CN1331557A - 全蒸发设备和灌溉底板 - Google Patents
全蒸发设备和灌溉底板 Download PDFInfo
- Publication number
- CN1331557A CN1331557A CN99813159A CN99813159A CN1331557A CN 1331557 A CN1331557 A CN 1331557A CN 99813159 A CN99813159 A CN 99813159A CN 99813159 A CN99813159 A CN 99813159A CN 1331557 A CN1331557 A CN 1331557A
- Authority
- CN
- China
- Prior art keywords
- unit
- iii
- pervaporation
- equipment
- substituted
- 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.)
- Granted
Links
- 238000005373 pervaporation Methods 0.000 title claims abstract description 20
- 238000003973 irrigation Methods 0.000 title description 10
- 230000002262 irrigation Effects 0.000 title description 10
- 150000001408 amides Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010612 desalination reaction Methods 0.000 claims abstract description 11
- 239000013535 sea water Substances 0.000 claims description 22
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 10
- 229920000570 polyether Polymers 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 20
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920002614 Polyether block amide Polymers 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229940100630 metacresol Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- FXQUKTSPZGJNSL-UHFFFAOYSA-N C1(CCCCC1)C.NNC(NN)=O Chemical class C1(CCCCC1)C.NNC(NN)=O FXQUKTSPZGJNSL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 102100028735 Dachshund homolog 1 Human genes 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000915055 Homo sapiens Dachshund homolog 1 Proteins 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- WULPUQZASCZTPO-UHFFFAOYSA-N azacycloundecan-2-one Chemical compound O=C1CCCCCCCCCN1 WULPUQZASCZTPO-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamic acid amide Natural products NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 238000010026 decatizing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 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
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyamides (AREA)
- External Artificial Organs (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
一种用于海水脱盐的全蒸发设备,它包括一个用于容纳或运输海水的渠道或腔和一个液态水不可透过、水蒸汽可透过的无孔膜,该膜由共聚醚酰胺制得,其中聚醚和(聚)酰胺链段通过酰胺桥键合。
Description
本发明涉及用于海水脱盐的全蒸发设备,该设备包括一个容纳或运输海水的渠道或腔和一个液态水不可透过、水蒸汽可透过的膜。
