CN114262401B - Photoinduced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair - Google Patents
Photoinduced reversible solid-liquid conversion azobenzene high polymer material and application thereof in trenchless pipeline repair Download PDFInfo
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 230000008439 repair process Effects 0.000 title claims abstract description 25
- 239000002861 polymer material Substances 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 title claims description 7
- 230000002441 reversible effect Effects 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 17
- 230000007704 transition Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000009412 basement excavation Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- -1 4-decylphenyl Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- WGENWPANMZLPIH-UHFFFAOYSA-N 4-decylaniline Chemical compound CCCCCCCCCCC1=CC=C(N)C=C1 WGENWPANMZLPIH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- DMLAVOWQYNRWNQ-BUHFOSPRSA-N (E)-azobenzene Chemical compound C1=CC=CC=C1\N=N\C1=CC=CC=C1 DMLAVOWQYNRWNQ-BUHFOSPRSA-N 0.000 description 2
- DMLAVOWQYNRWNQ-YPKPFQOOSA-N (Z)-azobenzene Chemical compound C1=CC=CC=C1\N=N/C1=CC=CC=C1 DMLAVOWQYNRWNQ-YPKPFQOOSA-N 0.000 description 2
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000005553 drilling Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
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- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007699 photoisomerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
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- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 description 1
- YFILBNCPXYOFKP-UHFFFAOYSA-N 4-[(4-decylphenyl)diazenyl]phenol Chemical compound C(CCCCCCCCC)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O YFILBNCPXYOFKP-UHFFFAOYSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
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Abstract
本发明公开了一种光致可逆固液转变偶氮苯高分子材料及其在非开挖管道修复中的应用,其中光致可逆固液转变偶氮苯高分子材料具有反式和顺式两种构型,分别如下式I‑(E)和下式I‑(Z)所示:
反式构型的式I‑(E)高分子在室温下为固态,顺式构型的式I‑(Z)高分子在室温下为液态。本发明偶氮苯高分子材料可以作为非开挖管道修复内衬材料使用,通过喷涂或灌输偶氮苯高分子溶液的方式获得管道内衬层;管道破损时,对内衬层施加紫外光,可使内衬材料流动填补裂缝,实现管道修复。The invention discloses a photoreversible solid-liquid transition azobenzene polymer material and its application in non-excavation pipeline repair, wherein the photoreversible solid-liquid transition azobenzene polymer material has two types: trans and cis Configuration, shown in following formula I-(E) and following formula I-(Z) respectively:
The polymer of formula I-(E) in trans configuration is solid at room temperature, and the polymer of formula I-(Z) in cis configuration is liquid at room temperature. The azobenzene polymer material of the present invention can be used as a non-excavation pipeline repair lining material, and the pipeline lining layer is obtained by spraying or pouring the azobenzene polymer solution; when the pipeline is damaged, ultraviolet light is applied to the lining layer, Allows lining material to flow to fill cracks for pipeline repair.Description
技术领域technical field
本发明属于管道修复技术领域,具体涉及一种光致可逆固液转变偶氮苯高分子材料及其在非开挖管道修复中的应用。The invention belongs to the technical field of pipeline repair, and in particular relates to a photoreversible solid-liquid transition azobenzene polymer material and its application in trenchless pipeline repair.
背景技术Background technique
2020年,城市排水管道长度已超过80万公里,管道使用时间过久就会出现老化、腐蚀、裂缝和坍塌等损坏现象,需要及时对其进行维修。管道非开挖修复技术是指利用各种岩土钻掘设备和技术手段,通过导向、定向钻进等方式在地表极小部分开挖的情况下,敷设、更换和修复各种地下管线的施工新技术,不会阻碍交通、破坏植被,不会影响社会的正常运行,具有较高的社会经济价值。In 2020, the length of urban drainage pipelines has exceeded 800,000 kilometers. If the pipelines are used for a long time, they will be damaged such as aging, corrosion, cracks and collapses, and they need to be repaired in time. Pipeline trenchless repair technology refers to the construction of laying, replacing and repairing various underground pipelines under the condition of excavating a very small part of the surface by using various geotechnical drilling equipment and technical means through guided and directional drilling. The new technology will not hinder traffic, destroy vegetation, and will not affect the normal operation of society, so it has high social and economic value.
