, 15.5901g 112.8mmol), 178mL N-Methyl pyrrolidone (NMP) mixes, and is heated to 180 ℃, reacted 48 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white powder, filters, and washed with isopropyl alcohol, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the wetting ability fragment of phenol potassium ending, 30.1g, yield: 94%, intrinsic viscosity: 0.18dL/g.
Embodiment 4:
Chlorine ending wetting ability segmental synthetic (is that 5000g/mol is an example with the molecular weight)
By reaction unit shown in Figure 2, with 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone (SDCDPS, 27.8539g, 56.7mmol), 4,4 '-'-biphenyl diphenol (BP, 9.3105g, 50mmol), Anhydrous potassium carbonate (K
2CO
3, 13.8210g 100mmol), 186mL N-Methyl pyrrolidone (NMP) mixes, and is heated to 180 ℃, reacted 48 hours.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white powder, filters, and washed with isopropyl alcohol, oven dry again 100 ℃ of following vacuum-dryings 24 hours, obtains the wetting ability fragment of chlorine ending, 31.8g, yield: 95%, intrinsic viscosity: 0.19dL/g.
Embodiment 5:
Synthetic-phenol potassium ending wetting ability the fragment of block polymer and chlorine ending lipotropy fragment
By reaction unit shown in Figure 2, with embodiment 1 (10.0g, 2mmol) and embodiment 4 (10.0g, 2mmol) (1.1057g 8mmol), NMP (100mL) mixes, and is heated to 180 ℃, reacted 48 hours for synthetic fragment polymkeric substance, Anhydrous potassium carbonate.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white fiber shape solid, filters, and washed with isopropyl alcohol, oven dry 100 ℃ of following vacuum-dryings 24 hours, obtains block polymer again, 18.8g, yield: 94%, intrinsic viscosity: 0.75dL/g.
Embodiment 6:
Synthetic-phenol potassium ending lipotropy the fragment of block polymer and chlorine ending wetting ability fragment
By reaction unit shown in Figure 2, with embodiment 2 (10.0g, 2mmol) and embodiment 4 (10.0g, 3mmol) (1.1057g 8mmol), NMP (100mL) mixes, and is heated to 180 ℃, reacted 48 hours for synthetic fragment polymkeric substance, Anhydrous potassium carbonate.Stop heating and stirring, naturally cool to room temperature.Suction filtration in the filtrate impouring 1000mL Virahol, is separated out white fiber shape solid, filters, and washed with isopropyl alcohol, oven dry 100 ℃ of following vacuum-dryings 24 hours, obtains block polymer again, 19.0g, yield: 95%, intrinsic viscosity: 0.81dL/g.
After the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the present invention also is not subjected to the restriction of the embodiment that gives an actual example in the specification sheets.
Claims (3)
1. the preparation method of block sulfonated poly aromatic ether or block sulfonated poly aromatic thioether is characterized in that comprising following step:
(1) be starting raw material with sulfonated monomers, biphenol monomer or two thiophenol monomer, add bis-phenol or two thiophenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in non-protonic solvent, temperature is controlled at 150-200 ℃, makes with phenol or thiophenol to be end group or to be the wetting ability fragment of end group with the halogen;
(2) be starting raw material with non-sulfonated monomers, biphenol monomer or two thiophenol monomer, add bis-phenol or two thiophenol total mole number 2-2.25 carbonate doubly as alkali, reaction is 10-24 hour in non-protonic solvent, temperature is controlled at 150-200 ℃, makes with phenol or thiophenol to be end group or to be the lipotropy fragment of end group with the halogen;
What (3) the wetting ability fragment that the phenol or the thiophenol of step (1) preparation is end group and step (2) prepared is the lipotropy fragment of end group with the halogen, press 1: 1 mixed of end group mole number, make mixed solution, add carbonate as alkali, reaction is 10-24 hour in non-protonic solvent, temperature of reaction is controlled at 150-200 ℃, wherein mixed solution: the mole number 1 of alkali: 2-2.25;
(4) with step (1) preparation what with the halogen be that wetting ability fragment and the step (2) of end group prepare is the lipotropy fragment of end group with phenol or thiophenol, press 1: 1 mixed of end group mole number, make mixed solution, add carbonate as alkali, reaction is 10-24 hour in non-protonic solvent, temperature of reaction is controlled at 150-200 ℃, wherein mixed solution: the mole number 1 of alkali: 2-2.25;
(5) with in the slow impouring deionized water of the reaction solution that obtains in (3) and (4), obtain the white fiber shaped polymer, under 60-80 ℃ of condition, soaked 5-10 hour then, repeat 3-5 time, filter, oven dry, vacuum-drying obtains block sulfonated poly aromatic ether or poly aromatic thioether; Non-protonic solvent wherein is N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or N-Methyl pyrrolidone.
2. preparation method as claimed in claim 1, wherein the mol ratio of bis-phenol or two thiophenol and sulfonated monomers or non-sulfonated monomers is phenol or thiophenol greater than 1 to guarantee prepared fragment end; The mol ratio of bis-phenol or two thiophenol and sulfonated monomers or non-sulfonated monomers is halogen less than 1 to guarantee prepared fragment end.
3. preparation method as claimed in claim 1, wherein said carbonate is Na
2CO
3, K
2CO
3Or Cs
2CO
3
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