现有技术中已有用于从海水中制备淡水(即脱盐)的全蒸发设备。国际专利申请WO94/28706公开了一种灌溉底板。包括至少四层(结合第5页第7行至第7页第13行,特别参考图1和2):由水不可透过的材料,例如PE,PP或PVC制得的顶层,;液态水不能透过,但水蒸气能透过的疏水性多孔材料,例如聚四氟乙烯组成的第二层,它和所述顶层形成容纳海水的渠道;第三层和第四层形成用于冷却液的渠道。用来冷凝透过第二层的水蒸汽。
US专利公开US4,698,135公开了用太阳能驱动的脱盐滴灌器(结合第5栏第11-65行,特别参考图1和2)。该滴灌器包括一个由疏水性多孔材料制得的延长的蒸发盘(见图2中标号12),该蒸发盘通过一套从属裙部(depending skirts)(20)支撑在土壤上。在蒸发盘的上方,很多加长的、平行的输送管(26)用来引导海水。这些输送管由太阳辐射吸收材料制得,它为黑色,以最大程度地保存太阳能。一旦暴露在太阳辐射中,海水被加热,水蒸发并扩散通过蒸发盘;在下面的土壤上被冷凝。
遗憾的是,在长时间使用上面所说的设备过程中,出现疏水性多孔膜发生结垢和生物於积,这阻碍了广泛使用,否则需要昂贵维护。
国际专利申请WO95/24260涉及一种设备,它特别是,借助用于全蒸发分离的膜来提纯物质,例如废水。这种液态水不可透过、水蒸汽可透过的膜是无孔的,由基于亲水性醚酯共聚物的聚合物组成(见首页的摘要和第7页第13-27行)。
最后,US5,595,662公开了一种脱盐设备,包括一个运输海水的腔。该设备由无孔聚合物材料,例如亲水性聚氨酯或PEBAX组成。PEBAX是聚醚和聚酰胺链段通过酯桥键合的聚醚-聚酰胺嵌段聚合物。
WO95/24260和US5,595,662的膜虽然可能不会产生结垢和生物於积,但是,当这些膜暴露于热和海水时会很快地劣化因此不适用于脱盐全蒸发器。
本发明的目的是提供一个脱盐全蒸发器,它没有现有技术中的缺点。该目的是通过使用一种无孔膜达到的,该膜由共聚醚酰胺制得,该共聚醚酰胺包括(a)下述结构(I)的单元和/或(II)其中,R1为可被取代或不被取代的3-11个碳原子的亚烷基R2和R3相同或不同,表示可被取代或不被取代的4-11个碳原子的(环)亚烷基,或双官能芳基;(b)下式(III)的含聚氧化亚烷基的单元其中,G代表聚氧化亚烷基;和(c)下式(IV)的单元其中,R4为可被取代或不被取代的(环)亚烷基、聚氧化亚烷基或双官能芳基并且其中单元(III)通过酰胺桥键合到单元(I)和/或(II)和/或(IV)。
发明人发现,本发明的聚合物尤其对热和海水的侵蚀性组合具有长期抵抗性,这使它们非常适用于太阳加热的全蒸发设备。
需要说明的是,DE 42 37 604 A1描述了由包括聚醚链段的聚合物制成的膜在超滤中的用途提到聚酰胺-聚醚嵌段共聚物(例如PEBAX)作为优选的聚合物。该文献绝没有公开或暗示脱盐、灌溉及与这些应用领域相关的问题。而且,如上所述,已经发现,当由该聚合物制得的膜暴露在热和海水中,它很快地劣化。
还要说明的是,EP 0761715A1公开了本发明中用到的由聚合物制得的膜。然而,这篇文献针对的是完全不同的领域。即,这种聚合物用于雨衣、帐篷、座罩、屋顶的底板(underslating)、防水鞋、床垫罩、医用外衣和衣服。这篇文献没有提到这种聚合物材料与海水有关的长期稳定性问题,其中既没有公开也没有暗示由这种聚合物制得的膜在全蒸发设备中的用途。
下面,详细地描述本发明。
如上所述,本发明涉及一种用于海水脱盐的全蒸发设备,该设备包括一个用来容纳或运输海水的渠道或腔和一个液态水不可透过、水蒸汽可透过的无孔膜,其中该膜由共聚醚酰胺制得,该共聚醚酰胺包括(a)下述结构(I)的单元和/或(II)其中,R1为可被取代或不被取代的3-11个碳原子的亚烷基R2和R3可相同或不同,表示可被取代或不被取代的4-11个碳原子的(环)亚烷基,或者为双官能芳基;(b)下式(III)的含聚氧化亚烷基的单元其中,G代表聚氧化亚烷基;和(c)下式(IV)表示的单元其中,R4为可被取代或不被取代的(环)亚烷基聚氧化亚烷基或双官能芳基并且其中单元(III)通过酰胺桥键合到单元(I)和/或(II)和/或(IV)。
以共聚醚酰胺中含有的单元(I)、(II)和(III)的总重量为基准,优选共聚醚酰胺包括30-80wt%,更优选40-70wt%,最优选55-65wt%的单元(I)和/或(II),和20-70wt%,更优选30-60wt%,最优选35-45wt%的单元(III)。进一步优选聚合物包括单元(III)和(IV),其摩尔比为0.8-1.2,更优选0.9-1.1,更加优选摩尔比为0.95-1.05,和最优选1.0。
单元(I)通常由内酰胺的开环形成。适合的内酰胺为,例如,γ-丁内酰胺、δ-戊内酰胺、ε-己内酰胺、ω-十二内酰胺、或癸内酰胺,其中优选ε-己内酰胺。一般情况下,在本发明的共聚醚酰胺中,单元(I)键合到另一个单元(I),于是形成本身的嵌段物,例如,聚己内酰胺。
单元(II)通常由二羧酸和二胺的反应形成。适合的二胺为四亚甲基二胺、六亚甲基二胺、二氨基环己烷、4,4’-二氨基二环亚己基二胺,异氟尔酮二胺和1,4-双二氨基甲基环己烷。适合的二羧酸例子为己二酸、癸二酸、对苯二酸、间苯二酸、2,6-萘二甲酸、和环己烷二酸。一般情况下,在本发明的共聚醚酰胺中,单元(II)键合到另一个单元(II),于是形成其本身的嵌段物。优选嵌段物为聚酰胺-6,6和/或聚酰胺-6,12。