现有的非开挖管道修复技术是一种来源于德国的紫外光固化修复管道技术,是市政管道非开挖修复的主流技术。但是该修复技术的内衬管再次受到破坏后,由于传统的交联聚合物无法熔融或溶解,不能再次修复。想要阻止水管渗漏,只能再次冲入内衬管或者直接进行开挖更换管道。The existing trenchless pipeline repair technology is a kind of ultraviolet curing pipeline repair technology from Germany, which is the mainstream technology of municipal pipeline trenchless repair. However, after the lining pipe of this repair technology is damaged again, it cannot be repaired again because the traditional cross-linked polymer cannot be melted or dissolved. If you want to stop the water pipe from leaking, you can only flush the lining pipe again or directly excavate and replace the pipe.
发明内容Contents of the invention
有鉴于此,本发明提供了一种光致可逆固液转变偶氮苯高分子材料及其在非开挖管道修复中的应用。本发明偶氮苯高分子材料可以多次在紫外光下发生从固态到液态的转变,并在停止光照后回复成固态,满足管道多次非开挖修复的需求。In view of this, the present invention provides a photoreversible solid-liquid transition azobenzene polymer material and its application in trenchless pipeline repair. The azobenzene macromolecule material of the present invention can change from solid state to liquid state under ultraviolet light for many times, and return to solid state after stopping the light, which meets the requirement of multiple non-excavation repairs of pipelines.
本发明光致可逆固液转变偶氮苯高分子材料,具有反式和顺式两种构型,分别如下式I-(E)和下式I-(Z)所示:The photoreversible solid-liquid transition azobenzene polymer material of the present invention has two configurations of trans and cis, respectively shown in the following formula I-(E) and the following formula I-(Z):
反式构型的式I-(E)高分子在室温下为固态,顺式构型的式I-(Z)高分子在室温下为液态。The trans-configuration formula I-(E) macromolecule is solid at room temperature, and the cis-configuration formula I-(Z) macromolecule is liquid state at room temperature.
所述偶氮苯高分子材料的聚合度n=n1+n2,n的取值范围为14-200;多分散性指数为1.1-2。The degree of polymerization of the azobenzene polymer material is n=n 1 +n 2 , and the range of n is 14-200; the polydispersity index is 1.1-2.
本发明偶氮苯高分子材料的制备方法,包括如下步骤:The preparation method of azobenzene polymer material of the present invention comprises the steps:
步骤1:将单体6-(4-((4-癸基苯基)二氮基)苯氧基)甲基丙烯酸己酯、溴化亚铜、引发剂放入耐压瓶中,接着在手套箱中操作,用注射器向瓶中加入配体和无水苯甲醚,密封后从手套箱中取出,室温反应20-320min,过碱性氧化铝柱,然后用倒入石油醚中,抽滤,干燥,用四氢呋喃溶解固体,然后在乙醚中多次沉淀除去未反应的单体,45℃真空过夜干燥,制备得到如式I-(E)所示结构的偶氮苯高分子。Step 1: Put the monomer 6-(4-((4-decylphenyl)diazo)phenoxy)hexyl methacrylate, cuprous bromide, and initiator into a pressure-resistant bottle, and then Operate in a glove box, add ligand and anhydrous anisole into the bottle with a syringe, take it out from the glove box after sealing, react at room temperature for 20-320min, overbasic alumina column, then pour it into petroleum ether, pump Filter, dry, dissolve the solid with tetrahydrofuran, and then remove unreacted monomers by multiple precipitations in ether, and dry overnight in vacuum at 45°C to prepare an azobenzene polymer with the structure shown in formula I-(E).