也可能使用单元(I)和(II)的组合。特别重要的是己内酰胺和聚酰胺-6,6的组合,优选在由己内酰胺组成的组合物中掺入最大量高达30wt%的聚酰胺-6,6,或在由聚酰胺-6,6组成的组合物中掺入最大量高达约40wt%的己内酰胺。
在单元(III)中,G为聚氧化烯基(也称为聚亚烷基氧化物)。通常,它有600-6000的分子量,优选1000-4000。优选在G中碳和氧的原子比在2.0-4.3范围内。
单元(III)可具有,例如,下面的结构:其中,n为25-40,优选30-40,最优选=±33(中间值)和/或其中,c至少为1,(a+c)至少为1,但小于6,优选±5.5(中间值);b至少为10,但不大于90,优选35-45,最优选±37.5(中间值)。
G的一个具体例子为聚氧化乙烯。在这个例子中,共聚醚酰胺优选含有10-30wt%,更优选15-25wt%的氧化乙烯基,以共聚醚酰胺中含有的单元(I)、(II)和(III)的总重量为基准。
如上所述,单元(IV)中的R4为可被取代或不被取代的(环)亚烷基、聚氧化亚烷基或双官能芳基用于生成单元(IV)的初始材料通常为二羧酸。这种二羧酸可以是例如不饱和二羧酸或具有一个官能团的二羧酸,例如,苹果酸。这种二羧酸的使用使官能团能掺入到聚合物中。
也优选脂(环)族二羧酸,其中R4为四亚甲基或亚环己基。其它优选的单元(IV)是从含有至少36个碳原子,例如含有44个碳原子的二聚脂族脂肪酸衍生而来的那些。
如果R4代表聚氧化亚烷基,它可,例如,全部或部分由氧化乙烯基组成;且它的分子量通常为600-6000,碳和氧的原子比为2.0-4.3。
可参考EP 0761 715 A1制备本发明中的共聚醚酰胺。通常步骤是这样的:第一步,将要聚合的单体,优选单元(I)的单体和最优选ε-己内酰胺,预先加到氮气氛中,该气氛中含有少量ε-氨基己酸或例如己二酸和六亚甲基二胺的单体,然后,加入二羧酸和优选等摩尔量的聚氧化亚烷基二胺。用氮清洗后,在4-20小时内将反应混合物加热到190℃-270℃的温度。通常,聚合反应在热稳定剂,例如1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟苄基)苯和/或N,N′-六亚甲基-双(3,5-二叔丁基-4-羟基肉桂酰胺)存在下进行。产品暴露在高温下太长时间,会导致潜在的不可逆的热解,为了避免这种情况,如果需要可使用一种催化剂。经常使用的催化剂是次磷酸钠、磷酸和次磷酸。聚合反应通常进行到得到的共聚物有至少2.0的相对粘度时(25℃下,1g聚合物在100g间甲酚的溶液中测量),优选2.4-2.8;然后,在固态下进行后缩合反应,分子量进一步增长,直到粘度值达到3-4。
本发明一个优选的实施方案是灌溉底板.这样的底板可用于,例如,没有足够的降水、有充足的阳光和海水或其他的海水资源的地方,作为一种得到淡水的装置。该底板包括至少一个能吸收阳光的上层和一个包括液态水不可透过、水蒸汽可透过的无孔膜的下层,所述下层和上层形成至少一个渠道或腔,其中的膜如上所述是由共聚醚酰胺制得的。
当该底板装满了水并暴露在阳光下,在底板中的水将被加热到约60-80℃,无盐的水蒸汽在底部发散。水蒸气随后冷凝成无盐的水。于是,底板可以同时脱盐和灌溉。在底板的尽头的存留水,其盐含量增加,将不得不被排出。
在一个优选的实施方案中,底板包括恰好两层,即所说的上层和所说的下层。很惊讶地发现这里不需要另外的冷却装置或裙部(skirt)来保证全蒸发水的冷凝。试验已实现日夜交替分别提供用于全蒸发充足的热量和用于冷凝土壤中大量水的足量的冷却。有恰好两层的底板对于生产而言可靠且简单,因此具有提供这种负担得起的脱盐设备的附加的益处。
为了进一步延长底板的寿命和改善它的机械性能,例如强度、撕裂强度、耐磨性和耐穿刺性,优选下层包括一种用于增强膜的无纺织物(nonwoven)。
特别适合和强(纺粘型)无纺织物是包含热粘合的单丝的那些。该无纺织物优选基重为20-150g/m2。
不必说,本发明膜的水蒸汽透过程度既依赖于聚合物的组成,也依赖于膜的厚度。一般来说,用于脱盐的水蒸汽可透过膜应当满足至少为500g/m2的水蒸气可透过值,根据ASTM E96-66(改进的方法B:水温度30℃,在60%相对湿度(RH)下环境温度为21℃)测量。发明人发现,一般情况下,当手中的膜的厚度为5-200μm时,可得到满意的结果。当聚合物膜的厚度为10-100μm时通常得到最优选的结果。
而且,本发明中用到的聚合物优选相对粘度为2.0-4.0,更优选2.5-3.5,因为这样的聚合物将好的物理性能和易挤出性结合起来。
在本发明的框架中,用到的海水的定义是取自北海的海水。相对粘度的测定:
相对粘度(ηrel)是根据ISO1628/1(1984)在Ubbelohde粘度计中,在1g聚合物溶于25℃的100g间甲酚的溶液中测定的。该溶液必须这样制备,即,在溶解过程中避免聚合物的降解。对于共聚醚酰胺,建议通过在90℃下将1g聚合物在100g间甲酚中溶解制得溶液(这用大约40分钟)。对于醚-酯共聚物(下面有一个比较实施例),溶液优选在135℃下通过将1g聚合物在100g间甲酚中溶解而制得(这用大约15分钟)。
现在通过下面的非限定性实施例描述本发明。实施例I:共聚醚酯和本发明的共聚醚酰胺之间的比较测试下面的样品:1.聚醚酯样品(PEE):由70%聚对苯二甲酸丁二酯(PBT)和30%聚乙二醇(PEG)4000组成。而且它们还包含0.5%的酚类稳定剂,即,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟苄基)苯。样品的厚度为1μm。2.依据本发明的共聚醚酰胺(PEA)样品,从下述材料制得(i)50wt%的ε-己内酰胺,(ii)25wt%的含有2-氨基丙基封端基的分子量约2000(Jeffamine D2000 exHuntsman)的聚(氧化丙烯),(iii)25wt%的含有2-氨基丙基封端基的分子量约2000(Jeffamine ED2003 exHuntsman)的聚(氧化乙烯),以ε-己内酰胺、PPO和PEO的总重量为基准;和(iv)以PPO和PEO的总摩尔量为基准,等摩尔量的己二酸。而且,它们包括0.5%非封端剂(微滑石)和0.5%上述的酚类稳定剂。样品的厚度为10μm。
将装有水冷却器的一个容器充满海水。海水通过加热盘加热到60℃。该容器用黑色的绝缘材料绝缘。磁搅拌海水。在该容器中放置一不锈钢支架,其上放置要被测试的尺寸为25cm×5cm×10μm的聚合物膜。一定时间间隔后,取出样品,用水冲洗,80℃下减压干燥16小时,然后测量它的相对粘度,这些测量结果见表1。
表1
相对粘度时间(周) PEE PEA(依据本发明)0 3.53 2.743 1.79 -6 1.50 -12 - 3.0523 - 2.9331 - 2.99(-=没有测量)
六周后,聚醚酯样品分解(肉眼观察),因此测量结束。相比之下,本发明的膜在整个试验中表现出基本恒定的相对粘度。
实施例II:其中聚醚和(聚)酰胺链段通过酯桥键合的共聚醚酰胺(PEBAX)和依据本发明的共聚醚酰胺(聚醚和(聚)酰胺链段是通过酰胺桥键合的)之间的比较。测量下面的样品:1.PEBAX,它是聚醚嵌段聚酰胺,商购于Atochem。样品由66wt%的聚酰胺11或12及34wt%的聚氧化乙烯,以聚氧化乙烯、聚酰胺的总重量为基准,以及还包括二酸。与本发明的共聚醚酰胺相反,该聚醚和聚酰胺链段通过酯桥键合(本发明中的术语,在PEBAX中,单元(III)于是由-O-G-O-细成。而不是-HN-G-NH-)。2.根据本发明的共聚醚酰胺(PEA)样品,包括(i)60wt%的ε-己内酰胺,(ii)20wt%的含有2-氨基丙基封端基的分子量约2000(Jeffamine D2000 exHuntsman)的聚(氧化丙烯),(iii)20wt%的含有2-氨基丙基封端基的分子量约2000(Jeffamine ED2003 exHuntsman)的聚(氧化乙烯),以ε-己内酰胺、PPO和PEO的总重量为基准和(iv)以PPO和PEO的总摩尔量为基准的等摩尔量的己二酸;和(v)如实施例I所述的0.5%非封端剂(微滑石)和0.5%的酚类稳定剂。
样品的厚度15μm。
相对粘度测量如实施例I所述。这些测量结果见表2。表2
相对粘度时间(周) PEBAX 依据本发明的PEA0 3.10 3.294 2.80 -11 - 3.1723 - 2.95(-=没有测量到)于是,在4周内PEBAX相对粘度降低了约10%,然而本发明的共聚醚酰胺只是大约23周后达到相同数量级的粘度降低。实施例III:依据本发明的灌溉底板
在Colblbk T 100型(100g/m2,由Akzo Nobel Industrial Nonwovens生产)无纺织物上通过挤出涂覆得到平均厚度为40μm的实施例I的共聚醚酰胺膜。
在它的边缘(和在聚醚酰胺的一侧),将得到的复合膜同厚度为300μm、长度和宽相同的黑PVC膜粘合在一起(Beiersdorf strip No.8401)。以这种方式形成了由二层组成的底板,底层由水蒸气可透过层组成。顶层由不可透过层组成。然后给底板安装供给和排出喷头。
在尺寸为1m2的沙盒中,通过许多灯用~1000kW/m2的模拟太阳能输入值进行试验。升高水的温度到60~80℃,对于一天12小时(12个小时黑暗),得到估计的淡水产出,平均为31/m2/天。在干燥的地区,有较多晴朗的日子(每年>300天)和较少的降水量,它每年每m2能产出大约1.0-1.3m3水。一般认为有效的灌溉是每年每m2要求大约0.5m3水。
底板可以长带的形式放置在一排排植物间。利用这样的底板,土地的50%覆盖率就可提供充足的灌溉。
Claims (10)
2.根据权利要求1的全蒸发设备,其中共聚醚酰胺包括40-70wt%单元(I)和/或(II)和30-60wt%单元(III),以单元(I)、(II)和(III)的总重量为基准。
3.根据以上任一权利要求的全蒸发设备,其中共聚醚酰胺中包含的单元(III)和(IV)的摩尔比为0.9-1.1。
4.根据以上任一权利要求的全蒸发没备,其中共聚醚酰胺含有10-30wt%的氧化乙烯基以共聚醚酰胺中含有的单元(I)、(II)和(III)的总重量为基准。
5.根据以上任一权利要求的全蒸发设备,其中在单元(III)中,G为分子量600-6000的聚氧化亚烷基。
6.根据以上任一权利要求的全蒸发设备,其中该设备包括至少一个能吸收阳光的上层和一个包括液态水不可透过、水蒸汽可透过的膜的下层,所述下层和上层形成至少一个渠道或腔。
7.根据权利要求6的全蒸发设备,其中该设备包括恰好二层,即所说的上层和所说的下层。