步骤2:反式构型的偶氮苯高分子I-(E)在1-100mW/cm2的365nm紫外光照射下转化为顺式构型的偶氮苯分子I-(Z),相态由固态转换为液态;顺式构型的偶氮苯高分子I-(Z)在室温下自然放置,或者在1-100mW/cm2的530nm可见光照射下转化为反式构型的偶氮苯高分子I-(E),相态由液态转换为固态。Step 2: Azobenzene polymer I-(E) in trans configuration is converted into azobenzene molecule I-(Z) in cis configuration under 1-100mW/ cm2 365nm ultraviolet light irradiation, phase state From solid state to liquid state; cis-configuration azobenzene polymer I-(Z) is placed naturally at room temperature, or converted to trans-configuration azobenzene under 530nm visible light irradiation of 1-100mW/ cm2 Polymer I-(E), phase transition from liquid to solid.
重复上述步骤2,即可实现固液转变的可逆循环。Repeating the
步骤1中,所述单体的结构如下式Ⅱ所示:In
式Ⅱ所示单体具有反式和顺式两种构型,在制备式I-(E)所示结构的反式偶氮苯高分子时,只要保证式Ⅱ所示单体中反式构型含量≥85%即可,在该条件下可直接用于步骤1偶氮苯高分子材料的制备。The monomer shown in formula II has two configurations: trans and cis. When preparing the trans azobenzene polymer with the structure shown in formula I-(E), as long as the trans configuration in the monomer shown in formula II is guaranteed The content is ≥85%. Under this condition, it can be directly used in the preparation of
步骤1中,所述引发剂为1,8-二酰基双(2-溴-2-甲基丙酸酯)辛烷。这种两端引发剂比偶氮苯常规聚合用的引发剂,可以提高最少一倍的聚合效率,适合工业生产。In
所述引发剂1,8-二酰基双(2-溴-2-甲基丙酸酯)辛烷是通过包括如下步骤的方法制备获得:The
将1,8-辛二醇(1.65g,11.3mmol)溶于二氯甲烷溶剂中,然后向其中加入三乙胺(8.2mL,58.9mmol),搅拌均匀,在冰水浴中冷却到5℃以下;以3s/滴的速度向体系中滴加2-溴代异丁酰溴(7ml,56.5mmol),滴加过程中有白色烟雾产生,温度略有上升;滴加完毕后,用封口膜密封瓶口,继续过夜搅拌反应12h;反应结束后用二氯甲烷(下层)和氯化钠饱和水溶液萃取三次,收集有机相,无水硫酸钠干燥除水,过滤,40℃旋蒸除溶剂,过硅胶柱,洗脱剂为石油醚:二氯甲烷100:0-4:1(v/v),45℃真空干燥4h,得到1.8g引发剂。Dissolve 1,8-octanediol (1.65g, 11.3mmol) in dichloromethane solvent, then add triethylamine (8.2mL, 58.9mmol) to it, stir well, and cool to below 5°C in an ice-water bath ; Add dropwise 2-bromoisobutyryl bromide (7ml, 56.5mmol) in the system at a speed of 3s/ drop, white smoke is produced during the dropwise addition process, and the temperature rises slightly; after dropwise addition, seal with parafilm bottle mouth, continue overnight stirring reaction for 12h; after the reaction is completed, extract three times with dichloromethane (lower layer) and saturated aqueous solution of sodium chloride, collect the organic phase, dry over anhydrous sodium sulfate to remove water, filter, and remove the solvent by rotary evaporation at 40°C. Silica gel column, the eluent is petroleum ether: dichloromethane 100:0-4:1 (v/v), vacuum dried at 45°C for 4h to obtain 1.8g initiator.
本发明通过ATRP聚合方法,得到了一种室温下具有光致可逆固液转变特性的偶氮苯高分子材料,可以作为非开挖管道修复内衬材料使用。具体是通过喷涂或灌输偶氮苯高分子溶液的方式获得管道内衬层。管道破损时,对内衬层施加紫外光,可使内衬材料流动填补裂缝,实现管道修复。The invention obtains an azobenzene polymer material with photoreversible solid-liquid transition characteristics at room temperature through an ATRP polymerization method, and can be used as a non-excavation pipeline repair lining material. Specifically, the inner lining layer of the pipeline is obtained by spraying or pouring the azobenzene polymer solution. When the pipeline is damaged, applying ultraviolet light to the lining layer can make the lining material flow to fill the cracks and realize pipeline repair.