8.根据权利要求6或7的全蒸发设备,其中下层包括用于增强所述膜的无纺织物。
9.根据权利要求8的全蒸发设备,其中元纺织物的基重为20-150g/m2。
10.根据权利要求6-9的全蒸发设备,其中膜的水蒸气渗透性至少为500g/m2。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98203808.5 | 1998-11-13 | ||
EP98203808 | 1998-11-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1331557A true CN1331557A (zh) | 2002-01-16 |
CN1159090C CN1159090C (zh) | 2004-07-28 |
Family
ID=8234323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998131598A Expired - Fee Related CN1159090C (zh) | 1998-11-13 | 1999-10-25 | 用于海水脱盐的全蒸发设备 |
Country Status (14)
Country | Link |
---|---|
US (1) | US6679991B1 (zh) |
EP (1) | EP1128719B1 (zh) |
JP (1) | JP3998420B2 (zh) |
CN (1) | CN1159090C (zh) |
AT (1) | ATE300170T1 (zh) |
AU (1) | AU758752B2 (zh) |
BR (1) | BR9915300B1 (zh) |
DE (1) | DE69926389D1 (zh) |
HU (1) | HUP0104176A3 (zh) |
IL (1) | IL143066A0 (zh) |
PL (1) | PL347939A1 (zh) |
TR (1) | TR200101328T2 (zh) |
WO (1) | WO2000028807A1 (zh) |
ZA (1) | ZA200103805B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102177775A (zh) * | 2011-02-06 | 2011-09-14 | 胡盼成 | 一种用海水或淡水开发缺水土壤的方法 |
CN101679628B (zh) * | 2007-05-10 | 2013-03-13 | 雅培血管企业有限公司 | 包含改性聚酰胺与聚醚的共聚物的医用装置 |
US8500960B2 (en) | 2007-01-20 | 2013-08-06 | Dais Analytic Corporation | Multi-phase selective mass transfer through a membrane |
CN105050696A (zh) * | 2013-03-05 | 2015-11-11 | 阿卜杜拉国王科技大学 | 包括纳米结构的蒸馏用膜、膜制备方法及脱盐和分离方法 |
TWI775337B (zh) * | 2018-04-30 | 2022-08-21 | 美商恩特葛瑞斯股份有限公司 | 以聚醯胺塗覆之過濾薄膜、過濾器及方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6793824B2 (en) * | 1998-02-05 | 2004-09-21 | E. I. Du Pont De Nemours And Company | Water purification apparatus |
US6484439B1 (en) * | 1999-08-06 | 2002-11-26 | E.I. Du Pont De Nemours And Company | Irrigation device |
IL147715A0 (en) * | 1999-08-06 | 2002-08-14 | Du Pont | Water still and method of operation thereof |
US7258767B2 (en) * | 2000-01-17 | 2007-08-21 | Akzo Nobel N.V. | Solar dew tube |
US7344767B2 (en) * | 2004-07-26 | 2008-03-18 | Serena Giori | Self-cooling beverage container with permeable wall |
US20060091076A1 (en) * | 2004-11-01 | 2006-05-04 | Marcellus Michael T | Solar powered rescue and/or utility device for producing portable water from salt water, brine water or impure water |
US20080142428A1 (en) * | 2005-02-24 | 2008-06-19 | Sympatex Technologies Gmbh | Evaporation Reservoir |