所述内衬层厚度为0.1-1mm。The thickness of the inner lining layer is 0.1-1 mm.
所述偶氮苯高分子溶液的有机溶剂可以采用氯仿、四氢呋喃、苯甲醚或二氧六环中任意一种。The organic solvent of the azobenzene polymer solution can be any one of chloroform, tetrahydrofuran, anisole or dioxane.
所述偶氮苯高分子溶液的浓度为20-50wt%。The concentration of the azobenzene polymer solution is 20-50wt%.
所述偶氮苯高分子溶液中,由于顺式构型的偶氮苯高分子I-(Z)具有流动性,可能被管道中的液体冲洗带走,反式构型的偶氮苯高分子I-(E)含量需超过80%,溶剂挥发后可形成力学性能较好的内衬层,起到保护管道的作用。In the azobenzene macromolecule solution, because the azobenzene macromolecule I-(Z) of the cis configuration has fluidity, it may be washed away by the liquid in the pipeline, and the azobenzene macromolecule of the trans configuration The I-(E) content needs to exceed 80%. After the solvent volatilizes, an inner lining layer with better mechanical properties can be formed to protect the pipeline.
与现有的非开挖管道修复用内衬材料相比,本发明具有如下优点:Compared with the existing lining materials for trenchless pipeline repair, the present invention has the following advantages:
本发明非开挖管道修复用光致液化内衬材料是一种线性结构,既可以通过加热到熔点以上使其流动,也可以利用光致顺反异构特性发生光致固液转变。一旦管道发生破损,就可以通过加热或光照使偶氮苯高分子发生流动,实现多次非开挖修复管道。并且,由于顺式偶氮苯高分子材料的可流动性,在加压和重力作用下,顺式偶氮苯高分子可以被毛细力吸入裂缝内部,实现整个裂缝的完全填充,达到更好的修复效果。The photo-liquefied inner lining material for non-excavation pipeline repair of the present invention has a linear structure, which can be heated above the melting point to make it flow, and can also undergo photo-induced solid-liquid transformation by utilizing photo-induced cis-trans isomerism. Once the pipeline is damaged, the azobenzene polymer can be made to flow through heating or light, so as to realize multiple non-excavation repairs of the pipeline. Moreover, due to the fluidity of the cis-azobenzene polymer material, under the action of pressure and gravity, the cis-azobenzene polymer can be sucked into the crack by capillary force to completely fill the entire crack and achieve better Repair effect.
附图说明Description of drawings
图1示出了聚合单体的核磁共振氢谱图。Figure 1 shows the H NMR spectra of polymerized monomers.
图2示出了偶氮苯聚合物的核磁共振氢谱图。Figure 2 shows the H NMR spectrum of the azobenzene polymer.
图3示出了反式偶氮苯固体样品在紫外光(365nm LED光源)照射下发生液化的显微镜照片(标尺为50μm)。Fig. 3 shows the photomicrograph (scale bar is 50 μm) of liquefaction of trans-azobenzene solid sample under the irradiation of ultraviolet light (365nm LED light source).
图4示出了涂覆有偶氮苯高分子的PVC-U管的修复前后的电子计算机断层扫描结果(标尺为6mm)。Fig. 4 shows the computerized tomography results (the scale is 6 mm) of the PVC-U pipe coated with azobenzene polymer before and after repair.
具体实施方式detailed description
为了进一步说明本发明,下面结合实施例对本发明提供的具有光致可逆固液转变特性的偶氮苯高分子材料的合成方法及其作为管道修复内衬的应用进行详细描述。In order to further illustrate the present invention, the synthesis method of the azobenzene polymer material with photoreversible solid-liquid transition characteristics provided by the present invention and its application as a pipeline repair lining will be described in detail below in conjunction with examples.
以下实施例中使用的4-正癸基苯胺购自TCL,浓盐酸、四氢呋喃、亚硝酸钠、苯酚、氢氧化钠、碳酸氢钠、无水碳酸钾、无水硫酸钠、氯仿和甲醇购自国药,石油醚和二氯甲烷购自科隆化学,并且6-氯-1-己醇购自安耐吉,甲基丙烯酰氯购自麦克林。The 4-n-decylaniline used in the following examples was purchased from TCL, concentrated hydrochloric acid, tetrahydrofuran, sodium nitrite, phenol, sodium hydroxide, sodium bicarbonate, anhydrous potassium carbonate, anhydrous sodium sulfate, chloroform and methanol were purchased from Sinopharm, petroleum ether and methylene chloride were purchased from Cologne Chemicals, 6-chloro-1-hexanol was purchased from Anaiji, and methacryloyl chloride was purchased from McLean.
实施例1:聚合单体的合成Embodiment 1: the synthesis of polymerization monomer
1、将4-正癸基苯胺(10g,42.8mmol)加入到稀盐酸(11.0ml,ρ=1.18g/ml,128.8mmol)和四氢呋喃(40ml)的混合溶液中,然后置于冰水浴内。搅拌均匀后,向其中缓慢加入亚硝酸钠(2.950g,42.8mmol)水溶液,混合20min。将苯酚(4.6mL,1.071g/ml,49.5mmol)溶于氢氧化钠(1.7g,43.0mmol)和碳酸钾(6.0g,43.4mmol)的水溶液,搅拌20min。将含有4-正癸基苯胺的混合溶液缓慢滴加至含有苯酚的混合溶液中反应,溶液由黄色逐渐变为棕色,室温搅拌4h。用稀盐酸中和至pH=6,抽滤,水洗三次,得到黄棕色固体。45℃真空干燥过夜,石油醚热重结晶,过滤,再次真空干燥,得到13.8g产物。产率:95%。1. 4-n-decylaniline (10g, 42.8mmol) was added to a mixed solution of dilute hydrochloric acid (11.0ml, ρ=1.18g/ml, 128.8mmol) and tetrahydrofuran (40ml), then placed in an ice-water bath. After stirring evenly, an aqueous solution of sodium nitrite (2.950 g, 42.8 mmol) was slowly added thereto, and mixed for 20 min. Phenol (4.6 mL, 1.071 g/ml, 49.5 mmol) was dissolved in an aqueous solution of sodium hydroxide (1.7 g, 43.0 mmol) and potassium carbonate (6.0 g, 43.4 mmol), and stirred for 20 min. The mixed solution containing 4-n-decylaniline was slowly added dropwise to the mixed solution containing phenol to react, the solution gradually changed from yellow to brown, and stirred at room temperature for 4 h. Neutralize to pH=6 with dilute hydrochloric acid, filter with suction, and wash with water three times to obtain a yellow-brown solid. Vacuum-dried at 45°C overnight, thermally recrystallized from petroleum ether, filtered, and vacuum-dried again to obtain 13.8 g of the product. Yield: 95%.