EP1942128B1 (en) | 2006-12-29 | 2016-09-14 | Abbott Laboratories Vascular Enterprises Limited | Modified polyamides |
EP1990357A1 (en) | 2007-05-10 | 2008-11-12 | Abbott Laboratories Vascular Enterprises Limited | Co-polymer of a polyamide and a polycarbonate diamine |
CN101965422B (zh) * | 2008-05-15 | 2013-04-10 | 东洋纺织株式会社 | 共聚聚醚聚酰胺树脂 |
US8403902B2 (en) * | 2010-05-18 | 2013-03-26 | Kci Licensing, Inc. | Reduced-pressure medical systems and methods employing a moisture processing device |
CN110681272B (zh) * | 2018-07-06 | 2022-02-01 | 中国石油化工股份有限公司 | 聚酰亚胺渗透汽化膜及其制备方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4698135A (en) | 1983-02-10 | 1987-10-06 | Sirdan Research Limited | Desalinating drip-irrigation system |
JPH02126925A (ja) * | 1988-07-28 | 1990-05-15 | Mitsubishi Kasei Corp | 複合分離膜 |
EP0465306B1 (en) * | 1990-06-26 | 1995-08-16 | Terumo Kabushiki Kaisha | Permeable membrane excellent in biocompatibility |
DK0543171T3 (da) * | 1991-10-26 | 1997-07-28 | Hoechst Ag | Semipermeable, porøse, asymmetriske polyetheramidmembraner. |
US5562826A (en) | 1991-10-26 | 1996-10-08 | Hoechst Aktiengesellschaft | Semipermeable, porous, asymmetric polyether amide membranes |
JPH0750939A (ja) * | 1993-06-10 | 1995-02-28 | Shimizu Corp | 灌漑用膜材及び灌漑方法 |
WO1995024260A1 (de) * | 1994-03-11 | 1995-09-14 | Akzo Nobel Nv | Vorrichtung zur trennung von stoffgemischen bzw. zum reinigen von stoffen mittels pervaporation |
AU684210B2 (en) | 1994-08-19 | 1997-12-04 | Water Research Commission | A water purification device |
US5744570A (en) | 1995-08-17 | 1998-04-28 | Akzo Nobel Nv | Copolyether amide and water vapour permeable film made therefrom |
US6187696B1 (en) * | 1997-12-03 | 2001-02-13 | E. I. Du Pont De Nemours And Company | Breathable composite sheet structure |
EP0963760A1 (en) * | 1998-06-09 | 1999-12-15 | The Procter & Gamble Company | Low viscosity thermoplastic compositions for moisture vapour permeable structures and the utilisation thereof in absorbent articles |
-
1999
- 1999-10-25 EP EP99972068A patent/EP1128719B1/en not_active Expired - Lifetime
- 1999-10-25 AU AU11557/00A patent/AU758752B2/en not_active Ceased
- 1999-10-25 JP JP2000581874A patent/JP3998420B2/ja not_active Expired - Fee Related