2、称量步骤1的产物4-(4-癸基苯基偶氮)苯酚(13.5g,39.8mmol)溶于300ml N,N-二甲基甲酰胺,向其中加入碳酸钾(6.0g,43.4mmol),搅拌20min。向其中加入6-氯-1-己醇(8ml,ρ=1.024g/ml,60.0mmol)和几粒碘化钾,110℃反应22h。冷却后,用乙酸乙酯和碳酸氢钠水溶液进行萃取,分离得到有机相,无水硫酸钠干燥,过滤,45℃旋蒸除去乙酸乙酯,得到粗产物。用二氯甲烷和石油醚分别作为良溶剂和不良溶剂,对粗产物进行两次重结晶。45℃真空过夜干燥,得到17.0g产物。产率:90%。2. Weigh the product 4-(4-decylphenylazo)phenol (13.5g, 39.8mmol) in
3、称量步骤2的产物6-(4-((4-癸基苯基偶氮)苯氧基)己烷-1-醇(10.2g,23.1mmol)、三乙胺(3.6ml,ρ=0.73g/ml,25.5mmol)和150mL二氯甲烷加入到250mL单口烧瓶中,置于冰水浴中。搅拌均匀后,通过滴液漏斗,以3~4秒/滴的速度,向其中加入甲基丙烯酰氯(2.7mL,ρ=1.1g/ml,28.5mmol)和30mL二氯甲烷的混合溶液。过夜反应14h,点板原料均反应完毕。在搅拌情况下,向溶液中加入碳酸氢钠饱和水溶液中和剩余的甲基丙烯酰氯,然后用二氯甲烷萃取三次。分离得到有机相,无水硫酸钠干燥,过滤,并旋蒸除溶剂。然后用四氢呋喃和甲醇进行两次重结晶,抽滤,40℃真空过夜干燥,得到9.6g聚合单体,产率:80%。3. Weigh the product 6-(4-((4-decylphenylazo)phenoxy)hexan-1-ol (10.2g, 23.1mmol), triethylamine (3.6ml, ρ =0.73g/ml, 25.5mmol) and 150mL dichloromethane join in the 250mL one-necked flask, place in ice-water bath.After stirring evenly, through the dropping funnel, with the speed of 3~4 seconds/drop, add formazan wherein A mixed solution of acryloyl chloride (2.7mL, ρ=1.1g/ml, 28.5mmol) and 30mL of dichloromethane. Overnight reaction for 14h, all the raw materials on the spot plate were reacted. Under the condition of stirring, sodium bicarbonate was added to the solution to saturate Neutralize the remaining methacryloyl chloride with aqueous solution, and then extract three times with dichloromethane. Separate the organic phase, dry it with anhydrous sodium sulfate, filter, and remove the solvent by rotary evaporation. Then recrystallize twice with tetrahydrofuran and methanol, and filter with suction , dried overnight at 40° C. under vacuum to obtain 9.6 g of polymerized monomers, yield: 80%.
图1示出了所制备的聚合单体的核磁氢谱图。Figure 1 shows the H NMR spectra of the prepared polymerized monomers.
实施例2:偶氮苯高分子的聚合Embodiment 2: Polymerization of azobenzene macromolecule
将1,8-辛二醇(1.65g,11.3mmol)溶于80mml二氯甲烷溶剂中,然后向其中加入三乙胺(8.2mL,58.9mmol),搅拌均匀,在冰水浴中冷却到5℃以下;通过滴液漏斗,以3s/滴的速度向该溶液中加入2-溴代异丁酰溴(7ml,56.5mmol),滴加过程中有白色烟雾产生,温度略有上升。滴加完毕后,用封口膜密封瓶口,继续过夜搅拌12h。用二氯甲烷(下层)和氯化钠饱和水溶液萃取三次,收集有机相。用无水硫酸钠干燥除水,过滤,40℃旋蒸除溶剂。过硅胶柱,洗脱剂为石油醚:二氯甲烷100:0-4:1。45℃真空干燥4h,得到1.8g引发剂。Dissolve 1,8-octanediol (1.65g, 11.3mmol) in 80mml of dichloromethane solvent, then add triethylamine (8.2mL, 58.9mmol) to it, stir well, and cool to 5°C in an ice-water bath Below; through the dropping funnel, add 2-bromoisobutyryl bromide (7ml, 56.5mmol) in this solution with the speed of 3s/ drops, white mist is produced in the dropping process, and temperature rises slightly. After the dropwise addition, seal the mouth of the bottle with parafilm and continue to stir overnight for 12h. Extract three times with dichloromethane (lower layer) and saturated aqueous sodium chloride, and collect the organic phase. Dry with anhydrous sodium sulfate to remove water, filter, and remove solvent by rotary evaporation at 40°C. Pass through a silica gel column, and the eluent is petroleum ether:dichloromethane 100:0-4:1. Vacuum-dry at 45°C for 4 hours to obtain 1.8g of initiator.
取实施例1中的单体6-(4-((4-癸基苯基)偶氮)苯氧基)甲基丙烯酸己酯(2.000g,4mmol)、溴化亚铜(38.0mg,26.4μmol)、双端引发剂1,8-二酰基双(2-溴-2-甲基丙酸酯)辛烷(57.2mg,128.8μmol)放入15mL的厚壁耐压瓶中,接着在手套箱中操作,用微量注射器向瓶中加入配体PMDETA(110μl,529.0μmol),然后加入4mL无水苯甲醚,密封后从手套箱中取出。在31℃水浴锅中搅拌40min,单体转化率51.7%。过碱性氧化铝柱,然后用倒入石油醚中,抽滤,干燥。用四氢呋喃溶解固体,然后在乙醚中沉淀除去未反应的单体,45℃真空过夜干燥,得到如式Ⅱ-(E)所示聚合物。通过GPC测得聚合物Mn=15K,PDI=1.18。图2示出了所制备的偶氮苯高分子的核磁氢谱图。Take the monomer 6-(4-((4-decylphenyl)azo)phenoxy)hexyl methacrylate (2.000g, 4mmol), cuprous bromide (38.0mg, 26.4 μmol), double-ended
实施例3:偶氮苯高分子在微米尺度下的光致固液转变Example 3: Photo-induced solid-liquid transition of azobenzene polymers at the micron scale
在室温下,取少量偶氮苯高分子(实施例2)固体样品于光滑干净的载玻片上,将载玻片放在显微镜的载物台上,用365nm(5.5mW/cm2)紫外光照射固体样品表面,使其发生光致异构化,照射15min后,实现完全的固液转变。图3示出了反式固体样品在紫外光照射下发生液化。At room temperature, take a small amount of azobenzene polymer (embodiment 2) solid sample on a smooth and clean glass slide, place the glass slide on the stage of the microscope, and use 365nm (5.5mW/cm 2 ) ultraviolet light The surface of the solid sample is irradiated to cause photoisomerization, and after 15 minutes of irradiation, a complete solid-liquid transition is achieved. Figure 3 shows the liquefaction of trans solid samples under UV light irradiation.
实施例4:偶氮苯高分子为内衬的PVC-U管修复结果Example 4: Repair result of PVC-U pipe lined with azobenzene polymer
在室温下,将800mg偶氮苯高分子(实施例2)溶于4ml四氢呋喃中,配置成质量分数为23wt%的溶液,并将其旋涂在内径为28mm、长10cm的PVC-U管上。室温放置2h后,放入45℃真空烘箱干燥过夜。用数控机床对PVC-U管穿透性破坏(裂缝长12mm,宽0.5mm),然后用365nm(8mW/cm2)紫外灯管照射PVC-U管内部,使偶氮苯高分子内衬发生光致异构化,并产生流动性,约4h后裂缝被修复。图4示出了涂覆有偶氮苯高分子的PVC-U管的修复前后的电子计算机断层扫描结果(标尺为6mm)。At room temperature, 800mg of azobenzene macromolecule (Example 2) was dissolved in 4ml of tetrahydrofuran, configured into a solution with a mass fraction of 23wt%, and spin-coated on a PVC-U tube with an inner diameter of 28mm and a length of 10cm . After standing at room temperature for 2 hours, put it into a vacuum oven at 45°C to dry overnight. Use a CNC machine tool to penetrate the PVC-U pipe (the crack is 12mm long and 0.5mm wide), and then irradiate the inside of the PVC-U pipe with a 365nm (8mW/cm 2 ) ultraviolet lamp to make the azobenzene polymer lining occur. After photoisomerization and fluidity, the cracks were repaired after about 4 hours. Fig. 4 shows the computerized tomography results before and after the repair of the PVC-U pipe coated with azobenzene polymer (the scale bar is 6mm).
由上述实施例可知,本发明提供的偶氮苯高分子具有高效的合成效率以及优异的光致可逆固液转变特性,可以用于实现管道的修复。It can be seen from the above examples that the azobenzene polymer provided by the present invention has high synthesis efficiency and excellent photoreversible solid-liquid transition characteristics, and can be used for repairing pipelines.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
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