- 1999-10-25 HU HU0104176A patent/HUP0104176A3/hu unknown
- 1999-10-25 BR BRPI9915300-9A patent/BR9915300B1/pt not_active IP Right Cessation
- 1999-10-25 AT AT99972068T patent/ATE300170T1/de not_active IP Right Cessation
- 1999-10-25 TR TR200101328T patent/TR200101328T2/xx unknown
- 1999-10-25 US US09/831,789 patent/US6679991B1/en not_active Expired - Fee Related
- 1999-10-25 WO PCT/EP1999/008159 patent/WO2000028807A1/en active IP Right Grant
- 1999-10-25 IL IL14306699A patent/IL143066A0/xx unknown
- 1999-10-25 PL PL99347939A patent/PL347939A1/xx unknown
- 1999-10-25 DE DE69926389T patent/DE69926389D1/de not_active Expired - Lifetime
- 1999-10-25 CN CNB998131598A patent/CN1159090C/zh not_active Expired - Fee Related
-
2001
- 2001-05-10 ZA ZA200103805A patent/ZA200103805B/en unknown
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8500960B2 (en) | 2007-01-20 | 2013-08-06 | Dais Analytic Corporation | Multi-phase selective mass transfer through a membrane |
CN101679628B (zh) * | 2007-05-10 | 2013-03-13 | 雅培血管企业有限公司 | 包含改性聚酰胺与聚醚的共聚物的医用装置 |
CN102177775A (zh) * | 2011-02-06 | 2011-09-14 | 胡盼成 | 一种用海水或淡水开发缺水土壤的方法 |
CN105050696A (zh) * | 2013-03-05 | 2015-11-11 | 阿卜杜拉国王科技大学 | 包括纳米结构的蒸馏用膜、膜制备方法及脱盐和分离方法 |
TWI775337B (zh) * | 2018-04-30 | 2022-08-21 | 美商恩特葛瑞斯股份有限公司 | 以聚醯胺塗覆之過濾薄膜、過濾器及方法 |
Also Published As
Publication number | Publication date |
---|---|
BR9915300A (pt) | 2001-08-07 |
US6679991B1 (en) | 2004-01-20 |
AU1155700A (en) | 2000-06-05 |
WO2000028807A1 (en) | 2000-05-25 |
DE69926389D1 (de) | 2005-09-01 |
PL347939A1 (en) | 2002-04-22 |
BR9915300B1 (pt) | 2009-01-13 |
TR200101328T2 (tr) | 2004-11-22 |
JP3998420B2 (ja) | 2007-10-24 |
CN1159090C (zh) | 2004-07-28 |
JP2002529236A (ja) | 2002-09-10 |
HUP0104176A3 (en) | 2003-03-28 |
ZA200103805B (en) | 2002-08-12 |
IL143066A0 (en) | 2002-04-21 |
AU758752B2 (en) | 2003-03-27 |
HUP0104176A2 (hu) | 2002-04-29 |
EP1128719B1 (en) | 2005-07-27 |
ATE300170T1 (de) | 2005-08-15 |
EP1128719A1 (en) | 2001-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1331557A (zh) | 全蒸发设备和灌溉底板 | |
JP2635259B2 (ja) | ブロックポリエーテル―アミドの合成方法 | |
US5989697A (en) | Copolyether amide and water vapor permeable film made therefrom | |
US5166309A (en) | Block polyetheramides | |
EP0451953B1 (en) | Process for the preparation of polyether amides from mixed amines | |
US5086162A (en) | Polyether amide from polyalkylene glycol diamine and diacid mixture | |
Jayarani et al. | Thin-film composite poly (esteramide)-based membranes | |
KR20080093056A (ko) | 적어도 부분적으로 폴리트리메틸렌 에테르 글리콜에서 유래하는 폴리아미드 블록 및 폴리에테르 블록을 포함하는 공중합체의 새로운 용도 | |
KR101313515B1 (ko) | 열가소성 탄성중합체를 기재로 한 혼합물 | |
JPS62527A (ja) | ポリアミド共重合体 | |
EP0451951A2 (en) | Polyether amide from tetraethylene glycol diamine and terephthalic acid | |
GB1561792A (en) | Process for the production of polyesteramides | |
Theiler et al. | Synthesis and characterization of biodegradable polyester/polyether resins via Michael-type addition | |
Ogata et al. | Effect of crystallinity of condensation polymers on platelet adhesion | |
D'Angelo et al. | Segmented poly (ether–ester–amide) s based on poly (l, l-lactide) macromers | |
Zhang et al. | Synthesis and characterization of phosphoryl-choline-capped poly (ε-caprolactone)-poly (ethylene oxide) di-block co-polymers and its surface modification on polyurethanes | |
Arvanitoyannis et al. | Novel biodegradable copolyamides based on adipic acid, isophorone diamine and α‐amino acids, 3. Synthesis, study of properties and evaluation of their biodegradability for food packaging applications | |
IL44761A (en) | Poly-and copolypiperazinamides membranes for reverse osmosis made therefrom and their preparation | |
Dennis | High Performance Engineering Polymers: Design, Properties, and Performance | |
Mochizuki et al. | Polyether‐segmented nylon hemodialysis membranes. III. Preparation and properties of new polyether‐segmented nylon | |
JP4441032B2 (ja) | 二官能性有機リン化合物、重合体、及び用途 | |
JPH0621164B2 (ja) | ポリアミドエラストマ−の製法 | |
Seo et al. | Composite membranes prepared from 2, 2-bis [4-(2-hydroxy-3-methacryloyloxy propoxy) phenyl] propane derivatives and their mixtures for the reverse osmosis | |
Nakata et al. | Preparation of copolyamides based on aramid blocks with 7–9 phenylene monomer units and regularly inserted 1, 6-hexanediamino units | |
EP0239626A1 (en) | Polyamide resins capable of forming containers having improved gas barrier properties |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
C10 | Entry into substantive examination | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040728 Termination date: 20101025 |